JP2005314402A - Moisture retention polymer compound - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a moisture retention polymer compound which gives moisture to the skin and has a structural unit containing a multi-branched polysaccharide derivative suitable for an external preparation for the skin, which shows a moderate viscosity and solubility. <P>SOLUTION: (1) The moisture retention polymer compound comprises the structural unit containing the multi-branched polysaccharide derivative [wherein the hydroxyl group (OH) is optionally substituted by OR (wherein R represents a hydrogen atom, a 1-30C hydrocarbon or a 1-30C hydrocarbon having a hetero atom)] and a structural unit without the multi-branched polysaccharide derivative. (2) The external preparation for the skin contains 0.1 to 99.9 mass% of the polymer compound. (3) A cosmetic agent comprises the external preparation for the skin. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a novel moisturizing polymer compound. More specifically, the present invention relates to a moisturizing polymer compound having an effect of keeping the skin moisturized and suitable for use in a skin external preparation.

  A moisturizer is often used as a compound having an effect of keeping the skin moist in the external preparation for skin. Moisturizers are blended into topical skin preparations for the purpose of preventing moisture evaporation, adjusting moisture on the skin surface, and moisturizing and moisturizing. The amount of water in the skin stratum corneum is closely related to the protective function against various stimuli from the outside world, and plays a large role in the feeling of skin aging prevention, moisture, smoothness and the like. Moisture retention of this stratum corneum is usually controlled by NMF (Natural moisturizing factor) and sebum membrane, but its function easily deteriorates due to aging or stimulation from the outside. Supplementation is an important matter for topical skin preparations, especially cosmetics. Examples of moisturizing components that supplement skin moisture include amino acids, peptides, proteins, sugars, polysaccharides, lipids, glycoproteins, and the like as biological components.

  In particular, a wide variety of compounds are known for saccharides, such as alginic acid, pullulan, dextrin, glycogen, mucopolysaccharide, hyaluronic acid, chondroitin sulfate, chitin, chitosan, and cellulose. Japanese Patent Application Laid-Open No. 11-180818 (Patent Document 1) discloses an external preparation for skin containing plant glycogen, Japanese Patent Application Laid-Open No. 2001-89381 (Patent Document 2) describes an external preparation for skin containing mucopolysaccharide, Japanese Patent No. 145753 (Patent Document 3) discloses cosmetics containing hyaluronic acid, and Japanese Patent Application Laid-Open No. 9-249520 (Patent Document 4) discloses cosmetics containing cellulose and starch. The derived polysaccharide is composed of a plurality of types of monosaccharides, and the composition ratio is not constant and the structure is not constant, so quality control is difficult. There are drawbacks such as homogenization to cause gelation and precipitation, and an unpleasant feel and odor when applied to the skin.

  Many synthetic polymers are also known as moisturizing components. Examples include sodium polyacrylate, polyethyleneimine, polyethylene glycol, polyvinyl alcohol, polyvinylpyrrolidone, polyacrylamide, polyacrylic acid, polymethacrylic acid, vinyl pyridine, silicones, polyoxyethylene, and the like. JP-A-2000-143484 (Patent Document 5) discloses a polyacrylic acid-containing cosmetic sheet, and JP-A-9-124878 (Patent Document 6) discloses an acrylic acid polymer cosmetic gel composition. ing. Synthetic polymers can create polymers with various properties and properties due to their ease of molecular weight control, but on the other hand they are sufficiently comparable to natural polysaccharides when used for topical skin preparations. It can not be said that it has both sufficient moisture retention and high affinity for the skin to give the skin sufficient moisture.

Japanese Patent Laid-Open No. 11-180818 JP 2001-89381 A JP 2002-145753 A JP-A-9-249520 JP 2000-143484 A Japanese Patent Laid-Open No. 9-124878

  The subject of this invention makes it a subject to provide the skin external preparation which has the characteristics of moisturizing skin and showing moderate viscosity and solubility. In general, external preparations for skin contain a wide variety of compounds such as a compound that imparts moisture retention and a compound that imparts viscosity. However, due to differences in solubility, separation, precipitation, crystallization, etc. occur. Therefore, the performance and feel of the external preparation for skin may be significantly reduced. Another object of the present invention is to provide an external preparation for skin containing a polymer that reduces or avoids these obstacles.

  In the present invention, as a result of intensive studies to solve the above problems, a unit having a repeating structure of a unit that imparts moisture retention in the molecule, further imparting viscosity, and / or a unit imparting solubility, etc. By preparing a polymer containing the same in the same molecule and blending it into the external preparation for skin, it retains moderate viscosity and solubility, moisturizes the skin, and also feels good to the skin. As a result, the present invention has been completed.

That is, the present invention relates to the following matters.
1. A structural unit containing a multi-branched polysaccharide derivative (wherein the hydroxyl group (OH) in the multi-branched polysaccharide derivative is OR (R is a hydrogen atom, a hydrocarbon having 1 to 30 carbon atoms, or a carbon atom having a hetero atom) 1 to 30 hydrocarbons)) and a structural unit that does not contain a multi-branched polysaccharide derivative.
2. 2. The moisturizing polymer compound according to 1 above, wherein the main chain of the polymer compound is composed of a structural unit containing a multi-branched polysaccharide derivative.
3. 3. The moisturizing polymer compound according to 2 above, which is a polymer compound obtained by copolymerization of a multi-branched polysaccharide derivative having at least two hydroxyl groups and dicarboxylic acids and / or diisocyanates.
4). 2. The moisturizing polymer compound according to 1, wherein the polymer compound has a structural unit containing a multibranched polysaccharide derivative in a side chain thereof.
5). 5. The moisturizing polymer compound according to 4 above, which is a polymer compound obtained by reacting a polymer compound having a carboxyl group and / or an isocyanate group in the main chain with a hydroxyl group (OH) of a multi-branched polysaccharide derivative.
6). In the multi-branched polysaccharide derivative, at least one hydroxyl group (OH) of anhydrous sugar and / or anhydrous sugar is OR (R is a hydrogen atom, a hydrocarbon having 1 to 30 carbon atoms, or a carbon atom having 1 hetero atom. 6. The moisturizing polymer compound according to 1 to 5, which is a polymer having an anhydrosugar derivative substituted as a monomer.
7). The anhydrosugar part of an anhydrosugar or an anhydrosugar derivative consists of 1,6-anhydro sugar, 1,4-anhydro sugar, 1,3-anhydro sugar, 1,2-anhydro sugar, and 5,6-anhydro sugar 7. The moisturizing polymer compound as described in 6 above, which is at least one selected from the group consisting of:
8). 8. The moisturizing polymer compound according to 1 to 7, wherein the degree of branching of the multibranched polysaccharide derivative is 0.05 to 1.00.
9. The moisturizing polymer compound according to 1 to 8, wherein the solubility in water, ethanol, or a mixture of water and ethanol is 1.0% by mass or more.
10. A humectant comprising the polymer compound according to any one of 1 to 9 above.
11. The skin external preparation characterized by containing 0.1-99.9 mass% of high molecular compounds in any one of said 1-9.
12 A cosmetic comprising the humectant described in 10 above.
13. 12. A cosmetic comprising the skin external preparation described in 11 above.

The polymer compound of the present invention is a polymer compound having a structural unit containing a multibranched polysaccharide derivative and a structural unit not containing a multibranched polysaccharide derivative. However, in the multibranched polysaccharide derivative, the hydroxyl group OH of the multibranched polysaccharide is OR (R is a hydrogen atom, a hydrocarbon having 1 to 30 carbon atoms, a hydrocarbon having 1 to 30 carbon atoms having a hetero atom. .) May be substituted.
More specifically, it is a polymer compound having a multi-branched polysaccharide derivative in either the main chain or the side chain.

  As an example when the main chain of the polymer compound is composed of structural units containing a multi-branched polysaccharide derivative, a polymer is obtained by reacting a plurality of hydroxyl groups of the multi-branched polysaccharide derivative with a dicarboxylic acid compound, a diisocyanate compound, etc. Things.

  When the side chain of the polymer compound has a structural unit containing a multibranched polysaccharide derivative, for example, the multibranched polysaccharide derivative may be bonded from the main chain of the polymer compound via an appropriate spacer. Examples of such a spacer include an organic group having 1 to 30 carbon atoms and optionally having a hetero atom. Examples of the hetero atom in such an organic group include atoms such as oxygen, nitrogen, sulfur, silicon, and phosphorus. Specific examples of the organic group containing a hetero atom include a hydrocarbon group, a carbonyl group, a urethane group, Examples thereof include a peptide group, a sulfonyl group, a phosphate group and the like as a part or all of the spacer.

  More specifically, a polymer obtained by reacting a carboxyl group of a polymer copolymerized with acrylic acid, methacrylic acid or the like, a isocyanate group of a polymer copolymerized with isocyanate ethyl methacrylate or the like with a hydroxyl group of a multi-branched polysaccharide derivative. It can be illustrated.

  As a method for synthesizing the polymer compound of the present invention, there is a method in which a compound having two functional groups that react with a hydroxyl group in a molecule and a multibranched polysaccharide derivative are mixed and subjected to condensation polymerization. For example, a polyurethane polymer compound containing a multi-branched polysaccharide in the main chain by mixing and reacting a compound selected from dicarboxylic acids and diisocyanates (for example, diisocyanate hexane) and a multi-branched polysaccharide in an appropriate ratio. Can be obtained.

  In addition, a monomer containing a polymerizable functional group and a multi-branched polysaccharide derivative is synthesized, and this is a method of subjecting it alone or with other monomers to condensation polymerization, radical polymerization, ionic polymerization, ring-opening polymerization, block polymerization, graft polymerization, etc. be able to.

  Furthermore, a polymer having a functional group is polymerized first, and then a multi-branched polysaccharide derivative is reacted and bonded to the functional group, for example, methyl methacrylate and isocyanate ethyl methacrylate are mixed in an appropriate ratio. A polymer compound having a multi-branched polysaccharide derivative in the side chain by reacting a hydroxyl group of the multi-branched polysaccharide derivative with an isocyanate group of a polymethacrylic acid copolymer obtained by radical polymerization However, it is not limited to these methods.

  The multibranched polysaccharide constituting the skeleton of the multibranched polysaccharide derivative of the present invention is a compound composed of one kind or many kinds of sugars as its constituent components. The structure is a dendritic structure having many branch points due to the presence of three or more binding sites with adjacent sugar molecules in the same sugar molecule having a plurality of hydroxyl groups. In general, polysaccharides that exist in various natural products are straight-chain polysaccharides and branched polysaccharides with few branch points, and each has a main chain. A hyperbranched polysaccharide is a compound that does not have a clear main chain because of its many branch points.

  Examples of the sugar constituting the multi-branched polysaccharide of the present invention include ribose and deoxyribose as the 5 monosaccharide, and glucose, fructose and galactose as the 6 monosaccharide.

  As a method for producing the multibranched polysaccharide of the present invention, a conventionally known method can be applied. For example, as a method produced by a chemical synthesis method, a production method for obtaining a multi-branched polysaccharide by polymerizing a monosaccharide derivative as a monomer can be cited as an example, as disclosed in JP-A-2003-252904. In addition, there is a production method for obtaining a multibranched polysaccharide by ionic polymerization using an anhydrous sugar as a monomer. In this case, as the anhydrous sugar, for example, 1,6-anhydro sugar, 1,4-anhydro sugar, 1,3-anhydro sugar, 1,2-anhydro sugar, 5,6-anhydro sugar, and derivatives thereof, Specifically, 1,6-anhydro-β-D-glucopyranose, 1,6-anhydro-β-D-mannopyranose, 1,6-anhydro-β-D-galactopyranose, 1,6-anhydro -Β-D-allopyranose, 1,6-anhydro-β-D-altropyranose, 1,4-anhydro-β-D-ribopyranose, 1,4-anhydro-α-D-xylopyranose, 1,4 -Anhydro-α-L-arabinopyranose, 1,4-anhydro-α-D-lyxopyranose, 1,3-anhydro-β-D-glucopyranose, 1,3-anhydro-β-D-mannopyra North, 1,2-anhydro-α-D-glucopyranose, 1,2-anhydro-β-D-mannopyranose, 5,6-anhydro-α-D-glucopyranose and the like and their derivatives. it can.

  Examples of ionic polymerization include cationic polymerization and anionic polymerization. There are also production methods for obtaining multibranched polysaccharides by using animals, plants, microorganisms, or using methods such as breeding, cultivation and culture thereof. In this case, a multi-branched polysaccharide having a desired degree of branching can be used as it is, or as a method for producing a multi-branched polysaccharide having an increased degree of branching, for example, branching by a production method as described in JP-A-8-41104 The degree of branching from a polysaccharide to a multibranched polysaccharide can also be increased.

  The multi-branched polysaccharide derivative of the present invention has a structure in which a part and / or all of the hydroxyl groups of the multi-branched polysaccharide serving as a skeleton is substituted with a substituent, for example, at least one of the hydroxyl groups OH of the multi-branched polysaccharide is Examples include a compound substituted with OR (R is a hetero compound containing a hydrogen atom, a hydrocarbon having 1 to 30 carbon atoms, or a hydrocarbon having 1 to 30 carbon atoms).

  As R, for example, methyl group, ethyl group, propyl group, isopropyl group, butyl group, 1-methylpropyl group, 2-methylpropyl group, pentyl group, 1-methylbutyl group, 2-methylbutyl group, 3-methylbutyl group 1-ethylpropyl group, hexyl group, 1-methylpentyl group, 2-methylpentyl group, 3-methylpentyl group, 4-methylpentyl group, 1-ethylbutyl group, 2-ethylbutyl group, heptyl group, 1-methyl Hexyl group, 2-methylhexyl group, 3-methylhexyl group, 4-methylhexyl group, 5-methylhexyl group, 1-ethylpentyl group, 2-ethylpentyl group, 3-ethylpentyl group, octyl group, 1- Methylheptyl group, 2-methylheptyl group, 3-methylheptyl group, 4-methylheptyl group, 5-methylheptyl group, -Methylheptyl group, 1-ethylhexyl group, 2-ethylhexyl group, 3-ethylhexyl group, 4-ethylhexyl group, 1-propylpentyl group, 2-propylpentyl group, nonyl group, decyl group, undecyl group, 10-undecenyl group , Dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, 9-hexadecenyl group, heptadecyl group, octadecyl group, isostearyl group, cis-9-octadecenyl group, 11-octadecenyl group, cis, cis-9,12 -Octadecadienyl group, 9,12,15-octadecatrienyl group, 6,9,12-octadecatrienyl group, 9,11,13-octadecatrienyl group, nonadecyl group, 2,6, 10,14-tetramethylpentadecyl group, icosanyl group, 8,11-icosa Enyl group, 5,8,11-icosatrienyl group, 5,8,11,14-icosatetraenyl group, 3,7,11,15-tetramethylhexadecyl group, henicosanyl group, docosanyl group, acetyl group, propionyl Group, isopropionyl group, butyryl group, 1-methylpropionyl group, 2-methylpropionyl group, valeryl group, 1-methylbutyryl group, 2-methylbutyryl group, 3-methylbutyryl group, 1-ethylpropionyl group, hexanoyl group, 2- Methylpentanoyl group, 3-methylpentanoyl group, 4-methylpentanoyl group, 2-ethylbutanoyl group, heptanoyl group, 2-methylhexanoyl group, 3-methylhexanoyl group, 4-methylhexanoyl group, 2-ethylpentanoyl group, 3-ethylpentanoyl group, octanoyl group, 2- Methylheptanoyl group, 3-methylheptanoyl group, 4-methylheptanoyl group, 5-methylheptanoyl group, 6-methylheptanoyl group, 2-ethylhexanoyl group, 3-ethylhexanoyl group, 4-ethyl Hexanoyl group, 2-propylpentanoyl group, nonanoyl group, decanoyl group, undecanoyl group, 10-undecenoyl group, dodecanoyl group, tridecanoyl group, tetradecanoyl group, pentadecanoyl group, hexadecanoyl group, 9-hexadecenoyl group , Heptadecanoyl group, octadecanoyl group, isostearyl group, cis-9-octadecenoyl group, 11-octadecenoyl group, cis, cis-9,12-octadecadienoyl group, 9,12,15-octadecatrienoyl group 6,9,12-octadecatrienoyl group, 9, 1,13-octadecatrienoyl group, nonadecanoyl group, 2,6,10,14-tetramethylpentadecanoyl group, icosanoyl group, 8,11-icosadienoyl group, 5,8,11-icosatrienoyl group, 5 , 8,11,14-icosatetraenoyl group, 3,7,11,15-tetramethylhexadecanoyl group, henicosanoyl group, docosanoyl group, phosphatidyl group and the like. Furthermore, a compound in which R is bonded with an isocyanate group is also included.

  Examples of the method for synthesizing a multibranched polysaccharide derivative of the present invention include a method of synthesizing a multibranched polysaccharide derivative by obtaining a multibranched polysaccharide as a skeleton and then modifying the hydroxyl group of the sugar with a desired functional group, or a multibranched polysaccharide. There is a method of synthesizing a multi-branched polysaccharide derivative by modifying a hydroxyl group of an anhydrous sugar as a monomer of the above with a desired functional group and then polymerizing it.

  The hydroxyl group can be modified by, for example, a usual esterification method using a carboxylic acid derivative. Specifically, a method of reacting carboxylic acid as an acid chloride or mixed acid anhydride, a method of reacting with carbodiimide, a method of using an acid anhydride, and the like can be mentioned. In the case of a compound having an isocyanate group, there are a modification method for forming a urethane bond by using a catalyst such as heating or a tin-based or amine-based catalyst.

The degree of branching of the multibranched polysaccharide constituting the skeleton of the multibranched polysaccharide derivative of the present invention is 0.05 to 1.00, preferably 0.2 to 1.0, more preferably 0.4 to 1.0. In this case, the degree of multi-branching is generally calculated by the following Frechet equation.

  As a method of blending the polymer compound used in the present invention into the external preparation for skin, a method for producing a skin external preparation by mixing as a solid, powder or semisolid, a method for producing an external preparation for skin by mixing as an aqueous solution And a method of producing a skin external preparation by mixing as a solution of alcohols or an appropriate solvent, and a method of adding or adding a skin external preparation by mixing or adding by a known method.

  The polymer compound used in the present invention can be isolated, for example, in the form of a powder, but the solution obtained in the production process can be directly blended with the external preparation for skin. In addition, it is generally preferable for aqueous skin preparations to have high water solubility. Specifically, the solubility in water, ethanol, or a mixture of water and ethanol is preferably 1.0% by mass or more.

  The polymer compound used in the present invention can be blended in an amount of 0.01 to 100% by mass, preferably 0.1 to 99.9% by mass, more preferably 1 to 50% by mass, as long as it is an amount that can be blended as a form of external skin preparation. %. When the blending amount is less than 0.01% by mass with respect to the external preparation for skin, adhesion to the skin and affinity are not sufficient, and a feeling such as moisturizing feeling on the skin may not be sufficiently obtained. As an external preparation for skin, it can be blended within a range that does not impair the original function.

  The topical skin preparation in the present invention includes cosmetics, cleaning agents, bathing agents, soaps and the like that directly touch the skin.

  Examples of the skin external preparation of the present invention include skin milk, skin cream, foundation cream, massage cream, cleansing cream, shaving cream, cleansing foam, lotion, lotion, pack, lipstick, blusher, eye shadow, nail polish, soap, body Shampoo, hand soap, shampoo, rinse, hair tonic, treatment, hair cream, hair spray, hair restorer, hair nourishing agent, hair dye, hair styling agent, hair removal agent, anti-dandruff agent, toothpaste, denture adhesive, gargle, permanent wave Agents, curling agents, styling agents, ointments, poultices, tape agents, bathing agents, antiperspirants, sunscreen agents, etc. are included in a broad sense, and any type can be used as long as they come into contact with the skin during use. It is particularly preferable to use it as a cosmetic. Regardless of the gender and age of the user. Furthermore, in addition to humans, those that come into contact with animal skin are also included.

  In addition to solid, liquid, semi-solid, and gas, the shape of the present invention includes many forms such as powder, granule, tablet, gel, and foam.

  In the external preparation for skin of the present invention, as components other than the polymer compound, components generally used for external preparations for skin can be blended as necessary within the range not impairing the effects of the present invention. There are compounds that can be blended, compounds used as raw materials for quasi-drugs, pharmaceuticals, and pharmaceutical additives.

Specifically, as such a component, for example,
Ozokerite, α-olefin oligomer, light isoparaffin, light liquid isoparaffin, squalene, squalane, synthetic squalane, vegetable squalane, ceresin, paraffin, polyethylene powder, polybutene, microcrystalline wax, liquid isoparaffin, liquid paraffin, mineral oil, petroleum jelly, etc. Hydrocarbons;

  Jojoba oil, carnauba wax, candelilla wax, rice bran wax, shellac, lanolin, mink sebum wax, whale wax, sugar cane wax, sperm whale oil, beeswax, montan wax and other natural waxes, avocado oil, almond oil, olive oil, extra virgin olive oil, Sesame oil, rice bran oil, rice oil, rice germ oil, corn oil, safflower oil, soybean oil, corn oil, rapeseed oil, persic oil, palm kernel oil, palm oil, castor oil, sunflower oil, high oleic sunflower oil, Grape seed oil, cottonseed oil, palm oil, hydrogenated palm oil, beef tallow, hardened oil, horse oil, mink oil, egg yolk oil, egg yolk fat oil, rosehip oil, cucumber nut oil, evening primrose oil, wheat germ oil, peanut oil, camellia oil Oil, sasanqua oil, cacao butter, molasses, beef bone fat, beef leg oil, pork fat, horse fat, sheep fat, sheabata , Macadamia nut oil, natural fats and oils of meadowfoam oil, and the like;

  Fatty acids such as lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, oleic acid, linoleic acid, linolenic acid, γ-linolenic acid, isostearic acid, 12-hydroxystearic acid, undecylenic acid, coconut oil fatty acid;

  Higher alcohols such as isostearyl alcohol, octyldodecanol, hexyldecanol, cholesterol, phytosterol, lauryl alcohol, myristyl alcohol, cetanol, stearyl alcohol, oleyl alcohol, behenyl alcohol, cetostearyl alcohol;

  Alkyl glyceryl ethers such as batyl alcohol, chimyl alcohol, ceralkyl alcohol, isostearyl glyceryl ether;

  Isopropyl myristate, butyl myristate, isopropyl palmitate, ethyl stearate, butyl stearate, ethyl oleate, ethyl linoleate, isopropyl linoleate, cetyl caprylate, hexyl laurate, isooctyl myristate, decyl myristate, myristic acid Myristyl, cetyl myristate, octadecyl myristate, cetyl palmitate, stearyl stearate, decyl oleate, oleyl oleate, cetyl ricinoleate, isostearyl laurate, isotridecyl myristate, isocetyl myristate, isostearyl myristate, myristic acid Octyldodecyl, 2-ethylhexyl palmitate, isocetyl palmitate, isostearyl palmitate, 2-ethyl stearate Ruhexyl, isocetyl stearate, isodecyl oleate, octyldodecyl oleate, octyldodecyl ricinoleate, ethyl isostearate, isopropyl isostearate, cetyl 2-ethylhexanoate, cetostearyl 2-ethylhexanoate, stearyl 2-ethylhexanoate, Hexyl isostearate, ethylene glycol dioctanoate, ethylene glycol dioleate, propylene glycol dicaprylate, propylene glycol di (capryl / capric acid), propylene glycol dicaprate, propylene glycol dioleate, neopentyl glycol dicaprate, neopentyl glycol dioctanoate , Glyceryl tricaprylate, glyceryl tri-2-ethylhexanoate, tri (capryl caprin ) Glyceryl, tri (caprylic acid / capric acid / stearic acid) glyceryl, glyceryl triundecylate, glyceryl triisopalmitate, glyceryl triisostearate, trimethylolpropane tri-2-ethylhexanoate, trimethylolpropane triisostearate, tetra-2 -Pentaerythrityl ethylhexanoate, pentaerythrityl tetramyristate, pentaerythrityl tetraisostearate, diglyceryl tetraisostearate, octyldodecyl neopentanoate, isocetyl octoate, isostearyl octoate, 2-ethylhexyl isoperargonate, Hexyldecyl dimethyloctanoate, octyldodecyl dimethyloctanoate, 2-ethylhexyl isopalmitate, isocetyl isostearate, Isostearyl isostearate, octyldodecyl isostearate, lauryl lactate, myristyl lactate, cetyl lactate, octyldodecyl lactate, triethyl citrate, acetyl triethyl citrate, acetyl tributyl citrate, trioctyl citrate, triisocetyl citrate, trioctyl dodecyl citrate Diisostearyl malate, 2-ethylhexyl hydroxystearate, di-2-ethylhexyl succinate, diisopropyl adipate, diisobutyl adipate, dioctyl adipate, diheptyl undecyl adipate, diethyl sebacate, diisopropyl sebacate, sebacic acid Dioctyl, cholesteryl stearate, cholesteryl isostearate, cholesteryl hydroxystearate, cholesteryl oleate Dihydrocholesteryl oleate, phytosteryl isostearate, phytosteryl oleate, isocetyl 12-stearoylhydroxystearate, stearyl 12-stearoylhydroxystearate, isostearyl 12-stearoylhydroxystearate, polyoxyethylene acetate (3) polyoxypropylene (1) ) Esters such as cetyl ether, polyoxyethylene acetate (3) polyoxypropylene (1) isocetyl ether, isononyl isononanoate, octyl isononanoate, tridecyl isononanoate, isotridecyl isononanoate;

  Methylpolysiloxane, methylphenylpolysiloxane, methylhydrogenpolysiloxane, methylcyclopolysiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, octamethyltrisiloxane, decamethyltetrasiloxane, tetradeca Methyl hexasiloxane, highly polymerized methyl polysiloxane, dimethyl siloxane methyl (polyoxyethylene) siloxane methyl (polyoxypropylene) siloxane copolymer, dimethyl siloxane methyl (polyoxyethylene) siloxane copolymer, dimethyl siloxane methyl (Polyoxypropylene) siloxane copolymer, dimethylsiloxane / methylcetyloxysiloxane copolymer, dimethylsiloxane / Chill stearoxysiloxane copolymer, polyether-modified silicones, alcohol-modified silicones, alkyl-modified silicones, silicone oils such as amino-modified silicone;

  Ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, pentanediol, glycerin, diglycerin, polyglycerin, isoprene glycol, 1,3-butylene glycol, 3-methyl-1,3 Polyhydric alcohols such as butanediol, 1,3-butanediol, 1,2-pentanediol, 1,2-hexanediol;

  Sugars such as mannitol, sorbitol, xylitol, maltitol, erythritol, pentaerythritol, glucose, sucrose, fructose, lactose, maltose, xylose, trehalose;

Sodium alginate, carrageenan, agar, fur celerin, guar gum, quince seed, konjac mannan, tamarind gum, tara gum, dextrin, starch, locust bean gum, gum arabic, gati gum, karaya gum, tragacanth gum, arabinogalactan, pectin, quince, chitosan, card Orchid, xanthan gum, gellan gum, cyclodextrin, dextran, pullulan, microcrystalline cellulose, methylcellulose, ethylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, hydroxypropylmethylcellulose, carboxymethylcellulose, carboxystarch, cationized cellulose, starch phosphate ester, cationized guar gum , Carboxymethyl hydroxyp Pilled guar gum, hydroxypropylated guar gum, albumin, casein, gelatin, sodium polyacrylate, polyacrylamide, carboxyvinyl polymer, polyethyleneimine, highly polymerized polyethylene glycol, polyvinyl alcohol, polyvinylpyrrolidone, polyvinyl ether, polyacrylamide, acrylic Acid copolymer, methacrylic acid copolymer, maleic acid copolymer, vinyl pyridine copolymer, ethylene / acrylic acid copolymer, vinyl pyrrolidone polymer, vinyl alcohol / vinyl pyrrolidone copolymer, nitrogen-substituted acrylamide polymer , Amino-modified silicone, cationized polymer, dimethylacrylammonium polymer, acrylic acid-based anion polymer, methacrylic acid-based anion polymer, modified silica Over emissions, alkyl methacrylate acrylate acid (C _{10 to 30)} copolymer, a polymer such as polyoxyethylene / polyoxypropylene copolymer;

  Alcohols such as ethanol, isopropyl alcohol, 1-butanol, 2-butanol, benzyl alcohol;

  Palm oil fatty acid potassium, coconut oil fatty acid sodium, coconut oil fatty acid triethanolamine, potassium laurate, sodium laurate, triethanolamine laurate, potassium myristate, sodium myristate, isopropanolamine myristate, potassium palmitate, palmitic acid Sodium, isopropanolamine palmitate, potassium stearate, sodium stearate, triethanolamine stearate, potassium oleate, sodium oleate, castor oil fatty acid sodium, zinc undecylenate, zinc laurate, zinc myristate, magnesium myristate, Zinc palmitate, zinc stearate, calcium stearate, magnesium stearate, aluminum stearate, myristi Calcium oxide, magnesium myristate, aluminum dimyristate, aluminum isostearate, polyoxyethylene lauryl ether acetic acid, sodium polyoxyethylene lauryl ether acetate, polyoxyethylene tridecyl ether acetic acid, sodium polyoxyethylene tridecyl ether acetate, stearoyl lactic acid Sodium, isostearoyl sodium lactate, lauroyl sarcosine sodium, coconut oil fatty acid sarcosine, coconut oil fatty acid sarcosine sodium, coconut oil fatty acid sarcosine triethanolamine, lauroyl sarcosine, lauroyl sarcosine potassium, lauroyl sarcosine triethanolamine, oleoyl sarcosine, myristoyl sarcosine sodium , Sodium stearoyl glutamate, Oil fatty acid acyl glutamic acid, coconut oil fatty acid potassium acyl glutamate, coconut oil fatty acid acyl glutamic acid sodium, coconut oil fatty acid acyl glutamic acid triethanolamine, lauroyl acyl glutamic acid, lauroyl acyl glutamic acid potassium, lauroyl acyl glutamic acid sodium, lauroyl acyl glutamic acid triethanolamine, myristoyl Acyl glutamic acid, potassium myristoyl acyl glutamate, sodium myristoyl acyl glutamate, stearoyl acyl glutamate, potassium stearoyl acyl glutamate, disodium stearoyl acyl glutamate, sodium hard beef tallow fatty acid acyl glutamate, coconut oil fatty acid / cured tallow fatty acid sodium acyl glutamate, coconut oil fatty acid me Sodium tilalanine, lauroylmethylalanine, sodium lauroylmethylalanine, lauroylmethylalanine triethanolamine, sodium myristoylmethylalanine, sodium lauroylmethyltaurine, coconut oil fatty acid methyltaurine potassium, coconut oil fatty acid methyltaurine sodium, coconut oil fatty acid methyltaurine magnesium , Myristoyl methyl taurine sodium, palmitoyl methyl taurine sodium, stearoyl methyl taurine sodium, oleoyl methyl taurine sodium, sodium alkane sulfonate, sodium tetradecene sulfonate, dioctyl sodium sulfosuccinate, disodium lauryl sulfosuccinate, palm oil fatty acid ethyl ester sulfone Acid sodium, lauryl sulfate Thorium, triethanolamine lauryl sulfate, sodium cetyl sulfate, alkyl (11,13,15) triethanolamine sulfate, alkyl (12,13) sodium sulfate, alkyl (12,13) triethanolamine sulfate, alkyl (12,14) , 16) Ammonium sulfate, alkyl (12-13) diethanolamine sulfate, alkyl (12-14) triethanolamine sulfate, alkyl (12-15) triethanolamine sulfate, palm oil alkyl magnesium sulfate / triethanolamine, ammonium lauryl sulfate, lauryl Potassium sulfate, magnesium lauryl sulfate, monoethanolamine lauryl sulfate, diethanolamine lauryl sulfate, sodium myristyl sulfate, sodium stearyl sulfate, sodium oleyl sulfate, Rail ethanol triethanolamine, polyoxyethylene lauryl ether sodium sulfate, polyoxyethylene lauryl ether triethanolamine sulfate, polyoxyethylene (1) alkyl (11,13,15) ether sodium sulfate, polyoxyethylene (1) alkyl ( 11,13,15) ether sulfate triethanolamine, polyoxyethylene (3) alkyl (11-15) sodium ether sulfate, polyoxyethylene (2) alkyl (12,13) sodium ether sulfate, polyoxyethylene (3) Alkyl (12-14) ether sodium sulfate, polyoxyethylene (3) alkyl (12-15) sodium ether sulfate, polyoxyethylene (2) sodium lauryl ether sulfate, polyoxyethylene (3) Sodium listyl ether sulfate, sodium higher fatty acid alkanolamide sulfate, lauryl phosphate, sodium lauryl phosphate, potassium cetyl phosphate, diethanolamine cetyl phosphate, polyoxyethylene oleyl ether phosphate, polyoxyethylene lauryl ether phosphate, polyoxyethylene Sodium lauryl ether phosphate, polyoxyethylene cetyl ether phosphate, polyoxyethylene cetyl ether sodium phosphate, polyoxyethylene stearyl ether phosphate, polyoxyethylene oleyl ether phosphate, polyoxyethylene oleyl ether sodium phosphate, polyoxy Ethylene alkyl phenyl ether phosphate, polyoxyethylene alkyl phenyl ether sodium phosphate, polyoxy ester Lenalkylphenyl ether phosphate triethanolamine, polyoxyethylene octyl ether phosphate, polyoxyethylene (10) alkyl (12,13) ether phosphate, polyoxyethylene alkyl (12-15) ether phosphate, polyoxyethylene Anionic surfactants such as alkyl (12-16) ether phosphate, polyoxyethylene lauryl ether phosphate triethanolamine, polyoxyethylene oleyl ether phosphate diethanolamine;

  Dioctylamine, dimethylstearylamine, trilaurylamine, diethylaminoethylamide stearate, lauryltrimethylammonium chloride, cetyltrimethylammonium chloride, cetyltrimethylammonium bromide, cetyltrimethylammonium saccharin, stearyltrimethylammonium chloride, alkyl chloride (20-22) Trimethylammonium, lauryltrimethylammonium bromide, alkyl (16,18) trimethylammonium chloride, stearyltrimethylammonium bromide, stearyltrimethylammonium saccharin, alkyl (28) trimethylammonium chloride, di (polyoxyethylene) oleylmethylammonium chloride (2EO) ), Dipolyoxyethylene stearylmethylammonium chloride Polyoxyethylene chloride (1) polyoxypropylene (25) diethylmethylammonium chloride, tri (polyoxyethylene) stearylammonium chloride (5EO), distearyldimethylammonium chloride, dialkyl (12-15) dimethylammonium chloride, dialkylchloride (12 -18) Dimethyl ammonium, dialkyl chloride (14-18) dimethyl ammonium, dicocoyl dimethyl ammonium chloride, dicetyl dimethyl ammonium chloride, isostearyl lauryl dimethyl ammonium chloride, benzalkonium chloride, myristyl dimethyl benzyl ammonium chloride, lauryl dimethyl chloride ( Ethylbenzyl) ammonium, stearyldimethylbenzylammonium chloride, laurylpyridinium chloride, cetylpyridinium chloride Lauroyl kola amino formyl methyl pyridinium chloride, stearoyl colaminoformyl methylpyridinium bromide alkyl isoquinolizinyloxy potassium, chloride methyl benzethonium, cationic surfactants such as benzethonium chloride;

  2-alkyl-N-carboxymethyl-N-hydroxyethylimidazolinium betaine, alkyldiaminoethylglycine hydrochloride, sodium lauryldiaminoethylglycine, sodium undecylhydroxyethylimidazolium betaine, undecyl-N-carboxymethylimidazolium betaine Coconut oil fatty acid acyl-N-carboxyethyl-N-hydroxyethylethylenediamine disodium, coconut oil fatty acid acyl-N-carboxyethoxyethyl-N-carboxyethylethylenediamine disodium, coconut oil fatty acid acyl-N-carboxymethoxyethyl-N -Carboxymethylethylenediamine disodium, sodium laurylaminopropionate, sodium laurylaminodipropionate, laurylaminopropyl Triethanolamine pionate, palm oil fatty acid acyl-N-carboxyethyl-N-hydroxyethylethylenediamine sodium, lauryldimethylaminoacetic acid betaine, coconut oil alkyldimethylaminoacetic acid betaine, stearyldimethylaminoacetic acid betaine, stearyldimethylbetaine sodium, coconut oil Amphoteric surfactants such as fatty acid amidopropyl betaine, palm oil fatty acid amidopropyl betaine, lauric acid amidopropyl acetic acid betaine, ricinoleic acid amidopropyl betaine, stearyl dihydroxyethyl betaine, lauryl hydroxysulfo betaine;

  Polyoxyethylene (10) alkyl (12,13) ether, polyoxyethylene lauryl ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene (3, 7, 12) alkyl ( 12-14) ether, polyoxyethylene tridecyl ether, polyoxyethylene myristyl ether, polyoxyethylene-sec-alkyl (14) ether, polyoxyethylene isocetyl ether, polyoxyethylene cetostearyl ether, polyoxyethylene (2 , 10, 20) Isostearyl ether, polyoxyethylene oleyl cetyl ether, polyoxyethylene (20) aralkyl ether, polyoxyethylene octyldodecyl ether Polyoxyethylene behenyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene nonyl phenyl ether, polyoxyethylene dinonyl phenyl ether, polyoxyethylene (1) polyoxypropylene (1,2,4,8) cetyl ether, poly Oxyethylene (5) polyoxypropylene (1,2,4,8) cetyl ether, polyoxyethylene (10) polyoxypropylene (1,2,4,8) cetyl ether, polyoxyethylene (20) polyoxypropylene (1,2,4,8) cetyl ether, polyoxyethylene polyoxypropylene lauryl ether, polyoxyethylene (3) polyoxypropylene (34) stearyl ether, polyoxyethylene (4) polyoxypropylene (30) Allyl ether, polyoxyethylene (34) polyoxypropylene (23) stearyl ether, polyoxyethylene polyoxypropylene cetyl ether, polyoxyethylene polyoxypropylene decyl tetradecyl ether, polyethylene glycol monolaurate, ethylene glycol monostearate, mono Polyethylene glycol stearate, polyethylene glycol monooleate, ethylene glycol fatty acid ester, self-emulsifying ethylene glycol monostearate, diethylene glycol laurate, polyethylene glycol myristate, polyethylene glycol palmitate, diethylene glycol stearate, polyethylene monostearate self-emulsifying Glycol (2), polyethylene isostearate Recall, ethylene glycol dioctanoate, diethylene glycol dilaurate, polyethylene glycol dilaurate, polyethylene glycol dipalmitate (150), ethylene glycol distearate, diethylene glycol distearate, polyethylene glycol distearate, ethylene glycol dioleate, polyethylene glycol dioleate, diglycol Polyethylene glycol ricinoleate, polyoxyethylene (20) sorbitan monolaurate, polyoxyethylene (20) sorbitan monopalmitate, polyoxyethylene (6) sorbitan monostearate, polyoxyethylene (20) sorbitan monostearate, tristearin Acid polyoxyethylene (20) sorbitan, monooleic acid polyoxy Tylene (6) sorbitan, polyoxyethylene monooleate (20) sorbitan, polyoxyethylene trioleate (20) sorbitan, polyoxyethylene (20) coconut oil fatty acid sorbitan, polyoxyethylene monolaurate (10-80) sorbitan , Polyoxyethylene sorbitan tristearate, polyoxyethylene (20) sorbitan isostearate, polyoxyethylene (150) sorbitan tristearate, polyoxyethylene castor oil, polyoxyethylene hydrogenated castor oil, polyoxyethylene (10) cured Castor oil, polyoxyethylene (20) hydrogenated castor oil, polyoxyethylene (40) hydrogenated castor oil, polyoxyethylene (50) hydrogenated castor oil, polyoxyethylene (60) hydrogenated castor oil, lipophilic monos Glyceryl allate, glyceryl monooleate, glyceryl monostearate, self-emulsifying glyceryl monostearate, glyceryl coconut oil, glyceryl laurate, glyceryl myristate, glyceryl isostearate, glyceryl ricinoleate, glyceryl monohydroxystearate, glyceryl oleate , Glyceryl linoleate, glyceryl erucate, glyceryl behenate, wheat germ oil fatty acid glyceride, safflower oil fatty acid glyceryl, hydrogenated soybean fatty acid glyceryl, saturated fatty acid glyceride, cottonseed oil fatty acid glyceryl, monoisostearate monomyristate glyceryl, mono-bovine fatty acid Glycerides, monolanolin fatty acid glyceryl, glyceryl sesquioleate, glyceryl distearate, glyceryl diisostearate, diarachin Glyceryl acid, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monoisostearate, sorbitan monooleate, sorbitan sesquistearate, sorbitan sesquioleate, sorbitan tristearate, sorbitan trioleate, coconut oil fatty acid Sorbitan, sorbitan isostearate, sorbitan sesquiisostearate, sorbitan distearate, diglyceryl isopalmitate, poly (4-10) glyceryl monolaurate, poly (10) glyceryl monomyristate, poly (2-10) glyceryl monostearate , Poly (2-10) glyceryl monoisostearate, poly (2-10) glyceryl monooleate, diglyceryl sesquioleate, diisostearate Poly (2-10) glyceryl acid, poly (6-10) glyceryl distearate, diglyceryl triisostearate, poly (10) glyceryl tristearate, poly (10) glyceryl trioleate, poly (2) tetraisostearate ) Glyceryl, decaglyceryl pentastearate, poly (6-10) glyceryl pentaoleate, poly (10) glyceryl heptearate, decaglyceryl decastearate, poly (10) glyceryl dekaoleate, poly (6) condensed ricinoleate Glyceryl, sucrose fatty acid ester, coconut oil fatty acid sucrose ester, alkyl glucoside, coconut oil alkyl dimethylamine oxide, lauryl dimethylamine oxide, dihydroxyethyl lauryl dimethylamine oxide, stearyl dimethyl ester Le amine oxide, oleyl dimethyl amine oxide, and nonionic surfactants such as polyoxyethylene coconut oil alkyldimethylamine oxide;

  Saponin, lecithin, soybean phospholipid, hydrogenated soybean phospholipid, soybean lysophospholipid, hydrogenated soybean lysophospholipid, egg yolk lecithin, hydrogenated egg yolk lysophosphatidylcholine, phosphatidylcholine, phosphatidylethanolamine, phosphatidylserine, sphingophospholipid, sphingomyelin, ganglioside Natural surfactants such as bile acid, cholic acid, deoxycholic acid, sodium cholate, sodium deoxycholate, spicrispolic acid, rhamnolipid, trehalose lipid, sophorolipid, mannosylerythritol lipid;

  Paraaminobenzoic acid derivatives such as paraaminobenzoic acid, ethyl paraaminobenzoate, glyceryl paraaminobenzoate, amyl paradimethylaminobenzoate, 2-ethylhexyl paradimethylaminobenzoate, benzyl cinnamate, di-2 methoxycinnamate mono-2 -Glyceryl ethylhexanoate, methyl 2,4-diisopropylcinnamate, ethyl 2,4-diisopropylcinnamate, potassium paramethoxycinnamate, sodium paramethoxycinnamate, isopropyl paramethoxycinnamate, paramethoxycinnamate Cinnamic acid derivatives such as 2-ethylhexyl cinnamate, 2-ethoxyethyl paramethoxycinnamate, ethyl paraethoxycinnamate, urocanic acid derivatives such as urocanic acid, ethyl urocanate, 2,4-dihydroxybenzophenone, 2, 2 ', 4, '-Tetrahydroxybenzophenone, 2-hydroxy-4-methoxy-5-sulfobenzophenone sodium, 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid, 2-hydroxy-4-methoxybenzophenone, 2,2'-dihydroxy- Benzophenone derivatives such as sodium 4,4′-dimethoxybenzophenone and sodium 2,2′-dihydroxy-4,4′-dimethoxy-5-sulfobenzophenone, ethylene glycol salicylate, 2-ethylhexyl salicylate, phenyl salicylate, benzyl salicylate, salicylic acid p -Salicylic acid derivatives such as tert-butylphenyl, homomenthyl salicylate, salicylic acid-3,3,5-trimethylcyclohexyl, 2- (2'-hydroxy-5'-methoxyphenyl) benzoto Azole, 4-tert-butyl-4'-methoxybenzoyl ultraviolet absorbers such as methane;

  Kaolin, anhydrous silicic acid, magnesium aluminum silicate, sericite, talc, boron nitride, mica, montmorillonite, hemp cellulose powder, wheat starch, silk powder, corn starch, nitro dye, azo dye, nitroso dye, triphenyl Methane dyes, xanthene dyes, quinoline dyes, anthraquinone dyes, indigo dyes, pyrene dyes, phthalocyanine dyes, flavonoids, quinone, porphyrin, water-soluble anato, squid powder, caramel, guaiazulene, gardenia blue, gardenia yellow , Cochineal, shikonin, copper chlorophyllin sodium, paprika dye, safflower red, safflower yellow, lacqueric acid, riboflavin butyrate, and other natural dyes, carbon black, yellow iron oxide, black iron oxide, red rose, conger, group , Zinc oxide, chromium oxide, titanium oxide, black titanium oxide, zirconium oxide, chromium hydroxide, alumina, magnesium oxide, barium sulfate, aluminum hydroxide, calcium carbonate, lithium cobalt titanate, manganese violet, pearl pigment powder, etc. And coloring materials;

  Ashitaba extract, Acacia extract, Avocado extract, Achacha extract, Achachazul extract, Altea extract, Arnica extract, Oil-soluble Arnica extract, Almond extract, Aloe extract, Anthony extract, Ginkgo biloba extract, Nettle extract, Iris root extract, Fennel extract , Turmeric extract, Ages extract, Echinacea leaf extract, Ogon extract, Oat extract, Prunus extract, Barley extract, Okra extract, Hypericum extract, Oil-soluble Hypericum extract, Adriatic extract , Orange flower water, seaweed extract, oyster tannin, cuckoo extract, valerian extract, cattail extract, chamomile extract, oil-soluble chamomile extract, chamomile Water, oat extract, carrot extract, oil-soluble carrot extract, carrot oil, pearl millet extract, licorice extract, licorice extract powder, licorice flavonoids, cantalis tincture, raspberry extract, kiwi extract, quina extract, cucumber extract, kyonin extract, quince seed extract , Gardenia extract, Kumazasa extract, Clara extract, walnut shell extract, grapefruit extract, clematis extract, brown sugar extract, chlorella extract, mulberry extract, cinnamon extract, gentian extract, gentian pepper extract, black tea extract, citrus extract, burdock extract, oil-soluble burdock Extract, wheat germ extract, hydrolyzed wheat powder, rice bran extract, rice bran fermented extract, comfrey extract, saicin extract, saffron extract, savonso Kiss, oil-soluble salvia extract, hawthorn extract, salamander extract, shiitake extract, shiitake extract powder, georium extract, sycamore extract, oil-soluble citrus extract, perilla extract, linden extract, oil-soluble linden extract, citrus extract, peonies extract, juniper extract, ginger Extract, Oil-soluble Pepper extract, Pepper tincture, Ginger root extract, Birch extract, Oil-soluble birch extract, Birch sap, Honeysuckle extract, Japanese horsetail extract, Oil-soluble Japanese horse chestnut extract, Scorginin, Stevia extract, Atlantic kizuta extract, Hawthorn extract , Elderberry extract, black rat extract, yarrow extract, oil-soluble yarrow extract, mint extract, sage extract, oil-soluble Di extract, sage water, mallow extract, celery extract, nematode extract, nematode water, assembly extract, soy extract, tiso extract, thyme extract, tea extract, tea dry extract, tea seed extract, clove extract, chimpi extract, camellia extract, camellia extract, oil Soluble Teuchigurumi extract, Duke extract, Terminaria extract, Capsicum tincture, Toki extract, Oil-soluble Toki extract, Toki water, Toki-senka extract, Oil-soluble Toki-senka extract, Soy milk powder, Tonin extract, Spruce extract, Dokudami extract, Tomato extract, Toll Mentilla extract, natto extract, carrot extract, oil-soluble carrot extract, garlic extract, wild rose extract, oil-soluble wild rose extract, buckthorn extract, buckthorn root extract, buckthorn extract, parsley extract Concentrated leaf juice, distilled mint water, hamamelis water, hamamelis extract, rose extract, parietalia extract, toadsock extract, loquat leaf extract, oil-soluble loquat leaf extract, dandelion extract, butcher bloom extract, butcher bloom extract, butcher bloom extract powder , Grape extract, Grape leaf extract, Grape water, Hayflower extract, Loofah extract, Loofah water, Safflower extract, Oil soluble bodai extract, Bodaiju water, Button extract, Hop extract, Oil soluble hop extract, Pine extract, Maria thistle extract, Maronier Extract, Oil-soluble Maronnier extract, Mukuroji extract, Melissa extract, Merirot extract, Peach leaf extract, Oil-soluble Peach leaf extract, Peach extract, Cornflower extract, Cornflower water, Eucalyptus extract, Yukinoshita Eki , Lily extract, Yokuinin extract, oil soluble Yokuinin extract, mugwort extract, mugwort water, lavender extract, lavender water, apple extract, litchi extract, lettuce extract, lemon extract, lotus extract, rose water, rosemary extract, oil soluble rosemary extract , Plant extracts such as Roman chamomile extract, bitumen extract;

  Glycine, alanine, valine, leucine, isoleucine, serine, threonine, phenylalanine, tyrosine, tryptophan, cystine, cysteine, methionine, proline, hydroxyproline, aspartic acid, asparagine, glutamic acid, glutamine, arginine, histidine, lysine, γ-aminobutyric acid Amino acids and peptides such as DL-pyrrolidone carboxylic acid, ε-aminocaproic acid, hydrolyzed elastin, water-soluble elastin, hydrolyzed collagen, water-soluble collagen, casein, glutathione, wheat peptide, soybean peptide;

  Vitamins A such as retinol, retinal, retinoic acid, retinol acetate, retinol palmitate, etc., carotenoids such as α-carotene, β-carotene, γ-carotene, δ-carotene, lycopene, zeaxanthin, cryptoxanthine, echinone, astaxanthin, Vitamin B1 such as thiamine, vitamin B2 such as riboflavin, vitamin B6 such as pyridoxine, pyridoxal, pyridoxamine, vitamin B12 such as cyanocobalamin, folic acid, nicotinic acid, nicotinamide, pantothenic acid, biotins, L -Ascorbic acid, sodium L-ascorbate, L-ascorbyl stearate, L-ascorbyl palmitate, L-ascorbyl dipalmitate, L-ascorbyl tetraisopalmitate, L-ascorb Vitamin C such as disodium acid sulfate ester, magnesium L-ascorbyl, sodium L-ascorbyl phosphate, L-ascorbic acid-2-glucoside, L-ascorbic acid-2-magnesium phosphate, ergocalciferol, cholecalci Vitamins D such as ferrol, vitamins such as d-α-tocopherol, DL-α-tocopherol, dl-α-tocopherol acetate, dl-α-tocopherol succinate, β-tocopherol, γ-tocopherol, d-δ-tocopherol Vitamins and vitamin-like agents such as E, ubiquinones, vitamin K, carnitine, ferulic acid, γ-oryzanol, α-lipoic acid, orotic acid;

  Benzoic acid, sodium benzoate, undecylenic acid, salicylic acid, sorbic acid, potassium sorbate, dehydroacetic acid, sodium dehydroacetate, isobutyl paraoxybenzoate, isopropyl paraoxybenzoate, ethyl paraoxybenzoate, butyl paraoxybenzoate, propyl paraoxybenzoate , Preservatives such as benzyl paraoxybenzoate, methyl paraoxybenzoate, methyl sodium paraoxybenzoate, phenoxyethanol, photosensitive element 101, photosensitive element 201, photosensitive element 401;

  Antioxidants such as butylhydroxyanisole, butylhydroxytoluene, propyl gallate, erythorbic acid, sodium erythorbate, parahydroxyanisole, octyl gallate;

  Sequestering agents such as trisodium ethylenediaminehydroxyethyl triacetate, edetic acid, disodium edetate, trisodium edetate, tetrasodium edetate, sodium citrate, gluconic acid, phytic acid, sodium polyphosphate, sodium metaphosphate;

  Moisturizers such as hyaluronic acid, sodium hyaluronate, sodium chondroitin sulfate, sodium lactate, sodium pyrrolidonecarboxylate, betaine, lactic acid bacteria culture, yeast extract, ceramide;

  Anti-inflammatory agents such as glycyrrhizic acid, trisodium glycyrrhizinate, dipotassium glycyrrhizinate, monoammonium glycyrrhizinate, β-glycyrrhetinic acid, glyceryl glycyrrhetinate, stearyl glycyrrhetinate, lysozyme chloride, hydrocortisone, allantoin;

PH adjusters such as sodium hydroxide, potassium hydroxide, triethanolamine;
Salts such as sodium chloride, potassium chloride, magnesium chloride, sodium sulfate;
Α-hydroxy acids such as citric acid, glycolic acid, tartaric acid, lactic acid;
Whitening agents such as arbutin, α-arbutin, placenta extract;

  Angelica oil, Ylang-Ylang oil, Elemi oil, Orange oil, Chamomile oil, Roman chamomile oil, Cardamom oil, Calamus oil, Galvanum oil, Camphor oil, Carrot seed oil, Clarage sage oil, Grapefruit oil, Clove oil, Keihi oil, Coriander oil , Cypress oil, Sandalwood oil, Cedarwood oil, Citronella oil, Cinnamon leaf oil, Jasmine absolute, Juniper berry oil, Ginger extract, Spearmint oil, Sage oil, Cedar oil, Geranium oil, Thyme oil, Tea tree oil, Nutmeg oil , Near uri oil, neroli oil, pine oil, basil oil, peppermint oil, patchouli oil, palmarosa oil, fennel oil, petitgren oil, black pepper oil, frankincense oil, vetiver oil, peppermint oil, bergamot oil Zoin oil, Boad Rose oil, Marjoram oil, Mandarin oil, Myrrh oil, Melissa oil, Eucalyptus oil, Yuzu oil, Lime oil, Lavensara oil, Lavandin oil, Lavender oil, Linden oil, Lemon oil, Lemongrass oil, Rose oil, Rose Essential oils such as wood oil, rosemary oil, lobe oil;

Terpenes such as limonene, pinene, terpinene, terpinolene, myrcene, longiferin, etc .;
A fragrance | flavor, water, etc. are mentioned.

  Furthermore, existing cosmetic raw materials can be added to the skin external preparation of the present invention at a general concentration. For example, Cosmetic Material Standards Second Edition Annotation, Japan Official Church Church, 1984 (Pharmaceutical Daily Report), Cosmetic Raw Material Standards Non-Standard, Supervised by Ministry of Health and Welfare Pharmaceutical Affairs Bureau Examination Division, 1993 (Pharmaceutical Daily Report), Cosmetic Raw Material Non-Standard Components Standards supplement, supervised by the Ministry of Health and Welfare Pharmacy Examination Division, 1993 (Pharmaceutical Daily), permission standards by cosmetic type, supervision by the Ministry of Health and Welfare Pharmacy Examination Division, 1993 (Pharmaceutical Daily), formulation standard by cosmetic variety, Ministry of Health and Welfare Pharmacy Examination Division All cosmetic raw materials described in Supervision, 1997 (Pharmaceutical Daily), Cosmetic Raw Material Dictionary, 1991 (Nikko Chemicals), and new cosmetic functional materials 300, 2002 (CMC Publishing) can be used. .

  EXAMPLES The present invention will be specifically described below based on examples, but the present invention is not limited to these examples.

Example 1
1,6-Anhydro-β-D-glucopyranose (manufactured by Tokyo Chemical Industry Co., Ltd., 13.0 g) in a Schlenk tube sufficiently dried under a nitrogen atmosphere was dried propylene carbonate (manufactured by Aldrich, 12.5 ml) ), And 66% by mass of 2-butynyltetramethylenesulfonium hexafluoroantimonate (Asahi Denka Kogyo Co., Ltd., 65.8 μl). Next, immerse this Schlenk tube in an oil bath, heat the oil bath to 100 ° C. to dissolve 1,6-anhydro-β-D-glucopyranose well, then raise the temperature to 130 ° C. and stir well. Polymerization was started. After reacting for 30 minutes, the polymerization solution was poured into methanol to stop the polymerization. After the solvent was distilled off, reprecipitation was repeated with water and methanol, followed by further dialysis and purification, and freeze-drying to obtain white powdered multibranched polysaccharide A (5.3 g). The yield was 41%. The structure of this multibranched polysaccharide A was confirmed by ¹ H-NHR and ¹³ C-NMR. The weight average molecular weight was 20000 (light scattering method), and the degree of branching was 0.38.

Example 2
In the well-dried flask, add the multi-branched polysaccharide A (1.0 g) obtained in Example 1, 1,8-diisocyanate octane (0.2 g) and dry pyridine (10 ml), and well at 100 ° C. for 3 hours. The reaction was carried out with stirring. After the reaction, the reaction solution was poured into methanol. After the solvent was distilled off, reprecipitation was repeated with water and methanol, and freeze-dried to obtain a white powder of polymer compound B (1.1 g). This 1% aqueous solution of polymer compound B was transparent.

Example 3
Isocyanate ethyl methacrylate (Showa Denko Co., Ltd., 204 mg), methyl methacrylate (Aldrich, 903 mg), azobisisobutyronitrile (AIBN, 50.8 mg) in a pressure-resistant flask sufficiently dried under a nitrogen atmosphere Then, dimethylformamide (DMF, 10 ml) was added, and the mixture was thoroughly stirred to dissolve completely. The flask was then evacuated and dry nitrogen introduced 5 times, and finally evacuated and capped. This flask was immersed in an oil bath at 60 ° C. and allowed to react for 20 hours. After the reaction, the temperature was sufficiently lowered, the container was opened, and the reaction solution was poured into hexane. After removing hexane, a small amount of chloroform was added and dissolved, and this was poured into hexane and reprecipitated. This reprecipitation operation was repeated, the precipitate was collected by filtration, and a white powder polymer C (1.07 g) was obtained by vacuum drying. The yield was 97%. The structure of the polymer C was confirmed by FT-IR, ¹ H-NHR and ¹³ C-NMR. Moreover, the weight average molecular weight was 13900 (GPC / THF, polystyrene conversion).

Example 4
In the well-dried flask, the multibranched polysaccharide A (1.0 g) obtained in Example 1, the polymer C (1.0 g) obtained in Example 3 and dry pyridine (10 ml) were added, and the mixture was added at 100 ° C. The reaction was allowed to stir for an hour. After the reaction, the reaction solution was poured into methanol. After distilling off the solvent, reprecipitation was repeated with water and methanol, and freeze-dried to obtain white powder of polymer compound D (1.1 g). A 1% aqueous solution of this polymer compound was transparent.

Example 5
An emulsion having the composition shown in Table 1 was prepared based on a conventional method. This was used by 10 women between the ages of 20 and 30, and the impressions after use are shown in Table 2. It was shown that the moist feeling of the skin can be maintained by using Sample 1-1 containing the polymer compound D obtained in Example 4. Moreover, since the sample 1-2 had a rough feeling, it was shown that solubility is bad.

Example 6
An emulsion having the composition shown in Table 1 was applied to the forearm flexion side of three women aged 30 to 40 years twice a day in the morning and evening for 7 days. Table 3 shows the results of comparing the amount of horny water in the morning of the 8th day with the conductivity measured by the high frequency inductance method using an impedance meter (manufactured by IBS, SKICON-200) as an index. By using Sample 1-1 containing the polymer compound D obtained in Example 4, the conductivity was improved, and it was shown that the amount of keratin water was increased and the moisture of the skin was increased.

The polymer compound of the present invention contains such a polymer compound having a repeating structural unit that imparts water retention to an external preparation for skin, and further has a structure that imparts viscosity and solubility in the same molecule. By doing so, it is possible to provide an excellent external preparation for skin that moisturizes the skin, has a good feeling on the skin, and has reduced separation, precipitation and crystallization.

Claims (13)

  A structural unit containing a multi-branched polysaccharide derivative (wherein the hydroxyl group (OH) in the multi-branched polysaccharide derivative is OR (R is a hydrogen atom, a hydrocarbon having 1 to 30 carbon atoms, or a carbon atom having a hetero atom) 1 to 30 hydrocarbons)) and a structural unit that does not contain a multi-branched polysaccharide derivative.   The moisturizing polymer compound according to claim 1, wherein the main chain of the polymer compound is composed of structural units containing a multi-branched polysaccharide derivative.   The moisturizing polymer compound according to claim 2, which is a polymer compound obtained by copolymerization of a multi-branched polysaccharide derivative having at least two hydroxyl groups and dicarboxylic acids and / or diisocyanates.   The moisturizing polymer compound according to claim 1, wherein the polymer compound has a structural unit containing a multi-branched polysaccharide derivative in a side chain thereof.   The moisturizing polymer compound according to claim 4, which is a polymer compound obtained by reacting a polymer compound having a carboxyl group and / or an isocyanate group in the main chain with a hydroxyl group (OH) of a multi-branched polysaccharide derivative.   In the multi-branched polysaccharide derivative, at least one hydroxyl group (OH) of anhydrous sugar and / or anhydrous sugar is OR (R is a hydrogen atom, a hydrocarbon having 1 to 30 carbon atoms, or a carbon atom having 1 hetero atom. The moisturizing polymer compound according to any one of claims 1 to 5, which is a polymer having an anhydrosugar derivative substituted as a monomer.   The anhydrosugar part of an anhydrosugar or an anhydrosugar derivative consists of 1,6-anhydro sugar, 1,4-anhydro sugar, 1,3-anhydro sugar, 1,2-anhydro sugar, and 5,6-anhydro sugar The moisturizing polymer compound according to claim 6, which is at least one selected from the group consisting of:   The degree of branching of the multi-branched polysaccharide derivative is 0.05 to 1.00. The moisturizing polymer compound according to claim 1.   The moisture-retaining polymer compound according to claim 1, wherein the solubility in water, ethanol, or a mixture of water and ethanol is 1.0% by mass or more.   A humectant comprising the polymer compound according to claim 1.   An external preparation for skin containing 0.1 to 99.9% by mass of the polymer compound according to any one of claims 1 to 9.   A cosmetic comprising the humectant according to claim 10. A cosmetic comprising the skin external preparation according to claim 11.