JP6116258B2 - External preparation for skin and method for producing the same - Google Patents

Description

  The present invention relates to a skin external preparation containing a tocopherol phosphate and / or a salt thereof, and a method for producing the same.

Conventionally, tocopherol (vitamin E) and various derivatives thereof have a blood circulation promoting action and a high antioxidant action, and are blended in cosmetics and the like for the purpose of preventing and improving rough skin.
As an example of a tocopherol derivative, a tocopherol phosphate ester obtained by converting a hydroxyl group of tocopherol into a phosphate ester to impart water solubility is known, and these are often used in the form of a salt. As the salt, a sodium salt or the like is common.

Tocopherol phosphates and / or their salts are amphipathic and have high affinity to living bodies, so that they can be rapidly transferred to living tissues such as skin, so that they can be applied to external preparations such as cosmetics. Expected.
However, when a tocopherol phosphate ester and / or a salt thereof is formulated as an external preparation for skin, there is a problem that decomposition occurs in the agent and changes in appearance. The occurrence of turbidity and coloring not only changes the appearance, but also reduces the commercial value of the product, and causes a deterioration in touch when an external preparation for skin is applied to the skin.
Degradation of tocopherol phosphate ester and / or its salt is mainly caused by hydrolysis of phosphoric acid ester-bonded to a hydroxyl group. This decomposition produces water-insoluble tocopherols that cause separation in the agent. Although it is difficult to visually check in a cloudy dosage form such as a cream, the transparent lotion system or the cosmetic liquid system has a problem that appearance changes such as turbidity, precipitation, and coloring.

So far, various methods for stabilizing an external preparation for skin by blending other components with tocopherol phosphate and / or its salt have been proposed.
In patent document 1, the method of mix | blending a polyhydric alcohol and / or an acid and / or its salt is disclosed as a method of stabilizing the skin external preparation containing a tocopherol phosphate ester and / or its salt. According to this method, it is said that the stability over time of the external preparation for skin can be obtained.
In patent document 2, the method of mix | blending an oil-soluble component is disclosed as a method of mix | blending a tocopherol phosphate ester and / or its salt with a skin external preparation uniformly. According to this method, it is said that the external preparation for skin can be uniformly dispersed. Further, it describes the effect of obtaining a highly safe preparation by further adding an amphoteric surfactant thereto, and there is a description that hydrogenated phospholipid is preferable among the amphoteric surfactants.
In Patent Document 3, a water-in-oil emulsion composition emulsified with a poly (12-hydroxystearic acid) ester of a polyhydric alcohol contains sodium tocopheryl phosphate to increase the viscosity of the composition. And the method of making the difference of the viscosity by storage temperature small by making it contain a chelating agent is disclosed.

  However, it is difficult to say that either method can provide sufficient formulation stability. Under such circumstances, it contains a tocopherol phosphate ester and / or a salt thereof, and has excellent formulation stability. There is still a strong demand for the creation of an external preparation for skin that is suppressed in coloring and excellent in touch.

JP-A-11-199424 Japanese Patent Laid-Open No. 9-309813 JP 2012-131733 A

  This invention is made | formed in view of the said situation, It aims at providing the skin external preparation which was tocopherol phosphate ester and / or its salt, and was excellent in formulation stability, and its manufacturing method. .

As a result of earnest research to solve the above-mentioned problems, the present inventors have formulated the above-mentioned problems by combining a tocopherol phosphate ester and / or a salt thereof with a topical skin preparation, and combining this with a specific amphoteric surfactant. It has been found that this has been achieved, and the present invention has been completed.
The present invention has the following aspects.

[1] A skin external preparation containing a tocopherol phosphate and / or a salt thereof, and at least one betaine type selected from the group consisting of compounds represented by the following formulas (1) and (2) It is seen containing a amphoteric surfactant, a chelating agent, wherein the chelating agent is selected diethylenetriaminepentaacetic acid and salts thereof, L- glutamic acid diacetate and its salts, and from the group consisting of ethylenediamine tetramethylene phosphonic acid and its salts A skin external preparation characterized by being one or more chelating agents.

[In formula (1), ^{R 1} is a linear or branched alkyl group having 6 to 30 carbon atoms. In the formula (2), R ² is a linear or branched alkyl group having 8 to 30 carbon atoms. ]
[2] As described in [1], the betaine amphoteric surfactant contains a compound in which R ¹ in the general formula (1) is a linear or branched alkyl group having 12 to 24 carbon atoms. Topical skin preparation.
[3] The betaine-type amphoteric surfactant contains a compound in which R ² in the general formula (2) is a linear or branched alkyl group having 12 to 24 carbon atoms, [1] or [ 2] The external preparation for skin described in 2].
[4] The skin external preparation according to any one of [1] to [3], wherein the content of the tocopherol phosphate and / or salt thereof is 0.01 to 10% by mass.
[5] The external preparation for skin according to any one of [1] to [4], wherein the amount of the betaine amphoteric surfactant is 0.1 to 10% by mass.
[6] The external preparation for skin according to any one of [1] to [5], wherein the pH is 6.0 to 8.5 .
[ 7 ] The external preparation for skin according to any one of [1] to [ 6 ], which is a cosmetic.

[ 8 ] A method for producing a skin external preparation containing a tocopherol phosphate and / or a salt thereof,
A tocopheryl phosphate and / or its salts, mixed with at least one betaine type amphoteric surfactant selected from the group consisting of compounds represented by the following formula (1) and (2), and a chelating agent, a The chelating agent is one or more chelating agents selected from the group consisting of diethylenetriaminepentaacetic acid and salts thereof, L-glutamic acid diacetic acid and salts thereof, and ethylenediaminetetramethylenephosphonic acid and salts thereof. A method for producing an external preparation for skin.

[In formula (1), ^{R 1} is a linear or branched alkyl group having 6 to 30 carbon atoms. In the formula (2), R ² is a linear or branched alkyl group having 8 to 30 carbon atoms. ]

  ADVANTAGE OF THE INVENTION According to this invention, the skin external preparation which contains tocopherol phosphate ester and / or its salt, and was excellent in formulation stability, and its manufacturing method can be provided.

<Tocopherol phosphate ester and / or salt thereof>
In the present invention, a tocopherol phosphate ester and / or a salt thereof represented by the following formula (3) (wherein X, Y and Z independently represent a hydrogen atom or a methyl group) can be used.

  Among the tocopherol phosphates represented by the above formula (3), X, Y and Z are all methyl groups, α-tocopherol; X, Z is a methyl group, Y is a hydrogen atom, β -Tocopherol; X and Y are methyl groups, Z is a hydrogen atom, γ-tocopherol; X is a methyl group, and δ-tocopherol, wherein Y and Z are hydrogen atoms; The most common. Of these, α-form and γ-form are preferably used.

  In addition, since the tocopherol phosphate represented by the above formula (3) has an asymmetric carbon atom at the 2-position of the chroman ring, there are d-form, l-form stereoisomer, and dl-form. Includes any of these isomers.

  Preferred examples of the tocopherol phosphate salt include alkali metal salts such as sodium salt and potassium salt of tocopherol phosphate ester; alkaline earth metal salts such as magnesium salt and calcium salt; ammonium salt and alkylammonium salt. Examples include salts and zinc salts.

Of these, alkali metal salts, particularly sodium salts, of tocopherol phosphates are particularly preferred because they have the advantages of high solubility in water and ease of handling because of their powder properties.
As the tocopherol phosphate and / or salt thereof, one kind may be used alone, or two or more kinds may be used in combination.
0.01-10 mass% is preferable in the skin external preparation whole quantity, and, as for the compounding quantity of a tocopherol phosphate ester and / or its salt, 0.5-5 mass% is more preferable. When it is 0.01% by mass or more, when the external preparation for skin of the present invention is applied to the skin, the tocopherol phosphate and / or its salt are rapidly transferred to the skin, and the efficacy required for the external preparation for skin The effect is fully demonstrated. Even if it exceeds 10% by mass, a higher effect is not always obtained, so it is not economical.

<Betaine-type amphoteric surfactant>
The skin external preparation of the present invention comprises at least one betaine amphoteric surfactant selected from the group consisting of compounds represented by the following formulas (1) and (2) together with a tocopherol phosphate and / or a salt thereof ( Hereinafter, it may be referred to as a specific betaine-type amphoteric surfactant).

[In formula (1), ^{R 1} is a linear or branched alkyl group having 6 to 30 carbon atoms. In the formula (2), R ² is a linear or branched alkyl group having 8 to 30 carbon atoms. ]

The compound represented by the general formula (1) (hereinafter referred to as compound (1)) has a betaine structure in which a linear or branched alkyl tertiary amine and acetic acid are bonded. By taking a betaine structure, it exhibits excellent solubilizing power and stabilizing power of tocopherol phosphate and / or its salt.
The compound represented by the general formula (2) (hereinafter referred to as compound (2)) has a betaine structure in which a fatty acid, dimethylpropyldiamine and acetic acid are bonded. Like compound (1), by taking a betaine structure, it exhibits excellent solubilizing power and stabilizing power of tocopherol phosphate and / or salt thereof.
The compounds (1) and (2) each have a specific betaine structure (having a cation part of a quaternary ammonium salt), so that they have the property of being soluble in water even in a pH region close to the isoelectric point, thereby providing excellent tocopherol. It is considered that the solubilizing power of the phosphate ester and / or its salt is exhibited.

In the general formula (1), R ¹ is a linear or branched alkyl group having 6 to 30 carbon atoms, and has 10 to 10 carbon atoms from the viewpoint of raw material availability, surfactant solubilizing power, and the like. A linear or branched alkyl group having 30 is preferable, and a linear or branched alkyl group having 12 to 24 carbon atoms is more preferable. Although it does not specifically limit as a C6-C30 linear or branched alkyl group, For example, a lauryl group, a myristyl group, a cetyl group, a stearyl group, an isostearyl group etc. are mentioned.
Specific examples of the compound (1) include, but are not limited to, lauryldimethylaminoacetic acid betaine, myristyldimethylaminoacetic acid betaine, stearyldimethylaminoacetic acid betaine, and coconut oil alkylaminoacetic acid betaine.
Compound (1) may be produced by a known production method, or a commercially available product may be used. Examples of commercially available products include trade names “Amphithol 24B” and “Amphithol 86B” manufactured by Kao Corporation, trade names “NIKKOL AM-301” manufactured by Nikko Chemicals Corporation, and products manufactured by NOF Corporation. Names “Nissan Anon BF”, “Nissan Anon BL”, trade names “Rikabion A-100”, “Rikabion A-110”, “Rikabion A-200”, “Rikabion A-700” manufactured by Shin Nippon Rika Co., Ltd. Etc.

In the general formula (2), R ² is a linear or branched alkyl group having 8 to 30 carbon atoms, and has 10 to 10 carbon atoms from the viewpoint of raw material availability, surfactant solubilizing power, and the like. A linear or branched alkyl group having 30 is preferable, and a linear or branched alkyl group having 12 to 24 carbon atoms is more preferable. Although it does not specifically limit as a C8-C30 linear or branched alkyl group, For example, a lauryl group, a myristyl group, a cetyl group, a stearyl group etc. are mentioned.
Specific examples of the compound (2) include, but are not limited to, lauric acid amidopropyl dimethylaminoacetic acid betaine, myristic acid amidopropyldimethylaminoacetic acid betaine, coconut oil fatty acid amidopropyldimethylaminoacetic acid betaine, palm kernel oil Examples include fatty acid amidopropyldimethylaminoacetic acid betaine and isostearic acid amidopropyldimethylaminoacetic acid betaine.
Compound (2) may be produced by a known production method, or a commercially available product may be used. Commercially available products include, for example, trade name “NIKKOL AM-3130N” manufactured by Nikko Chemicals Co., Ltd., trade names “SOFTAZOLINE CPB-R”, “SOFTAZOLINE LPB-R”, “SOFTAZOLINE” manufactured by Kawaken Fine Chemicals Co., Ltd. PKPB ”, trade names“ Ovazoline BC ”,“ Ovazoline LB ”,“ Ovazoline LB-SF ”,“ Ovazoline CAB-30 ”,“ Ovazoline ISAB ”manufactured by Toho Chemical Industry Co., Ltd., and the like.

Any one of these specific betaine-type amphoteric surfactants may be used alone, or two or more thereof may be used in combination.
0.1-10 mass% is preferable in the total amount of skin external preparations, and, as for the compounding quantity of the said specific betaine type | mold amphoteric surfactant, 0.5-5 mass% is more preferable. When the content is 0.1% by mass or more, the stability of the preparation is excellent, and precipitation and turbidity during storage are less likely to occur. When the amount exceeds 10% by mass, there is a possibility that an effect commensurate with the amount to be blended cannot be obtained, for example, the feel of the preparation is deteriorated.

<Chelating agent>
In the external preparation for skin of the present invention, it is preferable to further contain a chelating agent in addition to the tocopherol phosphate and / or salt thereof and the betaine amphoteric surfactant (1) or (2). Thereby, the effect of preventing coloring of the preparation and preventing the occurrence of turbidity becomes more remarkable. The cause is not clear, but it is probably due to the chelating agent trapping trace metals in the formulation.
The chelating agent in the present invention is not particularly limited as long as it has chelating ability, and examples thereof include aminocarboxylic acid chelating agents, phosphonic acid chelating agents, and the like. Can be used in combination. Considering from the viewpoint of use, specific examples of aminocarboxylic acid chelating agents include ethylenediaminetetraacetic acid and its salt, diethylenetriaminepentaacetic acid and its salt, hydroxyethylethylenediaminetriacetic acid and its salt, dicarboxymethylglutamic acid and its salt Examples of the phosphonic acid chelating agent include ethylenediaminetetra (methylenephosphonic acid) and a salt thereof, hydroxyethylidene diphosphonic acid and a salt thereof, and the like. Of these, diethylenetriaminepentaacetic acid and its salt, which are excellent in iron adsorption capacity, are more preferred. Examples of the salt include alkali metal salts such as Na and K, ammonium salts, and the like, but Na salts are more preferable.
The addition amount of the chelating agent in the present invention is preferably 0.01 to 5.0% by mass of the chelating agent with respect to the total amount of the composition, although it depends on the production conditions and the raw materials used. In consideration of the amount of trace metals that may be mixed under various manufacturing conditions, 0.02 to 2.0% by mass is more preferable. When the addition amount of the chelating agent is 0.01% by mass or less, coloring and turbidity may not be completely suppressed, and when it is 5.0% by mass or more, it corresponds to the blending amount such as a decrease in feeling of use. The effect may not be obtained.

<Other optional components>
The skin external preparation of this invention may mix | blend at least 1 sort (s) chosen from tocopherol and tocopherol phosphates other than the tocopherol phosphate ester and / or its salt in the range which does not impair the effect of this invention.
Examples of tocopherol derivatives other than tocopherol phosphate and / or salts thereof include tocopherol acetate, tocopherol succinate, tocopherol nicotinate, tocopherol dimethylglycine ester, tocopherol sarcosine ester, retinoic acid tocopherol ester, (ascorbyl / tocopheryl) phosphorus Examples include acid esters, ascorbyl tocopheryl maleate, and the like, and salts thereof. Examples of the salt include sodium salt and potassium salt.
In addition, in a skin external preparation, a tocopherol phosphate ester and / or its salt may decompose | disassemble and a phosphoric acid and a tocopherol may arise. Therefore, the skin external preparation of the present invention may contain a trace amount of tocopherol even if it is not blended at the time of manufacture.

  In addition to the above, the external preparation for skin of the present invention contains components usually used for external preparation for skin, for example, a pharmaceutically acceptable carrier as an external preparation for skin, as long as the effects of the present invention are not impaired. An agent or the like may be contained. Examples of such components include hydrocarbons, natural fats and oils, fatty acids, higher alcohols, alkyl glyceryl ethers, esters, silicone oils, sugars, polymers, anionic surfactants, cations Surfactants, amphoteric surfactants not corresponding to the specific betaine-type amphoteric surfactants, nonionic surfactants, natural surfactants, ultraviolet absorbers, powders, color materials, amino acids, peptides, Vitamins, vitamin-like agents, preservatives, antioxidants, moisturizers, anti-inflammatory agents, pH adjusters, salts, organic acids, whitening agents, essential oils, terpenes, fragrances and the like can be mentioned.

  The external preparation for skin of the present invention may be adjusted by adding a solvent / dispersion medium to the above components as necessary. For example, ethylene glycol, diethylene glycol, polyethylene glycol, propylene glycol, polypropylene glycol, glycerin, diglycerin, polyglycerin, 1,3-butanediol, triethylene glycol, dipropylene glycol, 3-methyl-1,3-butanediol, 1 , 2-pentanediol, 1,4-pentanediol, 1,5-pentanediol, 2,4-pentanediol, 2-methyl-2,4-pentanediol, 3-methyl-1,5-pentanediol, 1, Examples thereof include polyhydric alcohols such as 2-hexanediol and 1,6-hexanediol, monovalent lower alcohols such as ethanol, isopropyl alcohol, 1-butanol, 2-butanol and benzyl alcohol, and water.

  Specific examples of the hydrocarbons include ozokerite, α-olefin oligomer, light isoparaffin, light liquid isoparaffin, squalene, squalane, synthetic squalane, vegetable squalane, ceresin, paraffin, polyethylene powder, polybutene, microcrystalline wax, Examples include liquid isoparaffin, liquid paraffin, mineral oil, and petroleum jelly.

  Specific examples of the natural fats and oils include jojoba oil, carnauba wax, candelilla wax, rice bran wax, shellac, lanolin, mink sebum wax, whale wax, sugar cane wax, sperm whale oil, beeswax, and montan wax. 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, coconut oil, hydrogenated coconut oil, beef tallow, hydrogenated oil, horse oil, mink oil, egg yolk oil, egg yolk fat oil, rosehip oil, cucuin nut oil , Evening primrose oil, wheat germ oil, peanut oil, camellia oil, sasanqua oil, cocoa butter, molasses, beef bone fat Neat's foot oil, and lard, horse fat, mutton tallow, shea butter, macadamia nut oil, meadowfoam oil, etc.

  Specific examples of the fatty acids include lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, oleic acid, linoleic acid, linolenic acid, γ-linolenic acid, isostearic acid, 12-hydroxystearic acid, undecylene. Examples include acids and coconut oil fatty acids.

  Specific examples of the higher alcohols include isostearyl alcohol, octyldodecanol, hexyldecanol, cholesterol, phytosterol, lauryl alcohol, myristyl alcohol, cetanol, stearyl alcohol, oleyl alcohol, behenyl alcohol, and cetostearyl alcohol.

  Specific examples of the alkyl glyceryl ethers include batyl alcohol, chimyl alcohol, seraalkyl alcohol, and isostearyl glyceryl ether.

  Specific examples of the esters include isopropyl myristate, butyl myristate, isopropyl palmitate, ethyl stearate, butyl stearate, ethyl oleate, ethyl linoleate, isopropyl linoleate, cetyl caprylate, hexyl laurate , Isooctyl myristate, decyl myristate, myristyl myristate, cetyl myristate, octadecyl myristate, cetyl palmitate, stearyl stearate, decyl oleate, oleyl oleate, cetyl ricinoleate, isostearyl laurate, isotridecyl myristate, Isocetyl myristate, isostearyl myristate, octyldodecyl myristate, 2-ethylhexyl palmitate, isocetyl palmitate, palmitate Isostearyl, 2-ethylhexyl stearate, 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) propylene, propylene glycol dicaprate, propylene glycol dioleate, neopentyl dicaprate Glycol, neopentyl glycol dioctanoate, glyceryl tricaprylate, tri-2-ethylhexanoic acid Lyceryl, tri (capryl / capric acid) glyceryl, tri (caprylic acid / capric acid / stearic acid) glyceryl, glyceryl triundecylate, glyceryl triisopalmitate, glyceryl triisostearate, trimethylolpropane tri-2-ethylhexanoate, tri Trimethylolpropane isostearate, pentaerythrityl tetra2-ethylhexanoate, pentaerythrityl tetramyristate, pentaerythrityl tetraisostearate, diglyceryl tetraisostearate, octyldodecyl neopentanoate, isocetyl octoate, isostearyl octoate, 2-ethylhexyl isoperargonate, hexyldecyl dimethyloctanoate, octyldodecyl dimethyloctanoate, 2-ethylhexylisopalmitate Xylyl, 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 , Trioctyldodecyl citrate, diisostearyl malate, 2-ethylhexyl hydroxystearate, di-2-ethylhexyl succinate, diisopropyl adipate, diisobutyl adipate, dioctyl adipate, diheptyl undecyl adipate, diethyl sebacate, Diisopropyl sebacate, dioctyl sebacate, cholesteryl stearate, cholesteryl isostearate, hydroxystearic acid Lesteryl, cholesteryl oleate, dihydrocholesteryl oleate, phytosteryl isostearate, phytosteryl oleate, isocetyl 12-stearoylhydroxystearate, stearyl 12-stearoylhydroxystearate, isostearyl 12-stearoylhydroxystearate, polyoxyethylene acetate (3 And polyoxypropylene (1) cetyl ether, polyoxyethylene acetate (3) polyoxypropylene (1) isocetyl ether, isononyl isononanoate, octyl isononanoate, tridecyl isononanoate, isotridecyl isononanoate, and dicapryl carbonate.

  Specific examples of the silicone oils include methylpolysiloxane, methylphenylpolysiloxane, methylhydrogenpolysiloxane, methylcyclopolysiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, Octamethyltrisiloxane, decamethyltetrasiloxane, tetradecamethylhexasiloxane, highly polymerized methylpolysiloxane, dimethylsiloxane-methyl (polyoxyethylene) siloxane-methyl (polyoxypropylene) siloxane copolymer, dimethylsiloxane-methyl (poly Oxyethylene) siloxane copolymer, dimethylsiloxane methyl (polyoxypropylene) siloxane copolymer, dimethylsiloxane methylcetyloxy Rokisan copolymer, dimethyl siloxane-methyl stearoxysiloxane copolymer, polyether-modified silicones, alcohol-modified silicones, alkyl-modified silicone, and an amino-modified silicone.

  Specific examples of the polyhydric alcohols include ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, glycerin, diglycerin, polyglycerin, and 3-methyl-1,3. -Butanediol, 1,3-butanediol, 1,2-pentanediol, 1,2-hexanediol, 1,2-octanediol, neopentyl glycol and the like.

  As said monohydric lower alcohol, C1-C7 monohydric alcohol is mentioned, Specifically, ethanol, isopropyl alcohol, 1-butanol, 2-butanol, benzyl alcohol, etc. are mentioned.

  Specific examples of the saccharide include mannitol, sorbitol, xylitol, maltitol, erythritol, pentaerythritol, glucose, sucrose, fructose, lactose, maltose, xylose, and trehalose.

  Specific examples of the polymers include sodium alginate, carrageenan, agar, fur celerane, guar gum, gellan gum, quince seed, konjac mannan, tamarind gum, tara gum, dextrin, starch, locust bean gum, gum arabic, gati gum, caraya gum , Tragacanth gum, arabinogalactan, pectin, quince, chitosan, starch, curdlan, xanthan gum, cyclodextrin, dextran, pullulan, microcrystalline cellulose, methylcellulose, ethylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, hydroxypropylmethylcellulose, carboxymethylcellulose, carboxy Starch, cationized cellulose, starch phosphate ester, cation Guar gum, carboxymethyl hydroxypropylated guar gum, hydroxypropylated guar gum, albumin, casein, gelatin, sodium polyacrylate, polyacrylate amide, 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 anion polymer , Methacrylic acid-based anionic polymers, modified silicones, alkyl methacrylate acrylate acid (C10-30) copolymers, polyoxyethylene / polyoxypropylene copolymer.

  Specific examples of the anionic surfactant include coconut oil fatty acid potassium, coconut oil fatty acid sodium, coconut oil fatty acid triethanolamine, potassium laurate, sodium laurate, triethanolamine laurate, potassium myristate, myristine. Acid sodium, myristic acid isopropanolamine, potassium palmitate, sodium palmitate, isopropanolamine palmitate, potassium stearate, sodium stearate, triethanolamine stearate, potassium oleate, sodium oleate, sodium castor oil fatty acid, undecylenic acid Zinc, zinc laurate, zinc myristate, magnesium myristate, zinc palmitate, zinc stearate, calcium stearate, mug stearate Cium, aluminum stearate, calcium myristate, magnesium myristate, aluminum dimyristate, aluminum isostearate, polyoxyethylene lauryl ether acetic acid, sodium polyoxyethylene lauryl ether acetate, polyoxyethylene tridecyl ether acetic acid, polyoxyethylene tri Sodium decyl ether acetate, sodium stearoyl lactate, sodium isostearoyl lactate, sodium lauroyl sarcosine, palm 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 natri , Sodium stearoyl glutamate, coconut oil fatty acid acyl glutamate, coconut oil fatty acid acyl glutamate potassium, coconut oil fatty acid acyl glutamate sodium, coconut oil fatty acid acyl glutamate triethanolamine, lauroyl acyl glutamate, lauroyl acyl glutamate potassium, lauroyl acyl glutamate, 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, hardened beef fatty acid acyl sodium glutamate, coconut oil fatty acid / hardened beef fatty acid Sodium acylglutamate, coconut oil fatty acid methylalanine sodium, lauroylmethylalanine, lauroylmethylalanine sodium, lauroylmethylalanine triethanolamine, myristoylmethylalanine sodium, lauroylmethyltaurine sodium, coconut oil fatty acid methyltaurine potassium, coconut oil fatty acid methyltaurine sodium Coconut oil fatty acid methyl taurine 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 ethi Sodium ester sulfonate, sodium lauryl sulfate, triethanolamine lauryl sulfate, sodium cetyl sulfate, alkyl (11,13,15) triethanolamine sulfate, alkyl (12,13) sodium sulfate, alkyl (12,13) triethanol sulfate Amine, 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 tri Ethanolamine, ammonium lauryl sulfate, potassium lauryl sulfate, magnesium lauryl sulfate, monoethanolamine lauryl sulfate, diethanolamine lauryl sulfate, sodium myristyl sulfate, steer Sodium sulfate, sodium oleyl sulfate, oleyl sulfate triethanolamine, polyoxyethylene lauryl ether sodium sulfate, polyoxyethylene lauryl ether sulfate triethanolamine, 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) ether sulfate Sodium, polyoxyethylene (3) alkyl (12-14) ether sodium sulfate, polyoxyethylene (3) alkyl (12-15) sodium ether sulfate, polyoxyethylene (2) lauryl ether Sodium sulfate, polyoxyethylene (3) sodium myristyl ether sulfate, higher fatty acid alkanolamide sulfate sodium ester, lauryl phosphate, sodium lauryl phosphate, potassium cetyl phosphate, diethanolamine cetyl phosphate, polyoxyethylene oleyl ether phosphate, polyoxy Ethylene lauryl ether phosphate, sodium polyoxyethylene lauryl ether phosphate, polyoxyethylene cetyl ether phosphate, sodium polyoxyethylene cetyl ether phosphate, polyoxyethylene stearyl ether phosphate, polyoxyethylene oleyl ether phosphate, polyoxy Ethylene oleyl ether sodium phosphate, polyoxyethylene alkyl phenyl ether phosphate, polyoxyethylene alkyl phosphate Sodium nyl ether phosphate, polyoxyethylene alkylphenyl ether triethanolamine phosphate, polyoxyethylene octyl ether phosphate, polyoxyethylene (10) alkyl (12,13) ether phosphate, polyoxyethylene alkyl (12-15) ) Ether phosphoric acid, polyoxyethylene alkyl (12-16) ether phosphoric acid, polyoxyethylene lauryl ether phosphoric acid triethanolamine, polyoxyethylene oleyl ether phosphoric acid diethanolamine and the like.

Specific examples of the cationic surfactant include dioctylamine, dimethylstearylamine, trilaurylamine, stearic acid diethylaminoethylamide, lauryltrimethylammonium chloride, cetyltrimethylammonium chloride, cetyltrimethylammonium bromide, cetyltrimethylammonium Saccharin, stearyltrimethylammonium chloride, alkyl (20-22) trimethylammonium chloride, lauryltrimethylammonium bromide, alkyl (16,18) trimethylammonium chloride, stearyltrimethylammonium bromide, stearyltrimethylammonium saccharin, alkyl (28) trimethyl chloride Ammonium, di (polyoxyethylene) oleylmethylammonium chloride (2EO), dipotassium chloride Oxyethylene stearylmethylammonium chloride, polyoxyethylene chloride (1) polyoxypropylene (25) diethylmethylammonium chloride, tri (polyoxyethylene) stearylammonium chloride (5EO), distearyldimethylammonium chloride, dialkyl (12-15) dimethyl Ammonium, dialkyl chloride (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 chloride Ammonium, lauryldimethyl (ethylbenzyl) ammonium chloride, stearyldimethylbenzylammonium chloride, chloride Uril pyridinium, cetylpyridinium chloride, lauroyl Kola amino formyl methyl pyridinium chloride, stearoyl colaminoformyl methylpyridinium bromide alkyl isoquinolizinyloxy potassium, chloride methyl benzethonium, such as benzethonium chloride.
Among the above, the numerical value attached | subjected before EO shows the average degree of polymerization of the oxyethylene group in a polyoxyethylene unit.

  Specific examples of the amphoteric surfactant that does not correspond to the specific betaine-type amphoteric surfactant include 2-alkyl-N-carboxymethyl-N-hydroxyethylimidazolinium betaine, alkyldiaminoethylglycine hydrochloride, and lauryldiaminoethyl. Sodium glycine, sodium undecylhydroxyethylimidazolium betaine, undecyl-N-carboxymethylimidazolium betaine, coconut oil fatty acid acyl-N-carboxyethyl-N-hydroxyethylethylenediamine disodium, coconut oil fatty acid acyl-N-carboxyl Ethoxyethyl-N-carboxyethylethylenediamine disodium, coconut oil fatty acid acyl-N-carboxymethoxyethyl-N-carboxymethylethylenediamine disodium, laurylamino Sodium propionate, sodium lauryl amino dipropionate acid, lauryl aminopropionic acid triethanolamine, palm oil fatty acid acyl -N- carboxyethyl -N- hydroxyethyl ethylenediamine sodium stearyl dihydroxyethyl betaine, lauryl hydroxy sulfobetaine.

Specific examples of the nonionic surfactant include polyoxyethylene (10) alkyl (12,13) ether, polyoxyethylene lauryl ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, and 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) alkyl ether, Reoxyethylene octyldodecyl ether, polyoxyethylene behenyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene nonyl phenyl ether, polyoxyethylene dinonyl phenyl ether, polyoxyethylene (2) polyoxypropylene (2) decyl ether, Polyoxyethylene (4) polyoxypropylene (2) decyl ether, polyoxyethylene (7) polyoxypropylene (2) decyl ether, polyoxyethylene (8) polyoxypropylene (2) decyl ether, polyoxyethylene (10 ) Polyoxypropylene (2) Decyl ether, Polyoxyethylene (15) Polyoxypropylene (2) Decyl ether, Polyoxyethylene (20) Polyoxypropylene (2) Deci Ether, polyoxyethylene (30) polyoxypropylene (2) decyl ether, polyoxyethylene (40) polyoxypropylene (2) decyl ether, polyoxyethylene (8) polyoxypropylene (2) lauryl ether, polyoxyethylene (15) polyoxypropylene (4) lauryl ether, polyoxyethylene (10) polyoxypropylene (4) cetyl ether, polyoxyethylene (20) polyoxypropylene (4) cetyl ether, polyoxyethylene (20) polyoxy Propylene (8) cetyl ether, polyoxyethylene (20) polyoxypropylene (6) decyl tetradecyl ether, polyoxyethylene (30) polyoxypropylene (6) decyl tetradecyl ether, polyoxyethylene (5) Polyoxypropylene (5) glycol, polyoxyethylene (5) polyoxypropylene (30) glycol, polyoxyethylene (10) polyoxypropylene (8) glycol, polyoxyethylene (16) polyoxypropylene (17 ) Glycol, polyoxyethylene (20) polyoxypropylene (20) glycol, polyoxyethylene (25) polyoxypropylene (30) glycol, polyoxyethylene (35) polyoxypropylene (40) glycol, polyoxyethylene (100 ) Polyoxypropylene (40) glycol, polyoxyethylene (300) polyoxypropylene (55) glycol, polyoxyethylene (400) polyoxypropylene (70) glycol, polyoxyethylene (1) Oxypropylene (1,2,4,8) cetyl ether, polyoxyethylene (5) polyoxypropylene (1) cetyl ether, polyoxyethylene (10) polyoxypropylene (1) cetyl ether, polyoxyethylene (20) Polyoxypropylene (1) cetyl ether, polyethylene glycol monolaurate, ethylene glycol monostearate, polyethylene glycol monostearate, 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 glycol monostearate (2), polyethylene glycol isostearate, ethylene glycol dioctanoate, diethylene glycol dilaurate, polyethylene glycol dilaurate, polyethylene glycol dipalmitate (150), ethylene glycol distearate, diethylene glycol distearate, polyethylene glycol distearate, dioleic acid Ethylene glycol, polyethylene glycol dioleate, polyethylene glycol diricinoleate, polyoxyethylene (20) sorbitan monolaurate, polyoxyethylene (20) sorbitan monopalmitate, polyoxyethylene (6) sorbitan monostearate, polymonostearate Oxyethylene (20) sorbitan, polyoxyethylene tristearate ( 20) sorbitan, polyoxyethylene monooleate (6) sorbitan, polyoxyethylene monooleate (20) sorbitan, polyoxyethylene trioleate (20) sorbitan, polyoxyethylene (20) coconut oil fatty acid sorbitan, monolauric acid Polyoxyethylene (10-80) sorbitan, polyoxyethylene sorbitan tristearate, polyoxyethylene (20) sorbitan isostearate, polyoxyethylene (150) sorbitan tristearate, polyoxyethylene sorbitol monolaurate, polyoxyoleate Ethylene (40) sorbite, polyoxyethylene tetraoleate (4) sorbite, polyoxyethylene tristearate (3) sorbitol, polyoxyethylene tetraoleate 30) Sorbit, polyoxyethylene tetraoleate (40) sorbite, polyoxyethylene tetraoleate (60) sorbite, polyoxyethylene isostearate (3) sorbite, polyoxyethylene oleate (40) sorbite, polytetrastearate Oxyethylene (60) sorbitol, polyoxyethylene (6) sorbite hexaoleate, polyoxyethylene sorbitol hexastearate, polyoxyethylene (40) sorbitol pentaoleate, polyoxyethylene (3) glyceryl triisostearate, triisostearin Polyoxyethylene (5) glyceryl acid, polyoxyethylene (10) glyceryl triisostearate, polyoxyethylene (20) glyceryl triisostearate, Polyoxyethylene (30) glyceryl triisostearate, polyoxyethylene (40) glyceryl triisostearate, polyoxyethylene (50) glyceryl triisostearate, polyoxyethylene (60) glyceryl triisostearate, polyoxyethylene isostearate ( 3) Glyceryl, polyoxyethylene isostearate (5) glyceryl, polyoxyethylene isostearate (6) glyceryl, polyoxyethylene isostearate (8) glyceryl, polyoxyethylene isostearate (10) glyceryl, polyoxyethylene isostearate ( 15) Glyceryl, polyoxyethylene isostearate (20) glyceryl, polyoxyethylene isostearate (25) glyceryl, isosteary Polyoxyethylene acid (30) glyceryl, polyoxyethylene (40) glyceryl isostearate, polyoxyethylene (50) glyceryl isostearate, polyoxyethylene (isostearate) (60) glyceryl, polyoxyethylene (3) glyceryl tristearate , Polyoxyethylene tristearate (4) glyceryl, polyoxyethylene tristearate (5) glyceryl, polyoxyethylene tristearate (6) glyceryl, polyoxyethylene tristearate (10) glyceryl, polyoxystearate Ethylene (20) glyceryl, polyoxyethylene distearate (4) glyceryl, polyoxyethylene trioleate (3) glyceryl, polyoxyethylene trioleate (5) glycerin , Polyoxyethylene (10) glyceryl trioleate, polyoxyethylene (20) glyceryl trioleate, polyoxyethylene (30) glyceryl trioleate, polyoxyethylene (40) glyceryl trioleate, polyoxytrioleate Ethylene (50) glyceryl, polyoxyethylene (60) glyceryl trioleate, polyoxyethylene castor oil, polyoxyethylene hydrogenated castor oil, polyoxyethylene (10) hydrogenated castor oil, polyoxyethylene (20) hydrogenated castor oil, Polyoxyethylene (40) hydrogenated castor oil, polyoxyethylene (50) hydrogenated castor oil, polyoxyethylene (60) hydrogenated castor oil, lipophilic glyceryl monostearate, lipophilic glyceryl monooleate, self-emulsifying mono Stearin Glycerin, palm oil fatty acid glyceryl, glyceryl laurate, glyceryl myristate, glyceryl isostearate, glyceryl ricinoleate, glyceryl monohydroxystearate, glyceryl oleate, glyceryl linoleate, glyceryl behenate, glyceryl behenate, wheat germ oil fatty acid glycerides , 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 glyceride, monolanolin fatty acid glyceryl, sesquioleate glyceryl, distearate glyceryl, diisostearic acid Glyceryl, glyceryl diarachiate, sorbitan monolaurate, sorbitan monopalmitate, monostea Sorbitan phosphate, sorbitan monoisostearate, sorbitan monooleate, sorbitan sesquistearate, sorbitan sesquioleate, sorbitan tristearate, sorbitan trioleate, sorbitan coconut oil fatty acid sorbitan, sorbitan isostearate, sorbitan sesquiisostearate, distearic acid Sorbitan, diglyceryl isopalmitate, tetraglyceryl monolaurate, hexaglyceryl monolaurate, decaglyceryl monolaurate, decaglyceryl monomyristate, diglyceryl monostearate, tetraglyceryl monostearate, hexaglyceryl monostearate, monostearic acid Decaglyceryl, diglyceryl monoisostearate, tetraglyceryl monoisostearate, monoiso Hexaglyceryl tearate, decaglyceryl monoisostearate, diglyceryl monooleate, tetraglyceryl monooleate, hexaglyceryl monooleate, decaglyceryl monooleate, diglyceryl sesquioleate, tetraglyceryl diisostearate, hexaglyceryl diisostearate , Deisoglyceryl diisostearate, hexaglyceryl distearate, decaglyceryl distearate, diglyceryl triisostearate, decaglyceryl tristearate, decaglyceryl trioleate, diglyceryl tetraisostearate, decaglyceryl pentastearate, hexaolea pentaoleate Glyceryl, decaglyceryl pentaoleate, decaglyceryl heptearate, decastearate Decaglyceryl, dekaglyceryl decaoleate, hexaglyceryl condensed ricinoleate, sucrose fatty acid ester, coconut oil fatty acid sucrose ester, alkyl glucoside, coconut oil alkyldimethylamine oxide, lauryldimethylamine oxide, dihydroxyethyl lauryldimethylamine oxide, stearyldimethyl Examples include amine oxide, oleyldimethylamine oxide, polyoxyethylene coconut oil alkyldimethylamine oxide, dextrin palmitate, dextrin stearate, dextrin myristate, and the like.
Among the above, the numerical value in parentheses after polyoxyethylene or polyoxypropylene indicates the average degree of polymerization of oxyethylene groups in the polyoxyethylene unit or the average degree of polymerization of oxypropylene groups in the polyoxypropylene unit.

  Specific examples of the natural surfactant include saponin, lecithin, hydrogenated lecithin, soybean phospholipid, hydrogenated soybean phospholipid, soybean lysophospholipid, hydrogenated soybean lysophospholipid, egg yolk lecithin, and hydrogenated egg yolk lysophosphatidylcholine. , Phosphatidylcholine, phosphatidylethanolamine, phosphatidylserine, sphingophospholipid, sphingomyelin, ganglioside, bile acid, cholic acid, deoxycholic acid, sodium cholate, sodium deoxycholate, spicrispolic acid, rhamnolipid, trehalose lipid, sophorolipid, mannosyl Examples include erythritol lipid and surfactin sodium.

  Specific examples of the ultraviolet absorber include paraaminobenzoic acid, ethyl paraaminobenzoate, glyceryl paraaminobenzoate, amyl paradimethylaminobenzoate, paraaminobenzoic acid derivatives such as 2-ethylhexyl paradimethylaminobenzoate, and cinnamon. Benzyl acid, diparamethoxycinnamate mono-2-ethylhexanoate glyceryl, methyl 2,4-diisopropylcinnamate, ethyl 2,4-diisopropylcinnamate, potassium paramethoxycinnamate, paramethoxycinnamate Cinnamic acid derivatives such as sodium, isopropyl paramethoxycinnamate, 2-ethylhexyl paramethoxycinnamate, 2-ethoxyethyl paramethoxycinnamate, ethyl paraethoxycinnamate, and urocanins such as urocanic acid and ethyl urocanate Acid derivative, 2,4-dihy Roxybenzophenone, 2,2 ′, 4,4′-tetrahydroxybenzophenone, 2-hydroxy-4-methoxy-5-sulfobenzophenone sodium, 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid, 2-hydroxy-4 Benzophenone derivatives such as -methoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxy-5-sulfobenzophenone sodium, ethylene glycol salicylate, salicylic acid-2 -Salicylic acid derivatives such as ethylhexyl, phenyl salicylate, benzyl salicylate, p-tert-butylphenyl salicylate, homomenthyl salicylate, salicylic acid-3,3,5-trimethylcyclohexyl, 2- (2'-hydro Shi-5'-methoxyphenyl) benzotriazole, and the like 4-tert-butyl-4'-methoxybenzoyl methane.

  Specific examples of the powders and coloring materials include kaolin, anhydrous silicic acid, magnesium aluminum silicate, synthetic magnesium magnesium silicate, sericite, talc, boron nitride, mica, montmorillonite, hemp cellulose powder, wheat Starch, silk powder, corn starch, nitro dye, azo dye, nitroso dye, triphenylmethane dye, xanthene dye, quinoline dye, anthraquinone dye, indigo dye, pyrene dye, phthalocyanine dye, Flavonoids, quinones, porphyrins, water-soluble anato, squid powder, caramel, guaiazulene, gardenia blue, gardenia yellow, cochineal, shikonin, copper chlorophyllin sodium, paprika pigment, safflower red, safflower yellow, lacaic acid, riboflavin butyrate Este Natural pigments such as carbon black, yellow iron oxide, black iron oxide, bengara, conger, ultramarine, zinc oxide, chromium oxide, titanium oxide, black titanium oxide, zirconium oxide, chromium hydroxide, alumina, magnesium oxide, barium sulfate, Examples thereof include aluminum hydroxide, calcium carbonate, lithium cobalt titanate, manganese violet, and pearl pigment.

  Specific examples of the plant extract include Ashitaba extract, Asenyaku extract, Avocado extract, Achacha extract, Achachazul extract, Altea extract, Arnica extract, Oil-soluble Arnica extract, Almond extract, Aloe extract, Ansokkou extract, Extract Soluble nettle extract, onionis extract, Dutch mustard extract, orange extract, orange flower water, seaweed extract, oyster tannin, cuckoo extract, valerian extract, cattail extract, chamomile Kiss, oil-soluble chamomile extract, chamomile water, oat extract, carrot extract, oil-soluble carrot extract, carrot oil, Chinese mugwort extract, licorice extract, licorice extract powder, licorice flavonoid, cantharis tincture, kiwi 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, Keihi Extract, Gentianana Extract, Genno Shoko Extract, Black Tea Extract, Kohone Extract, burdock extract, oil-soluble burdock extract, wheat germ extract, hydrolyzed wheat powder, rice bran extract, rice bran fermented extract, comfrey extract, Saishi Extract, saffron extract, bonito extract, oil-soluble salvia extract, hawthorn extract, salamander extract, shiitake extract, shiitake extract powder, dianthus extract, shikon extract, oil-soluble shikon extract, shiso extract, linden extract, oil-soluble linden extract, citrus extract, peony Extract, Juzudama extract, Pepper extract, Oil-soluble Pepper extract, Pepper tincture, Pepper root extract, Birch extract, Oil-soluble birch extract, Birch sap, Honeysuckle extract, Horsetail extract, Oil-soluble horsetail extract, Scordinin, Stevia extract, Kizuta extract, Hawthorn extract, Elderberry extract, Apricot extract, Achillea millefolium extract, Oil-soluble Achillea millet extract, Aries Katsu extract, sage extract, oil-soluble sage extract, sage water, mallow extract, celery extract, senkyu extract, senkyu water, senbu extract, soybean extract, thymus extract, thyme extract, tea extract, tea dry distillation solution, tea seed extract, clove extract, chimney extract , Camellia extract, camellia extract, oil-soluble euglena extract, Duke extract, Terminaria extract, red pepper tincture, cypress extract, oil-soluble pearl oyster extract, water-soluble eucalyptus extract, oil-soluble eucalyptus extract, soybean milk powder, tonin extract, spruce extract , Dokudami extract, tomato extract, tormentilla extract, natto extract, carrot extract, oil-soluble carrot extract, garlic extract, wild rose extract, oil-soluble wild rose extract, red pepper extract, red root extract , Bakumondou extract, Parsley extract, Hadakamugi leaf juice concentrate, Distilled mint water, Hamamelis water, Hamamelis extract, Rose extract, Parietalia extract, Butterberry extract, Loquat leaf extract, Oil-soluble loquat leaf extract, Fuquitan popo extract, Bucurio extract , Butcher bloom extract, butcher bloom extract powder, grape extract, grape leaf extract, grape water, hay flower 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, Maronie Extract, Oil-soluble Maronie Extract, Mukuroji Extract, Melissa Extract, Merirot Extract, Peach Leaf Extract, Oil-soluble Peach Leaf Extract, Peach Extract, Cornflower Extract, Cornflower Water, Eucalyptus extract, Saxifrage extract, Lily extract, Yokuinin extract, Oil soluble Yokuinin extract, Artemisia extract, Artemisia water, Lavender extract, Lavender water, Apple extract, Ganoderma extract, Lettuce extract, Lemon extract, Lotus root extract, Rose water, Rosemary Extract, oil-soluble rosemary extract, Roman chamomile extract, bitumen extract and the like.

  Specific examples of the amino acids and peptides include 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, DL-pyrrolidonecarboxylic acid, ε-aminocaproic acid, hydrolyzed elastin, water-soluble elastin, hydrolyzed collagen, water-soluble collagen, casein, glutathione, wheat peptide, soybean Peptide etc. are mentioned.

  Specific examples of the vitamins and vitamin-like agents include vitamins A such as retinol, retinal, retinoic acid, retinol acetate, and retinol palmitate, α-carotene, β-carotene, γ-carotene, δ- Carotenoids such as carotene, lycopene, zeaxanthin, cryptoxanthin, echinenone, astaxanthin, vitamin B1 such as thiamine, vitamin B2 such as riboflavin, vitamin B6 such as pyridoxine, pyridoxal, pyridoxamine, vitamin B12 such as cyanocobalamin, Vitamin D such as folic acid, nicotinic acid, nicotinic acid amide, pantothenic acid, biotin, ergocalciferol, cholecalciferol, ascorbic acid, ascorbic acid-2-phosphate derivative and salt thereof, ascorb Acid-3-phosphate derivative and salt thereof, ascorbic acid-6-higher fatty acid and salt thereof, ascorbic acid-2,6-di-higher fatty acid and salt thereof, ascorbic acid-2,3,5,6-tetra higher Fatty acids and salts thereof, ascorbic acid-2-sulfuric acid and salts thereof, vitamin C such as ascorbyl-2-glucoside, ubiquinones, vitamin Ks, carnitine, ferulic acid, γ-oryzanol, α-lipoic acid, orotic acid, etc. Is mentioned.

  Specific examples of the preservative include benzoic acid, sodium benzoate, undecylenic acid, salicylic acid, sorbic acid, potassium sorbate, dehydroacetic acid, sodium dehydroacetate, isobutyl parahydroxybenzoate, isopropyl parahydroxybenzoate, para Ethyl hydroxybenzoate, butyl parahydroxybenzoate, propyl parahydroxybenzoate, benzyl parahydroxybenzoate, methyl parahydroxybenzoate, methyl sodium parahydroxybenzoate, phenoxyethanol, photosensitizer 101, photosensitizer 201, photosensitizer 401 etc. are mentioned.

  Specific examples of the antioxidant include butylhydroxyanisole, butylhydroxytoluene, propyl gallate, erythorbic acid, sodium erythorbate, parahydroxyanisole, octyl gallate, and the like.

  Specific examples of the humectant include hyaluronic acid, sodium hyaluronate, sodium chondroitin sulfate, sodium lactate, sodium pyrrolidone carboxylate, lactic acid bacteria culture solution, yeast extract, ceramide and the like.

  Specific examples of the anti-inflammatory agent include glycyrrhizic acid, trisodium glycyrrhizinate, dipotassium glycyrrhizinate, monoammonium glycyrrhizinate, β-glycyrrhetinic acid, glyceryl retinoic acid, stearyl glycyrrhetinate, lysozyme chloride, hydrocortisone, and allantoin Can be mentioned.

  Specific examples of the pH adjuster include sodium hydroxide, potassium hydroxide, triethanolamine and the like.

  Specific examples of the salt include sodium chloride, potassium chloride, magnesium chloride, sodium sulfate, magnesium sulfate, sodium tartrate, sodium malate, sodium glutamate, and sodium aspartate.

  Examples of the organic acids include citric acid, glycolic acid, tartaric acid, lactic acid, malic acid and the like.

  Specific examples of the whitening agent include arbutin, α-arbutin, and placenta extract.

  Specific examples of the above essential oils include angelica oil, ylang ylang oil, elemi oil, orange oil, chamomile oil, roman chamomile oil, cardamom oil, columnus oil, galvanum oil, camphor oil, carrot seed oil, clary sage oil, Grapefruit oil, clove oil, cinnamon oil, cypress 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, pebbly oil -Mint oil, Bergamot oil, Benzoin oil, Boadrose 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, rosewood oil, rosemary oil, lobe oil and the like.

  Specific examples of the terpenes include limonene, pinene, terpinene, terpinolene, myrcene, and longefylene.

The said component may be used individually by 1 type, and may be used in combination of 2 or more type.
Among the above components, at least one interface selected from the group consisting of an anionic surfactant, a cationic surfactant, an amphoteric surfactant not corresponding to the specific betaine-type amphoteric surfactant, and a nonionic surfactant An activator is preferably used.

Examples of the external preparation for skin of the present invention include cosmetics and pharmaceuticals.
When the skin external preparation of the present invention is a cosmetic, an existing cosmetic raw material can be added at a general concentration. For example, Cosmetic Material Standards Second Edition Commentary, Japan Official Church Church, 1984 (Pharmaceutical Daily Report), Cosmetic Raw Material Standards Independent Component Standard, Ministry of Health and Welfare Pharmaceutical Affairs Bureau Supervision Division, 1993 (Pharmaceutical Daily Report), Cosmetic Ingredients Nonstandard Component 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 the supervision, 1997 (Pharmaceutical Daily), cosmetic raw material dictionary, 1991 (Nikko Chemicals), etc. can be used.

The dosage form of the external preparation for skin of the present invention is not particularly limited as long as it is used in contact with the skin at the time of use, and is appropriately set according to the use. For example, it can be applied to lotions, emulsions, creams, packs and the like.
The external preparation for skin of the present invention is particularly effective in a lotion preparation with a noticeable precipitate.

The pH of the external preparation for skin of the present invention is preferably 6.0 to 8.5. When the pH is within this range, the stability of the tocopherol phosphate ester and / or its salt is good, and the formulation stability is better.
The pH is a value at 25 ° C. and can be measured with a pH meter.

  The external preparation for skin of the present invention is produced by formulating a tocopherol phosphate ester and / or salt thereof, the specific betaine amphoteric surfactant and other optional ingredients. Formulation can be performed according to a conventional method according to the dosage form.

In the present invention, a tocopherol phosphate ester and / or a salt thereof and a specific betaine-type amphoteric surfactant are blended to suppress the precipitation and turbidity of the external preparation for skin over time.
Therefore, the skin external preparation of the present invention can be usefully used for all skin external preparations including cosmetics and pharmaceuticals, and is particularly useful for cosmetics.
Although the reason why generation of precipitation and turbidity over time is suppressed is not clear, the following may be considered. In a skin external preparation containing a tocopherol phosphate ester and / or a salt thereof, the tocopherol phosphate ester and / or salt thereof is decomposed to produce water-insoluble tocopherol, resulting in turbidity and coloring. It is considered that the tocopherol produced by the decomposition is solubilized by blending the specific betaine-type amphoteric surfactant. In addition, in a skin external preparation containing a tocopherol phosphate and / or a salt thereof, the formulation of a specific betaine amphoteric surfactant causes some interaction with the tocopherol phosphate and / or a salt thereof, and the tocopherol phosphate It is considered that the stability of the preparation is improved by suppressing the occurrence of turbidity and coloring due to the decomposition of the ester and / or its salt .

  EXAMPLES Hereinafter, although this invention is demonstrated more concretely based on an Example, this invention is not limited to these Examples.

[Examples 1 to 8 (Reference Examples 1 to 8), Examples 9 to 24, Examples 25 to 28 (Reference Examples 9 to 12), Examples 29 to 44, Examples 45 to 48 (Reference Examples 13 to 16) ) , Comparative Examples 1-20 ]
Each component was uniformly dispersed and dissolved so as to have the composition (unit: mass%) shown in Table 1, and a lotion was obtained by stirring. As a mixing method, first, sodium tocopherol phosphate , glycerin, pentylene glycol, and phenoxyethanol are mixed using a magnetic stirrer, purified water is added to this, and the mixture is stirred and dissolved, and then the remaining components in the table are added and mixed. It is a thing.
The obtained lotion was evaluated for turbidity and coloring immediately after preparation and after storage for 6 months according to the following procedure. Storage was performed by leaving the lotion in a thermostat set at 4 ° C., 25 ° C. or 40 ° C. with the lotion sealed in a glass vial. The results are shown in Tables 1 to 8.

[1. Turbidity evaluation method]
Visual evaluation was performed according to the following evaluation criteria.
-: Turbidity is not seen at all.
±: Although it is within an acceptable range as a lotion preparation, turbidity is slightly observed.
+: Turbidity is clearly observed.

[2. Coloring evaluation method]
Visual evaluation was performed according to the following evaluation criteria.
-: Coloring is not seen at all.
±: Although it is within an acceptable range as a lotion preparation, coloring is slightly observed.
+: Coloring is clearly recognized.

From the results of the precipitation and storage stability evaluation shown in Table 1, in Examples 1 to 4 in which the betaine amphoteric surfactant represented by the general formula (1) or (2) was blended, a surfactant was blended. Compared to the system using no non-ionic surfactant (Comparative Examples 2 and 3), anionic surfactant (Comparative Example 4), and cationic surfactant (Comparative Example 5) Thus, it was found that the stability of sodium tocopherol phosphate in the lotion was improved and the occurrence of turbidity and coloring over time was suppressed.
From the results shown in Table 2, the same behavior was exhibited in the systems (Examples 5 to 8 and Comparative Examples 6 to 10) using γ-tocopherol sodium phosphate instead of α-tocopherol sodium phosphate.
Also, in the results shown in Tables 3 to 5, the compositions of the systems containing various betaine surfactants (Examples 9 to 28) are better than the systems not containing the surfactant (Comparative Examples 11 to 15). Showed good storage stability. Among them, in particular, the composition in the system (Examples 9 to 24) containing both the betaine surfactant and the chelating agent is more than the composition of the system (Examples 25 to 28) containing only the betaine surfactant. Also showed better storage stability. As shown in Tables 6 to 8, the same behavior was exhibited in the systems using Examples γ-tocopherol sodium phosphate instead of sodium α-tocopherol phosphate (Examples 29 to 48, Comparative Examples 16 to 20). .

  Among the components shown in Tables 1 to 8, the following were used as the surfactant and the chelating agent, respectively.

[Betaine-type amphoteric surfactant]
Lauryldimethylaminoacetic acid betaine 26% aqueous solution: “Amphitor 24B” manufactured by Kao Corporation.
Lauric acid amidopropyl betaine 30% aqueous solution: “Softazoline LPB-R” manufactured by Kawaken Fine Chemical Co., Ltd.
Coconut oil fatty acid amidopropyldimethylaminoacetic acid betaine 30% aqueous solution: “Obazoline CAB-30” manufactured by Toho Chemical Co., Ltd.
Isostearate amidopropyldimethylaminoacetate betaine 31% aqueous solution: “Obazoline ISAB” manufactured by Toho Chemical Co., Ltd.

[Other surfactants]
POE (50) hydrogenated castor oil: “NIKKOL HCO-50” manufactured by Nikko Chemicals Corporation.
POE (20) POP (4) cetyl ether: “NIKKOL PBC-34” manufactured by Nikko Chemicals Co., Ltd.
POE (3) Lauryl ether sulfate Na 25% aqueous solution: “Emar 20C” manufactured by Kao Corporation.
Cetyltrimethylammonium chloride 30% aqueous solution: “Coatamine 60W” manufactured by Kao Corporation.

[Chelating agent]
Ethylenediaminetetraacetic acid tetrasodium tetrahydrate: “Chillest 2DS” manufactured by Kirest Corporation.
Diethylenetriaminepentaacetic acid pentasodium 40% solution: “Kyrest P” manufactured by Kirest Corporation.
L-glutamic acid diacetic acid / tetrasodium 40% solution: “GLDA-4Na 40% aqueous solution” manufactured by Showa Denko KK
Ethylenediaminetetramethylene phosphonic acid pentasodium: “Chirest PH-540” manufactured by Kirest Corporation.

Claims (8)

A skin external preparation containing a tocopherol phosphate ester and / or a salt thereof, and at least one betaine-type amphoteric surfactant selected from the group consisting of compounds represented by the following formulas (1) and (2) agent and, seen containing a chelating agent, wherein the chelating agent is diethylenetriaminepentaacetic acid and salts thereof, L- glutamic acid diacetate and its salts, and one or two selected from the group consisting of ethylenediamine tetramethylene phosphonic acid and its salts A skin external preparation characterized by being a chelating agent as described above .

[In formula (1), ^{R 1} is a linear or branched alkyl group having 6 to 30 carbon atoms. In the formula (2), R ² is a linear or branched alkyl group having 8 to 30 carbon atoms. ] As the betaine type amphoteric surfactant, wherein R ¹ in the general formula (1) contains a compound which is linear or branched alkyl group having 12 to 24 carbon atoms, skin external of claim 1 Agent. As the betaine type amphoteric surfactants, the R ² of the general formula (2) contains a compound which is linear or branched alkyl group having 12 to 24 carbon atoms, according to claim 1 or 2 Skin external preparation.   The skin external preparation as described in any one of Claims 1-3 whose content of the said tocopherol phosphate ester and / or its salt is 0.01-10 mass%.   The external preparation for skin as described in any one of Claims 1-4 whose compounding quantity of the said betaine type | mold amphoteric surfactant is 0.1-10 mass%.   The skin external preparation as described in any one of Claims 1-5 whose pH is 6.0-8.5. The skin external preparation as described in any one of Claims 1-6 which is cosmetics. A method for producing a topical skin preparation containing a tocopherol phosphate and / or a salt thereof,
A tocopheryl phosphate and / or its salts, mixed with at least one betaine type amphoteric surfactant selected from the group consisting of compounds represented by the following formula (1) and (2), and a chelating agent, a The chelating agent is one or more chelating agents selected from the group consisting of diethylenetriaminepentaacetic acid and salts thereof, L-glutamic acid diacetic acid and salts thereof, and ethylenediaminetetramethylenephosphonic acid and salts thereof. A method for producing an external preparation for skin.

[In formula (1), ^{R 1} is a linear or branched alkyl group having 6 to 30 carbon atoms. In the formula (2), R ² is a linear or branched alkyl group having 8 to 30 carbon atoms. ]