JP2008266250A - Emulsifier form external preparation for skin - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a technique for stably emulsifying a carbonic diester such as ethylene carbonate or propylene carbonate, or a solvent type oil and fat such as a short chain branched fatty acid polyhydric alcohol ester. <P>SOLUTION: This emulsifier form external preparation for skin contains (1) an alkyl-modified carboxyvinyl polymer and/or its salt, and (2) one or more esters selected from carbonic diesters and branched fatty acid (the number of carbon atoms is 4 to 10) polyhydric alcohol esters. One or more esters selected from the carbonic diesters and the 4 to 10C branched fatty acid polyhydric alcohol esters are preferably selected from ethylene carbonate, propylene carbonate, dicapryl carbonate and propylene glycol mono-2-ethylhexanoate. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a skin external preparation, and more particularly to an emulsifier type skin external preparation.

  Make-up cosmetics are cosmetics that make use of the optical effect of powder to cover unpleasant color-specific parts such as spots and freckles and to be beautifully dressed. Changes in the optical effect of the powder due to the collapse of the cosmetic film is a phenomenon that should be avoided most in make-up cosmetics. Cosmetics with excellent durability have been developed. Examples of such cosmetics include cosmetics containing a polymer that forms a highly hydrophobic film, and powders that have excellent adhesion and adhesion to the skin, such as silicone having a three-dimensional structure. Examples thereof include a technique in which a body is dispersed, a water-in-oil emulsifier form, and a film having high water resistance is formed. With the development of these new technologies, makeup lasting has been improved, but on the other hand, it is becoming difficult to remove the cosmetic film by conventional cleansing and facial cleansing methods. The development of removal cosmetics has been desired.

  For removal of such difficult-to-remove cosmetic films, a method using a solvent-based oil or fat such as a carbonic acid diester such as ethylene carbonate or propylene carbonate or a polyhydric alcohol ester of a short-chain branched fatty acid, which is a nail color removal technique ( For example, see Patent Document 1, Patent Document 2, Patent Document 3, and Patent Document 4), but for amphiphilic components such as powder, such solvent oils and fats can also be used. There were cases where the body or film remained on the skin, and this was thought to be due to a lack of hydrophilic components. Such a situation can be said to be the same situation in an ultraviolet care cosmetic containing an ultraviolet shielding agent such as titanium dioxide if the optical effect is read as an ultraviolet protective effect.

  As a technique for solubilizing and dispersing both a lipophilic substance and a hydrophilic substance, there is a technique in which an emulsion is used as a medium. However, the solvent-based fat or oil is an indispensable condition for emulsification. There was a problem that it could not be easily emulsified because the orientation of the polymer was inhibited by dissolving the surfactant in the oil phase.

  From a different viewpoint, the dosage form emulsified with “solvent oils and fats” is also considered suitable as a vehicle for transdermal administration of poorly water-soluble or fat-soluble oils such as polyene macrolide antibiotics and dihydropyridine calcium antagonists. From this point of view, it can be said that development of an external dosage form emulsified with solvent-based fats and oils is desired.

  On the other hand, alkyl-modified carboxyvinyl polymers and / or salts thereof are known as thickeners having an emulsifying action, and are used in the form of oil-in-water emulsifiers in the field of skin external preparations such as cosmetics ( For example, Patent Document 5, Patent Document 6, Patent Document 7, and Patent Document 8) are not used for emulsification of the solvent-based fats and oils. It is not known at all that emulsification can be achieved.

JP 2004-269540 A JP-A-9-227357 JP-T-2001-521881 JP 2006-28177 A JP 2006-111542 A JP 2006-104131 A Japanese Patent Laid-Open No. 2005-232088 JP 2004-285017 A

  The present invention has been made under such circumstances, and provides a technique for stably emulsifying solvent-based fats and oils such as carbonic acid diesters such as ethylene carbonate and propylene carbonate, and polyhydric alcohol esters of short chain branched fatty acids. This is the issue.

In view of such circumstances, as a result of earnest research, seeking a technique for stably emulsifying solvent-based fats and oils such as carbonic acid diesters such as ethylene carbonate and propylene carbonate, polyhydric alcohol esters of short-chain branched fatty acids, 1) By using an alkyl-modified carboxyvinyl polymer and / or a salt thereof, it was found that the solvent-based fats and oils can be emulsified, and the present invention has been completed. That is, the present invention is as follows.
(1) 1) Alkyl-modified carboxyvinyl polymer and / or salt thereof, and 2) 1 type or 2 types or more selected from carbonic acid diesters and polyhydric alcohol esters of branched fatty acids (4 to 10 carbon atoms) Emulsifier type skin external preparation.
(2) One type or two or more types selected from the carbonic acid diester and a polyhydric alcohol ester of a branched fatty acid having 4 to 10 carbon atoms are ethylene carbonate, propylene carbonate, dicapryl carbonate, propylene glycol mono-2-ethylhexane. The emulsifier-type skin external preparation according to (1), characterized in that it is one or more selected from acid esters and ethylene glycol di-2-ethylhexanoate.
(3) One type or two or more types selected from the carbonic acid diester and a polyhydric alcohol ester of a branched fatty acid having 4 to 10 carbon atoms are ethylene carbonate, propylene carbonate, dicapryl carbonate, propylene glycol mono-2-ethylhexane. The content of one or more selected from acid esters and ethylene glycol di-2-ethylhexanoate is 5 to 30% by mass based on the total amount of the external preparation for skin, based on the total amount. The skin external preparation in the form of an emulsifier according to (1) or (2).
(4) The emulsifier-type skin external preparation according to any one of (1) to (3), further comprising an antibacterial polyhydric alcohol.
(5) The skin external preparation in the form of an emulsifier according to any one of (1) to (4), which is a cleansing cosmetic.
(6) The skin external preparation in the form of an emulsifier according to (5), which should be used in a wash-off mode.

  ADVANTAGE OF THE INVENTION According to this invention, the technique which emulsifies solvent fats and oils, such as carbonic acid diesters, such as ethylene carbonate and a propylene carbonate, the polyhydric alcohol ester of a short chain branched fatty acid, can be provided.

(1) Solvent-based fats and oils that are essential components of the external preparation for skin of the present invention The external skin preparation of the present invention is selected from a carbonic acid diester and a polyhydric alcohol ester of a branched fatty acid (4 to 10 carbon atoms). Contains two or more, and is characterized by being in an emulsifier form. Here, one or more selected from carbonic acid diesters and polyhydric alcohol esters of branched fatty acids (4 to 10 carbon atoms) are used in skin external preparations such as cosmetics to smooth the skin, and In addition, it has an action as an oil and fat that moisturizes the skin due to its occlusive property, and also has a character as a solvent that is excellent in the action of dissolving hardly soluble components such as polymers, copolymers, and high melting point waxes. Such a component has an effect of dissolving and facilitating the removal of the copolymers which are formed on the skin after application and are a skeleton part of the cosmetic film which is difficult to remove by the cosmetic containing the copolymers. If one or more specific examples selected from such carbonic acid diesters and polyhydric alcohol esters of branched fatty acids (4 to 10 carbon atoms) are illustrated, methylene carbonate, carbonic acid Cyclic diesters having 1 to 4 carbon atoms such as ethylene, propylene carbonate and butylene carbonate or diesters of medium chain alcohols having 6 to 12 carbon atoms such as dicaprin carbonate and dicapryl carbonate are preferred. Particularly preferred are ethylene carbonate, propylene carbonate, and dicapryl carbonate. In addition, as polyhydric alcohol esters of branched fatty acids (4 to 10 carbon atoms), isobutanoic acid, 2-methylpropanoic acid, 2-methylpentanoic acid, 2-methylhexanoic acid, 2-ethylhexanoic acid, 2-methylheptane Examples thereof include ethylene glycol ester, propylene glycol ester, 1,3-butanediol ester, glycerol ester and the like such as acid and 2-ethyloctanoic acid, and propylene glycol ester and ethylene glycol ester are particularly preferable. There are no particular restrictions on the ester, whether it is a diester or a monoester. Particularly preferred specific examples include 2-ethylhexanoic acid monopropylene glycol ester, 2-ethylhexanoic acid dipropylene glycol ester, 2-ethylhexanoic acid monoethylene glycol ester, 2-ethylhexanoic acid ethylene glycol diester, 2-ethylhexane. Acid monoglyceryl ester and the like can be mentioned, among which 2-ethylhexanoic acid monopropylene glycol ester and 2-ethylhexanoic acid ethylene glycol diester are particularly preferred. These esters preferably have at least one hydroxyl group. Particularly preferred is the form of a monoester of a polyhydric alcohol. Such a component may contain only one species or may contain two or more species in combination. In order to express the solvent effect and the oil and fat effect at the same time, the total amount of such components is preferably 5 to 30% by mass, more preferably 8 to 25% by mass, based on the total amount of the external preparation for skin. More preferably, it is 9-22 mass%. This is because if the amount is too small, the solvent effect may not be achieved, and if the amount is too large, emulsification of the emulsifier form, which is the effect of the present invention, may be impaired.

(2) Alkyl-modified carboxyvinyl polymer which is an essential component of the skin external preparation of the present invention The skin external preparation of the present invention contains an alkyl-modified carboxyvinyl polymer and / or a salt thereof as an essential component. These salts can be used without any particular limitation as long as they are used in skin external preparations, for example, alkali metal salts such as sodium salts and potassium salts, alkaline earth metal salts such as calcium salts and magnesium salts. Preferred examples include organic amine salts such as ammonium salt, triethylamine salt, triethanolamine salt, and monoethanolamine salt, and basic amino acid salts such as lysine salt and alginate. Particularly preferred are alkali metal salts, with sodium or potassium salts being particularly preferred. Moreover, as an alkyl group which comprises the said alkyl modified carboxy vinyl polymer, a C10-C30 thing is preferable and it is preferable to use the derivative | guide_body which the alkyl group with a carbon number distribution combined. Such alkyl-modified carboxyvinyl polymer has raw materials already on the market, and such commercial products can be purchased and used. Examples of preferable commercial products include “Carbopol 1382”, “Pemlen TR-1”, “Pemlen TR-2” and the like manufactured by BF Goodrich. In the external preparation for skin according to the present invention, such a component has an action of stably dispersing the oil phase containing the solvent-based oil and fat as oil droplets in the aqueous phase. In order to exert such an action, it is preferable to contain 0.1 to 1% by mass of the total amount of such components with respect to the total amount of the external preparation for skin, more preferably 0.2 to 0.5% by mass. is there.

(3) External preparation for skin of the present invention The external preparation for skin of the present invention is characterized by containing the essential components and taking an emulsifier form. The emulsifier form is not particularly limited, but is preferably an oil-in-water emulsifier form. Here, the oil-in-water emulsifier form referred to in the present invention is a general term for an emulsifier form in which the outermost phase is an aqueous phase and has an oil droplet phase in the inner phase, and a composite emulsifier form such as a water-in-oil-in-water form. As long as the above conditions are satisfied.

  In the external preparation for skin of the present invention, optional components usually used in external preparations for skin can be contained in addition to the essential components. Such optional ingredients include, for example, macadamia nut oil, avocado oil, corn oil, olive oil, rapeseed oil, sesame oil, castor oil, safflower oil, cottonseed oil, jojoba oil, coconut oil, palm oil, liquid lanolin, hydrogenated coconut oil Oil, wax, oils such as beeswax, owl, hardened castor oil, beeswax, candelilla wax, carnauba wax, botarou, lanolin, reduced lanolin, hard lanolin, jojoba wax , Hydrocarbons such as microcrystalline wax; higher fatty acids such as oleic acid, isostearic acid, lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, undecylenic acid; cetyl alcohol, stearyl alcohol, isostearyl Higher alcohols such as alcohol, behenyl alcohol, octyldodecanol, myristyl alcohol, cetostearyl alcohol; cetyl isooctanoate, isopropyl myristate, hexyldecyl isostearate, diisopropyl adipate, di-2-ethylhexyl sebacate, cetyl lactate, malic acid Diisostearyl, neopentyl glycol dicaprate, glycerin di-2-heptylundecanoate, glycerin tri-2-ethylhexanoate, trimethylolpropane tri-2-ethylhexanoate, trimethylolpropane triisostearate, tetra-2- Synthetic ester oils such as ethylhexanoic acid pentane erythritol; chains such as dimethylpolysiloxane, methylphenylpolysiloxane, diphenylpolysiloxane Cyclic polysiloxanes such as octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexanesiloxane; modified polysiloxanes such as amino-modified polysiloxane, polyether-modified polysiloxane, alkyl-modified polysiloxane, and fluorine-modified polysiloxane Oils such as silicone oils; fatty acid soap (sodium laurate, sodium palmitate, etc.), anionic surfactants such as potassium lauryl sulfate, alkylsulfuric triethanolamine ether; stearyltrimethylammonium chloride, benzalkonium chloride, Cationic surfactants such as laurylamine oxide; imidazoline-based amphoteric surfactants (2-cocoyl-2-imidazolinium hydroxide-1-carboxyethyl) Roxy disodium salt, etc.), betaine surfactants (alkyl betaine, amide betaine, sulfobetaine, etc.), and amphoteric surfactants such as acylmethyl taurine; sorbitan fatty acid esters (sorbitan monostearate, sorbitan sesquioleate, etc.) ), Glycerin fatty acids (such as glyceryl monostearate), propylene glycol fatty acid esters (such as propylene glycol monostearate), hydrogenated castor oil derivatives, glycerin alkyl ether, POE sorbitan fatty acid esters (POE sorbitan monooleate, monostearin) Acid polyoxyethylene sorbitan, etc.), POE sorbite fatty acid esters (POE-sorbitol monolaurate, etc.), POE glycerin fatty acid esters (POE-glycerin monoisosteale) POE fatty acid esters (polyethylene glycol monooleate, POE distearate, etc.), POE alkyl ethers (POE2-octyldodecyl ether, etc.), POE alkyl phenyl ethers (POE nonylphenyl ether, etc.), Pluronic types, POE -POP alkyl ethers (POE / POP2-decyltetradecyl ether, etc.), Tetronics, POE castor oil / hardened castor oil derivatives (POE castor oil, POE hardened castor oil, etc.), sucrose fatty acid esters, alkyl glucosides, etc. Nonionic surfactants: polyethylene glycol, glycerin, 1,3-butylene glycol, erythritol, sorbitol, xylitol, maltitol, propylene glycol, dipropylene glycol, diglyceride Polyhydric alcohols such as sodium, isoprene glycol, 1,2-pentanediol, 2,4-hexanediol, 1,2-hexanediol, 1,2-octanediol; sodium pyrrolidone carboxylate, lactic acid, sodium lactate, etc. Moisturizing ingredients; powders such as mica, talc, kaolin, synthetic mica, calcium carbonate, magnesium carbonate, anhydrous silicic acid (silica), aluminum oxide, barium sulfate, etc., whose surface may be treated; Bengara, yellow iron oxide, black iron oxide, cobalt oxide, ultramarine, bitumen, titanium oxide, zinc oxide inorganic pigments; surface may be treated, mica titanium, fish phosphorus foil, oxy Pearl agents such as bismuth chloride; red 202, red 228, red 226, yellow 4 and blue 40 which may be raked No. 4, Yellow No. 5, Red No. 505, Red No. 230, Red No. 223, Orange No. 201, Red No. 213, Yellow No. 204, Yellow No. 203, Blue No. 1, Green No. 201, Purple No. 201, Red No. 204 Organic pigments such as polyethylene powder, polymethyl methacrylate, nylon powder, organopolysiloxane elastomer, etc .; paraaminobenzoic acid UV absorbers; anthranilic acid UV absorbers; salicylic acid UV absorbers; Cinnamic acid UV absorbers; benzophenone UV absorbers; sugar UV absorbers; 2- (2′-hydroxy-5′-t-octylphenyl) benzotriazole, 4-methoxy-4′-t-butyldi UV absorbers such as benzoylmethane; lower alcohols such as ethanol and isopropanol; vitamin A or a derivative thereof; Mineral B6 hydrochloride, vitamin B6 tripalmitate, vitamin B6 dioctanoate, vitamin B2 or derivatives thereof, vitamin B12 such as vitamin B12, vitamin B15 or derivatives thereof; α-tocopherol, β-tocopherol, γ-tocopherol, vitamin E acetate Preferred examples include vitamins such as vitamin E, vitamin D, vitamin H, pantothenic acid, panthetin, pyrroloquinoline quinone, and the like; and antibacterial agents such as phenoxyethanol.

  Among the above optional components, nonionic surfactants are particularly preferable, and among them, lipophilic surfactants that are excellent in structure formation in an emulsified state are preferable. As the agent, sorbitan stearate ester, glycerin monostearate ester and the like can be particularly preferably exemplified. The preferable content of such components is 0.1 to 5% by mass, and more preferably 0.2 to 3% by mass. By adding such a component, the adhesiveness with the skin becomes excellent.

  In the external preparation for skin of the present invention, parabens are easily taken into the oil phase by solvent-based oils and fats, and therefore it is preferable to use an antiseptic means instead of parabens. Examples of such preservatives include isoprene glycol, hexylene glycol, 1,2-pentanediol, 1,2-hexanediol, 1,2-octanediol, 1,2-decanediol, and more preferably 1 Suitable examples include 2 to 6% by mass, more preferably 3 to 5% by mass of an antibacterial polyhydric alcohol such as 1,2-pentanediol or 1,2-hexanediol. Furthermore, it is preferable to contain 0.1 to 1% by mass, more preferably 0.2 to 0.8% by mass of phenoxyethanol, since the antiseptic power is further improved. It is preferable not to contain butylparaben which is easily incorporated into the oil phase because there are cases where the blending effect cannot be obtained.

  The external preparation for skin of the present invention can be applied without particular limitation as long as it is applied for external use on the skin. For example, moisturizing cream, moisturizing milk, whitening cream, massage cream, nutritional milk, nutritional cream Cosmetic preparations such as cleansing creams, antifungal skin external medicines, anti-inflammatory skin external medicines, steroid skin external medicines, sterilized wound healing skin external medicines and the like can be particularly preferably exemplified. Particularly preferred is a cleansing cosmetic that can utilize both the solvent effect of the solvent-based fats and oils and the effect of including and removing the aqueous component. In cleansing cosmetics, as described above, it is preferable to include a nonionic surfactant having an HLB of 10 or more to provide a wash-off effect. In addition, the cleansing cosmetics to be removed include polymers or copolymers, and cosmetics having a high probability of containing poorly water-soluble components such as powders and waxes. In addition, eyeliner and mascara It is a cosmetic applied in the vicinity of a sensitive part. For such cosmetics, the effect of the external preparation for skin of the present invention is particularly prominent.

  In addition, the external preparation for skin of the present invention is also preferably applied to an external preparation for skin containing a hardly soluble drug as an active ingredient. This is because the characteristics of the external preparation for skin of the present invention can be utilized for solubilization and percutaneous absorption of poorly soluble drugs. Examples of such poorly soluble drugs include antibiotics such as polyene macrolide, triterpenic acids such as steroids, ursolic acid and oleanolic acid, esters of triterpenic acids such as stearyl ursolate and benzyl ursolate, and ursolic acid glucoside. Preferable examples include phytosterols such as triterpenic acid glycosides, sphingosine, sphingoglycolipids, sphingophospholipids, and stigmasteranol, and phytosterol glycosides such as stigmasteranol glucoside and stigmasteranol maltoside. The preferable content of such a poorly soluble drug is 0.01 to 10% by mass.

  The external preparation for skin of the present invention can be produced by treating the above components according to a conventional method. Hereinafter, the present invention will be described in more detail with reference to examples, but it goes without saying that the present invention is not limited to such examples.

  According to the formulation shown below, cleansing cosmetic 1 which is a skin external preparation of the present invention was produced. In other words, the components of A, B, and C are each heated to 80 ° C., and the mixture is neutralized by adding B to the mixture under stirring, and then the components of C are gradually added and emulsified with stirring, cooled with stirring, and cleaned. Cosmetic 1 was obtained. In the same manner, Comparative Example 2 in which “Pemlen TR-2” was substituted with POE (25) stearic acid 1,2-ethylhexanoic acid propylene glycol monoester was substituted with cetyl 2-ethylhexanoate Comparative Examples 2, 2 When Comparative Example 3 in which propylene glycol monoester of ethylhexanoic acid was substituted with cetyl 2-ethylhexanoate and “Pemlen TR-2” was substituted with POE (25) stearic acid was also prepared in the same manner, Comparative Example 1 Was separated immediately after production, and no emulsion was obtained.

<Test Example 1>
The cleansing effect was compared for cleansing cosmetic 1, comparative example 2, and comparative example 3. In this method, four molds were prepared by copying the shape of the upper eyelid using silicone rubber for shaping, and the eyeliner shown in Table 2 below was applied to the eyelid portion of the eyelid mold and dried. After that, three of these were placed on an electronic balance and rubbed 20 times with a cotton swab impregnated with cleansing 1, comparative example 2 and comparative example 3 so that the crimping force was reduced to 15 to 25 g. Exposure, remove moisture with "Kimwipe", capture as an image with enlarged video, disassemble into GBR with "Photoshop" for the application site, create a B channel image, calculate total luminance, compare did. No cleansing operation was performed, and the total luminance of the B channel image was obtained in the same manner. That is, if the eyeliner remains, the total luminance increases, and if the eyeliner is removed, the total luminance decreases. Table 3 below shows the B channel total luminance ratio, which is a value obtained by dividing the total luminance of treatment by the total luminance of no treatment. As a result, the cleansing cosmetic that is an external preparation for skin of the present invention has a fine undulation and is applied to a site where it is difficult to apply force, and contains a copolymer or wax, such as an eye makeup cosmetic such as an eyeliner. It turns out that it is excellent in the effect | action which removes makeup cosmetics.

  According to the formulation shown below, a cleansing cosmetic 2 that is a skin external preparation of the present invention was prepared in the same manner as in Example 1. The evaluation result in Test Example 1 was 0.15 in terms of the B channel total luminance ratio, and the same effect was recognized.

  According to the prescription shown below, cleansing cosmetics 3 to 5, which are skin external preparations of the present invention, were prepared in the same manner as in Example 1. Evaluation results in Test Example 1 are shown in Table 6. Similar effects were confirmed.

  Creams 6 to 14 containing a sparingly soluble active ingredient were prepared according to the formulation shown below. Any poorly soluble component was blended without precipitating crystals. From this, it can be seen that the external preparation for skin of the present invention has excellent properties as a base for external preparations for skin.

  According to the formulation shown below, a cleansing cosmetic 15 that is an external preparation for skin of the present invention was prepared in the same manner as in Example 1. The evaluation result in Test Example 1 was 0.13 as the B channel total luminance ratio, and the same effect was recognized.

  According to the formulation shown below, creams 16 to 24 containing hardly soluble active ingredients were prepared. Any poorly soluble component was blended without precipitating crystals. From this, it can be seen that the external preparation for skin of the present invention has excellent properties as a base for external preparations for skin.

  The present invention can be applied to skin external preparations in general, such as cleansing cosmetics and skin external preparations containing hardly soluble active ingredients.

Claims (6)

1) An emulsifier form containing an alkyl-modified carboxyvinyl polymer and / or a salt thereof, and 2) one or more selected from a diester carbonate and a polyhydric alcohol ester of a branched fatty acid (4 to 10 carbon atoms). Topical skin preparation. One or more selected from the carbonic acid diester and a polyhydric alcohol ester of a branched fatty acid having 4 to 10 carbon atoms are ethylene carbonate, propylene carbonate, dicapryl carbonate, propylene glycol mono-2-ethylhexanoate, and The emulsifier-type skin external preparation according to claim 1, wherein the skin external preparation is one or more selected from ethylene glycol di-2-ethylhexanoate. One or more selected from the carbonic acid diester and a polyhydric alcohol ester of a branched fatty acid having 4 to 10 carbon atoms are ethylene carbonate, propylene carbonate, dicapryl carbonate, propylene glycol mono-2-ethylhexanoate, and The content of one or more selected from ethylene glycol di-2-ethylhexanoate is 5 to 30% by mass based on the total amount of the external preparation for skin, The emulsifier-type external skin preparation according to claim 1 or 2. Furthermore, antibacterial polyhydric alcohol is contained, The emulsifier type skin external preparation in any one of Claims 1-3 characterized by the above-mentioned. It is a cleansing cosmetic, The emulsifier type skin external preparation in any one of Claims 1-4 characterized by the above-mentioned. The skin external preparation in the form of an emulsifier according to claim 5, characterized in that it should be used in a wash-off mode.