JP2009149554A - Skin preparation for external use, having oil-in-water emulsion form - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a skin preparation for external use of an oil-in-water emulsion form, having high pH tolerance and less powder cohesion. <P>SOLUTION: This skin preparation for external use is obtained by incorporating a fatty acid ester of polyoxyethylene having 100 to 200 degree of polymerization and a fatty acid ester of polyoxyethylene having 20 to 60 degree of polymerization as hydrophilic surfactants, into a salt of a polymer of acrylic acid and/or methacrylic acid which may be alkyl-modified, and an oil-in-water emulsion cosmetic without substantially containing a fatty acid soap, further incorporating as lipophilic surfactants, a stearic acid mono-glyceride and ≥2 kinds of sorbitan fatty acid esters at least any one of which is a liquid state under the condition of 1 atm and 25°C, and furthermore, incorporating 1 kind or ≥2 kinds selected from cetyl alcohol, stearyl alcohol, behenyl alcohol and batyl alcohol, and a branched fatty acid. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to an external preparation for skin, and more particularly to an external preparation for skin in the form of an oil-in-water emulsifier. Here, the oil-in-water emulsifier form is a general term for an emulsifier form in which the outer continuous phase facing the air is an aqueous phase, and a composite emulsifier form such as water-in-oil-in-water is also an aqueous continuous phase. Includes as much as possible.

  Emulsification is a system obtained by processing one of two kinds of phases having different specific gravities into fine droplets and dispersing them metastable in the other phase. The phase consists of an aqueous phase and an oil phase. The oil-in-water emulsifier form is an emulsifier form in which oily fine particles are dispersed in an aqueous continuous phase, reflects the properties of the external phase, has a refreshing feeling of use, and is effective for moisturizing ingredients such as hyaluronic acid. In such emulsification, there is a difference in specific gravity between the two phases, so that the dispersed fine particles associate and do not separate into two phases. It is necessary to stabilize the dispersion of the particles by forming a structure with an agent. Examples of the structure with such a surfactant include a surfactant gel structure with a fatty acid soap and a water solution by van der Waals with a salt of a carboxyvinyl polymer. An electroconductive polymer cross-linked gel structure is used (see, for example, Patent Document 1). However, the use of a carboxylic acid salt requires that the system be weakly basic or basic in order to maintain such a structure, or isoelectricity such as powder. In the case of containing a large amount of components having points, there is a problem that the system may become unstable by inducing powder aggregation due to ionization of the carboxylic acid moiety, and there are limitations of the system. did.

  For this reason, as a result of repeated research to find a dosage form that contains a component that weakens the gel structure and can follow the feeling of use of the oil-in-water emulsifier form, a high internal phase water-in-oil emulsifier form using organically modified clay minerals. Technology has been developed (see, for example, Patent Document 2), but the water-in-oil emulsifier type has become quite refreshing in terms of usability. There was still a problem in terms of drawing out, and there was something difficult in this dosage form for greasy after use. In this sense, it can be said that development of an oil-in-water emulsifier type that has high pH tolerance and does not cause powder aggregation is desired.

  On the other hand, as an emulsification system using a polyoxyethylene fatty acid ester having a polymerization degree of 100 to 200, a lamella structure is formed together with phosphatidylcholine, and this may be used to modify alkyl, acrylic acid and / or methacrylic acid. A technique for embodying an oil-in-water emulsifier form substantially free of fatty acid soap and a salt of a polymer of the above is disclosed (see, for example, Patent Document 3), but with other components derived from phosphatidylcholine. Problems remain in the absolute stability of the system by using compatibility and lamellar structure. For this reason, such a system cannot contain powder, and it can be said that one of the above problems has not been solved.

  On the other hand, it may be an alkyl-modified salt of acrylic acid and / or methacrylic acid polymer, and a cosmetic in the form of an oil-in-water emulsifier substantially free of fatty acid soap, as a hydrophilic surfactant No skin external preparation containing a polyoxyethylene fatty acid ester having a polymerization degree of 100 to 200 and a polyoxyethylene fatty acid ester having a polymerization degree of 20 to 60 is known at all. In such a system, It is not known at all that the pH tolerance is high and the powder cohesion is low.

JP 2007-39371 A JP-A-8-20529 JP 2007-314442 A

  The present invention has been made under such circumstances, and an object of the present invention is to provide an oil-in-water emulsifier type skin external preparation having high pH tolerance and low powder cohesion.

In view of such circumstances, as a result of intensive research efforts to find an oil-in-water emulsifier type skin external preparation with high pH tolerance and low powder agglomeration properties, as a hydrophilic surfactant, It is found that an oil-in-water emulsifier form containing a polyoxyethylene fatty acid ester of 100 to 200 and a polyoxyethylene fatty acid ester having a polymerization degree of 20 to 60 has such characteristics and completes the invention. It came to. That is, the present invention is as follows.
<1> A salt of a polymer of acrylic acid and / or methacrylic acid, which may be alkyl-modified, and an oil-in-water emulsifier type cosmetic substantially free of fatty acid soap, which is a hydrophilic surfactant And a polyoxyethylene fatty acid ester having a polymerization degree of 100 to 200 and a polyoxyethylene fatty acid ester having a polymerization degree of 20 to 60.
<2> A lipophilic surfactant containing stearic acid monoglyceride and at least one of two or more sorbitan fatty acid esters which are liquid under conditions of 1 atm and 25 ° C. <1> The external skin preparation described in <1>.
<3> Furthermore, 1 type or 2 types or more selected from cetyl alcohol, stearyl alcohol, behenyl alcohol, and batyl alcohol, and a branched fatty acid, <1> or <2> Topical skin preparation.
<4> Any one of <1> to <3>, characterized in that it is a skin external preparation to which a makeup cosmetic should be applied on a film obtained by applying the skin external preparation to the skin. The skin external preparation as described.
<5> The skin external preparation according to any one of <1> to <4>, which is a cosmetic.

  ADVANTAGE OF THE INVENTION According to this invention, the skin external preparation of the oil-in-water emulsifier form with high pH tolerance and little powder agglomeration property can be provided.

(1) Fatty acid ester of polyoxyethylene having a polymerization degree of 100 to 200, which is an essential component of the external preparation for skin of the present invention, is a skin external preparation of the present invention, which may be an alkyl-modified acrylic acid and / or methacrylic acid. A polymer salt and an oil-in-water emulsifier type cosmetic substantially free of fatty acid soap, containing a fatty acid ester of polyoxyethylene having a polymerization degree of 100 to 200 as an essential component as a hydrophilic surfactant It is characterized by doing. In such surfactants, mono-fatty acid esters can be used as esters, and di-fatty acid esters can be used, but it is preferable to use mono-fatty acid esters from the viewpoint of emulsification characteristics. The fatty acid residues include lauric acid residues, myristic acid residues, palmitic acid residues, stearic acid residues, behenic acid residues, isopalmitic acid residues, isostearic acid residues, oleic acid residues, linoleic acid residues. Acid residues, linolenic acid residues and the like can be preferably exemplified, and specifically, polyethylene glycol monostearate is preferably used. The average degree of polymerization of polyethylene glycol is preferably from 100 to 200, more preferably from 140 to 160, since it forms an oil-in-water emulsion system with high stability and a firm gel structure. Such fatty acid esters of polyoxyethylene having an average degree of polymerization of 100 to 200 already exist in the market, and such commercial products can be purchased and used. Examples of such commercially available products include “AEC PEG-100 Stearate” (monostearic acid ester having an average polymerization degree of 100; manufactured by A & E Connock), “Botanimulse 100-S” (monostearic acid ester having an average polymerization degree of 100 Bodogenics), “Crodet S100” (monostearic acid ester having an average degree of polymerization of 100; Crodet Chemicals Europe), “Emarex 6300MST” (monostearic acid ester having an average degree of polymerization of 150; manufactured by Nippon Emulsion Co., Ltd.) Etc. can be preferably exemplified. Such a component can contain only one species, or can contain two or more species in combination, and works together with a polyoxyethylene fatty acid ester having a polymerization degree of 20 to 60 described later, and has high pH tolerance. Realizes oil-in-water emulsifier form with less powder cohesion. For this purpose, the component is preferably contained in a total amount of 0.1 to 2% by mass, more preferably 0.2 to 1% by mass, based on the total amount of the external preparation for skin.

(2) Fatty acid ester of polyoxyethylene having a polymerization degree of 20 to 60, which is an essential component of the external preparation for skin of the present invention, the external skin preparation of the present invention may be alkyl-modified acrylic acid and / or methacrylic acid And an oil-in-water emulsifier-type cosmetic substantially free of fatty acid soap, and an essential component comprising a fatty acid ester of polyoxyethylene having a polymerization degree of 20 to 60 as a hydrophilic surfactant It is characterized by containing as. In such surfactants, mono-fatty acid esters can be used as esters, and di-fatty acid esters can be used, but it is preferable to use mono-fatty acid esters from the viewpoint of emulsification characteristics. The fatty acid residues include lauric acid residues, myristic acid residues, palmitic acid residues, stearic acid residues, behenic acid residues, isopalmitic acid residues, isostearic acid residues, oleic acid residues, linoleic acid residues. Acid residues, linolenic acid residues and the like can be preferably exemplified, and specifically, polyethylene glycol monostearate is preferably used. In the polyethylene glycol monostearate, the preferable average polymerization degree of polyethylene glycol is 20 to 60, and more preferably 25 to 50. Such components work together with the polyoxyethylene fatty acid ester having a polymerization degree of 100 to 200 to realize an oil-in-water emulsifier form having high pH tolerance and low powder cohesion. For this purpose, such components are preferably contained in a total amount of 0.5 to 3% by mass, more preferably 1 to 2% by mass, based on the total amount of the external preparation for skin. Moreover, it is preferable that this content is 3-6 mass times with respect to the total content of the polyoxyethylene fatty acid ester of the said polymerization degree 100-200.

(3) External preparation for skin of the present invention The external preparation for skin of the present invention contains substantially the above-mentioned essential ingredients and may be alkyl-modified, a polymer salt of acrylic acid and / or methacrylic acid, and a fatty acid soap. It is characterized by being a cosmetic in the form of an oil-in-water emulsifier that is not contained. In other words, the external preparation for skin of the present invention is an oil-in-water emulsifier type in which the stability is not entrusted to fatty acid soap gels or crosslinked gel structures of water-soluble thickeners. It also has a characteristic that the body cohesiveness is low. In order to make such characteristics clearer, as a lipophilic surfactant, at least one of stearic acid monoglyceride is liquid under the condition of 1 atm. It is preferable to contain sorbitan fatty acid ester. Examples of the sorbitan fatty acid ester include sorbitan monostearate (solid), sorbitan sesquistearate (solid), sorbitan distearate (solid), sorbitan monolaurate (liquid), sorbitan sesquilaurate (liquid), sorbitan oleate ( Liquid), sorbitan sesquioleate (liquid), sorbitan monoisostearate (liquid), sorbitan sesquiisostearate (liquid) and the like can be preferably exemplified. Among such combinations, the preferred combination is particularly preferably a combination of sorbitan distearate and sorbitan sesquiisostearate. The mass ratio of such a combination is preferably 20: 1 to 10: 1. Moreover, the preferable mass ratio of stearic acid monoglyceride and sorbitan fatty acid ester is 3: 1 to 1: 1, and 2: 1 to 1: 1 is particularly preferable. Furthermore, the total content of the lipophilic nonionic surfactant is preferably 1 to 10% by mass, and more preferably 2 to 5% by mass. More specifically, a form containing 1 to 5% by mass of stearic acid monoglyceride and 0.5 to 3% by mass of sorbitan fatty acid ester can be suitably exemplified.

  The external preparation for skin of the present invention can contain, in addition to such components, optional components that are usually used in external preparations for skin. Examples of such optional ingredients include 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, and hardened coconut oil. Oil, wax, oil such as beeswax, canola wax, carnauba wax, ibotarou, lanolin, reduced lanolin, hard lanolin, jojoba wax, liquid paraffin, squalane, pristane, ozokerite, paraffin, ceresin, petrolatum , 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, di-2-ethylhexanoic acid ethylene glycol, dicaprate neopentyl glycol, di-2-heptylundecanoic acid glycerin, tri-2-ethylhexanoic acid glycerin, tri-2-ethylhexanoic acid trimethylolpropane, tri Synthetic ester oils such as trimethylolpropane isostearate and pentane erythritol tetra-2-ethylhexanoate; dimethylpolysiloxane, methylphenylpoly Linear polysiloxanes such as oxane and diphenylpolysiloxane; cyclic polysiloxanes such as octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, and dodecamethylcyclohexanesiloxane; amino-modified polysiloxane, polyether-modified polysiloxane, alkyl-modified polysiloxane, Oil agents such as silicone oils such as modified polysiloxanes such as fluorine-modified polysiloxanes; Anionic surfactants such as fatty acid soap (sodium laurate, sodium palmitate, etc.), potassium lauryl sulfate, triethanolamine ether of alkyl sulfates; Cationic surfactants such as stearyltrimethylammonium, benzalkonium chloride, laurylamine oxide; imidazoline-based amphoteric surfactants (2-cocoyl-2-imida Zolinium hydroxide-1-carboxyethyloxy disodium salt, etc.), betaine surfactants (alkyl betaine, amide betaine, sulfobetaine, etc.), amphoteric surfactants such as acylmethyl taurine; glycerin fatty acids (monostearin) Glycerin acid, propylene glycol fatty acid esters (such as propylene glycol monostearate), hardened castor oil derivatives, glycerin alkyl ethers, POE sorbitan fatty acid esters (POE sorbitan monooleate, polyoxyethylene sorbitan monostearate, etc.), POE sorbite fatty acid esters (POE-sorbite monolaurate, etc.), POE glycerin fatty acid esters (POE-glycerin monoisostearate, etc.), POE alkyl ethers (POE2) Octyldodecyl ether, etc.), POE alkylphenyl ethers (POE nonylphenyl ether, etc.), Pluronic types, POE / POP alkyl ethers (POE / POP2-decyltetradecyl ether, etc.), Tetronics, POE castor oil / cured Nonionic surfactants such as castor oil derivatives (POE castor oil, POE hydrogenated castor oil, etc.), sucrose fatty acid ester, alkyl glucoside; polyethylene glycol, glycerin, 1,3-butylene glycol, erythritol, sorbitol, xylitol, multi Thor, propylene glycol, dipropylene glycol, diglycerin, isoprene glycol, 1,2-pentanediol, 2,4-hexanediol, 1,2-hexanediol, 1,2-octanediol Polyhydric alcohols; moisturizing ingredients such as sodium pyrrolidone carboxylate, lactic acid, sodium lactate; surface-treated mica, talc, kaolin, synthetic mica, calcium carbonate, magnesium carbonate, silicic anhydride (silica) ), Powders such as aluminum oxide and barium sulfate; inorganic pigments such as bengara, yellow iron oxide, black iron oxide, cobalt oxide, ultramarine, bitumen, titanium oxide, and zinc oxide, the surface of which may be treated; Pearl agents such as mica titanium, fish phosphorus foil, bismuth oxychloride, etc. whose surface may be treated; red 202, red 228, red 226, yellow 4 and blue 404 which may be raked No. 5, 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. 2 Organic pigments such as 01, purple 201, red 204, etc .; organic powders such as polyethylene powder, polymethyl methacrylate, nylon powder, organopolysiloxane elastomer; paraaminobenzoic acid ultraviolet absorbers; anthranilic acid ultraviolet rays Absorber; salicylic acid UV absorber; cinnamic acid UV absorber; benzophenone UV absorber; sugar UV absorber; 2- (2′-hydroxy-5′-t-octylphenyl) benzotriazole, 4 UV absorbers such as methoxy-4'-t-butyldibenzoylmethane; lower alcohols such as ethanol and isopropanol; vitamin A or its derivatives, vitamin B6 hydrochloride, vitamin B6 tripalmitate, vitamin B6 dioctanoate, vitamin B2 or its derivatives, vitamin B12, vitamin B15 or so Vitamin B such as derivatives; vitamin E such as α-tocopherol, β-tocopherol, γ-tocopherol, vitamin E acetate, vitamin D, vitamin H, vitamins such as pantothenic acid, panthetin, pyrroloquinoline quinone, etc .; phenoxyethanol Preferred examples include antibacterial agents such as estradiol, estriol and hydrocortisone, antifungal agents such as butenafine, amorolfine, terbinafine, bifonazole and fluconazole, anti-inflammatory agents such as indomethacin and bufexamac, and analgesics.

  The skin external preparation of this invention can be manufactured by processing the said essential component and arbitrary component in accordance with a conventional method. Preferred examples of the external preparation for skin of the present invention include cosmetics including quasi-drugs, external preparations for skin, sundries for skin use, and the like. Particularly preferred are cosmetics, which are attributed to the comfortable feeling of use of the external preparation for skin of the present invention. In addition, since it does not substantially contain a salt of a polymer of acrylic acid and / or methacrylic acid, which may be alkyl-modified, and fatty acid soap, it is possible to suppress the ease of disintegration due to these components, It is preferable to use the makeup cosmetic in a form to be applied. By using in such a form, it is possible to remarkably improve the makeup life of the makeup cosmetic applied on the cosmetic film formed by the external preparation for skin of the present invention.

  Hereinafter, the present invention will be described in more detail with reference to examples.

  According to the following formulation, the external preparation for skin of the present invention (cosmetics; oil-in-water emulsifier form) was prepared. That is, a and b were heated to 80 ° C., and b was gradually added to a with stirring, followed by stirring and cooling to obtain the skin external preparation 1 of the present invention as an emulsion. In the same manner, Comparative Example 1 in which “Emalex 6000MST” was replaced with POE (45) stearic acid, Comparative Example 2 in which POE (45) stearic acid was replaced with “Emalex 6000MST”, POE (20) behenyl ether Comparative Example 3 in which “Emalex 6000MST” and POE (45) stearic acid were both substituted with POE (20) was also prepared.

<Test Example 1>
For skin external preparation 1, Comparative Examples 1 to 3 and Reference Example (Emulsion using carboxyvinyl polymer; Table 2) shown below, the temperature stability under the condition of 40 ° C. for 1 month when acid is added Examined. Citric acid was used as the acid. A predetermined acid was added to the sample and stored at 40 ° C. for 1 month. This was constanted at 20 ° C. over 24 hours, and the state was observed. The results are shown in Table 3. This shows that the skin external preparation of this invention is excellent in pH tolerance. This means that a large amount of an ionizable active ingredient can be retained, which proves useful as a vehicle for the active ingredient.

<Test Example 2>
A site of 2 cm × 4 cm is created on the inner side of the forearm, and 40 μl of the cosmetic preparation for external skin 1, Comparative Examples 1 to 3 and Reference Example is applied thereto, and the following foundation (Table 4) is applied with a puff. After standing still for 1 minute, warm water was allowed to flow for 1 minute, the moisture was lightly wiped with a towel, and the color difference with the background was measured with a color difference meter CR400 manufactured by Konica Minolta. The results are shown in Table 5. From this, it can be seen that when the foundation is applied after applying the skin external preparation of the present invention, the foundation remains in resistance to running water. This is considered to be because, in the case of the external preparation for skin of the present invention, the structure of the cosmetic film formed by applying the cosmetic by contact with the powder is less susceptible to change compared to other samples. This also shows that the external preparation for skin of the present invention is suitable for cosmetics used on the premise that makeup cosmetics are subsequently applied.

  The skin external preparation 2 of the present invention was prepared in the same manner as in Example 1. Even when 1% by mass of citric acid was added to this product and stored at 40 ° C. for 1 month, no separation was observed. In addition, as a result of the evaluation test of Test Example 2, ΔE was 1.7, and the effect was confirmed.

  The skin external preparation 3 of the present invention was prepared in the same manner as in Example 1. Even when 1% by mass of citric acid was added to this product and stored at 40 ° C. for 1 month, no separation was observed. Moreover, as a result of the evaluation test of Test Example 2, ΔE was 1.8, and the effect was confirmed.

  According to the prescription shown below, the skin external preparation 4 (whitening milk cosmetic) of the present invention was prepared. Although it contained as much as 5% by mass of arbutin, which is an ionizable active ingredient, it did not change under visual observation under storage conditions at 40 ° C. for one month.

  According to the formulation shown below, the skin external preparation 5 of the present invention (antifungal milk external skin medicine) was prepared. Although it contained as much as 5% by mass of terbinafine hydrochloride, which is an ionizable active ingredient, it did not change under visual observation under storage conditions at 40 ° C. for one month.

  The present invention can be applied to skin external preparations such as cosmetics and skin external medicines.

Claims (5)

A polymer salt of acrylic acid and / or methacrylic acid, which may be alkyl-modified, and an oil-in-water emulsifier type cosmetic substantially free of fatty acid soap, and polymerized as a hydrophilic surfactant A skin external preparation comprising a polyoxyethylene fatty acid ester having a degree of 100 to 200 and a polyoxyethylene fatty acid ester having a degree of polymerization of 20 to 60. The lipophilic surfactant contains stearic acid monoglyceride and at least one of two or more sorbitan fatty acid esters which are liquid under conditions of 1 atm and 25 ° C. The external preparation for skin according to 1. The skin external preparation according to claim 1 or 2, further comprising one or more selected from cetyl alcohol, stearyl alcohol, behenyl alcohol, and batyl alcohol, and a branched fatty acid. The skin external preparation according to any one of claims 1 to 3, which is a skin external preparation to which a makeup cosmetic is to be applied on a film obtained by applying the skin external preparation to the skin. . It is cosmetics, The skin external preparation in any one of Claims 1-4 characterized by the above-mentioned.