JP5695289B2 - Emulsifier type skin external preparation - Google Patents

Description

  The present invention relates to an external preparation for skin, and more particularly to an external preparation for skin suitable for a cosmetic in the form of a water-in-oil emulsifier.

Triterpenes or related substances such as triterpenic acid such as oleanolic acid and ursolic acid, esters of triterpenic acid, or salts thereof have various favorable effects such as photoaging inhibition action and lipase inhibition action on the skin. (See, for example, Patent Document 1 and Patent Document 2), however, there are cases where there is a problem in compatibility with other formulation components. There was a case to reduce. There are cases where the stability of the emulsification system is impaired by such a reduction in surface activity. The background to this phenomenon is that the triterpenes have a bulky hydrocarbon structure and have appropriate hydrophilic groups such as hydroxyl groups and carboxyl groups. This is thought to be partly due to the effect of reducing Furthermore, since the triterpenes themselves have high crystallinity and easily precipitate as solids, it is considered that the fact that the interface formed by the surfactant is easily broken physically is also a factor that promotes the tendency. From such a situation, it can be said that in the field of external preparation for skin, development of a dosage form that can stably contain triterpenes, particularly an emulsifier form, has been desired. As part of this approach, there has been an attempt to modify triterpenes into derivatives having physical properties suitable for topical skin preparations, and esterification of triterpenic acid has been carried out. Although such derivatization significantly improved the formulation compatibility of triterpenes, there are some parts that cannot be said to be sufficient when stored at high or very low temperatures. For this reason, the emulsification method has been devised (see, for example, Patent Document 3), but it seems that the basic character of triterpenes is that it is oriented at the interface, which also has a sufficient effect. It is the current situation that cannot be said to be playing.

  On the other hand, organically modified clay minerals such as dimethyldistearylammonium modified hectorite form a gel with an oily component and have the property of incorporating water into the gel. It is used as an emulsifying component. (For example, see Patent Document 4 and Patent Document 5) In such an emulsification system, the stability of the system depends on the solid fat because the system stability is maintained by the gel structure made by the clay mineral. There are features that do not.

  On the other hand, there is no known skin external preparation in the form of a water-in-oil emulsifier containing a triterpene or its related substance, nor is any known emulsifier using an organically modified clay mineral as an emulsifier. It is not known at all that the effect of emulsification of triterpenes can be suppressed by adopting such an emulsifier form.

JP-A-9-143050 Japanese Patent Laid-Open No. 9-118611 JP-T-2004-519411 JP-A-11-76799 JP-A-10-194924

  The present invention has been made under such circumstances, and an object of the present invention is to provide an emulsifier-type skin external preparation that stably contains triterpenes even under extreme temperature conditions.

In view of such a situation, the present inventors have sought to obtain an emulsifier-type skin external preparation that stably contains triterpenes even under extreme temperature conditions. It has been found that such an external preparation for skin can be obtained by containing in a water-in-water emulsifier form, and the present invention has been completed. That is, the present invention is as follows.
<1> betulin, wherein betulinic acid, oleanolic acid, ursolic acid, and one or more phosphoric acid esters and / or salts thereof of triterpenes selected or ursolic acid et al, in that it contains an organic modified clay mineral A skin external preparation in the form of a water-in-oil emulsifier.
<2> The external preparation for skin according to <1>, wherein the triterpene is ursolic acid .
<3> The skin external preparation according to <1> or <2>, further comprising a diester of an acylated acidic amino acid.

  ADVANTAGE OF THE INVENTION According to this invention, the emulsifier type skin external preparation which contains a triterpene stably even under extreme temperature conditions can be provided.

<1> Triterpenes as essential components of the external preparation for skin of the present invention The external preparation for skin of the present invention is characterized by containing a triterpene or a related substance. The triterpene-related substance has a triterpene skeleton, which may be appropriately acylated or alkylated hydroxyl group, esterified or amidated carboxyl group, acyl A compound having a substituent such as an amino group which may be converted to a specific group. Specifically, triterpenes or related substances include betulin, betulinic acid, oleanolic acid, ursolic acid, esters thereof, and the like. Preferred examples include salts. In particular, esters of ursolic acid are particularly preferred. Particularly preferred examples of the ester include an ester with a hydrocarbon group and an ester with a mineral acid such as phosphoric acid and sulfuric acid. Particularly preferable examples include, for example, ursolic acid hydrocarbon group ester having 1 to 20 carbon atoms or ursolic acid phosphate ester. Examples of the hydrocarbon group ester having 1 to 20 carbon atoms include methyl ester, ethyl ester, hexyl ester, cyclohexyl ester, octyl ester, isooctyl ester, lauryl ester, cetyl ester, stearyl ester, isostearyl ester, and oleyl ester. Preferred examples include hydrocarbon group esters having aromatic rings such as aliphatic esters, benzyl esters, and phenethyl esters. Such components can be derived from ursolic acid according to conventional methods. In the case of a hydrocarbon group ester, ursolic acid may be converted to a sodium salt with sodium hydride or the like, and a halogenated hydrocarbon obtained by reacting alcohol with thionyl chloride or the like may be added thereto for reaction. The reaction may be performed at room temperature or under reflux conditions for 1 to 12 hours. The phosphate ester can be obtained by reacting dimethyl-N, N-diethyl phosphoramidate with ursolic acid to form ursolic acid methyl phosphate, which is demethylated with bromotrimethylsilane or the like. Various esters can be produced by treating oleanolic acid, betulin, and betulinic acid according to this treatment. Such components can be contained in the form of a salt by reacting with an alkali to form a salt. 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. Such a component can express an action known so far, and a content that can express these actions can also be adopted. Specifically, it is preferable to contain 0.01-5 mass%, respectively, More preferably, it is 0.05-1 mass%.

<2> Organically modified clay mineral which is an essential component of the external preparation for skin of the present invention The external preparation for skin of the present invention is characterized by containing an organically modified clay mineral as an essential component. Here, organic modification means that a part or all of the properties of an organic compound is made into a clay mineral by causing a part of the organic compound to form a strong or loose bond via a covalent bond or an ionic bond. This means that it is imparted to minerals. Examples of such modifications include a method of binding a quaternary amine group and an anion portion of a clay mineral, and a method of binding a carboxyl group and a cation portion of a clay mineral. A method of combining the group and the anion portion of the clay mineral is particularly preferable.

Although it does not necessarily limit as a compound which has a quaternary amino group which modifies a clay mineral, The compound called quaternium is illustrated. Quotanium is a low molecular weight substituted quaternary ammonium salt, and is preferably a cosmetic raw material registered in International Standard Cosmetic Ingredients (INCI). Furthermore, the compound having a quaternary amino group that modifies the clay mineral is preferably a quaternium compound contained in a conventional external skin preparation among quaternium compounds. Preferred examples of the quaternium compound used in conventional external preparations for skin include stearyl trimethyl ammonium chloride and dimethyl distearyl ammonium chloride. Stearyl trimethyl ammonium chloride, dimethyl distearyl ammonium chloride, and the like are preferable because they can form a stable aqueous oil-in-water component emulsion structure together with clay minerals. In particular, when the aqueous component is an oil-in-water emulsion, an emulsion having a continuous phase as an oil phase can be formed without significantly affecting the oil-in-water emulsion. preferable.

  On the other hand, as a clay mineral (unmodified clay mineral) modified with a compound having a quaternary amino group, any clay mineral contained in a conventional external preparation for skin can be used without particular limitation. Preferred clay minerals contained in conventional skin external preparations include smectite-type hectorite, bentonite and montmorillonite; kaolinite; illite; marine clay mineral (sea mud); desert rose clay mineral; Among these, bentonite, hectorite, montmorillonite or kaolinite which can stabilize the water-in-oil emulsion structure is preferably exemplified.

An example of a method for producing a clay mineral modified with a compound having a quaternary amino group contained in the external preparation for skin of the present invention will be described below.
The unmodified clay mineral is dispersed in a dispersion medium. The dispersant is preferably an aqueous solvent, and may be water. A compound having a quaternary amino group is further added to the dispersion containing the dispersed unmodified clay mineral and stirred well. The compound having a quaternary amino group may be added after being dissolved in water. The amount of the compound having a quaternary amino group to be added is preferably 0.1 to 20% by mass, and more preferably 0.5 to 15% by mass with respect to the amount of the dispersed unmodified clay mineral. This is because by taking such a configuration, a preferable feeling of use is exhibited in the emulsification system. After stirring, the dispersoid is filtered, dehydrated and dried to obtain the modified clay mineral in the present invention. Or the modified clay mineral in this invention can also be obtained by removing a dispersing agent by concentrating under reduced pressure without filtering a dispersoid, and making it dry. The obtained modified clay mineral is preferably pulverized to a desired size (preferably having a particle size of 1 to 1000 μm) and contained in the skin external preparation of the present invention.

  The modified clay mineral in the present invention can be prepared and used as described above, but commercially available ones can also be used. Preferable examples of commercially available modified clay minerals include dimethyl distearyl ammonium modified hectorite sold under the name “Benton 38V” by Elementis.

  In the skin external preparation of the present invention, such components are preferably contained in an amount of 0.5 to 10% by mass, more preferably 1 to 5% by mass. In such a range, the triterpene solution can be stabilized and formulated into a water-in-oil emulsifier form. Here, the water-in-oil emulsifier form referred to in the present invention is a general term for an emulsifier form in which an oil phase is present in the outermost phase, a form in which water phase drops are dispersed in the oil phase, and an oil-in-water emulsion drop in the oil phase. Any form in which the is dispersed can be employed.

<3> External preparation for skin of the present invention The external preparation for skin of the present invention contains the above-mentioned essential components and is in the form of a water-in-oil emulsifier. In such an emulsifier form, the triterpenes are considered to exist at the interface between the oil phase and the emulsified droplets, which are continuous phases. However, the presence of such triterpenes may cause crystallization even at extremely low temperatures. It is suppressed. This is presumably because crystal growth is suppressed by interfacial coordination. Such interfacial coordination action is particularly remarkable in phosphoric esters of triterpenic acid. In this sense, triterpenic acids are preferably phosphoric esters of triterpenic acid, and more preferably phosphoric esters of ursolic acid.

In the external preparation for skin of the present invention, as long as it takes a dosage form of a water-in-oil emulsifier form, it can contain optional components usually contained for external use on the skin. Examples of such optional components 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, hydrogenated coconut oil, hydrogenated oil, molasses, hydrogenated castor oil, Oils and waxes such as beeswax, candelilla wax, carnauba wax, ibotarou, lanolin, reduced lanolin, hard lanolin, jojoba wax; hydrocarbons such as liquid paraffin, squalane, pristane, ozokerite, paraffin, ceresin, petrolatum, 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 alcohol, behenyl alcohol, Higher alcohols such as cutyl decanol, myristyl alcohol, cetostearyl alcohol; cetyl isooctanoate, isopropyl myristate, hexyldecyl isostearate, diisopropyl adipate, di-2-ethylhexyl sebacate, cetyl lactate, diisostearyl malate, Di-2-ethylhexanoic acid ethylene glycol, dicaprate neopentyl glycol, di-2-heptylundecanoic acid glycerin, tri-2-ethylhexanoic acid glycerin, tri-2-ethylhexanoic acid trimethylolpropane, triisostearic acid trimethylol Synthetic ester oils such as propane and tetra-2-ethylhexanoic acid pentane erythritol; dimethylpolysiloxane, methylphenylpolysiloxane, diphenylpolysiloxa Chain polysiloxanes such as octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexanesiloxane, and the like; amino-modified polysiloxane, polyether-modified polysiloxane, alkyl-modified polysiloxane, fluorine-modified polysiloxane, etc. Oils such as silicone oils such as modified polysiloxanes; Anionic surfactants such as diesters of acylated acidic amino acids, fatty acid soaps (sodium laurate, sodium palmitate, etc.), potassium lauryl sulfate, alkylethanol triethanolamine ether, etc. ; Cationic surfactants such as stearyltrimethylammonium chloride, 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.), and amphoteric surfactants such as acylmethyltaurine; sorbitan fatty acid esters (sorbitan) Monostearate, sorbitan sesquioleate, etc.), glycerin fatty acids (eg, glyceryl monostearate), propylene glycol fatty acid esters (eg, 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-sorbitol monolaurate, etc.), POE glycerin fatty acid ester Tells (POE-glycerol monoisostearate, etc.), POE fatty acid esters (polyethylene glycol monooleate, POE distearate, etc.), POE alkyl ethers (POE2-octyldodecyl ether, etc.), POE alkylphenyl ethers (POE nonylphenyl) Ethers, 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.), Nonionic surfactants such as sucrose fatty acid ester and alkyl glucoside; polyethylene glycol, glycerin, 1,3-butylene glycol, erythritol, sorbitol, xylitol, maltitol, propylene Polyhydric alcohols such as recall, dipropylene glycol, diglycerin, isoprene glycol, 1,2-pentanediol, 2,4-hexanediol, 1,2-hexanediol, 1,2-octanediol; sodium pyrrolidonecarboxylate Moisturizing ingredients such as lactic acid and sodium lactate; 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 Body; surface treated, bengara, yellow iron oxide, black iron oxide, cobalt oxide, ultramarine, bitumen, titanium oxide, zinc oxide inorganic pigments; surface treated, mica titanium Pearl agents such as fish phosphorus foil, bismuth oxychloride; red 202 which may be raked, red 228, Red 226, Yellow 4, Blue 404, Yellow 5, Red 505, Red 230, Red 223, Orange 201, Red 213, Yellow 204, Yellow 203, Blue 1 Organic dyes such as green 201, purple 201, red 204, etc .; organic powders such as polyethylene powder, polymethyl methacrylate, nylon powder, organopolysiloxane elastomer; paraaminobenzoic acid UV absorber, 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 −
UV absorbers such as methoxy-4′-t-butyldibenzoylmethane; lower alcohols such as ethanol and isopropanol; vitamin A or a derivative thereof, vitamin B ₆ hydrochloride,
Vitamin B ₆ tripalmitate, vitamin B ₆ dioctanoate, vitamin B ₂ or derivatives thereof, vitamin B ₁₂ such as vitamin B ₁₂ , vitamin B ₁₅ 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. Of these, particularly preferred are diesters of acylated acidic amino acids. Particularly preferred examples of such diesters of acylated acidic amino acids include dialkyl (C1-30) esters of N-acyl (C10-30) glutamic acid. The acyl group constituting the component may be saturated or unsaturated, for example, 2-ethylhexanoyl group, lauroyl group, myristoyl group, palmitoyl group, stearoyl group, behenoyl group, oleoyl group, isostearoyl group, A linolenoyl group etc. can be illustrated suitably, A lauroyl group is especially preferable. In addition, the alkyl group constituting the dialkyl ester may be branched, straight chain, or cyclic, for example, octyl group, lauryl group, cetyl group, stearyl group, isostearyl group, behenyl group, octyldodecyl. Preferred examples include phytosteryl groups such as campesteryl group and sitosteryl group, and cholesteryl group. Specific examples of the compound include N-lauroyl-L-glutamate di (cholesteryl / behenyl / octyldodecyl), N-lauroyl-L-glutamate di (cholesteryl / octyldodecyl), N-lauroyl-L-glutamate di (phytosteryl). / Behenyl / octyldodecyl), N-lauroyl-L-glutamate di (phytosteryl / octyldodecyl) and the like can be preferably exemplified, and N-lauroyl-L-glutamate di (cholesteryl / octyldodecyl) can be particularly suitably exemplified. Such an N-acylated glutamic acid diester is obtained by condensing glutamic acid and acyl chloride in the presence of an alkali to form N-acyl glutamic acid, and then in the presence of a base or acid, optionally in the presence of a solvent, and dehydrating with the corresponding alcohol. It can be produced by condensation. N-acylated glutamic acid diesters can be synthesized in this way, but some are already commercially available as cosmetic raw materials, and such commercial products can be purchased and used. . Particularly preferred commercially available products are “El Deu PS203” (N-lauroyl-L-glutamate di (phytosteryl / octyldecyl)) and “El Deu CL-301” (N-lauroyl glutamate di (cholesteryl / Behenyl / octyldodecyl)), “Elduu Cl-202” (N-lauroylglutamate di (cholesteryl / octyldodecyl)), “Elduu PS-304” (N-lauroylglutamate di (phytosteryl / behenyl / octyldodecyl)), etc. Among them, “El Dew PS203” is particularly preferable. These components can be contained alone or in combination of two or more. The preferred content is 0.005 to 5% by mass, more preferably 0.01 to 1% by mass, based on the total amount of the external preparation for skin.

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

<Example 1>
According to the formulation shown below, a cosmetic preparation in the form of a water-in-oil emulsifier, which is an external preparation for skin of the present invention, was produced. That is, the ingredients of (a), (b), and (c) are heated to 80 ° C., and (d) is added and dissolved in (a), kneaded to form a gel, and added to (b), diluted, and gradually stirred with stirring. The mixture was emulsified with emulsified and cooled with stirring to obtain a water-in-oil emulsifier type cosmetic 1 as an external preparation for skin of the present invention.

<Comparative Example 1>
As Comparative Example 1, a water-in-oil emulsifier type cosmetic with diglycerin fatty acid ester and maltitol, which is a water-in-oil emulsifier type not based on organically modified clay mineral, was prepared. That is, weigh the ingredients a, b, c and d, heat i to 80 ° C., add d to solubilize, knead well, and then add the b ingredient to dilute, After the temperature was adjusted to 80 ° C., the component C which had been temperature adjusted in advance to 80 ° C. was gradually added with stirring, and the mixture was stirred and cooled to obtain Comparative Example 1.

<Comparative example 2 >
In the same manner as in Example 1 and Comparative Example 1, an oil-in-water emulsifier type Comparative Example 2 was prepared according to the formulation shown below. That is, the ingredients (a) and (b) were heated to 80 ° C., and (b) was gradually added to a under stirring, followed by cooling with stirring to obtain an oil-in-water emulsifier type comparative example 2.

<Test Example 1>
For cosmetic 1, Comparative Example 1 and Comparative Example 2, changes with time were observed. That is, these specimens are stored for 3 months in a temperature cycle fluctuation storage (low temperature aging with a holding time of 24 hours, a heating time of 24 hours, and a cooling time of 24 hours) of −15 ° C. → 5 ° C.−15 ° C. After returning to 20 ° C., 20 mg is taken on a slide glass (2 × 5 cm), covered with a slide glass from above, and a gel-like lump (portion translucent), solid precipitate ( The white part) was counted. Counting averaged 5 fields. The results are shown in Table 4. From this, it can be seen that in the external preparation for skin of the present invention, triterpenes are specifically coordinated to the interface, and solid matter precipitation is suppressed.

<Comparative Example 3>
The cosmetics 2-5 of the comparative example of the prescription shown in Table 5 were created by replacing the ursolic acid phosphate of the cosmetic 1 with other triterpenes, and the same examination was performed. Table 6 shows the evaluation results of Test Example 1. Each shows the same effect as the cosmetic 1, but it can be seen that ursolic acid phosphate is particularly preferable in terms of stability.

<Example 2>
A cosmetic 6 in the form of a water-in-oil emulsifier was prepared in the same manner as the cosmetic 1 according to the following formulation. In the evaluation of Test Example 1, the appearance of a gel-like lump was 2.5 and the solid precipitate was 0. It can be seen that it preferably contains a diester of acylated glutamic acid.

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

Claims (2)

Baie Tsurin acid, oleanolic acid, and the one or more phosphoric acid esters of triterpene acids and / or salts thereof selected from ursolic acid, and 0.5 to 10 wt% organic modified clay mineral, acylated acidic amino acid A skin external preparation in the form of a water-in-oil emulsifier. The external preparation for skin according to claim 1, wherein the triterpenic acid is ursolic acid.