JP5653401B2 - Method for producing powder-containing external preparation for skin containing emulsifier - Google Patents

Description

  The present invention relates to an external preparation for skin, and more particularly to an emulsifier-type powder-containing external preparation for skin useful for cosmetics.

  Powders such as zinc oxide and titanium dioxide are widely used in makeup cosmetics and ultraviolet protective cosmetics because they have a concealing property and an ultraviolet protective effect. In UV protection cosmetics, since it is highly likely to be applied to damaged skin, it is desired to reduce irritation at the time of application, and an emulsifier form in which the powder does not easily scratch the skin is adopted. There are many cases.

  On the other hand, in an emulsifying system, it is necessary to disperse a powder such as zinc oxide or titanium dioxide having a specific gravity of 3 or more with a viscous fluid composition having a specific gravity of about 1, and to maintain the dispersion so that it does not settle in the moment. For this purpose, the viscous structure in the emulsification system is used. As such an emulsifying system, an oil-in-water emulsifying system using a fatty acid soap (see, for example, Patent Document 1), a cation-modified clay mineral, a polyalkylene oxide-modified silicone, or a low-order ester of polyglycerin having a low polymerization degree is used. A known water-in-oil emulsification system (see, for example, Patent Document 2 and Patent Document 3) is known. Therefore, in such a system, it was considered almost impossible to add a lower alcohol such as ethanol, which easily destroys the viscous structure. As a report, there is a report that the use of a branched silicone surfactant improves the emulsion stability even when ethanol is added (for example, see Patent Document 4). The stability is the stability with respect to the shaking test, and even if it is determined to be stable in such a test, it is deviated from the stability in actual use and it cannot be said that it can withstand practical use. It was.

  In skin external preparations containing powder, a method is known in which powder is preliminarily processed into a slurry together with liquid components and then formulated into an emulsified preparation (for example, Patent Document 5, However, no attempt has been made to contain such a lower alcohol such as ethanol in such a system, and in such a production method, it is possible to add a lower alcohol without impairing stability. It was impossible to expect.

  Addition of lower alcohol to the powder-containing emulsification system, because lower alcohol is a volatilizing component, it has no effect on cosmetics, improves spreading and improves usability, and from the standpoint of preserving However, since it increases the antiseptic power, it has been desired, but it has not been achieved due to the above circumstances.

JP 2006-83169 A JP 2007-145722 A JP 2007-217380 A JP-A-2005-232068 JP 2007-39363 A JP 2007-39362 A

The present invention has been made under such circumstances, and in a skin emulsifier type external preparation containing powder, developed a technique for containing a lower alcohol such as ethanol without impairing stability. Therefore, it is an object to improve the usability of the powder-containing emulsifier type skin external preparation.

In view of such a situation, the present inventors have sought for a technique for containing a lower alcohol such as ethanol without impairing stability in an emulsifier-type skin external preparation containing powder. As a result of intensive research efforts, it has been found that such a blending can be achieved by using glycerin-modified methylpolysiloxane (polyglyceryl-3-polydimethylsiloxyethyl dimethicone) as a surfactant, thereby completing the invention. It came. That is, the present invention is as follows.
<1> A method for producing an emulsifier-type skin external preparation containing 1) powder, 2) lower alcohol, and 3) glycerin-modified methylpolysiloxane,
A step of dispersing the 1) powder and 3) glycerin-modified methylpolysiloxane in an oily carrier to form a slurry ;
Step of the previous SL slurry and a mixture of other oil phase components an oil phase and,
A method for producing an external preparation for skin, comprising the step of mixing and emulsifying the oil phase and 2) an aqueous phase containing 3 to 20% by mass of a lower alcohol.

  According to the present invention, there is provided a technique for containing a lower alcohol such as ethanol without impairing stability in an emulsifier-type skin external preparation containing powder, and thus a powder-containing emulsifier form. Usability of the external preparation for skin can be improved.

<1> Powder 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 in an emulsifier form and contains powder. Examples of the powder include, for example, other metals such as iron oxide, silica, alumina, and zirconia, and titanium dioxide, zinc oxide, or iron oxide, talc, which may be combined by sintering, surface coating, etc. Preferred examples include body powders such as mica, sericite, kaolin, mica titania, and sericite titania. Among these, zinc oxide or titanium dioxide having a remarkable ultraviolet protection effect is particularly preferable. The powder is preferably contained in a surface-treated form, and if the emulsifier form is a water-in-oil emulsifier form, the surface treatment is preferably a hydrophobic treatment. Examples of the hydrophobizing treatment include coating treatment with a metal soap such as aluminum stearate and zinc stearate, coating treatment with an N-acylamino acid metal salt such as aluminum N-stearoyl glutamate and aluminum N-lauroyl glutamate, and lecithin. There are coating treatment with phospholipid, silicone baking treatment such as hydrogenmethylpolysiloxane and dimethylpolysiloxane, and silylation treatment by silane coupling agent treatment such as dimethoxydimethylsilane and methoxytrimethylsilane. Such treatment is preferably performed using 1 to 30 parts by mass, more preferably 10 to 25 parts by mass of the treatment agent with respect to 100 parts by mass of the powder. When the emulsifier form is a water-in-oil emulsifier form, in the present invention, it is preferable that the powder surface is subjected to a hydrophobic treatment in advance.

  In the case of a metal salt coating treatment, in the presence of powder, water or the like is used as a carrier, and the water-soluble salt of the metal and the soluble salt corresponding to the hydrophobic group are mixed in an aqueous solution state to form a base. An exchange reaction may be performed to precipitate the hydrophobic salt on the powder surface, which may be taken out and dried to form a hydrophobic coating film.

In the treatment method, in the baking treatment and silylation treatment of silicones, the treatment agent is dissolved in, for example, a non-reactive volatile solvent such as methylene chloride and uniformly coated on the surface of the powder. A hydrophobic coating film may be formed by volatilizing to form a thin film of the treating agent and performing a heat treatment at 200 to 400 ° C. for several hours to one day.

<Production Example 1>
32 parts by mass of fine particle titanium dioxide was charged into a flow coater, and coating was performed by blowing air while spraying a solution obtained by dissolving 6 parts by mass of hydrogenmethylpolysiloxane and 2 parts by mass of dimethicone in 100 parts by mass of methylene chloride. After the coating was completed, hot air at 40 ° C. was further blown for 4 hours to volatilize the solvent. This powder was charged into an electric furnace and baked by heating at 210 ° C. for a whole day and night to obtain a hydrophobized powder. This hydrophobized powder was pulverized with a pulverizer equipped with a 0.9 mm round hole screen to obtain treated powder 1.

<Production Example 2>
In the same manner as in Production Example 1, 87 parts by mass of zinc oxide was treated with a solution of 10 parts by mass of dimethicone and 3 parts by mass of hydrogenmethylpolysiloxane in 100 parts by mass of methylene chloride. 2 was obtained.

<2> Lower alcohol 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 a lower alcohol as an essential component. Suitable examples of the lower alcohol include ethanol and isopropanol. It is particularly preferable to employ ethanol. The content of the lower alcohol is preferably 3 to 20% by mass, more preferably 5 to 15% by mass, and still more preferably 6 to 10% by mass. The effect of the lower alcohol in the external preparation for skin of the present invention is to improve the feeling of use, for example, by reducing the friction coefficient with the skin at the time of application, volatilizes from the cosmetic film after application, and contains the hydrophilic component of the cosmetic film It is to reduce the amount, thereby improving the strength of the decorative film formed after application, and improving the antiseptic power in the product. When the amount is less than the above-mentioned blending amount, any or all of the above effects may not be exhibited, and when too large, the stability of emulsification or powder dispersion may be impaired.

<3> Glycerin-modified methylpolysiloxane (polyglyceryl-3-polydimethylsiloxyethyl dimethicone) 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 in an emulsifier form and contains glycerin-modified methylpolysiloxane (polyglyceryl-3-polydimethylsiloxyethyl dimethicone) as an essential component. As described above, the external preparation for skin of the present invention contains, as an essential component, ethanol that easily destroys the structure formed by emulsification. By adopting glycerin-modified methylpolysiloxane as a surfactant, such an external preparation is used. It is characterized by reducing the influence of alcohol. As such a glycerin-modified silicone, those commercially available as cosmetic raw materials can be used, and examples of such commercially available products include “silicone KF6104” manufactured by Shin-Etsu Chemical Co., Ltd., and the like. Such glycerin-modified methylpolysiloxane may contain only one species or may contain two or more species in combination. The preferable content of such components is 0.5 to 4% by mass, more preferably 0.8 to 1.5% by mass, based on the total amount of the external preparation for skin, as a total amount. Since this component has an excellent action for improving the dispersibility of the hydrophobized powder, the hydrophobized powder is previously dispersed in an oily carrier such as dimethicone or cyclomethicone together with the component and processed into a slurry form. Therefore, it is preferably used for the manufacture of a skin external preparation. In preparing the slurry, 10 to 20 parts by weight of powder and 10 to 20 parts by weight of an oily carrier are added to 1 part by weight of glycerin-modified methylpolysiloxane, and processed into a slurry using a media mill such as a ball mill, a covol mill, or a dyno mill. It can be preferably exemplified. Such glycerin-modified methylpolysiloxane can be added as an emulsifying surfactant to the oil phase separately from the slurry.

<4> External preparation for skin of the present invention The external preparation for skin of the present invention contains the essential components and is in the form of an emulsifier. As the emulsifier form, an oil-in-water emulsifier form utilizing a surfactant emulsified structure of fatty acid soap, or a water-in-oil emulsifier form utilizing an organically modified clay mineral, polyglycerin fatty acid ester, or silicone surfactant is suitable. It can be illustrated. In particular, the water-in-oil emulsifier form is preferred because it hardly affects the dispersibility of ethanol. In the case of the water-in-oil emulsifier type, it is preferable to contain polyoxyethylene / polyoxypropylene-modified methylpolysiloxane in addition to the glycerin-modified methylpolysiloxane. Improve sex. In order to exert such effects, the component is preferably contained in an amount of 0.1 to 4% by mass, particularly preferably 0.2 to 1% by mass, based on the total amount of the external preparation for skin. Here, the water-in-oil emulsifier form is a general term for the emulsifier form in which the oil phase is arranged in the outermost phase, and is a concept including a composite dosage form such as an oil-in-water oil form.

  The external preparation for skin of the present invention is in the form of an emulsifier, contains a lower alcohol such as ethanol, and has characteristics such as good stretchability and good longevity. For this reason, even when applied to damaged skin, the physical irritation caused by the powder directly rubbing the skin is low. In addition, when zinc oxide or titanium dioxide is used as a powder, the ultraviolet ray shielding effect is remarkable, and it has an excellent function as a cosmetic for UV protection. For this reason, it is preferable to apply to UV protection cosmetics.

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, oils such as beeswax, owl, hydrogenated castor oil, beeswax, candelilla 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 Chain polysiloxanes such as Loxane and diphenylpolysiloxane; Cyclic polysiloxanes such as octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, and dodecamethylcyclohexanesiloxane; amino-modified polysiloxanes, alkyl-modified polysiloxanes, fluorine-modified polysiloxanes, etc. Oils such as silicone oils such as modified polysiloxanes; Anionic surfactants such as fatty acid soap (sodium laurate, sodium palmitate, etc.), potassium lauryl sulfate, trisulfamine amine alkyl sulfate; stearyltrimethylammonium chloride, benzaza chloride Cationic surfactants such as luconium and laurylamine oxide; imidazoline-based amphoteric surfactants (2-cocoyl-2-imidazolinium hydroxide-1-carb Ruboxyethyloxy disodium salt), betaine surfactants (alkyl betaine, amide betaine, sulfobetaine, etc.), amphoteric surfactants such as acylmethyl taurine; sorbitan fatty acid esters (sorbitan monostearate, sesquiolein) Sorbitan acid, etc.), glycerin fatty acids (glyceryl monostearate, etc.), propylene glycol fatty acid esters (propylene glycol monostearate, etc.), hardened castor oil derivatives, glycerin alkyl ethers, POE sorbitan fatty acid esters (POE sorbitan monooleate) , Monostearic acid polyoxyethylene sorbitan, etc.), POE sorbite fatty acid esters (POE-sorbite monolaurate, etc.), POE glycerin fatty acid esters (POE-glycerin mono) Sotearate, etc.), POE fatty acid esters (polyethylene glycol monooleate, POE distearate, etc.), POE alkyl ethers (POE2-octyldodecyl ether, etc.), POE alkyl phenyl ethers (POE nonyl phenyl 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 , Diglycerin, isoprene glycol, 1,2-pentanediol, 2,4-hexanediol, 1,2-hexanediol, 1,2-octanediol and other polyhydric alcohols; sodium pyrrolidonecarboxylate, lactic acid, sodium lactate Moisturizing ingredients such as paraaminobenzoic acid UV absorbers; anthranilic acid UV absorbers; salicylic acid UV absorbers; cinnamic acid UV absorbers; benzophenone UV absorbers; sugar UV absorbers; UV absorbers such as'-hydroxy-5'-t-octylphenyl) benzotriazole and 4-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} Octanoate, vitamin _{B 2} or derivatives thereof, vitamin _{B 12,} vitamin B such as vitamin _{B 15} or a derivative thereof; alpha-tocopherol, beta-tocopherol, .gamma.-tocopherol, vitamin E such as vitamin E acetate, vitamin D, Preferable examples include vitamins such as vitamin H, pantothenic acid, pantethine and pyrroloquinoline quinone; and antibacterial agents such as phenoxyethanol.

The skin external preparation of this invention can be manufactured by processing the said essential component, a preferable component, and an arbitrary component in accordance with a conventional method.
Hereinafter, the present invention will be described in more detail with reference to examples.

<Example 1>
<Manufacture of slurry 1>
Slurry 1 was produced according to the formulation shown below. That is, the prescription ingredients were charged into a Covol mill, 0.1 mass times zirconia balls were added and dispersed at high speed for 1 hour, and the dispersion medium zirconia balls were removed by filtration to obtain slurry 1. In the same manner, Comparative Slurry 1 in which “silicone KF6104” was replaced with “silicone KF6017” (POE-modified methylpolysiloxane; manufactured by Shin-Etsu Chemical Co., Ltd.) was also prepared.

Slurry 1 and comparative slurry 1 were compared. The comparison was made by adjusting the whiteness at the time of spreading on the skin and the viscosity when reaching an equilibrium state at 20 ° C. To adjust the whiteness, take 20 μl of slurry,
This is extended to the 2 cm x 4 cm part of the inner forearm with fingers, and the whiteness of the appearance when spread is score 0: white is not felt, score 1: white is natural white, score 2: somewhat unnatural The score was assigned on the basis of whiteness, score 3: slightly unnatural whiteness, and score 4: unnatural whiteness. The results are shown in Table 2. It turns out that the slurry suitable for the skin external preparation of this invention has a low viscosity, and white does not protrude.

<Manufacture of slurry 2>
In the same manner as in the production of slurry 1, according to the following formulation, slurry 2 and comparative slurry 2 in which “silicone KF6104” was replaced with “silicone KF6017” (POE-modified methylpolysiloxane; manufactured by Shin-Etsu Chemical Co., Ltd.) were prepared. Evaluation was also performed according to the procedure described above. The results are shown in Table 4 and were similar results.

  The skin external preparation of this invention was created using the said slurry. That is, components (a) and (b) were each heated to 80 ° C., and gradually added to emulsify with stirring, followed by stirring and cooling to obtain a skin external preparation 1 (ultraviolet protective cosmetic) of the present invention. Similarly, Comparative Example 1 in which slurry 1 was replaced with comparative slurry 1 and slurry 2 was replaced with comparative slurry 2 was also prepared.

<Example 2>
In the same manner, skin external preparation 2 (ultraviolet protective cosmetic), which is the skin external preparation of the present invention, was prepared.

<Example 3>
In the same manner, skin external preparation 3 (ultraviolet protective cosmetic), which is the skin external preparation of the present invention, was prepared.

<Reference Example 4>
In the same manner, a skin external preparation 4 (ultraviolet protective cosmetic) was prepared.

<Evaluation Example 1>
About the skin external preparations 1-4 and the comparative example 1, the property was evaluated. Evaluation evaluated the viscosity and whiteness like the slurry. In addition, changes in properties when stored at 40 ° C. for 1 month or 3 months were also observed. Storage stability was determined by observing the appearance of separation and powder settling. The results are shown in Table 9. It turned out that the skin external preparation of this invention is excellent in use feeling, and its stability is also high. It has also been found that it is preferable to include glycerin-modified methylpolysiloxane in the slurry.

<Evaluation Example 2>
Five people a day after sunburn applied the topical skin preparation 1 on the right arm and Comparative Example 1 on the left arm, and answered the feeling of irritation during and after application. As a result, all five responded that the external preparation for skin 1 did not feel irritation. This is presumed to be due to the improvement of the spread by the addition of alcohol.

  The present invention can be applied to a skin external preparation such as an ultraviolet protective cosmetic.

Claims (7)

1) a powder, 2) a lower alcohol, and 3) a method for producing an emulsifier-type skin external preparation containing glycerin-modified methylpolysiloxane,
A step of dispersing the 1) powder and 3) glycerin-modified methylpolysiloxane in an oily carrier to form a slurry;
A step of mixing the slurry and other oil phase components to form an oil phase, and a step of mixing and emulsifying the oil phase and 2) an aqueous phase containing 3 to 20% by mass of a lower alcohol,
A method for producing a topical skin preparation comprising:   The method for producing a skin external preparation according to claim 1, wherein the oily carrier contains dimethicone and / or cyclomethicone.   The method for producing a skin external preparation according to claim 1 or 2, wherein the slurry contains 10 to 20 parts by mass of powder and / or 10 to 20 parts by mass of an oily carrier with respect to 1 part by mass of glycerin-modified methylpolysiloxane. .   Said 1) powder is a manufacturing method of the skin external preparation of any one of Claim 1 to 3 containing a titanium dioxide and / or a zinc oxide. Said 2) lower alcohol is a manufacturing method of the skin external preparation of any one of Claim 1 to 4 containing ethanol and / or isopropanol.   The method for producing a skin external preparation according to any one of claims 1 to 5, wherein the content of the 2) lower alcohol is 5 to 15% by mass.   The method for producing a skin external preparation according to any one of claims 1 to 5, wherein the content of the 2) lower alcohol is 6 to 10% by mass.