KR100376087B1 - Emulsifier-free finely cosmetic compositions of the water-in-oil type and a method of preparing thereof - Google Patents

Abstract

In the present invention, instead of using an emulsifier, polymethylsilsesquioxane particles having a controlled surface silanol concentration are arranged at the interface between the sap droplets of the inner phase and the oil phase of the outer phase, and the dispersion of the liquid droplets stabilizes the water-in-oil type. However, the present invention relates to providing a water-in-oil cosmetic composition having a feeling of use similar to an oil-in-water cosmetic, which can be easily erased when it is desired to be erased while maintaining the makeup's persistence, and which does not have skin photostimulation by an emulsifier.

Description

Emulsifier-free finely cosmetic compositions of the water-in-oil type and a method of preparing IEC}

The present invention relates to a water-in-oil cosmetic composition and a method for preparing the same, which do not contain an emulsifier. More specifically, instead of using an emulsifier that is easy to cause skin irritation, the surface silanol concentration of the particles is controlled. By dispersing and stabilizing the liquid droplets by arranging the polymethylsilsesquioxane particles at the interface of the inner liquid sap droplets and the outer oil phase, the oil-in-water type is similar to that of the oil-in-water cosmetics. The present invention relates to a water-in-oil cosmetic composition without skin photostimulation by an emulsifier.

In general, an oil-in-water type (O / W type) and an oil-in-water type (W / O type) emulsifying method using an emulsifier as a dispersed phase of an oil phase and an aqueous phase are used as a method for producing a cosmetic composition. The oil-in-water type is most commonly used as a general cosmetic composition because it has a merit of light, easy to manufacture, and excellent dispersion stability in the form of water. However, oil-in-water cosmetics are poor in water resistance, and in particular, when a substance having an effect such as salicylic acid in cosmetic ingredients is used in the oil-in-water type, the viscosity is lowered and an additional thickener should be used. It is lowered and has a problem which has the limit of a compounding quantity.

On the other hand, the water-in-oil type has the advantage of providing various functions because the external wound is an oil and improving the persistence of makeup by increasing the water resistance, but it is heavy and sticky by releasing wax among the oily components of the external wound. This has a problem of low emulsion stability. In particular, the oil-in-water emulsion emulsified a lot of silicone oil as an oil component, increasing the amount of silicone oil it is difficult to obtain a water-in-oil emulsion that is stable to changes over time and temperature. Therefore, efforts have been made to overcome this by using a silicone-based emulsifier to solve this problem. Specifically, for example, US Pat. No. 5,942,213 is added to the oil and water gelling agent (gelling agent) or wax, and using a silicone-based emulsifier to blend the amount of silicone oil up to 40% at 45 ℃ for 3 months A method for producing a water-in-oil emulsion that is stable even at a temperature change up to 4 ° C is disclosed. However, since the water-in-oil emulsion contains a large amount of oil components, it can provide excellent makeup sustainability, but since HLB uses a silicone-based emulsifier of about 2 to 6, it is hard to remove when removing makeup. It has a disadvantage.

On the other hand, emulsifiers generally used in cosmetics using water-in-oil emulsions seem to have no problem on their own, but they can induce mallorca acne as photodermatoses when exposed to light with various fat components. For products used on the premise of exposure to light, such as cosmetics, it is necessary to suppress skin irritation caused by emulsifiers. Accordingly, a study (US Pat. No. 5,804,167) has been made on a method for preparing a water-in-oil emulsion without using an emulsifier.

Accordingly, the present inventors can also provide a light and matte feeling, such as at least oil-in-water cosmetics, excellent durability and easy to erase when you want to erase, and does not use emulsifiers skin irritation due to using emulsifiers It has been studied how to provide a water-in-oil cosmetic composition.

As a result, the present inventors have found that water-in-oil cosmetics which do not use conventional emulsifiers are emulsified by preparing a water-in-oil type dispersed phase by forced dispersion and arranging fine particles or ultra-fine particles having an amphiphilic surface at the interface between oil and water. From stabilizing the state, it was intended to use microparticles or ultrafine particles having an amphipathic surface instead of an emulsifier.

However, the amphipathic surface composition particles used in the conventional cosmetics, the surface of the inorganic particles such as talc, silica, titanium dioxide, zinc, etc. partially coated with a silicone polymer to coexist surface hydroxyl groups and alkyl groups on the surface of the particles to form an amphiphilic surface Surface-treated powders having crosslinked polymers or crosslinked polysiloxanes as parent particles, and inorganic oxides coated as parent particles, and composite powders having an amphiphilic surface by coexisting an alkyl group on the surface of the mother particle and a hydroxyl group on the surface of the particle particle In the case of the surface-treated inorganic particles, it is easy to control the size of the particles and the surface composition, but it is difficult to stabilize the dispersion because the silicone polymer adsorbed on the surface is easily peeled off and the specific gravity is large as the inorganic particles. In the case of multiparticulates, since the fine particles are the parent particles, There is a problem that it is impossible to adjust the road.

Therefore, the present inventors searched to select particles having a new amphipathic surface composition which does not have the above-mentioned problems, and in order to solve the above problems, the specific gravity of the particles in the water-in-oil dispersion phase is low, so that the dispersibility is good and the particle size is controlled. It is preferable to use a single particle which is easy and has both a hydrophilic group and a lipophilic group on the surface of the particle, and finds the optimum polymethylsilsesquioxane particle having a controlled silanol concentration on the particle surface. The present invention has been completed.

Accordingly, an object of the present invention is to provide a light and matte feeling, excellent durability and can be easily erased when you want to erase, there is no problem in the oil-in-oil without using the emulsifier without using an emulsifier It is to provide a male cosmetic composition.

Another object of the present invention to provide a method for producing a water-in-oil cosmetic composition.

Other objects, features and advantages of the invention will be apparent to those skilled in the art from the construction of the following invention.

In order to achieve the above object, the water-in-oil cosmetic composition according to the present invention is characterized in that it contains polymethylsilsesquioxane particles having an average particle size of 0.3 ~ 1.0㎛ instead of an emulsifier.

Hereinafter, the present invention will be described in more detail.

The water-in-oil cosmetic composition of the present invention contains polymethylsilsesquioxane having a controlled surface silanol concentration instead of an emulsifier, and thus has no skin photostimulation, and may contain up to 40% of an oily component. It can be easily erased, and it is possible to use salicylic acid, etc., which was limited to 0.1% or less due to the viscosity decrease in conventional oil-in-water emulsions up to 0.5% by weight in the inner phase, thereby providing a feeling similar to at least oil-in-water type can do.

Polymethylsilsesquioxane is represented by the general formula [CH ₃ SiO _3/2 ] _n [CH ₃ Si (OH) O _2/2 ] _m , and the surface silanol concentration (of polymethylsilsesquioxane In general formula (m / n), it has an amphiphilic surface so that it can be arranged at the interface of oil and water to stabilize dispersion of the liquid droplets. Thus, in the present invention, it is used instead of an emulsifier.

On the other hand, the surface silanol concentration of polymethylsilsesquioxane is determined by the particle size since the specific surface area of the particles increases when the particle size of the polymethylsilsesquioxane decreases, thereby increasing the concentration of silanol. do.

Therefore, the average size of the polymethylsilsesquioxane particles in the present invention should be 0.3 ~ 1.0㎛ the concentration of silanol is 0.29 or more to form a stable water-in-oil emulsion.

The polymethylsilsesquioxane used in the present invention is prepared by, for example, mixing methyltrichlorosilane in an organic solvent and then dropping water to hydrolysis and condensation (US Pat. No. 4,399,266). A method of hydrolyzing and condensing by adding methyltrialkoxysilane to an aqueous solution containing a catalyst such as hydroxide or alkali metal carbonate (Japanese Patent No. 54-72300), an aqueous solution in which methyltrialkoxysilane is mixed with ammonia or amine or organic It can manufacture by well-known methods, such as the method of hydrolysis and condensation at the interface of a mixture of a solvent (Japanese Patent No. 63-77940). However, since the polymethylsilsesquioxane of the present invention has to control the size of the particles, it is preferable to prepare the particles by the method disclosed in Japanese Patent No. 63-77940.

In the method for producing a water-in-oil cosmetic composition of the present invention, the polymethylsilsesquioxane particles are dispersed in an oily component, and the aqueous phase is added to the aqueous solution of the polymethylsilsesquioxane particles into the aqueous phase and the oil of the external wound. Providing a stable water-in-oil emulsion arranged at the interface.

At this time, the content of the polymethylsilsesquioxane contained in the oily component is preferably 0.5 to 10% by weight based on the weight of the composition species. It can not act as an emulsifier when the content of polymethylsilsesquioxane is less than 0.5% by weight, and when it exceeds 10% by weight, the powder may appear visually dull after the cosmetic composition is absorbed into the skin. This is because it has a disadvantage.

The water-in-oil emulsion prepared by the above method is excellent in stability because the size of the water droplets is adjusted to 1 ~ 10㎛. That is, the larger the particles of the emulsion, the greater the aggregation or coalescence, the lower the stability of the emulsion. The water-in-oil cosmetic of the present invention is very excellent in stability since the particle size is controlled in the above-mentioned range using polymethylsilsesquioxane. Do.

On the other hand, the water-in-oil cosmetic composition according to the present invention has a volatile silicone oil in order to lighten the feel, and to easily remove the makeup by skin desorption of the polydimethylsilsesquioxane particles by evaporation of volatile silicone oil after skin application. 5 to 30% by weight based on the total weight of the composition.

Hereinafter, the present invention will be described in more detail with reference to Examples, and the present invention is not limited to these Examples.

Synthesis Example 1

Into a 5 L flask, 1,988 g of water and 12 g of 25% aqueous ammonia solution were added and stirred to prepare an aqueous ammonia solution. Then, 340 g of methyltrimethoxysilane was added thereto to form an upper layer of methyltrimethoxysilane. The lower layer was made. Then, the stirring speed of the stirrer was set to 25 rpm to allow the hydrolysis and condensation reactions to occur at the interface between the two layers. As the reaction proceeds, the reactant slowly precipitates in the lower layer, the lower layer becomes cloudy by the reactant, and the amount of methyltrimethoxysilane in the upper layer is reduced. When methyltrimethoxysilane was completely removed by the reaction, it was then warmed to 50-60 ° C. for 3 hours, stirred at the same stirring speed, and then cooled to 25 ° C. The cooled product was filtered and dehydrated, the filtrate was dried at 200 ° C. for 2 hours, and the dried product was crushed using a jet mill to finally prepare a white powder.

In this case, the average particle size of the prepared particles was 3 ㎛, and the amount of silanol was 0.21 per silicon atom as the ratio of m = 0.28n when analyzed by NMR spectrum (JEMINI 2000, VARIAN (manufacturer)).

<Synthesis example 2-5>

A polymethylsilsesquioxane white powder was prepared in the same manner as in Synthesis Example 1 except for the mixing prescription and stirring speed of Table 1 below, and the average size and amount of silanol of the prepared particles were shown in Table 1. .

Synthesis Example Methyltrimethoxysilane (g) Water (g) 25% aqueous ammonia solution (g) Stirring Speed (rpm) Particle Average Size (㎛) Amount of silaol (per silicone atom (m / n)) 2 150 1,932 68 10 0.3 0.26 (0.35) 3 200 1,954 46 10 0.5 0.24 (0.32) 4 200 1,922 30 10 0.8 0.22 (0.29) 5 300 1,944 56 200 10 0.20 (0.28)

<Examples 1-6 and Comparative Examples 1-3> Lotion

Raw material Example Comparative example One 2 3 4 5 6 One 2 3 Oily ingredients Cyclomethicone 25.0 25.0 25.0 25.0 25.0 - 25.0 25.0 20.0 Cetyloctanoate - - - - - 11.0 - - 1.0 Meadowfoam seed oil - - - - - 2.0 - - 2.0 Mineral oil - - - - - 12.0 - - 2.0 Beads wax - - - - - - - - 1.0 Liquid paraffin - - - - - - - - 0.5 Cetyl Dimethicone Copolyol - - - - - - - - 3.0 Polymethylsilsesquioxane 1 (Synthesis example 2, average particle size 0.3 micrometer) 4.0 - - - - - - - - Polymethylsilsesquioxane 2 (Synthesis example 3, average particle size 0.5 micrometer) - 4.0 - - - - - - - Polymethylsilsesquioxane 3 (Synthesis example 4, average particle size 0.8 micrometer) - - 4.0 3.0 5.0 5.0 - - - Polymethylsilsesquioxane 4 (Synthesis example 1, average particle size 3㎛) - - - - - - 6.0 - - Polymethylsilsesquioxane 5 (Synthesis example 5, average particle size 10 micrometers) - - - - - - - 6.0 - Aqueous ingredient 1 Purified water to 100 to 100 to 100 to 100 to 100 to 100 to 100 to 100 to 100 glycerin 3.0 3.0 3.0 3.0 3.0 3.0 3.0 3.0 3.0 1,3-butylene glycol 3.0 3.0 3.0 3.0 3.0 3.0 3.0 3.0 3.0 antiseptic 0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.4 Beta-glucan 3.0 3.0 3.0 3.0 3.0 3.0 3.0 3.0 3.0 Aqueous Ingredients 2 Ethyl alcohol 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 Salicylic acid 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3

<Production method>

(1) The aqueous component 2 was dissolved.

(2) Oily components were mixed uniformly.

(3) After mixing the aqueous component 1 uniformly, the above (1) was added and mixed.

(3) To (2), (3) was slowly added at room temperature under stirring to obtain a water-in-oil emulsion.

<Test Example 1>

In order to compare the uniformity of the water-in-oil emulsions prepared in Examples 1 to 3, Examples 6 and Comparative Examples 1 to 3, and the particle size of the liquid droplets, they were measured by optical microscopy. Emulsification stability was tested by standing for 3 months and evaluating the separation state, and the result is shown in Table 2.

division Example Comparative example One 2 3 6 One 2 3 Droplet particle size of water-in-oil emulsion, μm One 3 10 10 300 1,000 0.7 Silanol concentration, m / n 0.35 0.32 0.29 0.29 0.28 0.28 0 Room temperature 1 month ○ ○ ○ ○ △ × ○ 3 months ○ ○ ○ ○ × × ○ 4 ℃ 1 month ○ ○ ○ ○ △ × ○ 3 months ○ ○ ○ ○ × × ○ 37 ℃ 1 month ○ ○ ○ ○ △ × ○ 3 months ○ ○ ○ ○ × × ○ 45 ℃ 1 month ○ ○ ○ ○ △ × ○ 3 months ○ ○ △ △ × × ○ ○: Good · △: Normal · ×: Separation

From Table 2, it is shown that as the particle size of the polymethylsilsesquioxane increases, the size of the droplets dispersed in the oil increases, and at least when the particle size of the polymethylsilsesquioxane is 1 µm or less, an emulsifier is used. As in the water-in-oil emulsion (Comparative Example 3), it can be seen that a stable water-in-oil emulsion is obtained. In addition, as in Comparative Examples 1 and 2 it can be seen that the emulsion state becomes unstable as the size of the liquid droplets increases and the amount of silanol of polymethylsilsesquioxane decreases.

<Test Example 2>

In order to evaluate the emulsion stability according to the blending amount of polydimethylsilsesquioxane, the time point of separation at a temperature change of 45 ° C. to 4 ° C. was measured, and the results are shown in Table 3.

division Example 3 4 5 Polymethylsilsesquioxane (Synthesis Example 4, average particle size: 0.8 μm) Blending amount, wt% 4 3 5 Room temperature 1 month ○ ○ ○ 3 months ○ ○ ○ 4 ℃ 1 month ○ ○ ○ 3 months ○ ○ ○ 37 ℃ 1 month ○ ○ ○ 3 months ○ △ ○ 45 ℃ 1 month ○ △ ○ 3 months △ △ ○ ○: Good · △: Normal · ×: Separation

As the content of the polymethylsilsesquioxane particles decreases from the results of Table 3, the amount of particles present at the interface between the oil and the liquid droplets to replace the role of the surfactant is reduced, thereby reducing stability. Thus, it can be seen that the stability is also affected by the content of the polymethylsilsesquioxane particles.

<Test Example 3>

Relative comparative evaluation was performed on 40 women in their 20s to 40s with regard to the feeling of use, the persistence of makeup, and the cleaning power to remove makeup. The results are shown in Table 4.

division Example 5 Example 6 Comparative Example 3 Feeling ◎ ○ × Persistence ○ ○ ○ Cleansing power when removing makeup ◎ ◎ △ ◎: Very good. ○: good, △: normal, ×: bad

Table 4 shows that the water-in-oil cosmetics of the polymethylsilsesquioxane of the present invention are superior in terms of use than those made using a general surfactant (Comparative Example 3).

As described above, it is possible to manufacture a water-in-oil cosmetic composition that is stable by polymethylsilsesquioxane without using an emulsifier, thereby improving the disadvantages of the emulsifier to control the amount of silicone oil up to 40% It can be used to improve the disadvantages of water-in-oil cosmetics and to prepare a variety of formulations. In addition, the water-in-oil type cosmetics prepared without using an emulsifier have no skin light irritation, and do not use the wax used for stability in the existing water-in-oil type cosmetics, but instead can realize a light and matte feeling that the powder has and also underwater It is characterized by the fact that a high content of a raw material causing a viscosity decrease such as salicylic acid in the type emulsion can be used.

Claims (5)

A water-in- oil cosmetic composition comprising polymethylsilsesquioxane particles represented by the formula [CH ₃ SiO _3/2 ] n [CH ₃ Si (OH) O _2/2 ] m in place of an emulsifier , wherein the polymethyl The average particle size of silsesquioxane is 0.3-1.0 μm, the concentration of silanol expressed in m / n is 0.29 or more, and in the water-in-oil cosmetic, the polymethylsilsesquioxane particles are disposed at the interface between oil and water. A water-in-oil cosmetic composition having a structure in which a particulate film of polymethylsilsesquioxane is formed on the surface of water droplets . The water-in-oil cosmetic composition of claim 1, wherein the polymethylsilsesquioxane particles are used in an amount of 0.5 to 10% by weight. Polymethylsilsesquioxane particles having an average particle size of 0.3 to 1.0 µm are dispersed in the oil component in an amount of 0.5 to 10% by weight based on the total weight of the oil component, and the polymethylsilsesquioxane is introduced into the water phase. A method for stabilizing a water-in- oil cosmetic composition, wherein the particles are arranged at the interface between the droplets of the inner phase and the oil of the outer phase, thereby forming a fine particle film of polymethylsilsesquioxane . 4. The method of stabilizing a water-in-oil cosmetic composition according to claim 3, wherein the size of the water droplets, which is the inner phase of the water-in-oil emulsion, is adjusted to 1 to 10 µm. 4. The method of stabilizing a water-in- oil cosmetic composition according to claim 3, wherein 5 to 30% by weight of the oily component is volatile silicone oil.