KR101126008B1 - Mesoporous silica with Pentaerythritol derivatives and the method for manufacturing thereof - Google Patents

Abstract

The present invention relates to a mesoporous porous silica composite powder in which a pentaerythritol derivative is collected and a method for manufacturing the same, and more particularly, to improve the moisture retention ability of the stratum corneum layer on the porous silica having a high oil absorption, and in particular in a dry environment. The present invention relates to a mesoporous porous silica composite powder in which a pentaerythritol derivative is collected and a preparation method thereof.

 Pentaerythritol derivative, moisture retention ability, moisture retention ability, porous silica

Description

Mesoporous silica composite powder with pentaerythritol derivatives and a method for manufacturing the same

1 is a schematic diagram of a mesoporous silica composite in which a pentaerythritol derivative prepared in Example 1 is collected.

FIG. 2 is a scanning electron microscope photograph of the mesoporous silica material prepared in Reference Example 1. FIG.

FIG. 3 is a scanning electron microscope photograph of the mesoporous silica material prepared in Reference Example 2. FIG.

Figure 4 shows the skeleton of the mesoporous material prepared in Reference Example 1 and Reference Example 2.

5 is a thermogravimetric analysis graph of the mesoporous silica composite with pentaerythritol derivatives carried out in Test Example 1.

Figure 6 is a graph of the moisture absorption capacity and the water retention test results carried out in Test Example 2.

7 is a comparative photograph of the dispersion stabilization in the powder formulation carried out in Test Example 3.

The present invention relates to a mesoporous porous silica composite powder in which a pentaerythritol derivative is collected and a method for manufacturing the same, and more particularly, to improve the moisture retention ability of the stratum corneum layer on the porous silica having a high oil absorption, and in particular in a dry environment. The present invention relates to a mesoporous porous silica composite powder in which a pentaerythritol derivative is collected and a preparation method thereof.

Mesoporous porous silica is one of the mesoporous molecular sieves. It is a mesoporous molecular sieve with uniformly sized mesopores arranged regularly. In 1991, a new type of mesoporous molecular sieve materials, named M41S family, manufactured by Mobil researchers using ionic surfactants as structural derivatives, was described in US Pat. No. 5,057,296. And 5,102,643 and the like, research on such mesoporous molecular sieve materials is now actively conducted worldwide. Unlike the synthesis of conventional molecular sieves, these mesoporous molecular sieves are synthesized through the liquid crystal templating mechanism, and the pores are controlled by controlling the type of the surfactant used as the template material or the conditions of the synthesis. It has the advantage of controlling the size of 16 ~ 100Å.

U.S. Pat.Nos. 6,027,706, 6,054,111 and 1998, Volume 279, page 548 disclose mesoporous materials prepared using amphiphilic block copolymers, which are nonionic surfactants. Is disclosed. In the case of zeolites, one inorganic or organic molecule generally acts as a template to induce pore structure, whereas a mesoporous material is a single molecule, which is a micelle structure in which a plurality of surfactant molecules are aggregated to induce pores. . Surfactants are generally known to consist of hydrophilic heads and hydrophobic tails to form self-assembled micelles and liquid crystal structures of various structures under aqueous solutions. The mesoporous material may be obtained by forming an organic / inorganic nanocomposite and removing the surfactant through the interaction of the hydrophilic portion located on the surface of the micelle or liquid crystal structure with the precursor of the inorganic material. Mesoporous materials, unlike microporous materials whose pore size is 1.5 nm or less, like conventional zeolite or AIPO-based materials, extend the pore size to the mesopore range (2-50 nm). Application of molecular sieve materials to adsorption and separation of molecules having a size larger than the pore size of microporous materials, catalytic conversion reaction, and the like, which has been limited in the application of molecular sieve materials, has become possible. The mesoporous material having such regular pores has a very large surface area (> 700m ² / g), which is excellent in adsorption characteristics of atoms or molecules, and has a constant pore size, thereby supporting carriers of catalytically active agents such as transition metal compounds and amine oxides. It is applied to. There are also many applications and applications for conductive materials, optical display materials, chemical sensors, fine chemicals and biopowders, new mechanical and thermal insulators and packaging materials.

The stratum corneum of the skin protects the human body from harmful substances from the outside, and serves to keep the skin moist by inhibiting the evaporation of moisture in the skin to the outside. However, as the skin ages, the function of the stratum corneum deteriorates, making the skin easier to feel dry, and this tendency is greater in dry winter.

For this reason, many moisturizers have been developed to improve the dryness of the skin. As a typical example, a water-soluble moisturizer and ceramide can be mentioned. Water-soluble moisturizers such as amino acids, organic acids, urea, etc. are used as the most common moisturizers because they have excellent ability to absorb water and provide moisture to the stratum corneum. However, in a dry environment with low humidity, such as winter, the moisturizing power is showing a significant decrease. And ceramide is an important component of intercellular lipids of the stratum corneum, showing excellent effects on strengthening skin barrier function and maintaining skin moisture, but it is not compatible with oils used in cosmetics. The disadvantage is falling. This makes it difficult to use a substantial effective concentration.

Therefore, there is a need for the development of a moisturizer derived from a usefulness that is easy to use in cosmetics while showing a high moisturizing power even in a dry environment, and has a new form in Korean Patent Application No. 10-2004-0024704. A pentaerythritol derivative which is a moisturizing agent of is disclosed. However, the pentaerythritol derivative has a limited problem in its use because it cannot be used above a certain concentration due to the hydrophilic surfactant and the cohesion of powder in makeup cosmetics.

Accordingly, the present inventors provide a moisturizing effect by collecting a large amount of pentaerythritol derivative in mesoporous porous silica using an impregnation method in order to develop a new cosmetic that overcomes the disadvantages of using the pentaerythritol derivative as a cosmetic. It was confirmed that the formulation can be stabilized to prevent the aggregation phenomenon of the powder and completed the present invention.

Accordingly, it is an object of the present invention to provide a mesoporous porous silica composite powder in which a pentaerythritol derivative is collected and a method of manufacturing the same.

In order to achieve the above object, the present invention provides a mesoporous porous silica composite powder in which a pentaerythritol derivative is collected, and a method of manufacturing the same.

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

The mesoporous porous silica developed as a carrier in the present invention is one of mesoporous molecular sieves. It is a mesoporous molecular sieve with uniformly sized mesopores arranged regularly. According to the IUPAC definition, inorganic materials with pores are largely microporous (<2 nm), mesoporous (2-50 nm) and macroporous (> 50 nm) depending on the pore size. ) Are classified as substances. In general, zeolite, which is a microporous material, is synthesized under hydrothermal conditions using an organic ammonium salt or an inorganic cation as a template or a structure directing agent. Similarly, mesoporous materials are also synthesized through hydrothermal reactions using organic molecules such as surfactants or amphiphilic polymers as structural inducers. In the case of zeolites, one inorganic or organic molecule generally acts as a template to induce pore structure, whereas a mesoporous material is a single molecule, which is a micelle structure in which a plurality of surfactant molecules are aggregated to induce pores. . Surfactants are generally known to consist of hydrophilic heads and hydrophobic tails to form self-assembled micelles and liquid crystal structures of various structures under aqueous solutions. The mesoporous material may be obtained by forming an organic / inorganic nanocomposite and removing the surfactant through the interaction of the hydrophilic portion located on the surface of the micelle or liquid crystal structure with the precursor of the inorganic material. Application of these mesoporous materials is being actively conducted throughout the industry. For example, it is used as a fine chemical catalyst, because of its high surface area (> 500m ² / g) and uniform pore size of mesoporous has been applied as a carrier of catalytic actives such as transition metal compounds, amine oxides. It is also being studied as a separation / enhancement material, molecular sieve membrane, sensor, and capture carrier.

Generally, the microporous material zeolite is synthesized under hydrothermal conditions using an organic ammonium salt or an inorganic cation as a template or structure inducing material. Similar mesoporous materials are also synthesized by hydrothermal reaction using organic molecules such as surfactants or amphiphilic polymers as structure inducing substances. Representative examples of molecular sieves are porous crystalline aluminum silicates such as zeolite A, Y, L, ZSM-5, etc., and have a structure in which fine pores of uniform size are regularly arranged. Mesoporous molecular sieves have an MCM series and an SBA series.

Looking at the manufacturing method of the mesoporous porous silica composite powder in which the pentaerythritol derivative of the present invention is collected, the process is divided into two steps.

The first step is to prepare mesoporous porous silica.

Mesoporous silica is prepared with sodium metasilicate and tetraethoxyorthosilane (TEOS) as precursors. Polyethylene oxide block (polypropylene oxide) -polyethylene oxide, a polymer surfactant, is dissolved in water. The polyethylene oxide block (polypropylene oxide) polyethylene oxide acts as a template material and forms a self-assembled molecular structure at an appropriate concentration.

Hydrochloric acid is added to the solution as a silica precursor and a catalyst to proceed the reaction at 40 ° C. At this time, the silica precursor reacts on the surface of the formed polyethylene oxide block (polypropylene oxide) polyethylene oxide micelle to form an oligomer.

Thereafter, the oligomer formed by stirring again at 100 ° C. for 24 hours is polymerized by reacting again. At this time, the hydrochloric acid catalyst serves as a bridge to participate in the reaction.

The structure thus formed is dried through a filtration separation step, washed with ethanol, and then sintered at 400 to 600 ° C. for 0.3 to 30 hours to remove polyethylene oxide sideblock (polypropylene oxide) polyethylene oxide, which is a template material. Produce porous porous silica. In addition to the above method, it is possible to produce a mesoporous material by a method known in the art within a range that does not impair the object of the present invention.

The method for producing the mesoporous material is preferably carried out through the following steps:

(A) mixing the surfactant with a silica precursor;

(B) adjusting the pH of the mixture obtained in (A) with an acid or base;

(C) hydrothermally reacting the mixture of step (B);

(D) filtering, washing and drying the material obtained in step (C); And

(E) calcining the material obtained in step (D).

Hereinafter, the steps will be described in more detail.

In step (A), the aqueous surfactant solution may be prepared basic or acidic. The basic aqueous solution is 0.1 to 5.0% by weight of surfactant, preferably 0.5 to 3.0% by weight, and a strong base such as sodium hydroxide of 0.5 to 2.0. It is prepared by mixing by weight, preferably 0.7 to 1.0% by weight. The acidic aqueous solution is prepared by mixing 0.1 to 5.0% by weight of surfactant, preferably 0.5 to 3.0% by weight, and 0.5 to 10% by weight of strong acid, such as hydrochloric acid or sulfuric acid, preferably 1.0 to 5.0% by weight.

Preferred examples of the surfactant used in the present invention is cetyltrimethylammonium chloride (cetyltrimethylammonium chloride), cetyltrimethylammonium bromide, polyethylene glycol dodecyl ether, polyoxyethylene (23) Polyoxyethylene (23) lauryl ether, polyoxyethylene (2) cetyl ether, polyoxyyethylene (10) cetyl ether, polyethylene glycol hexadecyl ether (polyethylene glycol hexadecyl ether), polyoxyethylene (10) stearyl ether (polyoxyethylene (10) stearyl ether), polyethylene glycol octadecyl ether (polyethylene glycol octadecylether) and polyethylene glycol block (polypropylene glycol) polyethylene glycol (poly (ethylene glycol) ) -block-poly (propylene glycol) -block-poly (ethylene glycol)). Preferably, polyethylene oxide block (polypropylene oxide) polyethylene oxide is used.

Preferred examples of the precursor used in the present invention are tetraethylorthosilicate (TEOS), tetramethylorthosilicate (TMOS), methyltrimethoxysilane, dimethyldimethoxysilane, trimethylmethoxy Trimethylmethoxysilane, methyltriethoxysilane, dimethyldiethoxysilane, trimethylethoxysilane, methyltrichlorosilane, dimethyldichlorosilane, trimethylchlorosilane ( trimethylchlorosilane, bis (trichlorosilyl) methane, bis (trichlorosilyl) ethane, 1,2-bis (trichlorosilyl) ethane, bis (trimethoxysilyl) methane bis (trimethoxysilyl) methane), 1,2-bis (triethoxysilyl) ethane (1,2-bis (triethoxysilyl) ethane), 1,4-bis (trimethoxysilyl ) Benzene (1,4-bis (trimethoxysilyl) benzene), 1,4-bis (trimethoxysilylethyl) benzene (1,4-bis (trimethoxysilylethyl) benzene), sodium metasilicate, etc. are mentioned. More preferably, sodium metasilicate and tetraethylorthosilicate (TEOS) are used.

The precursor is preferably added slowly while vigorously stirring the aqueous surfactant solution at room temperature using a stirring device. At this time, the amount of the precursor to be added is preferably 1 to 100 moles based on 1 mole of the surfactant, preferably 10 to 50 moles. After the precursor is added to the aqueous surfactant solution, the reaction mixture is preferably stirred at room temperature for 1 to 2 hours.

In step (B), the pH of the aqueous solution prepared in step (A) is adjusted to 1 to 13, preferably 1 to 3, using an acid or a base.

In step (C), a mesoporous material is prepared through hydrothermal reaction. At this time, the hydrothermal reaction temperature is suitable 60 ~ 150 ℃, the reaction time is 1 hour to 144 hours, preferably 12 hours to 48 hours.

In step (D), the prepared precipitate is filtered through a filtration device, washed two to five times with distilled water, and dried at 50 to 200 ° C. for 3 to 30 hours.

In step (E), the resulting surfactant is calcined at 400 to 600 ° C. for 0.3 to 30 hours in an air or oxygen atmosphere to remove the surfactant contained therein.

The mesoporous porous silica particles prepared through the above steps are about 1 to 50 μm, the pores are about 7 to 10 nm, and the specific surface area is about 500 to 700 m 2 / g.

The second step is a process in which pentaerythritol derivative is dissolved in a solvent and supported on mesoporous porous silica. A process for synthesizing pentaerythritol derivatives is known from Korean Patent Application No. 10-2004-6024704, and the supporting process is a solvent such as ethanol or methanol in order to support the pentaerythritol derivative represented by Formula 1 below in the mesoporous silica. It is suitable to dissolve at room temperature using and preferably in anhydrous ethanol.

Wherein R is an alkyl group containing from 1 to 24 carbon atoms, saturated and unsaturated, straight and branched, containing or not the same or different hydrogen or hydroxy groups, and m is 0-10, n is 1-10 Are the same or different integers.)

The supporting method was performed using an incipient wetness method. The pentaerythritol derivative solution prepared above and mesoporous porous silica are mixed at an appropriate concentration. At this time, the mixing ratio of mesoporous porous silica and pentaerythritol derivative is 1: 1 to 3, and more preferably 10 to 60 g of pentaerythritol derivative is mixed with 10 to 20 g of mesoporous porous silica.

The mesoporous porous silica composite powder in which the pentaerythritol derivatives prepared in the above manner are collected can be solved by the collected pentaerythritol derivatives to improve skin moisturizing ability and feel, and to stabilize the formulation. In this case, the content of the mesoporous porous silica composite powder in which the pentaerythritol derivative is collected is preferably about 0.2 to 10% by weight based on the total weight of the cosmetic composition.

The cosmetic composition containing the mesoporous porous silica composite powder in which the pentaerythritol derivative is collected according to the present invention improves the moisture retention ability of the stratum corneum, and in particular, has a high moisturizing power even in a dry environment. To prevent powder agglomeration and improve the feeling of use. The mesoporous porous silica composite powder in which the pentaerythritol derivative is collected can be used as a cosmetic material because it is possible to formulate powder and lipstick such as base makeup.

The present invention will be described in more detail with reference to the following Examples. However, these examples are intended to illustrate the present invention, it is obvious to those skilled in the art that the scope of the present invention is not limited to these examples.

Reference Example 1 Preparation of Mesoporous Porous Silica (1)

Polyethylene oxide block (polypropylene oxide) 20 g of polyethylene oxide was dissolved in 602.57 g of 2N sulfuric acid, and 43.11 g of tetraethylorthosilicate was added thereto while stirring vigorously at room temperature using a magnetic stirring device. The reaction mixture was stirred at room temperature for 1 hour and then the solution was stirred at 40 ° C. for 24 hours. The reaction mixture was hydrothermally reacted in an oven at 100 ° C. for 24 hours. The precipitate was filtered off and dried at 100 ° C. In order to remove the surfactant contained in the dried sample was washed clean with ethanol and calcined for 10 hours at 550 ℃ in air.

Reference Example 2 Preparation of Mesoporous Porous Silica (2)

Polyethylene oxide block (polypropylene oxide) 20 g of polyethylene oxide was dissolved in 300 g of secondary distilled water, and sodium metasilicate was dissolved in 148.76 g of secondary distilled water, respectively. The reaction mixture was mixed and stirred at room temperature for 1 hour using a magnetic stirrer, and then 150.54 g of sulfuric acid was added thereto. The reaction mixture was hydrothermally reacted in an oven at 100 ° C. for 24 hours. The precipitate was filtered off and dried at 100 ° C. In order to remove the surfactant contained in the dried sample was washed clean with ethanol and calcined for 10 hours at 550 ℃ in air.

Example 1 Preparation of Mesoporous Porous Silica Collected with Pentaerythritol Derivatives

After completely dissolving 10 g of pentaerythritol derivative in 100 g of anhydrous ethanol, 10 g of mesoporous porous silica prepared in Reference Example 1 were mixed, mixed with the pentaerythritol derivative solution at room temperature, and stirred for about 1 to 3 hours. Filtration followed by vacuum drying at room temperature yielded 19.8 g of mesoporous porous silica containing the final pentaerythritol derivative.

Example 2 Preparation of Mesoporous Porous Silica Collected with Pentaerythritol Derivatives

After completely dissolving 20 g of pentaerythritol derivative in 100 g of anhydrous ethanol, 10 g of mesoporous porous silica prepared in Reference Example 1 was mixed, mixed with the pentaerythritol derivative solution at room temperature, stirred for about 1 to 3 hours, and then filtered. 29.8 g of mesoporous porous silica obtained by vacuum drying at room temperature and containing the final pentaerythritol derivative was obtained.

Example 3 Preparation of Mesoporous Porous Silica Collected with Pentaerythritol Derivatives

After completely dissolving 30 g of pentaerythritol derivative in 100 g of anhydrous ethanol, 10 g of mesoporous porous silica prepared in Reference Example 2 was taken, mixed with the pentaerythritol derivative solution at room temperature, stirred for about 1 to 3 hours, and then filtered. 39.8 g of mesoporous porous silica obtained by vacuum drying at room temperature and collecting the final pentaerythritol derivative was obtained.

Comparative Example 1 Preparation of Silica Collected with Glycerin

After completely dissolving 10 g of glycerin (C ₃ H ₈ O ₃ , MW = 92.0944) in 100 g of anhydrous ethanol, 10 g of silica prepared in Reference Example 1 was taken, mixed with the glycerin solution at room temperature, and stirred for about 1 to 3 hours. The mixture was then filtered and dried in vacuo at room temperature to obtain 21.1 g of silica containing the final glycerin.

Comparative Example 2 Preparation of Silica Collected with Glycerin

After completely dissolving 20 g of glycerin (C ₃ H ₈ O ₃ , MW = 92.0944) in 100 g of anhydrous ethanol, 10 g of silica prepared in Reference Example 1 was taken, mixed with the glycerin solution at room temperature, and stirred for about 1 to 3 hours. The mixture was then filtered and dried in vacuo at room temperature to obtain 31.6 g of silica containing the final glycerin.

[Test Example 1]

In order to measure the amount of pentaerythritol derivative collected in mesoporous porous silica in which the pentaerythritol derivative prepared in Example 1 was collected, it was analyzed by thermogravimetric analyzer (TGA (Thermal Gravimetry Analyzer), TA Instrument). The results are shown in FIG. 5.

Through the above results, it can be seen that the pentaerythritol derivative is 1: 1 in mesoporous porous silica according to the present invention.

[Test Example 2]

For the compounds obtained in Example 1 and Comparative Example 1 was measured and compared the moisture retention in a dry environment.

Specifically, to prepare a sample so that the moisture content of the compounds obtained in Example 1 and Comparative Example 1 to 60%, and store the sample in a thermo-hygrostat (18 ℃, 20% relative humidity) to measure the weight over time The water holding power of the compound was evaluated by observing the change in the water content. The results are shown in Figure 6 below.

 As shown in FIG. 6, the mesoporous silica in which the pentaerythritol derivative of the present invention was collected showed a higher moisture retention than the silica in which glycerin was collected, and in particular, exhibits high moisturizing power even in a dry environment.

[Test Example 3]

The dispersion stabilization in the formulation was compared for the compound obtained in Example 2.

Specifically, the mesoporous silica in which the pentaerythritol derivative of Example 2 was collected was used 10% in the formulation, and the pentaerythritol derivative was used in the 7.5% formulation and applied to the slide glass surface to observe the dispersion stability in the formulation. Acidity was evaluated. The results are shown in Figure 7 below.

 As shown in FIG. 7, the mesoporous silica in which the pentaerythritol derivative of the present invention was collected showed higher dispersibility without agglomeration of powder than the pentaerythritol derivative itself.

Therefore, in the case of the cosmetic composition containing the pentaerythritol derivative of the present invention, high moisturizing power and high moisturizing sustainability, in particular in a dry environment provides an excellent moisturizing effect, and can be expected to increase the usability and dispersion stability of mesoporous silica.

Hereinafter, based on the result of the said test example, the composition of the cosmetics of the various formulation containing the mesoporous porous silica by which the pentaerythritol derivative | guide_body by this invention was collected can be manufactured. However, the composition of the present invention is not limited only to the following examples.

[Formulation example]

Ingredient Name Two way cake formulation example
Content (% by weight) Powder Pact Formulation Example
Content (% by weight) Talc To 100 To 100 Examples 1-3 10.0 10.0 Nylon powder 5.0 5.0 Silica 2.0 2.0 Starch 3.0 3.0 Titanium dioxide 10.0 5.0 Mica 15.0 15.0 Ferric oxide 0.4 0.4 Yellow iron oxide 1.0 1.0 Black iron oxide 0.2 0.2 Squalene 5.0 2.0 Meadowfoam Seed Oil 3.0 2.0 antiseptic Quantity Quantity Spices 0.3 0.3

As described above, the mesoporous porous silica composite powder in which the pentaerythritol derivative is collected according to the present invention provides a high moisturizing effect and a high moisturizing sustainability, especially in a dry environment, and enhances the feeling of use and formulation of mesoporous silica. Dispersion stability can be expected.

Claims (7)

delete A mesoporous porous silica composite powder in which a pentaerythritol derivative is collected, wherein the composite powder has a particle size of 1 to 50 µm, a pore of 7 to 10 nm, and a specific surface area of 500 to 700 m 2 / g. The composite powder of claim 2, wherein the composite powder enhances skin moisturizing ability. The composite powder according to claim 2, wherein the composite powder maintains dispersion stability in the formulation. Preparing a mesoporous porous silica having a particle size of 1 to 50 µm, a pore of 7 to 10 nm, and a specific surface area of 500 to 700 m 2 / g; And Mixing a pentaerythritol derivative and the mesoporous porous silica; Method for producing a porous silica composite powder containing pentaerythritol derivative comprising a. The method of claim 5, wherein the mixing ratio of the porous silica and pentaerythritol derivative is 100: 30 ~ 400.      A cosmetic composition comprising the porous silica composite powder according to any one of claims 2 to 4.

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