KR100930874B1 - Method for preparing the surface-modified powder with water-repellent thin layer on the surface of organic or inorganic particle - Google Patents

Abstract

The present invention relates to a method for producing powder in which the surface of organic or inorganic particles is surface modified with a water repellent ultrathin layer. More specifically, the method for preparing the powder according to the present invention is organic through a gas phase reaction using a high boiling point acrylic silicone (OEt) series and alkyl chain silicone (branched alkyl & silicone OEt) and a relatively low boiling alkyl silane Or by modifying the surface of the inorganic particles with a water-repellent ultra-thin film layer to produce a powder, when the powder is used in cosmetics exhibits an excellent usability with improved water repellency.

Vapor Phase Reaction * Surface Modification * Ultra Thin Film * Coating * Acrylic Silicone * Alkyl Chain Silicone

Description

Method for preparing the surface-modified powder with water-repellent thin layer on the surface of organic or inorganic particle}

1 shows the principle of contact angle measurement.

According to the present invention, the surface of organic or inorganic particles is converted into a water-repellent ultrathin layer through a gas phase reaction using high boiling point acrylic silicone OEt and branched alkyl & silicone OEt and relatively low boiling point alkyl silane. It relates to a method for producing the modified powder.

Conventional powders commonly used in cosmetics have inherent properties. Powders having these characteristics are used in many ways to improve the disadvantages through surface modification according to the characteristics used in cosmetics. Among these techniques, the coating technique is commonly used to convert the surface properties of the powder from hydrophilic to lipophilic or from lipophilic to hydrophilic. Powders used in cosmetics can be classified as follows.

In the cosmetics, inorganic pigments are distinguished by their role and can be broadly classified into coloring pigments, white pigments, extender pigments, and functional pigments.

The coloring pigment is to adjust the color tone of the product, such as bengara, iron sulfate, black iron oxide, chromium oxide, carbon black and the like. The white pigment is to control the hiding power in addition to the color tone, titanium dioxide and zinc oxide belongs. The extender pigment is used as a diluent to adjust the color tone and to adjust the usability (extension, adhesion) and gloss of the product, and to maintain the formulation of the product. Specifically talc, kaolin, mica and the like.

Talc is represented by magnesium hydroxide (Mg ₃ Si ₄ O ₁₀ (OH) ₂ ), and usually forms a dense mass of fine crystals or a cluster of foliar adjustments. In addition, it is called talc because of its abundant smooth texture, and the particle shape is generally used in cosmetics to improve elongation and smoothness in a thin plate shape.

Kaolin, also known as China Clay, is derived from an age of mining high-purity white clay used as a porcelain raw material in ancient China. The composition of kaolin is aluminum hydroxide (Al ₂ Si ₂ O ₅ (OH) ₄ ), and a high crystallinity shows a regular hexagonal plate shape, while a low crystallinity results in a fine irregular plate shape. In addition, since the plate-shaped particles are thin, they have excellent adhesion to the skin and are widely used in cosmetics due to their oil absorption and absorption properties.

Mica (mica) is representative of the white mica belonging to potassium mica and the chemical formula is represented by KAl ₂ (AlSi ₃ ) O ₁₀ (OH) ₂ . The mica crystals are monoclinic and are formed in the form of light yellow or green hexagonal plates. Although the name of sericite is very well known, it is the same as the original mica, which is a mass of fine crystalline pieces, and the surface of the dried material has a silk gloss.

The functional pigment may block ultraviolet rays, and may have various effects of enhancing usability or product effectiveness. There exist many things, such as a photochromic pigment, a synthetic fluorine mica, an iron-containing synthetic fluorine mica, and a fine particle composite powder.

A well-dressed skin indoors has a bright white light, and the entire face looks white. This is called 'white phenomena'. If the color of the makeup is adjusted in response to the light intensity, it is an ideal makeup that maintains a natural finish without any pale feeling. That is, if a pigment having a change in brightness is developed in response to the intensity of light, makeup without a pale feeling is possible. The developed example is a titanium dioxide-based pigment in which a small amount of metal oxide is mixed with titanium dioxide to change color reversibly with light irradiation and corresponding brightness according to light intensity.

In addition, in the case of organic powder, various kinds have been developed and used in cosmetics. Representative examples thereof include polyethylene powder, polymethylmethacrylate powder, polyethylene terephthalate-polymethylmethacrylate laminate powder, nylon powder, cellulose derivatives, and the like. .

These cosmetic powders are applied to the skin and exfoliate and fall off after prolonged periods of time.The water resistance is weak and easily erased by sweat or water, and the oil resistance is weak, so that the powders become stronger to agglomerate with each other. Make breathing difficult

In order to improve skin adhesion, persistence, water resistance, oil resistance, etc., which are disadvantages of the inorganic powders, among the above cosmetic powders, the surface of the powder is surface-treated in an appropriate manner. That is, a method of coating the oily component on the powder is used, and the other powder is used by treating the surface by fatty acid treatment, metal soap treatment of fatty acid, silicon compound treatment, fluorine derivative compound treatment, and the like.

The surface modification method of the said powder is made by the wet method mostly. This wet surface treatment method has the following disadvantages according to various powders. The method of coating the powder surface with an oily component and a fatty acid improves the water resistance of the powder surface to increase water repellency, but when present simultaneously with the lipophilic component, the component modified on the surface of the powder and the lipophilic component present in the surroundings The phenomenon of agglomeration of powders with each other is caused by the force of mutual human forces with. Accordingly, this phenomenon is further accelerated by sweat or the like when the cosmetic containing such powder is applied to the skin. In order to overcome this disadvantage, in order to simultaneously impart water resistance and oil resistance, a technique of modifying the surface of the powder using a silane-based polymer of silicones has been developed. For example, Korean Patent Laid-Open No. 2004-64112 describes a technique for modifying the surface of a powder by a gas phase reaction method using a low boiling point alkylsilane or the like. However, the Si-H or Si-OH gas by-products of the above silicones have a dangerous disadvantage at high temperatures.

Recently, polymers containing fluorine have also been used for surface modification of powders. The powder modified using these various developed coating materials has overcome many disadvantages, but it is not enough to form a coating film uniformly on the surface of the particles to be modified. That is, the method of surface modification of powder using a wet coating has the limitation. On the other hand, silicon is excellent in water resistance and oil resistance, but due to the method of wet coating, the thickness of the coating film and uniform surface modification is not made due to affinity with the biological components of the skin, resulting in heterogeneity. The same applies to the fluorine-containing polymer. Therefore, there is a disadvantage that the molding process is difficult in the production of cosmetics.

On the other hand, in addition to the surface modification using the wet coating method, a technique using the sol-gel method of the method for producing an organic-inorganic composite is also being studied. The technique can be roughly divided into four categories. The first is to use sol-gel monomers containing carbon-silicon bonds. However, the organic reactors are present on the surface because they do not participate in the hydrolysis and condensation reactions that form the matrix. The second is to mix and collect the organics in the sol formulation. The third is to impregnation the organics into the gel using adsorption or the like. Fourth, intercalation polymerizes aniline or pyrrole in the vanadium oxide layer.

Such organic-inorganic complexes are expected to be used particularly in electrochemical applications. Of these technologies using sol-gel has been developed a water-repellent treatment technology using silicon, which has been applied to cosmetics. Silicone used as a water repellent is a methyl hydrogen silicone oil emulsion having Si-H bonds that form a coating film at low temperature, and its Si-H bonds react by heat treatment to form new siloxane bonds and A hydrogen bond is created between the hydrogen atom on the surface and the oxygen atom of the silicone oil. Then, it becomes a three-dimensional structure in which hydrophobic methyl groups are oriented outward, and covers the surface of the mother body to form a durable coating film. Thus, the silicone coating formed on the mother has an effect of imparting water repellency to push out water. When methyl hydrogen silicone oil is used as a raw material of the water repellent, the more Si-H bonds, the lower the heat treatment temperature but the harder the texture. Methyl hydrogen silicone oil containing dimethyl siloxane may be used for the softening finish. In addition, a metal organic acid salt or the like is used as a catalyst to promote the reaction of the Si-H bond at low temperature.

However, the above technique also has a difficulty in producing a powder imparted with excellent water repellency. First, in the case of using multiple alkyl silanes, it is difficult to form a uniform coating film because it is difficult to control the reaction temperature and other manufacturing process parameters, and eventually, many restrictions are placed on mass production.

Therefore, the inventors of the present invention have developed a thin film on the surface of a powder by a physico-chemical vapor reaction method using a high boiling point water repellent on a pigment particle of a fine size to overcome the disadvantages of surface modification by an existing coating method and to develop a new cosmetic. An attempt was made to develop a technique for forming a coating layer.

Accordingly, an object of the present invention is to provide a method for preparing powder in which the surface of organic or inorganic particles is modified to a water repellent ultrathin layer through a gas phase reaction using a high boiling point water repellent.

In order to achieve the above object, the method for producing powder whose surface of the organic or inorganic particles of the present invention is surface-modified with a water-repellent ultrathin layer (1) grinding the powder to be surface-modified to a uniform particle size; (2) a first surface modification step of adsorbing a vaporized water repellent agent by vaporizing a high boiling point water repellent agent at 100 to 250 ° C. on the surface of the powder having the uniform uniform particle size; And (3) a second surface modification step of modifying the surface again using a compound including a double bond in addition to the step (2).

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

The present invention relates to a method of forming a uniform water repellent ultrathin coating layer on powders such as titanium dioxide, silica, mica, talc, and the like, which are commonly used as cosmetics.

The gas phase reaction method in the present invention is a technique used for coating a semiconductor is a method of modifying the surface by depositing a coating material on a carrier such as a silicon wafer in a plasma state under high temperature, high pressure.

The method for producing powder whose surface of the organic or inorganic particles of the present invention is surface-modified with a water-repellent ultrathin film layer comprises the steps of: (1) grinding the powder to be surface-modified to a uniform particle size; (2) a first surface modification step of adsorbing a vaporized water repellent by vaporizing a high boiling point water repellent on the surface of the powder having a uniform uniform particle size; And (3) a second surface modification step of modifying the surface again using a compound including a double bond in addition to the step (2).

Each step will be described in more detail below.

(1) grinding the powder to be surface modified into a uniform particle size

In step (1), the powder to be surface-modified may be in a range of 2 to 15 μm through an appropriate method, such as a jet mill or a dry ball mill. Grinding is carried out to have a constant particle size.

(2) a primary surface modification step of adsorbing a vaporized water repellent agent by vaporizing a water repellent agent on the surface of the powder having the uniform uniform particle size;

Step (2) is a first surface modification step, in which the vaporized coating material is first adsorbed onto the surface of the powder to maintain a uniform particle size in the fluidization reactor. In the present invention, in order to impart water repellency to the desired powder, high boiling point acrylic silicone (OEt) series, alkyl chain silicone (branched alkyl & silicone OEt) and the like or a relatively low boiling point of 100 ~ 250 ℃ as a water repellent It is used in combination with an alkyl silane.

Examples of the acrylic silicone-based material include acrylate / tridecyl acrylate / triethoxysilyl methacrylate / dimethicone methacrylate copolymer (Acrylate / Tridecyl Acrylate / Triethoxysilypropyl Methacrylate / Dimethicone Methacrylate Copolymer), acrylate / dimethic Acrylate / Dimethicone Copolymer, Acrylate / Dimethicone Acrylate / Ethylhexyl Acrylate Copolymer, Acrylate / Stearyl Acrylate / Dimethicone Acrylate Copolymer Acrylate / Stearyl Acrylate / Dimethicone Acrylate Copolymer), acrylate / behenyl acrylate / dimethicone acrylate copolymer, acrylate / ethylhexyl acrylate / dimethicone methacrylate copolymer (Acrylate / Ethylhexy Acrylate / Dimethicone Methacrylate Copol ymer).

In addition, examples of the alkyl chain silicone include triethoxysilyethyl polydimethylsiloxyethylhexyl dimethicone and triethoxysilily ethyl polydimethylsiloxyethyl dimethicone.

Examples of the alkyl silane-based coating material include trimethyl siloxy silicate, methyl hydrogen polysiloxane, hexamethyl cyclo trisiloxane, octa methyl polysiloxane, methyl cyclo polysiloxane, octa methyl cyclo tetra siloxane, decamethyl cyclo penta siloxane and tetra deca methyl cyclo hepta siloxane. , Triethoxy capryl silane and the like can be used, and the above-mentioned kind does not define the limitation of the present invention, and alkyl silane system is possible as the coating material in the present invention.

On the other hand, in order to impart water repellency to the powder, it is preferably used in combination with an alkylsilane-based coating material together with the acrylic silicone OEt of high boiling point and branched alkyl & silicone OEt.

(3) a second surface modification step of modifying the surface again using a compound including a double bond in addition to step (2)

Step (3) is a secondary surface modification step, using an alkene series containing a double bond, polysiloxane series terminal group (vinyl). The double bond present in the secondary surface modification material reacts with Si-H formed on the surface of the powder during the primary surface modification, and the secondary surface modification step controls the reaction rate by using a platinum catalyst during the reaction. . Examples of the secondary surface modifying material include 1-tetradecene, 1-dodecene, and poly (dimethylsiloxane) and vinyl terminated at the end of vinyl. .

The feature of the secondary coating step is that it is possible to suppress the generation of hydrogen gas that may be generated in the final product when the remaining Si-H group formed on the surface of the atomized powder in the first surface modification step and water repellency is increased You can do it.

Referring to the first and second surface modification step of the present invention in more detail as follows.

The specific configuration of the surface modification technology of the first and second stages using a reactor capable of mixing and pulverizing using a high pressure air stream is as follows.

① First, add an appropriate amount of fine powder to be coated in the fluidization reactor, and warm and mix and grind to be the same temperature as the material used for surface modification.

② The material to be used for the primary surface modification can be heated through the boiling point and injected through the nozzle equipped with the device that can control the pressure by adjusting the air inflow. The nozzle is connected to a tube capable of carrying the vaporized surface modification material, and is connected to a high pressure temperature adjustable spray nozzle mounted in the fluidization reactor. Inside the fluidization reactor, nozzle nozzles capable of mixing and grinding using air pressure and an injection nozzle are located outside the nozzle holes. The bottom of the reactor is open with several air controls for internal fluidization. At this time, the flow rate of the gaseous phase flowing out of the high pressure nozzle was optimal when adjusted to about 0.5 ~ 2㎏ / ㎠, it was also progressed at more than this pressure. The temperature of the powder in the reactor and the temperature of the inlet cylinder should be maintained above the boiling point of the surface modified material. The temperature of the reactor is controlled to a residence time of 2 to 3 hours while maintaining a state of 0.1 ~ 10 ℃ lower than the boiling point of the surface modified material for physical and chemical adsorption of the vaporized surface modified material. The upper part of the reactor was fitted with a filter equipped with a fine membrane to prevent the outflow of the powder sample. In addition, the filter on the upper end to check the filter state by measuring the pressure, and a damper (damper) is installed to enable a smooth fluidization inside.

③ After the first surface modification is completed by the above method, two methods are available for the second surface modification, and in the case of using the above apparatus, the second surface modification material is capable of vaporizing, and if the vaporization is impossible Use wet coating equipment. Through secondary surface modification, hydrocarbon chains having a relatively long chain length are formed on the surface of the powder, thereby exhibiting uniform and improved water repellency.

The present invention has the advantage of simplifying the process step because no process other than process control factors for fluidization of the pigment particles during the reaction process of the existing coating process step, and also due to the uniform ultra-thin film aggregation of particles Can be removed. Furthermore, by optimizing the process, unnecessary coating can be removed by using the correct amount of coating of the coating material in the reaction.

Hereinafter, although an Example and a comparative example are given and this invention is demonstrated in detail, this invention is not limited only to these examples.

Example 1 Acrylate / Tridecyl Acrylate / Triethoxysilypropyl Methacrylate / Dimethicone Methacrylate Copolymer (hereinafter, 'Coating Liquid Mixture 1') Primary surface modification)

After injecting 600 ~ 900 g of finely divided titanium dioxide, talc, mica, and sericite into the fluidization reactor, the coating solution mixture 1 represented by the following Chemical Formula 1 was added to the inlet cylinder, and then the temperature was raised to about 200 ° C. This is a temperature for vaporizing by raising the temperature above the boiling point of the coating solution mixture 1. After passing through the heating unit of the nozzle unit by using air as a carrier gas, it is vaporized to be introduced into the fluidization reactor. At this time, it flowed into the fluidization reactor at a rate of about 0.5 ~ 2.0 kg / cm ² while passing through the nozzle. The residence time in the fluidization reactor is 2 to 3 hours, and the vaporized coating solution mixture reacts with the atomized powder of Si-OEt in the main reactor to form an ultra thin film on the surface.

Example 2 Primary Surface Modification of Triethoxysilyethyl Polydimethylsiloxyethylhexyl Dimethicone (hereinafter referred to as 'Coating Liquid Mixture 2')

As in Example 1, 600 ~ 900g of the finely divided powder titanium dioxide, talc, mica, and sericite were added to the main reactor, and then the coating solution mixture 2 represented by the following Chemical Formula 2 was added to the inlet cylinder, and then the temperature was decreased. Raised to about 160 ° C. This is a temperature for vaporizing by raising the temperature above the boiling point of the coating liquid mixture 2. Air was used as the carrier gas, and after passing through the heating unit of the nozzle unit, it was vaporized and introduced into the fluidization reactor. The subsequent process was prepared in the same manner as in Example 1.

Example 3 Triethoxy caprylyl silane and acrylate / tridecyl acrylate / triethoxysilpropyl methacrylate / dimethicone methacrylate copolymer (Acrylate / Tridecyl Acrylate / Triethoxysilypropyl Methacrylate / Primary Surface Modification of Dimethicone Methacrylate Copolymer) Substrate (Triethoxy caprylyl silane (TCS) & Acryl silicon mixture) (hereinafter referred to as 'Coating Liquid Mixture 3')

After injecting 600 ~ 900 g of finely divided titanium dioxide, talc, mica, and sericite into the fluidization reactor, the coating solution mixture 3 was added to the inlet cylinder, and the temperature was raised to about 120 to 200 ° C depending on the mixing ratio. This is a temperature for vaporizing by raising the temperature above the boiling point. Air was used as the carrier gas, and after passing through the heating apparatus of the nozzle unit, the gas was vaporized and introduced into the fluidization reactor. The subsequent process was prepared in the same manner as in Example 1.

Example 4 Mixed Substrate of Triethoxy caprylyl silane and Triethoxysilylethyl polydimethyl siloxyethylhexyl dimethicone (hereinafter referred to as 'coating liquid mixture 4') Primary surface modification

After the injection of 600 ~ 900 g of finely divided titanium dioxide, talc, mica, and sericite into the fluidization reactor, the coating solution mixture 4 was added to the inlet cylinder, and the temperature was raised to about 120 to 160 ° C depending on the mixing ratio. This is a temperature for vaporizing by raising the temperature above the boiling point. Air was used as the carrier gas, and after passing through the heating apparatus of the nozzle unit, the gas was vaporized and introduced into the fluidization reactor. The subsequent process was prepared in the same manner as in Example 1.

Example 5 Secondary Surface Modification of the Primary Surface Modified Powder Using Coating Liquid Mixture 3 (Weather Coating)

About 120 g of the primary surface-modified powder prepared in Example 3 was added to the main reactor, and then 1-tetradecene was added to the inlet cylinder to perform a gasification reaction. At this time, H ₂ PtCl ₆ was used as the organometallic catalyst, and the reaction temperature was maintained at about 60 ° C.

Example 6 Secondary surface modification of the primary surface-modified powder using the coating solution mixture 4 (gas phase coating)

About 120 g of the primary surface-modified powder prepared in Example 4 was added to the main reactor, and then 1-tetradecene was added to the inlet cylinder to perform a gasification reaction. At this time, H ₂ PtCl ₆ was used as the organometallic catalyst, and the reaction temperature was maintained at about 60 ° C.

Example 7 Secondary Surface Modification of Primary Surface Modified Powder Using Coating Liquid Mixture 3 (Wet Coating)

15 g of the primary surface-modified powder prepared in Example 3 was added to a three-neck round flask, and about 45 ml of ethanol was added thereto, followed by uniform stirring. Next, 0.002 ml of H ₂ PtCl ₆ , an organometallic catalyst, was added. Next, 1-dodecene, a secondary coating material, or 0.1-0.4 mol of polydimethylsiloxane having a vinyl group introduced into the terminal group is added, followed by stirring for about 2 to 3 hours while maintaining the reaction temperature at 70 ° C. Secondary surface modification.

Example 8 Secondary Surface Modification of Primary Surface Modified Powder Using Coating Liquid Mixture 4 (Wet Coating)

15 g of the primary surface-modified powder prepared in Example 4 was added to a three-neck round flask, and about 45 ml of ethanol was added thereto, followed by uniform stirring. Next, 0.002 ml of H ₂ PtCl ₆ , an organometallic catalyst, was added. Next, 1-dodecene, a secondary coating material, or 0.1-0.4 mol of polydimethylsiloxane having a vinyl group introduced into the terminal group is added, followed by stirring for about 2 to 3 hours while maintaining the reaction temperature at 70 ° C. Secondary surface modification.

Comparative Example 1 Surface Modification of Triethoxy Caprylyl Silane (TCS)

After adding 350 g of titanium dioxide, talc, and mica to the main reactor, triethoxy caprylyl silane (TCS) was added to the inlet cylinder, and the temperature was raised to about 86 to 90 ° C. This is a temperature for vaporizing by raising the temperature above the boiling point. Inert nitrogen gas as the carrier gas is used to introduce the vaporized OTS into the main reactor. At this time, while passing through the nozzle was introduced into the main reactor at a speed of about 100 ~ 150m / sec. The residence time in the main reactor is 2 to 3 hours, and the vaporized TCS reacts with the atomized pigments in the main reactor to form SH groups on the surface.

Comparative Example 2 Secondary Surface Modification of the Primary Surface Modified Powder

About 120 g of the primary surface-modified powder prepared in Comparative Example 1 was introduced into the main reactor, and then 1-tetradecene was introduced into the inlet cylinder to perform a gasification reaction. At this time, H ₂ PtCl ₆ was used as the organometallic catalyst, and the reaction temperature was maintained at about 60 ° C.

Comparative Example 3 Secondary Surface Modification of the Primary Surface Modified Powder (Wet Coating)

15 g of the first surface-modified powder with TCS prepared in Comparative Example 1 was added to a three-neck round flask, and about 45 ml of ethanol was added thereto, followed by uniform stirring. Next, 0.002 ml of H ₂ PtCl ₆ , an organometallic catalyst, was added. Next, 1-dodecene, a secondary coating material, or 0.1-0.4 mol of polydimethylsiloxane having a vinyl group introduced into the terminal group is added, followed by stirring for about 2 to 3 hours while maintaining the reaction temperature at 70 ° C. Secondary surface modification.

[Test Example 1] Water repellency comparison

In the above example, the water repellency after primary surface modification was compared with respect to the powder typically used in cosmetics. As a typical powder, water repellency after primary surface modification using the gas phase reaction of titanium dioxide, talc, and mica was compared.

The water repellency was measured using the contact angle, and the contact angle was measured as follows.

<Contact angle measurement method>

Contact angle is a measure of the wettability of a solid surface and is mostly measured by water droplets that are stuck. Low contact angles show high wettability (hydrophilic) and high surface energy, while high contact angles show low wettability (hydrophobic) and low surface energy. The contact angle of the liquid in contact with the flat solid surface is measured at the end point of the droplet curve at the liquid-solid-gas junction and the contact point of the solid surface.

The measuring principle of the contact angle is shown in FIG. 1.

First, the solid surface must be flat to measure the contact angle. The droplet then drops onto the solid surface. The diameter of the water droplets should normally be in the range of several millimeters. The double-sided adhesive film having excellent shear adhesion is fixed to the slide glass, and each primary surface-modified sample is measured by molding a flat plate.

The measurement results are shown in Table 1 below. In addition, the contact angle results of the Example 5 and 6 powders secondary surface-modified using the first surface-modified powder are shown in Table 2 below.

Contact angle measurement comparison Contact angle (°) Titanium dioxide Talc Mica Untreated 70 78 10 Comparative Example 1 121.4 110.5 115.3 Example 1 127.9 130.3 121.5 Example 2 137.7 144.9 136.7 Example 3 125.4 125.9 120.7 Example 4 130.7 134.2 130.1

As can be seen in Table 1, all of the first surface-modified powders compared to the untreated micronized powders were all significantly increased in water repellency. In terms of water repellency, the alkyl chain silicone (branched alkyl & silicone OEt) series was found to be somewhat higher than the acrylic silicone OEt series, and the mixtures with alkyl silanes had a smaller water repellency than the stock solution.

Contact angle measurement comparison Contact angle (°) Titanium dioxide Talc Mica Example 5 127.6 128.9 123.2 Example 6 132.7 136.2 131.2 Example 7 125.1 127.5 121.3 Example 8 130.7 134.2 130.2

As can be seen in Table 2, as a result of the secondary surface modification, it was found that the water repellency was improved as compared with the first surface-modified powder, and the gas phase coating method was found to have higher water repellency than the wet method. This confirmed that the reaction on the surface of the powder occurred more uniformly in the gas phase method compared to the wet method.

[Test Example 2] feeling comparison

The feeling of use was the biggest factor, and the comparison was made by dividing it into parts about adhesion and spreading force. These two factors were measured using a rheometer, and the spreading force was measured by the friction g force (g1) between the initial primary rubber and the coated surface, and the adhesion was measured after the first measurement. Using g force (g2) at the time, it was expressed as Δ (g1-g2) / g1 * 100. The smaller the measured value g1 of the spreading force and the measured adhesive force value? (G1-g2) / g1 * 100 are, the more significant the values are. The measurement results are shown in Tables 3 and 4 below.

Usability measurement comparison (primary coating material) division Titanium dioxide Talc Mica Feeling Adhesion Spreadability Adhesion Spreadability Adhesion Spreadability Untreated 7 150 7.5 135 5 110 Comparative Example 1 6.0 130 6.5 120 4.5 100 Example 1 5.0 135 5.0 120 4.0 105 Example 2 6.2 120 6.4 108 4.7 95 Example 3 4.5 130 6.0 115 4.5 100 Example 4 6.3 124 6.4 105 4.8 91

As can be seen in Table 3, the base surface treated with 'coating liquid mixture 1' was the greatest improvement for all the inorganic powders in terms of adhesion, and the base surface treated with 'coating liquid mixture 2' in terms of spreading force. The improvement was good.

Usability Measurement Comparison (Secondary Coating Material) division Titanium dioxide Talc Mica Feeling Adhesion Spreadability Adhesion Spreadability Adhesion Spreadability Comparative Example 2 6.3 131 6.5 122 4.2 100 Comparative Example 3 6.4 135 6.8 129 4.4 105 Example 5 4.4 124 6.0 110 4.1 94 Example 6 6.0 130 6.0 108 4.4 97 Example 7 4.5 128 6.2 114 4.5 103 Example 8 6.4 124 6.5 110 4.7 94

As can be seen in Table 4, there is no significant change after the first coating and then the second coating, but overall, 1-tetradecene in the secondary coating material showed better adhesion than 1-dodecene.

On the other hand, the cosmetic composition of the present invention is not particularly limited in the formulation, for example, supple cosmetics, astringent cosmetics, nourishing cosmetics, nutrition cream, essence, eye cream, body lotion, body cream, body gel, foundation, It may be a cosmetic formulation having a formulation of a makeup base, face powder, lipstick, lip gloss, lip liner, mascara eyebrow, eye shadow, nail enamel, hair foam, hair cream or hair mascara.

Formulation Example 1 Preparation of Nail Enamel

Name Content (% by weight) 1.Nitrocellulose 15 2.polyester copolymer 10 3.perfluoroalkyl silicone 10 4.butyl acetate 30 5.ethyl acetate TO 100 6.isopropyl alcohol 10 7.tributyl acetyl citrate 5 8.Hectorite One 9.Examples 5-8 10 10. Pigment 7

Formulation Example 2 Preparation of Lipstick

Name Content (% by weight) 1. Candelilla Wax 10.0 2. Beeswax 5.0 3. Isopropyl palmitate 5.0 4. Polyglyceryl-2-triisosterate 8.0 5. Caprylic / Capric Triglycerides 10.0 6. Castor Oil TO 100 7. Hydrogenated Polyisobutene 15.0 8. Phenyl Trimethicone 5.0 9.C10-11 Isoparaffin 2.0 10. Octyl Dodecanol 5.0 11.Examples 5-8 5 12. Iron Oxide 5 13.D / C RED No.7 CALCIUM LAKE handful 14.FD & C YELLOW NO.5 ALUMINUM-LAKE handful 15. Butylparaben handful 16. Spices handful

Formulation Example 3 Preparation of Water-in-oil Emulsified Pearl Foundation

Name Content (% by weight) 1. Ceresin 3.0 2. Candelilla Wax 3.0 3. Sesquioleic acid sorbitan 2.0 4. Octyl Palmitate 10.0 5. Floating Paraffin TO 100 6. Dimethicone 10.0 7. Titanium Dioxide 20.0 8. Examples 5-8 5.0 9. Ferric Oxide 4.0 10.Yellow Iron Oxide 5.0 11.Black Iron Oxide 1.0 12.purified water 20.0 13.collagen 2.0 14.Aluminum Sulfate 0.1 15.Fragrance handful

Formulation Example 4 Preparation of Face Powder (Powder Pact)

Ingredient Name Content (% by weight) Talc To 100 2. Examples 5-8 5.0 3. nylon powder 5.0 4. Titanium Dioxide 5.0 5. Mica 15.0 6. Ferric Oxide 0.4 7. Yellow Iron Oxide 1.0 8. Black Iron Oxide 0.2 9. Squalene 2.0 10. Meadowfoam seed oil 2.0 11. Preservative handful 12. Spices handful

As described above, the present invention provides a surface of an organic or inorganic particle through a gas phase reaction using a high boiling point acrylic silicone OEt series and an alkyl chain silicone (branched alkyl & silicone OEt) and a relatively low boiling point alkyl silane. As a method for producing powder modified with this water-repellent ultrathin layer, various base materials having a high boiling point can be used as surface treatments as they are stably maintained at a high temperature as compared to low boiling points, and they are used as materials of polymers in a base of low molecular weight limited properties. There is an effect of varying the width, and also widens the screening of materials having desired properties.

That is, although the base to be used relatively limited in the past, the present invention can be selectively surface-treated by designing the desired materials for the feeling of use, such as adhesion and spreadability other than water repellency. In addition, the analysis of the surface treatment bases can be compared and examined through the areas of water repellency, adhesion, and spreadability to secure a correlation with a wider range of bases.

Claims (10)

(1) grinding the powder to be surface modified to a uniform particle size; (2) a first surface modification step of adsorbing a vaporized water repellent by vaporizing a water repellent on the surface of the powder having a uniform uniform particle size; And (3) a second surface modification step of modifying the surface again by using a compound including a double bond in addition to step (2); In the manufacturing method of the powder surface-modified surface comprising a water-repellent ultra-thin layer, Examples of the water repellent include acrylate / tridecyl acrylate / triethoxysilyl methacrylate / dimethicone methacrylate copolymer (Acrylate / Tridecyl Acrylate / Triethoxysilypropyl Methacrylate / Dimethicone Methacrylate Copolymer), acrylate / dimethicone copolymer ( Acrylate / Dimethicone Copolymer, Acrylate / Dimethicone Acrylate / Ethylhexyl Acrylate Copolymer, Acrylate / Stearyl Acrylate / Dimethicone Acrylate Copolymer / Dimethicone Acrylate Copolymer, Acrylate / Behenyl Acrylate / Dimethicone Acrylate Copolymer, and Acrylate / Ethyl Hexyl Acrylate / Dimethicone Methacrylate Copolymer (Acrylate / Ethylhexyl) Group consisting of Acrylate / Dimethicone Methacrylate Copolymer At least one high boiling point acrylic silicone (acryl silicone OEt) compound selected from; Or an alkyl chain silicone compound which is triethoxysilyethyl polydimethylsiloxyethylhexyl dimethicone or triethoxysilyethyl polydimethylsiloxyethyl dimethicone Using; The compound containing the double bond is characterized in that the powder surface is selected from the group consisting of 1-tetradecene, 1-dodecene, and poly (dimethylsiloxane) at the end of vinyl group. A method for producing powder surface-modified with a water repellent ultrathin layer. delete delete According to claim 1, wherein the water repellent of the step (2) is a method of producing a powder surface-modified with a water-repellent ultra-thin layer, characterized in that to use a further mixture of alkylsilane. The method of claim 4 wherein the alkyl silane is trimethyl siloxy silicate, methyl hydrogen polysiloxane, hexamethyl cyclo trisiloxane, octa methyl polysiloxane, methyl cyclo polysiloxane, octa methyl cyclo tetra siloxane, decamethyl cyclo penta siloxane, tetra deca methyl A method for producing powder whose surface is modified with a water-repellent ultrathin layer, wherein the powder surface is at least one selected from the group consisting of cyclohepta siloxane and triethoxy capryl silane. The powder of claim 1, wherein the temperature of the reactor is controlled to a residence time of 2 to 3 hours while maintaining a temperature of 0.1 to 10 ° C lower than the boiling point of the water repellent agent for physical and chemical adsorption of the vaporized water repellent agent. A method for producing powder whose surface is surface modified with a water repellent ultrathin layer. According to claim 1, wherein the vaporized water repellent is introduced into the reactor through a nozzle in which the air flow rate is controlled, the flow rate of the gas phase flowing out of the nozzle is 0.5 ~ 2kg / ㎠ The powder surface characterized in that the manufacturing method of the powder surface modified with a water-repellent ultra-thin layer. The method of claim 1, wherein an alkene-based or siloxane-based terminal group is used as the compound of the double bond, and the surface of the powder is surface-modified with a water-repellent ultrathin layer. delete Cosmetic composition containing the powder manufactured by any one of Claims 1-4.

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