KR101116596B1 - Hybrid powder of halloysite nanotube-light scattering nanoparticle, method for preparing the same and cosmetic composition comprising the same for uv protection - Google Patents

Abstract

PURPOSE: A cosmetic composition containing hybrid powder of halloysite nanotube-light scattering nanoparticles is provided to prevent penetration of light scattering nanoparticles into the skin. CONSTITUTION: A method for preparing hybrid powder of halloysite nanotube-light scattering nanoparticles comprises: a step of putting titanium dioxide(TiO_2) in distilled water and dispersing by ultrasonic wave to prepare a colloid solution; a step of adding halloysite nanotube powder to the colloid solution; a step of performing vacuum pulling; a step of centrifuging to collect hybrid powder; and a step of washing and drying the hybrid powder. A cosmetic composition for blocking UV ray contains the hybrid powder as an active ingredient.

Description

Hybrid powder of halloysite nanotube-light scattering nanoparticle, method for preparing the same and cosmetic composition comprising the same for UV protection}

The present invention relates to a hybrid powder of halosite nanotube-light scattering nanoparticles, a method for preparing the same, and a cosmetic composition for sunscreen containing the same as an active ingredient.

Titanium dioxide (TiO ₂ ) nanoparticles, which are currently used as a main ingredient of sunscreens, are known to have a larger UV blocking effect as their size is smaller (below 30 nm). In addition to commercially available skin care creams and lotions, make-up foundations, BB creams, and even lip protectants contain sunscreen ingredients. However, when a lotion containing titanium dioxide nanoparticles is rubbed onto the skin wound by sunburn or acne, it may penetrate into the body through the skin and may have a harmful effect on the human body. In addition, titanium dioxide nanoparticles have been found to be toxic to humans through animal experiments, and the National Institute of Occupational Safety and Health (NIOSH) proposes a dose tolerance (0.1 mg / m 2).

Therefore, there is increasing interest in a method that can reduce the side effects of using titanium dioxide nanoparticles as an active ingredient of a sunscreen.

Halloysite is a material represented by Al ₂ Si ₂ O ₅ (OH) _{4 to} 2H ₂ O, and is an aluminum silicate clay mineral having a 1: 1 ratio of aluminum to silicon. The halosite is a nano-sized plate-like structure, in which different layers have a layered structure in which 1: 1 is alternately present, and is naturally present in aluminosilicates. The outer surface of the halosites consists of a silicate (SiO ₂ (−)) layer and the inner surface consists of an alumina (Al ₂ O ₃ (+)) layer. The halosite is a hollow nanotube structure. The inner diameter of the tube is 30-250 nm and the length is 0.2-0.4 μm, which shows excellent carrier properties. In addition, since the halosite is a natural mineral that is harmless to the human body, there is no problem in environmental pollution or human hazards at the time of application, and thus has excellent utility as a carrier. Therefore, nano-sized tubular halosite is used as a carrier for transporting perfume, cosmetics and drugs as a container for loading active substances.

However, there are no developments or studies on hybrid powders in which light scattering nanoparticles are loaded in the halosite nanotubes.

Therefore, if light scattering nanoparticles are loaded into the halosite nanotubes and used as a sunscreen agent, the side effects appearing on the skin may be reduced or eliminated. Therefore, there is an urgent need for the development of hybrid powders in which light scattering nanoparticles are loaded in the halosite nanotubes.

The inventors of the present invention while researching a material having excellent UV protection effect while minimizing the side effects on the skin, to produce a hybrid powder by loading light scattering nanoparticles in the halosite nanotubes, the UV blocking rate of the prepared hybrid powder is pure halogen It confirmed that it appeared better than a site, and completed this invention.

Accordingly, the present invention is to provide a hybrid powder of the halosite nanotube-light scattering nanoparticles, a method for preparing the same, and a cosmetic composition for sunscreen containing the same as an active ingredient.

The present invention provides a hybrid powder of halosite nanotube-light scattering nanoparticles, characterized in that light scattering nanoparticles are loaded into a halosite nanotube.

In addition,

1-1) preparing a colloidal solution by dispersing light scattering nanoparticles in distilled water by ultrasonic wave, and

1-2) adding the halosite nanotube powder to the colloidal solution prepared in step 1-1), vacuum pulling, and centrifuging to recover the hybrid powder, and washing and drying. It provides a method for producing a hybrid powder of the halosite nanotube-light scattering nanoparticles.

In addition,

2-1) Add halosite nanotube powder to light scattering nanoparticle precursor solution or light scattering nanoparticle precursor solution and halosite nanotube powder to hydrochloric acid solution Recovering, and

2-2) The hybrid powder recovered in step 2-1) is dispersed in a hydrochloric acid solution, stirred at 40-90 ° C. for 0.5-5 hours, the reaction solution is cooled to room temperature, and centrifuged to recover the hybrid powder. It provides a method for producing a hybrid powder of halosite nanotubes-light scattering nanoparticles, including washing and drying.

In addition, the present invention provides a cosmetic composition for sunscreen containing the hybrid powder of the halosite nanotubes-light scattering nanoparticles as an active ingredient.

Hereinafter, the present invention will be described in detail.

The hybrid powder of the halosite nanotube-light scattering nanoparticles according to the present invention is characterized by loading light scattering nanoparticles in the halosite nanotubes.

The light scattering nanoparticles include, but are not limited to, one or more selected from the group consisting of titanium dioxide (TiO ₂ ), zinc oxide (ZnO), Fe ₂ O _3, and Fe ₃ O ₄ .

The preparation method of the hybrid powder of the halosite nanotube-light scattering nanoparticles according to the present invention can be largely prepared by two methods.

The first method is a colloidal method in which light scattering nanoparticles are directly supported in halosite nanotubes. Specifically, colloidal solution is prepared by dispersing the light scattering nanoparticles in distilled water by ultrasonic wave, and then adding the halosite nanotube powder, vacuum pulling, and centrifuging to recover the hybrid powder. Wash with distilled water and dry.

The second method is to generate light scattering nanoparticles in the halosite nanotubes by first supporting the light scattering nanoparticle precursors in the halosite nanotubes. Specifically, the halosite nanotube powder is added to the light scattering nanoparticle precursor solution or the light scattering nanoparticle precursor solution and the halosite nanotube powder are added to the hydrochloric acid solution, followed by vacuum pooling, followed by centrifugation to hybrid powder. Is collected and washed with anhydrous ethanol. The recovered hybrid powder was dispersed in a hydrochloric acid solution and stirred at 40 to 90 ° C. for 0.5 to 5 hours, preferably at 60 ° C. for 3 hours, and then the reaction solution was cooled to room temperature and centrifuged to recover the hybrid powder. 1 Wash with aqueous solution and distilled water and dry.

The light scattering nanoparticle precursors include, but are not limited to, titanium tetraisopropoxide (TTIP), zinc chloride (ZnCl ₂ ), FeCl ₂ , FeCl ₃ , and the like.

The hybrid powder of the halosite nanotube-light scattering nanoparticles prepared by the above method exhibits a higher UV blocking rate than the pure halosite nanotubes. In particular, in the case of the hybrid powder manufactured using the colloidal method, the UV blocking rate is highest, which is because the light scattering nanoparticles are adsorbed not only on the inside but also on the outer surface of the halosite nanotubes. In addition, regardless of the size of the halosite nanotubes, the UV blocking rate of the hybrid powder is almost the same.

As described above, the hybrid powder of the halosite nanotube-light scattering nanoparticles according to the present invention loads the light scattering nanoparticles into the halosite nanotubes, thereby preventing the light scattering nanoparticles from penetrating the skin to minimize side effects. It has excellent UV protection effect. Therefore, the hybrid powder of the halosite nanotube-light scattering nanoparticles according to the present invention can be usefully used in the cosmetic composition for UV protection.

The cosmetic composition of the present invention may contain one or more known active ingredients having UV-blocking activity together with the hybrid powder of the halosite nanotube-light scattering nanoparticles.

In addition, the cosmetic composition of the present invention may be prepared in cosmetic formulations commonly prepared in the art including one or more cosmetically acceptable carriers in addition to the above-described active ingredients. Specifically, fatty substances, organic solvents, solubilizers, thickeners, gelling agents, softeners, antioxidants, suspending agents, stabilizers, blowing agents, fragrances, surfactants, water, ionic or nonionic emulsifiers, fillers, metal ions Containment and chelating agents, preservatives, vitamins, blockers, wetting agents, essential oils, dyes, pigments, hydrophilic or lipophilic active agents, lipid vesicles or any other ingredients commonly used in cosmetics, and those commonly used in the cosmetic field It may be formulated into solutions, suspensions, emulsions, pastes, gels, creams, lotions, powders, soaps, surfactant-containing cleansing oils, powder foundations, emulsion foundations, wax foundations and sprays, etc. It is not limited to this. More specifically, it may be prepared in the form of a flexible lotion, nutrition lotion, milk lotion, nutrition cream, massage cream, essence, eye cream, cleansing cream, cleansing foam, cleansing water, pack, spray or powder.

The content of the hybrid powder of the halosite nanotube-light scattering nanoparticles in the cosmetic composition of the present invention may include 0.01 to 25% by weight, preferably 0.1 to 5% by weight, based on the total weight of the cosmetic composition. If the content of the hybrid powder of the halosite nanotube-light scattering nanoparticles is less than 0.01% by weight, it is difficult to exhibit the sunscreen effect, and if it exceeds 25% by weight, it is highly likely to cause irritation to the skin and greatly affects the stabilization of the formulation. Can have

Hybrid powder of the halosite nanotube-light scattering nanoparticles according to the present invention by loading the light scattering nanoparticles in the halosite nanotubes, can prevent the light scattering nanoparticles penetrate the skin to minimize side effects and UV protection The effect is excellent.

1 is a schematic diagram showing a hybrid powder of halosite nanotube-light scattering nanoparticles according to the present invention.
Figure 2 is a simplified view showing the manufacturing process of the hybrid powder of the halosite nanotube-light scattering nanoparticles according to the present invention.
Figure 3 is a diagram showing the UV blocking rate of the hybrid powder of the halosite nanotube-titanium dioxide nanoparticles according to the present invention.
4 is a view showing a scanning electron microscope (SEM) observation result of the hybrid powder of the halosite nanotube-titanium dioxide nanoparticles according to the present invention.
5 is a view showing the total UV blocking rate obtained by integrating the UV blocking rate of the hybrid powder of the halosite nanotube-titanium dioxide nanoparticles according to the present invention in the ultraviolet (UV-B, UV-A) wavelength range.
Figure 6 is a diagram showing the UV blocking rate of the hybrid powder of the halosite nanotubes-titanium dioxide nanoparticles according to the size distribution of the halosite nanotubes.
7 is a view showing a scanning electron microscope (SEM) observation result of the hybrid powder of the halosite nanotubes-titanium dioxide nanoparticles according to the size distribution of the halosite nanotubes.

Hereinafter, preferred embodiments of the present invention will be described in order to facilitate understanding of the present invention. However, the following examples are provided only for the purpose of easier understanding of the present invention, and the present invention is not limited by the examples.

Example  One  : Colloid method  Used Halloysite  Of nanotube-titanium dioxide nanoparticles hybrid  Manufacture of powder

The colloidal method is a method of directly supporting separately prepared titanium dioxide nanoparticles in the halosite nanotubes.

Specifically, 1 M HCl (80 mL) was added to a 250 mL beaker, and TTIP (titanium tetraisopropoxide) (20 mL) was slowly added with stirring using a magnetic bar, followed by stirring at 60 ° C. for 3 hours. When the titanium dioxide nanoparticles were produced, the solution was cooled to room temperature and centrifuged (10000 rpm, 3 minutes) to recover the particles. The recovered titanium dioxide nanoparticles were placed in distilled water (20 ml) and dispersed in ultrasonic waves for 30 minutes to make a colloidal state. Then, halosite nanotube powder (3 g) was added thereto and vacuum pulled. Then, the hybrid powder was recovered by centrifugation, washed twice with an aqueous solution of pH 1, once with distilled water, and then dried at 60 ° C.

Example  2  : TTIP Solution method  Used Halloysite  Of nanotube-titanium dioxide nanoparticles hybrid  Manufacture of powder

The TTIP solution method is a method in which a TTIP solution is first loaded into a halosite nanotube, and then the powder is added to an HCl solution to produce titanium dioxide nanoparticles into the halosite nanotube.

Specifically, the halosite nanotube powder (3 g) was put into a TTIP solution (20 ml) and vacuum-pulled. The powder was then recovered by centrifugation and washed once with anhydrous ethanol. The recovered powder was dispersed in 1M HCl solution (80 mL) and stirred at 60 ° C. for 3 hours. The reaction solution was cooled to room temperature and then centrifuged to recover the hybrid powder, washed once with an aqueous pH 1 solution and once with distilled water, and then dried at 60 ° C.

Example  3  : TTIP - HCl Solution method  Used Halloysite  Of nanotube-titanium dioxide nanoparticles hybrid  Manufacture of powder

The TTIP-HCl solution method is a method of producing titanium dioxide nanoparticles in a halogenated nanotube by adding a halogenated nanotube in the middle of synthesizing the titanium dioxide nanoparticles.

Specifically, TTIP solution (20 mL) was added to 1 M HCl solution (80 mL), stirred at 60 ° C., and after 30 minutes, halosite nanotube powder (3 g) was added and vacuum-pulled. The powder was then recovered by centrifugation and washed once with anhydrous ethanol. The recovered powder was dispersed in 1M HCl solution (80 mL) and stirred at 60 ° C. for 3 hours. The reaction solution was cooled to room temperature and then centrifuged to recover the hybrid powder, washed once with an aqueous pH 1 solution and once with distilled water, and then dried at 60 ° C.

Experimental Example  One  : According to the present invention Halloysite  Measurement of UV Blocking Rate of Hybrid Powder of Nanotube-Titanium Dioxide Nanoparticles

In order to calculate the UV blocking rate of the hybrid powder of the halosite nanotube-titanium dioxide nanoparticles according to the present invention, the following experiment was performed.

Specifically, the hybrid powder of the halosite nanotube-titanium dioxide nanoparticles prepared in Examples 1 to 3 was added to distilled water and diluted to 0.0025% by weight to prepare a measurement sample. The sample was injected into a 1 cm path distance quartz cuvette and placed in a spectrometer. Then, the light transmittance of the sample was measured in the 250 ~ 500nm wavelength region using a UV / Vis spectrometer (UV-vis Spectrometer, Scinco, Korea, Model S3100). Using the measured light transmittance, the absorption rate of the measurement sample was calculated by Equation 1 by the Beer-Lambert method. If the concentration and the path distance of the nanoparticles are constant, the absorbance ( A ) and the absorbance ( ε ) are proportional, and thus the absorbance between samples can be quantitatively compared.

In addition, the UV blocking rate of the hybrid powder of the halosite nanotube-titanium dioxide nanoparticles prepared in Examples 1 to 3 was integrated in the ultraviolet (UV-B, UV-A) wavelength range to obtain the total UV blocking rate.

※ A : absorbance, ε : extinction coefficient,

c is the concentration of nanoparticles, l is the path length through which light passes through the sample,

I ₀ : initial luminance of light, I : intensity of light after passing through the sample,

I / I ₀ : Transmittance.

Ultraviolet ray blocking rate and scanning electron microscope (SEM) observation results of the hybrid powder of the halosite nanotube-titanium dioxide nanoparticles according to the present invention are shown in FIGS. 3 and 4, respectively. The total UV blocking rate obtained by integrating the UV blocking rate of the hybrid powder in the ultraviolet (UV-B, UV-A) wavelength range is shown in FIG. 5.

As shown in FIG. 3 and FIG. 4, when titanium dioxide nanoparticles were directly supported in the halosite nanotubes by using the colloid method (Example 1), the UV blocking rate was higher than that of pure halosite nanotubes. Next, TTIP-HCl solution method was used to support the TTIP and hydrochloric acid together to produce nanoparticles inside the halosite nanotubes (Example 3), followed by the TTIP method (Example 2). This is because the titanium dioxide nanoparticles are adsorbed not only on the inside of the halosite but also on the outer surface of the colloid method, and the hydrolysis reaction proceeded more efficiently than the TTIP solution method using the TTIP-HCl solution method. do.

In addition, as shown in Figure 5, when the titanium dioxide nanoparticles are directly supported in the halosite nanotubes by using the colloid method (Example 1) 17.2% improved UV blocking rate in the entire ultraviolet region compared to the pure halosite nanotubes (A = 17.6). This means that increasing the concentration of the hybrid colloid by 3.2 times (0.008% by weight) yields the same UV protection rate (A = 56.1) as that of the colloid (0.0025% by weight) composed of titanium dioxide nanoparticles alone.

Experimental Example  2  : Halloysite  Depending on the size distribution of the nanotubes Halloysite  Of nanotube-titanium dioxide nanoparticles hybrid  UV protection rate of powder

In Example 1, the halosite nanotubes were not classified by ① size, halloysite (mixed halloysite), ② halosite having a submicron size distribution (fine halloysite, 0.2-1.0 μm), and ③ having a size distribution of more than microns A hybrid powder of halosite nanotube-titanium dioxide nanoparticles was prepared using the colloid method using a coarse halloysite (1.0-8.0 μm). The UV blocking rate of the hybrid powder of the prepared halosite nanotube-titanium dioxide nanoparticles was measured in the same manner as in Experimental Example 1.

The UV blocking rate and the scanning electron microscope (SEM) observation results of the hybrid powder of the halosite nanotube-titanium dioxide nanoparticles according to the size distribution of the halosite nanotubes are shown in FIGS. 6 and 7, respectively.

As shown in Figure 6 and 7, regardless of the size of the halosite nanotubes, the UV blocking rate of the hybrid powder appeared almost the same. It is thought that this is because in the case of the halosite having a micron size distribution, the titanium dioxide nanoparticles are supported in the halosite nanotubes, and then the titanium dioxide nanoparticles are released to the outside and adsorbed on the outer surface of the halosite.

The preparation example for the cosmetic composition of this invention is illustrated below.

Formulation example  One  : Preparation of flexible lotion

ingredient Content (% by weight) Hybrid powder of halosite nanotube-titanium dioxide nanoparticles 0.5 1,3-butylene glycol 5.2 Oleyl alcohol 1.5 ethanol 3.2 Polysorbate 20 3.2 Benzophenone-9 2.0 Carboxyl Vinyl Polymer 1.0 glycerin 3.5 incense a very small amount antiseptic a very small amount Purified water Balance system 100

After mixing the above components, it was prepared in accordance with the conventional method for producing a flexible lotion.

Formulation example  2  : Milk croissant  Produce

ingredient Content (% by weight) Hybrid powder of halosite nanotube-titanium dioxide nanoparticles 0.6 glycerin 5.1 Propylene glycol 4.2 Tocopheryl acetate 3.0 Liquid paraffin 4.6 Triethanolamine 1.0 Squalane 3.1 Macadamia Nut Oil 2.5 Polysorbate 60 1.6 Sorbitan sesquioleate 1.6 Propylparaben 0.6 Carboxyl Vinyl Polymer 1.5 incense a very small amount antiseptic a very small amount Purified water Balance system 100

After mixing the above components, it was prepared in accordance with the conventional method for producing a milk lotion.

Formulation example  3  : Manufacture of nutrition cream

ingredient Content (% by weight) Hybrid powder of halosite nanotube-titanium dioxide nanoparticles 1.0 glycerin 4.0 vaseline 3.5 Triethanolamine 2.1 Liquid paraffin 5.3 Squalane 3.0 Beeswax 2.6 Cotoperyl Acetate 5.4 Polysorbate 60 3.2 Carboxyl Vinyl Polymer 1.0 Sorbitan sesquioleate 3.1 incense a very small amount antiseptic a very small amount Purified water Balance system 100

After mixing the above components, it was prepared in accordance with the conventional manufacturing method of nutrition cream.

Claims (8)

A hybrid powder of halosite nanotubes-light scattering nanoparticles, characterized in that titanium dioxide (TiO ₂ ), which is a light scattering nanoparticle, is loaded into a halosite nanotube. delete 1-1) preparing a colloidal solution by dispersing light scattering nanoparticles titanium dioxide (TiO ₂ ) in distilled water by ultrasonic wave, and
1-2) adding the halosite nanotube powder to the colloidal solution prepared in step 1-1), vacuum pulling, and centrifuging to recover the hybrid powder, and washing and drying. , Method for producing hybrid powder of halosite nanotube-light scattering nanoparticles. 2-1) Add halosite nanotube powder to TTIP (titanium tetraisopropoxide) solution as light scattering nanoparticle precursor or TTIP (titanium tetraisopropoxide) solution and halosite nanotube powder as hydrochloric acid solution Recovering the hybrid powder by addition, vacuum pooling, followed by centrifugation, and
2-2) The hybrid powder recovered in step 2-1) is dispersed in a hydrochloric acid solution, stirred at 40-90 ° C. for 0.5-5 hours, the reaction solution is cooled to room temperature, and centrifuged to recover the hybrid powder. Method for producing a hybrid powder of halosite nanotubes-light scattering nanoparticles, comprising the step of washing and drying. delete delete The cosmetic composition for sunscreen containing a hybrid powder of the halosite nanotube-light scattering nanoparticles of claim 1 as an active ingredient. According to claim 7, Content of the hybrid powder of the halosite nanotube-light scattering nanoparticles is characterized in that 0.01 to 25% by weight based on the total weight of the cosmetic composition, the cosmetic composition for sunscreen.

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