KR102548209B1 - A Cosmetic Composition for Blocking High Energy Radiation in a Wide Range of Wavelengths and Preventing Fine Dusts Comprising Core-Shell Particles having a Coating Layer Containing Nanomaterials - Google Patents

Abstract

It relates to a cosmetic composition for blocking high energy rays and preventing fine dust comprising core-shell particles surface-modified with a coating layer containing nanomaterials, wherein the core of the core-shell particles is bismuth (Bi), vanadium (V), hafnium (Hf), barium (Ba), tantalum (Ta), cerium (Ce), and/or tungsten (W), and at least one oxide, nitride, halide, and/or sulfide of one or more elements selected from The shell of the core-shell particle includes one or more oxides, nitrides, halides, and/or sulfides of one or more elements selected from titanium (Ti), zinc (Zn), copper (Cu), and silicon (Si). The nanomaterial coating layer is composed of nanomaterials and a coating agent, and has excellent UV-A and UV-B blocking effects, as well as showing an effect in blocking X-rays, and at the same time, the effect of preventing fine dust is also excellent. .

Description

Cosmetic Composition for Blocking High Energy Radiation in a Wide Range of Wavelengths and Preventing Fine Dusts Comprising Core-Shell Particles having a Coating Layer Containing Nanomaterials}

The present invention relates to a cosmetic composition for blocking high energy rays and preventing fine dust.

The present invention relates to a cosmetic composition for blocking high energy rays and preventing fine dust.

Republic of Korea Patent Publication No. 10-2007-0001262 WO 2016/151537 Republic of Korea Patent Registration No. 10-1575591 Republic of Korea Patent Publication No. 10-1410043 Korean Patent Publication No. 10-1710907 Republic of Korea Patent Publication No. 10-2017-0106062 Republic of Korea Patent Publication No. 10-2020-0168538 Republic of Korea Patent Publication No. 10-2022-0012118

(Non-Patent Document-0001) Chen, Jinyu, et al. "Large-scale synthesis of p?n heterojunction Bi2O3/TiO2 nanostructures as photocatalysts for removal of antibiotics under visible light." ACS Applied Nano Materials 5.1 (2021): 1296-1307. (Non-Patent Document-0002) Yoon, Hyewon, et al. "Extraordinary enhancement of UV absorption in TiO2 nanoparticles enabled by low-oxidized graphene nanodots." The Journal of Physical Chemistry C 122.22 (2018): 12114-12121.

The most common type of high-energy electromagnetic waves found in the environment around us is ultraviolet rays from sunlight, and sunscreens have the most important purpose of blocking the skin from these ultraviolet rays. UV-A (320 ~400nm), UV-B (280~320nm), and UV-C (100~280nm). Electromagnetic waves have higher energy as the wavelength is shorter, but UV-C and shorter wavelength high-energy rays reaching the earth from sunlight are mostly absorbed by the ozone layer in the stratosphere and reach the ground if the ozone layer is not destroyed. the amount is insignificant

Most of UV-B is also absorbed by the ozone layer, but some of it reaches the surface. When too much of it is irradiated to human or animal skin, the molecular bonds formed between the double helix structures of DNA are broken, DNA is deformed, and damage accumulates. Even if some of it is restored, the possibility of mutation or skin cancer increases. It can also lower the immune system and cause damage to the eyes and internal organs of the body. In addition, UV-A is usually not absorbed by the ozone layer and reaches the surface, but there is also a study that makes the skin red and may cause various skin cancers when exposed for a long time.

Cosmetic compositions that block UV-A and UV-B have undergone many studies and patent applications (Patent Documents 1 to 8 and Non-Patent Documents 1 and 2), and inorganic or organic sunscreens, which are mainly used sunscreens, are In many cases, the scope of blocking is limited. For example, titanium dioxide, a typical sunscreen, absorbs only the UV-B range intensively, but recently, in order to overcome this, many new organic or inorganic UV absorbers have been developed that cover UV-A and UV-B ranges, providing high UV rays in a wide range. Ingredients having a blocking effect are also being developed.

In general, there is no need to worry about high-energy rays with shorter wavelengths than UV-A and UV-B. In addition to ultraviolet rays from the sun, such as ultraviolet rays from the sun, there are cases where damage caused by high-energy rays cannot be ignored due to human-made or environmental influences. could be a potential risk factor. In particular, people working in medical institutions and research institutes and nuclear power plants that handle radioactive materials are at high risk of being exposed to high-energy rays from radioactive materials in their daily work environments. It remains in every corner of the surrounding facilities in combination with the back, and damage can occur due to continuous exposure to radiation. Although they are protected by special regulations, such as restrictions on working hours, there is no difference in sensitivity to radiation depending on the individual, so even in situations where there is no general concern, a blocker with high energy ray blocking effect is usually used. need to be developed and provided.

On the other hand, as another factor that threatens skin health, in areas where fine dust caused by air pollution is a concern, such as China and Korea, fine dust along with UV exposure can be a problem, and high energy that is relatively strong even in desert areas with high insolation Although there is a high probability of being exposed to ultraviolet rays, a lot of fine dust can exist in the air, and the density of fine dust is high indoors, so there is a demand for a cosmetic composition that has the effect of blocking ultraviolet rays or higher energy rays and the effect of preventing fine dust at the same time. is expected to increase over time.

Fine dust is an air pollutant including ionic components such as nitrate (NO ^3- ), carbon compounds or metal compounds, and refers to particulate matter with a diameter of 10 μm or less that floats in the air for a long time. Most of the ultra-fine dust is generated by artificial factors such as automobile exhaust gas, industrial processes, and dust dancing on roads.

In particular, it has been reported that fine dust deposited in the body induces oxidative stress and inflammatory reactions and causes acute exacerbation of diseases of the respiratory and circulatory systems. In addition, passing through olfactory epithelial cells can reach the brain directly without passing through the blood-brain barrier, and it is reported to induce inflammation of the cranial nerve and further induce cognitive impairment, and research and patent applications for cosmetics that prevent fine dust have also been conducted. A lot has been done (patent literature).

Assuming damage caused by high-energy rays and fine dust as the most extreme case, radioactive materials may leak from nuclear facilities to areas where people live due to accidents or, in extreme cases, the use of nuclear weapons. In fact, when radioactive materials are leaked into the surrounding area due to a nuclear power plant accident in Chernobyl or Fukushima, after a long time after the direct radiation damage, the general public naturally enters and lives in the area where the radiation was leaked. A problem arises when the radioactive material present is combined with fine dust and comes into contact with the skin.

As a result of diligent examination to overcome the limitations of existing sunscreens, the inventors of the present invention can expect the effect of blocking not only general ultraviolet rays (UV-A and UV-B) but also high-energy rays of various wavelengths having higher energy than that. At the same time, a cosmetic composition having a function of protecting the skin from fine dust was developed. More specifically, the present invention relates to a core-shell particle having a core structure having a high density and/or bandgap value and a shell structure having a relatively low density and/or bandgap value, and the surface of the core-shell particle is made of graphene or the like. It relates to a cosmetic composition for blocking high energy rays and preventing fine dust, which can function as a general sunscreen and is effective in a more dangerous environment by including core-shell particles surface-modified with a coating layer containing nanomaterials.

The present invention is directed to a cosmetic composition capable of blocking high-energy rays in various wavelength bands having higher energy than UV-A and UV-B, which are general ultraviolet regions, and at the same time protecting the skin from fine dust. As a related art, by including core-shell particles surface-modified with a coating layer containing nanomaterials such as graphene, it can function as a general sunscreen while protecting humans even in a more dangerous high-energy ray exposure environment. .

Hereinafter, the present invention will be described in detail.

The present invention relates to a cosmetic composition capable of blocking ultraviolet rays as well as high-energy rays of various wavelength bands having higher energy than UV rays and at the same time protecting the skin from fine dust. In the case of core-shell particles, the core It contains an energy band suitable for absorbing high-energy rays with a shorter wavelength and higher energy than UV-A or UV-B and inorganic components with high density, and the shell can mainly reflect and block UV-A or UV-B. Therefore, it contains appropriate inorganic components.

The present invention is a cosmetic composition for blocking high energy rays and preventing fine dust comprising core-shell particles surface-modified with a coating layer containing nanomaterials, wherein the cores of the core-shell particles are bismuth ( Oxides, nitrides, halides and/or sulfides of one or more elements selected from Bi), vanadium (V), hafnium (Hf), barium (Ba), tantalum (Ta), cerium (Ce) and/or tungsten (W) and the shell of the core-shell particle is an oxide, nitride, halide and/or sulfide of one or more elements selected from titanium (Ti), zinc (Zn), copper (Cu), and silicon (Si). It comprises at least one, and the nanomaterial coating layer relates to a cosmetic composition for blocking high energy rays and preventing fine dust, characterized in that it comprises nanomaterials and a coating agent, and in particular, the coating layer containing nanomaterials is itself It is characterized by its ability to prevent the adhesion of fine dust.

The nanomaterial is a quantum dot, nano rod, nano wire, nano fiber, nano belt, nano sheet, nano dot ), fullerene, graphene, nano graphite, carbon nanotube, carbon nanodot, carbon black, transition metal disulfide (dioxide of transition metals), hexagonal boron nitride (hBN), black phosphate, silicene, germanene, or MXene. These components may directly absorb high-energy rays, and it is preferable to select those that can show an antistatic effect, and fullerene, graphene, nano graphite, carbon nanotubes nanotube) and carbon nanodot (carbon nanodot), such an effect is more expected.

The following table compares the density and bandcap values of several inorganic components that can be used for core and shell:

Inorganic (Metal Oxides) Density (g/cm3) Bandgap (eV) Bi2O3 8.9 2.8 V2O5 3.4 2.6 HfO2 9.7 5.3-6.0 BaO 5.7 4.9 Ta2O5 8.2 4.0 CeO2 7.1 3.2 WO 7.2 2.6-3.0 CuO 6.3 1.2-1.9 TiO2 3.8-4.2 3.0-3.2 ZnO 5.6 3.4

In another embodiment of the present invention, the coating agent is silica, alumina, silane-based compounds or polymers, metal halides, glycol-based polymers, vinylpyrrolidone-based polymers, (meth)acrylic polymers, amide-based polymers, urethane-based polymers or their It is characterized in that it is at least one selected from precursors.

In another embodiment of the present invention, the core is characterized in that at least one selected from bismuth oxide, tungsten oxide, and cobalt oxide.

The shell is characterized in that at least one selected from titanium oxide, zinc oxide, copper oxide, or silicon oxide.

In another embodiment of the present invention, the particle size of the surface-modified core-shell particles is 50 nm or more, 100 nm or more, 200 nm or more, 500 nm or more, 750 nm or more, or 1000 nm or more, and 100 or less, 75 or less, 50 or less, 25 or less, 10 or less, 7.5 or less, 5 or less, or 2.5 or less.

In another embodiment of the present invention, the composition for external application for skin for blocking high energy rays includes a solvent, an anti-dust agent, an inorganic sunscreen component, an organic sunscreen component, an organic/inorganic composite sunscreen component, a thickener, an oil, a lubricant, a stabilizer, a preservative, It is characterized in that it further comprises at least one or more components of a moisturizing agent, fragrance, humectant, surfactant or amphiphilic surfactant.

As for the organic UV-blocking component that may be further included in another embodiment of the present invention, Korean Patent Publication No. 10-2007-0001262 may be referred to, but is not limited thereto.

In another embodiment of the invention, the inorganic sunscreen component that may be further included is

In another embodiment of the present invention, reference may be made to Korean Patent Registration No. 10-1410043 for the organic-inorganic composite sunscreen component that may be further included, but is not limited thereto.

In another embodiment of the present invention, the composition is characterized in that it is a cosmetic composition of a spray, lotion, or cream type.

In another embodiment of the present invention, the composition further includes a fine dust prevention component, wherein the core-shell particles are 0.5 to 60% by weight of the total composition, and the fine dust prevention component is 0.1 to 10% by weight of the total composition. It is characterized in that it contains %.

In the present invention, the core-shell particles further including the nanomaterial in the shell layer include: (1) mixing the core-shell particles without a coating layer and the coating agent by introducing them into a mixing reactor; (2) injecting a dispersion containing a one-dimensional or two-dimensional nanomaterial and a coating agent or a precursor of the coating agent into the mixing reactor; (3) coating the core-shell particles in the mixing reactor; and (4) removing the dispersion by adjusting the temperature and pressure.

The present invention relates to a cosmetic composition capable of blocking ultraviolet rays as well as high-energy rays of various wavelength bands having higher energy than UV rays and at the same time protecting the skin from fine dust, and more particularly, to a cosmetic composition having high density Functions of a general sunscreen by including core-shell particles of a shell structure with a relatively low density and core-shell particles whose surface is surface-modified with a coating layer containing nanomaterials such as graphene. Although the present invention is described in detail through preparation examples and examples to achieve the object of the present invention, it relates to a cosmetic composition for blocking high energy rays and preventing fine dust that is effective in a more dangerous environment while being able to The invention is not limited to these examples.

[Preparation Example 1] Preparation of bismuth oxide-titanium dioxide (Bi2O3-TiO2) core-shell nanoparticles having a PVA coating layer containing graphene oxide.

<Synthesis of Bi2O3-TiO2 core-shell nanoparticles>

In a round bottom flask, 8 mL of titanium isopropoxide (TTIP) was added to 25 mL of ethanol, and the solution was stirred at room temperature for 30 minutes to obtain a clear solution. A dispersion obtained by dispersing Bi2O3 nanoparticles with an average particle size of 40-80 nm (median value 56 nm) in ethanol purchased from Nanostructure & Amorphous Materials in the US was slowly added, and the mixture was slowly heated to 80-90 ° C. The step of adding 5 mL of deionized water dropwise to the mixed solution while stirring was repeated, and after the addition of Bi2O3 was completed, the mixture was further heated while stirring for 6 hours. The resulting white precipitate was centrifuged and washed repeatedly with ethanol and deionized water to obtain Bi2O3-TiO2 core-shell nanoparticles, which were dried in a vacuum oven overnight at 60 °C.

<Preparation of PVA solution>

A PVA solution was prepared by adding 2 g of PVA powder to 100 mL of deionized water with continuous stirring, heating the solution to 80 °C, then stirring for an additional 2 hours until the PVA powder was completely dissolved and then cooling to room temperature.

<Preparation of graphene oxide solution>

A graphene oxide solution was prepared by dissolving 100 mg of GO powder in 50 mL of deionized water with stirring, and ultrasonicating the solution for 30 minutes for uniform dispersion.

<Coating of TiO2@Bi2O3 nanoparticles>

While stirring, 100 mg of Bi2O3-TiO2 nanoparticles were added to 50 mL of the PVA solution, and heated at 80 °C for 2 hours to allow the PVA to adsorb onto the surface of the nanoparticles. At the same time, while stirring, 10 mL of the graphene oxide solution was added dropwise to the mixture, The mixture is sonicated for 30 minutes to improve the uniformity of the dispersion. The mixture is then evaporated using a rotary evaporator to remove the solvent and form PVA-coated Bi2O3-TiO2 core-shell nanoparticles with a graphene oxide layer. The resulting coated nanoparticles were washed repeatedly with ethanol and deionized water and dried in a vacuum oven overnight at 60 °C. The average size of the finally prepared particles measured by light scattering was 112 nm.

[Preparation Example 2] Preparation of hafnium oxide-titanium dioxide core-shell nanoparticles having a PVA coating layer containing graphene oxide.

Hafnium oxide-dioxide having a PVA coating layer containing raffin oxide in the same manner as in [Preparation Example 1] except for using HfO2 particles (5 to 100 nm, particle diameter as measured by light scattering: 41 nm) purchased from American Element Co., Ltd. in the United States. Titanium (TiO2@HfO2) core-shell nanoparticles were prepared. The average size of the finally prepared particles measured by light scattering was 130 nm.

[Example 1] Preparation of cosmetics

2 parts by weight of sorbitan monostearate, 2 parts by weight of glycerin, 1 part by weight of collagen, 3 parts by weight of polysorbate 80 (TW-80) as components other than the two core-shell nanoparticles with the graphene oxide layer After preparing a suspension consisting of 6 parts by weight of poloxamer-407, an amphiphilic polymer, 3 parts by weight of water-dispersible polyurethane (AU-419), and 60 parts by weight of water, the two core-shell nanoparticles prepared above were mixed with each other. Cosmetic compositions were prepared to include 2.5, 5, 7.5, 10, 20 and 40% by weight.

[Test Example 1] Measurement of UV-A and UV-B absorbance (SPF and PA values)

SPF measurement and PA measurement (ISO 24444: 2010 and ISO 24443:2011) The results are shown in the table below.

Core-shell particles and content (% by weight) of cosmetic composition SPF PA TiO2@Bi2O3 (2.5) 9.60 6.5(+) TiO2@Bi2O3 (5.0) 21.59 12.07(++) TiO2@Bi2O3 (7.5) 32.54 19.85(+++) TiO2@Bi2O3 (10.0) 48.11 26.31(++++) TiO2@HfO2 (2.5) 9.88 5.8(+) TiO2@HfO2 (5.0) 20.54 9.66(++) TiO2@HfO2 (7.5) 35.89 16.09(+++) TiO2@HfO2 (10.0) 50.12 20.25(+++)

As seen in the table above, it can be seen that significantly superior SPF and PA values are exhibited at 10% by weight, which is a commonly used particle content.

[Test Example 2] Measurement of X-ray absorbance

The cosmetic composition containing PVA-coated Bi2O3-TiO2 core-shell nanoparticles with a graphene oxide layer prepared above was applied to an X-ray meter (10 kV) to a thickness of 1 mm, compared to the case where the content of the particles was 0. Relative transmittance The results of measuring are shown in the following table.

Particle content (% by weight) X-ray relative transmittance TiO2@Bi2O3(0) 100 TiO2@Bi2O3(10) 95.4 TiO2@Bi2O3(20) 82.5 TiO2@Bi2O3(40) 56.5 TiO2@HfO2(0) 100 TiO2@HfO2(10) 96.1 TiO2@HfO2(20) 88.4 TiO2@HfO2 (40) 63.7

[Test Example 3] Measurement of fine dust absorption prevention effect

The results of measuring the anti-absorption effect by applying the cosmetic composition containing the PVA-coated Bi2O3-TiO2 core-shell nanoparticles with the graphene oxide layer prepared above are shown in the following table. The measurement method referred to the method of Korean Patent Publication No. 10-2020-0144770.

Measurement time Before adsorption of fine dust After adsorption of fine dust (average) Pixel Variation of Test Product (Average) 0 21.5 Pixel change amount of control product (average) 0 30.8 % improvement of the test product compared to the control product - 30.2%

Looking at the results of Test Examples 1-3 as described above, the cosmetic composition for blocking high energy rays and preventing fine dust of the present invention not only has excellent UV-A and UV-B blocking effects, but also has an effect on blocking X-rays. At the same time, the effect of preventing fine dust is also excellent. Due to these characteristics, not only is the effect of protecting the skin from ultraviolet rays and fine dust even in dry or heavily polluted areas even with a low-content cream alone, but also high-energy radioactive contaminants when used in a high-content cream or thickly applied. Even in an environment where this fine dust exists, it is expected to have an excellent effect to protect the skin and internal organs.

Claims (10)

In the cosmetic composition for blocking high energy rays and preventing fine dust comprising core-shell particles surface-modified with a coating layer containing nanomaterials,
The core of the core-shell particle is an oxide of one or more elements selected from bismuth (Bi), vanadium (V), hafnium (Hf), barium (Ba), tantalum (Ta), cerium (Ce) and tungsten (W) , nitride, halide, or sulfide, and the shell of the core-shell particle is an oxide or nitride of one or more elements selected from titanium (Ti), zinc (Zn), copper (Cu), and silicon (Si). , It is made of one or more halides or sulfides, and the coating layer including the nanomaterial is made of a nanomaterial and a coating agent, and the nanomaterial is fullerene, graphene, and nanographite ), a cosmetic composition for blocking high energy rays and preventing fine dust, characterized in that at least one selected from carbon nanotubes and carbon nanodots. delete delete The method of claim 1, wherein the coating agent is silica, alumina, silane-based compounds or polymers, metal halides, glycol-based polymers, vinylpyrrolidone-based polymers, (meth)acrylic polymers, amide-based polymers, urethane-based polymers, or precursors thereof. A cosmetic composition for blocking high energy rays and preventing fine dust, characterized in that at least one selected. The cosmetic composition for blocking high energy rays and preventing fine dust according to claim 1, wherein the core is at least one selected from bismuth oxide, tungsten oxide, hafnium oxide, and cobalt oxide. The cosmetic composition for blocking high energy rays and preventing fine dust according to claim 1, wherein the shell is at least one selected from titanium oxide, zinc oxide, copper oxide, and silicon oxide. The method of claim 1, wherein the cosmetic composition for blocking high energy rays and preventing fine dust includes a solvent, an anti-dust agent, an inorganic UV blocking component, an organic UV blocking component, an organic/inorganic composite UV blocking component, a thickener, an oil, a lubricant, a stabilizer, a preservative, A cosmetic composition for blocking high energy rays and preventing fine dust, characterized in that it is a cosmetic composition of a spray, lotion, or cream type, further comprising at least one component of a moisturizer, perfume, moisturizer, surfactant or amphiphilic surfactant . delete The method of claim 1, wherein the composition further comprises an anti-fine dust component, wherein the core-shell particles are 0.1 to 60% by weight of the total composition, and the anti-fine dust component is 0.1 to 10% by weight of the total composition. A cosmetic composition for blocking high energy rays and preventing fine dust, characterized in that it comprises. delete