KR102099428B1 - A composition for intercepting ultraviolet comprising carbon group non-oxide nanoparticles and manufacturing method thereof - Google Patents

Abstract

One embodiment of the present invention provides a sunscreen composition comprising an average particle size of 5 ~ 400nm and carbon group non-oxide nanoparticles made of Si or Ge, and a binder resin.

Description

A sunscreen composition comprising carbon group non-oxide nanoparticles and a manufacturing method therefor {A COMPOSITION FOR INTERCEPTING ULTRAVIOLET COMPRISING CARBON GROUP NON-OXIDE NANOPARTICLES AND MANUFACTURING METHOD THEREOF}

The present invention relates to a sunscreen composition comprising carbon-based non-oxide nanoparticles and a method of manufacturing the same, and more particularly, to a sunscreen composition comprising multi-component carbon-based non-oxide nanoparticles and a method of manufacturing the same.

Ultraviolet rays irradiated from sunlight are the main causes of erythema, edema, freckles, and skin cancer on the skin. Recently, many studies on various skin diseases caused by ultraviolet rays have been actively conducted, and many treatment means have been proposed to protect the skin from such ultraviolet rays.

In general, ultraviolet rays are a type of sun rays, and rays having a wavelength of 200 nm to 400 nm, in particular, ultraviolet rays from sunlight reaching the surface of the earth through the upper atmosphere can be classified as ultraviolet rays A, ultraviolet rays B, and ultraviolet rays C.

Ultraviolet ray A has a wavelength of 320 ~ 400nm and penetrates the dermis layer of the skin, causing skin cancer and skin aging. Ultraviolet ray B is absorbed directly above the dermis layer with ultraviolet rays of a wavelength of 290 ~ 320nm, sunburn and inflammation (inflammation) ). In addition, ultraviolet C is 200 ~ 290nm wavelength, which is fatal to life, but is completely absorbed by the ozone layer. In order to block ultraviolet rays, inorganic ultraviolet scattering agents and organic ultraviolet absorbers have been used.

The organic UV absorber mainly absorbs the medium wavelength UVB and converts it into energy to protect the skin, and the inorganic UV scattering agent mainly refracts the UV light A, which is the long wavelength, by an inorganic material to scatter ultraviolet rays. However, the amount of the organic UV absorber is limited due to the toxicity of the organic material. For this reason, the use of inorganic ultraviolet scattering agents is predominant, and titanium dioxide and zinc oxide are typically used.

As the particle size of titanium dioxide decreases, the ratio of the atoms constituting the surface to the atoms present inside the particle increases and the surface area increases, so that the blocking rate of ultraviolet rays increases. However, if the particle size is reduced to the nano level, there is a potential risk of adversely affecting cells by the free radicals on the surface or penetrating the central nervous system.

Accordingly, there is a continuous need for research on a sunscreen composition having excellent sunscreen characteristics, reasonable cost, and harmless to the human body.

The present invention is to solve the above-mentioned problems of the prior art, the object of the present invention is to provide an excellent UV-blocking composition that has excellent UV-blocking performance and a simple manufacturing process.

One aspect of the present invention provides a sunscreen composition comprising an average particle size of 5 ~ 400nm and carbon group non-oxide nanoparticles made of Si or Ge, and a binder resin.

Another aspect of the present invention provides a sunscreen composition comprising a carbon group non-oxide nanoparticle composed of two elements of Si, Ge and B, and an binder resin having an average particle size of 5 to 400 nm.

Another aspect of the present invention provides a sunscreen composition comprising an average particle size of 5 to 400 nm, carbon group non-oxide nanoparticles made of SiGeB or SiGeC, and a binder resin.

Another aspect of the present invention is an average particle size of 5 ~ 400nm and made of Si or Ge, or composed of two elements of Si, Ge and B, or SiGeB or SiGeC to produce a carbon group non-oxide nanoparticles ; Preparing a carbon group nanoparticle solution by adding the carbon group non-oxide nanoparticles to a solvent and irradiating ultrasound; And diluting the carbon group nanoparticle solution in the solvent or binder resin solution.

As used herein, the term "carbon group non-oxide nanoparticles" refers to particles containing at least one carbon group (group 14) element of C, Si, or Ge, and heterogeneous carbon group elements are alloyed or at least one. It can be understood as a concept including particles in which boron (B) is alloyed with the carbon group element of.

As used herein, the term “non-oxide nanoparticles” refers to particles that do not substantially contain an oxygen element (O), and an oxide layer (oxide) generated on the surface of non-oxide nanoparticles by a naturally occurring oxidation reaction layer).

In the sunscreen composition, the carbon group non-oxide nanoparticles may be included in the form of a solution diluted to a concentration of 1 to 5,000 ppm.

For example, among the carbon group non-oxide nanoparticles, silicon-boron alloy nanoparticles, silicon-germanium-boron alloy nanoparticles, silicon-germanium-carbon alloy nanoparticles, and silicon-germanium alloy nanoparticles block ultraviolet (UV) light When it is included in the above-mentioned sunscreen composition, it can exhibit excellent sunscreen effect and can be applied to various fields such as films, lenses, and fibers with UV blocking function as well as cosmetics that are harmless to the human body and contact skin such as UV blocking cream. You can. In addition, it has excellent antibacterial / sterilization, air purification, and deodorizing functions, and has been applied to various fields.

The binder resin is low density polyethylene (lowdensity polyethylene, LDPE), high density polyethylene (highdensity polyethylene, HDPE), polyvinyl alcohol (polyvinylalcohol, PVA), polyester (polyester), EPM (copolymer of ethylene and propylene), polyurethane (polyurethan) ), Polyurea, silicone resin, epoxy resin, acrylic resin, alkyd resin, and mixtures of two or more of them, preferably one. , May be polyurethane, but is not limited thereto.

The polyurethane may be synthesized by using a polyol and (poly) isocyanate as precursors, wherein the polyol is a group consisting of a polycarbonate-based, polyester-based, polyacrylate-based, polyalkylene-based, and mixtures of two or more of them. It may be one selected from. The polyol may have a weight average molecular weight (Mw) of 50 to 5,000. In addition, the polyol may include a low molecular weight crosslinking agent having a weight average molecular weight (Mw) of 20 to 500 in an amount of 45% by weight or less.

The said polyester refers to the polyester obtained by polycondensing aromatic dicarboxylic acid and aliphatic glycol. Typical polyesters include polyethylene terephthalate (PET) and polyethylene-2,6-natalenedicarboxylate (PEN). The polyester may also be a copolymer containing a third component. As the dicarboxylic acid component of the copolymerized polyester, isophthalic acid, phthalic acid, terephthalic acid, 2,6-naphthalenedicarboxylic acid, adipic acid, sebacic acid, oxycarboxylic acid (for example, P-oxybenzoic acid, etc.) ), And examples of the glycol component include ethylene glycol, diethylene glycol, propylene glycol, butanediol, 1,4-cyclohexanedimethanol, and neopentyl glycol. The dicarboxylic acid component and the glycol component may be used in combination of two or more.

In one embodiment, the sunscreen composition may include 5 to 2000 ppm of the carbon group non-oxide nanoparticles with respect to 100 parts by weight of the binder resin.

In one embodiment, the carbon group non-oxide nanoparticles may be surface-modified by one selected from the group consisting of alkoxy groups, hydroxyl groups, carboxyl groups, and combinations thereof.

The sunscreen composition according to one aspect of the present invention is excellent in sunscreen performance by controlling the particle size and content of the carbon group non-oxide nanoparticles to a certain range, and the manufacturing process is simple, which is advantageous in terms of productivity and economy.

It should be understood that the effects of the present invention are not limited to the above-described effects, and include all effects that can be deduced from the configuration of the invention described in the detailed description or claims of the present invention.

Hereinafter, the present invention will be described with reference to the accompanying drawings. However, the present invention may be implemented in various different forms, and thus is not limited to the embodiments described herein. In addition, in order to clearly describe the present invention in the drawings, parts irrelevant to the description are omitted, and like reference numerals are assigned to similar parts throughout the specification.

Throughout the specification, when a part is "connected" to another part, this includes not only "directly connected" but also "indirectly connected" with another member in between. . Also, when a part is said to “include” a certain component, this means that other components may be further provided instead of excluding the other component unless otherwise stated.

Hereinafter, embodiments of the present invention will be described in detail.

Example  One

Silicon nanoparticles may be prepared according to (1) or (2) in Reaction Scheme 1 below.

<Scheme 1>

(1) SiH ₄ + SF ₆ + N ₂ → Si (-S, -F) + H ₂ + N ₂

(2) SiH ₄ + N ₂ → Si + 2H ₂ + N ₂

Through the raw material gas supply nozzle, mixed gas mixed with 100 volumes of monosilane (SiH ₄ ) as the source gas, 400 volumes of nitrogen (N ₂ ) as the control gas, and 40 volumes of sulfur hexafluoride (SF ₆ ) catalyst gas It is supplied to the inside of the reaction chamber with an internal pressure of 500 torr, and the laser generated by the CO ₂ laser generator is supplied to the mixed gas supplied to the inside of the reaction chamber in the form of a line beam of continuous wave with a wavelength of 10.6 μm through a laser irradiation unit 3 Irradiated for a time to prepare silicon nanoparticles (Si-NPs) having an oxide layer.

The average particle size of the silicon nanoparticles on which the oxide layer is formed is 5 to 400 nm, the thickness of the oxide layer is 0.32 nm, and the production yield is 97.1%.

Example  2

Germanium nanoparticles can be prepared according to (1) or (2) in Scheme 2 below.

<Reaction Scheme 2>

(1) 2GeH ₄ + SF ₆ → S + 2Ge + 6HF + H ₂

(2) GeH ₄ + N ₂ → 2Ge + 2H ₂ + N ₂

Through the raw material gas supply nozzle, mixed gas with 100 volumes of raw gas (GeH ₄ ), 400 volumes of hydrogen (H ₂ ) as control gas, and 40 volumes of sulfur hexafluoride (SF ₆ ) catalyst gas is mixed inside. It is supplied to the inside of the reaction chamber with a pressure of 500 torr, and the laser generated by the CO ₂ laser generator is supplied to the mixed gas supplied into the reaction chamber through a laser irradiation unit for 3 hours in the form of a continuous wave line beam with a wavelength of 10.6 μm. During the irradiation, germanium nanoparticles (Ge-NPs) having an oxide layer were prepared.

The average particle size of the germanium nanoparticles on which the prepared oxide layer is formed is 5 to 400 nm, the thickness of the oxide layer is 0.47 nm, and the yield is 98.7%.

Example  3

Silicon-germanium alloy nanoparticles can be prepared according to (1) or (2) in Scheme 3 below.

<Scheme 3>

(1) SiH ₄ + GeH ₄ + SF ₆ → S + SiGe + 6HF + H ₂

(2) SiH ₄ + GeH ₄ → SiGe + 4H ₂

Through the raw material gas supply nozzle, 100 parts by volume of raw gas (GeH ₄ ) (raw gas 1), 100 parts by volume of monosilane (SiH ₄ ) (raw gas 2), and 400 parts by volume of carrier gas nitrogen (N ₂ ) Line gas of a continuous wave with a wavelength of 10.6 µm is supplied to the mixed gas mixed with the gas inside the reaction chamber having an internal pressure of 100 to 500 torr, and the laser generated by the CO ₂ laser generator is supplied to the mixed gas supplied into the reaction chamber. (Line Beam) was irradiated for 3 hours to form silicon-germanium alloy nanoparticles (SiGe-NPs). The average particle size of SiGe-NPs is 5 to 400 nm, and the thickness of the oxide layer formed on the surface is 0.47 nm.

Example  4

Silicon-boron alloy nanoparticles or silicon boride nanoparticles may be prepared according to the following scheme 4.

<Reaction Scheme 4>

2SiH ₄ + 2B ₂ H ₆ + N ₂ → SiB ₄ + 8H ₂ + N ₂

Monosilane (SiH ₄ ), diborane (B ₂ H ₆ ) and nitrogen are mixed and injected into the reaction chamber to irradiate a CO ₂ laser beam. At this time, diborane acts as a catalyst gas and a raw material gas, and energy absorbed at a wavelength of 10.6 µm is efficiently transferred to monosilane, and Si-H bonds of monosilane are easily broken, so that silicon-boron alloy nanoparticles (SiBx -NPs).

In addition, diborane is decomposed into boron and hydrogen atoms, so that boron forms an alloy with silicon nanoparticles and prevents oxidation of silicon. The raw material gas monosilane is 90% or more of the total volume (the volume of the raw material gas and the catalyst gas combined), and the catalyst gas is adjusted to a range of 10% or less of the total volume. In addition, the carrier gas, nitrogen, does not exceed 400 parts by volume compared to the raw material gas, monosilane. The gas flow rate is in sccm. The process pressure inside the reaction chamber is set in the range of 100 to 400 torr to manufacture. In this range, silicon-boron alloy nanoparticles (SiBx-NPs) having an average particle size of 5 to 400 nm and an oxide layer thickness of 0.57 nm are manufactured.

Example  5

Silicon-germanium-boron alloy nanoparticles can be prepared according to the following Reaction Scheme 5.

<Scheme 5>

2SiH ₄ + 2GeH ₄ + B ₂ H ₆ → 2SiGeB + 11H ₂

Through the raw material gas supply nozzle, 100 parts by volume of monosilane (SiH ₄ ), 100 parts by volume of germane (GeH ₄ ), and 40 to 80 parts by volume of diborane (B ₂ H ₆ ) and nitrogen (N ₂ ) as carrier gas ) The mixed gas mixed with 400 volume is supplied into the reaction chamber with an internal pressure of 80 to 400 torr, and the laser generated by the CO ₂ laser generator in the mixed gas supplied into the reaction chamber has a wavelength of 10.6 µm through the irradiation unit. Silicon-germanium-boron alloy nanoparticles (SiGeB-NPs) were prepared by irradiation in the form of a line beam of continuous waves for 3 hours. The average particle size of SiGeB-NPs is 5 to 400 nm, and the thickness of the oxide layer formed on the surface is 0.75 nm.

Example  6

Silicon-germanium-carbon alloy nanoparticles can be prepared according to the following Scheme 6.

<Scheme 6>

2SiH ₄ + 2GeH ₄ + C ₂ H ₂ → 2SiGeC + 9H ₂

100 volumes of monosilane (SiH ₄ ), 100 volumes of germain (GeH ₄ ), and 40 ~ 80 volumes of acetylene (C ₂ H ₂ ) and nitrogen (N ₂ ) as carrier gas through the feed gas supply nozzle A continuous wave with a wavelength of 10.6 µm is supplied through the irradiating unit by supplying the mixed gas mixed with 400 volumes into the reaction chamber with an internal pressure of 80 to 400 torr, and the laser generated by the CO ₂ laser generator in the mixed gas supplied into the reaction chamber. Irradiated for 3 hours in the form of a line beam of (Si) to prepare silicon-germanium-carbon alloy nanoparticles (SiGeC-NPs). The average particle size of SiGeC-NPs is 5 to 400 nm, and the thickness of the oxide layer formed on the surface is 0.68 nm.

Example  7

Germanium-boron alloy nanoparticles or germanium boride nanoparticles may be prepared according to the following Reaction Scheme 8.

<Scheme 7>

2GeH ₄ + 2B ₂ H ₆ + N ₂ → GeB ₄ + 8H ₂ + N ₂

Through the raw material gas supply nozzle, the mixed gas mixed with 100 parts by volume of the main gas (GeH ₄ ), 40 to 80 parts by volume of diborane (B ₂ H ₆ ), and 400 parts by volume of the carrier gas nitrogen (N ₂ ) It is supplied to the inside of the reaction chamber with an internal pressure of 100 to 400 torr, and the laser generated by the CO ₂ laser generator is supplied to the mixed gas supplied into the reaction chamber in the form of a line beam of continuous wave with a wavelength of 10.6 μm through an irradiation unit. After irradiation for 3 hours, germanium-boron alloy nanoparticles (GeBx-NPs) were prepared. The particle size of GeBx-NPs is 5 to 400 nm, and the thickness of the oxide layer formed on the surface is 0.52 nm.

Manufacturing example  One

100 mg of carbon group nanoparticles prepared in Examples 1 to 7 were added to 100 ml of distilled water, and ultrasonic waves were irradiated for 10 minutes to prepare a carbon group nanoparticle solution surface-modified with a hydroxy group having a concentration of 1000 pm and diluting it in distilled water to give a concentration of 10 ppm. Solutions 1-1 to 1-7 were prepared.

Manufacturing example  2

100 mg of carbon group nanoparticles prepared in Examples 1 to 7 were added to 100 ml of ethanol, and ultrasonic waves were irradiated for 10 minutes to prepare a carbon group nanoparticle solution surface-modified with an alkoxy group having a concentration of 1000 pm and diluted with ethanol to dilute it in 10 ppm. Solutions 2-1 to 2-7 were prepared.

Manufacturing example  3

100 mg of carbon group nanoparticles prepared in Examples 1 to 7 were added to 100 ml of acetic acid, and ultrasonic waves were irradiated for 10 minutes to prepare a carbon group nanoparticle solution surface-modified with a carboxyl group having a concentration of 1000 pm and diluted with acetic acid to dilute acetic acid to a concentration of 10 ppm. Solutions 3-1 to 3-7 were prepared.

Manufacturing example  4

100 mg of carbon group nanoparticles prepared in Examples 1 to 7 were added to 100 ml of glycerin, and ultrasonic waves were irradiated for 10 minutes to prepare a carbon group nanoparticle solution surface-modified with a glyceryl group having a concentration of 1000 pm and diluted with glycerin to dilute it in 10 ppm concentration. Solutions 4-1 to 4-7 were prepared.

Manufacturing example  5

Carbon group nanoparticles prepared in Examples 1 to 7 were added to 100 ml, 300 mg, and 500 mg of a 100 ml water-soluble urethane coating solution, and ultrasonic waves were irradiated for 10 minutes to prepare urethane coating solutions having concentrations of 1000 pm, 3000 ppm, and 5000 ppm. 5-1-1 to solution 5-7-3).

Experimental example  One

5 ml of solutions 1-1 to 1-7, solutions 2-1 to 2-7, solutions 3-1 to 3-7, and solutions 4-1 to 4-7 were each taken and added to a measuring cell having a thickness of 10 mm and UV-Vis Each blocking rate was measured at a wavelength of 400 nm using a device.

solution Nanoparticles menstruum 400nm
UV blocking rate (%) Remark 1-1 Si Distilled water 52 1-2 Ge Distilled water 43 1-3 SiGe Distilled water 46 1-4 SiB Distilled water 58 1-5 SiGeB Distilled water 50 1-6 SiGeC Distilled water 15 1-7 GeB Distilled water 49 2-1 Si ethanol 54 2-2 Ge ethanol 47 2-3 SiGe ethanol 48 2-4 SiB ethanol 54 2-5 SiGeB ethanol 53 2-6 SiGeC ethanol 17 2-7 GeB ethanol 48 3-1 Si Acetic acid 53 3-2 Ge Acetic acid 43 3-3 SiGe Acetic acid 45 3-4 SiB Acetic acid 55 3-5 SiGeB Acetic acid 53 3-6 SiGeC Acetic acid 14 3-7 GeB Acetic acid 15 4-1 Si glycerin 50 4-2 Ge glycerin 45 4-3 SiGe glycerin 46 4-4 SiB glycerin 57 4-5 SiGeB glycerin 52 4-6 SiGeC glycerin 15 4-7 GeB glycerin 52

Experimental example  2

After 1000 ppm, 3000 ppm, and 5000 ppm concentrations of the solutions prepared in Preparation Example 5 were spray coated on a PET film to a thickness of 10 μm, each blocking rate was measured at a wavelength of 400 nm using UV-Vis equipment.

solution Nanoparticles density 400nm
UV blocking rate (%) Remark 5-1-1 Si 1,000ppm 23 5-1-2 Si 3,000ppm 64 5-1-3 Si 5,000ppm 100 5-2-1 Ge 1,000ppm 20 5-2-2 Ge 3,000ppm 58 5-2-3 Ge 5,000ppm 98 5-3-1 SiGe 1,000ppm 20 5-3-2 SiGe 3,000ppm 62 5-3-3 SiGe 5,000ppm 100 5-4-1 SiB 1,000ppm 29 5-4-2 SiB 3,000ppm 72 5-4-3 SiB 5,000ppm 100 5-5-1 SiGeB 1,000ppm 29 5-5-2 SiGeB 3,000ppm 70 5-5-3 SiGeB 5,000ppm 100 5-6-1 SiGeC 1,000ppm 8 5-6-2 SiGeC 3,000ppm 30 5-6-3 SiGeC 5,000ppm 48 5-7-1 GeB 1,000ppm 23 5-7-2 GeB 3,000ppm 68 5-7-3 GeB 5,000ppm 100

For reference, when the concentration is 1 ppm or less, the UV absorption hardly occurs, and when the concentration is 5000 ppm or more, the viscosity becomes too large, making film coating difficult.

Therefore, the nanoparticle concentration in the sunscreen composition according to the embodiment of the present invention is 1 to 5000 ppm, preferably 5 to 2000 ppm.

The above description of the present invention is for illustration only, and those skilled in the art to which the present invention pertains can understand that it can be easily modified to other specific forms without changing the technical spirit or essential features of the present invention. will be. Therefore, it should be understood that the embodiments described above are illustrative in all respects and not restrictive. For example, each component described as a single type may be implemented in a distributed manner, and similarly, components described as distributed may be implemented in a combined form.

The scope of the present invention is indicated by the following claims, and all changes or modifications derived from the meaning and scope of the claims and equivalent concepts should be interpreted to be included in the scope of the present invention.

Claims (8)

A sunscreen composition comprising an average particle size of 5 to 400 nm and comprising carbon group non-oxide nanoparticles made of SiB, GeB or SiGeB, and a binder resin. delete delete According to claim 1,
The sunscreen composition comprises the carbon group non-oxide nanoparticles 5 ~ 2000ppm sunscreen composition. According to claim 1,
The carbon-based non-oxide nanoparticles are a sunscreen composition that is surface-modified by one selected from the group consisting of hydroxy group, alkoxy group, carboxyl group, glyceryl group and combinations thereof. Preparing a carbon group non-oxide nanoparticle having an average particle size of 5 to 400 nm and composed of SiB, GeB or SiGeB;
Preparing a carbon group nanoparticle solution by adding the carbon group non-oxide nanoparticles to a solvent and irradiating ultrasound;
And diluting the carbon group nanoparticle solution in the solvent or a binder resin solution. The method of claim 6,
The solvent is at least one of distilled water, ethanol and acetic acid, and the binder resin is one of urethane and acrylic. The method of claim 6,
The step of preparing the carbon group nanoparticle solution,
A method of manufacturing the sunscreen composition comprising the step of surface-modifying the carbon group non-oxide nanoparticles through the ultrasonic irradiation as one selected from the group consisting of a hydroxy group, an alkoxy group, a carboxyl group, a glyceryl group, and combinations thereof.