WO2018147684A1 - Ultraviolet-barrier material composition comprising carbon group non-oxide nanoparticles and method for producing same - Google Patents

Abstract

An embodiment of the present invention provides an ultraviolet-barrier material composition comprising carbon group non-oxide nanoparticles having an average particle size of 5 to 400 nm and made of Si or Ge, and a binder resin.

Description

A sunscreen composition comprising carbon group non-oxide nanoparticles and a method of manufacturing the same

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

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

In general, ultraviolet rays are a kind of sunlight rays, the wavelength of 200nm ~ 400nm, especially ultraviolet rays from sunlight passing through the upper atmosphere to reach the surface of the earth can be classified as ultraviolet A, ultraviolet B, ultraviolet C.

Ultraviolet A has a wavelength of 320 ~ 400nm and transmits to the dermis of the skin, causing skin cancer and skin aging.UVB is absorbed just above the dermis with ultraviolet rays of 290 ~ 320nm, and sunburn and inflammation ). In addition, ultraviolet C is deadly to life with a wavelength of 200-290 nm, 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 ultraviolet B, which is a medium wavelength, and converts it into energy to protect the skin. The inorganic UV scattering agent scatters ultraviolet rays by refracting UVA, which is mainly a long wavelength, by an inorganic material. However, the amount of organic UV absorbers is limited due to the toxicity of organic substances. Because of this, the use of inorganic ultraviolet scattering agent is the main, titanium dioxide and zinc oxide are typically used.

As the particle size of titanium dioxide decreases, the surface area increases while the ratio of atoms constituting the surface to the atoms present in the particles increases, so that the blocking rate of ultraviolet rays increases. However, if the particle size is reduced to nanoscale, there is a potential risk that the free radicals on the surface will adversely affect the cells or penetrate the central nervous system.

Therefore, there is a continuing need for research of a sunscreen composition having excellent UV protection properties and reasonable cost and harmless to a human body.

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

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

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

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

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

As used herein, the term "carbon group non-oxide nanoparticle" means a particle including 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 may be understood as a concept including particles in which boron (B) is alloyed with a carbon group element of.

As used herein, the term "non-oxide nanoparticle" means a particle substantially free of an oxygen element (O), the oxide layer (oxide) generated on the surface of the non-oxide nanoparticles by a naturally occurring oxidation reaction (oxide) It can be understood as a concept including a layer).

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

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 rays (UV). When it is included in the sunscreen composition, it can exert an excellent sunscreen effect and is harmless to the human body, and can be applied to various fields such as UV blocking film, lens, and fiber as well as cosmetics that contact skin. Can be. In addition, it has excellent antibacterial / sterilization function, air purification function, and deodorization function, and has been applied to various fields.

The binder resin is low density polyethylene (LDPE), high density polyethylene (HDPE), polyvinyl alcohol (polyvinylalcohol, PVA), polyester (polyester), copolymer of ethylene and propylene (EPM), polyurethane (polyurethan) ), Polyurea, silicone resin, sillicon resin, epoxy resin, acrylic resin, alkyd resin and mixtures of two or more thereof, and preferably It may be, but is not limited to, polyurethane.

The polyurethane may be synthesized using a polyol and a (poly) isocyanate as a precursor, wherein the polyol is a group consisting of polycarbonate-based, polyester-based, polyacrylate-based, polyalkylene-based and mixtures of two or more thereof It may be one selected from. The weight average molecular weight (Mw) of the polyol may be 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 up to 45% by weight.

The said polyester refers to the polyester obtained by polycondensing aromatic dicarboxylic acid and aliphatic glycol. Typical polyesters include polyethylene terephthalate (PET), polyethylene-2,6-naphthalenedicarboxylate (PEN), and the like. The polyester may also be a copolymer containing a third component. Examples of the dicarboxylic acid component of the copolymerized polyester include isophthalic acid, phthalic acid, terephthalic acid, 2,6-naphthalenedicarboxylic acid, adipic acid, sebacic acid, oxycarboxylic acid (for example, P-oxybenzoic acid and the like). ) And ethylene glycol, diethylene glycol, propylene glycol, butanediol, 1,4-cyclohexanedimethanol, neopentylglycol, etc. are mentioned as a glycol component. The dicarboxylic acid component and glycol component may use 2 or more types together.

In one embodiment, the sunscreen composition may include 5 to 2000ppm of the carbon group non-oxide nanoparticles based on 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, amino groups and combinations thereof.

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

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

Hereinafter, with reference to the accompanying drawings will be described the present invention. As those skilled in the art would realize, the described embodiments may be modified in various different ways, all without departing from the spirit or scope of the present invention. In the drawings, parts irrelevant to the description are omitted in order to clearly describe the present invention, and like reference numerals designate like parts throughout the specification.

Throughout the specification, when a part is "connected" to another part, it includes not only "directly connected" but also "indirectly connected" with another member in between. . In addition, when a part is said to "include" a certain component, this means that it may further include other components, without excluding the other components unless otherwise stated.

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

Example 1

Silicon nanoparticles can be prepared according to (1) or (2) in 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

A mixed gas obtained by mixing 100 parts of monosilane (SiH ₄ ), 400 parts of nitrogen (N ₂ ), and 40 parts of sulfur hexafluoride (SF ₆ ) catalyst gas, which is a source gas, is supplied through the source gas supply nozzle. The internal pressure is supplied into the reaction chamber with 500torr, 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 having a wavelength of 10.6㎛ through the laser irradiation unit. Irradiation for a time to produce a silicon nanoparticles (Si-NPs) in which the oxide layer was formed.

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

Example 2

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

<Scheme 2>

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

(2) GeH ₄ + N ₂ → 2Ge + 2H ₂ + N ₂

Through the source gas supply nozzle, a mixed gas containing 100 parts of Germain (GeH ₄ ) source gas, 400 parts of hydrogen (H ₂ ) control gas and 40 parts of sulfur hexafluoride (SF ₆ ) catalyst gas is mixed. It is supplied into the reaction chamber with a pressure of 500torr, 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 continuous beam line beam having a wavelength of 10.6㎛ through the laser irradiation unit for 3 hours. During irradiation, germanium nanoparticles (Ge-NPs) in which an oxide layer was formed were prepared.

The average particle size of the germanium nanoparticles having the prepared oxide layer 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

100 parts of germane (GeH ₄ ) raw material gas (raw material gas 1), 100 parts of monosilane (SiH ₄ ) raw material gas (raw material gas 2), and 400 parts of nitrogen (N ₂ ) carrier gas through the source gas supply nozzle Is supplied to the inside of the reaction chamber of the internal pressure of 100 ~ 500torr, the continuous gas line beam having a wavelength of 10.6㎛ through the irradiation section of the laser generated by the CO ₂ laser generator to the mixed gas supplied into the reaction chamber Irradiation for 3 hours in the form of (Line Beam) to prepare 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 thereof is 0.47 nm.

Example 4

Silicon-boron alloy nanoparticles or silicon boride nanoparticles may be prepared according to Scheme 4 below.

<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, the diborane acts as a catalyst gas and a source gas, the energy absorbed at 10.6㎛ wavelength is efficiently transferred to the monosilane, and the Si-H bond of the monosilane is well broken, so that the silicon-boron alloy nanoparticles (SiBx -NPs).

In addition, diborane is decomposed into boron and hydrogen atoms, boron alloys with silicon nanoparticles, and prevents oxidation of silicon. Monosilane as a source gas is 90% or more of the total volume (volume of the raw material gas and the catalyst gas combined), and the catalyst gas is adjusted to the range of 10% or less of the total volume. In addition, the carrier gas nitrogen is not more than 400 parts by volume compared to the source gas monosilane. The flow rate of gas is in sccm. Process pressure inside the reaction chamber is prepared by setting in the range of 100 ~ 400torr. 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 prepared.

Example 5

Silicon-germanium-boron alloy nanoparticles can be prepared according to Scheme 5 below.

Scheme 5

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

100 parts by weight of monosilane (SiH ₄ ), 100 parts by weight of germane (GeH ₄ ), and diborane (B ₂ H ₆ ) by 40 to 80 parts by volume through the feed gas supply nozzle and nitrogen (N ₂₎ A mixed gas containing 400 parts of volume is supplied into a reaction chamber having an internal pressure of 80 to 400 torr, and a laser generated by a CO ₂ laser generator to a mixed gas supplied into the reaction chamber has a wavelength of 10.6 μm. Irradiation for 3 hours in the form of a line beam of continuous waves to produce silicon-germanium-boron alloy nanoparticles (SiGeB-NPs). The average particle size of SiGeB-NPs is 5 to 400 nm, and the thickness of the oxide layer formed on the surface thereof is 0.75 nm.

Example 6

Silicon-germanium-carbon alloy nanoparticles may be prepared according to Scheme 6 below.

<Scheme 6>

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

100 parts by volume of monosilane (SiH ₄ ), 100 parts by weight of germane (GeH ₄ ), and 40 to 80 parts by weight of acetylene (C ₂ H ₂ ) and nitrogen (N ₂ ) Continuous gas having a wavelength of 10.6 μm is supplied through the irradiator with a laser generated by a CO ₂ laser generator to the mixed gas supplied with 400 parts by volume into a reaction chamber having an internal pressure of 80 to 400 torr. Irradiated for 3 hours in the form of a line beam (Line Beam) of silicon-germanium-carbon alloy nanoparticles (SiGeC-NPs) was prepared. The average particle size of SiGeC-NPs is 5 to 400 nm, and the thickness of the oxide layer formed on the surface thereof is 0.68 nm.

Example 7

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

Scheme 7

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

Through the feed gas supply nozzle, a mixed gas obtained by mixing 100 parts of germane (GeH ₄ ), diborane (B ₂ H ₆ ), 40-80 parts, and 400 parts of nitrogen (N ₂ ), carrier gas, is mixed. The internal pressure is supplied into the reaction chamber 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 continuous beam line beam having a wavelength of 10.6 μm through the irradiation unit. Irradiation for 3 hours to prepare germanium-boron alloy nanoparticles (GeBx-NPs). The particle size of GeBx-NPs is 5-400 nm, and the thickness of the oxide layer formed on the surface is 0.52 nm.

Preparation Example 1

100 mg of the carbon group nanoparticles prepared in Examples 1 to 7 were added to 100 ml of distilled water and ultrasonic wave was irradiated for 10 minutes to prepare a solution of carbon group nanoparticles surface-modified with a hydroxy group at a concentration of 1000 pm and diluted in distilled water to 10 ppm concentration. Solutions 1-1 to 1-7 were prepared.

Preparation Example 2

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

Preparation Example 3

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

Preparation Example 4

100 mg of the carbon group nanoparticles prepared in Examples 1 to 7 was added to 100 ml of glycerin and irradiated for 10 minutes to prepare a solution of carbon group nanoparticles surface-modified with a glyceryl group at a concentration of 1000 pm and diluted in glycerin to 10 ppm concentration. Solutions 4-1 to 4-7 were prepared.

Preparation Example 5

100 mg, 300 mg, and 500 mg of the carbon group nanoparticles prepared in Examples 1 to 7 were added to 100 ml of a water-soluble urethane coating solution, and ultrasonic irradiation was performed for 10 minutes to prepare a urethane coating solution having a concentration of 1000 pm, 3000 ppm, and 5000 ppm (solution). 5-1-1 to solution 5-7-3).

Experimental Example 1

5 ml of solution 1-1 to 1-7, solution 2-1 to 2-7, solution 3-1 to 3-7, and solution 4-1 to 4-7 were each added to a measuring cell of 10 mm thickness and UV-Vis Each block was measured at 400 nm wavelength using the instrument.

solution	Nanoparticles	menstruum	400nm UV Blocking Rate (%)	Remarks
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

1000 ppm, 3000ppm, 5000ppm solution prepared in Preparation Example 5 was spray-coated to a PET film with a thickness of 10um and then measured the blocking rate at 400nm wavelength using a UV-Vis equipment.

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

For reference, when the concentration is 1 ppm or less, UV absorption hardly occurs, and when the concentration is 5000 ppm or more, the viscosity becomes too large and film coating becomes 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 foregoing description of the present invention is intended for illustration, and it will be understood by those skilled in the art that the present invention may be easily modified in 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 exemplary 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 invention is indicated by the following claims, and it should be construed that all changes or modifications derived from the meaning and scope of the claims and their equivalents are included in the scope of the invention.

Claims (8)

1. A sunscreen composition comprising a carbon group non-oxide nanoparticle having an average particle size of 5 to 400 nm and consisting of Si or Ge, and a binder resin.
2. A sunscreen composition having an average particle size of 5 to 400 nm and comprising carbon group non-oxide nanoparticles composed of two elements of Si, Ge, and B, and a binder resin.
3. A sunscreen composition having an average particle size of 5 to 400 nm and comprising carbon group non-oxide nanoparticles composed of SiGeB or SiGeC, and a binder resin.
4. The method according to any one of claims 1 to 3,

   The sunscreen composition is a sunscreen composition comprising 5 to 2000ppm of the carbon group non-oxide nanoparticles based on 100 parts by weight of the binder resin.
5. The method according to any one of claims 1 to 3,

   The carbon group non-oxide nanoparticles are surface-modified by one selected from the group consisting of a hydroxyl group, an alkoxy group, a carboxyl group, a glyceryl group and combinations thereof.
6. Preparing a carbon group non-oxide nanoparticle having an average particle size of 5 to 400 nm and consisting of Si or Ge, consisting of two elements of Si, Ge, and B, or consisting of SiGeB or SiGeC;

   Adding the carbon group non-oxide nanoparticles to a solvent and irradiating ultrasonic waves to prepare a carbon group nanoparticle solution;

   And diluting the carbon group nanoparticle solution in the solvent or binder resin solution.
7. The method of claim 6,

   The solvent is at least one of distilled water, alcohol, fatty acid, the binder resin is one of urethane, acrylic, PE wax, sunscreen composition manufacturing method.
8. The method of claim 6,

   Preparing the carbon group nanoparticles solution,

   Surface modification of the carbon group non-oxide nanoparticles by one selected from the group consisting of a hydroxyl group, an alkoxy group, a carboxyl group, a glyceryl group, and combinations thereof through the ultrasonic irradiation, sunscreen composition manufacturing method.