KR20190081353A - Gold-nanodiamond composite, and cosmetic composition comprising the same - Google Patents

Abstract

The present invention relates to a gold-nanodiamond composite which has color stability maintained for a long time even under heating, acidic, and neutral conditions by binding gold to the surface of a nanodiamond, and a cosmetic product comprising the same. The present invention can maintain dispersion characteristics of nanodiamonds and intrinsic characteristics (intrinsic color and anti-oxidative activity) of gold nanoparticles by forming gold in an island form on the surface of a nanodiamond which is a three-dimensional support. In addition, the composite of the present invention uses a nanodiamond as a three-dimensional support and thus has no toxicity, and prevents agglomeration between the gold nanoparticles due to the dispersion characteristics of diamonds, thereby facilitating re-dispersion and maintaining the inherent color of the gold nanoparticles without discoloration despite the heating or pH varying conditions applied during the manufacture of cosmetic products. Moreover, according to the present invention, gold nanoparticles (4-20 nm) can be uniformly formed on the surface of the nanodiamond for a short period of time, thereby achieving a simple process and obtaining a composite in which gold nanoparticles having a uniform size are formed on the surface of the nanodiamond at a high yield.

Description

Gold-Nano Diamond Composite and Cosmetic Composition Including the Same <br> <br> <br> Patents - stay tuned to the technology GOLD-NANODIAMOND COMPOSITE AND COSMETIC COMPOSITION COMPRISING THE SAME

The present invention relates to a gold-nano diamond composite and a cosmetic composition containing the same, and relates to a gold-nano diamond composite which binds gold to a surface of a nano diamond and maintains color stability and antioxidative effect for a long period of time will be.

Over the past decade, gold nanoparticles have been applied in many areas, including inorganic pigments, antioxidants, electrochemical biosensors, and antimicrobial agents. It is known that gold fine particles having a size of 100 nm or less exhibit a specific color different from that of gold. In particular, when gold particles are manufactured at a level of several nanometers, the surface plasmon resonance absorption phenomenon absorbs light of a specific wavelength region, and a specific color differs depending on the region of the particle size. The gold particles in the region of 2 to 5 nm absorb visible light of 520 nm and become yellow orange. The gold particles in the 10 to 20 nm region are wine red, and the particles in the 30 to 64 nm region are blue-green. However, the gold particles in the colloidal form are generally reduced in electric double layer due to the ions present in the water phase, causing aggregation of the particles, resulting in a change in the color of the trauma. Korean Patent Application No. 2002-701195 and Katherine C. et al. Disclose specific colors depending on the size range of such gold nanoparticles. : Langmuir 1996, 12, 2353, M.A. HAYAT: Colloidal gold 1989, detailed in ACADEMIC PRESS.

Some inventors have attempted to introduce gold, which is a noble metal material, into cosmetics to develop the properties of gold. Korean Patent Application No. 1994-0019541 discloses a method of plating a magnet and introducing it into a cosmetic composition. In addition, US Pat. No. 5,587,168 describes a method of finely crushing gold into flakes and introducing them into cosmetics. Although the above-mentioned patents describe methods for introducing a precious metal such as gold into general cosmetics, high activity can not be expected due to a low surface area of gold in the form of plating or flake, and the amount of gold May cause skin allergy phenomenon, which limits practical application. Furthermore, as a limited appearance form such as flake, there are many restrictions on application of various cosmetic formulations. In addition, when gold nanoparticles are directly introduced into cosmetics in the form of colloids, sedimentation and discoloration due to aggregation of gold particles are known to occur. Thus, it is difficult to apply them to various formulations.

In Korean Registered Publication No. 0-1071788, gold nanoparticles are deposited and fixed on a large surface area of porous polymer particles to maintain the unique color of gold nanoparticles and maximize the efficacy of gold nanoparticles due to their large specific surface area. However, the above-mentioned patent has a complicated process of obtaining a monomer as an emulsion and polymerizing an emulsion to obtain a porous polymer, and it is difficult to obtain a porous polymer of uniform size and performance. To control the size and distribution of these gold nanoparticles, a surfactant containing a ligand having an affinity for gold particles or forming micelles or reverse micelles is used. However, since the surfactant containing a ligand has an affinity for gold ions, the gold nanoparticles interfere with the interaction with the outside (light, molecules, microorganisms).

In addition, when a surfactant that forms micelles or reverse micelles is used, the chemical stability or physical stability of the synthesized gold nanoparticles depends on the surfactant located on the surface of the gold nanoparticles because the gold nanoparticles are located inside the micelles. Therefore, the conventional synthesis of gold nanoparticles using a surfactant has a disadvantage that it is difficult to use the characteristics of the gold nanoparticles as they are unless the molecules for a specific purpose are intentionally placed on the surfaces of the gold nanoparticles.

Recently, gold nanocomposites using a carbon-based support have been actively developed as a support for overcoming disadvantages of manufacturing gold nanoparticles using a surfactant and using a pure gold surface. Carbon nanotubes and graphenes have been proposed as sensors for detecting biomolecules and the like because they are used as supports for gold nanoparticles based on their excellent electrical properties. However, when carbon nanotubes and graphenes are dispersed in a solvent, the dispersing ability is remarkably lowered. Particularly, graphene is formed by a strong van der Waals attractive force between the layer and the layer after formation of the complex with gold, There is a problem that re-dispersion is difficult. Moreover, carbon nanotubes and graphene are toxic, making them difficult to use in cosmetics and the like.

The present invention introduces gold nanoparticles into a cosmetic without using a surfactant to provide the characteristics of the gold nanoparticles as they are.

The present invention provides a gold complex which is free from toxicity and easy to redisperse.

The present invention is to provide a composite that is simple in process and uniform in size.

The present invention provides a composite which is excellent in stability and can keep the unique color of gold nanoparticles without discoloration for a long period of time despite changes in conditions such as heat and pH, and a cosmetic comprising the composite.

According to one aspect of the present invention for achieving the above object,

Nanodiamond complexes in which one or more gold nanoparticles are formed on the surface of a nanodiamond aggregate formed by agglomerating nanodiamond particles of several nanometers in size.

In another aspect,

Surface-modifying the nanodiamond aggregates;

Dispersing the surface-modified nanodiamond aggregates in a solvent;

Mixing the dispersion with a gold salt and adjusting the pH;

Adding a reducing agent to the dispersion to reduce gold; And

And separating and drying the gold-nano diamond composite from the dispersion.

    In the present invention, gold islands are formed on the surface of a nanodiamond aggregate, which is a three-dimensional support, so that dispersion characteristics of the nanodiamond and the intrinsic properties (inherent color, antioxidant ability) of the gold nanoparticles can be maintained. In addition, since the composite of the present invention uses nanodiamond as a three-dimensional support, there is no toxicity, and since dispersion of diamond prevents the aggregation of gold nanoparticles, it is easy to redisperse, The unique color of the gold nanoparticles can be maintained without discoloration. In addition, since the present invention can uniformly form gold nanoparticles on the surface of a nano diamond for a short time, a composite having a simple process and a uniform size can be obtained.

FIG. 1 is a conceptual diagram showing a manufacturing process of a gold-nanodiamond composite.
FIG. 2 is a TEM photograph of a gold-nanodiamond composite. FIG.
FIG. 3 is a graph of dynamic light scattering analysis of the nano diamond-COOH and the gold-nano diamond composite obtained in the production example.
4 is a Fourier transform infrared spectroscopy graph of the nano diamond-COOH and the gold-nano diamond composite obtained in the Production Example.
Fig. 5 compares redispersibility of water of Example 1 and Comparative Example 1 in water.
6 shows the dispersion stability of Example 1 and Comparative Example 1 for 30 days.
Fig. 7 shows the dispersion of Comparative Example 2, the dispersion of Example 1, the dried powder (composite powder), and the redispersed powder.
Fig. 8 is a photograph of a dispersion solution after warming Comparative Example 2 (gold nanoparticle dispersion) and Example 1 at 100 占 폚 for 30 minutes.
Figure 9 shows the antioxidant efficacy persistence and vitamin C stability of Example 1
10 compares the results of Example 2 and Comparative Example 3 before and after heating to 60 ° C.
Fig. 11 is a graph comparing color stability by changing the pH of Example 2 and Comparative Example 3. Fig.

Hereinafter, preferred embodiments of the present invention will be described with reference to the drawings. However, the scope of the present invention is not limited to the description or drawings of the following embodiments. That is, the terminology used herein is for the purpose of describing particular embodiments only and is not intended to limit the present invention. The singular expressions include plural expressions unless the context clearly dictates otherwise. It is also to be understood that the terms such as " comprises "or" having ", as used herein, are intended to specify the presence of stated features, integers, steps, operations, But do not preclude the presence or addition of other features, numbers, steps, operations, elements, or combinations thereof.

The present invention relates to a gold-nano diamond composite and a cosmetic comprising the same.

In the gold-nanodiamond composite of the present invention, one or more gold nanoparticles are attached to the surface of a nanodiamond aggregate in which several nanometer-sized (explosive) nanodiamond particles are entangled.

Nanodiamonds are composed of core (carbon SP3 structure) and surrounding graphite (SP2 structure), and on the graphite surface, single and multiple functional groups of C, O, H and N exist. Representative functional groups thereof include functional groups such as COOH, C = O, NH2, CHO, OH, NO2, -C-O-C-, phenol groups and -SH. Generally, the core size of the explosive nanodiamonds is about 4 to 7 nm and the graphite layer is about 1 nm.

The nanodiamond aggregates represent nanodiamonds in which single-phase nanodiamond particles are clustered in several to several tens, preferably less than ten.

The surface functional group of the nanodiamond aggregates may be surface modified with at least one of Carboxyl, Lactone, Hydroxy and Thiol, and preferably surface modified with a carboxyl group. The functional groups on the surface of the nanodiamond aggregates and the electrostatic attraction between the gold ions may act to form gold nuclei on the surface of the nanodiamonds.

The average size of the nanodiamond aggregates may be 10 to 500 nm, preferably 10 to 300 nm. The number of functional groups on the surface of the nanodiamond aggregates may be 10,000 or more and 1,000,000 or less.

Regarding the structure and properties of the nano-diamond of the present invention, reference can be made to the prior applications 10-2015-0064876, 10-2015-0064874, 10-2014-0166749, and 10-2014-0166755 of the present applicant.

The size of the gold-nanodiamond composite may be 20 to 600 nm, preferably 20 to 400 nm. The size of the gold nanoparticles formed on the surface of the nanodiamond may be 4 to 100 nm, preferably 4 to 20 nm.

The gold-nanodiamond composite includes a nanodiamond aggregate used as a three-dimensional support and gold particles formed in a plurality of islands on the surface of the nanodiamond aggregate.

The nanodiamond aggregates form a gold ligand complex through interaction with gold ions (through a surface functional group), and gold nanoparticles are formed on the surfaces of the nanodiamonds by adding a reducing agent thereto. Therefore, a three-dimensional support .

The gold nanoparticles are not coated on the entire surface of the nanodiamond aggregates but are formed in a plurality of islands.

The surface density of the gold in the gold-nanodiamond composite may depend on the particle size of the nanodiamond aggregates used, the gold precursor content, and the size of the gold nanoparticles formed. For example, the gold-nanodiamond composite may have 0.0006 to 30, 0.0006 to 25, 0.0006 to 20, 0.0006 to 15, 0.0006 to 10, 0.0006 to 4 gold particles per 100 nm ² of nano diamond surface area 4 to 20 nm). Referring to FIG. 2, a nanodiamond aggregate having an average particle size of 50 nm (Z average distribution) includes 1 to 3 gold nanoparticles having a size of 8 nm on its surface.

As the gold nanoparticles are formed on the surface of the nanodiamonds in the form of gold nanodiamonds, the dispersion characteristics of the nanodiamonds can be maintained. That is, the gold-nanodiamond composite may be dispersed in a hydrophilic solvent such as an aqueous solution for a long period without being aggregated with each other.

As a result, since the gold nanoparticles are formed on the surfaces of the nanodiamond clusters, aggregation between the gold nanoparticles does not occur, so that re-dispersion is easy, and in spite of physical and chemical changes such as heating and pH The unique color of gold nanoparticles can be maintained without discoloration.

FIG. 1 is a conceptual diagram showing a manufacturing process of a gold-nanodiamond composite. 1, the method for preparing a gold-nanodiamond composite of the present invention comprises the steps of: surface-modifying a nanodiamond aggregate; mixing the surface-modified nanodiamond aggregates and gold salts (gold spheres) into a hydrophilic solvent; To reduce the gold, and separating and drying the gold-nano diamond composite from the solution.

The present invention can surface-modify nano-diamonds by acid treatment.

The weight ratio of the gold precursor and the nanodiamond added in the mixing step may be 1: 0.4 to 100, preferably 1: 1 to 50, more preferably 1: 2 to 25.

In the mixing step, the nanodiamonds may be mixed by adding 0.001 to 10 wt%, 0.001 to 5 wt%, a gold salt (gold precursor), 0.00001 to 15 wt%, and 0.00001 to 12.5 wt%.

The pH of the mixing step and the reducing step may be adjusted to 3 to 13, preferably 7 to 12, by using a pH adjusting agent.

For example, the reducing step may be performed by mixing a gold precursor solution in a solution in which nanodiamonds are uniformly dispersed, adjusting the pH to 8 to 13, and then adding a reducing agent. The method can control the density and size of gold formed on the surface of the nano diamond by controlling the amount of the gold precursor and the pH of the solution.

As the reducing agent, known lithium alumina hydride (LiAlH4) or sodium borohydride (NaBH4) may be used.

In the separation and drying step, the synthesized gold-nano diamond composite is subjected to repetitive centrifugation to remove reaction by-products and the gold-nano diamond composite can be separated. In addition, in the separation and drying step, the separated composite is dispersed again in ethanol and dried using a rotary evaporator to obtain a powdery composite.

The gold-nano diamond composite may be used as a pigment.

The present invention may be a cosmetic comprising the gold-nanodiamond composite.

. The present invention can provide a cosmetic composition including the gold-nano diamond composite and the solvent.

The solvent may be hydrophilic or hydrophobic.

The gold-nanodiamond composite may be contained in cosmetics as a powder itself or may be dispersed in cosmetics under acidic and neutral conditions to maintain its warming and color stability.

The gold-nanodiamond composite can be referred to above.

The cosmetic may contain 0.00001 to 15 wt% and 0.00001 to 12.5 wt% of the gold-nanodiamond composite.

The cosmetic may be, but not limited to, a lotion, a serum, a cream, an emulsion, a cream pack, a mask pack, a liquid body cleansing liquid, a UV care cosmetic, a lipstick, a makeup cosmetic or a hair cosmetic.

The cosmetic may include water, a skin conditioner, a moisturizer, a whitening agent, an antioxidant, a sunscreen agent, a surfactant, a thickener, an alcohol, a preservative, a gelling agent, an incense, a filler or a dye.

The cosmetic may not contain a surfactant.

The cosmetic composition may contain cosmetic ingredients such as water, a skin conditioner, a moisturizer, a whitening agent, an antioxidant, a sunscreen agent, a surfactant, a stabilizer, a viscosity adjuster, an alcohol, a preservative, a gelling agent, Diamond complexes and hydrophilic solvents.

Since the cosmetic of the present invention has the gold nanoparticles formed on the surface of the nanodiamonds, the original color of the gold nanoparticles can be maintained without discoloration and can have antioxidant properties despite the heating or pH fluctuation conditions applied in the production of cosmetics.

  Hereinafter, the present invention will be described in more detail with reference to the following examples, but they should be construed as merely illustrative of preferred embodiments of the present invention, and the examples do not limit the scope of the present invention.

Manufacturing example  One

Manufacture of nanodiamond-COOH (ND-COOH)

10 g of finely dispersed nanodiamonds having an average particle size of 50 nm were placed in 600 ml of sulfuric acid and nitric acid at a volume ratio of 3: 1 and reacted at 140 ° C for 12 hours. The particles obtained through centrifugation were confirmed to be ND-COOH through FT-IR.

 gold- Nanodiamond  Composite manufacturing

7 mg of ND-COOH prepared above was added to 14 ml of distilled water and ultrasonicated to disperse. 0.1 ml of an aqueous solution containing 1.48 mg of HAuCl4 was added to the dispersion of nanodiamonds and then stirred. Then, 0.1 ml of an aqueous solution containing 0.14 mg of sodium borohydride (NaBH4) was further introduced into the dispersion and stirred at room temperature for 2 hours . The centrifugal separation was repeated and dried to obtain a powder-shaped gold-nano diamond composite.

Graphene oxide / Production of gold (GO / Au) nanocomposite

7 mg of graphene oxide, which was supplied by Graphenol Co., was added to 14 ml of distilled water titrated to pH 11 with sodium hydroxide (NaOH) and dispersed by ultrasonication. 0.1 ml of HAuCl4 dissolved in 0.1 ml of water was added to the graphene oxide dispersion and stirred for 30 minutes. Then, 0.1 ml of an aqueous solution containing 0.14 mg of sodium borohydride (NaBH4) was added to the dispersion and the mixture was stirred for 2 hours at room temperature Lt; / RTI &gt; The centrifugal separation was repeated and dried to obtain a powdery sample.

Example  1 and Comparative Example  One

The dispersion stability of the 30 day sample was observed and confirmed by DLS by dispersing the gold-nanodiamond composite (Example 1) and the graphene-gold complex (Comparative Example 1) prepared previously in 100 ml of distilled water of pH 7.4, respectively.

Comparative Example  2

A citrate-stabilized gold nanoparticle dispersion (gold nanoparticle size 8 nm, 10 ml aqueous solution) synthesized by the Turkevich method was prepared and dried to obtain a gold nanoparticle powder. The obtained powder was redispersed in 10 ml of distilled water.

Example 2, Comparative Example 3 (Preparation of cosmetic composition)

Cosmetic materials were prepared with the ingredients and contents shown in Table 1 below. Surfactants were not added to the ingredients of Table 1.

ingredient Example 2 (% by weight) Comparative Example 3 Nolly Water 72.85% Same as left Butylene glycol 9.4% Panthenol 8% Phage-7 glyceryl cocoate 5% Propylene glycol 3% 1,2-hexanediol 1.5% Carbomer 0.1% The gold-nano diamond composite dispersion (5000 ppm) 5% Gold nanoparticle dispersion (5000 ppm)

The cosmetic composition having the components as shown in Table 1 was mixed and stirred while heating at 60 ° C, and a dispersion of the gold-nano diamond composite (Example 2) and a gold nanoparticle dispersion (Comparative Example 2) were respectively added to obtain a cosmetic.

2 is a TEM photograph of a gold-nano diamond composite. Referring to FIG. 2, it can be seen that three gold nanoparticles having a size of 8 nm are formed on a surface of a nanodiamond aggregate having an average particle size of 50 nm (Z average distribution), and are spaced apart from each other by a predetermined distance.

3 is a graph of the dynamic light scattering analysis (volume-average distribution) of the nano diamond-COOH and the gold-nano diamond composite obtained in the production example. 4 is a Fourier transform infrared spectroscopy graph of the nano diamond-COOH and the gold-nano diamond composite obtained in the Production Example. 3 and 4, the volume of the gold-nanodiamond composite increased compared to that of the nanodiamond-COOH (FIG. 3), indicating that the absorption wavelength of COOH in the gold- It can be predicted that there was.

5 compares the redispersibility of Example 1 and Comparative Example 1 (graphene-gold complex) in water. Referring to FIG. 5, in Comparative Example 1, the disappeared gold remained in the redispersed aqueous solution, but it was confirmed that the gold-nano diamond composite redispersed in Example 1 remained intact.

6 shows the dispersion stability of Example 1 and Comparative Example 1 for 30 days. Referring to FIG. 6, it can be seen that in Example 1, after 30 days have elapsed, the uniqueness of the gold color is not changed.

Fig. 7 shows the dispersion of Comparative Example 2, the dispersion of Example 1, the dried powder (composite powder), and the redispersed powder. Referring to FIG. 7, Example 1, which is redispersed in powder, shows the original unique color of gold.

FIG. 8 is a photograph of a dispersion solution after warming Comparative Example 2 (gold nanoparticle dispersion) and Example 1 at 100 ° C. for 30 minutes. Referring to FIG. 8, in Comparative Example 2, the gold nanoparticles aggregated and precipitated through the warming process. In Example 1, however, the gold nanoparticles were formed in island form in the nanodiamonds, .

Fig. 9 shows the antioxidant efficacy persistence and vitamin C stability of Example 1. Fig. Referring to FIG. 9, the gold-nano diamond composite of Example 1 maintains the antioxidative effect for 3 months. However, it can be confirmed that the vitamin C is denatured more than 90% within 1 week.

FIG. 10 is a graph comparing the color stability of Example 2 and Comparative Example 3 before and after heating to 60 ° C, and FIG. 11 is a graph comparing the color stability of Example 2 and Comparative Example 3 by changing the pH. 10 and 11, the cosmetic material of Comparative Example 3 was inferior in color stability due to particle size increase and precipitation phenomenon due to the aggregation of gold nanoparticles under heating or acidic conditions, but the cosmetic material of Example 2 was heated to 60 ° C Or even if the pH is changed to acidic, it still can be confirmed that the unique color of gold is maintained.

While the present invention has been particularly shown and described with reference to exemplary embodiments thereof, it is to be understood that the invention is not limited to the disclosed exemplary embodiments.

Claims (9)

A gold-nanodiamond composite in which one or more gold nanoparticles are formed on the surface of a nanodiamond aggregate formed by agglomerating nanometer-sized nanodiamonds. The gold-nano diamond composite according to claim 1, wherein the size of the gold-nanodiamond composite is 20 to 600 nm and the size of the gold nanoparticle is 4 to 20 nm. The gold-nano diamond composite according to claim 1, wherein the surface density of gold in the gold-nano diamond composite is 0.0006 to 30 gold particles per 100 nm ^{2 of the} surface area of the nano-diamond aggregate.
Here, the diameter of the gold nanoparticles is 4 to 20 nm. The gold-nano diamond composite according to claim 1, wherein the nanodiamond aggregates are used as a three-dimensional support, and the gold nanoparticles are formed in the form of islands on the surface of the nanodiamond aggregates. A cosmetic comprising the gold-nanodiamond composite according to any one of claims 1 to 4. 5. A pigment comprising a gold-nanodiamond composite according to any one of claims 1 to 4. 6. The cosmetic according to claim 5, wherein the cosmetic comprises 0.0001 to 15% by weight of the gold-nanodiamond composite. Surface-modifying the nanodiamond aggregates;
Dispersing the surface-modified nanodiamond aggregates in a solvent;
Mixing the dispersion with a gold salt and adjusting the pH;
Adding a reducing agent to the dispersion to reduce gold; And
And separating and drying the gold-nano diamond composite from the dispersion. The method of claim 8, wherein the gold nanodiamond composite is prepared by mixing 0.001 to 15 wt% of a gold precursor with 0.001 to 10 wt% of a nanodiamond aggregate dispersion.

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