KR101819713B1 - Patch composition comprising gold nanoroad - Google Patents

Abstract

The present invention relates to a patch composition containing gold nano-rods. When skin temperature rises by 10C, the absorbency of a drug or functional cosmetic composition can increase three times due to expanded skin pores. Accordingly, the patch composition can induce the light emitting effects of the gold nano-rods by using a near-infrared LED light source to raise the skin temperature, being 30C in average, up to 40C, thereby increasing the delivery efficiency of the beneficial substances into the skin. By inducing the light emitting effects, the blood circulation in the human body can be promoted while maintaining the optimal body temperature state. The patch composition can discharge the heavy metals from the human body and alleviate skin pain while deodorizing, purifying, and detoxing the skin as well as preventing harmful bacteria or fungus from affecting the human body.

Description

[0001] Patch compositions comprising gold nanoroad [0002]

The present invention relates to a patch composition containing gold nanorods. In particular, the present invention relates to a patch composition containing gold nanorods coated with silica or polyethylene glycol, which has an effect of increasing the drug delivery efficiency into the skin by utilizing an exothermic reaction action of gold nanorods.

Recently, various LED masks have been developed based on the fact that mask treatment products utilizing LED light sources are different from each other in light of the effect of skin treatment according to the light source wavelength. However, conventional LED masks have been reported to be performed at dermatological hospitals or skin beauty shops because they are expensive to be purchased by the general public. Most of LED masks sold domestically and overseas are using UV light and near-infrared light mixed with light based on the improvement effect of skin by wavelength of light. Infrared rays have wavelengths of 700 nm to 1 mm and are classified into IR-A (near IR, λ = 750 to 1,400 nm), IR-B (Mid IR, λ = 1,400 to 3,000 nm) IR-B is the most common type of IR-A, and IR-C is the most common IR-IR. . Thus, since there is almost no substance that absorbs light in the near infrared (NIR) region in the human body, the human penetration power is the highest, and thus the near infrared ray wavelength region is called the near infrared ray window or optical window of our body and is widely used for medical treatment .

Metal nanoparticles, such as gold, form surface plasmon resonance (SPR) by free electron clouds oscillating through free electron interactions with external electromagnetic waves. For example, gold nanoparticles with a particle size of about 10 nm meet the SPR conditions at a wavelength of about 520 nm according to the Mie theory and cause strong extinction (scattering + absorption) (Phys. Chem. , 2005, 7, 3258-3268; Solid State Physics, 1976, Brooks Cole). The spherical gold nanoparticles have the same SPR phenomenon in all directions, while the gold nanorods are different in the path of oscillation of the electron clouds in the longitudinal and transverse directions due to the external electromagnetic wave, and the SPR condition occurring in the longitudinal direction is in the transverse direction Is generated by light of a longer wavelength than the SPR condition of FIG. That is, as the aspect ratio increases, the longer the length of the gold nanorods becomes, the more the absorption peak at the longer wavelength causes the red-shift. Generally, at the wavelength of the near infrared region of 700 to 1,200 nm, Strong absorption occurs. In this case, when the light in the strong near infrared region is irradiated to the gold nanorod, free electrons oscillate rapidly along the longitudinal axis of the gold nanorod, and collide with the gold atom and are converted into heat. In this way, Photothermal effect.

The inventors of the present invention have studied various features of gold nano-rods and confirmed that the composition containing gold nano-rods can be used as a patch composition having excellent drug transferability by using exothermic phenomenon.

Korean Registered Patent No. 10-1333962 (Name of the invention: Method for manufacturing gold nano-rods, Applicant: Industry-Academic Collaboration Foundation, Kumoh National Institute of Technology, Registered on November 21, 2013) Korean Patent Laid-Open No. 10-2015-0122869 (title of the invention: cosmetic composition for blocking near-infrared rays and near-infrared ray blocking agent, applicant: Kumho University Industry & University Collaboration Foundation, publication date: November 03, 2015)

C. Vericat, M. E. Vela, and R. C. Salvarezza, Phys. Chem. Chem. Phys., 2005, 7, 3258-3268. N. W. Ashcroft, and N. D. Mermin, Solid State Physics, 1976, Brooks Cole.

It is an object of the present invention to provide a patch composition containing gold nanorods. More specifically, it is an object of the present invention to provide a patch composition containing gold nanorods coated with silica or polyethylene glycol, which has an effect of increasing the drug delivery efficiency into the skin by utilizing an exothermic reaction action of gold nano rods .

The present invention relates to a patch composition containing gold nanorods.

The gold nanorods may be coated with silica or polyethylene glycol.

The drug composition may be carried on the patch composition.

The drug may be at least one selected from the group consisting of anti-wrinkle agents, whitening agents, antioxidants, anti-inflammatory agents, hair growth agents, skin cancer treatment agents, allergy inhibitors and atopic inhibitors.

The patch composition may contain a thickening agent.

The patch composition may be added with a moisturizing agent.

At least one selected from the group consisting of hyaluronic acid, carrageenan gum, agarose, agaropectin, cellulose gum, xanthan gum, gellan gum, agar, tamarind gum, guar gum and gum arabic can be selected as the above- have.

The concentration of the gold nano-rods contained in the patch composition of the present invention is 0.02 to 0.40 wt%.

As the moisturizing agent, at least one selected from the group consisting of glycerin, glycerol, urea, amino acid, lactate and pyroglutamic acid may be used.

The present invention also relates to a gel patch for transdermal delivery comprising a shaped body in which the patch composition is physically crosslinked. The gel patch has a thickness of 0.5 to 3 mm.

The present invention also provides a method for producing a gel mask comprising the following steps.

(Step 1) To a solution of hexadecylsethyltrimethylammonium bromide aqueous solution and hydrogen tetrachloroaurate (III) tetrahydrate aqueous solution was added an aqueous sodium borohydride solution to prepare a solution containing a gold seed ≪ / RTI >

An aqueous solution of silver nitrate and an aqueous solution of ascorbic acid as a reducing agent, which are catalysts for synthesizing gold nano rods, were added with stirring to prepare a growth solution. The aqueous solution of gold nitrate and the aqueous solution of ascorbic acid Producing;

(Step 2) mixing and stirring the solution containing the gold seed and the growth solution, removing the upper layer solution by centrifugation, and dispersing the remaining solution in distilled water to obtain a solution containing the gold nanorod;

(Step 3) adding a polyethylene glycol thiol or a silane-based material to a solution containing gold nano-rods to obtain a solution containing gold nanorods coated with polyethylene glycol or silica; And

(Step 4) Stirring a mixture solution of a solution containing a gold nanorod coated with polyethylene glycol or silica and a thickener and a humectant, and then pouring the mixture into a mold to form a gel mask .

Hereinafter, the present invention will be described in detail.

The present invention relates to a patch composition containing gold nano-rods, wherein the gold nano-rods have an aspect ratio of 2 to 7. If the aspect ratio of the gold nano-rods is less than 2 or more than 7, the heat transfer efficiency of the patch composition may be reduced. The length of the gold nano-rods may be from 30 to 1000 nm, preferably from 30 to 500 nm.

The concentration of the gold nano-rods included in the patch composition of the present invention is 0.02 to 0.40 wt%, preferably 0.022 to 0.33 wt%. Based on 100% by weight of the patch composition of the present invention, 1 to 5% by weight of the thickener and 2.5 to 25% by weight of the moisturizer may be included.

The patch composition of the present invention may be coated with silica or polyethylene glycol, more preferably silica coated with polyethylene glycol. In this case, as shown in FIG. 14, since GNR @ SiO ₂ coated with Silica can carry various drugs (eg, wrinkle remover, whitening agent, moisturizer, hair remover, skin cancer remedy) in the porous silica layer, .

The patch composition of the present invention may contain a target material, and the target material may be any drug capable of delivering the skin. The target substance may be at least one drug selected from the group consisting of a wrinkle reducing agent, a whitening agent, an antioxidant, an anti-inflammatory agent, a hair growth agent, a skin cancer treatment agent, an allergic inhibitor and an atopic inhibitor. The drug may be a natural compound, a natural extract, a powder of a natural product, a synthetic compound, a natural peptide, a recombinant peptide, a microorganism or a culture thereof, a mineral or the like. As the wrinkle-reducing agent, silicate acid, N-methyl-L-serine, and the like, which inhibit MMP-1, an extracellular matrix (ECM) Isoflavonoids, Dehydroepiendrosterone, Paoniflorin, and the like can be selected, and it is possible to remove active oxygen which promotes the collapse of ECM, Benzene, benzastatins, coenzyme Q10, and the like. In addition, adenosine, ascorbyl glucoside, kinetin, auxin, peptides, retinoic acid, peptide, retinol, retinyl palmitate, polyethoxylated retinamide, alpha hydroxyl acid, and the like. The whitening agent may be at least one selected from the group consisting of arbutin, niacinamide, ascorbic acid, magnesium ascorbyl phosphate, ascorbyl acid-2-glucoside, , Mulberry extract, ethyl ascorbyl ether, oil soluble licorice extract, etc. In addition, collagen and various vitamins can be added as the above drug, and it is possible to promote the epidermal cell proliferation, Roxy < / RTI > proline, and the like.

The type of the thickening agent included in the patch composition of the present invention is not limited to a wide range, but includes hyaluronic acid, carrageenan gum, agarose, agaropectin, cellulose gum, xanthan gum, gellan gum, agar, tamarind gum, guar gum, Gum, and the like.

In the method for producing a gel mask of the present invention, the following methods can be used in more detail.

(Step 1) To a solution of hexadecylsethyltrimethylammonium bromide aqueous solution and hydrogen tetrachloroaurate (III) tetrahydrate aqueous solution was added an aqueous sodium borohydride solution to prepare a solution containing a gold seed ≪ / RTI >

An aqueous solution of silver nitrate and an aqueous solution of ascorbic acid as a reducing agent, which are catalysts for synthesizing gold nano rods, were added with stirring to prepare a growth solution. The aqueous solution of gold nitrate and the aqueous solution of ascorbic acid Producing;

(Step 2) mixing and stirring the solution containing the gold seed and the growth solution, removing the upper layer solution by centrifugation, and dispersing the remaining solution in distilled water to obtain a solution containing the gold nanorod;

(Step 3) adding a polyethylene glycol thiol or a silane-based material to a solution containing gold nano-rods to obtain a solution containing gold nanorods coated with polyethylene glycol or silica; And

(Step 4) Stirring a mixture solution of a solution containing a gold nanorod coated with polyethylene glycol or silica and a thickener and a humectant, and then pouring the mixture into a mold to form a gel mask .

In this case, in the first step, the volume and concentration of each solution are not particularly limited, but preferably 0.05 to 5 mM of hexadecylsethyltrimethylammonium bromide aqueous solution, hydrogen tetrachloroaurate (III) tetrahydrate It is preferable to use an aqueous solution having a concentration of 0.05 to 5 mM and a sodium borohydride aqueous solution having a concentration of 1 to 50 mM, and the mixing ratio of each solution is preferably 1: 0.1 to 5: 0.05 to 0.5.

Also, in the first step, the solution containing the gold seed is preferably 90 minutes or more after the preparation, and the time for the solution is not particularly limited, but is preferably aged for 90 minutes to 6 hours.

In the second step, the solution containing the gold seed and the gold nanorod growth solution may be mixed at a volume ratio of 1: 500-2000.

The gold concentration of the gold nano-rod solution obtained in the second step may be 400-600 μg Au / ml.

In the second step, the volume and concentration of each solution or sample for preparing the growth solution is not particularly limited, but preferably 300 to 3000 ml of 0.5 to 5 mM chloroauric acid (HAuCl ₄ .4H ₂ O) (40 to 300 mM hexadecylsethyltrimethylammonium bromide (CTAB) and 30 to 70 mM benzyldimethylhexahexa (BDAB) mixed with hexadecyltetrimethylammonium bromide (CTAB) and 30 benzyldimethylhexadecylammonium chloride Decyl ammonium chloride (BDAC)), 20 to 70 ml of 1 to 10 mM silver nitrate, which is a catalyst for synthesizing gold nano rods, was added, and 10 to 20 ml of a reducing agent, 50 to 100 mM aqueous ascorbic acid solution, And the like.

In the second step, the solution containing the gold nano-rods may be centrifuged again, the upper layer solution may be removed, and the remaining solution may be dispersed in the distilled water. The washing step may be added one to three times. In this step, hexadecylsethyltrimethylammonium bromide Can be removed to obtain a solution containing more refined gold nanorods.

In the third step, 10 to 50 mg of polyethylene glycol-thiol per 100 ml of the solution containing the gold nano-rods may be added, and the reaction may be performed for 3 to 30 hours. More preferably, the reaction can be carried out for 3 to 24 hours.

In preparing the gold nanorods coated with silica in the third step, for the silica coating, trimethoxysilylpropyl aniline (TMSPA), tetramethylorthosilicate, tetraethylorthosilicate, tetrapropylorthosilicate, tetrabutylorthosilicate And a mixture of these materials may be used.

When the silane-based material is added to the solution containing the gold nano-rods in the third step, alcohol is mixed and stirred in the solution, then distilled water and a sodium hydroxide solution are added, and an alcohol solution containing a silane-based material is added And stirred to obtain a solution of gold nanorods coated with silica. Preferably, 1 to 10 ml of alcohol is mixed per 10 ml of the solution containing the gold nano-rods and stirred. Then, 5 to 10 ml of distilled water and 100 to 300 μl of a 0.03 to 0.5 M sodium hydroxide solution are added, and 10 to 30 (v / v )% Of an alcohol solution containing silane-based material is added at intervals of 10 to 60 minutes for 1 to 5 times and stirred to obtain a silica-coated gold nano-rod solution. The alcohol is preferably ethanol or methanol.

In the fourth step, the solution containing the gold nanorods coated with polyethylene glycol or silica, the mixture of the thickener and glycerin may be stirred at 60 to 80 ° C.

At this time, 0.01 to 0.1 g of the gradually increasing agent and 0.025 to 0.5 g of the moisturizing agent were mixed with 1 ml (140 to 580 ㎍ Au / ml) of the solution containing the gold nanorod coated with polyethylene glycol or silica in the fourth step .

In each step of the production of the gel mask of the present invention, each stirring time or mixing time may be 1 minute to 48 hours, and centrifugation may be performed at 200 to 2000 rpm.

The present invention relates to a patch composition containing gold nanorods. It is known that when the skin temperature rises by about 10 ° C, the absorbency of drug or functional cosmetic is increased about three times or more through the enlarged skin pores. Therefore, by using the patch composition of the present invention, it is possible to increase the skin temperature of about 30 ° C to about 40 ° C by inducing the photothermal effect of the gold nanorod using a near-infrared LED light source to increase the delivery efficiency of the usable substance into the skin It can be easily induced. In addition, this induction of light effect promotes blood circulation in the body, maintains optimal body temperature condition, can affect the body's heavy metal discharge, skin pain, deodorization, purification and detoxification and prevents harmful bacteria and mold Can be obtained. Korean Patent No. 10-1333962 and Korean Patent Laid-Open No. 10-2015-0122869 disclose techniques for producing gold nanorods and cosmetics for blocking near-infrared rays using the same, No description has been made about a patch composition containing gold nano-rods with enhanced drug transfer through irradiation of LEDs.

FIG. 1 is a transmission electron microscope photograph of the GNR produced in Example 1 and the GNR @ SiO ₂ produced in Example 2. In the following description, GNR denotes a gold nano-rod, GNR @ SiO ₂ denotes a silica- Respectively.
2 is a graph showing the UV-Vis absorption spectrum of GNR and GNR @ SiO ₂ .
Fig. 3 is a photograph showing an average skin temperature according to a face region (forehead, eyes, mouth, wrinkles) of a person.
4 GNR @ SiO ₂ 6 is a photograph showing the state of a coated slide glass substrate.
5 is a graph showing a temperature change when laser irradiation is performed on a slide glass (Control).
6 is a graph showing a temperature change when a laser is irradiated on a slide glass (GNR @ SiO ₂ according to concentration).
7 is a photograph of a commercial nude gel coated with GNR @ SiO ₂ .
8 is a graph showing the temperature change of a commercial nude Gel mask (concentration-GNR @ SiO ₂ ) coated with commercial nude Gel mask (Control) and GNR @ SiO ₂ .
9 is a photograph showing the state of a Gel mask to which various concentrations (0.017-0.33 wt%) of GNR @ SiO ₂ solution are added.
10 is a photograph showing the temperature change when a laser mask is irradiated with Gel mask (Control) to which distilled water is added instead of GNR @ SiO ₂ solution.
Fig. 11 is a photograph showing the temperature change when a Gel mask made of GNR @ SiO ₂ (574.8 쨉 g Au / ml [0.33 wt% GNR @ SiO ₂ ]) in a raw solution state was laser-irradiated.
When Figure 12 is a laser hayeoteul Gel mask made of SiO ₂ of the GNR @ undiluted state 2, 4, 8, 16-fold diluted with a GNR _{@ SiO 2 [0.093, 0.072,} 0.022, 0.017wt% GNR @ SiO 2] Survey Fig.
13 is a photograph showing the temperature change when a Gel mask to which GNR (PEG-GNR) coated with polyethylene glycol is added is irradiated with laser.
14 is a schematic diagram showing GNR < _{RTI ID = 0.0} > SiO2 < / _RTI >
15 is a schematic diagram showing the principle of exposing the anti-wrinkle agent / drug to GNR @ SiO ₂ and irradiating near infrared rays to release the anti-wrinkle agent / drug due to the temperature rise.

Hereinafter, preferred embodiments of the present invention will be described in detail. However, the present invention is not limited to the embodiments described herein but may be embodied in other forms. Rather, these embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the concept of the invention to those skilled in the art.

≪ Example 1: Production of gold nano rods >

Example 1-1. Synthesis of Gold seed

First, a gold seed was synthesized to synthesize a gold nanorod (GNR). Gold seed was prepared by adding 0.01 M NaBH ₄ aqueous solution cooled to about 4 ° C to a solution of 5 ml of 0.5 mM hexadecylcetyltrimethylammonium bromide (CTAB) aqueous solution and 5 ml of 0.5 mM aqueous solution of hydrogen tetrachloroaurate (III) tetrahydrate (HAuCl ₄ .4H ₂ O) 0.6 ml was added and vortexed for 3 minutes to prepare a solution containing 2 to 3 nm of gold seed. The synthesized seed solution was aged for 2 hours and 30 minutes at room temperature before use and used for GNR growth.

Examples 1-2. Growth solution preparation

GNR growth solution was prepared to fabricate gold seeds in GNR. First, 1mM of HAuCl ₄ · 4H ₂ O 1,000 mL of aqueous solution was mixed with 1,000 mL of hexadecylcetyltrimethylammonium bromide (CTAB) and benzylhexadecylammonium chloride (BDAB) aqueous solution (CTAB 150 mM, 50 mM of benzylhexadecylammonium chloride and about 1/3 of BDAC / CTAB) ₃ 4 mM (50 ml) was added and 79 mM (14 ml) of reducing agent, ascorbic acid, was added with stirring. At this time, the color of the solution changes from dark yellow to colorless as Au (III) is reduced to Au (I).

Examples 1-3. GNR growth and cleaning

When 2.4 mL of the aged Gold seed solution prepared in Example 1-1 was added to GNR growth solution (2064 mL) under stirring, the color of the solution changed from colorless to wine color within about 1 hour, and the reaction was further continued for 24 hours A solution containing GNR (aspect ratio: about 4, length: about 60 nm, width: about 15 nm) was obtained. Next, to remove excess CTAB present in the solution, the solution was centrifuged at 15,000 rpm for 20 minutes. Then, the upper layer solution was removed and the remaining solution was dispersed in 200 ml of distilled water. This washing procedure was repeated twice to prepare the final GNR solution. The concentration of final GNR solution was measured by AAS (Atomic Absorption Spectroscopy) analysis.

≪ Example 2: Preparation of gold nano-rods coated with polyethylene glycol >

The GNR finally prepared in Example 1 is coated with a small amount of CTAB even after the surface cleaning. CTAB is known to have high cytotoxicity because it decomposes the cell wall. Therefore, to reduce cytotoxicity, the surface of GNR was coated. For this, CTAB was removed by coating with Polyethyleneglycol thiol (PEG-SH, M.W = 2000). For the PEG-SH coating, 34 mg of PEG-SH was added to 100 ml of the GNR solution finally prepared in Example 1, followed by reaction for 24 hours. After the reaction was completed, the final solution was centrifuged at 15,000 rpm for 20 minutes, then the upper layer solution was removed, and the remaining solution was dispersed in 100 ml of distilled water. This cleaning process was repeated twice to finally prepare a solution containing PEG-coated GNR.

≪ Example 3: Preparation of silica-coated gold nanorods &

As another method for reducing the toxicity of CTAB, there is a method of coating the surface of GNR with Silica (SiO ₂ ). To this end, 4 ml of ethanol was added to 10 ml of the GNR solution prepared in Example 1 and stirred at 800 rpm for 3 hours. Then, 6 mL of distilled water and 200 mu l of 0.1 M NaOH solution were added. Then, 60 μl of a 20% (v / v) tetraethylorthosilicate (TEOS) methanol solution was injected in three times at intervals of 30 minutes in total of 180 μl. Thereafter, a solution containing final Silica-coated GNR (hereinafter referred to as GNR @ SiO ₂ ) was prepared by stirring at 800 rpm for 2 days at 30 ° C. The concentration of final produced GNR @ SiO ₂ solution (574.8 ㎍ Au / ㎖) was measured using AAS (Atomic Absorption Spectroscopy) analysis.

Example 4. GNR and GNR @ SiO ₂ Transmission electron microscope photograph and UV-Vis absorption spectrum characteristics>

The states of GNR and GNR @ SiO ₂ prepared in Examples 1 and 3 are shown in FIG. 1 by transmission electron microscopy (TEM). At this time, the synthesized GNR was found to be about 30 to 60 nm, and the thickness of the coated SiO ₂ was 10 to 15 nm, indicating that SiO ₂ was uniformly coated.

In addition, the UV-Vis absorption spectrum of GNR and GNR @ SiO ₂ prepared in Examples 1 and 3 is shown in FIG. 2. The longitudinal surface plasmon resonance (LSPR) peak of GNR appears at about 740 nm and the GNR @ The LSPR peak of SiO ₂ is slightly red-shifted from GNR as shown in FIG. 2 and appears at about 750 nm. The red-shift of the LSPR peak is due to the increase of the plasmon wavelength of the GNR by the coating of the GNR with Silica, which is a substance with a large dielectric environment ( ε _m ) (see Scheme 1).

[Reaction Scheme 1]

<Example 5> Measurement of average face skin temperature of human>

In order to measure the skin temperature of the face, which is the starting temperature, 8 men and 20s of 20 ~ 40s were used for the purpose of increasing the facial skin temperature using the photothermal effect of GNR and improving the wrinkle remover or various drug absorption rate in the dermal layer. The average skin temperature and standard deviation of four skin areas (forehead, eyes, mouth) where aging occurred most frequently with the infrared camera were searched to measure the skin temperature. The results are shown in FIG.

Referring to FIG. 3, the skin temperature of the face was not significantly different from that of the sex or age, and it was confirmed that the average skin temperature was about 34 ° C. Therefore, the starting temperature of each sample prepared above was set to 34 ° C using a hot plate. In addition, near infrared ray laser with wavelength of about 780nm which is the absorption wavelength band of GNR was irradiated with power of 0.60 ~ 0.65A without cytotoxicity, and the photothermal effect was measured. At this time, the cytotoxicity test was confirmed by irradiating a 1 mA laser onto the fibroblast cells for 30 minutes, and cell viability of about 85% or more was confirmed at each wavelength. As a result, it can be seen that there is almost no cytotoxicity under laser irradiation of 1 mA or less.

Example 6 GNR @ SiO with Slide glass as a Substrate ₂ Photothermal effect of>

To make a sample of 1x1 cm on the slide glass, the remaining portion excluding the space of 1x1 cm was wrapped with a paraffin film. Then, 10 쨉 l (5.748 쨉 g Au) of the GNR @ SiO ₂ solution prepared in Example 3 was dropped in a 1x1 cm empty space, Oven dried up. This procedure was repeated to prepare a sample by repeatedly dropping a total of 5 drops (28.74 μg Au), 10 drops (57.48 μg Au), 15 drops (86.22 μg Au) and 20 drops (114.96 μg Au). The final product was made in the shape of a circle and the areas were 2.01, 3.14, 2.54, and 2.54 cm ² , respectively. Therefore, the GNR @ SiO ₂ concentration per unit area of each sample was 14.30, 18.31, 33.94, 45.26 ㎍ Au / cm ² .

The thus prepared slide glass sample is shown in Fig. Figure 4 shows a rectangular display in the Slide glass pane units of 1x1cm, the Slide glass (Control) and Slide glass-GNR @ count of the number to the right of Slide glass from the SiO ₂ photos have dropped 10㎕ GNR @ SiO ₂ 1, 5, 10, 15, and 20, respectively. In this case, a near infrared ray laser having a wavelength of 780 nm generated from various output energies is irradiated to each sample, and the temperature change is observed using a thermal camera, as shown in FIG. 5 and FIG. Power density according to 780nm laser current; The current and power density of the laser are shown in Table 1 and measured using an optical power detector (Thorlabs, Model: PM100D).

Laser current (A) Laser power density (mW / cm ² ) 0.60 35 0.61 82.5 0.62 115 0.63 152.5 0.64 192.5 0.65 267.5

slide glass Refer to the laser irradiation when the temperature change (λ = 780 nm, current = 0.60 ~ 0.65A, power density = 35 ~ 267.5mW / cm 2) of the (Control) not include (Fig. 5), GNR @ SiO ₂ When the 780nm laser was irradiated on the slide glass for 3 minutes at the power density of 35 ~ 267.5 mW / cm ² , it was confirmed that there was almost no temperature change.

However GNR @ Referring to SiO ₂ during the laser irradiation concentrations temperature (λ = 780 nm, current = 0.60 ~ 0.65A, power density = 35 ~ 267.5mW / cm 2) of the (Fig. 6), GNR @ SiO ₂ It is confirmed that the dropped slide glass has a temperature increasing effect under the same laser irradiation condition. Also, it can be seen that as the concentration of GNR @ SiO ₂ per unit area increases, the temperature increase effect increases as the laser output power increases.

In order to avoid the problem of low-temperature burning, a preferable skin temperature rise should be made to about 40-45 ° C as a condition to be used as a composition suitable for use as a composition for a skin patch having a heat effect. Referring to the temperature increase, it can be seen that the composition of the present invention has no possibility of a low-temperature image.

Photothermal effect 14.30 Au Au / cm ²
(Laser current) 18.31 [mu] g Au / cm &lt; ² &gt;
(Laser current) 33.94 [mu] g Au / cm &lt; ² &gt;
(Laser current) 45.26 Au Au / cm ²
(Laser current) 40 to 45 ° C 0.63 to 0.65 0.63 to 0.65 0.65 A × > 45 ° C × × × ×

Example 7. GNR @ SiO based on a gel mask ₂ Photothermal effect of>

A commercially available product, the Medihil NMF aqua-ring nude Gel mask, was used as a substrate to determine if the photothermal effect occurred when the GNR @ SiO ₂ solution was dropped on the gel mask (the gel mask is a transparent product Was used.

To prepare each sample, 10 μl of GNR @ SiO ₂ solution (5.748 μg Au) was added to the nude gel mask and dried in an oven at 70 ° C. This procedure was repeated to prepare a sample by repeatedly dropping a total of 5 (28.74 μg Au), 10 (57.48 μg Au), 15 (86.22 μg Au), and 20 (114.96 μg Au) drops. On the other hand, unlike the slide glass, uniform coating was difficult due to various liquid materials present on the surface of the gel mask (see FIG. 7). As a result, it was difficult to sample the exact size and gold content as in the slide glass. ₂ concentration was difficult to confirm. A photograph of each sample thus prepared is shown in Fig. FIG. 7 is a photograph of a NMF aqua ring nude gel mask manufactured by Mediill Co., Ltd. used in the experiment, and a photograph of GNR @ SiO _{2 using} the same as a substrate.

The photothermal effect was confirmed by using the sample thus prepared. As shown in FIG. 8, the temperature change (λ = 780 nm, current = 0.60 to 0.65 A, power density = 35 to 267.5 mW / cm ₂ ) of the NMF nude Gel mask (Control) and nude Gel mask- ² ), when the 780nm laser was irradiated to the NMF nude gel mask for 3 minutes by power, the temperature increase effect was not high compared with the case where the slide glass was used as the substrate. This is because the GNR @ SiO ₂ solution spreads widely due to various wrinkle-improving liquid phases present on the surface of the NMF nude gel mask, and the coating is not well-behaved, and the concentration of GNR @ SiO ₂ per unit area is considerably lowered. Also, although not shown in FIG. 8, the sample treated with 28.74 占 퐂 Au hardly caused a temperature rise.

Example 8. Synthesis of GNR @ SiO ₂ The photothermal effect of a gel mask containing>

The conventional method of coating the gel mark does not show the effect of photothermal effect. Next, we fabricated a gel mask containing GNR @ SiO ₂ directly. First, ₂ ml (1.1496 mg Au) of GNR @ SiO ₂ solution, 0.06 g of carrageenan gum powder as a thickening agent and 0.2 g of glycerin were added to a 10 ml vial and stirred at 450 rpm while heating to 75 ° C. After 10 minutes, the homogeneously mixed solution was poured into a mask mold and hardened at room temperature for 1 to 2 minutes to prepare a gel mask containing GNR @ SiO ₂ . To prepare a gel mask containing various concentrations of GNR @ SiO ₂ , GNR @ SiO ₂ solution at a concentration of 574.8 μg Au / ml was diluted 2 times (287.4 μg Au / ml) and 2 ml was sampled to prepare a gel mask Respectively. Similarly, a gel mask was prepared using a 4 to 16x diluted GNR @ SiO ₂ solution.

This process is shown in eotneunde 9 for producing a Gel mask (574.8㎍ / ㎖ concentration of SiO ₂ of GNR @ undiluted solution and a dilution of this stock solution 2, times 4, 8, 16, manufactured by GNR @ SiO ₂ solution Gel mask), and on the right side of the photo, the amount of gold contained in the weight of each mask was calculated as wt% from the concentration of GNR @ SiO ₂ . For example, the concentration of GNR @ SiO ₂ stock solution was 574.8 μg Au / ㎖, which was used as 2 mg for the production of Gel mask. Therefore, the concentration of 1.15 mg Au / 2 ml and the final weight of gel mask was 352 mg Therefore, the concentration of Gold contained in the gel mask is 0.33 wt%. As can be seen from the left sample, the concentration of the GNR @ SiO ₂ solution (wt%) increases, and the wine light, which is the color of the GNR @ SiO ₂ solution, becomes stronger.

The photothermal effect of the thus-prepared Gel mask (0.017-0.33 wt% Au) was confirmed and shown in FIG. 10 and FIG. At this time, as described above, it was confirmed that the effective laser output was about 0.62 ~ 0.65 A, and the laser output was 0.63 ~ 0.65A for the photothermal effect test.

10 shows the temperature variation (λ = 780 nm, current = 0.63, 0.64, 0.65 A, power density = 152.5, 192.5, 267.5 mW / cm ² ) of the laser mask of the Gel mask , And in the case of the Gel mask (Control) made with distilled water, the temperature change was not observed even when the 780 nm laser was irradiated for 10 minutes.

However, in FIG. 11, the temperature of the laser mask irradiated with GNr @ SiO ₂ (574.8 μg Au / ml) as the undiluted solution (λ = 780 nm, current = 0.63, 0.64, 0.65 A, power density = 152.5, 192.5, 267.5 mW / cm ² ), the gel mask fabricated with GNR @ SiO ₂ solution with a concentration of 574.8 ㎍ Au / ㎖ gels within 30 seconds as the output current or power density of the irradiated near- the temperature of the mask is raised to about 41 to 45 DEG C, and it is confirmed that the temperature rise value to be used for the skin patch mask is appropriate.

On the other hand, in Fig. 12, the temperature variation (lambda = 780 nm, current = 0.63, 0.64, 0.65 A, power density = 152.5) at the laser irradiation of the gel mask made of GNR @ SiO ₂ diluted with 2, 4, , 192.5, 267.5 mW / cm ² ), it can be seen that as the concentration of GNR @ SiO ₂ contained in the gel mask decreases, the photothermal effect decreases gradually. Table 3 summarizes the conditions for satisfying the temperature of the gel mask suitable for application to the skin and about 40 to 45 캜. Referring to Table 3 below, the target gel mask temperature is about 40 to 45 캜 , The content of GNR @ SiO ₂ should be at least about 0.022 wt%, and the output current of near infrared laser is found to be 0.62 A to 0.65 A depending on the concentration of GNR @ SiO ₂ (Sample e 0.022 wt% In the case of GNR @ SiO ₂ , the laser exceeded 40 ° C when irradiated for more than 380 seconds).

Photothermal effect Sample c
(Laser current) Sample d
(Laser current) Sample e
(Laser current) Sample f
(Laser current) 40 to 45 ° C 0.63 to 0.65 0.63 to 0.65 0.65 A × > 45 ° C × × × ×

The GNR @ SiO to indicate a photo-thermal effect of the _second one Gel mask containing not have to use the laser GNR @ SiO different light sources (ex having a wavelength matching the _second absorption wavelength (± 100 ~ 300 nm) in the. LED ) Can be adjusted to induce the photothermal effect of the gel mask.

In addition to the above results, the photothermal effect when a gel mask is prepared using GNR (PEG-GNR manufactured in Example 2) coated with polyethylene glycol (PEG) instead of silica is shown in FIG. At this time, the method of manufacturing the gel mask is the same as that shown in FIG. 9 except that a PEG-GNR solution is used instead of the GNR @ SiO ₂ solution.

Referring to FIG. 13, when a laser (λ = 780 nm, current = 0.65 A, power density = 267.5 mW / cm ² ) was irradiated onto a gel mask made of PEG-GNR of 600 μg Au / S1 is a Gel mask made from distilled water (2 mL), S2 is a Gel mask made by mixing 600 μg Au / mL PEG-GNR (1 mL) and distilled water (1 mL), and S3 is 600 The results for the Gel mask made after mixing PEG-GNR (0.5 mL) and distilled water (1.5 mL) are shown. In this case, the laser irradiation time is 5 minutes, and the distance between the sample and the light source is 2 cm. In the case of S1, the temperature is almost unchanged even when the laser is irradiated, whereas in S2 and S3, the temperature rises to about 30.57 ° C. and 32.78 ° C. .

Claims (8)

Wherein the gold nanorod is contained in an amount of 0.02 to 0.40 wt% and causes an exothermic reaction at a near infrared ray wavelength of 750 to 1,400 nm. The method according to claim 1,
Wherein the gold nano-rods are coated with silica or polyethylene glycol. The method according to claim 1,
Wherein the composition contains a functional cosmetic composition selected from the group consisting of a wrinkle reducing agent, a whitening agent, an antioxidant, an anti-inflammatory agent, a hair growth agent, an allergy improving agent and an atopic remedy. delete The method according to claim 1,
Wherein the composition contains an aging agent. The method according to claim 1,
Wherein the composition contains a moisturizing agent. delete (Step 1) To a solution of hexadecylsethyltrimethylammonium bromide aqueous solution and hydrogen tetrachloroaurate (III) tetrahydrate aqueous solution was added an aqueous sodium borohydride solution to prepare a solution containing a gold seed &Lt; / RTI &gt;
An aqueous solution of silver nitrate and an aqueous solution of ascorbic acid as a reducing agent, which are catalysts for synthesizing gold nano rods, were added with stirring to prepare a growth solution. The aqueous solution of gold nitrate and the aqueous solution of ascorbic acid Producing;
(Step 2) mixing and stirring the solution containing the gold seed and the growth solution, removing the upper layer solution by centrifugation, and dispersing the remaining solution in distilled water to obtain a solution containing the gold nanorod;
(Step 3) adding a polyethylene glycol thiol or a silane-based material to a solution containing gold nano-rods to obtain a solution containing gold nanorods coated with polyethylene glycol or silica; And
(Step 4) stirring a mixture solution of a solution containing a gold nanorod coated with polyethylene glycol or silica and a thickening agent and a humectant, and then pouring the mixture into a mold to form a gel mask;
2. The method of manufacturing a mask pack cosmetic composition according to claim 1,

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