KR102316264B1 - Method for improving water-dispersibility of natural fullerene with amphiphilic polymers and use of natural fullerene prepared thereby - Google Patents

Abstract

The present invention relates to a method for improving water dispersibility of natural fullerene using the Poly-B series and to the use of the natural fullerene prepared by the method. More specifically, in the present invention, natural fullerene is coated with a Poly-B series containing benzyl methacrylate (BMA) and poly(ethylene glycol)-methacrylate (PEGMA). It relates to a method for producing a natural fullerene with improved water dispersibility and stability, comprising the step of, and use of the prepared natural fullerene in cosmetic compositions, pharmaceutical compositions, food compositions, building materials, and household goods.

Description

Method for improving water dispersibility of natural fullerene using an amphiphilic polymer and use of natural fullerene prepared by the method

The present invention relates to a method for improving water dispersibility of natural fullerene using the Poly-B series and to the use of the natural fullerene prepared by the method. More specifically, in the present invention, natural fullerene is coated with a Poly-B series containing benzyl methacrylate (BMA) and poly(ethylene glycol)-methacrylate (PEGMA). It relates to a method for producing a natural fullerene with improved water dispersibility and stability, comprising the step of, and use of the prepared natural fullerene in cosmetic compositions, pharmaceutical compositions, food compositions, building materials, and household goods.

Fullerenes are carbon allotropes such as graphite and diamond. However, because fullerenes have a different structural form from graphite or diamond, they are commonly referred to as third carbon allotropes. Fullerene has a carbon ring in which carbon (C) atoms are arranged in a pentagon or hexagonal arrangement. And these carbon rings are combined in the shape of a substantially sphere (spherical), etc. to form a hollow. In general, fullerenes have C ₆₀ to C ₈₀ or greater carbon number. In addition, in its structural form, fullerene has a shape of a soccer ball, or a shape of a sphere similar to a soccer ball, and has a hollow structural characteristic. Fullerene has excellent physical and chemical properties due to the above carbon ring arrangement and hollow structure. Specifically, fullerene has several useful physical and chemical properties, such as strong antioxidant, adsorption, catalytic (degradability of adsorbed material), sterilizing power, electromagnetic wave absorption, electrical conductivity, and in some cases higher strength than diamond. Its application value is high. Accordingly, fullerene is applied not only to electrodes, electromagnetic wave shielding agents, etc., but also to cosmetic compositions. For example, Korean Patent Application Laid-Open No. 10-2006-0076254 discloses a cosmetic composition containing fullerene. Fullerene is contained in the cosmetic composition, for example, to promote antioxidant properties and bactericidal properties. In addition, fullerene has a carrier function for supporting the active ingredient of cosmetics.

In relation to the production of fullerenes as described above, in general, fullerenes are artificially synthesized and manufactured through an arc discharge method or a continuous combustion method using carbon black or graphite as a raw material. However, this artificial synthesis method has problems in that the price of fullerene itself is very expensive and productivity is low due to the cost of raw materials such as carbon black or a complicated production process. In addition, in the production of fullerene, there is a method of extraction and manufacturing from a natural mineral. In the case of natural fullerene (Nat-F), the production process is simpler than synthetic fullerene, so the price is low and productivity is high. However, like other fat-soluble carbon-based materials, natural fullerenes are difficult to disperse in water and thus have difficulties in application.

The present invention solves the above problems and was devised by the above necessity, and an object of the present invention is to provide a method for producing natural fullerene with improved water dispersibility and stability.

Another object of the present invention is to provide a use in a cosmetic composition, a pharmaceutical composition, a food composition, a building material, and a household product of a natural fullerene prepared by the method for producing a natural fullerene having improved water dispersibility and stability.

According to the first embodiment,

The present invention discloses a method for producing a natural fullerene with improved water dispersibility and stability, comprising the step of coating the natural fullerene with a Poly-B series.

In the method for producing a natural fullerene according to the present invention, the Poly-B series includes benzyl methacrylate (BMA) and poly(ethylene glycol)-methacrylate (PEGMA). characterized by including. The molar ratio of the benzyl methacrylate and poly(ethylene glycol)-methacrylate is 1:1. In addition, the Poly-B series may further include methyl acrylate (MA), wherein the molar ratio of benzyl methacrylate:poly(ethylene glycol)-methacrylate:methyl acrylate is 5:3 : It is characterized as 1.5.

In the method for producing natural fullerene according to the present invention, the method is characterized in that it further comprises the step of homogenizing with an ultrasonic homogenizer after coating with Poly-B series. The homogenizing step is characterized in that it is carried out for 1 to 5 hours, preferably for 4 hours.

In the method for producing natural fullerene according to the present invention, the natural fullerene is characterized in that it has a carbon number _{of C 60} to C _80.

According to the second embodiment,

The present invention discloses the use of natural fullerenes prepared by the method for producing natural fullerenes with improved water dispersibility and stability in cosmetic compositions, pharmaceutical compositions, food compositions, building materials, and household products.

Natural fullerenes have unique physical and chemical properties due to their unique structure. For example, fullerene molecular crystals have very high-energy intermolecular attractive forces that are much greater than molecular crystals of similarly sized organic materials. In addition, fullerenes have many double bonds that can be readily applied to oxidation-reduction (Redox) reactions. Thereby, fullerene has a strong antioxidant property that blocks a chain radical oxidation reaction by inducing a strong reverse catalysis in the cosmetic composition. In addition, it has been known that free radicals generated during metabolic reactions in skin cells are one of the main factors of skin aging. The ability of cells to defend against oxidative damage initiated by free radicals decreases with time. When additional sources of free radicals appear, aging accelerates and hair becomes lifeless. Fullerene can prevent the damage of free radicals to cells, thereby reducing the accelerated aging of the skin, and revitalize the hair. In addition, fullerene reduces the activity of active oxygen and melanin due to its unique properties. In addition, fullerene has a bactericidal and anti-inflammatory action and the like, thereby promoting wound healing, or promoting regeneration and/or repair of soft tissue. Therefore, the cosmetic composition according to the present invention has strong antioxidant and bactericidal properties by containing natural fullerene, as well as lowering the activity of active oxygen and melanin, and preventing skin aging, wrinkle improvement, acne and atopic treatment/prevention , and characterized in that it has an effect such as wound healing.

The cosmetic composition according to the present invention is not limited in its type or formulation. In the present invention, the cosmetic composition is included here as long as it is applied to the skin or hair of the human body. Specifically, the cosmetic composition according to the present invention, in the type of the product form, cosmetics for aesthetic beauty or skin protection; Soap for the beauty and cleanliness of the skin; A therapeutic agent for skin diseases applied to the skin to treat or prevent skin diseases such as atopic dermatitis; Shampoo or conditioner to clean the hair; dyes for dyeing hair; anti-hair loss agent to prevent hair loss; and products such as hair growth agents that promote hair growth. That is, the cosmetic composition according to the present invention may be one or more products selected from cosmetics, soap, shampoo, conditioner, colorant, skin treatment agent (such as atopic treatment agent), hair loss prevention agent and hair growth agent. In addition, in some cases, the cosmetic composition according to the present invention may be selected from oral products such as toothpaste or mouthwash.

The cosmetic composition according to the present invention is a skin lotion, skin softener, skin toner, astringent, lotion, milk lotion, moisture lotion, nourishing lotion, massage cream, nourishing cream, moisture cream, hand cream, essence, pack, mask pack, mask sheet , exfoliant, soap, shampoo, cleansing foam, cleansing lotion, cleansing cream, body lotion, body cleanser, emulsion, press powder, loose powder, eye shadow, mist, and toothpaste. have.

The method for producing natural fullerenes of the present invention enables the production of stable and excellent natural fullerenes with excellent water dispersibility, and thus has the potential to be used in various formulations. In addition, natural fullerene has excellent antioxidant and antibacterial effects, so it can improve and treat various diseases. It is expected to be widely used (soap, cleanser, etc.).

1 shows a schematic diagram of a chemical structure of natural fullerene and Poly-B series according to the present invention, and a method for improving water dispersibility of natural fullerene using the same.
Figure 2 shows the dispersibility comparison results of natural fullerene / Poly-B series.
3 shows the comparison results of the size, dispersion value and surface charge of natural fullerene/Poly-B series.
Figure 4 shows the UV-Vis spectra comparison results of natural fullerene / Poly-B series.
Figure 5 shows the dispersibility comparison results according to the ratio of natural fullerene and Poly-B series.
6 shows the comparison results of size, dispersion value and surface charge according to the ratio of natural fullerene and Poly-B-1.
Figure 7 shows the UV-Vis spectra comparison results according to the ratio of natural fullerene and Poly-B-1.
8 shows the storage stability of natural fullerene and Poly-B-1 in a 1:1 ratio.

Hereinafter, various examples are presented to help the understanding of the invention. The following examples are provided for easier understanding of the invention, and the protection scope of the invention is not limited to the following examples.

<Example>

Example 1. Preparation of natural fullerenes and Poly-B series

Prepare 5 kinds of Poly-B (Poly-B-1, Poly-B-2, Poly-B-3, Poly-B-4 and Poly-B-5, 15mg) in 1ml of tertiary distilled water, Each Poly-B solution was added to natural fullerene (5mg, C ₆₀ ~ C ₈₀ ) and reacted by stirring at 300 rpm for 2 hours at room temperature. After addition of 4 ml of tertiary distilled water to the reaction solution, the mixture was stirred at 450 rpm for 1 hour. After homogenization using an ultrasonic homogenizer (amplitude = 20%, 5 sec on/15 sec off) for 1 hour, and then using a centrifuge to remove uncoated natural fullerene, freeze-drying was carried out for 3 days. The size and dispersion of Nat-F/Poly-B series were analyzed using Zetasizer (ELSZ-2000, Otsuka) equipment, and absorbance was measured using UV-Vis spectrophotometer (Mega900, Scinco) equipment. The water dispersion rate was confirmed. After freeze-drying, the shape of Nat-F/Poly-B was observed, and size and dispersion were analyzed after redispersion in tertiary distilled water to confirm stability after freeze-drying.

Example 2. Characterization of natural fullerene coated with Poly-B series

2-1. Comparison of dispersibility of natural fullerene/Poly-B series

When uncoated fullerene is removed through a centrifuge after ultrasonic homogenization of natural fullerene and Poly-B series, natural fullerene itself (Nat-F) is partially dispersed in water, but has a transparent black color after removing aggregates, whereas Poly-B series It was confirmed that the fullerene coated with -B series showed a dark black color (Fig. 2). That is, it has been proven that fullerene can be stably dispersed in an aqueous solution when coated with Poly-B. On the other hand, Poly-B-5 among the Poly-B series did not dissolve in tertiary distilled water, so it was found that Nat-F/Poly-B-5 could not be prepared.

2-2. Comparison of size, dispersion value and surface charge of natural fullerene/Poly-B series

Natural fullerene was dispersed in a size of 120 nm and it was confirmed that it grew slightly after being coated with Poly-B series. All of the natural fullerenes/Poly-B series were prepared with a dispersion value of less than 0.2, and it was found that they were ideally prepared with a dispersion value of about 0.15, especially when coated with Poly-B-1. In addition, the surface charge of the natural fullerene was -25mV, and it was confirmed that it fell down to -22mV when coated with the Poly-B series (FIG. 3).

2-3. UV-Vis spectra comparison of natural fullerene/Poly-B series

Natural fullerenes have a characteristic peak at a specific wavelength (λ=265 nm). When the yield was calculated based on this, it was found that the yield increased when the Poly-B series was coated than when only natural fullerene was dispersed (14%). In particular, in the case of coating with Poly-B-1 among the Poly-B series, the yield was 38.3%, and it was confirmed that the coating was best ( FIG. 4 ).

Example 3. Characteristic evaluation according to the ratio of natural fullerene and Poly-B-1

In order to investigate the effect of the concentration of Poly-B on the properties of natural fullerene, 2.5, 5, 15 and 25 mg of Poly-B-1 was prepared in 1 ml of tertiary distilled water, and Nat was prepared in the same manner as in Example 1 above. -F/Poly-B-1 was prepared and the characteristics of Nat-F/Poly-B-1 were evaluated according to Example 2.

3-1. Comparison of dispersibility according to the ratio of natural fullerene and Poly-B-1

As a result of coating various Poly-B-1s on natural fullerenes, when coated with Poly-B-1, the dispersibility of natural fullerenes was improved, resulting in a darker black color (FIG. 5). In particular, when the ratio of natural fullerene and Poly-B-1 is 1:1, it was confirmed that the dispersibility of natural fullerene was the most excellent by showing the darkest black color.

3-2. Comparison of size, dispersion value and surface charge according to the ratio of natural fullerene and Poly-B-1

Natural fullerene was dispersed in a size of 120 nm, and when coated with Poly-B-1, it was found to be dispersed in a size of about 120 nm to 135 nm. It was found that as the polymer ratio increased, the size of Poly-B-1 became smaller. Both Nat-F/Poly-B-1 were ideally prepared with a dispersion value of less than 0.2, and it was confirmed that Poly-B-1 was stably coated on the fullerene surface with a surface charge of about -24 mV (FIG. 6).

3-3. Comparison of UV-Vis spectra according to the ratio of natural fullerene and Poly-B-1

As a result of analyzing the yield according to the ratio of natural fullerene and Poly-B-1, it was found that when the ratio of natural fullerene and Poly-B-1 was 1:1 and 1:3, 47.8% and 38.3% were excellent, respectively (Fig. 7).

3-4. Stability comparison between natural fullerene and Poly-B-1 with a 1:1 ratio when stored at room temperature

As a result of observing the natural fullerene and Poly-B-1 in a 1:1 ratio confirmed above at room temperature with a yield of 95% without purification for 4 weeks, in the case of natural fullerene, partial aggregation occurred from the 1st week, Nat-F / Poly-B-1 was confirmed to be able to maintain a yield of 81% even after 4 weeks (Fig. 8). Therefore, Nat-F/Poly-B-1 according to the present invention is expected to be easily applied to cosmetic formulations such as ampoules, creams, lotions, and skins.

Example 4. Confirmation of yield according to time of sonification in the preparation of natural fullerene and Poly-B-1

Nat-F/Poly-B-1 was prepared in the same manner as in Example 1, but by changing the sonification time from 1 hour to 4 hours, and the size, dispersion value, surface charge and yield thereof were compared. As can be seen from Table 1 below, when the sonification was increased to 4 hours, the yield was increased from about 47% to about 57%.

polymer Nat-F polymer sonic time(hour) Number
(nm) PDI Zeta
(mV) Yield
(%) Poly-B-1 1:1 One 134±13 0.15±0.01 -25 47.8 Poly-B-1 1:1 4 133±13 0.14±0.01 -25±1 57.2

As described above in detail a specific part of the present invention, for those of ordinary skill in the art, this specific description is only a preferred embodiment, and it is clear that the scope of the present invention is not limited thereto. Accordingly, the substantial scope of the present invention will be defined by the appended claims and their equivalents.

Claims (7)

Coating the natural fullerene with a poly-B (Poly-B) polymer comprising benzyl methacrylate (BMA) and poly(ethylene glycol)-methacrylate (PEGMA). A method for producing a natural fullerene with improved water dispersibility and stability comprising a.
According to claim 1,
The molar ratio of benzyl methacrylate and poly(ethylene glycol)-methacrylate is 1:1, characterized in that
A method for producing natural fullerenes with improved water dispersibility and stability.
3. The method of claim 2,
The Poly-B series further includes methyl acrylate (MA),
The molar ratio of the benzyl methacrylate: poly (ethylene glycol)-methacrylate: methyl acrylate is 5:3: 1.5, characterized in that
A method for producing natural fullerenes with improved water dispersibility and stability.
According to claim 1,
The method is characterized in that it further comprises the step of homogenizing for 1 to 5 hours with an ultrasonic homogenizer after coating with the Poly-B series,
A method for producing natural fullerenes with improved water dispersibility and stability.
According to claim 1,
The natural fullerene is characterized in that it is used in a cosmetic composition, a pharmaceutical composition, a food composition, a building material or a household product,
A method for producing natural fullerenes with improved water dispersibility and stability.
6. The method of claim 5,
The cosmetic composition is characterized in that it has the effects of strong antioxidant and bactericidal properties, active oxygen and melanin activity reduction, skin aging prevention, wrinkle improvement, acne and atopy treatment / prevention, and wound healing,
A method for producing natural fullerenes with improved water dispersibility and stability.
6. The method of claim 5,
The cosmetic composition includes skin lotion, skin softener, skin toner, astringent, lotion, milk lotion, moisture lotion, nourishing lotion, massage cream, nourishing cream, moisture cream, hand cream, essence, pack, mask pack, mask sheet, exfoliant , soap, shampoo, cleansing foam, cleansing lotion, cleansing cream, body lotion, body cleanser, emulsion, press powder, loose powder, eye shadow, mist and toothpaste characterized in that it has any one formulation selected from the group consisting of sign,
A method for producing natural fullerenes with improved water dispersibility and stability.

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