KR101495038B1 - Cosmetic composition containing stabilized active component - Google Patents

Abstract

The present invention relates to a cosmetic composition comprising a cyclodextrin-maltose complex and a cyclodextrin-pullerone complex as an active ingredient and stabilizing it by a complex formation between a pharmacologically active ingredient of a plant-derived pharmacologically active ingredient, maltol, poulgone and cyclodextrin, According to the present invention, there is provided a method for stabilizing a complex between maltose and cyclodextrin derived from red ginseng, ultraviolet rays and heat generated by a complex between a phlorogaster and a cyclodextrin derived from a mold, and a cosmetic composition containing the same as an active ingredient According to the present invention, there is provided a cosmetic composition which maintains its stability against ultraviolet rays and heat by forming a complex between a pharmacologically active ingredient and a cyclodextrin, while simultaneously maintaining its pharmacological activity.

Maltol, poulgene, cyclodextrin, stabilization

Description

COSMETIC COMPOSITION CONTAINING STABILIZED ACTIVE COMPONENT [0002]

1 is an absorption spectrum diagram of a maltol fraction purified from standard malt extract and red ginseng extract,

Figure 2 is an analysis of standard maltol (A), partially purified maltol fraction (B) and purified maltol fraction (C) by HPLC,

Figure 3 is an analysis view of a partially purified fulleren fraction (A) and a purified fulleren fraction (B) by TLC,

Fig. 4 is an absorption spectrum diagram of the standard poultry (A) and the pulolig fraction (B)

FIG. 5 is an analysis chart of standard pulpalone (A) and pulolig fraction (B) by MS,

6 is a graph showing the pH effect in the complex formation of maltol and cyclodextrin,

7 is a graph showing the temperature effect in the formation of a complex of maltol and cyclodextrin,

8 is a graph showing the UV ray exposure effect of the maltol and cyclodextrin complex,

9 is a ¹ H NMR spectrum of a? -Cyclodextrin-pulleron complex identified in a heavy water solvent,

10 is a ¹ H NMR spectrum of a? -Cyclodextrin-pulleron complex identified in a heavy water solvent,

FIG. 11 is a UV-vis spectrum of a? -Cyclodextrin-pulleron complex identified in an aqueous solution,

12 is a UV-vis spectral diagram of the? -Cyclodextrin-pulleron complex identified in aqueous solution,

13 is an IR spectrum diagram of a? -Cyclodextrin-pulleron complex,

14 is an IR spectrum diagram of a gamma -cyclodextrin-pulleron complex,

15 is a TGA diagram of a? -Cyclodextrin-pulleron complex,

16 is a TGA diagram of a gamma -cyclodextrin-pulleron complex.

TECHNICAL FIELD The present invention relates to a cosmetic composition containing a stabilized active ingredient, and more particularly to a cosmetic composition in which the active ingredients maltol and fullerone are encapsulated in cyclodextrin to improve stability.

Cyclodextrins obtained from starch can enclose small compounds using internal void spaces to remove aromatic compounds. Therefore, cyclodextrins obtained from starches can be used in environmental fields (Murai, S, et al., Environ. Sci. Technol., Vol (Hirayama, F., et al., Adv. Drug Del. Rev., 32, pp. 782-787, 1998), and encapsulated with a hydrophobic anticancer drug or drug, Vol. 36, pp. 125-141, 1999), and it is also known to have excellent biocompatibility, which is used in various applications such as foods, cosmetics and agrochemicals (Szejtli, J et al., Comprehensive supramolecular chemistry, vol. 3, Cyclodextrins, Pergamon, 1996).

Maltol is a large amount of antioxidant in red ginseng. It is known to enhance hepatic function, renal function, cardiac function, inhibit the accumulation of aging substances, and restore fatigue, thereby exhibiting great efficacy against aging (J. Biochem. Molec Pharm Bull 29 (4) 750-754 (2006), J. Agri. Food Chem., 2006, 54, 2558-2562; ). However, as with most antioxidants, there is a problem of poor stability to heat or light.

Pulegone is a monoterpene ketone with the following structure and is mainly found in mints such as peppermint and spearmint. Poulgon protects plants from insects and herbivores in nature. Poulgon is also known to have bactericidal activity against bacteria, especially against Salmonella.

Puregon is a phytochemical that exists as a liquid that does not mix with water at room temperature. In order to water-soluble such a water-insoluble phytochemical, there is a method of introducing a water-friendly functional group into a compound by an organic chemical method. However, this method does not only require a lot of time and effort, but also risks the loss of its value as a phytochemical because it changes the efficacy, stability and other physical / chemical properties of the phytochemical itself. Therefore, it is a very important step in practical application to hydrolyze this substance without chemical change of the pidochemical. For this purpose, there is a need for further research to enable stable presence in water by utilizing supramolecular interactions between water-soluble molecular carriers and water-insoluble phytochemicals.

Among the effective ingredients of functional cosmetics, there are many chemical substances which are unstable due to heat, light, moisture and so on. In order to apply these substances to cosmetics, it is necessary to stabilize the original activity without deterioration in manufacturing and distribution processes . Recently, studies for stabilizing an active ingredient of functional cosmetics have been actively carried out, and methods such as microencapsulation, liposomes, and cyclodextrin complexes have been used, and further studies are required .

It is an object of the present invention to provide a phytochemical active ingredient derived from a useful plant, which is extracted from red ginseng and mold to improve the stability of maltol and fullerene which can be mass-purified, To provide a cosmetic composition which is excellent in moisturizing effect and at the same time has excellent temporal stability. Another object is to provide a method for stabilizing the pharmacologically active ingredients of plant-derived maltol and poulgon against heat and ultraviolet rays.

According to a preferred embodiment of the present invention, there is provided a cosmetic composition comprising a β- or γ-cyclodextrin-maltose complex and a β- or γ-cyclodextrin-pullerone complex as an active ingredient .

Also provided is a cosmetic composition comprising a β- or γ-cyclodextrin-maltose complex and a β- or γ-cyclodextrin-pullerone complex in a weight ratio of 1: 0.1 to 20.

Also provided is a cosmetic composition comprising the active ingredient in a proportion of 0.01 to 10% by weight based on the total weight of the composition.

According to another aspect of the present invention, there is provided a method for preparing a solution of a maltol solution and a solution of a? - or? -Cyclodextrin solution, mixing at pH 6-8, at 30-70 ° C, and recovering by centrifugation of the resulting inclusion complex of cyclodextrin-maltol, to obtain a mixture of maltol A stabilization method is provided.

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According to a preferred embodiment of the present invention, there is also provided a method of preparing a phlorogonal solution and a beta or gamma -cyclodextrin solution, respectively, a method of mixing the phlorogonal solution and a beta or gamma -cyclodextrin solution, There is provided a method of stabilizing a poulgene through the production of a? Or? -Cyclodextrin-pullerone complex, comprising centrifuging and recovering the inclusion complex of cyclodextrin-fullerone.

Hereinafter, the present invention will be described in more detail.

In the present invention, as a substance for stably holding and supporting the maltol or the poulgene, there may be mentioned β- or γ-cyclodextrins each having 7 or 8 glucopyranose units or C1- Substituted? - or? -Cyclodextrin.

The relative weight ratio of the above-mentioned cyclodextrin in the clathrate complex of the maltol and the fullerene is not limited in the present invention but is generally 1: 0.1 to 20, preferably 1: 1 to 6 , And maltol or poulgry is entrapped or captured in the steric network structure of the above cyclodextrin.

The present inventors have conducted extensive tests on various materials and methods for easily and effectively stabilizing maltol or poulgon, and found that by using? Or? -Cyclodextrin, an inclusion complex of maltol or fullerene is efficiently formed And the present invention is based on this finding.

 Hypermolecularization of a plant-derived useful ingredient such as maltol maintains the stability of the molecule itself, and when used as an external preparation for skin, increases the skin permeability or improves the absorption rate in the body during ingestion. That is, the functionality of the useful ingredient can be enhanced to further enhance the applicability.

The change in the formation of cyclodextrin-maltol complex was measured by UV-Vis spectroscopy and the effect of pH and temperature on complex formation was determined. As a result of the experiment, it has been confirmed that the complex of maltol with? Or? -Cyclodextrin forms the most stable complex at pH 6 to 8, preferably at pH 7, and the temperature is 30 to 70 ° C, The most stable complex was formed.

It is important for practical applications that the fullergan is present as a liquid that does not mix with water at room temperature, and that it can stably exist even in an aqueous solution. For this purpose, supramolecular interactions with several molecular carriers such as cyclodextrins, cucurbiturils, and calixarenes were investigated in aqueous solution. As a result, only cyclodextrin was found to contain fullerenes in aqueous solution to form supramolecular complexes I could.

The complex formation of cyclodextrin and fullerene was confirmed by NMR analysis and UV spectrum analysis. It is confirmed by ¹ H NMR spectroscopy that the pherogland is hydrolyzed through cyclodextrin and supramolecular interactions in aqueous solution. The fact that the signal due to pherogel can be confirmed on D ₂ O means that the interaction with pherogel cyclodextrin To form the supramolecular body contained in the cyclodextrin, which shows the fact that it retains the water-soluble properties of the cyclodextrin and dissolves in water. The hydrolysis of fullerenes by supramolecular interactions with cyclodextrins was also confirmed by UV-vis spectroscopy.

In addition, the thermal stability of fullergan and cyclodextrin complexes was examined by thermogravimetric analysis (TGA). As a result, it was confirmed that thermal stability of fullerenes was improved by supramolecular interaction with cyclodextrin.

The method for preparing the inclusion complex of the cyclodextrin and the maltol according to the present invention (i.e., the method for stabilizing the maltol) includes the steps of adding cyclodextrin 0.1 to the ethyl alcohol, water or a mixed solvent thereof in an amount of 0.001 to 15% To 25 wt.% Concentration of ethyl alcohol, water or a mixed solvent thereof, and recovering the resulting inclusion complex of cyclodextrin-maltol by appropriate separation means such as centrifugation or the like.

The mixing step is preferably carried out at a pH of 6 to 8, preferably at about pH 7, and the temperature is preferably 30 to 70 ° C, preferably about 50 ° C.

Following the mixing step described above, an optional stirring step may be carried out. In addition, following the above recovering step, the recovered inclusion complex can be selectively subjected to a crystallization step, for example, crystallization at room temperature.

The inclusion amount and stabilization degree of the maltol in the inclusion complex can be easily measured by using a unique ultraviolet absorbance standard curve specific to the maltol.

The method for preparing the inclusion complex of the cyclodextrin and the fullerene according to the present invention (i.e., the method for stabilizing the fullerenes) will be described below. The fullerene is dissolved in ethyl alcohol, water or a mixed solvent thereof in a concentration of 0.001 to 15% Mixing the ethyl alcohol, water or a mixed solvent thereof in a concentration of 0.1 to 25% by weight of cyclodextrin with each other, and recovering the resulting inclusion complex of cyclodextrin-fullerene by appropriate separation means such as centrifugation or the like .

Following the mixing step described above, an optional stirring step may be carried out. In addition, following the above recovering step, the recovered inclusion complex can be selectively subjected to a crystallization step, for example, crystallization at room temperature.

The inclusion amount and the degree of stabilization of the pulp content in the inclusion complex can be easily measured by using a unique ultraviolet absorbance standard curve unique to Poulter.

According to the method for stabilizing a maltol or a fullerene according to the present invention as described above, it is possible to stably maintain the structure even if a long period of time over a conventional distribution period elapses in a relatively wide range of temperature range including room temperature, It can be safely applied to the production of a cosmetic preparation or a pharmaceutical external preparation which is produced through a general process commonly used in the production of a product such as a cosmetic, that is, a heating process at a temperature of about 70 ° C or higher. It should be noted that the structure is not easily changed even under the UV irradiation condition with high energy, and further, it is advantageous that it can be easily formulated into an aqueous phase.

The cosmetic composition according to the present invention comprising the cyclodextrin-maltocopter complex and the cyclodextrin-poulter block inclusion complex according to the present invention as a main active ingredient can be used as a shampoo, a body creamer, a hair conditioner, a moisturizer, a hair tonic, Lotion, hair lotion, and the like.

The cyclodextrin-maltol clathrate complex and the cyclodextrin-fullerene clathrate complex according to the present invention may be contained in a proportion of 0.01 to 10% by weight based on the total weight of the composition. If the amount is less than the above-mentioned range, there is a fear that the effect of the addition becomes insufficient. Conversely, if it exceeds the above-mentioned range, there is a fear that it becomes economically undesirable.

The above ratios may also be varied by various parameters such as the formulations of the cosmetic composition, the age and the skin tendency to be applied, the kind of the surfactant to be added, and the like.

The cosmetic composition according to the present invention comprises at least one conventional anionic surfactant, nonionic surfactant, amphoteric surfactant, cationic surfactant and mixtures thereof, which are customarily used in the production of conventional cosmetic compositions And the content thereof is generally 2 to 40% by weight, preferably about 2 to 25% by weight, based on the total weight of the composition. It is needless to say that, in addition to the above surfactants, ordinary components specified in the cosmetic laws such as a viscosity adjusting agent, a pH adjusting agent, a flavoring agent, a colorant, and an antioxidant may be used.

Hereinafter, the present invention will be described in more detail with reference to examples, comparative examples and test examples, but it should be noted that these examples are for illustrative purposes only and are not intended to limit the present invention. There is a need.

Purification of maltol

(1) Extraction of red ginseng

When 10.4 g of powdered red ginseng was added to 200 ml of distilled water and the mixture was lyophilized and dried at 90 ° C for 9 hours, the amount of powder was 1.3 g, which was 12.5%.

200 mg of red ginseng extract powder is dissolved in 2 ml and mixed with hexane again. The hexane layer was then removed and the water layer again mixed with chloroform. At this time, the water layer was removed and the chloroform layer was collected. The chloroform layer was dissolved under reduced pressure in a third distilled water (Millipore) containing 0.01% TFA after removing the solvent. The sample thus obtained was purified by open column chromatography.

(2) Purification and analysis of maltol

The C ₁₈ silica gel was equilibrated with tertiary distilled water containing 0.01% TFA and the prepared sample was loaded onto the column. The solvent was run in gradient conditions using tertiary distilled water containing 0.01% TFA and 10% acetonitrile. Chromatography was performed and fractions obtained were analyzed by HPLC and UV spectroscopy. Fractions obtained after column chromatography were analyzed by HPLC.

The HPLC separation conditions are as follows. The column was C ₁₈ (4 μm, 4.6 id × 150 mm) manufactured by YMC and the column temperature was 40 ° C. Buffer A is distilled water containing 0.01% TFA and buffer B is 70% acetonitrile containing 0.01% TFA. The mobile phase for separation is of two types. Gradient separation composition is shown in the following table. The detection wavelength is 260 nm and the flow rate is 1 ml / min.

Absorbance was measured using UV-Vis spectrometry to determine whether the fraction separated by column chromatography and the reference material of the malt correspond to the spectroscopic characteristics.

Time (min) Buffer A (%) Buffer B (%) 0 100 0 5 96 4 10 94 6 15 90 10 20 80 20 30 70 30

(3) Results and discussion

To purify the maltol from red ginseng extract, first solvent fraction was added. Hexane was added to the red ginseng extract, and the mixture was shaken. Then, the hexane was removed, and chloroform was added to the red ginseng extract. The chloroform layer was selected and subjected to HPLC analysis. As a result, it was confirmed that the maltol was dissolved in the chloroform layer at a high concentration. Open column chromatography gave a fraction of maltol with high purity. The presence of maltol and its purity were verified by UV-Vis spectrometer and HPLC. The spectroscopic characteristics of the fraction containing maltol were confirmed by measuring the absorbance using a UV-vis spectrometer. Figure 1 shows the absorbance of a fraction containing maltol reference material and maltol. The maximum absorption wavelength of the maltool reference material is 274 nm. One of the fractions containing the maltol changed to 279 nm, not 274 nm, which is the maximum absorption wavelength of the maltool reference material, as shown in Fig. It is expected that it contains maltol but contains other ingredients than maltol. The fractions corresponding to the maximum absorption wavelength of the maltose reference material are expected to contain no components other than the maltol, and later HPLC analysis was performed to confirm a more accurate purity. Figure 2 shows the results of HPLC analysis. The retention time of the main peak of the fraction containing the maltol was 9.0 min, which was consistent with the reference material of the maltol.

Figure 2 (B) shows the HPLC analysis of the partially purified maltose fraction. As a result of the analysis, it was confirmed that the specific gravity occupied by the malt contained in the total components was 60%, and that the impurities contained a large amount. It is predicted that the maximum absorption wavelength was changed in the UV-Vis spectrum due to the influence of these impurities. FIG. 2 (C) shows that maltol containing 97% of all the components was obtained with high purity. The fractions having a maltol content of 97% or more were selected and the amount of the pure maltol obtained in the red ginseng extract was determined. As a result, it was found that the yield was 6%.

Poulgon's Tablet

(1) Extraction and purification of molds

220 g of mold was put into 4.5 L of chloroform and extracted at 55 캜 for 12 hours. The mold extract was filtered through a filter paper and then concentrated under reduced pressure to maintain the temperature at 50 ° C. 2.8 g of the mold extract was loaded onto silica gel (3 cm x 18 cm) equilibrated with hexane. Elution was carried out in stepwise conditions using hexane and chloroform. And eluted by sequentially increasing chloroform from 0% to 50%. The fraction obtained after column chromatography was subjected to TLC in order to confirm the presence and purity of fullerenes in a short time. The fractions were spotted on a silica gel 60 TLC plate (aluminum backed), dried and developed with hexane (chloroform, 1: 1). Sprayed on a TLC plate in which a vanillin / sulfuric acid solution was developed, and developed by heating at 100 DEG C for 5 minutes.

(2) Identification and purity analysis of pullegon

Absorbance was measured using UV-Vis spectrometry to determine whether the spectroscopic properties of the fractions separated by silica gel column chromatography were consistent with those of the reference material. The molecular weight of the separated fullergan was determined by MS. MS was performed in APCI positive ion mode. The ionization conditions using APCI are as follows: [conrona-discharge current, 0.5 mA; capillary temperature, 150 캜; and vaporiser temperature, 350 ° C. In addition, GC (shimadzu GC-2010) and GC-MS (shimadzu GCMS-QP2010) were used to analyze the purity of the purified poulger.

The GC analysis conditions are as follows. The column was a DB-5MS (60 m, Id = 0.32 mm, stationary phase thickness = 0.25 μm) manufactured by Agilent Inc. and a detector using a flame ionization detector (FID). N ₂ was used as a carrier gas and the flow rate was set at 1 ml / min. The oven temperature is as follows. The temperature was first maintained at 60 ° C for 5 minutes and then increased to 200 ° C at 3 ° C / min. Then, the temperature was increased from 200 ° C to 260 ° C at a rate of 30 ° C / min and then maintained for 5 minutes.

(3) Results

end. Refining and searching of pulgon

The fractions obtained after performing silica gel column chromatography were carried out from TLC with fast analysis time in order to firstly select fractions containing Fragon. As a result, it was confirmed that the elution was started when the chloroform content in the elution solution composition reached 40% or more. Figure 3 shows the fractions obtained after purification performed on TLC. 3 (A) contains unknown compounds other than fullerenes, so pure separation of fullerenes is not achieved. In FIG. 3 (B), no components other than pherogelin were detected in the fraction, and the same results as those of the reference substance pulpone were obtained on TLC. The minimum detection limit for fullerenes that can be detected by vanillin staining on TLC is as high as 5 nmole. In other words, since it is difficult to detect the components which are not sensitive to vanillin coloring or the components that can not be colored, the purity of separated poultry requires different analytical methods such as GC and GC / MS.

I. Pula Gon

The fractions obtained after the silica gel column chromatography purification procedure were first screened using TLC for fragile-containing fractions, and then whether or not the optical characteristics of the fullerenes detected in the reference material pulp and the fractions were the same were measured with a UV-vis spectrometer Respectively. Figure 4 shows the UV-Vis absorbance of the pulolig reference material and the pulolig fraction. The maximum absorption wavelength of the Fullergan fraction is 253 nm, which is the same as that of the pullegord reference material, and the absorption at different wavelengths is also similar. FIG. 5 shows the MS results of the pullegon reference material and the pulverone fraction. APCI positive mode (quantitative mode), and compared with the Puregan reference material and Puregan fraction. APCI positive mode (positive mode) in the molecular weight of the parent peak (peak mother) of the molecule since the place the ionization of the molecules and H ⁺ are combined is obtained by [M + H ^+]. The molecular weight of the fullerene is 152 and the molecular weight of the mother peak is 153 in the APCI positive mode. FIG. 5 (A) shows the MS spectrum of the pulverized reference material, and a mother peak of 153 was confirmed. FIG. 5 (B) shows the MS spectrum of the Fullergan fraction, and the same molecular weight 153 as the Fullergan reference material was obtained.

Examples: Maltol and cyclodextrin complex formation

Preparation of Examples 1 and 2 and Comparative Examples 1 and 2

Maltol and?,? -Cyclodextrin were prepared to be 0.1 mM, 4.4 mM and 3.85 mM, respectively. The complex was formed under the same conditions as in Table 1 below.

Example 1 Comparative Example 1 Example 2 Comparative Example 2 Complex ? -cyclodextrin + maltol ? -cyclodextrin + maltol γ -cyclodextrin + maltol γ -cyclodextrin + maltol pH 7 2 7 2 Temperature 50 ℃

Specifically, the aqueous solution of maltol and the aqueous solution of cyclodextrin were prepared, mixed according to the conditions of Table 1, and the reaction solution was incubated for 1 hour. The pH was set at pH 7 and pH 2, and each pH was adjusted by using NaOH and HCl. The temperature was maintained at 50 占 폚.

Test Example  One: pH end Cyclodextrin - Malcolm  Effect on Complex Formation

In order to investigate the effect of pH on the formation of cyclodextrin-maltol complex, complexes were formed by varying pH conditions as described above. Kinetic assays were used to measure the absorbance change of the maltol by time, Respectively. The detailed conditions of the kinetic assay are as follows. [UV-Visible range; 200-400 nm, cycle time; 10 min (pH effect assay), 10 sec, integration time; 1.7 sec, interval; 1 nm.]

Figure 6 shows the effect of pH on the complex formation of maltol with?,? -Cyclodextrin. At pH 2 and pH 7, the change in absorbance at 274 nm was similar for the control, but for the complex between maltol and β-, γ-cyclodextrin, different results were obtained depending on the pH. 2, the complex of maltol with β-, γ-cyclodextrin was similar to that of control, but at pH 7, the decrease in absorbance decreased from that of control. In other words, at pH 7, it is expected that complex formation of maltol with β-, γ-cyclodextrin has been achieved.

Preparation of Comparative Examples 3 and 4

The cyclodextrin-maltose complex was formed under the same conditions as in Examples 1 and 2, except that the temperature was changed, in order to evaluate the effect of the temperature on the complex formation.

Example 1 Comparative Example 3 Example 2 Comparative Example 4 Complex ? -cyclodextrin + maltol ? -cyclodextrin + maltol γ -cyclodextrin + maltol γ -cyclodextrin + maltol Temperature 50 ℃ 25 ℃ 50 ℃ 25 ℃ pH 7

Test Example  2: Temperature Cyclodextrin - Malcolm  Effect on Complex Formation

In order to investigate the effect of temperature on the formation of cyclodextrin-maltol complex, complexes were formed by varying the temperature conditions as described above. Kinetic assays were used to measure the absorbance change of the maltol with time, Respectively. The detailed conditions of the kinetic assay are as follows. [UV-Visible range; 200-400 nm, cycle time; 10 min (pH effect assay), 10 sec, integration time; 1.7 sec, interval; 1 nm.]

Fig. 7 (A) shows the effect of temperature on the complex formation of maltol with?,? -Cyclodextrin. When the temperature is 25 ° C, The rate of decrease of the absorbance of the complex with β-, γ-cyclodextrin was similar at the beginning of the reaction, but the rate of decrease of the absorbance was decreased from 3600 sec for the β-cyclodextrin complex and that of the γ-cyclodextrin complex increased from 5000 sec. Showed higher absorbance than the control. At a temperature of 50 ° C, the control showed a rapid decrease in absorbance, The decrease in the absorbance of the complex with?,? -cyclodextrin gradually took place. That is, when the temperature is 50 ° C, It is expected that the formation of a complex with?,? -cyclodextrin will be better accomplished. FIG. 7 (B) shows a more detailed view of the change in absorbance in time (A), and shows the change in absorption wavelength at 4000 sec.

Test Example 3: Stability against UV ray exposure by formation of cyclodextrin-maltose complex

Figure 8 (A) The influence of UV-ray exposure on the formation of a complex with β-, γ-cyclodextrin was confirmed by measuring the change in absorbance at 274 nm over time. The pH was fixed at 7 and the temperature was fixed at 25 ° C. When irradiated with UV rays for 0.1 sec, the absorbance changes of the complex between maltol (control), maltol and β-, γ-cyclodextrin were similar, but when irradiated with UV rays for 25.5 sec, the content of maltol and β- and γ-cyclodextrin The change range of the absorbance was smaller than that of the control. FIG. 8 (B) shows absorbance changes with time, and FIG. 6 shows the absorbance at 1800 sec. Maltol The absorbance decrease of the complex with β-, γ-cyclodextrin was much longer than that of UV irradiation for 0.1 sec, The complex with β-, γ-cyclodextrin showed less decrease in absorbance than the control. Taken together, it is believed that complex formation reduces the degree of degradation of the maltol by UV radiation. That is, it is believed that the formation of the complex has an effect of increasing the stability of the maltol.

Example 3: Formation of fullergan and? -Cyclodextrin complex

0.1 mM fullergan and 4.4 mM [beta] -cyclodextrin solution were prepared and mixed and the reaction solution was incubated for 1 hour.

Example 4: Formation of fullergan and? -Cyclodextrin complex

0.1 mM fullergan and 3.85 mM? -Cyclodextrin solution were prepared and mixed, and the reaction solution was incubated for 1 hour.

Test Example 4: Confirmation of water solubility and thermal stability of supramolecules

end. ¹ H NMR spectroscopy

It was confirmed by ¹ H NMR spectroscopy that the water solubility of phragmites through cyclodextrin and supramolecular interactions in aqueous solution was confirmed.

FIG. 9 shows the ¹ H NMR spectrum of β-cyclodextrin alone dissolved in D ₂ O and the spectrum obtained by adding fullerene thereto. As can be easily seen from the figure, it can be seen that fullerone is water-soluble in an aqueous solution containing cyclodextrin. As mentioned above, fullerone is a water-insoluble liquid that does not mix with water. Therefore, when D ₂ O is used as a solvent, ¹ H NMR signals are not obtained. Therefore, the fact that the signal of Fuller'sone as shown in the figure can be confirmed on D ₂ O interacts with the pherogel cyclodextrin to form the supramolecular body contained in the cyclodextrin, which retains the water-soluble property of the cyclodextrin, It shows that it melts. These results were also obtained using γ-cyclodextrin, which is shown in FIG.

I. Analysis by UV spectrum

The hydrolysis of fullerenes by supramolecular interactions with cyclodextrins was also confirmed by UV-vis spectroscopy. As can be seen from FIG. 11, it can be easily found that a new absorber band is present unlike the absorption spectrum of? -Cyclodextrin alone. Cyclodextrins are molecules formed only by a single bond. They do not have a specific chromophore, so they absorb only the wavelength (about 190 nm) of the ultraviolet region with a very short wavelength. On the other hand, Poulgon contains a chromophore of C = CC = O, which absorbs light of longer wavelength (about 260 nm) than β-cyclodextrin, which is also observed in aqueous solution. The same results were obtained in the experiment using? -cyclodextrin, which is shown in Fig. The titration experiments using UV-vis spectroscopy showed that the binding constant between cyclodextrin and fullerene was about 5 × 10 ^-2 M.

All. Analysis by IR

We found one interesting phenomenon during the titration experiment. That is, the superalloys and the cyclodextrins are aggregates of supramolecules at a certain point in time in aqueous solution, resulting in enormous complexes. The concentration time point was confirmed to be about 10 < ^-3 > M. At this concentration, the cyclodextrin itself has sufficient solubility in water, so it can be expected to be a complex due to aggregation between supramolecules. In fact, the IR spectroscopy of the solid samples obtained by this coagulation showed a characteristic peak due to cyclodextrin and fullerenes. 13 and 14 show the IR spectra of samples obtained using? -Cyclodextrin and? -Cyclodextrin. As shown in the figure, there is a new peak near 1,700 cm ^-1 , which is a signal due to the stretching vibration of the C = O bond of Fullergan.

la. Thermogravimetry

Thermogravimetric analysis (TGA) was used to further characterize the stability and stability of supramolecular complexes formed by coagulation in aqueous solution. 15 (a) shows a thermogravimetric analysis diagram of only? -Cyclodextrin. It can be confirmed that the weight is gradually reduced to 100 ° C. This shows the desorption of water molecules contained in the solid state? -Cyclodextrin. The absence of weight loss up to about 270 ° C thereafter means that the β-cyclodextrin is stable up to this temperature, after which the rapid weight loss means the decomposition of β-cyclodextrin. In fact, the melting point of β-cyclodextrin reported in the literature is well known to be decomposed at 260 ° C or higher, which is in good agreement with the experiment. FIG. 15 (b) shows a TGA diagram of a β-cyclodextrin-pulleron supramolecular complex sample, which is different from the TGA diagram of β-cyclodextrin alone shown in FIG. 15 (a) .

That is, similar to the removal of water molecules up to 100 ° C, a new peak due to weight reduction starting at around 280 ° C can be observed. This is believed to be due to the excretion of fullerenes implicated in? -Cyclodextrin. Notable is that the boiling point of the pullegons is 224 ° C, and the weight reduction temperature starts at around 280 ° C, which is higher. It can be said that the thermal stability of fullerenes is improved by supramolecular interaction with? -Cyclodextrin. A similar pattern could be found in samples using γ-cyclodextrin. This is shown in Fig.

Example 5: Preparation of cosmetic composition

(1) Shampoos

A shampoo having compositional components and composition ratios as shown in Table 3 below was prepared.

weight% ingredient Example 5 Comparative Example 5 Ammonium laureth sulfate 12.0 12.0 Ammonium lauryl sulfate 4.0 4.0 Cocamidopropyl betaine 7.0 7.0 Alkylpolyglycoside 1.5 1.5 Polyquaternium 10 0.5 0.5 glycerin 1.5 1.5 ^{* 1} complex of the present invention 4.0 - Spices 0.2 0.2 Purified water Remaining amount Sum 100

^{* 1} : Complex of Example 1: Complex of Example 3 = 1: 1 (weight ratio)

(2) Hair conditioner

A hair conditioner having compositional components and composition ratios as shown in Table 4 below was prepared.

weight% ingredient Example 6 Comparative Example 6 Set rimonium chloride 3.0 3.0 Cetanol 3.5 3.5 Glyceryl monostearate 2.0 2.0 Wax 0.5 0.5 Panthenol 3.0 3.0 PEG / PPG-15/15 Dimethicone 1.0 1.0 ^{* 1} complex of the present invention 4.0 - Spices 0.2 0.2 Purified water Balance Sum 100

^{* 1} : Complex of Example 1: Complex of Example 3 = 1: 1 (weight ratio)

(3) Hair tonics

Hair tonics having compositional components and composition ratios as shown in Table 5 below were prepared.

weight% ingredient Example 7 Comparative Example 7 Lauric acid sorbitan 0.5 0.5 glycerin 1.0 1.0 Butylene glycol 2.0 2.0 Dimethicone copolyol 0.2 0.2 Castor oil 0.2 0.2 Alcohol 20.0 20.0 Salicylic acid 0.1 0.1 ^{* 1} complex of the present invention 4.0 - Spices 0.2 0.2 Purified water Remaining amount Sum 100

^{* 1} : Complex of Example 1: Complex of Example 3 = 1: 1 (weight ratio)

Test Example  5: Half head test of shampoo and conditioner ( Half - head test )

The shampoo and conditioner compositions of Example 5-6 and Comparative Example 5-6 were subjected to the half head test [C. Robbins. Chemical and physical behavior of human hair, Von Nostrand Reinhold, New York, 102-110 (1979)].

㉮ Evaluation items: foam, gloss, smoothness, touch when using, touch after drying and combing

㉯ Evaluation Criteria

5 points: good / 4 points: somewhat good / 3 points: no difference / 2 points: somewhat defective / 1 point: defective

* Half head test result

Evaluation items Example Comparative Example 5 6 5 6 burnish 5 5 4 4 lubricity 4 4 4 4 Tactile use 5 5 4 4 After the dry touch 5 5 3 4

As a result of the evaluation, it was confirmed that the shampoo and hair conditioner composition of the present invention are excellent in gloss, smoothness, touch in use, and touch after drying.

Test Example  6: Usability evaluation of shampoo and hair tonic

The usability evaluation of the shampoo and hair tonic for Examples 5 and 7 and Comparative Examples 5 and 7 was conducted in 20 male and female adults who had itch and dandruff problems. The questionnaire about dandruff, itching, Were measured. The period of use was 6 weeks, and it was washed once a day before sleeping, and 3 ~ 5ml was used at a time. After 4 weeks, the amount of dandruff was measured and questioned. The composition of the present invention was washed once with shampoo once a day, and 3 to 4 ml of hair tonic sample was applied to the scalp three times a day.

㉮ Evaluation items: removing dandruff and itch of hair, improvement of scalp disease and hair loss

㉯ Evaluation Criteria

4. No dandruff itching, hair loss reduction

3. Dandruff itching improvement, hair loss improvement

2. Dandruff itching persist, hair loss continuation

1. Dandruff itching worse, hair loss worse

* Usability evaluation results of shampoo and hair tonic

Evaluation items Example Comparative Example 5 + 7 5 + 7 Dandruff, itching removal effect 4.6 4.1 Scalp disease and hair loss improvement effect 3.6 3.1

Within 3 ~ 4 weeks of use, improvement of hair loss progression was observed in 70% of subjects, 30% of dandruff and itching reduction, improvement of scalp disease such as seborrheic dermatitis or scalp psoriasis, and improvement of hair thickness were recognized.

The present invention is the result of a local innovation manpower training business (KB-05-1-012) carried out by the Korea Industrial Technology Foundation of the Ministry of Commerce, Industry and Energy, and the cosmetic composition according to the present invention is a β- or γ-cyclodextrin- Or a? -Cyclodextrin-pullerone complex as an active ingredient, pharmacological activities such as blood circulation promoting action, antibacterial action, and anti-inflammatory action of the maltol and fullergan are sufficiently maintained to maintain the cleanliness of the scalp and skin cells and to decline due to aging By supplying nutrients to one hair rouge and activating the living tissue of the scalp, problems such as dandruff and itch can be sufficiently satisfactorily improved, and stability against heat and ultraviolet rays due to the complex formation with cyclodextrin can be enhanced And has a beneficial effect to be improved.

Claims (7)

A cosmetic composition comprising a? - or? -cyclodextrin-maltose complex and a? - or? -cyclodextrin-pullerone complex as an active ingredient. The cosmetic composition according to claim 1, wherein the weight ratio of β- or γ-cyclodextrin-maltose complex: β- or γ-cyclodextrin-pullerone complex is 1: 0.1~20. The cosmetic composition according to claim 1 or 2, wherein the total amount of the above-mentioned effective ingredients is contained in a proportion of 0.01 to 10% by weight of the whole composition. Preparing a maltol solution and a? - or? -Cyclodextrin solution, respectively; Mixing the maltol solution and the? Or? -Cyclodextrin solution at a pH of 6 to 8 at 30 to 70 占 폚; And recovering the resulting inclusion complex of cyclodextrin-maltol by centrifugation, thereby preparing a β- or γ-cyclodextrin-maltose complex. delete delete Preparing a Fullergan solution and a? - or? -Cyclodextrin solution, respectively; Mixing the Poulter's solution with a? - or? -Cyclodextrin solution; And recovering the resulting inclusion complex of cyclodextrin-fullerenes by centrifugation, thereby preparing a β- or γ-cyclodextrin-pullerone complex.

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