KR100581215B1 - Flavonoid-deposited polymer composite particles and a process for preparation of the same, and cosmetic compositions containing the same - Google Patents

Abstract

The present invention relates to a flavonoid / polymer composite sphere and a method for producing the same, and a cosmetic composition containing the same, the flavonoid / polymer composite sphere of the present invention is a flavonoid such as epigallocatechin gallate (EGCg) porous polymer particles It is deposited and fixed on a large surface area, and it is expected to be applied to various cosmetic formulations by minimizing the molecular denaturation of flavonoids by external stimulation such as oxygen or light. Especially, the particle size range of 0.01 ~ 1000㎛ is 5-10 on average. Since it is a spherical body having a particle size of μm, when applied to a cosmetic formulation, it is excellent in feeling such as spreadability and can provide the physiological activity effect of flavonoids in the cosmetic formulation.

Flavonoids * Porous Polymer Particles * Surface Interacters * Antioxidants * Spherical Complexes

Description

Flavonoid-deposited polymer composite particles and a process for preparation of the same, and cosmetic compositions containing the same

1 is a scanning electron micrograph of the porous polymer particles.

FIG. 2 is an enlarged scanning electron micrograph of the surface of the porous polymer particle of FIG. 1.

FIG. 3 is a scanning electron micrograph of a porous polymer composite sphere (hereinafter, "EGCg / polymer composite sphere") on which EGCg is deposited.

The present invention relates to a flavonoid / polymer composite sphere and a method for producing the same, and a cosmetic composition containing the same, the flavonoid / polymer composite sphere of the present invention is a flavonoid such as epigallocatechin gallate (EGCg) porous polymer particles As it is deposited and fixed on a large surface area of, it is expected to be applied to various cosmetic formulations by minimizing molecular denaturation of flavonoids by external stimulation such as oxygen or light, and in particular, the average particle size ranges from 0.01 to 1000 μm. Since it is a spherical body having a particle size of 10 ㎛, when applied to the cosmetic formulations, it is excellent in feeling such as spreadability and can provide the physiological activity effect of flavonoids in cosmetic formulations.

The excellent efficacy of green tea is due to the flavonoids present in abundance in green tea, and is particularly known to be due to catechin. Epicatechin [(-) EC], epigallocatechin [(-) EGC], epicatechin gallate [(-) ECg], epigallocatechin gallate [(-) EGCg], etc. are referred to as 'tea catechin' do. Among them, epigallocatechin gallate (hereinafter referred to as "EGCg") having a molecular structure of the formula (1) is known to have the highest composition ratio among tea catechins and excellent in various physiological activity effects.

Recently, the efficacy of green tea on the human body has been attracting attention from around the world, and research on bioefficacy has been actively conducted in various countries around the world. In particular among the green tea catechins, EGCg has antioxidant and anticancer effects {(1) Jovanovic, SV et al , (1994) Flavonoids as antioxidants. J. Am. Chem. Soc . 116, 4846-4851. (2) Salah, N. et al , (1995) Polyphenolic flavanols as scavengers of aqueous phase radicals and as chain-breaking antioxidants. Arch. Biochem. Biophys . 322, 339-346. (3) Dreosti, IE (1996) Bioactive ingredients: Antioxidants and polyphenols in tea. Nutr. Rev. 54, 51-58. (4) Yang, CS et al , (1993) Tea and cancer. J. Natl. Cancer Inst. 85, 1038-1049.}, Is known to have a cholesterol-lowering effect. In addition, when applied to the skin, it inhibits the oxidative action by active oxygen in the living body and inhibits the formation of peroxides, thereby preventing the aging of the biofilm and promoting the biosynthesis of collagen, thereby increasing the elasticity of the skin and preventing and improving skin aging. In addition, it is attracting attention as an effective bioactive substance because it has no skin irritation.

However, since EGCg has a low solubility in water or oil used as a cosmetic base and is dispersed and blended in the form of acicular crystals, EGCg shows a lot of coarse grains, and despite its excellent physiological activity effect, it is limited to application to cosmetics. In addition, since molecular degeneration occurs rapidly due to instability to external stimuli such as moisture, oxygen, light, etc., there is also a problem that it is difficult to preserve the titer in the formulation.

Therefore, there is an urgent need to develop a new stabilization system that can improve the rough feeling of EGCg and minimize molecular denaturation by external stimuli.

Thus, the inventors of the present invention while improving the rough feeling of EGCg when applied to the cosmetic formulation and studying the stabilization method of EGCg against external stimulation, the composite spherical body obtained by depositing and fixing a large amount of EGCg on the large surface area of the porous polymer particles When formulated as a skin, the spreadability is improved and the feeling of use is improved because there is no coarse particle feeling, and the molecular denaturation caused by external stimulus such as oxygen or light is minimized. The invention was completed.

Accordingly, a first object of the present invention is to provide a stabilization system for external stimulation of flavonoids containing EGCg.

It is a second object of the present invention to provide a method for improving their feeling when applying flavonoids containing EGCg to cosmetic formulations.

It is also a third object of the present invention to provide a flavonoid / polymer composite sphere obtained by uniformly depositing and fixing flavonoids containing EGCg on the surface of porous polymer particles.

It is a fourth object of the present invention to provide a method for producing the flavonoid / polymer composite sphere.

A fifth object of the present invention is to provide a cosmetic composition containing the above-described flavonoids / polymer composite spheres as an active ingredient.

The first and second objects of the present invention can be achieved by the third object described above, and the present invention provides a flavonoid such as EGCg (hereinafter referred to as "EGCg") of porous polymer particles in order to achieve the above objects. It is characterized by being deposited and fixed on a large surface area.

According to the present invention, there is provided an EGCg / polymer composite sphere in which a large amount of EGCg is fixed in molecular units on the surface of the porous polymer particles, and the composite sphere of the present invention has a fine powder having a mean particle size of 5 to 10 μm. Because of this, it is easy to mix in various cosmetic formulations, and also the molecular degeneration of flavonoids by external stimulation such as oxygen or light is minimized to preserve the titer in the formulation, and the flavonoids have excellent feeling of spreadability when applying skin. The bioactive effect of can be provided in the cosmetic formulation.

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

The flavonoid / polymer composite spherical body of the present invention is obtained by depositing and fixing flavonoids on a large surface area of porous particles prepared by suspension polymerization. The manufacturing method includes the following steps:

(1) dissolving monomers, crosslinkers and initiators in a solvent;

(2) emulsifying the monomer solution in the presence of a dispersion stabilizer to obtain an emulsion;

(3) after polymerizing the emulsion, removing the solvent and recovering the porous polymer particles; And

(4) depositing flavonoids on the recovered porous polymer particles.

In the present invention, the porous polymer particles having a large surface area are prepared by using suspension polymerization. The monomer / crosslinker / initiator is dissolved in a solvent and then emulsified using a homogenizer in the presence of a suitable dispersion stabilizer to obtain an emulsion, followed by suspension polymerization when the polymerization temperature is maintained while stirring.

The porous structure can be obtained by inducing phase separation of the polymer crosslinked network during suspension polymerization. As the polymerization proceeds in droplets including monomers, crosslinkers, initiators, and solvents, the growing polymer crosslinking network loses its solubility in solvents and forms aggregates into microspheres of several nanoscales. Since these fine spherical bodies are formed in the droplets and the hard properties are strong, the solvent fills the aggregates. Therefore, if only the solvent is selectively removed, it is possible to obtain a polymer particle having a porosity with a maximum surface area.

In this case, copolymerizing a monomer having a hydroxyl group, an amine group, a nitrile group, or the like may produce a porous polymer particle having an interaction group capable of inducing the deposition of flavonoids on the surface. The presence of such interacting groups on the particle surface can induce strong hydrogen bonding with flavonoids in the water phase, which can further enhance the surface deposition of the flavonoids and increase the amount of deposition.

Deposition of flavonoids is carried out in the water phase, specifically, the porous polymer particles are dispersed in water, followed by deposition by addition of an aqueous solution of flavonoids, and then the filtration and drying process is applied to obtain a porous polymer composite sphere in which flavonoids are surface deposited. Can be. In this case, the flavonoids may be fixed on the surface of the polymer by being deposited on the surface of the porous polymer in molecular units, and may be used in various cosmetic compositions.

Flavonoids deposited on the porous polymer particles are hesperetin, genistein, apigenidin, epicatechin [(-) epicatechin, epigallocatechin [(-) epigallocatechin], epicatechingal At least one selected from the group consisting of late [(-) epicatechingallate], epigallocatechin gallate [(-) epigallocatechingallate] and resveratrol can be used. Epigallocatechin gallate (EGCg) is described herein as representative of the flavonoids described above. The surface deposition amount of flavonoids is 0.01 to 90% by weight relative to the total polymer weight.

The monomer that can be used to prepare the polymer particles having a porous structure in the above step (1) is not particularly limited as long as it is capable of radical polymerization. In addition, the monomer and the crosslinking agent may be mixed to prepare the porous polymer particles in the form of a copolymer, or the porous polymer particles may be prepared using only the crosslinking agent. As a monomer, Styrene; Acrylates; Vinyl acetate; Vinyl ethers; Unsaturated carboxylic acids including maleic acid; Alkyl (meth) acrylamides; (Meth) acrylonitrile and derivatives thereof. Specifically, styrene, p- or m -methylstyrene, p- or m -ethylstyrene, p- or m -chlorostyrene, p- or m -chloromethylstyrene, styrenesulfonic acid, p- or m- t-part Oxystyrene, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, polyethylene glycol (meth ) Acrylate, methoxypolyethylene glycol (meth) acrylate, glycidyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, vinyl acetate, vinyl propionate, Vinyl butyrate, non It can be used an ether, an allyl ether, allyl glycidyl ether, (meth) acrylic acid, unsaturated carboxylic acids, alkyl (meth) acrylamides containing a maleic acid, such as (meth) acrylonitrile.

In addition, the cross-linking agent that can be used in the step (1) is capable of radical polymerization, allyl compounds including divinylbenzene and diallyl phthalate; (Poly) alkylene glycol di (meth) acrylate including (poly) ethylene glycol di (meth) acrylate; Urethane acrylates; Epoxy acrylates and derivatives thereof. Specifically, the allyl compound containing divinylbenzene, 1, 4- divinyloxy butane, divinyl sulfone, diallyl phthalate, diallyl acrylamide, triallyl (iso) cyanurate, and triallyl trimellitate; (Poly) ethylene glycol di (meth) acrylate, (poly) propylene glycol di (meth) acrylate, penta erythritol tetra (meth) acrylate, penta erythritol tri (meth) acrylate, penta Ryltritol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, and glycerol tri (meth) (Poly) alkylene glycol di (meth) acrylate including) acrylate; Urethane acrylates; Epoxy acrylate and the like can be used. The concentration of the crosslinker determines the porosity of the final polymer particles. Generally at least 30% by weight relative to the total monomer weight is appropriate. At concentrations below this, phase separation tends to be weakened, resulting in poor porosity and reduced surface area.

Initiators used in the present invention include oil-soluble initiators, peroxide-based containing benzoyl peroxide; It can be selected from the group consisting of azo compounds including 2,2-azobisisobutyronitrile and derivatives thereof. Specifically, benzoyl peroxide, lauryl peroxide, o -chlorobenzoyl peroxide, o -methoxybenzoyl peroxide, t-butylperoxy-2-ethylhexanoate, t-butylperoxy isobutylate, 1 , 1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, dioctanoyl peroxide and

Peroxides, including didecanoyl peroxide; And azo compounds including 2,2-azobisisobutyronitrile, 2,2-azobis (2-methylbutyronitrile), and 2,2-azobis (2,4-dimethylvaleronitrile). Can be. As for the usage-amount of an initiator, 0.1-3 weight% is preferable with respect to the total monomer weight. The solvent used in the above step (1) has a solubility parameter similar to that of the monomer selected, and includes linear alkanes including hexane; Alcohols having 4 to 10 carbon atoms including butanol; alkyl esters having at least 7 carbon atoms including n-hexyl acetate; Aliphatic ketones; Aromatic hydrocarbons including toluene; It can be selected from the group consisting of chlorine compounds including methylene chloride and derivatives thereof. Specifically, linear alkanes including hexane, heptane, octane, nonane and decane; Alcohols having 4 to 10 carbon atoms including butanol, linear or branched pentanol, hexanol, heptanol, octanol, nonanol and decanol; alkyl esters having at least 7 carbon atoms including n-hexyl acetate, 2-ethylhexyl acetate, methyl oleate, dibutyl sebacate, dibutyl adipate and dibutyl carbamate; Aliphatic ketones including methyl isobutyl ketone and isobutyl ketone; Aromatic hydrocarbons including benzene, toluene, o- or p -xylene; Chlorine compounds including methylene chloride, chloroform and carbon tetrachloride may be used, but is not limited thereto. Preferably, toluene, ketone, or the like may be used to facilitate phase separation and form a pore structure well.

The dispersion stabilizer used in the above step (2) is a polymer that can be dissolved in an aqueous phase, specifically gelatin, starch, hydroxyethyl cellulose, carboxymethylcellulose, polyvinylpyrrolidone, polyvinyl alkyl ether, poly Vinyl alcohol, polydimethylsiloxane / polystyrene block copolymer, and the like. The amount of the polymer particles used in the emulsification process is preferably used to the extent that the polymer particles produced during the emulsification can suppress the deposition due to gravity and the aggregation between the particles, but is preferably used in the range of 0.1 to 30% by weight based on the total reactants. This is because, at a concentration of less than 0.1% by weight, the dispersion stability due to interfacial deposition is sharply lowered, and when it exceeds 30% by weight, the viscosity of the system increases rapidly, making the process impossible.

The porous polymer particles thus prepared are spherical bodies having a particle size of 0.01 to 1,000 μm, on average 5 to 10 μm, and have a large surface area of 10 m 2 / g or more and small pores of 10 to 20 nm in size to deposit flavonoids. This is easy.

In the step (4), the deposition of flavonoids is carried out in an aqueous phase. Specifically, after dispersing the porous polymer particles in water at pH 2-7, the flavonoids are introduced to introduce the interaction groups and flavonoid molecules present on the surface of the porous polymer particles. Induces the complexation of the hydroxyl groups present within. When the pH is less than 2, hydrogen bonding may be interrupted by an excess of hydrogen ions, and when the pH is above 7, hydrogen bonding may be interrupted by an excess of hydroxide ions.

The flavonoid / polymer composite sphere provided by the above manufacturing method is a fine powdery spherical body in which a large amount of flavonoids are deposited and fixed on the surface of porous polymer particles in a molecular unit, and various formulations are possible by being easily dispersed and blended in a cosmetic base. In addition, the spreadability is improved when the skin is applied and there is no coarse grain to provide an excellent feeling of use. In addition, molecular denaturation due to external stimuli is minimized, which allows preservation of titers in the formulation. Therefore, according to the present invention can provide the physiological activity effect of the flavonoids in the cosmetic formulation.

When the flavonoid / polymer composite spherical body of the present invention is blended into the cosmetic composition, it is not particularly limited in the formulation, but anhydrous formulation which can exclude molecular denaturation by moisture is more preferable. Specifically, flexible cosmetics, nourishing cosmetics, massage creams, nutrition creams, gels, packs, essences, lipsticks, makeup bases, foundations, lotions, ointments, creams, patches and sprays.

Hereinafter, the present invention will be described in more detail with reference to Examples, Comparative Examples, and Experimental Examples. However, these examples are intended to illustrate the present invention, it is obvious to those skilled in the art that the scope of the present invention is not limited to these examples.

Example 1 Preparation of Porous Polymer Particles and EGCg Deposition

Porous polymer particles were prepared by the following procedure. 100 g was prepared by mixing methyl methacrylate / ethylene glycol dimethacrylate (crosslinking agent) / toluene in a ratio of 18/42/40 to weight in the reactor. 2,2-Azobis (2,4-dimethyl valeronitrile), which is an initiator, was introduced into the solution at 1 wt% based on the monomer, followed by stirring at room temperature to completely dissolve it. Subsequently, the prepared solution was placed in an aqueous solution in which 1% of polyvinyl alcohol (average degree of saponification of 89%) was dissolved and emulsified at 6,000 rpm for 5 minutes using a mechanical homogenizer. At this time, the methyl methacrylate / crosslinker / initiator / toluene solution has a concentration of 15% by weight in the water phase. Subsequently, after raising the temperature of the reactor to 70 ° C. and polymerizing for 10 hours, the porous polymer particles prepared through the filter paper were collected by filtration. The unreacted material and the dispersion stabilizer were repeatedly washed with methanol, and then dried in a vacuum oven for 24 hours to obtain a powder.

The porous polymer particles thus obtained were dispersed in water at 20% by weight relative to the total weight. In addition, EGCg was dissolved in 3% by weight of the total weight to prepare an aqueous solution, and then slowly mixed into the dispersion in which the porous polymer particles were dispersed. After 30 minutes of further stirring, the porous polymer particles having EGCg deposited thereon were filtered through a filter paper and then dried in a vacuum oven for 24 hours to obtain a powder.

Example 2 Preparation of Porous Polymer Particles Having Nitrile Group and EGCg Deposition

Except for using methyl methacrylate / acetonitrile / ethylene glycol dimethacrylate / toluene in a ratio of 12/6/42/40 to the weight by the same procedure as in Example 1, having a nitrile group on the surface Porous polymer particles were prepared. EGCg deposition process was the same as in Example 1.

Example 3 Preparation of Porous Polymer Particles Having Hydroxy Group and EGCg Deposition

The polymerization reaction was carried out in the same manner as in Example 1 except that methyl methacrylate / vinylacetate / ethylene glycol dimethacrylate / toluene was mixed at a ratio of 12/6/42/40 to weight. After the completion of the polymerization, 0.8 wt% sodium hydroxide was added to the reaction to saponify acetate at room temperature for 10 hours to prepare porous polymer particles having a hydroxyl group on the surface. EGCg deposition process was the same as in Example 1

Example 4 Preparation of Porous Polymer Particles Having a Carboxyl Group and EGCg Deposition

The same procedure as in Example 1 was carried out except that methyl methacrylate / methacrylic acid / ethylene glycol dimethacrylate / toluene was mixed at a ratio of 12/6/42/40 to weight, and a carboxyl group was formed on the surface. The porous polymer particles having were prepared. EGCg deposition process was the same as in Example 1.

Experimental Example 1 Characterization of the EGCg / Polymer Composite Spheres Prepared in Examples 1 to 4

The EGCg / polymer composite spheres prepared in Examples 1 to 4 were analyzed using BET (Brunauer, Emmett and Teller) and liquid chromatography. The results are summarized in Table 1 below.

Example Surface area (㎡ / g) Pore size (nm) EGCg deposition amount (% by weight) One 210 12 2.5 2 220 15 10 3 225 14 12 4 218 11 6.8

As shown in Table 1, the porous polymer particles prepared in Examples 1 to 4 have a large surface area of 200 m 2 / g or more and small pores of 10-20 nm size, regardless of the presence or absence of surface functional groups. Able to know. However, it can be seen that the amount of EGCg introduced depends on the presence or absence of functional groups having interaction force rather than porosity. In particular, it can be seen that the porous particles having a nitrile group and a hydroxyl group capable of hydrogen bonding with the hydroxy group present in the EGCg are more effective for EGCg deposition. Overall, EGCg deposition efficiency is adjustable around 75%.

Experimental Example 2 Structural Analysis of the EGCg / Polymer Composite Spheres Prepared in Examples 1 to 4

The powder form of the porous polymer particles prepared in Examples 1 to 4 and the composite spherical body on which the EGCg was surface deposited was confirmed by scanning electron microscope, and the results are shown in FIGS. 1 to 3. The porous polymer particles prepared in Examples 1 to 4 all have the same particle shape. Among them, porous polymer particles having a nitrile group prepared in Example 2 are shown in FIG. 1. The prepared particles have a polydispersity as a whole due to the suspension polymerization method, but have an average particle size of 5 to 10 μm and all have porosity on the surface. Surface porosity can be directly confirmed from the surface magnified scanning electron micrograph in FIG. In addition, FIG. 3 shows an electron scanning micrograph of EGCg-deposited porous polymer particles. Even when EGCg was deposited on the prepared porous polymer particles, no change in appearance was observed.

Experimental Example 3 Storage Stability of EGCg / Polymer Composite Spheres Prepared in Examples 1 to 4

The storage stability of the EGCg / polymer composite spheres prepared in Examples 1 to 4 was observed using liquid chromatography while storing at room temperature and 45 ℃ for 6 months. Storage was by using a normal polyethylene plastic tube blocked water. As a result, it was confirmed that the stability of the EGCg / polymer composite sphere of the present invention in the powder phase only within 2%. Thus, it is suggested that storage is possible in powder form.

Experimental Example 4 Stability in Water-Based Cosmetic Formulations

In order to confirm the stability in the aqueous cosmetic formulation of the EGCg / polymer composite spheres prepared in Examples 1 to 4, an aqueous formulation was prepared with the composition of Table 2 below. It was also prepared by adding EGCg not deposited on the porous particles to compare the stability. The EGCg content in the formulation was adjusted to 0.1% by weight.

Aqueous Cosmetic Formulations Ingredient (wt%) Formulation example Comparative Formulation Example 1 One 2 3 4 glycerin 5 5 5 5 5 Propylene glycol 4 4 4 4 4 EGCg / Polymer Composite Spheres Example 1 4 - - - - Example 2 - One - - - Example 3 - - 0.83 - - Example 4 - - - 1.47 - EGCg - - - - 0.1 ethanol 10 10 10 10 10 Sodium Polyacrylate 0.5 0.5 0.5 0.5 0.5 antiseptic Quantity Quantity Quantity Quantity Quantity Purified water To 100 To 100 To 100 To 100 To 100

The prepared samples were stored in an oven at room temperature and 40 ° C., respectively, and after a certain period of time, the residual EGCg content was measured using liquid chromatography. Compared with the initial content it is shown in Table 3 as a percentage of the content retention.

Storage temperature (℃) Initial concentration retention (%) 1 day later 3 days later 7 days later Formulation Example 1 25 98 54 0 40 78 25 0 Formulation Example 2 25 95 58 0 40 70 21 0 Formulation Example 3 25 97 61 0 40 80 33 0 Formulation Example 4 25 89 34 0 40 54 6 0 Comparative Formulation Example 1 25 82 21 0 40 32 0 0

All the samples observed in this experimental example showed a result of losing stability in a short time. When deposited on porous particles, stability was more stable than pure EGCg, but ultimate stability was not reached. The above results demonstrate once again that water is the decisive factor in causing EGCg denaturation. Therefore, it can be seen that anhydrous system is suitable for EGCg stabilization. However, the stability of EGCg, which was previously considered impossible to use in an aqueous phase due to its stability, is improved as described above in the present invention, which suggests the possibility of using EGCg in an aqueous phase. In (formulations used by mixing just before use, etc.), such stability improvement suggests many applications.

Experimental Example 5 Stability in Anhydrous Cosmetic Formulation

In order to confirm the stability in the anhydrous cosmetic formulation of the EGCg / polymer composite spheres prepared in Examples 1 to 4, anhydrous formulations were prepared with the composition of Table 4 below. It was also prepared by adding EGCg not deposited on the porous particles to compare the stability. The EGCg content in the formulation was adjusted to 0.1% by weight.

Anhydrous Cosmetic Formulation Ingredient (wt%) Formulation example Comparative Formulation Example 2 5 6 7 8 Dimethicone 5 5 5 5 5 Cyclomethicone 10 10 10 10 10 EGCg / Polymer Composite Spheres Example 1 4 - - - - Example 2 - One - - - Example 3 - - 0.83 - - Example 4 - - - 1.47 - EGCg - - - - 0.1 Polydesin 10 10 10 10 10 Siloxane polymer To 100 To 100 To 100 To 100 To 100

The prepared samples were stored in an oven at room temperature and 40 ° C., respectively, and after a certain period of time, the residual EGCg content was measured using liquid chromatography. Compared with the initial content it is shown in Table 5 as a percentage of the content retention.

Storage temperature (℃) Initial concentration retention (%) 1 week later after 2 weeks 4 weeks later 8 weeks later 12 weeks later Formulation Example 5 25 100 100 100 98 96 40 100 100 99 96 95 Formulation Example 6 25 100 100 100 100 99 40 99 99 98 98 95 Formulation Example 7 25 100 100 100 100 100 40 100 100 100 100 97 Formulation Example 8 25 100 100 100 100 98 40 100 98 95 95 92 Comparative Formulation Example 2 25 100 100 100 98 98 40 100 100 98 98 96

In addition, the prepared samples were stored in the air at room temperature exposed to sunlight, respectively, and after three months, the content of residual EGCg was measured using the change in appearance color and liquid chromatography, and compared with the initial content. , Stability against oxygen and light was compared. The results are shown in Table 6.

Storage temperature (25 ℃) Initial concentration retention (%) Initial state 1 month later 3 months later Formulation Example 5 Stability 100 100 95 color Light pink Light pink Light pink Formulation Example 6 Stability 100 100 96 color Light pink Light pink Light pink Formulation Example 7 Stability 100 100 100 color Light pink Light pink Light pink Formulation Example 8 Stability 100 100 98 color Light pink Light pink Light pink Comparative Formulation Example 2 Stability 100 100 91 color Light pink Light brown Reddish brown

As shown in Table 5 and Table 6, the EGCg deposited on the polymer particles retained the initial pale pink after three months and showed excellent stability of 95% or more. This is because the EGCg is deposited on a large surface of the porous particles in a molecular unit and is fixed, so that the EGCg is maintained as it is without modification of molecular structure against heat, moisture, oxygen, and light in the air, thereby preserving its active titer in the formulation. Suggests.

On the other hand, in Comparative Example 2, the thermal stability is excellent, but the molecular color of EGCg is changed due to moisture, oxygen, light, etc. in the air, so that the appearance color becomes reddish brown (browning phenomenon), and the initial content is also reduced. It can be seen that it is not possible to preserve its active titer in the formulation.

Experimental Example 6 Comparison

For Formulation Example 5 and Comparative Formulation Example 2, the usability was evaluated through sensory tests. The sensory test was performed on 30 subjects according to the criterion of Table 7 below, and the results of averaging the results are shown in Table 8 below.

Criteria 3 2 One 0 Spreadability Spread gently Spread well is average Do not spread well Moist when applied Very moist Moist is average Not moist Particle feeling when applied There is a lot of particle feeling There is a little graininess Particle feeling is felt No graininess

Formulation Example 5 Comparative Formulation Example 2 Spreadability 2.7 ± 0.14 0.9 ± 0.19 Moist 2.1 ± 0.11 1.3 ± 0.24 Particle 0.8 ± 0.21 2.5 ± 0.12

From Table 8 above, it can be confirmed that the formulation containing the EGCg / polymer composite sphere of the present invention is excellent in feeling. This suggests that spherical EGCg may be fixed on the surface of the porous polymer particles to be spherical to improve spreadability during application of the skin and provide excellent feeling without rough grain. On the other hand, in Comparative Formulation Example 2 in which the needle-like EGCg itself was formulated, the spreadability was poor, and in particular, the feeling was poor because of the coarse graininess.

As described above, the porous polymer spherical complex in which the EGCg proposed in the present invention is excessively deposited on the surface can contain EGCg having excellent antioxidant capacity and can be introduced into the formulation while maintaining stability, and thus various cosmetics containing EGCg in the future. Development is expected to be possible. In addition, it is expected to be useful in developing a stabilization system for various antioxidants such as flavonoids or terpenoids having extremely low stability and low solubility in water or oil.

Claims (15)

Flavonoids / polymer composite spheres in which flavonoids are deposited and fixed on the surface of porous polymer particles. The method of claim 1, wherein the flavonoids are hesperetin, genistein, apigenidin, epicatechin [(-) epicatechin], epigallocatechin [(-) epigallocatechin], epicatechingal Flavonoid / polymer composite spheres characterized in that at least one member selected from the group consisting of the rate [(-) epicatechingallate], epigallocatechingallate [(-) epigallocatechingallate] and resveratrol. The flavonoid / polymer composite sphere according to claim 1, wherein the flavonoid is deposited and fixed on the surface of the porous polymer particles in an amount of 0.01 to 90% by weight based on the total weight of the polymer. The flavonoid / polymer composite sphere according to claim 1, wherein the porous polymer particles have a particle size of 0.01 to 1,000 µm. Method for producing a flavonoid / polymer composite sphere comprising the following steps: (1) dissolving monomers, crosslinkers and initiators in a solvent; (2) emulsifying the monomer solution in the presence of a dispersion stabilizer to obtain an emulsion; (3) after polymerizing the emulsion, removing the solvent and recovering the porous polymer particles; And (4) depositing flavonoids on the recovered porous polymer particles. The method of claim 5, wherein the monomer of step (1) is styrene; Acrylates; Vinyl acetate; Vinyl ethers; Unsaturated carboxylic acids including maleic acid; Alkyl (meth) acrylamides; (Meth) acrylonitrile and a method for producing a flavonoid / polymer composite sphere characterized in that at least one member selected from the group consisting of. 6. The method of claim 5, wherein the crosslinking agent of step (1) comprises an allyl compound including divinylbenzene and diallyl phthalate; (Poly) alkylene glycol di (meth) acrylate including (poly) ethylene glycol di (meth) acrylate; Urethane acrylates; Method for producing a flavonoid / polymer composite sphere characterized in that at least one selected from the group consisting of epoxy acrylate and derivatives thereof. 6. The method of claim 5, wherein the initiator of step (1) comprises a peroxide system comprising benzoyl peroxide; Azo compounds comprising 2,2-azobisisobutyronitrile and a method for producing flavonoids / polymer composite spheres, characterized in that at least one selected from the group consisting of these derivatives. The method of claim 5, wherein the solvent of step (1) is a linear alkanes comprising hexane; Alcohols having 4 to 10 carbon atoms including butanol; alkyl esters having at least 7 carbon atoms including n-hexyl acetate; Aliphatic ketones; Aromatic hydrocarbons including toluene; Method for producing flavonoids / polymer composite spheres characterized in that at least one selected from the group consisting of chlorine compounds containing methylene chloride and derivatives thereof. The method of claim 5 wherein the dispersion stabilizer of step (2) is gelatin, starch, hydroxyethylcellulose, carboxymethylcellulose, polyvinylpyrrolidone, polyvinyl alkyl ether, polyvinyl alcohol and polydimethylsiloxane / Method for producing flavonoids / polymer composite spheres characterized in that at least one member selected from the group consisting of polystyrene block copolymer. delete A cosmetic composition comprising the flavonoid / polymer composite sphere according to claim 1 as an active ingredient. 13. The cosmetic composition according to claim 12, wherein the cosmetic composition has an anhydrous formulation. The cosmetic composition according to claim 12 or 13, wherein the cosmetic composition is a softening lotion, nourishing cream, massage cream, nourishing cream, gel, pack, essence, lipstick, makeup base, foundation, lotion, ointment, cream, patch or spray Cosmetic composition, characterized in that formulated as. delete

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