KR20110035459A - Egcg/polyester resin complex, process for preparing the same and cosmetic composition comprising the same - Google Patents

Abstract

PURPOSE: An EGCG/polyester resin composite is provided to minimize the molecular modification of EGCG caused by water, oxygen, heat, air, light, and other chemical substances and to ensure excellent stability and spreadability. CONSTITUTION: A method for manufacturing an EGCG/polyester resin composite comprises the steps of: (i) adding EGCG and polyester resin in a solvent, and dissolving the materials in a room temperature; (ii) injecting the solution in a surfactant solution, raising a reactor temperature to 50~60 °C, and decompressing and distilling the mixed solution to remove the solvent; and (iii) cooling the reactant from which solvent is removed at room temperature, washing the reactant with water, and drying the washed reactant.

Description

EVC / polyester resin composite, preparation method thereof and cosmetic composition comprising same {EGCG / polyester resin complex, process for preparing the same and cosmetic composition comprising the same}

The present invention relates to an EVC / polyester resin composite, a preparation method thereof and a cosmetic composition comprising the same.

EGCG (epigallocatechin gallate) is known to increase the immune function of the human body and excellent antioxidant effect, and excellent anti-cancer and antioxidant action upon oral administration. In addition, when EGCG is applied to the skin, it promotes the production of collagen, which is a component of cartilage, capillaries, muscles, etc. It not only plays a role in preventing skin damage by destroying chemicals generated by UV rays penetrating the skin, It is also known to prevent, to keep the skin healthy, and excellent whitening action, it is expected to be able to exhibit an excellent function when applied to pharmaceutical compositions, household goods and the like as well as cosmetic compositions.

However, since EGCG has a strong antioxidant function as a chemical structure of polyphenols, EGCG itself is sensitive to air, particularly oxygen, heat, and light, and is easily decomposed by oxidation. The oxidation reaction of EGCG seems to have a mechanism in which the adjacent phenol groups are usually decomposed by oxidizing agents such as radicals and converted to ketone groups to break the ring structure of the phenyl group. In addition, EGCG has about 4% solubility in water in aqueous solution, but due to fast oxidation, sufficient amount of EGCG is not stabilized, so only a small amount of EGCG can be used as an active substance in medicine, food, and cosmetics. Has been reported.

In order to supplement the inherent problems of EGCG and improve the stability, many studies have been actively conducted. For example, Korean Patent No. 10-449228 discloses a method of using an EGCG derivative, and in addition to the above patent, a method for stabilizing EGCG by lipophilic microcapsules has been studied. However, the above-mentioned EGCGs have a disadvantage that they are made only under very limited stability. To compensate for this drawback, Korean Patent No. 10-646365 discloses a water-stabilized EGCG composition and a method for preparing the same. However, the method shows very good stability compared to other existing methods, but becomes unstable when other polar substances are added to the stabilizing formulation. In other words, when applied to cosmetics, food, pharmaceuticals, other substances other than EGCG is added, and if the added substance interacts very strongly with the bipolar polymer, the negative polymer, and the antioxidant used as a stabilizer, the degree of stabilization Will be reduced. Therefore, in order to overcome this disadvantage, Korean Patent No. 10-720333 describes a water-stabilized EGCG capsule composition and its preparation method.

In addition, Korean Patent No. 10-581215 discloses a flavonoid / polymer composite sphere and a method for producing the same, and a cosmetic composition containing the same. The flavonoid / polymer composite sphere is a flavonoid such as EGCG is deposited and fixed on a large surface area of the porous polymer particles, minimizing molecular denaturation of flavonoids by external stimulation such as oxygen or light. Specifically, the monomer, the crosslinking agent and the initiator are dissolved in a solvent, then emulsified with a dispersion stabilizer to emulsion polymerization, the solvent is removed, the porous polymer particles are recovered, and the flavonoids are deposited on the recovered porous polymer particles. However, the method requires two or more filtration and drying steps to recover the porous polymer particles, and there is a problem in that unreacted monomers remain in the porous polymer particles. In addition, since the solubility of EGCG in water is about 4%, there is a disadvantage in that the deposition concentration of EGCG that can be impregnated into a spherical polymer is low.

Therefore, there is a need for a study on a method of stabilizing EGCG in an economical manner that improves the problems of the method.

While studying the method of stabilizing EGCG, the present inventors prepared an EGCG / polyester resin composite by impregnating EGCG in a polyester resin, and the titer of the EGCG / polyester resin composite was not only at high temperature but also at room temperature. Compared to the EGCG of the very high stability and very excellent spreading properties when applying the skin, there is no rough grain, excellent texture and excellent feeling, and completed the present invention.

The present invention is to provide an EB / K polyester resin composite, a manufacturing method thereof and a cosmetic composition comprising the same.

The present invention provides an EVC / polyester resin composite, wherein the EVCV is impregnated with the polyester resin.

In addition,

1) adding EGCG and polyester resin to a solvent and dissolving at room temperature,

2) adding the solution to the aqueous surfactant solution and heating the reactor temperature to 50 ~ 60 ℃ and distilled under reduced pressure to remove the solvent in the reaction solution, and

3) cooling the reaction solution from which the solvent has been removed to room temperature, and then washing with water and drying, it provides a method for producing an EVC / polyester resin composite.

In addition, the present invention provides a cosmetic composition comprising the EVC / polyester resin composite.

Hereinafter, the present invention will be described in detail.

The EVC / polyester resin composite of the present invention is characterized in that the EVC is impregnated into the polyester resin, and is made of 0.1 to 25% by weight of ECCV and 75 to 99.9% by weight of the polyester resin.

The EGCG comprises 0.1 to 25% by weight, preferably 0.5 to 20% by weight, based on the total weight of the composite. If the content of EGCG is less than 0.1% by weight, the amount of EGCG is so small that the dissolution rate is too slow to exert the effect of EGCG. If it exceeds 25% by weight, EGCG remains at a high concentration in the polyester resin, resulting in rapid dissolution. Skin irritation occurs when applied to the skin.

The polyester resin has a glass transition temperature (T _g ) of 40 to 90 ° C., a number average molecular weight (Mn) of 2,000 to 10,000, a molecular weight distribution index of 2 to 15, and a sodium sulfonate group based on 100 parts by weight of the resin. It is preferable to contain 0.5-5.0 weight part. The content of the polyester resin is preferably 75 to 99.9 wt%, and if the content of the polyester resin is less than 75 wt%, EGCG is difficult to impregnate in the polyester to form a composite, and if it exceeds 99.9 wt% The amount of EGCG impregnated in the polyester is so small that the dissolution time of the EGCG takes a long time.

The EVCＧ / polyester resin composite of the present invention may further contain an antioxidant.

Antioxidants are used to further enhance the stabilizing effects of some unstabilized EGCGs, including tyrosine, tryptophan, lipoic acid , vitamin C and its derivatives, vitamin E and its derivatives, vitamin A and its derivatives, sodium sulfite and sodium disulfide. Pit and the like are preferable. The content of the antioxidant is suitably contained in an amount of 0.1 to 10.0% by weight, preferably 0.1 to 3.0% by weight based on the total weight of the complex. If the content of the antioxidant exceeds 10.0% by weight can form a complex directly with the polyester resin forming a complex with the EGCG can reduce the stability effect, if less than 0.1% by weight the problem that the stabilization effect of the EGCG is insufficient There may be.

The EVC / polyester resin composite of the present invention is prepared by adding EGCG and a polyester resin to a solvent and dissolving it at room temperature, and then adding the solution to an aqueous solution of a surfactant and distilling under reduced pressure after heating the reactor temperature to 50 to 60 ° C. The solvent in the solution is removed, cooled to room temperature, washed with water and dried to prepare a powder.

As the surfactant, any hydrophilic-lipophilic balance (HLB) of 10 or more may be used. For example, sodium stearoyl lactylate, polyethylene glycol cocamine, polyethylene glycol sorbitan hexanolate , Polyethylene glycol dilaurate, steamine acetate, taloamine acetate, glyceryl stearate, polyethylene glycol lanate, polyethylene glycol palmitate, polypropylene glycol hydroxyethyl cocamine, polyethylene glycol glyceryl laurate, polyethylene glycol stearate It may include one or more selected from the group consisting of latex, triethylamine oleate, polyethylene glycol taloamine, sucrose laurate, sodium dodecyl sulfate, potassium dodecyl sulfate, alkylammonium chloride and alkylammonium bromide, but It does not specified.

The solvent is preferably methanol, ethanol, butanol, chloroform, dichloromethane, ethyl acetate, hexane, diethyl ether, acetonitrile, benzene, toluene, acetone, methyl ethyl ketone, and the like. Can be used.

The particles of the EVC / polyester resin composite produced by the above method are 1 to 100 µm spherical, preferably 4 to 20 µm spherical. The EGCＧ / polyester resin composite is EGCG impregnated in the polyester resin in molecular units, thereby minimizing molecular denaturation of EGCG due to external stimulus such as water, oxygen, heat, air, light, and other chemicals, thereby potency in the formulation. Preservation is possible, and stability is very excellent. In addition, since the inside and the outside of the composite particles are porous and EGCG is impregnated with polyester resin in molecular units, it is easily dispersed and blended in the cosmetic base, so that EGCG can be released slowly, and various types of cosmetic formulations are possible. When spreading, the spreadability is improved and there is no grainy feeling, so the feel is excellent and the feeling is excellent.

Therefore, the EVC / polyester resin composite of the present invention can be usefully used in cosmetic compositions.

The EVC / polyester resin composite may be contained in an amount of 0.01 to 10% by weight, preferably 0.1 to 2% by weight, based on the total weight of the cosmetic composition.

The composition of the present invention is in addition to the EVC / polyester resin composite, in addition to the additives commonly used in cosmetic compositions, for example, conventional auxiliaries and / or carriers such as antioxidants, stabilizers, solubilizers, vitamins, pigments and flavorings. It can be prepared, including a cosmetic composition. In addition, the cosmetic composition may further include a skin absorption promoting substance.

The cosmetic composition of the present invention is not particularly limited in its formulation, and may be prepared in any formulation commonly prepared in the art, and more preferably anhydrous formulations capable of excluding molecular denaturation by moisture. Specifically, it may be formulated as a solution, suspension, emulsion, paste, gel, cream, lotion, powder, soap, surfactant-containing cleansing, oil, powder foundation, emulsion foundation, wax foundation and spray, It is not limited to this. More specifically, flexible lotion, nourishing lotion, nourishing cream, massage cream, essence, eye cream, cleansing cream, cleansing foam, cleansing water, pack, essence, lipstick, makeup base, foundation, lotion, ointment, patch or spray It can be formulated as.

When the formulation is a paste, cream or gel, animal oils, vegetable oils, waxes, paraffins, starches, trachants, cellulose derivatives, polyethylene glycols, silicones, bentonites, silicas, talc or zinc oxide may be used as carrier components. have.

If the formulation is a powder or a spray, lactose, talc, silica, aluminum hydroxide, calcium silicate or polyamide powder may be used as the carrier component, in particular in the case of sprays additionally chlorofluorohydrocarbon, propane Propellant such as butane or dimethyl ether.

If the formulation is a solution or emulsion, a solvent, solubilizer or emulsifier is used as carrier component, for example water, ethanol, isopropanol, ethyl carbonate, ethyl acetate, benzyl alcohol, benzyl benzoate, propylene glycol, Fatty acid esters of 1,3-butylene glycol oil, glycerol aliphatic esters, polyethylene glycols or sorbitan.

If the formulation is a suspension, a liquid diluent such as water, ethanol or propylene glycol as a carrier component; Suspending agents such as ethoxylated isostearyl alcohol, polyoxyethylene sorbitol ester, and polyoxyethylene sorbitan ester; Microcrystalline cellulose; Aluminum metahydroxide; Bentonite; Agar or tracant and the like can be used.

Hereinafter, preferred embodiments of the present invention will be described in order to facilitate understanding of the present invention. However, the following examples are provided only for the purpose of easier understanding of the present invention, and the present invention is not limited by the examples.

Preparation Example 1  : Preparation of Polyester Resin (Number Average Molecular Weight: 3,000)

0.5 mol of dimethyl terephthalate, 0.47 mol of dimethyl isophthalate, 0.03 mol of dimethyl 5-sulfoisophthalate, 2.3 mol of 1,2-propylene glycol, in a 10 liter glass reactor equipped with a paddle stirrer and a 20 cm fractional distillation column; 0.02 mol of trimellitic acid was charged. Tetrabutyl titanate was added in an amount of 500 ppm relative to the total weight of the monomer as a catalyst for the polymerization reaction. The temperature was heated to 150 ° C. while stirring at a reactor stirring speed of 100 rpm. The reaction proceeded for approximately 5 hours. During the reaction, the reactants form methanol as a by-product starting the ester reaction. When the side reactions were no longer formed in the cooler, the reactor was depressurized to 0.1torr to warm to 220 ° C and facilitate the removal of the side reactions, and the reaction was completed for 15 hours under the same pressure conditions.

The number average molecular weight (Mn) of the prepared polyester resin was about 3,000.

Production Example 2  : Preparation of Polyester Resin (Number Average Molecular Weight: 10,000)

A polyester resin was prepared in the same manner as in Preparation Example 1, except that the number of mol of the reactant used in Preparation Example 1 was used twice, and the reaction time was performed in about 8 to 10 hours. The number average molecular weight (Mn) of the prepared polyester resin was about 10,000.

Example 1  : Preparation of EGCG / Polyester Resin (Number Average Molecular Weight: 3,000) Composite

The polyester resin (number average molecular weight: 3,000) / EGCG / ethyl acetate of Preparation Example 1 was added to the reactor at a ratio of 85/15/400 to the weight and dissolved at room temperature. The solution was added to a solution in which 3 g of sodium dodecyl sulfate was dissolved in 800 g of distilled water, and the reactor temperature was raised to 50-60 ° C., followed by distillation under reduced pressure to remove ethyl acetate in the reaction solution. Then, the reaction solution was cooled to room temperature, washed with a large amount of water and dried to obtain 100g of EGCG / polyester resin composite in powder form.

The shape and particle surface of the prepared EGCG / polyester resin composite were observed by scanning electron microscopy, respectively, and are shown in FIGS. 1 and 2, respectively. The particle distribution of the EGCG / polyester resin composite is shown in FIG. 3.

As shown in Figures 1 to 3, it was confirmed that the EGCG / polyester resin composite of the present invention is spherical, porous, particle distribution is shown to 4 ~ 20㎛.

Example 2  : Preparation of EGCG / Polyester Resin (Number Average Molecular Weight: 10,000) Composite

A powder was prepared in the same manner as in Example 1 except for using the polyester resin of Preparation Example 2 (number average molecular weight: 10,000) instead of the polyester resin (number average molecular weight: 3,000) of Preparation Example 1 in Example 1. 100 g of EGCG / polyester resin composite in the form was obtained.

Experimental Example 1  : Measurement of Titer of EGCG / Polyester Resin Composite

The initial titer of the EGCG / polyester resin composite prepared in Example 1 was 100, and the titers of EGCG for 3 months were measured at room temperature, 37 ° C, and 45 ° C. As a comparative example, EGCG alone was used. The titer was measured using Hewlett-Packard's HP 1090 HPLC system, the detector was DAD 280nm, the column was Agilent XDB C-18. Before the measurement, the sample was used after dissolving in acetone and performing a pretreatment of diluting 100 times with acetonitrile.

The results are shown in Table 1.

Example 1
(EGCG / Polyester Resin Composite) Comparative example
(EGCG) Week 0 1 week 2 weeks 3 weeks 4 Weeks 5 Weeks 6 weeks 8 Weeks 9 Weeks 1 week 2 weeks Room temperature 100 99 100 100 100 99 99 99 98 75 70 37 ℃ 100 99 98 98 97 97 96 95 90 65 60 45 ℃ 100 98 99 95 95 94 93 90 85 57 40

As shown in Table 1, the titer of the EGCG / polyester resin composite of the present invention was very high compared to EGCG alone at high temperature as well as at room temperature. Therefore, it can be seen that the EGCG / polyester resin composite of the present invention is very excellent in stability.

Experimental Example 2  : Unfolding distance measurement of EGCG / polyester resin composite

The EGCG / polyester resin composite (0.026 g) prepared in Example 1 was placed on a flat plane, stretched by pressing with a finger, and the spread distance was measured. As a comparative example, EGCG alone was used.

The results are shown in Table 2.

Example 1
(EGCG / Polyester Resin Composite) Comparative example
(EGCG) Measuring distance (cm) 13.0 10.0

As shown in Table 2, it was confirmed that the unfolded distance (13 cm) of the EGCG / polyester resin composite of the present invention was improved by about 30% compared to the unfolded distance (10 cm) of the EGCG alone. Therefore, it can be predicted that the EGCG / polyester resin composite of the present invention is excellent in spreadability.

Experimental Example 3  : Measurement of feeling of EGCG / polyester resin composite

The usability of the EGCG / polyester resin composite prepared in Example 1 was measured through the sensory test. The sensory test was performed on 40 subjects (20 males, 20 females) in their 20s and 40s, and after applying the EGCG / polyester resin composite prepared in Example 1 to the hands of the subjects, The criterion was evaluated for spreadability, moistness and graininess. As a comparative example, EGCG alone was used.

The results are shown in Table 4.

Criteria 3 2 One 0 Spreadability Very smooth and well spread Well spread usually Not spread out Particle Very grainy Slightly grainy Very little graininess No graininess

Example 1 (average value)
(EGCG / Polyester Resin Composite) Comparative example (average value)
(EGCG) Spreadability 2.8 ± 0.15 1.5 ± 0.13 Particle 2.9 ± 0.10 1.0 ± 0.12

As shown in Table 4, it was confirmed that the EGCG / polyester resin composite of the present invention has excellent spreadability and excellent texture without rough grain compared to EGCG alone when applied to the skin, and excellent in feeling. Therefore, it can be seen that the EGCG / polyester resin composite of the present invention is excellent in spreadability and usability.

The ECC / polyester resin composite of the present invention is impregnated in the polyester resin EGCG in molecular units, thereby minimizing molecular denaturation of EGCG by external stimulation such as water, oxygen, heat, air, light, other chemicals, etc. It is possible to preserve the titer at, so the stability is very good. In addition, since the inside and the outside of the composite particles are porous and EGCG is impregnated with polyester resin in molecular units, it is easily dispersed and blended in the cosmetic base, so that EGCG can be released slowly, and various types of cosmetic formulations are possible. When spreading, the spreadability is improved and there is no grainy feeling, so the feel is excellent and the feeling is excellent.

1 is a view of the EGCG / polyester resin composite of the present invention observed with a scanning electron microscope.

2 is a view of the particle surface of the EGCG / polyester resin composite of the present invention observed by a scanning electron microscope.

Figure 3 is a view showing the particle distribution of the EGCG / polyester resin composite of the present invention.

Claims (12)

EVCV / polyester resin composite characterized by being impregnated with polyester resin. The ECC / polyester resin composite according to claim 1, wherein the composite is composed of 0.1-25% by weight of EVC 'and 75 to 99.9% by weight of polyester resin. The ECC / polyester resin composite according to claim 1, wherein the composite particles have a spherical shape of 1 to 100 µm. The EVC / polyester resin composite according to claim 1, wherein the composite further comprises an antioxidant. The method of claim 4, wherein the antioxidant is at least one selected from the group consisting of tyrosine, tryptophan, lipoic acid , vitamin C and derivatives thereof, vitamin E and derivatives thereof, vitamin A and derivatives thereof, sodium sulfite and sodium disulfite. EVBC / polyester resin composite characterized by the above-mentioned. 1) adding EGCG and polyester resin to a solvent and dissolving at room temperature, 2) adding the solution to the aqueous surfactant solution and heating the reactor temperature to 50 ~ 60 ℃ and distilled under reduced pressure to remove the solvent in the reaction solution, and 3) cooling the reaction solution from which the solvent has been removed to room temperature, followed by washing with water and drying, wherein the EVC / polyester resin composite according to claim 1 is prepared. The method of claim 6, wherein the surfactant is sodium stearoyl lactylate, polyethylene glycol cocamine, polyethylene glycol sorbitan hexaoleate, polyethylene glycol dilaurate, steamine acetate, tallowamine acetate, glyceryl stearate, polyethylene Glycol lanoleate, polyethylene glycol palmitate, polypropylene glycol hydroxyethyl cocamine, polyethylene glycol glyceryl laurate, polyethylene glycol stearate, triethylamine oleate, polyethylene glycol taloamine, sucrose laurate, sodium dodecyl sulfate, A method for producing an ECC / polyester resin composite according to claim 1, which is at least one selected from the group consisting of potassium dodecyl sulfate, alkylammonium chloride and alkylammonium bromide. The method of claim 6, wherein the solvent is one or more selected from the group consisting of methanol, ethanol, butanol, chloroform, dichloromethane, ethyl acetate, hexane, diethyl ether, acetonitrile, benzene, toluene, acetone and methyl ethyl ketone. The manufacturing method of the EVCk / polyester resin composite of Claim 1 characterized by the above-mentioned. Cosmetic composition containing the EVC / polyester resin composite of Claim 1. The cosmetic composition according to claim 9, wherein the EVC / polyester resin composite is contained in an amount of 0.01 to 10% by weight based on the total weight of the composition. The cosmetic composition according to claim 9, wherein the cosmetic composition is an anhydrous formulation. The method of claim 9, wherein the cosmetic composition is a flexible lotion, nutrition lotion, nutrition cream, massage cream, essence, eye cream, cleansing cream, cleansing foam, cleansing water, pack, essence, lipstick, makeup base, foundation, lotion, ointment Cosmetic composition, characterized in that it is formulated as a patch or spray.

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