KR20140006124A - Nano suspension-some cosmetic composition in oil containing high content of stabilized l-ascorbic acid or its derivatives, and method for manufacturing the same - Google Patents

Abstract

The present invention relates to a cosmetic composition which is prepared by: primarily preparing L-ascorbic acid, a derivative thereof, or a mixture thereof into a water in oil formed emulsion; preparing nanosized particles from which water is removed by freeze drying; and secondarily dispersing the nanosized particles under high pressure into oil, and to a method for preparing the same. The cosmetic composition according to the present invention has enhanced dispersibility in oil, can be stably used under external stress such as heat, light, oxygen, moisture and the likes, and facilitates mixing with fat soluble vitamin E so that synergy effects of protecting from ultraviolet rays can be obtained. In addition, oxidation caused by external air and oxygen in water can be prevented, L-ascorbic acid, which is a hydrophilic substance and hard to be absorbed in skin, or a derivative thereof can be dispersed into fine particles, absorption into skin can be facilitated by fat solublizing, and titer loss during a manufacturing process can be prevented through freeze drying. [Reference numerals] (AA,CC,EE) At first; (BB,DD,FF) 12 weeks

Description

Nano suspension-some cosmetic composition in oil containing high content of stabilized L-ascorbic acid or its derivatives, and method for manufacturing the same}

In the present invention, L-ascorbic acid, L-ascorbic acid derivatives or mixtures thereof are prepared primarily in an emulsion of w / o (water in oil) form and then lyophilized to obtain nano-sized particles from which water is removed. It relates to a cosmetic composition and a method for preparing the same, which are prepared by dispersing the nano-sized particles in oil in high pressure under high pressure.

L-ascorbic acid is a derivative of white crystalline Hexosus, which is widely used as an antioxidant or reducing agent having high physiological activity and strong reducing power, which is safe and practical.

Plants and most animals themselves synthesize L-ascorbic acid, but lack synthetic ability due to lack of L-gulono-gamma lactone oxidase in the last stage of biosynthesis of L-ascorbic acid in the human body L-ascorbic acid should be supplied from outside the body.

L-ascorbic acid is used as a food and medicine material and participates in important metabolic processes such as bones, teeth, gums, ligaments, and blood vessels. In terms of the external preparation for skin, it protects and decomposes the free radicals and reactive oxygen species. It also plays a role of antioxidant which is very important to protect the skin and also shows the synergistic effect of the light protection effect against ultraviolet rays when used together with the fat soluble vitamins such as vitamin E.

L-ascorbic acid and L-ascorbic acid derivatives have been used for a long time as cosmetics and medicines, and have been widely used as wrinkle removers by whitening agents and collagen synthesis. However, L-ascorbic acid rapidly decomposes in an aqueous solution In addition, it is an unstable substance that changes very easily due to changes in air, heat, light and pH.

In order to prevent decomposition by oxygen, which is the first step in the decomposition process of L-ascorbic acid in the above Reaction Scheme 1, pure L-ascorbic acid or a derivative thereof is encapsulated in the form of various emulsions or colloidal carriers, There has been an attempt to stabilize it.

Korean Patent No. 0488798 discloses a method for preparing a water-in-oil-water multiple emulsion by dissolving a gelling agent and an ion-screening agent in an aqueous phase in which L-ascorbic acid is dissolved together, Ascorbic acid by stabilizing L-ascorbic acid by lowering the water activity through gelation and introducing salt to induce an ion-shielding effect to some extent, but it has a problem in that it can not prevent the secondary oxidation reaction due to dissolved oxygen in the water .

In order to solve this problem, Korean Patent Registration No. 0836032 discloses a method for blocking external oxygen by cross-linking with a multi-co-polymer microcapsule during the preparation of the water-in-oil-water multiple emulsion. However, It is not sufficient to prevent the secondary oxidation reaction, and there is a disadvantage that the release effect of L-ascorbic acid by the polymer matrix is insignificant.

Korean Patent No. 0477716 discloses a method of dispersing L-ascorbic acid in ethyl alcohol and a polyol, coating it with silica, mica, amphiphilic silicone and silicone oil, adding natural oil, wax or gum to these particles, - < / RTI > ascorbic acid.

In order to block external air, the present invention is coated in a water-free form and coated with a variety of inorganic materials and silicone to prevent coagulation. However, the weight of the particles is inevitably limited to lotions having high viscosity due to the weight of the particles themselves. There is a disadvantage that only the emission effect should be expected.

Disclosure of the Invention The object of the present invention is to provide a cosmetic composition and a cosmetic composition which prevent L-ascorbic acid or its derivative from oxygen to prevent the oxidation mechanism of L-ascorbic acid and inhibit their antioxidative and skin whitening activity, And a method for producing the same.

In order to solve the above problems, the present invention is 1.5 to 30.0% by weight of L- ascorbic acid, L- ascorbic acid derivatives or mixtures thereof are coated with 1.5 to 10.0% by weight of an emulsifier and dispersed in 60.0 to 99.0% by weight of oil. It provides a cosmetic composition.

In addition, the present invention is to prepare a water phase by dissolving L- ascorbic acid, L- ascorbic acid derivative or a mixture thereof in water; Preparing an oil phase by mixing an emulsifier in oil; Mixing the aqueous phase with an oil phase to prepare a w / o emulsion; Lyophilizing the w / o emulsion; And homogenizing the lyophilized w / o emulsion under high pressure; provides a method for producing a cosmetic composition comprising a.

At this time, the w / o emulsion is L- ascorbic acid, L- ascorbic acid derivative or a mixture thereof 1.0 to 15.0% by weight, water 35.0 to 50.0% by weight, oil 30.0 to 63.0% by weight and 1.0 to 5.0% by weight emulsifier It includes, the temperature of the water of the step of preparing the water phase is 45 ~ 60 ℃, the lyophilization is preferably dried for 20-30 hours after freezing the w / o emulsion to -20 ~-30 ℃.

In addition, the step of preparing the w / o emulsion is homogenized for 3 to 20 minutes at 2000 ~ 4000 rpm using a homogenizer after mixing the water phase in the oil phase, the step of homogenizing under the high pressure is a lyophilized w / o emulsion Using a high pressure homogenizer is preferably carried out 1 to 3 times at a pressure of 500 ~ 1500 bar.

In addition, the L- ascorbic acid derivative is calcium ascorbate, allantoin ascorbate, sodium ascorbate, methylsilanol ascorbate, glucosamine ascorbate, potassium ascorbyl tocopheryl phosphate, trisodium ascorbyl palmitate phosphate, ethyl ascorbyl Ether, ascorbyl palmitate, ascorbyl tocopheryl maleate, ascorbyl triisopalmitate, ascorbyl stearate, ascorbyl palmitate, ascorbyl glucoside, aminopropyl ascorbyl phosphate, sodium ascorbyl phosphate, magnesium ascorbyl phosphate And at least one selected from the group consisting of disodium ascorbyl sulfate.

In addition, the emulsifier is at least one selected from the group consisting of lecithin, cetyldimethicone copolyol and sorbitan laurate, the oil is caprylic / capric triglyceride, squalane, dimethicone, cyclomethicone and cetyl It is preferably at least one selected from the group consisting of ethyl hexanoate.

The cosmetic composition according to the present invention is excellent in dispersibility in oil phase by coating L-ascorbic acid or its derivative with an emulsifying agent for w / o emulsion and forming a uniform nano suspension, and is excellent in external stress such as heat, light, oxygen, And can be easily mixed with fat-soluble vitamin E. Therefore, synergy effect of ultraviolet ray protection can be obtained through this.

In addition, the coating of the emulsifier for w / o emulsions prevents L-ascorbic acid or its derivatives from air to prevent primary oxidation by oxygen in the air, and is a hydrophilic material which is difficult to absorb skin, such as L-ascorbic acid or Its derivatives are dispersed into fine particles and fat-solubilized to facilitate skin absorption.

In addition, freeze-drying prevents L-ascorbic acid or its derivatives unstable to heat from being lost in the process of manufacturing cosmetic composition, and since water is removed by freeze-drying, L- It is possible to prevent secondary oxidation of corbic acid or derivatives thereof.

BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a photograph showing stability of the cosmetic composition prepared according to Example 1 of the present invention. Fig.
2 is a photomicrograph of a cosmetic composition containing L-ascorbic acid prepared according to Example 3 of the present invention.
3 is a photomicrograph of a cosmetic composition containing ethyl ascorbyl ether prepared according to Example 4 of the present invention.

The cosmetic composition according to the present invention is a cosmetic composition comprising L-ascorbic acid, L-ascorbic acid derivative or a mixture thereof in an oil-in-water (w / o) Oxidation mechanism is prevented and stabilization is achieved.

The present invention relates to a method for producing a w / o type emulsion by first emulsifying L-ascorbic acid, L-ascorbic acid derivative or a mixture thereof dissolved in an aqueous phase into an oil phase, Drying and removing water, and homogenizing the cosmetic composition to prepare a cosmetic composition in which an oil-based nano suspension is dispersed.

The L-ascorbic acid, the L-ascorbic acid derivative or a mixture thereof used in the present invention may be selected from the group consisting of pure L-ascorbic acid, calcium ascorbate, allantoin ascorbate, Sodium Ascorbate, Methylsilanol Ascorbate, Glucosamine Ascorbate, Potassium Ascorbyl Tocopheryl Phosphate, Trisodium Ascorbyl Phosphate (Trisodium Ascorbyl Phosphate), Trisodium Ascorbyl Phosphate Palmitate Phosphate, 3-O-Ethyl Ascorbic acid, Ascorbyl Palmitate, Ascorbyl Tocopheryl Maleate, Ascorbyl Tetraisopalmitate, Ascorbyl Stearate, Ascorbyl Dipamitate, Ascorbyl Glucoside (Ascorbyl Glucoside), Ascorbyl Glucoside (1) from the group consisting of e), e), aminopropyl ascorbyl phosphate, sodium ascorbyl phosphate, magnesium ascorbyl phosphate and disodium ascorbyl sulfate Or two or more species can be selected.

First, 1.0 to 15.0 wt% of L-ascorbic acid, L-ascorbic acid derivative or a mixture thereof, 35.0 to 50.0 wt% of water, 30.0 to 63.0 wt% of oil, and emulsifier 1.0 To 5.0% by weight of a w / o emulsion.

The w / o type emulsion is prepared by first dissolving L-ascorbic acid, L-ascorbic acid derivative or a mixture thereof in water to prepare an aqueous phase, and preparing an o / w emulsion in an oil widely used in cosmetics An emulsifier is added to prepare an oil phase, and then the water phase and the oil phase are mixed to prepare a w / o emulsion.

The oil may be selected from the group consisting of Caprylic and Capric Triglyceride, Squalane, Dimethicone, Cyclomethicone and Cetyl Ethylhexanoate, from the group consisting of Caprylic and Capric Triglyceride, Squalane, Dimethicone, Cyclomethicone and Cetyl Ethylhexanoate. A species or two or more species can be selected.

The emulsifier may be selected from the group consisting of Lecithin, Cetyl PEG / PPG-10/1 Dimethicone and Sorbitan Laurate.

L-ascorbic acid is a white crystalline powder or powder having a strong acidity and melting point of 190 to 192 ° C. Solubility (25 ° C.) per 1 g of L-ascorbic acid is 3 ml of purified water, 30 ml of ethyl alcohol 100 ml of glycerin and 20 ml of propylene glycol are insoluble in ether, chloroform, benzene, petroleum ether, oils and fats.

In the present invention, the solvent used for dissolving L-ascorbic acid or a derivative thereof is water. L-ascorbic acid has a solubility of about 40% at 45 ° C and about 80% at 100 ° C in water, Since the content of L-ascorbic acid or its derivative in the aqueous phase is 2 to 43% by weight in the w-emulsion, the water temperature is preferably 45 to 60 ° C in order for L-ascorbic acid or a derivative thereof to be sufficiently dissolved in water, It is preferable to homogenize the emulsion at 2000 to 4000 rpm for 3 to 20 minutes using a homogenizer to form a w / o emulsion uniformly dispersed in the oil phase.

However, L-ascorbic acid or its derivative is rapidly oxidized by dissolved oxygen dissolved in water of water and converted to L-dehydroascorbic acid (DHA) , 3-L-diketoguronate (2,3-KDG), and the physiological activity of L-ascorbic acid itself is lost.

In order to prevent this, it is necessary to block L-ascorbic acid or its derivative from dissolved oxygen dissolved in the external air and the water of the water phase, and to remove the water of the water phase. To this end, L-ascorbic acid or its derivative The w / o emulsion containing the derivative is lyophilized to selectively remove only water.

As described above, when water is removed in the state that L-ascorbic acid or its derivative dissolved in water of water is emulsified in the form of w / o in the oil to which an emulsifying agent for oil is added, when the emulsifier is L-ascorbic acid or its derivative particle The surface is coated with a nano-scale, and oxygen can be appropriately blocked by a coating film of an emulsifier, thereby blocking the physiological activity destruction mechanism of L-ascorbic acid or its derivatives by oxygen.

In addition, the particles coated with the emulsifier are easily dispersed in the oil phase, and water is removed through the lyophilization method instead of the heat drying or vacuum distillation method, so that the destruction of L-ascorbic acid or derivatives thereof susceptible to heat can be prevented.

The lyophilization can be performed by freezing the w / o emulsion at -20 to -30 ° C for 20 to 30 hours under normal pressure so as to sufficiently remove water from the water phase, Lt; / RTI >

Upon completion of the lyophilization, the dried emulsion is homogenized with a homogenizer to prepare a nanosuspension cosmetic composition in which a high concentration of L-ascorbic acid or a derivative thereof is coated with an emulsifier and is stably dispersed in oil, It is preferable to perform 1 to 3 times at a pressure of 500 to 1500 bar.

The nanosuspension cosmetic composition prepared as described above comprises 1.5 to 30.0% by weight of L-ascorbic acid, L-ascorbic acid derivative or a mixture thereof, 60.0 to 97.0% by weight of oil and 1.5 to 10.0% by weight of emulsifier .

In addition, the nano-suspension cosmetic composition of the present invention produced by the above method may be contained in an amount of 0.1 to 50.0% by weight of the total weight of the cosmetic. The cosmetic composition may be selected from the group consisting of softening longevity, nutritional lotion, cream, massage cream, It can be applied to formulations of gel, gel, skin adhesive type, lipstick, makeup base, foundation, shampoo, rinse, body cleanser, soap, toothpaste, mouthwash, lotion, ointment, patch or spray.

The cosmetic composition according to the present invention protects and stabilizes L-ascorbic acid or derivatives thereof exhibiting physiological activity from the action of free radicals and active oxygen, and has a low solubility of L-ascorbic acid such as glycerin, butylene glycol or propylene Ascorbic acid component can be overcome by dissolving it in a polyol such as glycerol, glycerol or the like or dispersing it as fine particles in an oil which is widely used in cosmetics for a water-free formulation, Can be stably used from external stresses such as heat, light, oxygen, and moisture by coating with an emulsifier on acetic acid or its derivatives.

Hereinafter, the present invention will be described in more detail with reference to the following examples, comparative examples and test examples.

It is to be understood, however, that the invention is not to be construed as limited to the embodiments set forth herein, but is capable of modifications and equivalents within the spirit and scope of the invention. Will be apparent to those skilled in the art to which the present invention pertains.

<Example 1> Preparation of L- ascorbic acid stabilized composition

The w / o type emulsion was prepared according to the composition ratios shown in Table 1 below and then lyophilized to prepare a stabilizing composition.

First, 500 g of water as a solvent was heated to 50 占 폚, and 100 g of L-ascorbic acid was dissolved therein to prepare an aqueous phase. 375 g of dimethicone was heated to 50 占 폚 while cetyl dimethicone copolyol 25 g to prepare an oil phase.

The water phase was slowly added to the oil phase and emulsified at 3000 rpm for 10 minutes using a homogenizer (T.K. Homomixer Mark II Medel 2.5, PRIMIX, Japan) to prepare a w / o emulsion.

The w / o emulsion was cooled to -25 ° C using a freeze dryer (Freeze Dryer-FD8508, Ilshin BioBase Co., Ltd., Korea) and lyophilized for 24 hours. The microfludizer -110F, manufactured by Microfluidics, USA) was homogenized twice at 1,000 bar to prepare a nanosuspension cosmetic composition containing 20% by weight of L-ascorbic acid.

Example 2 Preparation of Ethyl Ascorbyl Ether Stabilizing Composition

In the same manner as in Example 1 except that 100 g of ethyl ascorbyl ether was used instead of L-ascorbic acid and 375 g of squalane was used in place of dimethicone in Example 1, ethyl ascorbyl ether was replaced with 20 % &Lt; / RTI &gt; by weight of a cosmetic composition.

Example 3 Preparation of L-ascorbic acid stabilizing composition

In the same manner as in Example 1, except that dimethicone (187.5 g) and squalane (187.5 g) were used instead of dimethicone alone as the oil in Example 1, 20 wt% of L-ascorbic acid Gt; &lt; RTI ID = 0.0 &gt; cosmetic &lt; / RTI &gt; composition.

Example 4 Preparation of Ethyl Ascorbyl Ether Stabilizing Composition

In the same manner as in Example 2, except that 187.5 g of dimethicone and 187.5 g of squalane were used instead of squalane alone as the oil in Example 2, the amount of nano-particles containing 20% by weight of ethyl ascorbyl ether A suspension cosmetic composition was prepared.

Comparative Examples 1 to 4 Preparation of w / o emulsion containing L-ascorbic acid or ethyl ascorbyl ether

In Examples 1 to 4, the w / o emulsion was prepared, followed by lyophilization and high pressure homogenization.

w / o Composition of emulsion (unit: wt%) division water L-ascorbic acid Ethyl ascorbyl ether Dimethicone Squalane Cetyl dimethicone copolyol Example One 50.0 10.0 - 37.5 - 2.5 2 50.0 - 10.0 - 37.5 2.5 3 50.0 10.0 - 18.75 18.75 2.5 4 50.0 - 10.0 18.75 18.75 2.5 Comparative Example One 50.0 10.0 - 37.5 - 2.5 2 50.0 - 10.0 - 37.5 2.5 3 50.0 10.0 - 18.75 18.75 2.5 4 50.0 - 10.0 18.75 18.75 2.5

&Lt; Test Example 1 >

The stabilizing composition of L-ascorbic acid and ethyl ascorbic ether and w / o emulsion prepared in the above Examples and Comparative Examples were subjected to property stability test and content stability test.

1. Constellation stability test

The stabilizing compositions and w / o emulsions of the above-mentioned Examples and Comparative Examples were stored in shaded environments at 4 캜, 25 캜 and 45 캜, and the change with time was visually observed to determine discoloration, Respectively.

Stability stability test result division After 1 day After 1 week after 2 weeks After 4 weeks After 8 weeks After 12 weeks Example One 4 ℃ ○ ○ ○ ○ ○ ○ 25 ℃ ○ ○ ○ ○ ○ ○ 45 ° C ○ ○ ○ ○ ◑ ◑ 2 4 ℃ ○ ○ ○ ○ ○ ○ 25 ℃ ○ ○ ○ ○ ○ ○ 45 ° C ○ ○ ○ ○ ○ ◑ 3 4 ℃ ○ ○ ○ ○ ○ ○ 25 ℃ ○ ○ ○ ○ ○ ○ 45 ° C ○ ○ ○ ○ ○ ◑ 4 4 ℃ ○ ○ ○ ○ ○ ○ 25 ℃ ○ ○ ○ ○ ○ ○ 45 ° C ○ ○ ○ ○ ○ ◑ Comparative Example One 4 ℃ ○ ○ ○ ○ ○ ◑ 25 ℃ ○ ○ ◑ ◑ ▣ ★ 45 ° C ○ ◑ ▣ ★ ★ ★ 2 4 ℃ ○ ○ ○ ○ ○ ◑ 25 ℃ ○ ○ ○ ◑ ◑ ★ 45 ° C ○ ◑ ◑ ▣ ▣ ★ 3 4 ℃ ○ ○ ○ ○ ○ ◑ 25 ℃ ○ ○ ○ ○ ◑ ▣ 45 ° C ○ ▣ ▣ ★ ★ ★ 4 4 ℃ ○ ○ ○ ○ ○ ◑ 25 ℃ ○ ○ ○ ○ ◑ ▣ 45 ° C ○ ◑ ▣ ▣ ★ ★

(○: no change, ◑: weak discoloration, ▣: many discoloration and suspension, ★: complete discoloration and precipitation)

As can be seen in Table 2, the cosmetic compositions of Examples 1 to 4, in which water of the w / o emulsion was removed by freeze-drying, were compared with the compositions of Comparative Examples 1 to 4, ℃) and high temperature (45 ℃) storage stability.

In the case of the examples, slight discoloration was observed after 8 weeks at a high temperature of 45 캜, but in the case of the comparative example, discoloration was observed after 12 weeks in all the refrigerating conditions at 4 캜, and discoloration and precipitation were started from 4 weeks at a high temperature of 45 캜 I could.

FIG. 1 shows a photograph showing the stability of the cosmetic composition of Example 1, which shows almost no color change after 12 weeks compared with the initial (after 1 day).

From the above results, it has been found that if water of the w / o emulsion is not removed, L-ascorbic acid or ethyl ascorbyl ether of the water reacts with oxygen dissolved in water and is hydrolyzed to lose its physiological activity and discolor and precipitate .

2 is a graph showing the results of a comparison between a cosmetic composition containing L-ascorbic acid prepared according to Example 3 and a cosmetic composition containing L-ascorbic acid prepared in Example 3 using a microscope (NSB-50T, Sanyuan Scientific Industries, Korea). FIG. 3 is a photograph of the cosmetic composition containing ethyl ascorbyl ether prepared in Example 4, magnified 1000 times by the above microscope.

2 and 3, it can be seen that the nanosuspension particles are uniformly dispersed in the oil phase. Thus, the L-ascorbic acid or its derivative of the present invention is coated with an emulsifier to form a uniform nanosuspension, Because of its acidity, stabilized nanosuspension can maintain its shape.

2. Content stability test

The content stability tests were carried out on the L-ascorbic acid and ethyl ascorbyl ether stabilizing composition and the w / o emulsion prepared in the above Examples and Comparative Examples, and the results are shown in Table 3 below.

The test was carried out using high performance liquid chromatography (HPLC) after the samples were stored at 4 &lt; 0 &gt; C and 45 &lt; 0 &gt; C in a shaded environment and immediately after, 2, 4, The analysis method is as follows.

1) Preparation of the test liquid

0.3 g of each of the cosmetic composition or the w / o emulsion sample was dissolved in 20 ml of tetrahydrofuran and dissolved in 25 ml of phosphoric acid (w / o) emulsified in each of the cosmetic compositions of Examples 1 to 4 and w / o emulsions of Comparative Examples 1 to 4 Dilute with 100 ml of a potassium hydrogen (KH ₂ PO ₄ ) buffer solution (pH 2.5), filter as necessary and use as the sample solution.

2) Standard solution preparation

10 ml of a solution prepared by dissolving 50.0 mg of L-ascorbic acid or ethyl ascorbyl ether in 100 ml of 25 mM potassium dihydrogenphosphate (KH ₂ PO ₄ ) buffer (pH 2.5) for 5 minutes was precisely taken to obtain 5 The diluted solution is used as the standard solution.

3) Analysis

The column was packed with C18 and the detector used an extinction absorptiometer with a wavelength of 240 nm.

The mobile phase used 25 mM potassium dihydrogen phosphate (KH ₂ PO ₄ ) buffer solution (pH 2.5) and the flow rate was 0.7 ml / min.

Content stability test result (Unit:%) division Immediately after manufacture after 2 weeks After 4 weeks After 8 weeks After 12 weeks Example One 4 ℃ 100 100 99.8 99.5 99.4 45 ° C 100 98.9 97.7 97.1 95.6 2 4 ℃ 100 100 100 99.3 99.2 45 ° C 100 99.4 98.2 97.9 96.4 3 4 ℃ 100 99.8 99.3 98.8 98.4 45 ° C 100 99.5 98.7 97.9 96.4 4 4 ℃ 100 100 99.5 99.4 99.3 45 ° C 100 100 99.3 98.6 97.2 Comparative Example One 4 ℃ 100 98.5 93.1 91.7 86.4 45 ° C 100 82.1 66.7 34.6 7.2 2 4 ℃ 100 90.5 82.7 73.4 67.7 45 ° C 100 94.7 88.5 73.1 66.4 3 4 ℃ 100 93.4 82.8 80.1 75.8 45 ° C 100 80.8 70.3 57.2 27.9 4 4 ℃ 100 96.9 93.7 89.9 84.6 45 ° C 100 92.5 80.5 68.9 55.4

As shown in Table 3 above, the compositions of the examples in which water of the w / o emulsion was removed by freeze-drying, based on the content of L-ascorbic acid or ethyl ascorbyl ether immediately after preparation, (L-ascorbic acid or ethyl ascorbyl ether) remained at 95% or more at 98% or more and 45 ° C or higher at 4 ° C.

On the other hand, in the case of the comparative example in which water of the w / o emulsion was not removed, it remained 67.7 ~ 86.4% in the refrigerated condition and 7.2 ~ 66.4% in the high temperature condition after 12 weeks, and L- The ether component is oxidized and hydrolyzed by the dissolved oxygen and water of the water phase of the w / o emulsion, and the content thereof is lowered.

< Test Example 2> Antioxidant effect test of L-ascorbic acid using DPPH method

In order to measure the antioxidative effect of the L-ascorbic acid stabilizing composition prepared in Examples 1 and 3, L-ascorbic acid aqueous solution and Butylated Hydroxytoluene (BHT), which is a strong antioxidant, were used as a control group The antioxidative effect was tested by comparing the free radical scavenging rate with the DPPH method.

The DPPH method is a test for measuring the antioxidative effect by reducing power using a free radical called DPPH (2,2-Di (4-tert-octylphenyl) -1-picrylhydrazyl) free radical. And comparing the degree of decrease of absorbance with the absorbance of the blank test solution to analyze the free radical scavenging rate (%) at a wavelength of 560 nm.

The used reagent was dissolved in methanol (100.8 ml) as a 0.1 mM solution of DPPH free radical (MW = 618.76, Aldrich Chem. Co., USA) in a quantity of 100 ml, and the antioxidant effect test method was as follows.

1) Absorbance of sample solution

0.15 ml of the DPPH reagent, 0.15 ml of the sample solution of Examples 1 and 3 and the control solution are added to a 96-well plate, and the mixture is stirred at 25 ° C for 10 minutes. Then, the absorbance St at 560 nm is measured.

2) Blank absorbance of the sample solution

In the absorbance measurement method of the sample solution, the absorbance So is measured in the same manner as in the method of measuring the absorbance St except that methanol is used instead of the DPPH reagent.

3) Absorbance of blank test solution

In the method of measuring the absorbance of the sample solution, the absorbance Bt is measured by operating in the same manner as the method of measuring the absorbance St except that distilled water is used instead of the sample solution.

4) Blank absorbance of blank test solution

In the method for measuring the absorbance of the sample solution, the absorbance Bo is measured in the same manner as in the method for measuring the absorbance St except that methanol is used instead of the DPPH reagent and distilled water is used instead of the sample solution.

The free radical scavenging ratio (%) was calculated by the following equation, and the results are shown in Table 4 below.

Free radical scavenging ratio (%) = [1- (St-So) / (Bt-Bo)] x 100

St: absorbance at 560 nm after free radical scavenging of the sample solution

So: absorbance at 560 nm when no free radicals are added to the sample solution

Bt: absorbance at 560 nm after free radical scavenging of the blank test solution

Bo: absorbance at 560 nm when no free radicals are added to the blank solution

Antioxidant effect test results using DPPH method Name of sample Treatment concentration (%, w / v) Antioxidative effect(%) Example 1 0.01 94.1 Example 3 0.01 94.7 L-ascorbic acid 0.01 96.1 BHT 0.01 99.2

As shown in Table 4, the samples tested at the concentration of 0.01% showed excellent antioxidative effects, and the stabilized L-ascorbic acid cosmetic compositions of Examples 1 and 3 according to the present invention were superior to the pure L-ascorbic acid It exhibits similar antioxidative effects and can be used in place of BHT, which is a strong antioxidant, to obtain an antioxidative effect and at the same time to obtain whitening and wrinkle-reducing effects of L-ascorbic acid.

As a result of the stability test of the cosmetic composition containing the stabilized L-ascorbic acid or its derivative of the present invention as described above, the water stability of the w / o emulsion was remarkably improved and the water of the aqueous phase was heated and dried Or by a lyophilization method other than a vacuum distillation method, thereby preventing the destruction of L-ascorbic acid or its derivatives weak to heat.

Further, the stabilized L-ascorbic acid composition was tested as a cosmetic formulation and as a result, it was confirmed that the cosmetic composition exhibited superior antioxidative and melanin production inhibitory effects as well as improved stability over time.

Claims (13)

Stabilized L-ascorbic acid, or a mixture thereof, wherein 1.5 to 30.0 wt% of L-ascorbic acid, L-ascorbic acid derivative or mixture thereof is coated with 1.5 to 10.0 wt% of emulsifier and dispersed in 60.0 to 99.0 wt% of oil. Nano-suspension-in-oil cosmetic composition containing a high concentration of the derivative. The method according to claim 1,
The L-ascorbic acid derivative is calcium ascorbate, allantoin ascorbate, sodium ascorbate, methylsilanol ascorbate, glucosamine ascorbate, potassium ascorbyl tocopheryl phosphate, trisodium ascorbyl palmitate phosphate, ethyl ascorbyl ether, Ascorbyl palmitate, ascorbyl tocopheryl maleate, ascorbyl tetraisopalmitate, ascorbyl stearate, ascorbyl palmitate, ascorbyl glucoside, aminopropyl ascorbyl phosphate, sodium ascorbyl phosphate, magnesium ascorbyl phosphate and di Nano-suspension-in-oil cosmetic composition containing a high concentration of stabilized L- ascorbic acid or derivatives thereof, characterized in that at least one selected from the group consisting of sodium ascorbyl sulfate. The method according to claim 1,
The emulsifier is at least any one selected from the group consisting of lecithin, cetyldimethicone copolyol and sorbitan laurate, nano-suspension oil-in-oil cosmetic containing a high concentration of stabilized L- ascorbic acid or derivatives thereof Composition. The method according to claim 1,
Said oil is at least one selected from the group consisting of caprylic / capric triglycerides, squalane, dimethicone, cyclomethicone and cetylethylhexanoate, stabilized L-ascorbic acid or its Nano-suspension-in-oil cosmetic composition containing a high concentration of the derivative. Dissolving L-ascorbic acid, L-ascorbic acid derivative or a mixture thereof in water to prepare an aqueous phase;
Preparing an oil phase by mixing an emulsifier in oil;
Mixing the aqueous phase with an oil phase to prepare a w / o emulsion;
Lyophilizing the w / o emulsion; And
Comprising: homogenizing the lyophilized w / o emulsion under high pressure; comprising, stabilized L- ascorbic acid or derivatives thereof in a high concentration of nano-suspension oil-containing cosmetic composition. The method according to claim 5,
The w / o emulsion comprises 1.0 to 15.0% by weight of L-ascorbic acid, L-ascorbic acid derivatives or mixtures thereof, 35.0 to 50.0% by weight of water, 30.0 to 63.0% by weight of oil and 1.0 to 5.0% by weight of emulsifier A method for producing a water-in-oil nanosuspension cosmetic composition comprising a stabilized L-ascorbic acid or a derivative thereof at a high concentration. The method according to claim 5,
The temperature of the water in the step of preparing the water phase is characterized in that 45 ~ 60 ℃, the method of producing a nano-suspension-in-oil cosmetic composition containing a high concentration of stabilized L- ascorbic acid or derivatives thereof. The method according to claim 5,
The step of preparing the w / o emulsion, characterized in that the mixture of the aqueous phase is homogenized for 3 to 20 minutes at 2000 ~ 4000 rpm using a homogenizer, high concentration of stabilized L- ascorbic acid or derivatives thereof Method for producing a nano-suspension little cosmetic composition in oil containing. The method according to claim 5,
The lyophilization is characterized in that the w / o emulsion is frozen at -20 ~-30 ℃ and dried for 20 to 30 hours, nano suspension suspension in oil containing a high concentration of stabilized L- ascorbic acid or derivatives thereof Method for producing a cosmetic composition. The method according to claim 5,
Homogenizing under the high pressure, stabilized L- ascorbic acid or derivatives thereof, characterized in that the lyophilized w / o emulsion is carried out 1 to 3 times at a pressure of 500-1500 bar using a high pressure homogenizer. A method for producing a water-containing nano suspension cosmetic composition containing a high concentration. The method according to claim 5,
The L-ascorbic acid derivative is calcium ascorbate, allantoin ascorbate, sodium ascorbate, methylsilanol ascorbate, glucosamine ascorbate, potassium ascorbyl tocopheryl phosphate, trisodium ascorbyl palmitate phosphate, ethyl ascorbyl ether, Ascorbyl palmitate, ascorbyl tocopheryl maleate, ascorbyl tetraisopalmitate, ascorbyl stearate, ascorbyl palmitate, ascorbyl glucoside, aminopropyl ascorbyl phosphate, sodium ascorbyl phosphate, magnesium ascorbyl phosphate and di A method for producing a nano-suspension oil-in-oil cosmetic composition containing a high concentration of stabilized L-ascorbic acid or a derivative thereof, characterized in that at least one selected from the group consisting of sodium ascorbyl sulfate. The method according to claim 5,
The emulsifier is at least any one selected from the group consisting of lecithin, cetyldimethicone copolyol and sorbitan laurate, nano-suspension oil-in-oil cosmetic containing a high concentration of stabilized L- ascorbic acid or derivatives thereof Method of Preparation of the Composition. The method according to claim 5,
Said oil is at least one selected from the group consisting of caprylic / capric triglycerides, squalane, dimethicone, cyclomethicone and cetylethylhexanoate, stabilized L-ascorbic acid or its A method for producing a nano suspension suspension oil-in-oil cosmetic composition containing a high concentration of a derivative.

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