KR100804096B1 - Cosmetic composition for cleansing containing enzyme capsules stabilized in the highly concentrated surfactant system and the process for preparing thereof - Google Patents

Abstract

An enzyme capsule formulation is provided to block effectively the inside swelling thereof caused by water and a highly concentrated surfactant at the concentration of more than 15% and maintain the activity of an enzyme inside thereof when included in a skin washing composition, thereby showing excellent skin washing and skin keratin removing effects. An enzyme capsule formulation comprises a seed consisting of white sugar or microcrystalline cellulose; an enzyme layer formed on the seed and consisting of an enzyme-stabilized microcapsule; a first coating layer formed on the enzyme layer and consisting of shellac; a second coating layer formed on the first coating layer and consisting of a polymer; a third coating layer formed on the second coating layer and consisting of wax; a fourth coating layer formed on the third coating layer and consisting of a cationic surfactant; a fifth coating layer formed on the fourth coating layer and consisting of a polymer; a sixth coating layer formed on the fifth coating layer and consisting of an anionic surfactant; and a seventh coating layer formed on the sixth coating layer and consisting of a polymer, where the enzyme stabilized microcapsule is a triple structured microcapsule consisting of an enzyme as an inner core such as lipase, amylase, pepsin, trypsin, urease, asparaginase and a hydrolase of papain; a hydrophobic polyol having the molecular weight of at least 1,000g/mol as a coating material of the enzyme such as polyethyleneglycol, polypropylene glycol and a copolymer thereof; and a polymer wall agent at the outermost thereof such as poly-L-lactic acid, poly-D,L-glycolic acid, poly-L-lactic acid-co-glycolic acid, poly-D,L-lactic acid-co-glycolic acid, polycaprolactone, polyvalerolactone, polyhydroxy butyrate, polyhydroxyvalerate, a copolymer prepared from poly o-ester and a monomer thereof, polystyrene, poly p- or m-methylstyrene, poly p- or m-ethyl styrene, poly p- or m-chlorostyrene, poly p- or m-chloromethylstyrene, poly styrene sulfonic acid, poly p- or m- or t-butoxy styrene, poly methyl(meth)acrylate, polyethyl(meth)acrylate, polypropyl(meth)acrylate, poly n-butyl(meth)acrylate, poly isobutyl(meth)acrylate, poly t-butyl(meth)acrylate, poly 2-ethylhexyl(meth)acrylate, poly n-octyl(meth)acrylate, polylauryl(meth)acrylate, polystearyl(meth)acrylate, poly 2-hydroxyethyl(meth)acrylate, polyethyleneglycol(meth)acrylate, methoxy polyethyleneglycol(meth)acrylate, polyglycidyl(meth)acrylate, poly dimethylaminoethyl(meth)acrylate, poly diethylaminoethyl(meth)acrylate, polyvinylacetate, polyvinylpropionate, polyvinylbutyrate, polyvinylether, polyallylbutylether, polyallylglycidylether, poly(meth)acrylic acid, polymaleic acid, polyalkyl(meth)acrylamide and poly(meth)acrylonitrile, and the formulation consists of 20-45 parts by weight of the whiter sugar or microcrystalline cellulose; 0.1-30 parts by weight of the enzyme stabilized microcapsule; 5-30 parts by weight of the shellac; 5-30 parts by weight of the polymer, 5-30 parts by weight of the wax, 1-10 parts by weight of the cationic surfactant; and 1-10 parts by weight of the anionic surfactant. A composition for washing skin or removing skin keratin comprises the enzyme capsule formulation.

Description

Cosmetic composition for cleansing containing enzyme capsules stable even in high concentration surfactant system and method for preparing the composition {Cosmetic composition for cleansing containing enzyme capsules stabilized in the highly concentrated surfactant system and the process for preparing}

1 is a scanning electron micrograph of a cross-section of a multilayer structure of an enzyme capsule formulation of the present invention.

2 shows the visual evaluation results of the keratin exfoliation evaluation clinical trial.

Figure 3 shows the results of image analysis of the keratin exfoliation evaluation clinical trial.

4 is a three-dimensional photographic result of a keratin exfoliation evaluation clinical trial.

The present invention relates to a skin cleanser composition containing an enzyme capsule formulation which is stable even in a high concentration surfactant system. More specifically, the enzyme capsule formulation of the present invention effectively blocks swelling in the capsule formulation by water and the surfactant and inhibits the activity of the enzyme in the capsule even in a skin cleanser composition containing a high concentration of a surfactant at least 15%. Maintaining shows excellent skin cleansing and exfoliating effect.

Proteolytic enzymes, such as papain, have excellent proteolytic efficacy and have no problem in stimulation to the skin, and thus, they are known as a skin cleanser or a skin exfoliant. However, since these enzymes are physically and chemically unstable, efforts have been made to stabilize them and to easily separate and use them physically and chemically. In most cases, immobilization methods are used as stabilization techniques.

The immobilization method refers to a method of immobilizing an enzyme on a suitable solid support, wherein the solid supports have an organic group on the surface and have a physical and chemical environment which is advantageous for immobilizing the enzyme. In general, enzymes are very sensitive to external temperatures and show significant differences in activity. When immobilized enzymes with these properties on various solid supports, the thermal stability is increased and the activity remains largely intact. The support on which the enzyme is immobilized is a polymer, a sol-gel matrix, mesoporous molecular sieve, or the like. Since most enzyme sizes are 30-60Å, the stabilization system was designed. To immobilize the enzyme, there is sufficient space for the enzyme to immobilize in the pores, but the immobilized enzyme can be easily pulled out without affecting the migration of buffer ions, substrates, products, and the enzyme itself. It should be the right size so it doesn't slip out.

Another technique for stabilizing enzymes is by chemical treatment. Although the R group of the polypeptide is chemically treated with alkaline phosphate or the like to secure heat stability, there is a disadvantage in that it shows a significantly lower activity than the enzyme activity in nature due to the limitation of the enzyme (conformation). A simple process and high stability of enzyme activity include adding an enzyme stabilizer. In other words, a compound known to make a major contribution to the stability of the enzyme, such as polyol, is mixed with the enzyme. This method requires the addition of different substances depending on the nature of the enzyme, but simply preparing a mixture can provide a high level of enzyme activity stabilization, particularly high thermal stability and exhibits close to natural enzyme activity. I have it. Currently, such a stabilizer addition method is known to have a high stabilizing effect against industrially applicable glucoside oxidase, papain α, β-amylase, and the like. However, polyol compounds have the disadvantage that their application range is extremely limited because of their high polarity and limited compatibility.

Another widely used enzyme stabilization method is the polymer encapsulation method. The outer wall of the polymer capsule protects the enzyme from external hazards. Despite the many industrial advantages of polymer capsules, strong hydrophilic enzymes become inherently unstable in strong hydrophobic polymers, causing degradation. This has the disadvantage that will occur.

Accordingly, the present applicant is a new enzyme stabilization system that satisfies the industrial advantages of polymer microcapsules, which is one of the enzyme stabilization techniques, along with the high enzyme stabilization effect of polyols, and the triple structure of 'protein hydrolase / polyol / polymer' By preparing microcapsules, a cosmetic composition prepared to maintain protease activity for a long time has been devised (Korean Patent Publication No. 2004-0034864). However, unlike general solubilized formulations or emulsifiers, it has been found that the proteolytic enzyme activity is not maintained even by the above method in the detergent composition having a high concentration of surfactant having a surfactant concentration of 15% or more.

Below is the activity data of 'Papine / Polyol / Polycaprolactone' microcapsules in the cleansing foam formulation.

Room temperature storage 40 ℃ storage Titer after 10 days 100% 67% Titer after 30 days 0% 0%

The present inventors found that in a detergent composition having a surfactant concentration of 15% or more, the microcapsules of the triple structure of 'enzyme / polyol / polymer' are swelled by water and a surfactant and the enzyme is exposed to the external environment. It was estimated to lose activity.

Thus, the inventors have intensively studied, and loaded the microencapsule of the existing enzyme / polyol / polymer into the sugar or microcrystalline cellulose seed (seed), and then shellac (shellac), polymer, wax, cationic surfactant, When anionic surfactants and the like are sequentially coated to form a multi-layered enzyme capsule formulation, when water swells into the formulation and swelling occurs, the cationic surfactant and anionic surfactant coated on the formulation form an insoluble complex. The invention was found to block the penetration of water or surfactant into the formulation and to complete the present invention.

Accordingly, an object of the present invention is to provide an enzyme capsule formulation that is stable even in a high concentration surfactant system.

Another object of the present invention is to provide a method for preparing the enzyme capsule formulation.

Still another object of the present invention is to provide a human cleanser composition having an excellent exfoliation effect by containing a stable enzyme capsule even in the high concentration surfactant system.

In order to achieve the above object, the present invention is a seed consisting of white sugar or microcrystalline cellulose; An enzyme layer formed on the seed and composed of enzyme stabilized microcapsules; A first coating layer formed on the enzyme layer and made of shellac; A second coating layer formed on the first coating layer and made of a polymer; A third coating layer formed on the second coating layer and made of wax; A fourth coating layer formed on the third coating layer and made of a cationic surfactant; A fifth coating layer formed on the fourth coating layer and made of a polymer; A sixth coating layer formed on the fifth coating layer and formed of an anionic surfactant; And a seventh coating layer formed on the sixth coating layer and made of a polymer.

Here, the enzyme stabilizing microcapsules forming the enzyme layer is an enzyme as the inner core; Hydrophobic high molecular weight polyol of 1000 g / mol or more as a coating material of the enzyme; And a microcapsule having a triple structure composed of a polymer wall on the outermost side; The enzyme is at least one selected from hydrolysases of lipase, amylase, pepsin, trypsin, urease, asparaginase and papain, and the high molecular weight polyol is polyethylene glycol and polypropylene glycol, copolymers and derivatives thereof. At least one selected from the group consisting of; The polymer wall material may be poly-L-lactic acid, poly-D, L-glycolic acid, poly-L-lactic acid-co-glycolic acid, poly-D, L-lactic acid-co-glycolic acid, polycaprolactone, polyvalero Copolymers prepared from lactones, polyhydroxy butyrates, polyhydroxy valerates, polyorsteresters and monomers thereof, polystyrene, poly p- or m-methylstyrene, poly p- or m-ethylstyrene, poly p- Or m-chlorostyrene, poly p- or m-chloromethylstyrene, poly styrenesulphonic acid, poly p- or m- or t-butoxystyrene, poly methyl (meth) acrylate, polyethyl (meth) acrylate , Polypropyl (meth) acrylate, polyn-butyl (meth) acrylate, polyisobutyl (meth) acrylate, polyt-butyl (meth) acrylate, poly2-ethylhexyl (meth) acrylate, poly n-octyl (meth) acrylate, polylauryl (meth) acrylate, Polystearyl (meth) acrylate, poly2-hydroxyethyl (meth) acrylate, polyethylene glycol (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, polyglycidyl (meth) acrylate, poly Dimethylaminoethyl (meth) acrylate, polydiethylaminoethyl (meth) acrylate, polyvinylacetate, polyvinylpropionate, polyvinylbutyrate, polyvinylether, polyallylbutyl ether, polyallylglycidyl ether, At least one selected from the group consisting of poly (meth) acrylic acid, polymaleic acid, polyalkyl (meth) acrylamide, and poly (meth) acrylonitrile.

In addition, the formulation is 20 to 45 parts by weight of the white sugar or microcrystalline cellulose; 0.1 to 30 parts by weight of the enzyme stabilized microcapsules; 5 to 30 parts by weight of the shellac; 5 to 30 parts by weight of the polymer; 5 to 30 parts by weight of the wax; 1 to 10 parts by weight of the cationic surfactant; And 1 to 10 parts by weight of the anionic surfactant.

In addition, in order to achieve the second object of the present invention, the present invention comprises the steps of coating the enzyme stabilized microcapsules dissolved in a solvent to a seed consisting of white sugar or microcrystalline cellulose to form an enzyme layer; Coating a shellac dissolved in a solvent on the enzyme layer to form a first coating layer; Coating a polymer dissolved in water on the first coating layer to form a second coating layer; Coating a wax dissolved in a solvent on the second coating layer to form a third coating layer; Coating a cationic surfactant dissolved in water on the third coating layer to form a fourth coating layer; Coating a polymer dissolved in water on the fourth coating layer to form a fifth coating layer; Coating an anionic surfactant dissolved in water on the fifth coating layer to form a sixth coating layer; And coating a polymer dissolved in water onto the sixth coating layer to form a seventh coating layer.

The coating is carried out by a fluid bed process.

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

Enzyme capsule formulation of the present invention, first, the seed used as a core (core), the enzyme layer consisting of enzyme stabilized microcapsules formed on the seed, the first coating layer formed on the enzyme layer and made of shellac, on the first coating layer A second coating layer formed of a polymer, a third coating layer formed on the second coating layer and formed of a wax, a fourth coating layer formed on the third coating layer and formed of a cationic surfactant, and formed on the fourth coating layer And a fifth coating layer formed on the fifth coating layer, the sixth coating layer formed on the fifth coating layer, and the seventh coating layer formed on the sixth coating layer and made of a polymer.

The seed is suitably composed of white sugar or microcrystalline cellulose, the content of which is 20 to 45 parts by weight. If it is less than 20 parts by weight, there is a problem that the coating is not easy to be spherical evenly, and if it exceeds 45 parts by weight, there is a disadvantage in forming a multilayer structure .

The enzyme stabilizing microcapsules forming the enzyme layer are triple microcapsules of enzyme / polyol / polymer as described in Korean Patent Laid-Open Publication No. 2004-0034864 of the applicant. Specifically, the enzyme stabilizing microcapsules forming the enzyme layer is an enzyme as the inner core; Hydrophobic high molecular weight polyol of 1000 g / mol or more as a coating material of the enzyme; And a microcapsule having a triple structure composed of a polymer wall on the outermost side; The enzyme is at least one selected from the group of lipases, amylases, pepsin, trypsin, urease, asparaginase and papain, and the high molecular weight polyols are polyethylene glycol and polypropylene glycol, copolymers and derivatives thereof. At least one selected from the group consisting of: The polymer wall material may be poly-L-lactic acid, poly-D, L-glycolic acid, poly-L-lactic acid-co-glycolic acid, poly-D, L-lactic acid-co-glycolic acid, polycaprolactone, polyvalero Copolymers prepared from lactones, polyhydroxy butyrates, polyhydroxy valerates, polyorteresters and monomers thereof, polystyrene, poly p- or m-methylstyrene, poly p- or m-ethylstyrene, poly p- Or m-chlorostyrene, poly p- or m-chloromethylstyrene, poly styrenesulphonic acid, poly p- or m- or t-butoxystyrene, poly methyl (meth) acrylate, polyethyl (meth) acrylate , Polypropyl (meth) acrylate, polyn-butyl (meth) acrylate, polyisobutyl (meth) acrylate, polyt-butyl (meth) acrylate, poly2-ethylhexyl (meth) acrylate, poly n-octyl (meth) acrylate, polylauryl (meth) acrylate , Polystearyl (meth) acrylate, poly2-hydroxyethyl (meth) acrylate, polyethylene glycol (meth) acrylate, methoxy polyethylene glycol (meth) acrylate, polyglycidyl (meth) acrylate, Polydimethylaminoethyl (meth) acrylate, polydiethylaminoethyl (meth) acrylate, polyvinylacetate, polyvinylpropionate, polyvinylbutyrate, polyvinylether, polyallylbutyl ether, polyallylglycidyl ether , Poly (meth) acrylic acid, polymaleic acid, polyalkyl (meth) acrylamide, and poly (meth) acrylonitrile. The content is 0.1-0.6 weight part. If less than 0.1 part by weight, the activity of the enzyme is disadvantageous to express in the formulation, if it exceeds 30 parts by weight there is a disadvantage in forming a multilayer structure .

Shellac forming the first coating layer (shellac) is a material resistant to water or acid, it can block the hygroscopicity and maintain the elution of the enzyme stabilized microcapsules from the enzyme layer properly. The content is 5 to 30 parts by weight. If less than 5 parts by weight of the high concentration anionic surfactant system has a problem that the hygroscopic blocking is impossible, if more than 30 parts by weight there is a problem that the microcapsules are not eluted during use .

The polymer forming the second coating layer, the fifth coating layer and the seventh coating layer is a polymer such as polyester, polyacrylate, polyvinyl ether, unsaturated carboxylic acid, copolymers or derivatives thereof, for example, hydroxypropyl Methyl cellulose, ethyl cellulose, polymethyl methacrylate, styrene butadiene copolymer and the like. These polymer layers serve as buffers between the first, third, fourth, and sixth coating layers. In addition, the total content of the polymer is 5 to 30 parts by weight. If it is less than 5 parts by weight, there is a problem in that the role of the interlayer buffer is insufficient, and if it exceeds 30 parts by weight, there is a disadvantage in forming a multilayer structure. The polymer content of each layer is 5 to 10 parts by weight.

The wax constituting the third coating layer is stearic acid, stearyl alcohol, behenic acid, behenyl alcohol or bis wax, and its role prevents moisture absorption in the high concentration anionic surfactant formulation while simultaneously decomposing the multilayer capsule during face washing. It plays a role . Also The content is 5 to 30 parts by weight. If less than 5 parts by weight does not block the moisture absorption, if more than 30 parts by weight there is a problem impossible to form a multi-layer structure .

The cationic surfactant constituting the fourth coating layer is polyquaternium-6, polyquaternium-7, polyquaternium-10, polyquaternium-39, or derivatives thereof, and water is introduced into the capsule formulation. When swelling occurs, it forms an insoluble complex with anionic surfactants to block the penetration of water or surfactant into the formulation. Also The content is 1 to 10 parts by weight. If less than 1 part by weight, there is a problem in that effective complex formation is impossible when water or surfactant penetrates, and if more than 10 parts by weight, there is a disadvantage in forming a multilayer structure .

The anionic surfactant constituting the sixth coating layer is carboxylic acid, isethionate, sulfate, sulfonate, sulfosuccinate, sulfosinate or derivatives thereof, for example sodium lauryl sulfate, sodium methyl cocoyl. Isethionate, sodium lauryl sarcosinate, sodium lauryl sulfosuccinate, and the like. When water swells into the capsule formulation and swelling occurs, it forms an insoluble complex with the cationic surfactant and serves to block the penetration of water or surfactant into the formulation. Also The content is 1 to 10 parts by weight. If less than 1 part by weight, there is a problem in that effective complex formation is impossible when water or surfactant penetrates, and if more than 10 parts by weight, there is a disadvantage in forming a multilayer structure .

Next, the manufacturing method of the enzyme capsule formulation which concerns on this invention is explained in full detail.

In the manufacturing method of the present invention, the coating is carried out by a fluid bed process, which is one of various encapsulation methods performed to prevent proteolytic enzymes from deactivating under the influence of heat or moisture in the preparation. Specifically, it is preferable to use a fluidized bed granulator coater (Fluid Bed Coater, manufactured by Glatt, Germany).

In the method for preparing an enzyme capsule of the present invention, first, the present inventors dissolve the enzyme / polyol / polymer microcapsules and hydroxypropyl methylcellulose in water so that the mixing ratio is 0.05: 1 to 1: 1, and then uniformly mix the nuclei. Dissolve and suspend. The mixed solution is poured into a fluid bed granulation coater (Fluid Bed Coater, manufactured by Glatt, Germany), and the mixed solution is sprayed onto the seed through a nozzle using a bottom spray method while flowing white sugar or microcrystalline cellulose seed (10 to 100 mesh). To coat an enzyme layer consisting of enzyme / polyol / polymer microcapsules.

Next, on the enzyme layer, a shellac coating base dissolved in a solvent is coated, for example, bottom spray coating, to form a first coating layer. At this time, it is preferable to use alcohol, such as ethanol, and, as for a solvent, the mixing ratio of shellac and a solvent is preferably 0.01: 1 to 1: 1.

Next, on the first coating layer, a coating base in which an appropriate amount of pigment is dissolved in a 0.01: 1 to 1: 1 solution of polymer and water is coated to form a second coating layer. Preferably it may contain a pigment, wherein the pigment is a means of visual differentiation in the formulation. When a 2nd coating layer is formed including an appropriate amount of water-soluble pigment | dye, a pigment | dye is stabilized without eluting in a high concentration anionic surfactant system.

Subsequently, the wax coating substrate dissolved in the solvent is coated on the second coating layer to form a third coating layer. At this time, it is preferable to use alcohol, such as ethanol, and 0.01: 1-1: 1 of a wax and alcohol are preferable as a solvent.

Next, on the third coating layer, a coating base having a 0.01: 1 to 1: 1 solution ratio of cationic surfactant and water is coated to form a fourth coating layer.

Subsequently, a fifth coating layer of the same polymer layer as the second coating layer is formed on the fourth coating layer.

Next, a coating base having a ratio of 0.01: 1 to 1: 1 solution of anionic surfactant and water is coated on the fifth coating layer to form a sixth coating layer.

Subsequently, a seventh coating layer of the same polymer layer as the second coating layer is formed on the sixth coating layer.

Enzymatic multilayer capsule formulation according to the present invention, when swelling occurs due to water seeps into the formulation, the cationic and anionic surfactants coated on the formulation form an insoluble complex, which blocks water or surfactant from penetrating into the formulation. Therefore, the activity of the protease in the capsules is not lowered, thereby exhibiting an excellent cleaning effect and skin exfoliation effect.

Therefore, if the composition comprising the enzyme multilayer capsule formulation of the present invention can be formulated in a formulation such as shampoo, rinse, body cleanser, soap, cleansing foam, etc., it can be used for skin cleansing or skin exfoliation.

Hereinafter, although an Example is given and this invention is demonstrated in detail, this invention is not limited only to these examples.

<Example 1>

First, the triple structure microcapsules of papain / polyol / polycaprolactone were prepared according to the method described in Example 5 of Korean Laid-Open Patent Publication No. 2004-0034864. However, the content of papain was 0.3% by weight in each capsule.

The mixing ratio of the microcapsules and hydroxypropyl methylcellulose was set to 0.05: 1 and mixed with water, and the mixed solution was dissolved and suspended uniformly.

The mixed nucleus was introduced into a fluidized bed granulator (Glatt GPCG-120), and 35 g of the seed per bag having a particle size of 500 to 1000 µm was flowed in the fluidized bed granulator, and the mixed solution was coated by a bottom spray method to enzymatically react on the seed. The layer was coated.

Next, 0.07: 1 solution of shellac and ethanol as the primary coating solution; 0.2: 1 solution of hydroxypropyl methylcellulose and water as the second, fifth and seventh coating liquids; 0.2: 1 solution of stearic acid and ethanol as the third coating solution; 0.05: 1 solution of polyquaternium-6 and water as the fourth coating solution; After preparing a 0.05: 1 solution of sodium lauryl sulfate and water as the sixth coating solution, the coating solution was introduced into a fluidized bed granulator, and the coating process was sequentially performed to proceed with the multilayer capsule of the present invention.

<Examples 2-3

A multilayer capsule was prepared in the same manner as in Example 1 except that the papain content was 0.6% by weight and 0.9% by weight of the total capsules, respectively.

<Test Example 1> Characterization of the prepared cation-anion complex multilayer capsule

 The capsule form of the multilayer capsule prepared in Example 1 was observed by scanning electron microscope in FIG. 1. As can be seen in Figure 1, the prepared particles form a multilayer structure therein.

Test Example 2 Analysis of Papain Enzyme Activity in Formulation

The activity of the enzyme expressed in the multilayer capsules prepared in Examples 1 to 3 was tested by papain enzyme content and is shown in Table 2 below.

Example 1 ( 0.3% Enzyme Capsule) Example 2 ( 0.6% Enzyme Capsule) Example 3 ( 0.9% Enzyme Capsule) activation 0.3 0.5 0.6

Only papain enzyme microcapsules were isolated and recovered from the samples, and enzyme activity was measured by Elisa Reader. Each activity value was expressed based on the average value after three measurements. Although activity was detected at low levels in all samples by the loss generated during the recovery and separation of the microcapsules, significant differences in enzyme activity by enzyme content were identified. In order to test whether the product can be applied to the level of keratin resolution, the prepared papain enzyme multilayer capsules were added to the following Formulation Examples 1 to 3 and verified by in vivo test.

Formulation Example 1 Cleansing Foam Formulation

To prepare a cleansing foam formulation in the form of a white paste having the composition of Table 3. The viscosity of the formulation is about 600,000 cps. On the other hand, the viscosity was measured by 0.5RPM the next day at 30 ℃ using a BROOKFIELD RVT SPINDLE T-D.

ingredient Content (% by weight) Stearic acid 20 Mystic acid 4 Lauric acid 7 glycerin 15 Glyceryl Stearate 2 Potassium hydroxide 5 Coca Middopropyl Betaine 5 antiseptic Quantity Papain Enzyme Multilayer Capsule of Example 1 0.5 Purified water To 100

The sample prepared according to Table 3, except that only the papain enzyme multilayer capsule in Formulation Example 1 of Table 3 as a control was verified by in vivo test. For 20 Korean women, Dansyl Chloride was patched and stained on the inner side of Habak for 24 hours, washed once a day using a sample and a control sample. After staining, the image was visually evaluated and photographed. As a result, it was verified that the exfoliation effect by the proteolysis of papain enzyme was excellent when used for 2 weeks or more.

2 shows a visual evaluation score graph. The x-axis of the graph represents a sample treatment period after removing the patch immediately after removing the patch (T0d), after 4 days (T4d), after 10 days (T10d), after 16 days (T16d), and after 21 days (T21d). The y-axis of the graph is a visual judgment value. The visual judgment value and its reference | standard are shown in Table 4 (A is Formulation Example 1, B is a control group, N is an untreated group).

Judgment Criteria 0 When no fluorescence is observed at the dyeing site 2 Fluorescence less than 20% of the stained area is observed, and at low intensity 4 When fluorescence is observed about half of the dyeing site, but the fluorescence is weak and the boundary is not clear 6 Fluorescence is observed about half of the staining area, and when the fluorescence is weak but the boundaries are clearly separated 8 When fluorescence is observed in most of the stained areas and the boundaries are clearly distinguished 10 When 100% of the dyeing site is observed intensive fluorescence

The fluorescein-treated sample treatment site maintained a deep staining state in the first week (T0d, T4d), but since the fluorescence began to decrease rapidly, it was difficult to distinguish between the samples after T16d. Therefore, when considering between T4d and T10d, which is the most suitable time for observing the effect difference between samples, the keratin turn over promoting effect of Formulation Example 1 was superior to no treatment and control. In particular, T10d and T16d showed 16% and 60% better effects than untreated controls, respectively.

3 also shows the fluorescence brightness change rate, which is an image analysis result. The photographs were always taken under the same conditions with a digital camera (canon G5, Japan), and after converting the photographed images into black and white images, only the area of the fluorescent dye region marked in white was selected and the value of whiteness from 128 to 255 of each pixel was selected. The intensity mean (density mean) of (part represented by white) was calculated. The image analysis program used Image Pro Plus (version.4.5). The x-axis means that the images were taken on T4d and T10d, where valid data were obtained (image analysis showed that the intensity of the fluorescence stained significantly decreased within the first 10 days of treatment, and the photos after T16d had no fluorescence staining). It is too blurred to analyze images). The y-axis is the percent variance before and after treatment, which is the ratio of the difference between the value after the sample treatment and the value before the sample treatment, divided by the value before the sample treatment.

               % variance = (Tnd-T0d) / T0d

As a result of image analysis, Formulation Example 1 was determined to be significantly better in promoting the keratin turn over compared to the untreated group. The control group was better than the untreated group, and the effect was weaker than Formulation Example 1.

Figure 4 shows the three-dimensional photograph results, the control group (B), no treatment group (N), 0, 4, 10, 16, 21 days stereoscopic picture of Formulation Example 1 (A). The brighter the dansyl chloride stained area, the higher the height of the circle. Photographs after T16d are too fluoresced, making it difficult to distinguish between samples. When interpreting 4 and 10 day stereoscopic results, the case of Formulation Example 1, which is smaller than the control and no treatment groups, has the effect of exfoliation. Can be interpreted as showing

As described above, according to the present invention, if the papain enzyme is encapsulated in a multi-layer structure using a cation-anion complex, there is an effect of effectively maintaining and expressing the activity of the enzyme even in a human detergent product.

Claims (17)

Seeds consisting of white sugar or microcrystalline cellulose; An enzyme layer formed on the seed and composed of enzyme stabilized microcapsules; A first coating layer formed on the enzyme layer and made of shellac; A second coating layer formed on the first coating layer and made of a polymer; A third coating layer formed on the second coating layer and made of wax; A fourth coating layer formed on the third coating layer and made of a cationic surfactant; A fifth coating layer formed on the fourth coating layer and made of a polymer; A sixth coating layer formed on the fifth coating layer and formed of an anionic surfactant; And An enzyme capsule formulation comprising a seventh coating layer formed on the sixth coating layer and made of a polymer. The enzyme stabilizing microcapsules forming the enzyme layer is an enzyme as the inner core; Hydrophobic high molecular weight polyol of 1000 g / mol or more as a coating material of the enzyme; And an outermost triple microcapsule composed of a polymer wall, The enzyme is at least one selected from lipase, amylase, pepsin, trypsin, urease, asparaginase and papain hydrolase; The high molecular weight polyol is at least one selected from the group consisting of polyethylene glycol and polypropylene glycol and copolymers thereof, The polymer wall material may be poly-L-lactic acid, poly-D, L-glycolic acid, poly-L-lactic acid-co-glycolic acid, poly-D, L-lactic acid-co-glycolic acid, polycaprolactone, polyvalero Copolymers prepared from lactones, polyhydroxy butyrates, polyhydroxy valerates, polyorsteresters and monomers thereof, polystyrene, poly p- or m-methylstyrene, poly p- or m-ethylstyrene, poly p- Or m-chlorostyrene, poly p- or m-chloromethylstyrene, poly styrenesulphonic acid, poly p- or m- or t-butoxystyrene, poly methyl (meth) acrylate, polyethyl (meth) acrylate , Polypropyl (meth) acrylate, polyn-butyl (meth) acrylate, polyisobutyl (meth) acrylate, polyt-butyl (meth) acrylate, poly2-ethylhexyl (meth) acrylate, poly n-octyl (meth) acrylate, polylauryl (meth) acrylate, Polystearyl (meth) acrylate, poly2-hydroxyethyl (meth) acrylate, polyethylene glycol (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, polyglycidyl (meth) acrylate, poly Dimethylaminoethyl (meth) acrylate, polydiethylaminoethyl (meth) acrylate, polyvinylacetate, polyvinylpropionate, polyvinylbutyrate, polyvinylether, polyallylbutyl ether, polyallylglycidyl ether, Enzyme capsule formulation, characterized in that at least one selected from the group consisting of poly (meth) acrylic acid, polymaleic acid, polyalkyl (meth) acrylamide and poly (meth) acrylonitrile. delete According to claim 1, wherein the polymer consisting of the second coating layer, the fifth coating layer and the seventh coating layer is at least one selected from the group consisting of polyester, polyacrylate, polyvinyl ether, unsaturated carboxylic acid and copolymers thereof Formulation characterized in that. The formulation of claim 1, wherein the wax forming the third coating layer is at least one selected from the group consisting of stearic acid, stearyl alcohol, behenic acid, behenyl alcohol, and bis wax. According to claim 1, wherein the cationic surfactant constituting the fourth coating layer is characterized in that at least one selected from the group consisting of polyquaternium-6, polyquaternium-7, polyquaternium-10 and polyquaternium-39 Formulation. According to claim 1, wherein the anionic surfactant constituting the sixth coating layer is characterized in that at least one selected from the group consisting of carboxylic acid, isethionate, sulfate, sulfonate, sulfosuccinate and sulfosinamate. Formulation. The method of claim 1 wherein the formulation is 20 to 45 parts by weight of the white sugar or microcrystalline cellulose; 0.1 to 30 parts by weight of the enzyme stabilized microcapsules; 5 to 30 parts by weight of the shellac; 5 to 30 parts by weight of the polymer; 5 to 30 parts by weight of the wax; 1 to 10 parts by weight of the cationic surfactant; And Formulation comprising 1 to 10 parts by weight of the anionic surfactant. Coating an enzyme stabilized microcapsule dissolved in a solvent on a seed made of white sugar or microcrystalline cellulose to form an enzyme layer; Coating a shellac dissolved in a solvent on the enzyme layer to form a first coating layer; Coating a polymer dissolved in water on the first coating layer to form a second coating layer; Coating a wax dissolved in a solvent on the second coating layer to form a third coating layer; Coating a cationic surfactant dissolved in water on the third coating layer to form a fourth coating layer; Coating a polymer dissolved in water on the fourth coating layer to form a fifth coating layer; Coating an anionic surfactant dissolved in water on the fifth coating layer to form a sixth coating layer; And On the sixth coating layer, coating the polymer dissolved in water to form a seventh coating layer comprising the step of preparing an enzyme capsule formulation, The enzyme stabilizing microcapsules forming the enzyme layer is an enzyme as the inner core; Hydrophobic high molecular weight polyol of 1000 g / mol or more as a coating material of the enzyme; And an outermost triple microcapsule composed of a polymer wall, The enzyme is at least one selected from lipase, amylase, pepsin, trypsin, urease, asparaginase and papain hydrolase; The high molecular weight polyol is at least one selected from the group consisting of polyethylene glycol and polypropylene glycol and copolymers thereof, The polymer wall material may be poly-L-lactic acid, poly-D, L-glycolic acid, poly-L-lactic acid-co-glycolic acid, poly-D, L-lactic acid-co-glycolic acid, polycaprolactone, polyvalero Copolymers prepared from lactones, polyhydroxy butyrates, polyhydroxy valerates, polyorsteresters and monomers thereof, polystyrene, poly p- or m-methylstyrene, poly p- or m-ethylstyrene, poly p- Or m-chlorostyrene, poly p- or m-chloromethylstyrene, poly styrenesulphonic acid, poly p- or m- or t-butoxystyrene, poly methyl (meth) acrylate, polyethyl (meth) acrylate , Polypropyl (meth) acrylate, polyn-butyl (meth) acrylate, polyisobutyl (meth) acrylate, polyt-butyl (meth) acrylate, poly2-ethylhexyl (meth) acrylate, poly n-octyl (meth) acrylate, polylauryl (meth) acrylate, Polystearyl (meth) acrylate, poly2-hydroxyethyl (meth) acrylate, polyethylene glycol (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, polyglycidyl (meth) acrylate, poly Dimethylaminoethyl (meth) acrylate, polydiethylaminoethyl (meth) acrylate, polyvinylacetate, polyvinylpropionate, polyvinylbutyrate, polyvinylether, polyallylbutyl ether, polyallylglycidyl ether, At least one selected from the group consisting of poly (meth) acrylic acid, polymaleic acid, polyalkyl (meth) acrylamide and poly (meth) acrylonitrile. delete According to claim 8, wherein the polymer consisting of the second coating layer, the fifth coating layer and the seventh coating layer is at least one selected from the group consisting of polyester, polyacrylate, polyvinyl ether, unsaturated carboxylic acid and copolymers thereof Method characterized by that. The method of claim 8, wherein the wax forming the third coating layer is at least one selected from the group consisting of stearic acid, stearyl alcohol, behenic acid, behenyl alcohol, and bis wax. The method of claim 8, wherein the cationic surfactant constituting the fourth coating layer is at least one selected from the group consisting of polyquaternium-6, polyquaternium-7, polyquaternium-10 and polyquaternium-39 How to. The method of claim 8, wherein the anionic surfactant constituting the sixth coating layer is at least one selected from the group consisting of carboxylic acid, isethionate, sulfate, sulfonate, sulfosuccinate and sulfosinate. Way. The method of claim 8, wherein the coating is carried out by a fluid bed process. 8. A skin cleansing composition comprising the enzyme capsule formulation of any one of claims 1 and 3. The enzyme capsule formulation of claim 15, wherein the enzyme capsule formulation prevents swelling in the capsule formulation by water and a surfactant even in a skin cleansing composition containing a high concentration of a surfactant at least 15%, and the activity of the enzyme in the capsule. Skin cleaning composition, characterized in that to maintain. Claim 1 and the skin exfoliation composition comprising an enzyme capsule formulation of any one of claims 3 to 7.

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