KR102007797B1 - Silk hydrogel composition and silk hydrogel mask - Google Patents

Abstract

The present invention provides a silk hydrogel composition comprising 0.01 to 30% by weight of silk fibroin powder and 0.01 to 10% by weight of urea and a method for producing a silk hydrogel mask using the same, based on the total weight of the composition. According to the present invention, the raw material solubility of the silk fibroin is increased and gelled in a short time, so that a continuous process is possible, and packaging can be performed immediately after cutting, thereby eliminating the need for an additional process, thereby increasing production safety and efficiency. In addition, the silk hydrogel composition according to the present invention can exhibit excellent strength and adhesion, and at the same time control the rate of water release, and because it is a silk material with high affinity with the human body, it can reduce the irritation, moisture content, moisturizing power, exfoliation It is effective for brightening and reducing redness, so it can be used in cosmetic masks.

Description

SILK HYDROGEL COMPOSITION AND SILK HYDROGEL MASK

The present invention relates to a silk hydrogel composition and a silk hydrogel mask, and more particularly, to a silk hydrogel composition and a silk hydrogel mask using the same by dissolving the silk fibroin powder in an aqueous urea solution.

Recently, skin care using hydrogels has been applied in various fields such as cosmetics and skin care. Hydrogel mask is a product that is evaluated as the most technologically advanced form in consideration of the efficacy, effect and formulation of the mask. By using the crosslinking or embrittlement of the effective cosmetic raw material in the water-soluble polymer in the hydrogel It is a skin care delivery system designed to continuously and effectively deliver the efficacy and effects of active ingredients by storing cosmetic ingredients inside a polymer. Hydrogel masks have no drawbacks and are superior in terms of use, but have a disadvantage in physical strength, compared to sheet mask types in which essences are immersed in nonwoven fabrics. Hydrogels themselves are so slippery that their adhesion is poor, and the diarrhea is so rapid that it is difficult to deliver enough effective substance to the skin. Attempts have been made to apply silk fibroin to overcome the physical disadvantages of such hydrogels.

On the other hand, silk generally can be classified into two types of proteins, fibroin and sericin, because of the degree of orientation of the fibers and the inside, the content, molecular weight, and crystallinity of amino acid constituents. Fibroin: Sericin is composed of 75:25 ratio. Sericin has high solubility and is generally removed in refining process, leaving only fibroin. This is commonly used for medical or medical purposes. Silk fibroin has excellent film forming ability and no rejection in use on the human body. Silk fibroin films or hydrogels have good dissolved oxygen permeability, in wet conditions, similar to human skin, suggesting the applicability of such films in wound dressings and artificial fibrous systems.

Conventionally, a case of making a skin care mask with silk is mostly a sheet mask dipped in an essence, and sericin is used a lot, not fibroin. Compared to water-insoluble fibroin, water-soluble sericin has a low molecular weight and is easy to use, and its natural moisturizing function is widely known. There is no case of using sericin in a hydrogel mask, because sericin having a low molecular weight can be used as an active ingredient in a hydrogel mask but is difficult to use as a gelling agent. Fibroin, a polymer, can be used as a gelling agent by causing structural variations when applied physically or chemically. Fibroin, when used as a gelling agent, provides better adhesion than normal hydrogels and facilitates effective mass transfer. Existing hydrogel mask using silk fibroin, but the use is poor and has the disadvantage that the productivity is inefficient by using the fibroin solution.

Silk fibroin is mainly prepared as a solution through an alkali refining method which is subjected to a predetermined time treatment by applying an appropriate temperature in alkaline water such as soap refining or soap soda. This sericin-free silk fibroin solution has the advantage that it does not need to be re-dissolved when applied to the formulation.However, a low-stable silk fibroin solution does not necessarily need to be refrigerated, but also has a physical impact or settles after a certain period of time. . In the case of making a hydrogel with a silk fibroin solution, there is a big disadvantage that the gel is completed by immersing in alcohol or adding a metal salt, and the final gelation time is not immediate. Silk fibroin powder, on the other hand, is resistant to physical impact, can be stored at room temperature, and is excellent in price. However, there is a disadvantage that the solubility is lower than the solution.

Since films made of silk fibroin can be dissolved in water without further manipulation due to the dominant random coil protein structure, the structural features of the protein are random coils by heat, mechanical stretching, immersion in polar organic solvents and curing in water vapor. To beta sheet form. Variations in this structure result in water insolubility but have a more flexible system than films made from some pure silk fibroin.

There are many masks using silk, but there are no masks that make good use of their characteristics. There is a need for an ideal silk hydrogel mask that can utilize the properties of the silk and make up for the disadvantages of the hydrogel.

Patent Publication No. 10-2007-0014485

In order to solve the above problems, the present invention is to dissolve silk fibroin powder in an aqueous solution of urea to increase the solubility of the raw material of silk fibroin and gelation in a short time to provide a method for producing a silk hydrogel mask and a silk hydrogel composition capable of a continuous process For that purpose.

In order to solve the above object, the present invention provides a silk hydrogel composition comprising 0.01 to 30% by weight of the silk fibroin powder and 0.01 to 10% by weight of urea based on the total weight of the composition.

In one embodiment of the present invention, the silk fibroin powder may have a molecular weight of 1,000 to 400,000.

In one embodiment of the present invention, the composition may further contain a thickener.

In one embodiment of the present invention, the thickener may be a silicone thickener, an oil thickener or an acrylic thickener.

In one embodiment of the present invention, the silicone thickener or oil thickener may be 0.01 to 30% by weight based on the total weight of the composition, the acrylic thickener may be 0.01 to 5% by weight relative to the total weight of the composition.

In one embodiment of the present invention, the composition may be one having a strength of 0.1kgf / cm ² to 1.5kgf / cm ^2.

In addition, the present invention comprises the steps of dissolving the silk fibroin powder in an aqueous solution of urea;

Gelling the composition of said step; And

It provides a method for producing a silk hydrogel mask comprising the step of molding the gelation of the step to the desired shape.

In one embodiment of the present invention, the gelation may be 0.1 seconds to 10 minutes.

In one embodiment of the present invention, the gelling step and the forming step may be a continuous process.

The present invention also provides a silk hydrogel mask prepared by the above method.

According to the manufacturing method of the silk hydrogel composition of the present invention, the raw material solubility of the silk fibroin is increased and gelled within a short time, and thus a continuous process is possible, and packaging can be performed immediately after cutting, thereby eliminating the need for an additional process, thereby increasing production safety and efficiency. In addition, the silk hydrogel composition of the present invention shows excellent strength and adhesion at the same time can control the rate of water release, because it is a silk material with high affinity with the human body can reduce the irritation, moisture content, moisture retention, exfoliation, Effective in brightening and redness reduction, it can be used in cosmetic masks.

1 is a schematic diagram of a method for producing a silk hydrogel according to the prior art.
Figure 2 is a schematic diagram of a method for producing a silk hydrogel according to an embodiment of the present invention.
Figure 3 is a graph showing the water release rate of the silk hydrogel according to an embodiment of the present invention.
4 is a graph showing the water content of the silk hydrogel according to an embodiment of the present invention.
5 is a graph showing the moisture content of the silk hydrogel according to an embodiment of the present invention.
6 is a graph showing the rate of change of the optical properties of the silk hydrogel according to an embodiment of the present invention.

Hereinafter, in order to enable those skilled in the art to easily carry out the present invention will be described in detail with respect to preferred embodiments of the present invention.

A method of manufacturing a conventional hydrogel mask is shown in FIG. 1. Since the conventional hydrogel takes a long time to gel, the contents 10 are removed (A) and placed on the tray 20, and then the metal gel or alcohol is added, followed by gelation for several hours, for example, 24 hours, to start cutting. By discontinuous process (FIG. 1).

The present invention, as shown in Figure 2, the coating (B) is started while the contents (10) is carried out (A), the rapid gelation proceeds as a continuous process to enable a continuous cut 40 silk hydrogel Provided is a method of manufacturing a mask.

The present invention provides a silk hydrogel composition comprising 0.01 to 30% by weight of silk fibroin powder and 0.01 to 10% by weight of urea relative to the total weight of the composition.

The silk fibroin powder may have a molecular weight of 1,000 to 400,000, but is not limited thereto.

In addition, the silk hydrogel composition of the present invention may further contain a thickener. The thickener may be a silicone thickener, an oil thickener or an acrylic thickener.

The silicone thickener or oil thickener may be 0.01 to 30% by weight based on the total weight of the composition, and the acrylic thickener may be 0.01 to 5% by weight based on the total weight of the composition, but is not limited thereto.

In addition, silk hydrogel mask according to the present invention has an excellent strength, 0.1kgf / cm ² to 1.5kgf / cm ^2, specifically 0.8kgf / cm ² to 1.5kgf / cm ^2,, more specifically 1.2kgf / cm May have a strength of ² to 1.35 kgf / cm ² .

Silk hydrogel composition of the present invention, dissolving silk fibroin powder in an aqueous urea solution; Gelling the composition of said step; And it may be prepared by the method for producing a silk hydrogel mask comprising the step of molding the gelation of the step to the desired shape.

Hereinafter, the manufacturing method of a silk hydrogel mask is demonstrated concretely.

First, the silk fibroin powder is dissolved in an aqueous urea solution to obtain a silk hydrogel composition.

The method of obtaining the silk fibroin powder used for this invention is not specifically limited, A well-known method can be used. Preferably, the silk fibroin powder may be prepared by grinding the degumming silk raw material after treating with an aqueous alkali solution. Silk fibroin solution has low stability and needs to be refrigerated and precipitates after a certain period of time, whereas silk fibroin powder has excellent stability. In the present invention, the silk fibroin powder itself acts as a gelling agent, thereby enabling gelation within a short time of several seconds to several minutes without additional thickening agent or gelling agent or with a small amount of thickening agent or gelling agent.

The silk fibroin powder may have a molecular weight of 1,000 to 400,000, but is not limited thereto.

The silk fibroin powder in the present invention may be 0.01 to 30% by weight, preferably 0.1 to 10% by weight, more preferably 1 to 5% by weight based on the total weight of the composition. If it is less than 0.01% by weight, the silk fibroin powder as the gelling agent is too small to reveal its inherent characteristics, and if it is more than 30% by weight, the salt ions remaining in the silk fibroin powder will interfere with gelation to obtain a proper hydrogel. However, from 1 to 5% by weight is most preferred because an appropriate amount of salt ions help gelation.

In the present invention, the urea aqueous solution may be one obtained by dissolving urea in water at room temperature or high temperature. The solubility of the silk fibroin powder can be increased by dispersing and dissolving the silk fibroin powder in an aqueous urea solution.

In the aqueous urea solution, urea may be included in an amount of 0.01 to 10% by weight, preferably 1 to 10% by weight, and more preferably 1 to 5% by weight, based on the total weight of the composition. Less than 0.01% by weight is not effective for improving the solubility of the silk fibroin powder. The greater the amount of urea, the more exfoliation and whitening effect can increase the efficacy, but more than 10% by weight not only causes irritation to the skin, but also decreases the usability of the hydrogel.

In addition, the concentration of the urea solution may be 0.01 to 10% by weight, but is not limited thereto.

The silk hydrogel composition of the present invention may further contain a thickener. The thickener is not particularly limited, but for example, butylene glycol, glycerin, 1,2-hexanediol, dimethicone and cyclomethicone, hydroxyethyl acrylate, sodium polyacrylate, polymethyl methacrylate and At least one of acrylate, carrageenan, xanthan gum, carob bean gum and gellan gum.

In the present invention, the thickener may be a silicone thickener, an oil thickener or an acrylic thickener.

The silicone thickener or oil thickener may be 0.01 to 30% by weight, preferably 0.1 to 5% by weight based on the total weight of the composition. If it is less than 0.01% by weight, the viscosity is too low to increase the loss when coating, and if it is more than 30% by weight, the viscosity is too high, making it difficult to mix.

In addition, the acrylic thickener may be 0.01 to 5% by weight, preferably 0.1 to 2% by weight based on the total weight of the composition. If it is less than 0.01% by weight, the viscosity is too low to increase the loss when coating, and if it is more than 5% by weight, the viscosity is too high, making it difficult to mix.

Then, the step of gelling the silk hydrogel composition of the above step.

The gelation may be by natural cooling.

At this time, the gelation time may be 0.1 seconds to 10 minutes, preferably 0.1 seconds to 3 minutes, but is not limited thereto.

Specifically, the gel solution of the obtained silk hydrogel composition is poured into the coater at a temperature of 10 to 80 ℃ to form a gel in a few seconds to several minutes by coating and at the same time by natural cooling. Gelation time can be 0.1 seconds to 3 minutes as described above. The gel hydrogel, which has undergone gelation, is molded into a mold or cut into a mold of a mold mold suitable for the shape of a part of the human body, thereby making a cosmetic mask.

Finally, the gelation of the above step is molded into the desired shape to obtain a mask. The target shape can be any shape suitable for the intended use, and can be formed by, for example, cutting the formed gel.

That is, the method of manufacturing a silk hydrogel mask according to the present invention, as can be seen in Figure 2, due to the short gelation time can be a continuous process. In the preparation of the conventional hydrogel mask, it takes a long time to gel, so there is a difference from that required by the discontinuous process (Fig. 1) to gel for several hours, for example 24 hours after the addition of metal salts or alcohol.

Further, the present invention provides a silk hydrogel mask having a strength of 0.1kgf / cm ² to 1.5kgf / cm ^2. That is, the silk hydrogel mask according to the present invention has an excellent strength, 0.1kgf / cm ² to 1.5kgf / cm ^2, specifically 0.8kgf / cm ² to 1.5kgf / cm ^2,, more specifically 1.2kgf / cm ² to 1.35kgf / cm ² May have strength.

The silk hydrogel composition of the present invention is a cosmetic agent or drug that is quickly delivered from the hydrogel composition to the skin due to silk fibroin, but is constantly delivered to the skin by controlling the migration rate of ingredient (migration rate of ingredient) or The drug can be controlled to release only acceptable quantities.

In addition, the silk hydrogel composition of the present invention has a tightening effect of shrinking the hydrogel itself when the structural change occurs by the silk fibroin temperature or physical change, which is excellent adhesion to accelerate the delivery of the effective ingredient to the skin It also provides convenience because it ensures activity when used as a beauty pack. This is a characteristic of silk hydrogels that are hardly seen in conventional hydrogel masks. In addition, the tightening effect can help elasticity and wrinkle management, as well as pores shrinkage. In addition, since silk, which is a natural material, has a high affinity for the skin, the silk hydrogel mask according to the present invention has a reduced irritation than a general mask.

Since the silk hydrogel composition of the present invention has a beta structure of silk fibroin, it has excellent strength and excellent swelling degree. The superior strength enhances the elasticity of the silk hydrogel, which is advantageous not only for increased usability but also for cutting and packaging during manufacturing.

In addition, the structural variation of silk fibroin in the composition of the present invention allows to control the moisture content. The inventors have confirmed that the hydrogel containing silk fibroin has a higher water content than the normal hydrogel, which means that it can supply more moisture to the skin. This is due to the structural features of silk fibroin.

The silk hydrogel composition of the present invention helps to dissolve low-solubility silk fibroin powder by using urea, and this urea finely exfoliates the skin. Therefore, the silk hydrogel of the present invention is also excellent in the skin brightening effect and redness reduction effect with sufficient moisture supply compared to the normal hydrogel.

The silk hydrogel composition of the present invention has improved the weak stability of the silk fibroin solution by using the silk fibroin powder, it is possible to gel in a few seconds to a short time in a few minutes without additional process to enable a continuous process to improve the process efficiency Can be.

The present invention is described in more detail through the following implementation. However, the examples are provided to illustrate the present invention, and the scope of the present invention is not limited only to these examples.

Preparation Example 1 Preparation of Silk Fibroin Powder

Natural silk and silkworms were boiled at 85 ° C. in 0.5% (w / v) aqueous sodium carbonate solution for 1 hour, washed several times with distilled water, and dried at 90 ° C. for 24 hours. Degumming silk was alkali hydrolyzed. For this purpose, water was charged with a liquid ratio of 10 to 40 based on fibroin. The alkali used was calcium hydroxide [Ca (OH) ₂ ] or barium hydroxide [Ba (OH) ₂ ] solution, and the concentration was adjusted to 0.4 to 2.0 w / v% (11.5 to 12.4 based on the pH of the solution). The mixture was heated at 90 to 100 ° C. for 8 to 48 hours and then cooled to obtain a precipitate. At this time, a sufficient amount of water was added to the separated precipitate, and the filtration separation process was repeated until no more alkali was eluted. The solid thus obtained was dried and pulverized to obtain a high molecular weight water insoluble silk fibroin powder.

Preparation Example 2 Preparation of Silk Fibroin Solution

Natural silk and silkworms were boiled at 85 ° C. in 0.5% (w / v) aqueous sodium carbonate solution for 1 hour, washed several times with distilled water, and dried at 90 ° C. for 24 hours. 8% by weight of the degumming silk was melted at 85 ° C. for 3 minutes in a solution prepared with a molar ratio of CaCl ₂ : dH ₂ O: EtOH 1: 8: 2 and then placed in a dialysis membrane having a molecular weight of 3500 and desalted for 3 days. Got it. The final concentration of the silk fibroin solution was 4%.

Example 1-3

The components and contents of the hydrogel mask pack composition used in Examples and Comparative Examples are shown in Table 1 below. Units of content are expressed in weight percent of the total composition.

(weight%) Silk Fibroin Powder (Manufacturing Example 1) Silk Fibroin Solution (Production Example 2) Urea glycerin Butylene Glycol Xanthan Gum Locus Beanst Sword Carrageenan Sword Sodium acrylate Example 1 2 2 5 10 0.3 0.2 0.5 0.2 Example 2 2 4 5 10 0.3 0.2 0.5 0.2 Example 3 4 2 5 10 0.3 0.2 0.5 0.2 Comparative Example 1 2 5 10 0.3 0.2 0.5 0.2 Comparative Example 2 2 5 10 0.3 0.2 0.5 0.2 Comparative Example 3 2 2 5 10 0.3 0.2 0.5 0.2

Experimental Example 1 Measurement of Water Release Rate

Sections of the hydrogel masks prepared in Example 1 and Comparative Example 1 were prepared in a size of 0.07 cm × 1.2 cm × 4 cm. The sections were placed on the skin and measured in 10, 20, 30, 60, and 90 minutes. To determine how much moisture was released. The results are shown in FIG.

Experimental Example 2 Measurement of Shrinkage

The hydrogel masks prepared in Examples 1, 3 and Comparative Example 1 were prepared in sections of 0.07 cm × 1.2 cm × 4 cm. The sections were placed on the skin and after 15 minutes the total area was measured to determine how much the hydrogel shrinks and indirectly measured the tightening effect. Hydrogel shrinkage was expressed as [(first area)-(area after shrinkage)] / (first area) × 100 (%). The results are shown in Table 2 below.

Example 1 Example 3 Comparative Example 1 Hydrogel Shrinkage 31.3% 36% 18.4%

Experimental Example 3 Stimulus Reduction Effect

The hydrogel masks prepared in Example 1 and Comparative Example 1 were prepared in sections of 0.07 cm × 1.2 cm × 4 cm. In 100 subjects, two sections were placed on the arm and 30 minutes later, the degree of irritation was assessed. The results are shown in Table 3 below.

Example 1 Comparative Example 1 Irritating mask 7 people 93 people

Experimental Example 4 Tensile Strength Measurement

The hydrogel mask packs prepared in Examples 1, 3 and Comparative Example 1 were prepared in sections of 1.0 cm × 8.0 cm × 0.07 cm. The sections were tensioned at both ends at a rate of 10 mm / min with a tensile strength tester (Minimat, Rheometric Scientific, USA) to measure the shear stress at break of the adhesive surface. Each experiment measured 5 times and calculated the average value. The results are shown in Table 4 below.

Example 1 Example 3 Comparative Example 1 Tensile strength (kgf / cm²) 1.2 1.35 0.39

Experimental Example 5 Measurement of Water Content

The hydrogel masks prepared in Example 1 and Comparative Example 1 were cut to a size of 0.07 cm × 1.2 cm × 4 cm, completely dried in an 80 ° C. oven, swelled again in water, and swelled by the following equation. The results are shown in FIG.

Swelling ratio = (first mass-dry mass) / first mass) × 100

Experimental Example 6 Measurement of Feeling

Hydrogel masks prepared in Example 1, Example 2 and Comparative Example 1 were prepared in the shape of a face. A survey was conducted on 100 women in their 20s and 30s. The results are shown in Table 5 below. Most participants had high satisfaction with all items on hydrogels containing silk (Examples 1 and 2). Comparing Example 1 and Example 2, the higher the urea content, the more active ingredients penetrate after exfoliation, so the satisfaction with moisture and moisture was high, and the satisfaction with brightening was particularly high.

Product satisfaction Moisture Elasticity Moisturizing Adhesion Retraction Brightening Example 1 82 people 42 persons 52 people 47 people 53 people 67 guests 18 people Example 2 12 people 51 people 39 persons 51 people 38 people 31 people 76 people Comparative Example 1 6 people 7 people 9 persons 2 people 9 persons 2 people 6 people

Experimental Example 7 Measurement of Water Content

The hydrogel masks prepared in Example 1 and Comparative Example 1 were prepared in sections of 0.07 cm × 1.2 cm × 4 cm. The sections were placed on the subject's cheek and 15 minutes later, the amount of water was measured with a corneometer. The results are shown in FIG.

Experimental Example 8 Brightening and Redness Reduction Effect

The hydrogel masks prepared in Example 1 and Comparative Example 1 were prepared in sections of 0.07 cm × 1.2 cm × 4 cm. 10 minutes after placing two sections under both eyes, the optical properties of the subject's cheekbone area were measured by using a polarization imaging apparatus to evaluate the improvement of brightening and redness. The results are shown in FIG.

Experimental Example 9 Comparison of Solubility by Urea

Hydrogels were prepared in the same manner as in Example 1 and Comparative Example 2. When visually observed, in Example 1, a smooth hydrogel was completed, whereas in Comparative Example 2 in which urea was missing, white silk fibroin crystals were also visible to the naked eye.

Experimental Example 10 Gelation Rate Comparison of Silk Fibroin Powder and Silk Fibroin Solution

The gelation rates of the contents prepared in Example 1 and Comparative Example 3 were compared. After preparing the two contents in the same amount, the gelation was performed at room temperature and no treatment was applied. The results are shown in Table 6 below.

Example 1 Comparative Example 3 Gel time 30 seconds 24 hours

10 Contents
11 conveying tube
20 trays
30 protective film
40 cutting machine
Export A Contents
B coating

Claims (10)

A silk hydrogel composition comprising 0.01 to 30% by weight of silk fibroin powder and 0.01 to 10% by weight of urea, based on the total weight of the composition,
The silk fibroin powder is a silk hydrogel composition which is subjected to alkali hydrolysis treatment of the degumming silk raw material. The method of claim 1,
The silk fibroin powder has a molecular weight of 1,000 to 400,000 silk hydrogel composition. The method of claim 1,
The composition is a silk hydrogel composition further containing a thickener. The method of claim 3, wherein
The thickener is a silicone hydrogel, oil thickener or acrylic thickener silk hydrogel composition. The method of claim 4, wherein
The silicone thickener or oil thickener is 0.01 to 30% by weight based on the total weight of the composition, the acrylic thickener is 0.01 to 5% by weight based on the total weight of the composition. The method according to any one of claims 1 to 5,
The composition silk hydrogel composition has a strength of 0.1kgf / cm ² to 1.5kgf / cm ^2. Alkali hydrolysis treatment of the degumming silk raw material to obtain silk fibroin powder;
Dissolving silk fibroin powder in an aqueous urea solution;
Gelling the composition of said step; And
The method of producing a silk hydrogel mask comprising the step of molding the gelation of the step to the desired shape. The method of claim 7, wherein
The gelation is 0.1 seconds to 10 minutes to prepare a silk hydrogel mask. The method of claim 7, wherein
The gelling step and the forming step is a method of producing a silk hydrogel mask made of a continuous process. Silk hydrogel mask prepared by the manufacturing method according to any one of claims 7 to 9.

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