KR20140069930A - Silk hydrogel composition and silk hydrogel mask - Google Patents

Abstract

The present invention provides a silk hydrogel composition containing 0.01-30 wt% of a silk fibroin powder and 0.01-10 wt% of urea, and a method for manufacturing a silk hydrogel mask using the same. According to the present invention, the solubility of silk fibroin in a raw material is increased and the silk fibroin is gelled for a short period of time, thereby allowing a continuous process, and the silk hydrogel can be packaged immediately after being cut, thereby requiring no additional process and thus improving production safety and efficiency. Further, the silk hydrogel composition according to the present invention can control the moisture release rate while exhibiting excellent hardness and adhesive strength, reduce irritation as it is a silk material having high affinity with the human body, and be effective in maintaining the moisture content and the moisturizing capability, removing dead skin cells, brightening, and reducing redness, and thus can be used in a cosmetic mask.

Description

SILK HYDROGEL COMPOSITION AND SILK HYDROGEL MASK < RTI ID = 0.0 >

TECHNICAL FIELD 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 silk hydrogel composition and a silk hydrogel mask using the silk hydrogel composition.

Recently, skin care using hydrogels has been applied in various fields such as cosmetics and skin care. The hydrogel mask is the most technologically advanced product considering the efficacy, effects and formulations of the mask. It can be used to crosslink the effective cosmetic material to the water-soluble polymer in the hydrogel, It is a skin care delivery system designed to store the cosmetic ingredients inside the polymer and deliver the efficacy and effectiveness of the active ingredient continuously and effectively. The hydrogel mask has a disadvantage that it has no flowing down than the sheet mask type in which the essence is impregnated in the nonwoven fabric and is superior in feeling on use but poor in physical strength. The hydrogel itself is too slippery to adhere to the skin, and the skin becomes sharper and it is difficult to sufficiently transmit the effective substance to the skin. There are attempts to apply silk fibroin to overcome the physical disadvantages of such hydrogels.

On the other hand, silk generally has two kinds of proteins, fibroin and sericin, which are different from each other in the degree of orientation of the fibers, the content of amino acid constituents, and molecular weight and crystallinity. Fibroin: Sericin has a ratio of 75:25, and sericin is generally soluble in water, so it is usually removed from the refining process, leaving only fibroin. This is generally used for medical and medical purposes. Silk fibroin has excellent film forming ability and has no rejection in human use. Silk fibroin films or hydrogels have good dissolved oxygen permeability in the wet state, similar to human skin, suggesting applicability of the films in wound dressings and artificial fingers systems.

Conventionally, in the case of making a skin care mask with silk, most of the sheet masks were immersed in the essence, and sericin, which is not fibroin, was used. The water-soluble sericin has lower molecular weight than the water-insoluble fibroin, which is easy to use and its natural moisturizing function is widely known. There is no case of using sericin as a hydrogel mask because sericin having a low molecular weight can be used as an effective ingredient in a hydrogel mask but hard to use as a gelling agent. Fibroin, a polymer, is sufficient to be used as a gelling agent by causing structural changes when subjected to physical or chemical stimuli. When fibroin is used as a gelling agent, adhesion is more excellent than general hydrogel, and effective substance transfer is facilitated. Although there is a hydrogel mask using silk fibroin in the past, it has a disadvantage that productivity is inefficient because a feeling of use is reduced and a fibroin solution is used.

Silk fibroin is prepared as a solution through an alkaline refining method which is mainly refined by treating with alkaline water such as soap refining or soap soda at a suitable temperature for a certain period of time. The silk fibroin solution without sericin has the advantage that it is not necessary to dissolve the silk fibroin solution when it is applied to the formulation. However, the silk fibroin solution with low stability must be stored in refrigeration as well as precipitated after physical shock or after a certain period of time . When hydrogels are made with silk fibroin solution, there is a major drawback that the gel is completed by immersing in alcohol or adding a metal salt, and the final gelation time is not immediate. On the other hand, silk fibroin powder is strong against physical shock, and it is not only stored at room temperature but also excellent in price. However, it has a disadvantage in that its solubility is lower than that of a solution.

Since the film made of silk fibroin can be dissolved in water without further manipulation due to the dominant random coil protein structure, the structural characteristics of the protein can be improved by heat, mechanical stretching, immersion in a polar organic solvent, Lt; RTI ID = 0.0 > beta-sheet < / RTI > This variation in structure leads to water insolubility but has a more flexible system than some pure silk fibroin film.

There are many masks using silk, but there are no masks that make good use of their characteristics. An ideal silk hydrogel mask capable of taking advantage of the characteristics of the silk and capable of compensating for the disadvantages of the hydrogel is required.

Published Patent No. 10-2007-0014485

In order to solve the above-mentioned problems, the present invention provides a method for producing a silk hydrogel mask and a silk hydrogel mask which can dissolve silk fibroin powder in an aqueous solution of urea to increase the solubility of silk fibroin in raw material, For that purpose.

In order to solve the above-mentioned problems, 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 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 comprise a thickening agent.

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 is 0.01 to 30 wt% based on the total weight of the composition, and the acrylic thickener is 0.01 to 5 wt% based on 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.

The present invention also relates to a method for producing silage fibroin powder, comprising the steps of: dissolving silk fibroin powder in an aqueous urea solution;

Gelling the composition of the step; And

And shaping the gelation of the above step into a desired shape. The present invention also provides a method of manufacturing a silk hydrogel mask.

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

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

In addition, the present invention provides a silk hydrogel mask produced by the above production method.

According to the production method of the silk hydrogel composition of the present invention, since the solubility of the raw material of silk fibroin is increased and the gel can be gelled in a short time, continuous processing is possible and packaging is possible immediately after cutting. In addition, the silk hydrogel composition of the present invention is capable of controlling the water release rate while exhibiting excellent strength and adhesion, and is a silk material having high affinity with the human body. Therefore, the silk hydrogel composition can reduce irritation and improve moisture content, It is effective for brightening and reduction of redness, so it can be used for cosmetic mask.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a schematic view of a conventional method for producing a silk hydrogel.
2 is a schematic view of a method for producing a silk hydrogel according to an embodiment of the present invention.
FIG. 3 is a graph illustrating moisture release rate of a silk hydrogel according to an embodiment of the present invention.
4 is a graph showing the water content of a silk hydrogel according to an embodiment of the present invention.
5 is a graph showing the moisture content of a silk hydrogel according to an embodiment of the present invention.
FIG. 6 is a graph showing the optical characteristic change rate of a silk hydrogel according to an embodiment of the present invention.

Hereinafter, preferred embodiments of the present invention will be described in detail in order to facilitate the present invention by those skilled in the art.

A conventional method for producing a hydrogel mask is shown in Fig. Since the conventional hydrogel takes a long time to gel, the contents 10 are taken out (A) and placed on the tray 20, and after metal salt or alcohol is added, the gel is gelled for several hours, for example 24 hours, Discontinuous process (Fig. 1).

As shown in FIG. 2, the continuous process of allowing the coating (B) to start and the rapid gelation to proceed so that the cut (40) can be continuously performed while the contents (10) A method of manufacturing a mask is provided.

The present invention provides a silk hydrogel composition comprising from 0.01 to 30% by weight of silk fibroin powder and from 0.01 to 10% by weight of urea based on 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 thickening agent. 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 ² to 1.35 kgf / cm < ² >

The silk hydrogel composition of the present invention comprises the steps of dissolving silk fibroin powder in an aqueous urea solution; Gelling the composition of the step; And molding the gelation of the above step into a desired shape.

Hereinafter, a method for producing a silk hydrogel mask will be described in detail.

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

The method for obtaining the silk fibroin powder to be used in the present invention is not particularly limited, and a known method can be used. Preferably, the silk fibroin powder may be prepared by treating a de-moistened silk raw material with an aqueous alkali solution and then pulverizing the silk fibroin powder. The silk fibroin solution has low stability and needs to be refrigerated. After a certain period of time, the silk fibroin powder has excellent stability. In the present invention, the silk fibroin powder itself acts as a gelling agent, so that gelation can be performed in a short time of several seconds to several minutes without an additional thickener or gellant or with a small amount of the thickener or gellant.

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

In the present invention, the silk fibroin powder 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 the amount is less than 0.01% by weight, the amount of the silk fibroin powder as a gelling agent is too small to reveal its inherent characteristics. If the amount is more than 30% by weight, salt ions remaining in the silk fibroin powder interfere with gelation and a proper hydrogel can not be obtained. However, 1 to 5% by weight is most preferred because an appropriate amount of salt ions helps gelation.

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

The urea aqueous solution may contain urea in an amount of 0.01 to 10% by weight, preferably 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, it is not effective to improve the solubility of the silk fibroin powder. As the amount of urea increases, the effect may be increased because of the exfoliation and whitening effect. However, when the amount of urea is more than 10% by weight, not only the irritation to the skin but also the deterioration of the usability of the hydrogel is caused.

The concentration of the urea aqueous 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 thickening agent. Examples of the thickener include, but are not limited to, butylene glycol, glycerin, 1,2-hexanediol, dimethicone and cyclomethicone, hydroxyethyl acrylate, sodium polyacrylate, polymethyl methacrylate, 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 present in an amount of 0.01 to 30% by weight, preferably 0.1 to 5% by weight, based on the total weight of the composition. If the content is less than 0.01% by weight, the viscosity becomes too low to increase the loss. When the content is more than 30% by weight, the viscosity becomes too high and it is difficult to mix.

The acrylic thickener may be used in an amount of 0.01 to 5% by weight, preferably 0.1 to 2% by weight based on the total weight of the composition. If the content is less than 0.01% by weight, the viscosity becomes too low to increase the loss. When the content exceeds 5% by weight, the viscosity becomes too high and it is difficult to mix.

Then, a step of gelling the silk hydrogel composition of the above step is performed.

The gelation may be by natural cooling.

In this case, the gelation time may be 0.1 second to 10 minutes, preferably 0.1 second to 3 minutes, but is not limited thereto.

Specifically, when the gel solution of the obtained silk hydrogel composition is poured into a coater at a temperature of 10 to 80 캜, a gel is formed within a few seconds to several minutes by natural cooling while being coated. The gelling time may be 0.1 seconds to 3 minutes as described above. The gelatinized silk hydrogel can be molded in a shaped mold or cut into a mold of a mold suitable for the shape of a part of the human body to be made into a cosmetic mask.

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

That is, as shown in FIG. 2, the process for producing a silk hydrogel mask according to the present invention is capable of a continuous process due to a short gel time. In the conventional preparation of the hydrogel mask, since the gelling time takes a long time, it differs from that required by the discontinuous process (FIG. 1) in which the gelation is required for several hours, for example, 24 hours after the addition of the metal salt or the alcohol.

Further, the present invention provides a silk hydrogel mask having a strength of 0.1 kgf / cm ² to 1.5 kgf / 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 1.35 kgf / cm ² It can have strength.

The silk hydrogel composition of the present invention is a cosmetic agent or a cosmetic agent that is rapidly transferred from the hydrogel composition to the skin due to the silk fibroin and is rapidly transferred to the skin by controlling the migration rate of ingredient constantly, The drug can be adjusted to release only acceptable quantities.

In addition, the silk hydrogel composition of the present invention exhibits a tightening effect that the hydrogel itself shrinks when a structural change is caused by the temperature or physical change of the silk fibroin. As a result, the adhesion of the hydrogel itself is excellent, And it provides convenience when it is used as a cosmetic pack to ensure the activity. This is characteristic of only silk hydrogels that are hardly visible in conventional hydrogel masks. Also, due to the tightening effect, it can help in elasticity management and wrinkle management, and also in pore contraction. In addition, since the natural silk has high affinity for the skin, the silk hydrogel mask according to the present invention has reduced irritation as compared with the conventional 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 excellent strength enhances the elasticity of the silk hydrogel, which not only increases the feeling of use but also is advantageous for cutting and packaging at the time of manufacture.

In addition, the structural variation of silk fibroin in the composition of the present invention makes it possible to control the water content. The present inventors have found that hydrogels containing silk fibroin have higher water content than general hydrogels, which means that they can supply more moisture to the skin. This is due to the structural characteristics of silk fibroin.

The silk hydrogel composition of the present invention helps to salt-in low-solubility silk fibroin powder by using urea, which removes minute exfoliation from the skin. Therefore, the silk hydrogel of the present invention has a sufficient water supply as well as a skin brightening effect and a red radish reduction effect as compared with a general hydrogel.

The silk hydrogel composition of the present invention improves the weak stability of the silk fibroin solution by using the silk fibroin powder and enables gelation in a short time within a few seconds to several minutes without any additional process, .

The present invention will be described in more detail through the following examples. However, the examples are for illustrating the present invention, and the scope of the present invention is not limited thereto.

[Manufacturing Example 1] Production of silk fibroin powder

The natural silk and silkworm cocoons were boiled in an aqueous solution of sodium carbonate 0.5% (w / v) for one hour at 85 ° C, washed several times with distilled water, and then dried at 90 ° C for 24 hours. The desaminated silk was subjected to alkali hydrolysis. For this purpose, water was filled with 10 to 40 liquids on the basis of fibroin. The alkali used here is a solution of calcium hydroxide [Ca (OH) ₂ ] or barium hydroxide [Ba (OH) ₂ ], adjusted to a concentration of 0.4 to 2.0 w / v% (11.5 to 12.4 based on the pH of the solution) , Heated at 90 to 100 DEG 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 the alkali was no longer 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

The natural silk and silkworm cocoons were boiled in an aqueous solution of sodium carbonate 0.5% (w / v) for one hour at 85 ° C, washed several times with distilled water, and then dried at 90 ° C for 24 hours. The 8% by weight of the desaminated silk was dissolved in a solution prepared from CaCl ₂ : dH ₂ O: EtOH in a molar ratio of 1: 8: 2 at 85 ° C for 3 minutes, and then put into a dialysis membrane having a molecular weight of 3,500, . The final concentration of the silk fibroin solution was 4%.

[Example 1-3]

The components and contents of the composition for a hydrogel mask pack used in Examples and Comparative Examples are shown in Table 1 below. The unit of the content is expressed as% by weight with respect to the total composition.

(weight%) Silk fibroin powder (Preparation Example 1) Silk fibroin solution (Preparation Example 2) Urea glycerin Butylene glycol Xanthan gum Locusvinst 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

The hydrogel mask prepared in Example 1 and Comparative Example 1 was cut into pieces each having a size of 0.07 cm × 1.2 cm × 4 cm. The cut pieces were placed on the skin and mass was measured in units of 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 degree

The hydrogel masks prepared in Examples 1 and 3 and Comparative Example 1 were cut into pieces having a size of 0.07 cm x 1.2 cm x 4 cm. The slice was placed on the skin. After 15 minutes, the total area was measured to measure the shrinkage of the hydrogel, and the tightening effect was indirectly measured. The hydrogel shrinkage was expressed as [(initial area) - (area after shrinkage)] / (initial 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] Reduction effect of irritation

The hydrogel mask prepared in Example 1 and Comparative Example 1 was cut to a size of 0.07 cm x 1.2 cm x 4 cm. 100 subjects were asked to place two slices on their arms and to assess the degree of stimulation after 30 minutes. The results are shown in Table 3 below.

Example 1 Comparative Example 1 Mask with stimulation 7 people 93 people

[Experimental Example 4] Measurement of tensile strength

The hydrogel mask packs prepared in Examples 1 and 3 and Comparative Example 1 were cut into pieces having a size of 1.0 cm x 8.0 cm x 0.07 cm. The sections were tensioned at a rate of 10 mm / min at both ends with a tensile tester (Minimat, Rheometric Scientific, USA) to measure the shear stress at the time of fracture of the adhesive surface. Each experiment was measured 5 times and the mean value was calculated. 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 mask prepared in Example 1 and Comparative Example 1 was cut to a size of 0.07 cm x 1.2 cm x 4 cm, completely dried in an oven at 80 ° C, and then immersed in water to swell, and the degree of swelling was determined by the following equation. The results are shown in Fig.

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

[Experimental Example 6] Measurement of feeling

The hydrogel masks prepared in Examples 1 and 2 and Comparative Example 1 were made into a face shape. A questionnaire survey was conducted on 100 women in their 20s and 30s. The results are shown in Table 5 below. Most participants were satisfied with all items for the hydrogels containing silk (Examples 1 and 2). Compared with Example 1 and Example 2, the higher the urea content, the higher the satisfactory satisfaction with moisture and moisturizing because the effective ingredient penetrated after the exfoliation, and the satisfaction with the brightening was particularly high.

Product Satisfaction Moisture Resilience Moisturizing Adhesion Contraction force Brightening Example 1 82 people 42 people 52 people 47 people 53 people 67 people 18 people Example 2 12 people 51 people 39 people 51 people 38 people 31 people 76 people Comparative Example 1 6 people 7 people 9 people 2 people 9 people 2 people 6 people

[Experimental Example 7] Water content measurement

The hydrogel mask prepared in Example 1 and Comparative Example 1 was cut into pieces having a size of 0.07 cm x 1.2 cm x 4 cm. The slice was placed on the subject's ball area and the moisture content was measured with a corneometer after 15 minutes. The results are shown in Fig.

[Experimental Example 8] Brightening and redness reduction effect

The hydrogel mask prepared in Example 1 and Comparative Example 1 was cut into pieces having a size of 0.07 cm x 1.2 cm x 4 cm. Two slices were placed under both eyes. Ten minutes later, the optical characteristics of the patient's cheekbones were measured using a polarimetric device to evaluate the improvement of luminance and redness. The results are shown in Fig.

[Experimental Example 9] Comparison of solubility by urea

A hydrogel was prepared by the method of Example 1 and Comparative Example 2. When observed with naked eyes, a smooth hydrogel was completed in Example 1, whereas in Comparative Example 2 in which urea was omitted, white silk fibroin crystals were visually observed.

[Experimental Example 10] Comparison of gelation speed 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 the two contents were prepared 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 The set includes
11 Feed tube
20 trays
30 protective film
40 cutters
A Contents removal
B coating

Claims (10)

From 0.01 to 30% by weight of silk fibroin powder and from 0.01 to 10% by weight of urea based on the total weight of the composition. The method according to claim 1,
Wherein the silk fibroin powder has a molecular weight of 1,000 to 400,000. The method according to claim 1,
Wherein the composition further comprises an agitation agent. The method of claim 3,
Wherein the thickener is a silicone thickener, an oil thickener, or an acrylic thickener. 5. The method of claim 4,
Wherein the silicone thickener or oil thickener is 0.01 to 30 wt% based on the total weight of the composition, and the acrylic thickener is 0.01 to 5 wt% based on the total weight of the composition. 6. The method according to any one of claims 1 to 5,
Wherein the composition has a strength of from 0.1 kgf / cm ² to 1.5 kgf / cm ² . Dissolving the silk fibroin powder in an aqueous urea solution;
Gelling the composition of the step; And
And molding the gelation of the step into a desired shape. 8. The method of claim 7,
Wherein the gelation is performed for 0.1 seconds to 10 minutes. 8. The method of claim 7,
Wherein the gelation step and the forming step comprise a continuous process. A silk hydrogel mask produced by the method according to any one of claims 7 to 9.

Images