KR101635923B1 - Manufacturing method of Silk fibroin films using spin drying method - Google Patents

Abstract

The present invention relates to a method for producing a silk fibroin film using a spin drying method.
A method of manufacturing a silk fibroin film using the spin drying method of the present invention comprises: a first step of preparing a solution containing silk fibroin; And a second step of preparing a silk fibroin film having a plate shape by immersing the solution in a cylinder and spinning it.
According to the present invention, it is possible to produce a film having both smooth and uniform shapes on both surfaces, and to produce a film in a shorter time than a conventional casting drying method, A method for producing fibroin film is provided.

Description

Technical Field [0001] The present invention relates to a method of manufacturing a silk fibroin film using a spin drying method,

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for manufacturing a silk fibroin film using a spin drying method, and more particularly, to a method for manufacturing a silk fibroin film using a spin drying method developed to produce a smooth and uniform surface using a silk fibroin ≪ / RTI >

Silk fibroin is a typical natural polymer material extracted from silkworms and has been used for many years as an engineering material such as textile materials and sutures.

Silk fibroin has been attracting much attention as an artificial skin material having excellent biocompatibility because it has excellent cell adhesion ability and proliferation effect on fibroblast and keratinocyte while causing little inflammatory reaction when applied to living body. Unlike other natural polymer materials, silk fibroin can easily obtain a large amount of pure protein through insects. Because of its excellent biocompatibility, it does not cause rejection to the human body without the special purification process, and the powder, membrane, Gel, and so on.

Recently, studies on the application of biomedical applications using silk fibroin have been actively carried out because of the structural and physically similar characteristics with the substrate of the cell, and it is known that the silk fibroin It is evaluated as a material.

Related prior arts are disclosed in Japanese Laid-Open Patent Publication No. P2014-51579A (published on Mar. 20, 2014, name: a method for producing a dried silk fibroin porous body).

However, even if silk fibroin with excellent effect is manufactured, it is difficult to uniformly produce a thin film of 10 μm or less when fabricating a silk fibroin fiber film through a general drying method (casting drying method). In addition, It is impossible to be flat and smooth. In addition, it takes a long time to produce the film and the tensile strength is weak, so it is difficult to apply to clinical practice.

It is an object of the present invention to provide a silk fibroin which can produce a film having both smooth and uniform surfaces on both sides thereof and can produce a film in a shorter time than a conventional casting drying method, And a method for producing the film.

It is to be understood that both the foregoing general description and the following detailed description are exemplary and explanatory and are not intended to limit the invention to the particular embodiments that are described. It is to be understood that both the foregoing general description and the following detailed description are exemplary and explanatory and are not restrictive of the invention, There will be.

In order to accomplish the above object, the present invention provides a method of manufacturing a silk fibroin film using a spin drying method, comprising the steps of: preparing a solution containing silk fibroin; And a second step of producing a silk fibroin film having a shape of a smooth shape and a uniform shape.

In the first step, the solution is prepared by dissolving silk fibroin obtained by separating from cocoon, refining, and then dialyzing it.

In the first step, the solution contains the silk fibroin in an amount of 1 to 25 wt% based on the total weight of the solution.

In the second step, the rotary drying is performed at a ratio of 1:50 to 500 between the solution and the rotation speed (rpm).

Preferably, in the second step, the spin drying is performed at a temperature of 24 to 27 ° C. for 2 to 3 hours at 500 to 1,500 rpm per 5 ml, thereby producing a film having a thickness of 10 μm to 90 μm .

And the pattern or pattern is stamped or inserted into the inside of the cylinder before the rotary drying in the second step to produce a film on which a pattern or a pattern is printed.

Another method for producing a silk fibroin film using the spin drying method of the present invention comprises a first step of preparing a solution containing silk fibroin and a natural polymer or a synthetic polymer and a step of spin drying the solution to prepare a silk fibroin having a plate- And a second step of producing a fibroin film so as to form a smooth and uniform type of film.

According to the present invention, it is possible to produce a film having both smooth and uniform surfaces on both sides, and to produce a film in a shorter time than a conventional casting drying method, It is possible to overcome the limitations of existing film production methods.

1 is a view showing a process for producing a silk fibroin film using the spin drying method of the present invention.
2 is a view showing transparency of a silk fibroin film.
A, C; The silk fibroin film produced through the spin drying method developed in the present invention
B, D; The silk fibroin film produced by the conventional drying method, casting drying method
3 is a view showing the tensile strength of the silk fibroin film.
A: Tensile strength of the film according to the concentration of the silk fibroin solution
B; 12 wt% silk fibroin solution was used to measure the tensile strength
C: Tensile strength of film produced by conventional casting drying method and rotary drying method
4 is a view showing a surface observation observation of a silk fibroin film through a scanning electron microscope
A; Silk fibroin film produced by rotary drying method
Flat, uniform surface without bending.
B; Silk fibroin film produced by casting drying method
; Roughness indicates rough and uneven surface.
5 is a view showing a surface observation observation of the silk fibroin film through an atomic force microscope
A; Silk fibroin film produced by rotary drying method
; The surface shows a flat, uniform surface with no bending.
B; Silk fibroin film produced by casting drying method
; The surface is rough, rugged and bends
FIG. 6 shows the cytotoxicity and proliferation rate of the silk fibroin film through CCK-8.
FIG. 7 is a diagram showing cell affinity and proliferation rate through DAPI staining.
A, B, C; Silk fibroin film (1st, 3rd, 7th day)
D, E, F; Silk fibroin film produced by casting drying method (1st, 3rd, 7th day)
8 is a view showing a micropatterning state of a silk fibroin film using a rotary drying method. - One side is kept smooth and the other side is micro patterned to show stripes (A, section, B, surface 1, C, surface 2)
9 is a view showing a lens shape of a silk fibroin film using a rotary drying method.

The terms, techniques, and the like described in this specification are used in the meaning commonly used in the technical field to which the present invention belongs, unless otherwise specified. Hereinafter, the present invention will be described in detail.

The method of manufacturing a silk fibroin film using the spin drying method of the present invention has not been studied and reported in the past, and is a new method to overcome the limitations of the casting drying method which is a conventional method of producing a silk fibroin film.

Specifically, silk fibroin is a natural polymer, and has various limitations in producing a film alone without a synthetic polymer or a mixture. As a typical example, it is not possible to uniformly produce a thin film having a thickness of 10 탆 or less, and it is impossible to flatten and smooth both the upper and lower sides of a thick film having a thickness of mm. In addition, there is a drawback that it takes a long time to produce a film.

However, in the spin drying method applied in the present invention, it is possible to easily and selectively produce a thick film in mm thickness from a thin film of 10 μm or less for silk fibroin. Especially, the drying time is shorter than the conventional film making (casting drying method) . This means that it is possible to easily produce films having various thicknesses according to the respective conditions if the rotation speed is controlled, the concentration of the silk fibroin solution is adjusted, the amount of the silk fibroin solution is adjusted, or the diameter of the cylinder is changed.

In addition, it showed better tensile strength than the film produced by the casting drying method (ordinary film production method), and it was confirmed that transparency was also excellent.

Based on these results, the method of manufacturing the silk fibroin film using the spin drying method developed in the present invention can be applied to the upper surface and the lower surface by using a natural polymer such as silk fibroin or other natural or synthetic polymer, The present invention can be applied not only to a biomembrane but also to various films requiring transparency such as contact lenses and various films requiring a refractive index (Fig. 9) Or microregions were patterned or inserted to produce a film having a pattern of nano unit or a pattern of micro unit, and the applicability to a drug delivery system was confirmed.

A method for producing a silk fibroin film using the spin drying method of the present invention will be described in detail with reference to FIG.

1. First step; Manufacture of solutions containing silk fibroin

This step is a step for producing a solution containing silk fibroin.

As described, silk fibroin is separated from a thread extracted from a silkworm cocoons, and has excellent biocompatibility and does not affect any surrounding tissues. Therefore, it is produced in various forms such as powder, gel, and aqueous solution, Lt; / RTI >

In this step, in order to prepare the silk fibroin in the form of a solution, the silk fibroin fiber is first extracted from the silkworm cocoon through a refining process for removing sericin and impurities, and the silk fibroin fiber is dissolved in an aqueous solution of calcium chloride or lithium bromide, ≪ / RTI >

At this time, the concentration of silk fibroin contained in the solution can be selectively controlled depending on the thickness of the film to be produced, and more preferably, the silk fibroin is added to the solution containing the silk fibroin in an amount of 1 to 25 wt% For controlling the concentration of silk fibroin, the concentration may be adjusted by diluting with distilled water or by using polyethylene glycol (polyethylene glycol).

When the silk fibroin is contained in an amount of less than 1 wt%, 99% of water evaporates in the process of producing the following film, resulting in a low efficiency. Thus, when the silk fibroin is contained in an amount exceeding 25 wt% The solution state is so unstable that spin drying is difficult in the process of preparing a film described below. Therefore, it is difficult to form a film having a desired smooth surface according to the present invention.

Further, in this step, in addition to the solution, a natural polymer or a synthetic polymer may be further added.

In other words, when a natural polymer or a synthetic polymer is further included, physical properties such as tensile strength and elasticity value are further improved, and thus it is easily usable for applications requiring elasticity, in order to improve the flexibility of the silk fibroin film .

Examples of the natural polymer or synthetic polymer used herein include collagen, gelatin, chitin, chitosan, keratin, cellulose, fibronectin, elastin, fibrinogen, pibromodulin, laminin, tenacin, bitonectin, alginate , Polylactic acid (PLA), polyglycolic acid (PGA), copolymers of polylactic acid and polyglycolic acid (PLGA), polycaprolactone (polycaprolactone), polylactic acid ; PCL), poly {poly (ethylene oxide) terephthalate-co-butylene terephthalate} (PEOT / PBT), polyphosphoester (PPE), polyphosphazene (PPA), polyanhydride ; PA), polyortho ester {polyortho ester; POE}, pluronic 127, glycerin, poly (propylene fumarate) -diacrylate; PPF-DA} and polyethylene glycol diacrylate; PEG-DA}, and the natural polymer or synthetic polymer is contained in an amount of 1 to 10 wt% based on the total weight of the solution. If it is contained less than 1 wt%, it is difficult to obtain higher physical properties compared to the use of silk fibroin alone. If it exceeds 10 wt%, its concentration is too high, so that the merit of silk fibroin single film such as transparency is lowered This is because problems can arise.

In this case, the terms "transparent" and "transparency" are used in a sense including a transparent state in which the inside of the film can be observed in addition to the completely transparent state.

2. The second step; Manufacture of silk fibroin film

In this step, the solution is put in a cylinder, and then it is spin-dried to prepare a silk fibroin film having a plate shape.

To explain, in order to spin-dry the solution containing the silk fibroin, it is first placed in a cylinder. At this time, the diameter of the cylinder is selectively adjusted according to the thickness of the film to be manufactured, and the film is manufactured by adjusting the rotational speed of rotation.

The ratio of the solution containing silk fibroin to rpm applied during spin drying is suitably about 1: 50 to 500. It is less than 0,01 N when the centrifugal force (F = mrw ² / m = mass of solution, r = radius of cylinder, w = The force of the present invention does not reach the minimum force required to produce the desired film, so that the film surface may not be smooth and may be manufactured in a rough state. If the film thickness exceeds 500 rpm, the film thickness variation is insufficient .

In an embodiment of the present invention, an inner diameter of 80 mm, an outer diameter of 90 mm, and a height of 100 mm is used, and the spin drying is performed at a temperature of 24 to 27 ° C at 500 to 1500 rpm for 5 to 3 hours , And the thickness of the silk fibroin film to be produced is made to be 10 mu m to 90 mu m. In other words, when the concentration of silk fibroin was 12 wt%, it was confirmed that the average thickness of the silk fibroin film at 500 rpm was 70 to 90 탆, 40 to 60 탆 at 1000 rpm, and 10 to 30 탆 at 1500 rpm.

As described above, according to the present invention, a variety of film thicknesses can be easily formed in a short time by suitably selectively applying the amount of the solution, the size of the cylinder, and the number of revolutions, and a film of both smooth and uniform shapes is produced It is possible to overcome the limitations of the conventional film production method.

In this step, as shown in FIG. 8, it is also applicable to a drug delivery system or the like by manufacturing a pattern or a pattern printed by inserting or inserting a pattern or a pattern into the inside of the cylinder before the rotary drying. In this case, as a method of inserting a pattern, a pattern to be printed on an OHP film or the like is inscribed on the inside of the cylinder, and after the rotational drying process, the film is completely dried and then the attached OHP film is removed so that the pattern and the pattern are transferred to the film .

Hereinafter, the present invention will be described in more detail with reference to Examples and Experimental Examples. However, these Examples and Experimental Examples are for illustrative purposes only and are not intended to limit the scope of protection of the present invention.

< Example  1 > using the spin drying method of the present invention silk fibroin  Film manufacturing

1) Preparation of silk fibroin solution

A cocoon of Bombyx mori 0.02 M Na ₂ heated to 100 ℃ for 60 minutes in a CO ₃ solution, and after the refining process of washing three times with distilled water to remove impurities and the like sericin proteins to give pure silk fibroin. The refined silk fibroin was dissolved in a mixed solvent of CaCl ₂ : H ₂ O: EtOH = 1: 8: 2 molar ratio at 90 ° C. for 2 hours and then distilled in distilled water for 72 hours, and 6 w / Fibroin solution (SF) was prepared. It was concentrated using polyethylene glycol (PEG) for various concentrations of silk fibroin. The prepared silk fibroin solutions were 8 wt%, 10 wt% and 12 wt%, respectively.

2) Manufacture of silk fibroin film

As shown in Fig. 1, a silk fibroin film is produced as follows.

That is, a silk fibroin solution of 80 mm in inner diameter, 90 mm in outer diameter and 100 mm in height, and 5 mL of silk fibroin solution at an rpm ratio of 1: 200 were dried at 1000 rpm at 26 ° C for 2 to 3 hours To prepare a silk fibroin film.

&Lt; Comparative Example 1 > Silk film prepared by the casting drying method

A silk fibroin film prepared by a conventional dry casting method was used. In the preparation method, 5 mL of silk fibroin solution was put in a 90 × 15 mm Petri dish, and one side was dried in an indoor temperature of 26 ° C. for 48 hours to prepare a film having an average thickness of 40-60 μm. The thus-finished silk fibroin film was hydrated at 65 DEG C for 15 minutes to be crystallized and used as a control of the present invention.

< Experimental Example  1> Check the sharpness of the letter Transparency of silk fibroin film )

1. Experimental Method

The transparency of the two types of films prepared by the casting drying method and the rotary drying method was measured. As the experimental method, the distance between the bottom and the film was 1 cm and the sharpness of the text was confirmed.

2. Experimental results

As shown in FIG. 2, in order to confirm the transparency of the silk fibroin film produced by the casting drying method and the rotary drying method, the degree of the text was observed at a height of 1 cm from the bottom of the written text.

The film used for the transparency measurement was a film made using 12% silk fibroin. Both of the films were formed to have the same thickness except that the thickness was 90 μm. It was observed that the films (B and D) prepared by the casting drying method, which is a conventional film making method, have significantly lower transparency than the films (A and C) produced by the spin drying method.

In addition, the film (B, D) produced by the casting drying method showed that the portion where the silk fibroin film was located was totally turbid and the sharpness of the black letter was also decreased. On the other hand, the spinning dry silk fibroin films (A and C) were much more transparent than the films (B and D) produced by the casting drying method and showed a clear lettering color.

This result is presumed to be due to the degree of refraction of light depending on the degree of roughness or curvature of each film surface. Therefore, it was found that the silk fibroin film produced by the rotary drying method exhibited a smooth surface and high transparency than the casting drying method.

< Experimental Example  2> Check strength ( Tensile strength )

1. Experimental Method

The films were fabricated by casting drying method and spin drying method using silk fibroin solution. Tensile strength (QM100S, Qmesys, Korea) was used for comparative measurement of tensile strength and change of each film. The specimen size was averaged 2.6 mm wide, 50 Kgf, and 40 mm for each specimen thickness. The averaged silk fibroin film was attached to each tensile strength machine and tension was measured. Tensile tests were carried out using 20 specimens per sample and statistical results were obtained.

2. Experimental results

3 is a graph showing the tensile strength of the silk fibroin film through the rotary drying method developed in the present invention. Each chart shows the tensile strength (A) of the film produced according to the concentration of the silk fibroin solution, the tensile strength (B) according to the thickness of the silk fibroin film, the silk fibroin film through the rotary drying method and the conventional casting drying method (C) by measuring the tensile strength of the resulting silk fibroin film.

The silk fibroin films were prepared by rotary dry process and the tensile strength was measured using an average thickness of 40 ~ 60 ㎛. The tensile strength of the films prepared with 8 wt% silk fibroin solution was 52.73 ± 10.61 MPa on average and showed elongation of about 1.7%. The tensile strengths of films prepared with 10 wt% and 12 wt% solutions were 63.74 ± 13.39 MPa and 76.00 ± 1.38 MPa, respectively, and elongation rates were 2.2% and 2.3%, respectively.

These results indicate that tensile strength increases with increasing silk fibroin concentration.

(A), 40-60 ㎛ (b), and 70-90 ㎛ (c), respectively, using a 12% silk fibroin solution with the highest tensile strength, Three kinds of films were produced and tensile strength was measured (Fig. 3B). The average tensile strength of (a) was 34.73 ± 11.29 MPa and (b) was 42.64 ± 6.04 MPa. As the thickness increased, tensile strength increased. However, the tensile strength of the thickest film (c) averaged 35.15 ± 11.49 MPa, showing a lower tensile strength than (b).

These results suggest that the thickness of 70 ㎛ or more causes a brittle phenomenon, which is one of the characteristics of silk fibroin film, resulting in lower tensile strength.

Based on the above results, a film with a thickness of 40-60 ㎛ was produced by spin drying and casting drying method using 12% silk fibroin solution with the highest tensile strength. The tensile strength of each film was found to be 17.35 ± 1.85 MPa on casting and 21.29 ± 3.24 MPa on spinning dried film, 1.6%), the elongation of the cast film was measured to be 0.5% higher at 2.1%.

That is, the spin drying method can withstand a force as high as about 4 MPa than the conventional casting drying method, while the casting drying film has a lower tensile strength and a better elongation.

< Experimental Example  3> Silk membrane  Cross section observation ( Scanning Electron  Microscope ( SEM )

1. Experimental Method

In order to compare the surface of the silk fibroin film made by the casting drying method and the spin drying method, each film was crystallized and then cut and coated with Au-Pd, and the cross section was observed with a scanning electron microscope (RUPRA55V VP-FESEM, Carl Zeiss, Germany) Respectively. Scanning electron microscopy was performed at the Basic Science Research Institute (Chuncheon).

2. Experimental results

As shown in FIG. 4, the surface of the silk fibroin film produced through the spin drying method developed in the present invention and the conventional casting drying method was observed through a scanning electron microscope. The concentration of the silk fibroin solution used in the rotary drying method and the casting drying method was 12% based on the above results, and each film was made using a silk fibroin solution having the highest tensile strength. The average thickness of the film was 40 to 60 μm The surface of the film was observed through the cut portion of the film. The SEM image shows that the silk fibroin film (B) of the conventional casting drying method exhibits a rough rough surface and a rough surface, whereas the silk fibroin film (A) And a flat, uniform surface without any visible light.

Therefore, it was confirmed that the rotating centrifugal force in the cylinder is flat and has a uniform surface symmetry.

< Experimental Example  4> silk  Check the surface roughness of the membrane ( Atomic Force Microscopy ; AFM )

1. Experimental Method

An atomic force microscope (MultiMode 8, Bruker, Santa Barbara CA USA) was used to compare the roughness of the silk fibroin film surface. The thickness of each film prepared by the casting method and rotary drying method was 50 μm, and the concentration of the silk fibroin solution was fixed to 12%. The size of the sample was prepared as 3 mm × 10 mm.

2. Experimental results

Fig. 5 shows the result of producing a silk fibroin film by a casting drying method and a rotary drying method, and observing each film surface (5 x 5 mu m &lt; 2 &gt;) according to the production method with an atomic force microscope. (A) is a silk fibroin film produced by spin drying and (B) is an atomic force microscope photograph of a silk fibroin film produced by casting drying, which is a conventional film making method. The thickness of each film was fixed at 50 탆, and the z value was set at 100 탆.

(A), the arithmetic mean roughness (Ra) is 2.42 nm and the maximum height (Rmax) is 74.7 nm, while the arithmetic average roughness value of (B) is 7.35 nm, which is 4.93 nm higher than (A) . In addition, the maximum height was also 104 nm, which was higher than that of 74.7 nm (A).

These results show that the surface of the silk fibroin film produced by the rotary drying method is smoother and more uniform than the conventional casting drying method. (A), the arithmetic average roughness was 2.42 nm, and the maximum height was measured as high as 74.7 nm even though the roughness of the graph was almost not shown. This is due to scratches and dust caused by external stimuli such as forceps .

< Experimental Example  5> cell affinity and adherence and Degree of culture  Confirm ( Cell proliferation )

1. Experimental Method

Each silk fibroin film was circularized using a biopsy punch of 8 mm in diameter, and 293T GARTP cells were seeded in 48 well Cell Culture Plate and cultured for 1, 3, and 7 days. 6-diamidino-2-phenylindole (DAPI) was used for gross observation, and CCK-8 assay was performed to observe the cell affinity, adhesion and culture of silk fibroin film after 1, The cells were stained using a fluorescence microscope (Imager, M2, Zeiss, USA).

2. Experimental results

FIGS. 6 and 7 show the result of confirming cell affinity and proliferation by seeding 293T GARTP cells on a film made by rotary drying and general drying method, and culturing for 7 days. Each sample used for cell seeding was a film made with a 12 wt% silk fibroin solution and an average thickness of 50 to 60 탆 was used. The nuclei of the cells were stained with DAPI staining and then observed with a fluorescence microscope.

As a result, the number of cells seeded on the film produced by the spin drying method and the casting drying method gradually increased with time.

FIG. 7 (A-C) shows the cells seeded on the film produced by the spin drying method, and (D-F) shows the cells seeded on the film produced by the casting drying method.

In both groups, it was confirmed that the cells adhered and proliferated. However, in the first day of cell seeding, more cells were observed than the film (D) obtained by the casting drying method in the film (A) It was observed that the proliferation of the cells was markedly increased with the passage of time. These results show that the roughness of the surface of the film (DF) produced by the casting drying method is rougher than that of the film (AC) produced by the spin drying method, and the shape of the attached cell As the cells grow at the same height, they show curvature, so they can observe atypical morphology in which the nucleus of the sown seeds (DF) is spread or linear in shape, while the shape is constantly circular.

These results show that the roughness of the surface of the film (DF) produced by the casting drying method is rougher than that of the film (AC) produced by the spin drying method, and the shape of the attached cell Since the cells are not at the same height but grow at the same height, the shape of the nucleus is observed irregularly. All the cells attached to the (AC) group with a smooth surface are present at a uniform height, Nuclear morphology is considered to be observed.

INDUSTRIAL APPLICABILITY As described above, the present invention has been developed to produce a film having smooth surface and uniform shape using silk fibroin. It is intended to overcome the disadvantage of the film obtained by casting using existing silk fibroin. In other words, conventional casting drying method not only can not produce a thick film in mm, but also has a disadvantage that it is difficult to produce a smooth film (or plate) on both sides and a long time for film making (drying time). However, the rotary drying method developed in this study has the advantage that the film can be produced in a faster time than the conventional casting drying method, since both surfaces can be made smooth and uniform. In addition, a film (or a plate) of mm unit can be manufactured from a thin film of 10 μm or less. Therefore, it will be a way to overcome the limitation of existing film production method.

It will be apparent to those skilled in the art that various modifications and variations can be made in the present invention without departing from the spirit or scope of the inventions. Examples and experiments may be implemented. The scope of the present invention is defined by the appended claims, and all differences within the scope of the claims are to be construed as being included in the present invention.

Claims (14)

delete delete delete delete delete delete A first step of preparing a solution containing silk fibroin contained in an amount of 1 to 25 wt% based on the total weight of the solution and 1 to 10 wt% based on the total weight of the solution,
The solution is transferred into a cylinder, and then the solution is spin-dried at 500 to 1500 rpm at 24 to 27 ° C for 2 to 3 hours per 5 ml to have a plate shape, and a silk fibroin film having a thickness of 10 μm to 90 μm And a second step of producing a &lt; RTI ID = 0.0 &gt;
Characterized in that a smooth and uniform form of the film is formed in a shorter time than the conventional casting drying method,
(Method for manufacturing silk fibroin film using spin drying method).
8. The method of claim 7,
In the first step, the natural polymer or synthetic polymer may be selected from the group consisting of collagen, gelatin, chitin, chitosan, keratin, cellulose, fibronectin, elastin, fibrinogen, pibromodulin, laminin, tenacin, bitronectin, alginate, hyaluronic acid, Polylactic acid (PLA), polyglycolic acid (PGA), copolymers of polylactic acid and polyglycolic acid (PLGA), polycaprolactone (PCL), polycaprolactone (PEOT / PBT), polyphosphoester (PPE), polyphosphazene (PPA), polyanhydride (PA), poly (ethylene oxide) Polyortho ester &lt; / RTI &gt; POE}, pluronic 127, glycerin, poly (propylene fumarate) -diacrylate; PPF-DA} and polyethylene glycol diacrylate; PEG-DA}. &Lt; / RTI &gt;
(Method for manufacturing silk fibroin film using spin drying method).
delete 8. The method of claim 7,
Wherein the solution is prepared by dissolving the silk fibroin obtained by separating the solution from the cocoon, refining the solution, and then dialyzing the silk fibroin.
(Method for manufacturing silk fibroin film using spin drying method).
delete delete delete 8. The method of claim 7,
Wherein a pattern or a pattern is printed by inscribing or inserting a pattern or a pattern into the cylinder before the rotary drying in the second step.
(Method for manufacturing silk fibroin film using spin drying method).

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