KR20220136529A - Hydrophilic-hydrophobic nanoporous membrane and manufacturing method thereof - Google Patents

Abstract

The present invention relates to a nanoporous membrane having hydrophilicity-hydrophobicity on both sides and a method for manufacturing the same, and more particularly, a hydrophobic surface formed by electrospinning a first solution containing a hydrophobic polymer and a second solution containing a hydrophilic polymer To provide a nanoporous membrane comprising a hydrophilic surface formed by electrospinning and a method for manufacturing the same. The nanoporous membrane has excellent biocompatibility and can be used for medical purposes.

Description

Nanoporous membrane having hydrophilicity-hydrophobicity on both sides and manufacturing method thereof {Hydrophilic-hydrophobic nanoporous membrane and manufacturing method thereof}

The present invention relates to a nanoporous membrane having hydrophilicity-hydrophobicity on both sides and a method for preparing the same.

A surgical cover material is generally used to protect the surgical site undergoing surgical treatment. For example, a surgical cover material is used for various surgical sites, such as alveolar bone tissue that has undergone dental surgery, bone tissue that has undergone orthopedic surgery, and organ tissue that has undergone surgical or gynecological surgery.

A thin gauze or film is generally used as a surgical cover material. The gauze-type cover material has a feature of having a large number of pores, and since the size of the pores is excessively large compared to 10 to 100 μm, which is a preferred size for tissue regeneration, it is difficult to expect an effect of promoting tissue regeneration, rather There is a disadvantage that bacteria or surrounding tissues are easy to penetrate into the surgical site by the pores. Since the film-type cover material has a dense structure without pores, it is effective in preventing bacteria or surrounding tissues from penetrating into the surgical site, but the effect of promoting tissue regeneration due to the pore structure cannot be expected at all.

On the other hand, a skin cover material for protecting the wounded skin is often used. A typical skin cover material may include a form composed of a foam layer directly in contact with a wound and an adhesive tape that helps the adhesion thereof.

Here, the foam layer serves to prevent external stimuli from being applied to the wound site and to create a wet environment for the rapid recovery of the wound site, and in general, polyurethane foam has been used.

Domestic Patent Publication No. 2001-0031628

In order to solve the above problems, the present invention is to provide a nanoporous membrane manufactured to have hydrophilicity and hydrophobicity on both sides and a method for manufacturing the same.

In order to solve the above problems, the present invention provides a nanoporous membrane comprising a hydrophobic surface formed by electrospinning a first solution containing a hydrophobic polymer and a hydrophilic surface formed by electrospinning a second solution containing a hydrophilic polymer do.

In one embodiment of the present invention, the hydrophobic polymer may be polyurethane.

In another embodiment of the present invention, the hydrophilic polymer may be a terpolymer of polyethylene oxide-polypropylene oxide-polyethylene oxide.

In another embodiment of the present invention, the first solution may include polyurethane and an organic solvent.

In another embodiment of the present invention, the second solution may include polyurethane, a terpolymer of polyethylene oxide-polypropylene oxide-polyethylene oxide, and an organic solvent.

In another embodiment of the present invention, the first solution may include 5 to 30% by weight of polyurethane and the balance of the organic solvent.

In another embodiment of the present invention, the second solution contains 5 to 30% by weight of polyurethane, 1 to 20% by weight of a ternary block copolymer of polyethylene oxide-polypropylene oxide-polyethylene oxide, and the remainder of the organic solvent it could be

In another embodiment of the present invention, the nano-porous membrane may be for medical use.

In addition, the present invention comprises the steps of preparing a first solution containing a hydrophobic polymer (S1);

Preparing a second solution containing a hydrophilic polymer (S2);

forming a hydrophobic surface by electrospinning the first solution (S3); and

Electrospinning a second solution on the hydrophobic surface to form a hydrophilic surface (S4), it provides a method for producing a nano-porous membrane.

The present invention is to provide a nano-porous membrane comprising a hydrophobic side and a hydrophilic side, and can be used as a medical membrane that can be attached and implanted in/outside the body for medical purposes in addition to a membrane as a filter.

1 shows a schematic diagram of the nanoporous membrane of the present invention.
Figure 2 shows the implementation conditions according to the electrospinning conditions of the nanoporous membrane of the present invention.
3 shows the results of confirming the behavior of the fluid according to the surface conditions of the nanoporous membrane.
4 shows a cross-section of the nanoporous membrane.
5 is a view showing the hydrophobic surface and the hydrophilic surface separately in the cross section of the nanoporous membrane.
6 shows the results of examining the PU surface (left) and the PU-PF surface (right) in the nanoporous membrane.
7 shows the result of confirming the contact angle with respect to both surfaces of the nanoporous membrane of the present invention.
8 shows the results of the fluorescent beads experiment of the PU/PU-PF Janus membrane.

The present invention relates to a nanoporous membrane having hydrophilicity and hydrophobicity on both sides and a method for manufacturing the same. It has the characteristic of showing both hydrophilicity and hydrophobicity in one membrane.

As shown in FIG. 2 , the membrane may have a hydrophobic surface or a hydrophilic surface partially or entirely formed by controlling the electrospinning conditions.

There is no limitation on the type of the hydrophobic material and the hydrophilic material, but preferably, one having excellent biostability should be used.

The hydrophobic polymer may be at least one selected from the group consisting of polyurethane, polyethylene, polyvinyl chloride, polystyrene, and polypropylene, and the hydrophilic polymer is polyacrylic acid, polyethylene glycol, polyvinylpyrrolidone, polyvinyl alcohol, and It may be at least one selected from the group consisting of a terpolymer of polyethylene oxide-polypropylene oxide-polyethylene oxide.

More preferably, as in the present invention, it is preferable to use a mixture of PU (Polyurethane) and PF (Pluronic F127) as a hydrophilic material and PU as a hydrophobic material. The PF is Pluronic F127 (polyethylene oxide (PEO: polyethylene oxide) - polypropylene oxide (PPO: poly propylene oxide) - means a triblock copolymer of polyethylene oxide (triblock copolymer).

That is, the present invention provides a nanoporous membrane comprising a hydrophobic surface formed by electrospinning a first solution containing a hydrophobic polymer and a hydrophilic surface formed by electrospinning a second solution containing a hydrophilic polymer.

In addition, the present invention comprises the steps of preparing a first solution containing a hydrophobic polymer (S1);

Preparing a second solution containing a hydrophilic polymer (S2);

forming a hydrophobic surface by electrospinning the first solution (S3); and

Electrospinning a second solution on the hydrophobic surface to form a hydrophilic surface (S4), it provides a method for producing a nano-porous membrane.

As an embodiment of the present invention, the first solution includes polyurethane and an organic solvent, and the second solution includes polyurethane, a terpolymer of polyethylene oxide-polypropylene oxide-polyethylene oxide, and an organic solvent. .

In more detail, the first solution may include 5 to 30% by weight of polyurethane and the remainder of the organic solvent, and the second solution is, 5 to 30% by weight of polyurethane, polyethylene oxide-polypropylene oxide-polyethylene It may contain 1 to 20% by weight of the ternary block copolymer of oxide and the balance of the organic solvent. Although not limited to the above range, excellent physical properties are confirmed in the content range as described above. The concentration is determined by the attractive and repulsive forces between the polymers, and the formation and average diameter of fibers can be controlled. When the polymer concentration is too low below the above range, beads can be formed, and when the polymer content is too high over the above range, the solution is easy to dry, so spinning is difficult and the average diameter of the fibers can be increased.

The electrospinning may be performed using a needle of 10 to 30 G at a current collector plate distance of 10 to 50 cm, a spinning speed of 0.01 to 10 mL/h, an applied voltage of 5 to 30 kV, and a current collecting plate speed of 1 to 30 rpm. have.

The distance of the collector plate controls the thickness of the fiber formed during electrospinning and the width of the entire membrane. As the distance decreases, the thickness of the fiber increases and the width of the membrane decreases. If the distance is too short (less than 10 cm), it is difficult to secure sufficient time before fiber formation.

The spinning speed is to control the thickness and aggregation of the fibers to be formed. If the spinning speed is as low as 0.01 mL/h, it appears in the form of a powder, resulting in increased fiber aggregation, and is very fast when the spinning speed exceeds 10 mL/h. In this case, the drying time is short and the blowing force is low, so the diameter of the fiber is thick and there is a possibility of bead occurrence.

The applied voltage controls conduction during electrospinning. When the applied voltage is lower than 5 kV, it is difficult to form a fiber, and when it is higher than 30 kV, the fiber breakage phenomenon may increase. The needle gauge controls the thickness of the formed fiber, and a needle of 10 to 30 G may be used.

The nano-porous membrane is capable of separating micro-sized particles of 20 μm or less, and the nano-porous membrane is used for medical purposes and has excellent biocompatibility, and is characterized in that it is easy to attach and implant inside/outside the body. When used for medical purposes, the hydrophobic surface is exposed outside the attachment site, so that external stimulation or inflow of foreign substances can be prevented.

Hereinafter, preferred embodiments of the present invention will be described in detail. In describing the present invention, if it is determined that a detailed description of a related known technology may obscure the gist of the present invention, the detailed description thereof will be omitted. Throughout the specification, when a part "includes" a certain component, it means that other components may be further included, rather than excluding other components, unless otherwise stated.

Since the present invention can apply various transformations and can have various embodiments, specific embodiments are illustrated and described in detail in the detailed description. However, this is not intended to limit the present invention to specific embodiments, and it should be understood to include all modifications, equivalents and substitutes included in the spirit and scope of the present invention.

Terms used in the present invention are only used to describe specific embodiments, and are not intended to limit the present invention. The singular expression includes the plural expression unless the context clearly dictates otherwise. In the present invention, the terms include or have is intended to designate that a feature, number, step, operation, component, part, or combination thereof described in the specification exists, but one or more other features, number, step , it should be understood that it does not preclude in advance the possibility of the presence or addition of an operation, component, part, or combination thereof.

Hereinafter, preferred embodiments of the present invention will be described so that those of ordinary skill in the art can easily implement them with reference to the accompanying drawings. In addition, in describing the present invention, if it is determined that a detailed description of a related known function or a known configuration may unnecessarily obscure the gist of the present invention, the detailed description thereof will be omitted. In addition, certain features presented in the drawings are enlarged, reduced, or simplified for ease of description, and the drawings and their components are not necessarily drawn to scale. However, those skilled in the art will readily appreciate these details.

[Example]

Example 1: Preparation of PU/PU-PF Janus Membrane

In order to synthesize a solution for producing a hydrophobic layer, THF and DMF were mixed in a ratio of 6:4 in a 50 mL tube first. 15 wt% of PU was prepared with respect to the mixed solution. The prepared PU was put in a mixture of THF and DMF and stirred until completely dissolved.

In addition, to synthesize a solution for producing a hydrophilic layer, THF and DMF were mixed in a ratio of 6:4 in a 50 mL tube. For the mixed solution, 15 wt% of PU and 9 wt% of PF were prepared. The prepared PU and PF were put into the THF and DMF mixture and stirred until completely dissolved.

A hydrophobic layer was prepared by electrospinning 4 mL of a PU solution for preparing the prepared hydrophobic layer, and then 2 mL of a PU-PF solution for producing a hydrophilic layer was electrospun thereon to form a hydrophilic layer. The electrospinning Janus membrane was dried at 40 ˚C for one day to remove the organic solvent. The conditions of the electrospinning are shown in Table 1 below.

Electrospinning conditions variable collector plate distance Radiation speed applied voltage needle collector plate speed experimental value 25 cm 0.2 mL/h 13.0 kV 23G 10 rpm

Example 2. Confirmation of membrane properties

In order to confirm the hydrophobicity and hydrophilicity of the membrane prepared in Example 1, ink was dropped on the hydrophobic surface or the hydrophilic surface. As can be seen in FIG. 3 , the ink was not absorbed on the hydrophobic side, but was well absorbed on the hydrophilic side.

The cross-sectional area of the prepared membrane was photographed and shown in FIG. 4 . The average thickness was found to be 137.36 um. As confirmed in FIG. 5 shown in more detail, it was confirmed that the hydrophobic side formed of polyurethane (PU) and the hydrophilic side formed of polyurethane-pluronic (PU-PF) coexist.

The results of examining the PU surface are shown on the left side of FIG. 6 , and the results of examining the PU-PF surface are shown on the right side of FIG. 6 . It is confirmed that different forms appear.

In addition, by dropping water on the PU surface and the PU-PF surface, the contact angle was confirmed. As a result, as shown in FIG. 7 , it can be seen that the contact angle was large on the PU surface due to hydrophobicity, and the water droplets spread on the PU-PF surface.

In addition, the results of the fluorescent beads experiment of the PU/PU-PF Janus membrane are shown in FIG. 8 . As can be seen in FIG. 8 , fluorescent beads were confirmed on the PU-PF surface, but not on the PU surface, indicating that the membrane had a particle blocking effect.

As a specific part of the present invention has been described in detail above, for those of ordinary skill in the art, it is clear that this specific description is only a preferred embodiment, and the scope of the present invention is not limited thereby. will be. Accordingly, it is intended that the substantial scope of the present invention be defined by the appended claims and their equivalents.

Claims (16)

A nanoporous membrane comprising a hydrophobic surface formed by electrospinning a first solution containing a hydrophobic polymer and a hydrophilic surface formed by electrospinning a second solution containing a hydrophilic polymer. According to claim 1,
The hydrophobic polymer is a nanoporous membrane, characterized in that at least one selected from the group consisting of polyurethane, polyethylene, polyvinyl chloride, polystyrene, and polypropylene. According to claim 1,
The hydrophilic polymer is characterized in that at least one selected from the group consisting of polyacrylic acid, polyethylene glycol, polyvinylpyrrolidone, polyvinyl alcohol, and a ternary block copolymer of polyethylene oxide-polypropylene oxide-polyethylene oxide, nano porous membrane. According to claim 1,
The first solution is a nanoporous membrane, characterized in that it contains a hydrophobic polymer and an organic solvent. According to claim 1,
The second solution is characterized in that it contains a hydrophobic polymer, a hydrophilic polymer and an organic solvent, nanoporous membrane. 5. The method of claim 4,
The first solution, 5 to 30% by weight of polyurethane and the balance of the organic solvent, characterized in that it comprises a nanoporous membrane. 6. The method of claim 5,
The second solution, polyurethane 5 to 30% by weight, polyethylene oxide-polypropylene oxide-polyethylene oxide ternary block copolymer 1 to 20% by weight and the balance of the organic solvent, characterized in that it comprises a nanoporous membrane. According to claim 1,
The nano-porous membrane, characterized in that for medical use, nano-porous membrane. Preparing a first solution containing a hydrophobic polymer (S1);
Preparing a second solution containing a hydrophilic polymer (S2);
forming a hydrophobic surface by electrospinning the first solution (S3); and
Electrospinning a second solution on the hydrophobic surface to form a hydrophilic surface (S4), the method for producing a nanoporous membrane. 10. The method of claim 9,
The hydrophobic polymer is polyurethane, polyethylene, polyvinyl chloride, polystyrene, and polypropylene, characterized in that the method for producing a nanoporous membrane. 10. The method of claim 9,
The hydrophilic polymer is characterized in that at least one selected from the group consisting of polyacrylic acid, polyethylene glycol, polyvinylpyrrolidone, polyvinyl alcohol, and a ternary block copolymer of polyethylene oxide-polypropylene oxide-polyethylene oxide, nano A method for producing a porous membrane. 10. The method of claim 9,
The first solution is a method for producing a nanoporous membrane, characterized in that it contains a hydrophobic polymer and an organic solvent. 10. The method of claim 9,
The second solution is a method for producing a nanoporous membrane, characterized in that it contains a hydrophobic polymer, a hydrophilic polymer, and an organic solvent. 13. The method of claim 12,
The first solution is, characterized in that it comprises 5 to 30% by weight of polyurethane and the balance of the organic solvent, a method for producing a nanoporous membrane. 14. The method of claim 13,
The second solution, polyurethane 5 to 30% by weight, polyethylene oxide-polypropylene oxide-polyethylene oxide tertiary block copolymer 1 to 20% by weight and the balance, characterized in that it contains an organic solvent, the production of a nanoporous membrane Way. 10. The method of claim 9,
The nanoporous membrane is a method of manufacturing a nanoporous membrane, characterized in that for medical use.

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