KR20230161564A - Anti-Fouling nanofiber separator and method for manufacturing thereof - Google Patents

Abstract

A fouling-resistant nanofiber separator is provided. The fouling-resistant nanofiber separator according to an embodiment of the present invention is formed by accumulating nanofibers containing a fluorine-based polymer and an amine-based polymer as a fiber-forming polymer, a nanofiber membrane with a hydrophilic group introduced on the surface, and the nanofibers It is formed including a hydrophilic coating layer formed on at least a portion of the membrane. According to this, it is possible to exhibit very excellent hydrophilicity and excellent anti-fouling and anti-biofilm effects at the same time, and furthermore, water permeability and removal rate through a fouling-resistant nanofiber separator with excellent anti-fouling and anti-biofilm effects. It can have the effect of fundamentally preventing deterioration of filtration performance, such as reduction.

Description

Anti-fouling nanofiber separator and method for manufacturing thereof}

The present invention relates to a fouling-resistant nanofiber separator, and more specifically, to a fouling-resistant nanofiber separator and a method of manufacturing the same.

The membrane separation process is widely used in various fields such as water purification, wastewater, seawater desalination, food, chemistry, and bio industry. Despite many advantages such as high efficiency and low energy consumption, the membrane separation process has problems that need to be improved in terms of membrane performance.

Membrane fouling by hydrophobic substances such as proteins and oils contained in filtration raw water, and biofilms formed on the membrane surface due to the presence of active microorganisms are major drawbacks of membrane separation, resulting in increased energy required for separation and filtration. It causes a decrease in water permeability and a decrease in the durability of the membrane. Due to the deterioration of operating performance due to fouling and hydrophobic properties, attempts are being made to improve the membrane through research on antifouling.

For example, methods such as surface modification such as membrane surface coating, surface grafting, blending, irradiation, etc. are mainly performed. In particular, among polymer membrane materials, polyvinylidene fluoride (PVDF) has the advantages of high strength, thermal stability, and chemical resistance, as well as the ability to form nanofiber membranes by electrospinning. However, PVDF membrane is prone to membrane fouling and biofilm formation on the membrane surface due to its high hydrophobicity, which reduces water permeability, reduces removal rate, and overall operating performance.

Accordingly, there is a need to develop a separation membrane that has excellent fouling resistance and prevents membrane fouling and biofilm formation on the membrane surface, while also exhibiting excellent overall operating performance such as permeability and removal rate.

Registered Patent Publication No. 10-1926832 (Publication date: 2018.12.07)

The present invention was developed in consideration of the above points, and its purpose is to provide a fouling-resistant nanofiber separator that exhibits excellent hydrophilicity through surface treatment and a method of manufacturing the same.

Another object of the present invention is to provide a fouling-resistant nanofiber separator with excellent anti-fouling and anti-biofilm effects due to its excellent hydrophilicity, and a method for manufacturing the same.

In addition, the present invention provides a fouling-resistant nanofiber membrane that can fundamentally prevent deterioration in filtration performance, such as a decrease in water permeability and removal rate, through a fouling-resistant nanofiber membrane with excellent anti-fouling and anti-biofilm effects, and a method for manufacturing the same. There is another purpose in providing.

In order to solve the above-described problems, the present invention provides a nanofiber membrane formed by accumulating nanofibers containing a fluorine-based polymer and an amine-based polymer as a fiber-forming polymer and having a hydrophilic group introduced to the surface, and at least a portion of the nanofiber membrane. Provided is a fouling-resistant nanofiber separator including a hydrophilic coating layer formed in the region.

According to one embodiment of the present invention, the fiber-forming polymer may include a fluorine-based polymer and an amine-based polymer at a weight ratio of 1:0.1 to 0.4.

Additionally, the nanofibers may have an average diameter of 100 to 500 nm, and the nanofiber membrane may have an average thickness of 10 to 30 μm.

Additionally, the hydrophilic group may include one or more of a hydroxyl group (-OH), a carboxylic group (-COOH), an ether (R-O-R'), an ester (R-COOR'), and an amino group (RNHH).

Additionally, the hydrophilic coating layer may include any one or more of polyphenol-based derivatives, tannic acid derivatives, and catechin-based derivatives.

In addition, the present invention provides a step of heat-sealing nanofibers formed by electrospinning a spinning solution containing a fiber-forming polymer containing a fluorine-based polymer and an amine-based polymer, and a first solvent to form a nanofiber aggregate, the nanofiber aggregate It provides a method for producing a fouling-resistant nanofiber separator comprising the steps of treating with alkali to form a nanofiber membrane with a hydrophilic group introduced to the surface, and forming a hydrophilic coating layer on at least a portion of the nanofiber membrane. .

According to one embodiment of the present invention, the electrospinning is performed at an applied voltage of 10 to 30 kV, a distance between the spinning nozzle and the current collector of 10 to 30 cm, a discharge amount per minute of 0.02 to 0.08 cc/ghole, a temperature of 10 to 50°C, and a relative humidity. It can be performed under conditions of 40 to 80%.

Additionally, the alkaline treatment can be performed by immersing the solution in a basic solution at a temperature of 65 to 95°C for 40 to 80 minutes.

In addition, the hydrophilic coating layer is prepared by immersing the nanofiber membrane in a coating solution in which the coating layer forming components are dissolved at a temperature of 30 to 70°C for 2.5 to 5.5 hours, and then drying it for 9 to 15 hours at a temperature of 40 to 80°C. It can be formed.

The fouling-resistant nanofiber separator according to the present invention and its manufacturing method exhibit excellent hydrophilicity and can simultaneously exhibit excellent anti-fouling and anti-biofilm effects. Furthermore, it is possible to fundamentally prevent deterioration of filtration performance, such as reduction in water permeability and removal rate, through a fouling-resistant nanofiber membrane with excellent anti-fouling and anti-biofilm effects.

1 is a manufacturing process diagram for manufacturing a fouling-resistant nanofiber separator according to an embodiment of the present invention;
Figure 2 is a scanning electron microscope photograph of a nanofiber assembly for manufacturing a fouling-resistant nanofiber separator according to an embodiment of the present invention;
Figure 3 is a photograph comparing the colors of the nanofiber aggregate and the pretreated nanofiber membrane according to an embodiment of the present invention;
Figure 4 is a photograph comparing the contact angles of a nanofiber assembly, a nanofiber membrane, and a nanofiber separator for manufacturing a fouling-resistant nanofiber separator according to an embodiment of the present invention;
Figure 5 is a chemical formula showing an example of the chemical structure of a hydrophilic coating layer compound on a fouling-resistant nanofiber separator according to an embodiment of the present invention;
Figure 6 is a photograph of the Staphylococcus aureus antibacterial test results according to Example 3 and Comparative Example 1 of the present invention;
Figure 7 is a photograph of the Staphylococcus aureus antibacterial test according to the control group, Example 1 of the present invention, and Comparative Example 1, and
Figure 8 is a graph of Staphylococcus aureus antibacterial test results according to the control group, Example 3 of the present invention, and Comparative Example 1.

Hereinafter, embodiments of the present invention will be described in detail so that those skilled in the art can easily implement the present invention. The present invention may be implemented in many different forms and is not limited to the embodiments described herein.

The fouling-resistant nanofiber separator according to the present invention is formed by accumulating nanofibers containing fluorine-based polymers and amine-based polymers as fiber-forming polymers, a nanofiber membrane with a hydrophilic group introduced on the surface, and at least a nanofiber membrane on the nanofiber membrane. It includes a hydrophilic coating layer formed in some areas.

Meanwhile, each configuration of the fouling-resistant nanofiber separator according to the present invention will be described through the manufacturing method of the fouling-resistant nanofiber separator according to the present invention.

The method for producing a fouling-resistant nanofiber membrane according to the present invention is to heat nanofibers formed by electrospinning a spinning solution containing a fiber-forming polymer containing a fluorine-based polymer and an amine-based polymer, and a first solvent, as shown in FIG. Forming a nanofiber aggregate by fusing, treating the nanofiber assembly with alkali to form a nanofiber membrane with a hydrophilic group introduced to the surface, and forming a hydrophilic coating layer on at least a portion of the nanofiber membrane. Includes steps.

First, the steps for forming the nanofiber aggregate will be described.

The step of forming the nanofiber aggregate can be performed by heat-sealing nanofibers formed by electrospinning a spinning solution containing a fiber-forming polymer containing a fluorine-based polymer and an amine-based polymer, and a first solvent, as described above.

The fluorine-based polymer can be used without limitation as long as it is a fluorine-based polymer commonly used in the art, and in order to achieve the purpose of the present invention, polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), and tetrafluoroethylene are preferably used. Fluoroethylene-perfluoroalkyl vinyl ether copolymer (PFA), tetrafluoroethylene-hexafluoropropylene copolymer (FEP), tetrafluoroethylene-hexafluoropropylene-perfluoroalkyl vinyl ether copolymer ( EPE), tetrafluoroethylene-ethylene copolymer (ETFE), polychlorotrifluoroethylene (PCTFE), and chlorotrifluoroethylene-ethylene copolymer (ECTFE). there is. More preferably, considering spinning ease, chemical properties, etc., the fluorine-based compound may be polyvinylidene fluoride (PVDF). For example, the PVDF may have a weight average molecular weight of 300,000 to 500,000, which may be advantageous for achieving the purpose of the present invention.

In addition, the amine-based polymer can be used without limitation as long as it is an amine-based polymer commonly used in the art. In order to achieve the purpose of the present invention, polyethyleneimine (PEI) and polyarylene etheramine (poly(arylene) It may contain one or more selected from the group consisting of ether amine)). More preferably, the amine-based compound may be polyethyleneimine (PEI).

Meanwhile, the fiber-forming polymer may include a fluorine-based polymer and an amine-based polymer at a weight ratio of 1:0.1 to 0.4, preferably a fluorine-based polymer and an amine-based polymer at a weight ratio of 1:0.15 to 0.35. If the weight ratio of the fluorine-based polymer and the amine-based polymer included in the fiber-forming polymer is less than 1:0.1, the fouling-resistant nanofiber separator produced may not express the desired level of fouling resistance, and the presence of the fluorine-based polymer and the amine-based polymer If the weight ratio exceeds 1:0.4, the mechanical strength of the fouling-resistant nanofiber separator may decrease, resulting in reduced durability under high temperature and/or high pressure conditions.

The first solvent may be any solvent typically contained in a spinning solution for electrospinning without limitation, and the specific type may vary depending on the type of fiber-forming polymer, so the present invention is not particularly limited thereto, but is preferably acetone. , dimethylacetamide, γ-butyrolactone, cyclohexanone, 3-hexanone, 3-heptanone, 3-octanone, N-methylpyrrolidone, dimethyl sulfoxide, dimethylformamide. It may contain one or more, more preferably, it may contain at least one of acetone and dimethylacetamide, and even more preferably it may contain acetone and dimethylacetamide. At this time, when the first solvent includes acetone and dimethylacetamide, the dimethylacetamide and acetone may be included in a weight ratio of 1:0.1 to 0.4, preferably 1:0.15 to 0.35.

In addition, the fiber-forming polymer in the spinning solution is preferably contained in an amount of 10 to 30% by weight, preferably 12 to 28% by weight, and more preferably 13 to 27% by weight. If the fiber-forming polymer is less than 10% by weight, it is not spun in the form of a fiber during electrospinning but is sprayed in the form of droplets to form a film shape, or even if spinning occurs, many beads are formed and the volatilization of the first solvent does not occur well, which will be described later. During heat fusion, pore blockage may occur. In addition, if the fiber-forming polymer exceeds 30% by weight, the viscosity increases and solidification occurs on the surface of the solution, making spinning for a long time difficult, and the fiber diameter increases, making it impossible to make a fiber with the desired diameter.

The above-described spinning solution can be electrospun using a commonly known electrospinning device. As an example, the electrospinning device may be equipped with a single spinning pack with one spinning nozzle, or for mass production, an electrospinning device may be provided with a plurality of single spinning packs or a spinning pack with a plurality of nozzles. Additionally, in the electrospinning method, dry spinning or wet spinning with an external coagulation tank can be used, and there are no restrictions on the method.

Meanwhile, in order to achieve the purpose of the present invention, the electrospinning is performed at an applied voltage of 10 to 30 kV, a distance between the spinning nozzle and the current collector of 10 to 30 cm, a discharge amount per minute of 0.02 to 0.08 cc/ghole, a temperature of 10 to 50°C, and a relative humidity. Conditions of 40 to 80%, preferably applied voltage of 15 to 25 kV, distance between spinning nozzle and current collector 15 to 25 cm, discharge amount per minute of 0.03 to 0.07 cc/ghole, temperature of 15 to 45℃, and relative humidity of 45 to 45. It can be performed under 75% conditions.

Nanofibers are formed by performing the electrospinning, and as shown in FIG. 2, the nanofibers may have an average diameter of 100 to 500 nm, preferably 150 to 450 nm. If the average diameter of the nanofibers is less than 100 nm, the mechanical strength of the fouling-resistant nanofiber separator may decrease, which may reduce durability under high temperature and/or high pressure conditions, and if the average diameter exceeds 500 nm, filtration such as water permeability and removal rate may decrease. Performance may deteriorate.

Thereafter, the nanofibers can be heat-sealed to form a nanofiber aggregate. The nanofibers formed by spinning through electrospinning are accumulated to form a three-dimensional network structure, and heat and/or pressure can be applied to the accumulated nanofibers to maintain the desired porosity, pore size, thickness, etc. The heat and/or pressure can be used without limitation as long as it is a method that can heat-seal polymer-derived fibers commonly used in the art, and is preferably performed through calendering using a heated roller. At this time, the temperature of the heat applied through the calendering may be 70 to 190°C, preferably 120 to 180°C, but it is preferably performed in a range where thermal melting of the nanofibers used does not occur.

Next, the step of treating the nanofiber aggregate with alkali to form a nanofiber membrane with hydrophilicity and reactive sites introduced to the surface will be described.

The alkaline treatment can be performed by immersing the nanofiber assembly in a basic solution, thereby improving the formation of a hydrophilic coating layer described later and further improving the hydrophilicity of the fouling-resistant nanofiber separator produced.

At this time, the basic solution may include a basic component and a second solvent, and the second solvent may include any one or more of water and lower alcohol. Since the basic component may be a known basic component such as sodium bicarbonate, the present invention is not particularly limited thereto. The lower alcohol may be a lower alcohol having 1 to 4 carbon atoms, for example, ethanol and/or isopropyl alcohol.

In addition, the basic component may be included in the basic solution in an amount of 20 to 60% by weight, preferably 25 to 55% by weight, and the alkaline treatment is performed at a temperature of 65 to 95 ° C. for 40 to 80 minutes, preferably at a temperature of 70 to 70 ° C. This can be performed by immersing at 80°C for 45 to 75 minutes. If the above ranges are not satisfied, it may be difficult to introduce sufficient hydrophilic groups and reactive seats to the surface of the nanofiber aggregate at the desired level.

The hydrophilic group may include one or more of a hydroxyl group (-OH), a carboxylic group (-COOH), an ether (R-O-R'), an ester (R-COOR'), and an amino group (RNHH), preferably may include one or more of a hydroxyl group (-OH) and a carboxy group (-COOH), and more preferably may be a hydroxyl group (-OH).

The nanofiber membrane to which a hydrophilic group is introduced to the surface through the alkali treatment may have an average thickness of 10 to 30 ㎛, preferably 15 to 25 ㎛. If the average thickness of the nanofiber membrane is less than 10㎛, the mechanical strength of the fouling-resistant nanofiber membrane may decrease, which may reduce durability under high temperature and/or high pressure conditions, and if the average thickness exceeds 30㎛, water permeability and removal rate may decrease. Filtration performance may deteriorate.

On the other hand, by performing the alkali treatment, it can be seen that the relatively white nanofiber aggregate before the alkali treatment changed to relatively brown after the alkali treatment, as shown in Figure 3, and this phenomenon is due to the nanofibers due to the alkali treatment. It can be seen that this is due to the formation of double bonds and hydroxyl groups in the polymer material that formed.

Next, the step of forming a hydrophilic coating layer on at least some areas on the nanofiber membrane will be described.

The hydrophilic coating layer can be used without limitation as long as it is a coating layer forming method commonly used in the art, and is preferably formed by immersing and drying the nanofiber membrane in a coating solution in which the coating layer forming component is dissolved.

In addition, the hydrophilic coating layer is created by immersing the nanofiber membrane in a coating solution for 2.5 to 5.5 hours at a temperature of 30 to 70 ℃, preferably for 3 to 5 hours at a temperature of 35 to 65 ℃, It can be formed by drying at a temperature of 40 to 80°C for 9 to 15 hours, preferably at a temperature of 45 to 75°C for 10 to 14 hours. If the above condition ranges are not satisfied, the desired level of hydrophilicity, anti-fouling and anti-biofilm effects may not be achieved.

The coating layer forming component may include any one or more of polyphenol derivatives, tannic acid derivatives, and catechin derivatives, and may preferably include any one or more of tannic acid derivatives and catechin derivatives, and more preferably, tannic acid derivatives. Including it may be more advantageous in achieving the purpose of the present invention. At this time, the hydrophilic coating layer formed through the coating layer forming ingredient containing a tannic acid derivative may include a catechol group and a galloyl group, as shown in FIG. 5.

At this time, the coating layer forming component may include one or more of polyphenol derivatives, tannic acid derivatives, and catechin derivatives, and a cross-linking agent at a weight ratio of 1:0.1 to 0.4, preferably 1:0.15 to 0.35. If the weight ratio of any one or more of the polyphenol derivatives, tannic acid derivatives, and catechin derivatives contained in the coating layer forming components and the cross-linking agent is less than 1:0.1, the cross-linking reaction may be relatively low and the hydroxyl groups on the hydrophilic coating layer may be relatively small. Therefore, the desired level of hydrophilicity may not be achieved, and if the weight ratio exceeds 1:0.4, overcrosslinking may cause deterioration of physical properties and low hydrophilicity.

Meanwhile, the cross-linking agent may be used without limitation as long as it is a cross-linking agent commonly used in the art, and preferably includes glutaraldehyde, which may be advantageous for achieving the purpose of the present invention.

The present invention will be described in more detail through the following examples, but the following examples do not limit the scope of the present invention, and should be interpreted to aid understanding of the present invention.

<Example 1>

First, to prepare a spinning solution, a fiber-forming polymer containing a fluorine-based polymer, which is polyvinylidene fluoride (PVDF), and an amine-based polymer, which is polyethyleneimine (PEI), at a weight ratio of 1:0.05, and dimethylacetamide and acetone at a weight ratio of 1:0.05. A spinning solution was prepared by dissolving it in a first solvent containing a weight ratio of 0.25 to 18% by weight based on the total weight of the spinning solution. The prepared spinning solution is transferred to the spinning nozzle pack, and electrospinning is performed in a spinning atmosphere with an applied voltage of 20kV, a distance between the spinning nozzle and the current collector of 20cm, a discharge rate of 0.05cc/g/hole per minute, and a temperature of 30℃ and a relative humidity of 60%. Nanofibers with an average fiber diameter of 300 nm were obtained (Figure 2). Then, a calendaring process was performed on the accumulated nanofibers through a roller heated to 150°C to produce a nanofiber aggregate with an average thickness of 20㎛ in which the nanofibers were heat-fused.

Then, the prepared nanofiber assembly was immersed in a basic solution at a temperature of 80°C containing water as a second solvent and 40% by weight of a basic component such as sodium hydroxide for 60 minutes, washed with ultrapure water, and dried to form a nanofiber assembly. A nanofiber membrane as shown in Figure 3 was manufactured by introducing a hydroxyl group (-OH), a hydrophilic group, to the surface.

Thereafter, the prepared nanofiber membrane was immersed in a coating solution containing 25% by weight of a coating layer forming component containing tannic acid and glutaraldehyde as a crosslinking agent at a weight ratio of 1:0.25 and 75% by weight of ethanol, and incubated at a temperature of 50°C for 4 hours. After reacting for a while, a fouling-resistant nanofiber separator was prepared by washing with water and drying in an oven at 60°C for 12 hours.

<Examples 2 to 4 and Comparative Examples 1 to 4>

A nanofiber separator as shown in Table 1 was manufactured in the same manner as in Example 1, except that the weight ratio of the fluorine-based polymer and the amine-based polymer, the presence or absence of alkali treatment, and the presence or absence of tannic acid treatment were changed as shown in Table 1 below.

<Experimental example>

1. Contact angle measurement

For each nanofiber separator prepared in Examples and Comparative Examples, the contact angle formed between the surface of the fiber web layer and the surface of the water droplet was measured using a contact angle (°) measuring device. After capturing the shape of the droplet with a CCD camera, a method was used to calculate the interfacial tension (γ) optimized for the shape of the final imaged droplet. The injection volume was set to 0.05 mL using a micro syringe, and double distilled water was used. The contact angle was measured within 20 seconds after droplet formation on the surface.

Among these, the photograph of Comparative Example 1 is shown in Figure 4a, the photograph of Comparative Example 2 in Figure 4b, and the photograph of Example 4 in Figure 4c, and the result values for all Examples and Comparative Examples are shown in Table 1.

2. Staphylococcus aureus antibacterial test

An antibacterial test was performed on each nanofiber separator prepared in Examples and Comparative Examples. First, each nanofiber separator prepared in the above examples and comparative examples was prepared by cutting 0.4 g. The cut nanofiber membrane was inoculated with 4 ml of a solution in which Staphylococcus aureus was cultured. At this time, the Staphylococcus aureus concentration was 106 CFU. After inoculation, the inoculated nanofiber membrane was cultured in suspension at 37°C for 21 hours using a shaking incubator, then diluted 5-fold by adding 16 ml of 1X PBS, and then vortexed for 30 minutes. I ordered it. After vortexing was completed, 100㎕ each was inoculated onto agar solid medium and smeared until absorbed into the medium. Afterwards, the solid medium was incubated at 37°C for 24 hours. Then, the antibacterial effect was tested by measuring the absorbance at a wavelength of OD450㎚ (if the OD450 value is 0.05 or less: ○○, if 0.2 or less: ○, if it exceeds 0.2: ×).

Among these, photographs and graphs of Comparative Example 1 and Example 3 are shown in Figures 6 and 8, and the numerical results for all Examples and Comparative Examples are shown in Table 1.

3. Relative water permeability

For each nanofiber separator prepared in Examples and Comparative Examples, an operating pressure of 50 kPa was applied to measure the water permeability per 0.5 m2 of specimen area, and the remaining water permeability was based on 100 for the nanofiber separator of Example 1. The water permeability of the nanofiber membrane according to Examples and Comparative Examples was measured.

4. Filtration efficiency evaluation

For each nanofiber membrane prepared in the Examples and Comparative Examples, test dust (ISO Test dust A2 fine grades) was dispersed in pure water to prepare a turbidity with a turbidity of 100 NTU, and then filtered by measuring the turbidity before and after filtration. Efficiency was measured.

5. Durability evaluation under high temperature and pressure conditions

For each nanofiber separator prepared in Examples and Comparative Examples, durability under high temperature and pressure conditions was evaluated by operating at a temperature of 80°C and an operating pressure of 100 kPa for 24 hours. If no abnormality occurs - ○, if any problems such as detachment and/or separation of nanofibers on the nanofiber separator, fracture of the nanofiber separator, peeling of the hydrophilic coating layer, etc. occur - ×, high temperature and high pressure conditions Durability was evaluated.

division Example
One Example
2 Example
3 Example
4 Comparative example
One Comparative example
2 Comparative example
3 Comparative example
4 Weight ratio of fluorine-based polymer and amine-based polymer 1:0.05 1:0.15 1:0.25 1:0.45 1:0.15 1:0.25 1:0.25 1:0.0 Alkaline treatment ○ ○ ○ ○ × ○ × ○ Hydrophilic coating
(tannic acid treatment) ○ ○ ○ ○ × × ○ ○ Contact angle (°) 0 0 0 0 120 60 60 0 antibacterial test × ○○ ○○ ○○ × × ○ × Relative water permeability (%) 100 98 98 98 91 96 96 100 Filtration efficiency (%) 95 97 97 98 90 92 92 91 High temperature/high pressure durability evaluation ○ ○ ○ × × × × ×

As can be seen from Table 1 above, Examples 2 and 3 satisfy all of the weight ratio of the fluorine-based polymer and the amine-based polymer according to the present invention, presence or absence of alkali treatment, presence of tannic acid, etc., while examples do not satisfy any one of them. 1, Example 4 and Comparative Examples 1 to 4, it was found that the hydrophilicity, antibacterial properties, relative water permeability, filtration efficiency, and durability evaluation results under high temperature/high pressure conditions were all significantly superior at the same time. Meanwhile, the hydrophilic treatment on the nanofiber separator And Comparative Example 1, in which no hydrophilic coating layer was formed, showed more Staphylococcus aureus than the control group (bacteria culture only, about 1.22) as a result of the antibacterial test.

Although one embodiment of the present invention has been described above, the spirit of the present invention is not limited to the embodiment presented in the present specification, and those skilled in the art who understand the spirit of the present invention can add components within the scope of the same spirit. , other embodiments can be easily proposed by change, deletion, addition, etc., but this will also be said to be within the scope of the present invention.

Claims (9)

A nanofiber membrane formed by accumulating nanofibers containing a fluorine-based polymer and an amine-based polymer as a fiber-forming polymer, and having a hydrophilic group introduced to the surface; and
A fouling-resistant nanofiber separator comprising a hydrophilic coating layer formed on at least a portion of the nanofiber membrane. According to paragraph 1,
The fiber-forming polymer is a fouling-resistant nanofiber separator containing a fluorine-based polymer and an amine-based polymer at a weight ratio of 1:0.1 to 0.4. According to paragraph 1,
The nanofibers have an average diameter of 100 to 500 nm,
The nanofiber membrane is a fouling-resistant nanofiber separator with an average thickness of 10 to 30㎛. According to paragraph 1,
The hydrophilic group is a fouling-resistant nanofiber separator containing one or more of a hydroxyl group (-OH), a carboxylic group (-COOH), an ether (RO-R'), an ester (R-COOR'), and an amino group (RNHH). According to paragraph 1,
The hydrophilic coating layer is a fouling-resistant nanofiber separator containing at least one of polyphenol-based derivatives, tannic acid derivatives, and catechin-based derivatives. Forming a nanofiber aggregate by heat-sealing nanofibers formed by electrospinning a spinning solution containing a fiber-forming polymer containing a fluorine-based polymer and an amine-based polymer, and a first solvent;
Treating the nanofiber aggregate with alkali to form a nanofiber membrane with a hydrophilic group introduced to the surface; and
A method of manufacturing a fouling-resistant nanofiber separator comprising: forming a hydrophilic coating layer on at least a portion of the nanofiber membrane. According to clause 6,
The electrospinning is performed under the conditions of an applied voltage of 10 to 30 kV, a distance between the spinning nozzle and the current collector of 10 to 30 cm, a discharge rate of 0.02 to 0.08 cc/ghole per minute, a temperature of 10 to 50°C, and a relative humidity of 40 to 80%. Method for manufacturing fouling-resistant nanofiber separator. According to clause 6,
The alkali treatment is a method of manufacturing a fouling-resistant nanofiber separator performed by immersing in a basic solution at a temperature of 65 to 95°C for 40 to 80 minutes. According to clause 6,
The hydrophilic coating layer is formed by immersing the nanofiber membrane in a coating solution in which the coating layer forming components are dissolved at a temperature of 30 to 70°C for 2.5 to 5.5 hours, and then drying the nanofiber membrane for 9 to 15 hours at a temperature of 40 to 80°C. Method for manufacturing fouling-resistant nanofiber separator.