KR20230165025A - Ultrafiltration hollow fiber membrane and manufacturing method thereof - Google Patents

Abstract

The present invention relates to an ultrafiltration hollow fiber membrane manufactured using a dope solution containing polyethersulphone (PES) and polyethylene glycol (PEG) and a method for manufacturing the same. The method of manufacturing an ultrafiltration hollow fiber membrane of the present invention has excellent membrane filtration capacity by controlling the size of the inner and outer diameters and the membrane thickness, making it possible to manufacture a separation membrane for hemodialysis, hemofiltration, or hemodiafiltration. Kidney disease is improved or treated using the manufactured ultrafiltration hollow fiber membrane.

Description

Ultrafiltration hollow fiber membrane and manufacturing method thereof}

The present invention relates to a hollow fiber membrane manufactured using a dope solution prepared by mixing polyethersulphone (PES) and polyethylene glycol (PEG) and a bore solution prepared by mixing NMP and water, and a method for manufacturing the same. It's about. The manufacturing method of the present invention can control the size of the inner and outer diameters and the membrane thickness of the hollow fiber membrane, making it possible to manufacture an ultrafiltration hollow fiber membrane that can be used as a separation membrane for hemodialysis, hemofiltration, or hemodiafiltration.

Chronic kidney disease is a condition in which damage to the kidneys (bean beans) or decline in function, such as proteinuria or hematuria, persists for more than 3 months. Due to decreased kidney function, waste products in the patient's body are not removed and moisture and electrolytes are not properly regulated. The number of patients with chronic kidney disease continues to increase worldwide, and the number of patients in Korea is also increasing every year as risk factors such as rapid aging, high blood pressure, diabetes, and metabolic syndrome increase.

Renal replacement therapy includes hemodialysis, peritoneal dialysis, and kidney transplantation as a method to excrete waste and water from the body of patients with chronic kidney disease who have reduced kidney function. According to the results of a survey in 2019, it is known that most patients receive hemodialysis treatment, with the proportion of renal replacement therapy patients being approximately 84%, hemodialysis approximately 4%, and kidney transplantation approximately 12% (Non-patent Document 1 ).

Hemodialysis (HD) is a treatment that purifies the body's blood using an external dialysis system and then returns it to the body. However, conventional hemodialysis is a method in which uremic substances with low molecular weight are mainly removed through diffusion due to concentration differences, and as a result, medium-molecular uremic substances with large molecular weight are not removed. Because solutes with a molecular weight of 1 KD or more cannot be removed, a new hemodiafiltration method was required.

Hemodiafiltration (HDF) is a treatment method that adds a filtration method to hemodialysis. While it is the same in that it removes uremic substances in the blood of kidney disease patients by filtering them through a dialysis membrane, it increases the purity of water and the convection movement of the solution. It is effective in removing medium sized waste products (e.g. urea). In addition, it is known through several clinical studies that the patient survival rate is higher than that of conventional hemodialysis.

Meanwhile, hollow fiber is a separation membrane in the form of a thread with an empty center, and is used as a separation membrane for the purpose of removing waste products from the blood. Polymer hollow fiber membranes include regenerated cellulose, cellulose derivatives, polyvinylpyrrolidone (PVP), polyethersulfone (PES), polysulfone (PSU), polyetherimide (PEI), polyimide (PI), and polyamide (PA). , polycarbonate (PC), polystyrene (PS), polymethyl methacrylate (PMMA), polyvinylidene fluoride (PVDF), polyacrylonitrile (PAN), polyurethane (PU) and polyester-based polymer alloys, or It consists of mixtures of these, etc. Polysulfone-based materials and polyvinylpyrrolidone, which show excellent blood compatibility, are mainly used as hemodialysis membrane materials. However, if there is a large amount of polyvinylpyrrolidone remaining in the hollow fiber membrane, it may be dissolved during hemodialysis and cause other side effects.

In addition, the hollow fiber membrane manufacturing method includes phase inversion method, thermally induced phase separation method, melt spinning method, dry-wet spinning method, and stretching. There is a stretching method, and it is mainly manufactured by the phase inversion method. However, the phase inversion method has poor filtration precision and filtration volume because the positions and sizes of pores are randomly determined during the phase inversion process.

Accordingly, there is a need for the development of hollow fiber membranes for hemodialysis and hemodiafiltration that have excellent filtration precision and high filtration capacity while having excellent blood compatibility.

Korean Patent No. 10-1810470 Korean Patent Publication No. 10-2005-0078748

Kidney Res Clin Pract 2021;40(1):52-61

The first object of the present invention is to provide a hollow fiber membrane that can be used as an ultrafiltration filtration membrane. The hollow fiber membrane can be used as a separation membrane for hemodialysis, hemofiltration, or hemodiafiltration.

The second object of the present invention is to provide a method for manufacturing a hollow fiber membrane that can be used as an ultrafiltration filtration membrane of the first object.

The present invention for achieving the first problem is polysulphone resin and glycol. An ultrafiltration hollow fiber membrane is manufactured using a dope solution containing a resin. The ultrafiltration hollow fiber membrane can be used as a separation membrane for hemodialysis, hemofiltration, or hemodiafiltration.

The present invention for achieving the second problem is,

Forming a mixed solution by dissolving polysulfone resin and glycol resin in a solvent;

Preparing a dope solution by stirring the mixed solution for 24 hours and then degassing it;

Supplying the dope solution to an external nozzle of a dual nozzle and supplying a bore solution to an internal nozzle of the dual nozzle;

forming a hollow fiber membrane by spinning the dope solution and bore solution supplied to the nozzle into a coagulation bath and winding it with a winder;

gelling the wound hollow fiber membrane in a water bath, washing it with water, and then immersing it in glycerol; and

It provides a method of manufacturing an ultrafiltration hollow fiber membrane including the step of drying the hollow fiber membrane immersed in glycerol at room temperature in the air.

The ultrafiltration hollow fiber membrane according to the present invention has a thin membrane thickness and a high porosity, so it has the effect of removing mid-molecular weight uremic toxins from the blood during hemodialysis, hemofiltration, or hemodiafiltration, while maintaining essential proteins and albumin at a safe level. there is.

Figure 1 is a scanning electron microscope (SEM) photograph showing the cross section of an ultrafiltration hollow fiber membrane manufactured by the manufacturing method of the present invention.
Figure 2 is a cross-section of an ultrafiltration hollow fiber membrane manufactured using a dope solution having a different mass ratio from that of the present invention, confirmed by SEM photography.
Figure 3 is a schematic diagram of a method for removing uremic toxins from blood using an ultrafiltration hollow fiber membrane manufactured by the production method of the present invention.
Figure 4 is a graph confirming the urea removal effect of the ultrafiltration hollow fiber membrane manufactured by the manufacturing method of the present invention.
Figure 5 is a graph confirming the creatinine removal effect of the ultrafiltration hollow fiber membrane manufactured by the production method of the present invention.
Figure 6 is a graph confirming the hippuric acid removal effect of the ultrafiltration hollow fiber membrane manufactured by the production method of the present invention.
Figure 7 is a graph confirming the indoxyl sulfate removal effect of the ultrafiltration hollow fiber membrane manufactured by the production method of the present invention.
Figure 8 is a graph confirming the p-cresol removal effect of the ultrafiltration hollow fiber membrane manufactured by the production method of the present invention.

Hereinafter, the present invention will be described in detail with reference to embodiments and drawings so that those skilled in the art can easily implement the present invention. Embodiments of the present invention are provided to more completely explain the present invention to those skilled in the art. Accordingly, the embodiments of the present invention may be modified in various other forms, and the scope of the present invention is not limited to the embodiments described below and may be embodied in other forms.

Throughout the specification of the present invention, when a part is said to “include” a certain component, this means that it may further include other components rather than excluding other components unless specifically stated to the contrary.

Throughout the specification of the present invention, “a step of” or “a step of” does not mean “a step for.”

Throughout the specification of the present invention, “improvement” or “treatment” means any action that improves or beneficially changes the symptoms of the disease.

Throughout the specification herein, “membrane” refers to a discrete, generally thin interface that regulates the permeation of contacting chemical species, the membrane comprising pores with finite dimensions as defined in the description below.

The present invention provides an ultrafiltration hollow fiber membrane that can be used as a separation membrane for hemodialysis, hemofiltration, or hemodiafiltration. The hollow fiber membrane can be manufactured using a dope solution containing polysulphone resin and glycol resin.

In one aspect of the present invention, the mass ratio of the polysulfone resin and the glycol resin in the dope solution may be 3:1 to 1:3, preferably 2:1 to 1:2, and more preferably may be 1:2. If an excessive amount of polysulfone resin or glycol resin is included compared to the above mass ratio, the thickness of the hollow fiber membrane may become thick and the effect of removing uremic toxins and waste products from the blood may be reduced.

In one aspect of the present invention, the polysulfone resin has excellent chemical resistance and mechanical properties and can be used as a membrane material at low economic cost. The polysulfone resin may be one or more resins selected from the group consisting of polyethersulfone (PES), polysulfone (PSU), and polyphenylenesulfone (PPSU), and is preferably hydrophilic. It may be polyethersulfone, which is high and causes less membrane contamination by organic substances.

In one aspect of the present invention, the glycol-based resin is a water-soluble resin and can contribute to increasing permeability by forming a uniform support layer in the internal coagulating liquid and forming pores during the phase transition process of the polysulfone-based resin. The glycol resin is one or more resins selected from the group consisting of ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, and polyethylene glycol. Preferably, it may be polyethylene glycol, which has high hydrophilicity, causes less membrane contamination by organic substances, and has a high tendency to escape out of the hollow fiber membrane during the coagulation and washing process after spinning.

In one aspect of the present invention, the ultrafiltration hollow fiber membrane can be used as a separation membrane for hemodialysis, hemofiltration, or hemodiafiltration to filter medium molecular weight uremic toxins and waste products in the blood. The uremic toxins or waste products include urea, uric acid, creatinine, hippuric acid, indoxyl sulfate, p-cresol, and oxalates. ), it may be one or more uremic toxins or waste products selected from the group consisting of guanidines, phenol, and homocysteine. The hollow fiber membrane removes uremic toxins or waste products to treat diabetic nephropathy, chronic renal failure, acute renal failure, subacute renal failure, glomerulonephritis, malignant nephrosis, vascular microangiopathy, transplant rejection, glomerulopathy, renal hypertrophy, renal hyperplasia, and proteinuria. , It may be used for the purpose of improving one or more kidney diseases selected from the group consisting of contrast agent-induced nephropathy, toxin-induced kidney damage, oxygen free-radical mediated nephropathy, and nephritis, but is not limited thereto. In addition, the ultrafiltration hollow fiber membrane has small pores, so essential proteins in the blood such as red blood cells, platelets, white blood cells, and albumin, which are components of blood, are not filtered, which can cause anemia and shock that can lead to death due to excessive loss of substances in the blood. It can be prevented, improved or treated.

In one aspect of the present invention, the membrane thickness of the ultrafiltration hollow fiber membrane may be 30 ㎛ to 75 ㎛, specifically 33 ㎛ to 73 ㎛, preferably 35 ㎛ to 70 ㎛. If the thickness of the hollow fiber membrane is less than 30 ㎛, sufficient strength may not be secured and mechanical properties and durability may be reduced, and if it is greater than 73 ㎛, material penetration performance may be reduced.

In one aspect of the present invention, the pore size of the ultrafiltration hollow fiber membrane may be 7 nm to 20 nm, specifically 7.5 nm to 18 nm, and preferably 8.5 nm to 16 nm. If the pore size of the hollow fiber membrane is smaller than 7 nm, water permeability may decrease and diafiltration efficiency may decrease, and if it is larger than 18 nm, essential proteins in the blood may be lost.

In addition, the porosity of the ultrafiltration hollow fiber membrane of the present invention may be 50% to 85%, specifically 55% to 85%, and preferably 60% to 85%, but is not limited thereto. In addition, the porosity relates to the ratio of pore volume to the total volume of the material in a porous material, and can be calculated using equation (1) below.

Equation (1):

Where ε (%) is the porosity, m _w is the weight of the hollow fiber membrane impregnated in the Bore solution, m _d is the weight of the dried hollow fiber membrane, ρ _w is the density of the Bore solution, and ρ _p is the density of the dope solution. am.

In one aspect of the present invention, the hollow fiber membrane may have an outer diameter of 200 ㎛ to 700 ㎛, specifically 230 ㎛ to 680 ㎛, preferably 250 ㎛ to 650 ㎛. If the outer diameter of the hollow fiber membrane is smaller than 200 ㎛ or larger than 700 ㎛, the blood flow rate is reduced or excessive, and blood compatibility, performance maintenance, and integration rate decrease due to adsorption of blood components due to interaction with the membrane surface. It can affect the patient's blood pressure control. Additionally, the hollow fiber membrane may have an inner diameter of 150 ㎛ to 650 ㎛, specifically 180 ㎛ to 620 ㎛, preferably 200 ㎛ to 600 ㎛. If the inner diameter of the hollow fiber membrane is smaller than 150 ㎛ or larger than 650 ㎛, the blood flow rate may be excessive or excessive, and blood compatibility and performance maintenance may be reduced due to adsorption of blood components due to interaction with the membrane surface. , may affect the patient's blood pressure control.

In one aspect of the present invention, the hollow fiber membrane may have a water permeability of 70 ㎖/㎡/h/mmhg to 200 ㎖/㎡/h/mmhg, preferably 90 ㎖/㎡/h/mmhg to 190 ㎖/㎖/㎡/h/mmhg. It may be ㎡/h/mmhg. If the water permeability of the hollow fiber membrane is less than 90 ㎖/㎡/h/mmhg or greater than 190 ㎖/㎡/h/mmhg, the filtration effect of uremic toxins and wastes in the blood may be reduced.

In addition, the present invention

Forming a mixed solution by dissolving polysulfone resin and glycol resin in a solvent;

Preparing a dope solution by stirring the mixed solution for 24 hours and then degassing it;

Supplying the dope solution to an external nozzle of a dual nozzle and supplying a bore solution to an internal nozzle of the dual nozzle;

forming a hollow fiber membrane by spinning the dope solution and bore solution supplied to the nozzle into a coagulation bath and winding it with a winder;

gelling the wound hollow fiber membrane in a water bath, washing it with water, and then immersing it in glycerol; and

It provides a method of manufacturing an ultrafiltration hollow fiber membrane including the step of drying the hollow fiber membrane immersed in glycerol at room temperature in the air.

In one aspect of the present invention, the polysulfone resin dissolved in the solvent may be one or more resins selected from the group consisting of polyethersulfone, polysulfone, and polyphenylenesulfone, and preferably may be polyethersulfone. . Additionally, the glycol-based resin may be one or more resins selected from the group consisting of ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, and polyethylene glycol, and preferably may be polyethylene glycol.

In one aspect of the present invention, the mass ratio of polysulfone resin and glycol resin dissolved in the solvent may be 3:1 to 1:3, preferably 2:1 to 1:2, and more preferably It could be 1:2. If the polysulfone resin or glycol resin is included in excess of the above mass ratio, the membrane thickness may be too thick or thin and may not be suitable for ultrafiltration.

In one aspect of the present invention, the solvent may be an aprotic polar solvent, and the aprotic polar solvent may be acetone, acetonitrile, dimethyl acetamide (DMAc), dimethyl formamide (dimethyl formamide (DMF), dimethyl sulfoxide (DMSO), methyl ethyl ketone, methyl n-propyl ketone, N-methyl-2-pyrrolidone (N-methyl) It may be one or more solvents selected from the group consisting of -2-pyrrolidone (NMP), propylene carbonate, nitromethane, sulforane, or hexamethylphosphoramide (HMP), , preferably N-methyl-2-pyrrolidone, but is not limited thereto.

In one aspect of the present invention, a process of applying pressure by supplying an inert gas to the mixed solution can be added, and a transparent dope solution can be prepared through this process. The inert gas may be one or more gases selected from the group consisting of neon, argon, nitrogen, and helium, preferably nitrogen, but is not limited thereto.

In one aspect of the present invention, the bore solution supplied to the dual nozzle acts as an internal coagulant and contributes to the formation of the hollow fiber membrane. The Bohr solution may be a solution containing one or more selected from the group consisting of glycerol, dimethoxyethanol, N-methyl-2-pyrrolidone, methanol, ethanol, isopropanol, acetone, dimethylacetamide, and water. Specifically, It may be a solution containing one or more selected from the group consisting of N-methyl-2-pyrrolidone and water, preferably a solution of N-methyl-2-pyrrolidone and water with a mass ratio of 2:1 to 1:2. It may be a mixed solution, and more preferably, it may be a mixed solution of N-methyl-2-pyrrolidone and water with a mass ratio of 1:1.

In one aspect of the present invention, in the step of supplying the dope solution and the bore solution to the dual nozzle, a pore forming agent capable of enlarging the size of the pores and increasing the permeate flow rate may be further included. The pore forming agent may be one or more pore forming agents selected from the group consisting of polyvinylpyrrolidone (PVP), camphorsulfonic acid (CSA), toluenesulfonic acid (TSA), and polyethylene glycol (PEG). Additionally, the pore former may be included in an amount of 1 to 28% by weight, preferably 5 to 28% by weight, based on the total weight of the dope solution. If the pore former is less than 1% by weight of the dope solution, there may be a problem in that the permeate flow rate does not increase because the size of the pores does not increase.

In one aspect of the present invention, the inner diameter size and film thickness of the hollow fiber membrane can be adjusted by adjusting the flow rates of the dope solution and the bore solution in the step of supplying the dope solution and the bore solution to the dual nozzle. The inner diameter size may be 200 ㎛ to 600 ㎛, and the film thickness may be 35 ㎛ to 70 ㎛. The faster the flow rate of the dope solution, the larger the outer diameter and inner diameter, and the faster the flow rate of the bore solution, the larger the inner diameter and thinner the film thickness.

In one aspect of the present invention, the flow rate of the dope solution supplied to the external nozzle may be 0.5 mL/min to 3 mL/min, and preferably may be 1 mL/min to 3 mL/min. Additionally, the flow rate of the bore solution supplied to the internal nozzle in step 3) may be 2 mL/min to 6 mL/min, and preferably 2 mL/min to 5 mL/min. As the flow rate of the dope solution and the flow rate of the bore solution decrease, the inner diameter and outer diameter may decrease, and the film thickness may become thinner.

In one aspect of the present invention, the coagulation tank into which the dope solution and the Bore solution are radiated may contain an external coagulating liquid, and the external coagulating liquid is not limited as long as it can replace the Bore solution, which is the internal coagulant, and is preferred. It may be, but is not limited to, one or more coagulants selected from the group consisting of N-methylpyrrolidone, N,N-dimethylacetamide, dimethyl sulfoxide, dimethylformamide, glycerol, water, and glycol resins. .

In one aspect of the present invention, the temperature of the coagulation bath containing the external coagulation liquid may be 10°C to 30°C, and preferably may be 10°C to 25°C. In the above temperature range, the phase transition rate is accelerated, and a hollow fiber membrane with an optimized pore structure can be manufactured.

In one aspect of the present invention, the air gap between the double nozzle and the coagulation tank may be 15 cm to 30 cm, preferably 20 cm to 30 cm. If the length of the air gap is less than 15 cm, the flow rate and strength of the hollow fiber membrane may decrease as a result of gases generated at the surface of the coagulating liquid reacting before solidification. In addition, when the length of the air gap is more than 30 cm, the exposure time to air is long, and the density of the hollow fiber membrane may increase, thereby reducing the flow rate. The atmospheric temperature between the double nozzle and the external coagulating liquid may be 20°C to 35°C, preferably 20 to 30°C, but is not limited thereto. Additionally, the atmospheric humidity between the double nozzle and the external coagulating liquid may be 45% to 55%, preferably 40% to 50%, but is not limited thereto.

In one aspect of the present invention, the winder is capable of winding the spun hollow fiber membrane at a speed of 5 m/min to 20 m/min, preferably at a speed of 8 m/min to 11 m/min. You can. If the winding speed is less than 5 m/min, uneven extrusion of the solution may occur and the membrane structure may be destroyed, and if it is more than 20 m/min, the size of the pores may become excessively large, causing albumin, a useful protein, to leak out into the blood. .

In one aspect of the present invention, the wound hollow fiber membrane can be immersed in 10 wt% to 30 wt% glycerol aqueous solution for 10 to 15 hours, preferably 12 hours. An ultrafiltration hollow fiber membrane can be manufactured by drying the immersed hollow fiber membrane.

In a specific example of the present invention, as a result of confirming the effect of the hollow fiber membrane manufactured by the manufacturing method of the present invention to remove uremic toxins, urea, creatinine, and hippuric acid, which are uremic toxins or waste products in the blood, were confirmed. ), indoxyl sulfate, and p-cresol were filtered, while essential proteins were not filtered and remained in the blood.

Hereinafter, the present invention will be described in detail through examples and experimental examples.

However, the following examples and experimental examples only illustrate the present invention, and the content of the present invention is not limited to the following examples and experimental examples.

<Example 1> Preparation of dope solution and bore solution

<1-1> Preparation of dope solution

140 g of polyethersulfone (PES) and 280 g of polyethylene glycol (PEG) were dissolved in a 1 L round bottom flask equipped with a stirrer containing 580 g of NMP (N-Methylpyrrolidone) solvent (PES: PEG = 1: 2 wt/wt).

The mixture was stirred at 60°C and 200 rpm for 1 day, and then degassed at room temperature to synthesize a yellow dope solution. A transparent dope solution was prepared by adding nitrogen at a pressure of 18 psi to the yellow dope solution.

<1-2> Bore solution preparation

A Bohr solution was prepared by mixing 500 g of NMP in 500 ml of water (NMP: H ₂ O = 1: 1 wt/wt).

<Example 2> Manufacturing of hollow fiber membrane

A hollow fiber membrane with controlled inner diameter and film thickness was manufactured by supplying the dope solution and bore solution prepared in <Example 1> to a double nozzle.

Specifically, in an environment where the air temperature is 20 ℃ to 30 ℃ and the atmospheric humidity is 40% to 50%, the flow rate is 4.0 ㎖/ min, a dope solution was supplied, and a bore solution with a flow rate of 2.0 mL/min was supplied to the internal nozzle. The supplied dope solution and bore solution were spun into a coagulation bath containing water at 28°C and taken up at a speed of 11 m/min using a winder to prepare a hollow fiber membrane. The prepared hollow fiber membrane was gelled in a water bath, washed with water, immersed in glycerol, and stored.

As a result, it was confirmed that a hollow fiber membrane with an outer diameter of 635 ㎛, an inner diameter of 586 ㎛, a film thickness of 49 ㎛, and a porosity of 83% was manufactured.

<Example 3> Manufacturing hollow fiber membranes with different inner and outer diameters

A hollow fiber membrane was manufactured in the same manner as in Example 2, except that a dope solution with a flow rate of 2.0 ml/min and a bore solution with a flow rate of 1.0 ml/min were used.

As a result, it was confirmed that a hollow fiber membrane with an outer diameter of 464 ㎛, an inner diameter of 412 ㎛, a film thickness of 39 ㎛, and a porosity of 77% was manufactured.

<Example 4> Manufacturing hollow fiber membranes with different inner and outer diameters

A hollow fiber membrane was manufactured in the same manner as in Example 2, except that a dope solution with a flow rate of 2.0 ml/min and a bore solution with a flow rate of 2.0 ml/min were used.

As a result, it was confirmed that a hollow fiber membrane with an outer diameter of 538 ㎛, an inner diameter of 400 ㎛, a film thickness of 69 ㎛, and a porosity of 83% was manufactured.

<Example 5> Manufacturing hollow fiber membranes with different inner and outer diameters

A hollow fiber membrane was manufactured in the same manner as in Example 2, except that a dope solution with a flow rate of 1.0 ml/min and a bore solution with a flow rate of 1.0 ml/min were used.

As a result, it was confirmed that a hollow fiber membrane with an outer diameter of 255 ㎛, an inner diameter of 218 ㎛, a membrane thickness of 37 ㎛, and a porosity of 79% was manufactured.

In conclusion, as a result of comparing <Example 1> to <Example 5>, it was confirmed that the outer diameter and inner diameter decreased as the flow rate of the dope solution and the bore solution decreased. In addition, when the flow rate of the dope solution in <Example 2> was 2.0 mL/min and the flow rate of the bore solution was 4.0 mL/min, the porosity of the hollow fiber membrane prepared was excellent and the film thickness was the thinnest, confirming that the most appropriate dope was selected. The flow rate conditions of the solution and bore solution were confirmed.

<Comparative Example 1> Manufacturing hollow fiber membranes with different ratios of PES and PEG

A hollow fiber membrane was prepared in the same manner as in Example 5, except that a dope solution prepared by mixing 210 g of PES and 210 g of PEG was used (PES : PEG = 1 : 1 wt/wt).

As a result, it was confirmed that a hollow fiber membrane with an outer diameter of 719.4 ㎛, an inner diameter of 566.8 ㎛, a membrane thickness of 53.1 ㎛, and a porosity of 58% was manufactured.

<Comparative Example 2> Manufacturing hollow fiber membranes with different ratios of PES and PEG

A hollow fiber membrane was prepared in the same manner as in Example 5, except that a dope solution prepared by mixing 168 g of PES and 252 g of PEG was used (PES: PEG = 1: 1.5 wt/wt).

As a result, it was confirmed that a hollow fiber membrane with an outer diameter of 811.2 ㎛, an inner diameter of 665.5 ㎛, a membrane thickness of 66.0 ㎛, and a porosity of 64% was manufactured.

<Comparative Example 3> Manufacturing hollow fiber membranes with different ratios of PES and PEG

A hollow fiber membrane was prepared in the same manner as in Example 5, except that a dope solution prepared by mixing 120 g of PES and 300 g of PEG was used (PES: PEG = 1: 2.5 wt/wt).

As a result, it was confirmed that a hollow fiber membrane with an outer diameter of 725.4 ㎛, an inner diameter of 600.1 ㎛, a membrane thickness of 57.4 ㎛, and a porosity of 71% was manufactured.

In conclusion, as a result of comparing <Example 2> and <Comparative Example 1> to <Comparative Example 3>, when the mass ratio of PES:PEG was 1:2, the porosity of the manufactured hollow fiber membrane was the highest and the membrane thickness was the thinnest. was confirmed to be the most appropriate mass ratio.

<Experimental Example 1> Confirmation of filtration effect of hollow fiber membrane

In order to confirm the effect of maintaining blood albumin and removing uremic toxins using the hollow fiber membranes with different inner and outer diameters prepared in <Example 2> to <Example 5>, 1500 mg/L of urea and 100 mg of urea were used. /L creatinine, 40 mg/L indoxyl sulfate, 40 mg/L p-cresol, 40 mg/L hippuric acid and 25 g Artificial blood (buffer + uremic toxin) containing /L HSA (Bovine Serum Albumin) was filtered through the hollow fiber membrane prepared in <Example 2> to <Example 5> above to confirm the removal ability.

Specifically, the average value of uremic toxins removed after supplying artificial blood at a flow rate of 10 mL/min and permeate at a flow rate of 40 mL/min for 6 hours to the hollow fiber membrane prepared in <Example 2> was confirmed. In addition, artificial blood with a flow rate of 6.5 ml/min and permeate with a flow rate of 26 ml/min were supplied to the hollow fiber membranes prepared in <Example 3> to <Example 4> for 6 hours, and the hollow fiber membranes prepared in <Example 5> Artificial blood with a flow rate of 2.5 ml/min and permeate with a flow rate of 10 ml/min were supplied to one hollow fiber membrane for 6 hours, and the average value of the removed uremic toxins was confirmed.

As a result, as shown in [Table 1] below, it was confirmed that the uremic toxin removal effect of the hollow fiber membrane manufactured in <Example 2>, which had a large inner diameter and a thin membrane thickness, was excellent overall. In addition, it was confirmed that the hollow fiber membranes manufactured in <Example 2>, <Example 3>, and <Example 5> hardly removed BSA in artificial blood.

Amount of uremic toxin removed after 6 hours (average value) g/㎡ Element Creatinine indoxyl sulfate p-cresol hippuric acid Example 2 195,884 9,372 4,785 7,322 4,449 Example 3 146,287 7,802 4,045 7,443 3,912 Example 4 143,773 4,903 3,260 6,408 2,932 Example 5 266,395 11,986 3,714 7,368 4,198

Claims (20)

An ultrafiltration hollow fiber membrane manufactured from a dope solution containing polysulphone resin and glycol resin.
According to paragraph 1,
The polysulfone resin is an ultrafiltration hollow fiber membrane comprising at least one selected from the group consisting of polyethersulfone (PES), polysulfone (PSU), and polyphenylenesulfone (PPSU).
According to paragraph 1,
The glycol resin is one or more selected from the group consisting of ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, and polyethylene glycol. Including, ultrafiltration hollow fiber membrane.
According to paragraph 1,
The dope solution is an ultrafiltration hollow fiber membrane containing polysulfone resin and glycol resin in a mass ratio of 3:1 to 1:3.
According to paragraph 1,
The dope solution is an ultrafiltration hollow fiber membrane containing polysulfone resin and glycol resin in a mass ratio of 2:1 to 1:2.
According to paragraph 1,
The dope solution is an ultrafiltration hollow fiber membrane containing polysulfone resin and glycol resin at a mass ratio of 1:2.
According to paragraph 1,
The hollow fiber membrane is an ultrafiltration hollow fiber membrane that is used as a separation membrane for hemodialysis, hemofiltration, or hemodiafiltration to filter uremic toxins and waste products in the blood.
According to paragraph 1,
The hollow fiber membrane is an ultrafiltration hollow fiber membrane having a membrane thickness of 35 ㎛ to 70 ㎛.
According to paragraph 1,
The hollow fiber membrane is an ultrafiltration hollow fiber membrane with a pore size of 8.5 nm to 16 nm.
According to paragraph 1,
The hollow fiber membrane is an ultrafiltration hollow fiber membrane having an outer diameter of 250 ㎛ to 690 ㎛ and an inner diameter of 200 ㎛ to 600 ㎛.
According to paragraph 1,
The hollow fiber membrane is an ultrafiltration hollow fiber membrane having a water permeability of 90 ㎖/㎡/h/mmhg to 190 ㎖/㎡/h/mmhg.
Forming a mixed solution by dissolving polysulfone resin and glycol resin in a solvent;
Preparing a dope solution by stirring the mixed solution for 24 hours and then degassing it;
Supplying the dope solution to an external nozzle of a dual nozzle and supplying a bore solution to an internal nozzle of the dual nozzle;
forming a hollow fiber membrane by spinning the dope solution and bore solution supplied to the nozzle into a coagulation bath and winding it with a winder;
gelling the wound hollow fiber membrane in a water bath, washing it with water, and then immersing it in glycerol; and
A method of producing an ultrafiltration hollow fiber membrane comprising: drying the hollow fiber membrane immersed in glycerol at room temperature in the air.
According to clause 12,
The polysulfone resin is a resin containing at least one selected from the group consisting of polyethersulfone, polysulfone, and polyphenylene sulfone, and the glycol resin is ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, and polyethylene. An ultrafiltration hollow fiber membrane, which is a resin containing at least one selected from the group consisting of glycol.
According to clause 12,
The dope solution is an ultrafiltration hollow fiber membrane containing polysulfone resin and glycol resin in a mass ratio of 2:1 to 1:2.
According to clause 12,
The dope solution is an ultrafiltration hollow fiber membrane containing polysulfone resin and glycol resin at a mass ratio of 1:2.
According to clause 12,
The bore solution is an ultrafiltration hollow fiber membrane comprising one or more selected from the group consisting of glycerol, dimethoxyethanol, N-methyl-2-pyrrolidone, methanol, ethanol, isopropanol, acetone, dimethylacetamide, and water.
According to clause 12,
A method of manufacturing an ultrafiltration hollow fiber membrane, wherein the inner diameter size and membrane thickness of the hollow fiber membrane are adjusted by controlling the flow rate of the dope solution and the bore solution.
According to clause 12,
The flow rate of the dope solution supplied to the nozzle is 0.5 to 3 ml/min, and the flow rate of the bore solution is 2 to 5 ml/min.
According to clause 12,
An air gap between the double nozzle and the coagulation tank is 20 cm to 30 cm.
According to clause 12,
A method of manufacturing an ultrafiltration hollow fiber membrane, wherein the winding speed of the winder is 8 to 11 m/min.