KR100416135B1 - Polysulfone hollow fiber membrane for hemodialysis and method for manufacturing the same - Google Patents
Polysulfone hollow fiber membrane for hemodialysis and method for manufacturing the same Download PDFInfo
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- KR100416135B1 KR100416135B1 KR1019970079121A KR19970079121A KR100416135B1 KR 100416135 B1 KR100416135 B1 KR 100416135B1 KR 1019970079121 A KR1019970079121 A KR 1019970079121A KR 19970079121 A KR19970079121 A KR 19970079121A KR 100416135 B1 KR100416135 B1 KR 100416135B1
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- hollow fiber
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- polysulfone
- hemodialysis
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- 239000012528 membrane Substances 0.000 title claims abstract description 77
- 229920002492 poly(sulfone) Polymers 0.000 title claims abstract description 63
- 239000012510 hollow fiber Substances 0.000 title claims abstract description 58
- 238000001631 haemodialysis Methods 0.000 title claims abstract description 25
- 230000000322 hemodialysis Effects 0.000 title claims abstract description 25
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 15
- 238000000034 method Methods 0.000 title claims abstract description 13
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims abstract description 44
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims abstract description 44
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims abstract description 44
- 239000011347 resin Substances 0.000 claims abstract description 25
- 229920005989 resin Polymers 0.000 claims abstract description 25
- 230000035699 permeability Effects 0.000 claims abstract description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000003960 organic solvent Substances 0.000 claims abstract description 17
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims abstract description 15
- 239000000203 mixture Substances 0.000 claims abstract description 12
- 150000002334 glycols Chemical class 0.000 claims abstract description 10
- 238000009987 spinning Methods 0.000 claims description 24
- 230000001112 coagulating effect Effects 0.000 claims description 18
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 17
- 239000011148 porous material Substances 0.000 claims description 16
- 238000005345 coagulation Methods 0.000 claims description 14
- 230000015271 coagulation Effects 0.000 claims description 14
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 13
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 12
- -1 glycol compound Chemical class 0.000 claims description 11
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 11
- 239000002202 Polyethylene glycol Substances 0.000 claims description 4
- 230000007717 exclusion Effects 0.000 claims description 4
- 229920001223 polyethylene glycol Polymers 0.000 claims description 4
- 102000036675 Myoglobin Human genes 0.000 claims description 3
- 108010062374 Myoglobin Proteins 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- 150000003457 sulfones Chemical class 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 6
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 abstract 2
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 abstract 1
- 239000001110 calcium chloride Substances 0.000 abstract 1
- 229910001628 calcium chloride Inorganic materials 0.000 abstract 1
- 235000011148 calcium chloride Nutrition 0.000 abstract 1
- 239000000470 constituent Substances 0.000 abstract 1
- 229910001629 magnesium chloride Inorganic materials 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 23
- 238000000926 separation method Methods 0.000 description 13
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- 239000000126 substance Substances 0.000 description 5
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 4
- 239000008280 blood Substances 0.000 description 4
- 210000004369 blood Anatomy 0.000 description 4
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 4
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 description 4
- 229920003169 water-soluble polymer Polymers 0.000 description 4
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 239000000701 coagulant Substances 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000000593 degrading effect Effects 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 229920001477 hydrophilic polymer Polymers 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- 239000003352 sequestering agent Substances 0.000 description 2
- LZDKZFUFMNSQCJ-UHFFFAOYSA-N 1,2-diethoxyethane Chemical compound CCOCCOCC LZDKZFUFMNSQCJ-UHFFFAOYSA-N 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- OWBTYPJTUOEWEK-UHFFFAOYSA-N butane-2,3-diol Chemical compound CC(O)C(C)O OWBTYPJTUOEWEK-UHFFFAOYSA-N 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 238000000502 dialysis Methods 0.000 description 1
- BTVWZWFKMIUSGS-UHFFFAOYSA-N dimethylethyleneglycol Natural products CC(C)(O)CO BTVWZWFKMIUSGS-UHFFFAOYSA-N 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000001471 micro-filtration Methods 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 238000001223 reverse osmosis Methods 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000011550 stock solution Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000000108 ultra-filtration Methods 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/66—Polymers having sulfur in the main chain, with or without nitrogen, oxygen or carbon only
- B01D71/68—Polysulfones; Polyethersulfones
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61M—DEVICES FOR INTRODUCING MEDIA INTO, OR ONTO, THE BODY; DEVICES FOR TRANSDUCING BODY MEDIA OR FOR TAKING MEDIA FROM THE BODY; DEVICES FOR PRODUCING OR ENDING SLEEP OR STUPOR
- A61M1/00—Suction or pumping devices for medical purposes; Devices for carrying-off, for treatment of, or for carrying-over, body-liquids; Drainage systems
- A61M1/14—Dialysis systems; Artificial kidneys; Blood oxygenators ; Reciprocating systems for treatment of body fluids, e.g. single needle systems for hemofiltration or pheresis
- A61M1/16—Dialysis systems; Artificial kidneys; Blood oxygenators ; Reciprocating systems for treatment of body fluids, e.g. single needle systems for hemofiltration or pheresis with membranes
- A61M1/1621—Constructional aspects thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0002—Organic membrane manufacture
- B01D67/0009—Organic membrane manufacture by phase separation, sol-gel transition, evaporation or solvent quenching
- B01D67/0016—Coagulation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/08—Hollow fibre membranes
- B01D69/085—Details relating to the spinneret
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/08—Hollow fibre membranes
- B01D69/087—Details relating to the spinning process
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2323/00—Details relating to membrane preparation
- B01D2323/12—Specific ratios of components used
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2323/00—Details relating to membrane preparation
- B01D2323/15—Use of additives
- B01D2323/218—Additive materials
- B01D2323/2181—Inorganic additives
- B01D2323/21811—Metals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2323/00—Details relating to membrane preparation
- B01D2323/15—Use of additives
- B01D2323/218—Additive materials
- B01D2323/2182—Organic additives
- B01D2323/21839—Polymeric additives
- B01D2323/2185—Polyethylene glycol
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2323/00—Details relating to membrane preparation
- B01D2323/15—Use of additives
- B01D2323/218—Additive materials
- B01D2323/2182—Organic additives
- B01D2323/21839—Polymeric additives
- B01D2323/2187—Polyvinylpyrolidone
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/02—Details relating to pores or porosity of the membranes
- B01D2325/026—Sponge structure
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/02—Details relating to pores or porosity of the membranes
- B01D2325/0283—Pore size
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/20—Specific permeability or cut-off range
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/34—Molecular weight or degree of polymerisation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/36—Hydrophilic membranes
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Urology & Nephrology (AREA)
- Engineering & Computer Science (AREA)
- Heart & Thoracic Surgery (AREA)
- Anesthesiology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Vascular Medicine (AREA)
- Dispersion Chemistry (AREA)
- Biomedical Technology (AREA)
- Hematology (AREA)
- Emergency Medicine (AREA)
- Animal Behavior & Ethology (AREA)
- General Health & Medical Sciences (AREA)
- Public Health (AREA)
- Veterinary Medicine (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
- External Artificial Organs (AREA)
- Artificial Filaments (AREA)
Abstract
Description
본 발명은 혈액투석용 폴리설폰 중공사 막 및 그의 제조방법에 관한 것이다.The present invention relates to a polysulfone hollow fiber membrane for hemodialysis and a method of manufacturing the same.
선택투과성을 갖는 분리막 재질에 관해서는 많은 연구가 이루어져, 셀룰로스계, 폴리아미드계, 폴리아크릴계, 폴리비닐계 등이 개발되어 사용되고 있다. 그러나 이러한 재질들은 내생물분해성, 내화학성, 내열성 등에 결점이 있어, 이러한 단점들을 보완하기 위해 엔프라로 사용되는 수지에 대한 분리막 재질에의 응용이 진행되어 폴리설폰 등의 엔프라 수지가 분리막의 재질로 사용되고 있다.Much research has been made on separator materials having selective permeability, and cellulose-based, polyamide-based, polyacryl-based, polyvinyl-based, and the like have been developed and used. However, these materials have drawbacks such as biodegradability, chemical resistance, heat resistance, etc. To compensate for these disadvantages, the application of the resin to the membrane used for the resin to be used as an enpra resin, such as polysulfone resin such as polysulfone Is being used.
폴리설폰 수지는 내생물분해성, 내화학성, 내열성, 난연성 및 기계적 성질 등이 우수하여 혈액투석용, 정밀여과용, 한외여과용, 역삼투용 및 기체분리용 복합막의 지지체로서 사용되고 있다.Polysulfone resins have excellent biodegradability, chemical resistance, heat resistance, flame retardancy, and mechanical properties, and are used as a support for hemodialysis, microfiltration, ultrafiltration, reverse osmosis, and gas separation composite membranes.
일반적으로 폴리설폰 중공사 막은 폴리설폰 수지, 유기용매 및 첨가제로 구성된 방사 도프(dope)와 내부응고액을 2중관형노즐로 공기중으로 방사한 후 외부응고액으로 고화시켜 제조한다.Generally, polysulfone hollow fiber membranes are prepared by spinning a spinning dope and an internal coagulating solution composed of a polysulfone resin, an organic solvent and an additive into the air with a double-tubular nozzle and then solidifying it with an external coagulating solution.
방사 도프 제조시 용매로는 m-크레졸, 클로로벤젠, N-메틸-2-피롤리돈, 디메틸설폭사이드, 디메틸아세트아마이드, 디메틸포름아마이드 및 / 또는 이들의 혼합물 등이 사용되며, 첨가제로는 폴리에틸렌글리콜, 폴리비닐알콜, 폴리비닐피롤리돈 및 / 또는 이들의 혼합물 등의 수용성 고분자가 많이 사용되고 있다. 상기 첨가제들은 방사 도프의 점도 상승과 막의 투수성 증가를 위해 사용된다.In the preparation of the spinning dope, m-cresol, chlorobenzene, N-methyl-2-pyrrolidone, dimethyl sulfoxide, dimethylacetamide, dimethylformamide and / or mixtures thereof are used. Water-soluble polymers such as glycol, polyvinyl alcohol, polyvinylpyrrolidone and / or mixtures thereof are frequently used. The additives are used to increase the viscosity of the spinning dope and to increase the permeability of the membrane.
내부 및 외부응고액으로는 주로 물이 많이 사용되고 있으나 상기 첨가제들이 함유되어 있는 수용액을 사용하기도 한다.As the internal and external coagulating solution, water is mainly used, but an aqueous solution containing the additives may be used.
일반적으로 분리막(membrane)에 있어서 가장 중요한 2가지 성능은 분리능 및 투과능이나 이 두가지 성능은 서로 양립할 수 없어서 분리능이 커지면 투과능은 상대적으로 작아질 수 밖에 없고 투과능을 키우려면 분리능이 낮아질 수 밖에 없다.In general, the two most important performances of the membrane are separation and permeability, but the two performances are not compatible with each other. As the resolution increases, the permeability is inevitably smaller and the resolution can be lowered to increase permeability. There is nothing else.
따라서 분리막 개발의 주요 과제는 일정한 분리능을 가지면서 더 높은 투과능을 갖는 분리막을 제조하는 것이다. 특히 혈액투석용 분리막인 경우에는 인간의 건강 등을 고려할 때 다양한 물질로 구성되어 있는 혈액중에서 분리하고자 하는 특정 분리물질만을 선택적으로 제거할 수 있는 분리능과 투석시간 단축을 위한 투과능이 동시에 요구되고 있다.Therefore, the main task of the membrane development is to prepare a membrane having a higher permeability while having a constant resolution. In particular, in the case of a hemodialysis membrane, in consideration of human health, a separation ability capable of selectively removing only a specific separation substance to be separated from blood composed of various substances and a permeability for shortening the dialysis time are simultaneously required.
먼저 분리막의 투과능을 향상시키기 위해서는 무엇보다도 분리막내에 크고 많은 공경을 형성시켜야 한다. 또한 투과능을 유지하면서 분리능을 향상시키기 위해서는 분리막내에 형성된 공경들의 사이즈(SIZE)가 균일해야 한다.First of all, in order to improve the permeability of the membrane, a large and large pore size must be formed in the membrane. In addition, in order to improve the resolution while maintaining the permeability, the sizes of the pores formed in the separator must be uniform.
한편 방사 도프에 첨가된 수용성 고분자가 제막공정 후에도 계속 중공사 막에 많이 잔존하는 경우 일정분자량 이상의 물질 제거율(이하 분리능이라고 한다)의 저하없이도 폴리설폰 중공사 막의 친수성이 향상되어 투과성능이 좋아진다.On the other hand, when a large number of water-soluble polymers added to the spinning dope remain in the hollow fiber membrane even after the film forming step, the hydrophilicity of the polysulfone hollow fiber membrane is improved and the permeation performance is improved without a decrease in the removal rate (hereinafter referred to as separation ability) of a certain molecular weight or more.
그러나 수용성 고분자는 친수성이 강해 방사 후 응고 및 수세과정에서 대부분 폴리설폰 중공사 막 밖으로 빠져나가게 되고, 일부만이 잔존하게 된다.However, since the water-soluble polymer is hydrophilic, most of the water-soluble polymer escapes from the polysulfone hollow fiber membrane during the coagulation and washing process, and only a part of it remains.
미국 특허 5,340,480호에서는 폴리설폰 수지, 폴리에틸렌글리콜, 폴리비닐피롤리돈 및 유기용매로 구성된 방사 도프와 폴리비닐피롤리돈이 0.1∼4% 첨가된 수용액인 내부응고제를 사용하여 내표면 및 외표면에 스킨층을 갖는 중공사 막을 제조하는 방법을 제시하고 있지만, 혈액투석용 분리막에서 요구하는 투과능을 얻을 수 없다.U.S. Patent No. 5,340,480 discloses internal and external surfaces using a spinning dope composed of polysulfone resin, polyethylene glycol, polyvinylpyrrolidone and an organic solvent and an internal coagulant which is an aqueous solution containing 0.1 to 4% polyvinylpyrrolidone. Although a method for producing a hollow fiber membrane having a skin layer has been proposed, the permeability required by the membrane for hemodialysis cannot be obtained.
일본 공개 특허 소 58-104940호에서는 가교제를 사용하여 친수성 고분자를 폴리설폰 중공사 막 표면에 고정하는 방법을 제시하고 있지만, 공정 및 조작이 복잡하다.Japanese Patent Laid-Open No. 58-104940 discloses a method of fixing a hydrophilic polymer to a polysulfone hollow fiber membrane surface using a crosslinking agent, but the process and operation are complicated.
일본 공개 특허 소 63-97205호 및 동 63-97634호에서는 열처리나 방사선처리에 의해 친수성 고분자를 폴리설폰 중공사 막 표면에 고정하는 방법을 제시하고 있지만, 공정이 복잡하고 고가의 설비가 필요한 문제가 있다.Japanese Patent Laid-Open Nos. 63-97205 and 63-97634 disclose a method of fixing a hydrophilic polymer on the surface of a polysulfone hollow fiber membrane by heat treatment or radiation treatment, but the problem of complicated process and expensive equipment is required. have.
따라서 분리능 및 투과능이 동시에 우수한 혈액투석용 폴리설폰 중공사 막의 개발이 요구되어 왔다.Therefore, development of polysulfone hollow fiber membranes for hemodialysis having excellent separation and permeability at the same time has been required.
본 발명은 분리능과 투과능이 동시에 우수한 혈액투석용 폴리설폰 중공사 막 및 그의 제조방법을 제공하고자 한다.The present invention is to provide a polysulfone hollow fiber membrane for hemodialysis having excellent separation and permeability at the same time and a manufacturing method thereof.
본 발명은 혈액투석용 폴리설폰 중공사 막 및 그의 제조방법에 관한 것이다.The present invention relates to a polysulfone hollow fiber membrane for hemodialysis and a method of manufacturing the same.
더욱 구체적으로 본 발명은 폴리설폰 수지, 유기용매 및 폴리비닐피롤리돈및 글리콜류 화합물로 구성된 방사 도프(dope)와 내부응고액을 2중관형노즐로 공기중으로 방사한 후 외부응고액으로 고화시켜 폴리설폰 중공사 막을 제조함에 있어서, 아래 조건으로 조성된 방사 도프와 물, 알칼리토금속 및 글리콜류 화합물들이 아래 조건으로 조성된 내부응고액을 사용하는 것을 특징으로 하는 혈액투석용 폴리설폰 중공사 막의 제조방법에 관한 것이다.More specifically, the present invention is to spun into the air after the spinning dope and the internal coagulation solution consisting of polysulfone resin, organic solvent and polyvinylpyrrolidone and glycol compounds in a double-tubular nozzle to solidify the external coagulation solution In preparing a polysulfone hollow fiber membrane, a polysulfone hollow fiber membrane for hemodialysis is characterized by using a spinning dope formed under the following conditions and an internal coagulating solution having water, alkaline earth metals and glycol compounds formed under the following conditions. It is about a method.
- 아 래 --Below-
·방사 도프 조성 조건Radiation dope composition condition
① 유기용매에 대한 유기용매외 모든 성분의 중량비 : 0.2∼0.5배① Weight ratio of all components other than organic solvent to organic solvent: 0.2 ~ 0.5 times
② 폴리설폰 수지에 대한 폴리비닐피롤리돈의 중량비 : 0.5~5배② Weight ratio of polyvinylpyrrolidone to polysulfone resin: 0.5-5 times
③ 폴리설폰 수지에 대한 글리콜류 화합물의 중량비 : 0.5~5배③ Weight ratio of glycol compound to polysulfone resin: 0.5 to 5 times
·내부응고액 조성 조건Internal coagulation liquid composition
① 물에 대한 알칼리토금속의 중량비 : 0.3∼0.6배① Weight ratio of alkaline earth metal to water: 0.3 ~ 0.6 times
또한 본 발명은 상기 제조방법으로 제조되어 막의 내부가 스폰지(Sponge) 구조이고, 막의 내표면은 배율이 10,000배인 주사전자현미경으로도 관찰되지 않는 작은 사이즈의 공경들이 형성된 스킨층이고, 내표면과 막 두께의 중앙부 사이에는 사이즈가 0.1~3㎛인 공경들이 형성되어 있는 혈액투석용 폴리설폰 중공사 막에 관한 것이다.In addition, the present invention is made by the manufacturing method of the inside of the membrane (Sponge) structure (Sponge), the inner surface of the membrane is a skin layer formed of pores of small size not observed even by scanning electron microscope with a magnification of 10,000 times, the inner surface and the membrane It relates to a polysulfone hollow fiber membrane for hemodialysis, in which pores having a size of 0.1 to 3 μm are formed between the central portions of the thickness.
이하, 본 발명을 상세하게 설명하기로 한다.Hereinafter, the present invention will be described in detail.
먼저, 폴리설폰 수지를 유기용매에 용해시킨 다음 여기에 폴리비닐피롤리돈(PVP)과 글리콜류 화합물을 첨가하여 방사 도프를 제조한다.First, polysulfone resin is dissolved in an organic solvent, and then polyvinylpyrrolidone (PVP) and a glycol compound are added thereto to prepare spinning dope.
폴리비닐피롤리돈(PVP)과 글리콜류 화합물은 분리막내에 공경(Pore)을 형성하는 역할을 하며 친수성이 강하여 방사 후 응고 및 수세과정에서 대부분 씻겨나가고 일부만이 분리막내에 잔존하게 된다.Polyvinylpyrrolidone (PVP) and glycol compounds play a role of forming pores in the membrane, and the hydrophilicity is strong so that most of them are washed off during the coagulation and washing process after spinning, and only some remain in the separator.
폴리비닐피롤리돈이 중공사 막내에 많이 잔존할 수 있도록 폴리비닐피롤리돈은 분자량이 10.000~2,000,000인 것을 사용한다. 글리콜류 화합물로는 폴리에틸렌글리콜 또는 폴리비닐알콜 등을 사용한다.Polyvinylpyrrolidone has a molecular weight of 10.000 to 2,000,000 so that polyvinylpyrrolidone can remain in the hollow fiber membrane. Polyethylene glycol, polyvinyl alcohol, etc. are used as a glycol compound.
유기용매로는 m-크레졸, 클로로벤젠, N-메틸-2-피롤리돈, 디메틸설폭사이드, 디메틸아세트아마이드, 디메틸포름아마이드 및 / 또는 이들의 혼합물 등을 사용한다.As the organic solvent, m-cresol, chlorobenzene, N-methyl-2-pyrrolidone, dimethyl sulfoxide, dimethylacetamide, dimethylformamide and / or mixtures thereof are used.
유기용매에 대한 유기용매의 기타 모든 성분(폴리설폰 수지, 폴리비닐피롤리돈 및 글리콜류 화합물)의 중량비는 0.2∼0.5배가 되도록 한다. 즉 유기용매 100중량부에 대해 유기용매외 기타 모든 성분 20∼50중량부를 사용한다.The weight ratio of all other components of the organic solvent (polysulfone resin, polyvinylpyrrolidone and glycol compounds) to the organic solvent is 0.2-0.5 times. That is, 20-50 weight part of all other components other than an organic solvent are used with respect to 100 weight part of organic solvents.
또한 폴리설폰 수지에 대한 폴리비닐피롤리돈의 중량비는 0.5~5배가 되도록 한다. 즉 폴리설폰 수지 100중량부에 대해 폴리비닐피롤리돈 50중량부 이상을 사용한다. 또한 폴리설폰 수지에 대한 글리콜류 화합물의 중량비는 0.5~5배가 되도록 한다. 즉 폴리설폰 수지 100중량부에 대해 글리콜류 화합물 50중량부 이상을 사용한다.In addition, the weight ratio of polyvinylpyrrolidone to polysulfone resin is 0.5 to 5 times. That is, 50 weight part or more of polyvinylpyrrolidone is used with respect to 100 weight part of polysulfone resins. In addition, the weight ratio of the glycol compound to the polysulfone resin is 0.5 to 5 times. That is, 50 weight part or more of glycol compounds are used with respect to 100 weight part of polysulfone resins.
방사 도프가 상기 조건들을 벗어나게 조성되는 경우에는 중공사 막 제조 공정성이 나빠지며 본 발명에서 희망하는 막의 구조를 얻을 수 없게 되어 중공사 막의 분리능 및 투과능이 저하된다.When the spinning dope is formulated out of the above conditions, the hollow fiber membrane manufacturing processability is deteriorated, and the structure of the membrane desired in the present invention cannot be obtained, thereby degrading the separation ability and permeability of the hollow fiber membrane.
다음으로는 통상의 2중관형노즐을 사용하여 상기 방사 도프와 내부응고액을 공기중으로 방사하고, 외부응고액에서 응고, 수세 및 권취하여 폴리설폰 중공사를 제조한다. 이때 2중관형노즐로는 외경 0.3~0.5mm, 내경 0.2∼0.25mm, 내부노즐 지름 0.1∼0.15mm 수준의 환상 슬릿 구금 등을 사용할 수 있다.Next, the spinning dope and the internal coagulating solution are spun into the air using a conventional double-tubular nozzle, and coagulated, washed with water and wound up in the external coagulated solution to produce polysulfone hollow fiber. In this case, as the double tube nozzle, an annular slit mold having an outer diameter of 0.3 to 0.5 mm, an inner diameter of 0.2 to 0.25 mm, and an inner nozzle diameter of 0.1 to 0.15 mm may be used.
방사시 2.5g/분 수준으로 폴리머를 토출하고, 에어 갭(air gap)은 약 10cm 정도가 되도록 한다.The polymer is discharged at the level of 2.5 g / min during spinning, and the air gap is about 10 cm.
상기 내부응고액으로는 물, 알칼리토금속 및 글리콜류 화합물로 구성된 용액을 사용한다. 내부응고액중 물에 대한 알칼리토금속의 중량비는 0.3∼0.6배로 한다. 즉 물 100중량부에 대해 알칼리토금속 30∼60중량부를 사용한다. 그리고 내부응고액내 알칼리토금속 함량은 0.01~10중량%로 한다. 알칼리토금속 함량이 10중량%를 초과하는 경우에는 중공사 막내에 너무 많은 공경이 형성되어 투과능은 증가하나 분획분자량이 낮은 물질을 제거할 수 없게 된다.As the internal coagulating solution, a solution composed of water, alkaline earth metals and glycol compounds is used. The weight ratio of alkaline earth metal to water in the internal coagulating solution is 0.3 to 0.6 times. That is, 30 to 60 parts by weight of alkaline earth metal is used based on 100 parts by weight of water. And the content of alkaline earth metal in the internal coagulating solution is 0.01 ~ 10% by weight. If the alkaline earth metal content exceeds 10% by weight, too much pore is formed in the hollow fiber membrane, so that the permeability is increased but the material having low fractional molecular weight cannot be removed.
내부응고액 조성시 사용하는 글리콜류 화합물로는 디에틸렌글리콜을 사용한다. 이들은 중공사 막내에 존재하는 폴리비닐피롤리돈과 복합체(Complex)를 구성하여 보다 많은 폴리비닐피롤리돈이 중공사 막내에 잔존하도록 하는 역할을 한다.Diethylene glycol is used as a glycol compound used for internal coagulating liquid composition. They form a complex with polyvinylpyrrolidone present in the hollow fiber membranes so that more polyvinylpyrrolidone remains in the hollow fiber membranes.
외부응고액으로는 물을 주로 사용하나 필요에 따라서 알칼리토금속 및 글리콜류 화합물을 첨가할 수도 있다.Water is mainly used as the external coagulant, but alkaline earth metals and glycol compounds may be added as necessary.
본 발명은 내부응고액중에 디에틸렌글리콜을 첨가하여 중공사 막 내부에 많은 양의 폴리비닐피롤리돈을 잔존시킴과 동시에 내부응고액중에 알칼리토금속을 첨가하여 중공사 막내에 사이즈가 크고 균일한 공경들을 많이 형성함을 특징으로 한다.In the present invention, diethylene glycol is added to the internal coagulation solution to retain a large amount of polyvinylpyrrolidone inside the hollow fiber membrane, and alkaline earth metal is added to the internal coagulation solution to increase the size and uniform pore size in the hollow fiber membrane. It is characterized by the formation of a lot of them.
디에틸렌글리콜(DEG)가 첨가되지 않은 내부응고액을 사용할 경우, 폴리비닐피롤리돈(PVP)은 친수성이 강하여 방사 후 응고 및 수세과정에서 대부분 물에 씻겨 폴리설폰 중공사 막 밖으로 빠져나가게 된다. 즉 방사 및 응고과정에서 폴리설폰 폴리머가 급속하게 고화될 때 상기 폴리머 메트릭스 안에 갖혀서 미처 빠져나오지 못한 일부의 폴리비닐피롤리돈(PVP)만이 폴리설폰 중공사 막내에 잔존하게 된다.In the case of using the internal coagulation solution without the addition of diethylene glycol (DEG), polyvinylpyrrolidone (PVP) is hydrophilic, and is washed out with water during the coagulation and washing process after spinning, and then escapes the polysulfone hollow fiber membrane. That is, when polysulfone polymer solidifies rapidly during spinning and solidification, only some of the polyvinylpyrrolidone (PVP) retained in the polymer matrix remains in the polysulfone hollow fiber membrane.
특히 상기 막 표면은 외부응고액과 직접 접촉하여 급속하게 고화되므로 막의 내부보다는 표면에 상대적으로 많은 폴리비닐피롤리돈(PVP)이 잔존하게 된다.In particular, the surface of the membrane is directly solidified by direct contact with the external coagulating solution, so that more polyvinylpyrrolidone (PVP) remains on the surface than the inside of the membrane.
본 발명의 경우에는 내부응고액내에 함유되어 있는 디에틸렌글리콜(DEG)이 폴리비닐피롤리돈(PVP)의 응고액 및 물에 대한 용해도를 저하시키고 폴리설폰 수지와의 친화력을 향상시켜서, 최종 폴리설폰 중공사 막내에 폴리비닐피롤리돈(PVP)의 잔존량을 많게할 수 있다.In the present invention, diethylene glycol (DEG) contained in the internal coagulation solution lowers the solubility of the polyvinylpyrrolidone (PVP) in the coagulation solution and water and improves the affinity with the polysulfone resin. The amount of polyvinylpyrrolidone (PVP) remaining in the sulfone hollow fiber membrane can be increased.
상기와 같이 폴리비닐피롤리돈(PVP)의 물에 대한 용해도가 저하되는 이유는 폴리비닐피롤리돈(PVP)의 친수성기인 피롤리돈기와 디메틸에틸렌글리콜의-OH기가 수소결합하여 복합체(Complex)를 구성하기 때문으로 판단된다.The reason why the solubility of polyvinylpyrrolidone (PVP) in water is lowered as described above is that the pyrrolidone, which is a hydrophilic group of polyvinylpyrrolidone (PVP), and the -OH group of dimethylethylene glycol are hydrogen-bonded to complex. It is judged because it constitutes.
이와 같이 폴리비닐피롤리돈과 디에틸렌글리콜의 복합체가 형성되면 폴리비닐피롤리돈(PVP)의 물 및 응고액에 대한 용해도가 떨어져 폴리설폰 중공사 막내에 많은 양의 폴리비닐피롤리돈이 잔존하게 된다. 또한 상기 복합체는 막내에 잔존하는 폴리비닐피롤리돈이 균일하게 분산시키는 역할도 한다.As such, when a complex of polyvinylpyrrolidone and diethylene glycol is formed, solubility of polyvinylpyrrolidone (PVP) in water and coagulant drops, and a large amount of polyvinylpyrrolidone remains in the polysulfone hollow fiber membrane. Done. The complex also serves to uniformly disperse the polyvinylpyrrolidone remaining in the membrane.
상기 복합체가 형성되지 않는 경우에는 폴리설폰 수지 자체의 소수성에 의해메트릭스내에 잔존하는 폴리비닐피롤리돈중 친수성 부분은 안쪽으로 집합(aggregation)되고 소수성 부분은 바깥쪽으로 집합하게 된다. 그 결과 실제 분리물질과 접촉하게 되는 중공사 막의 부분이 소수성일 가능성이 높아져 분리공정이 어렵게 된다.When the complex is not formed, the hydrophilic portion of the polyvinylpyrrolidone remaining in the matrix is aggregated inward and the hydrophobic portion is aggregated outward by the hydrophobicity of the polysulfone resin itself. As a result, the portion of the hollow fiber membrane which comes into contact with the actual separation material is more likely to be hydrophobic, making the separation process difficult.
그러나 본 발명의 경우에는 폴리비닐피롤리돈과 디에틸글리콜의 복합체가 형성되기 때문에 상기와 같은 문제를 해결할 수 있다.However, in the present invention, since a complex of polyvinylpyrrolidone and diethyl glycol is formed, the above problem can be solved.
또한 내부응고액중에 첨가된 알칼리토금속은 방사원액이 고화되기 전에 중공사 막을 통과하면서 주위의 소수성(예, 분리막 자체의 소수성) 때문에 수화된 침전상태로 존재하게 되어 상기 막내에 사이즈가 크고 균일한 공경형성을 촉진하게 된다.In addition, alkaline earth metals added to the internal coagulating solution pass through the hollow fiber membrane before the spinning stock solution solidifies and exist as a hydrated precipitate due to the surrounding hydrophobicity (e.g., hydrophobicity of the separator itself). Will promote formation.
본 발명의 혈액투석용 폴리설폰 중공사 막은 막의 내부가 스폰지(Sponge) 구조이고, 막의 내표면은 배율이 10,000배인 주사전자현미경으로도 관찰되지 않는 작은 사이즈의 공경들이 형성된 스킨층이고, 내표면과 막 두께의 중앙부 사이에는 사이즈가 0.1~3㎛인 공경들이 형성되어 있고, 막 두께의 중앙부로 부터 외표면까지는 0.01∼1㎛의 공경들이 형성되어 있다.The polysulfone hollow fiber membrane for hemodialysis of the present invention has a sponge structure inside the membrane, and the inner surface of the membrane is a skin layer in which pores of small size are not observed even with a scanning electron microscope having a magnification of 10,000 times. The pores having a size of 0.1 to 3 탆 are formed between the central portions of the film thickness, and the pores of 0.01 to 1 탆 are formed from the central portion of the film thickness to the outer surface.
본 발명의 혈액투석용 폴리설폰 중공사 막은 분획분자량이 20,000~500,000이고, 사이터크롬-씨(Cytochrome-C)의 배제율이 0∼30%이고, 마이오글로빈(Myoglobin)의 배제율이 80∼100% 이고, 순수투과계수가 0.2∼0.5㎖/분/kgf/㎠ 이다.The polysulfone hollow fiber membrane for hemodialysis of the present invention has a fractional molecular weight of 20,000 to 500,000, a cytochrome-C exclusion rate of 0 to 30%, and a myoglobin exclusion rate of 80 to 100%. % And the pure water transmission coefficient is 0.2 to 0.5 ml / min / kgf / cm 2.
본 발명의 방법으로 제조한 혈액투석용 폴리설폰 중공사 막은 친수성이 개선되고 사이즈가 크고 균일한 공경이 많이 형성되어 있어서 비슷한 제거능을 가진(비슷한 공경 사이즈를 가진) 다른 분리막에 비해 상대적으로 높은 투과능을 갖는다. 즉 분리능의 저하없이 투과능이 향상되어 분리공정의 효율성이 좋아진다.Polysulfone hollow fiber membranes for hemodialysis prepared by the method of the present invention have a relatively high permeability compared to other membranes having similar removal ability (similar pore size) due to improved hydrophilicity and large size and uniform pore size. Has In other words, the permeability is improved without degrading the resolution and the efficiency of the separation process is improved.
본 발명에 있어서 순수투과성능 및 분리물질 제거율은 아래와 같은 방법으로 측정한다.In the present invention, the pure water permeation performance and separation material removal rate are measured by the following method.
· 순수투과성능(LP) 평가· Pure Permeability (LP) Evaluation
길이 15cm의 중공사 20가닥을 사용하여 소형 유리관 모듈을 작성하여 막간 압력을 약 1kgf로 유지시킨 상태에서의 순수의 투과성을 산출한다.(LP:㎖/분/kgf/㎠)A small glass tube module was prepared using 20 strands of hollow fiber of 15 cm in length to calculate the permeability of pure water while maintaining the intermembrane pressure at about 1 kgf. (LP: ml / min / kgf / cm2)
· 분리물질 제거율 평가Evaluation of removal rate of separated substance
ATI-6000 스펙트로포토메터를 이용하여 비탁시간분석법으로 폴리설폰 중공사 막 투과 전후의 혈액내 사이터크롬-씨(Cytochrome-C) 또는 마이오그로빈(Myoglobin)의 농도를 측정한 다음 이들을 아래 식에 대입하여 산출한다.Using a ATI-6000 spectrophotometer, the concentrations of cytochrome-C or myoglobin in the blood before and after polysulfone hollow fiber membrane permeation were measured using a non-tax time analysis method. Calculate by substitution.
식에서, A는 폴리설폰 중공사 막 투과전 혈액내 분리물질의 농도이고 B는 투과후 혈액내 분리물질의 농도이다.Where A is the concentration of the sequestrant in the blood before permeation of the polysulfone hollow fiber membrane and B is the concentration of the sequestrant in the blood after permeation.
이하 실시예를 통하여 본 발명을 더욱 구체적으로 살펴본다. 그러나 본 발명이 아래 실시예에만 한정되는 것은 아니다.Hereinafter, the present invention will be described in more detail with reference to the following examples. However, the present invention is not limited only to the following examples.
실시예 1Example 1
폴리설폰 수지(P-3500 : 아모코 회사 제품) 15중량%, 폴리비닐피롤리돈 10중량% 및 폴리에틸렌글리콜 10중량%를 디메틸아세트아마이드 65중량%에 투입한 후 교반, 용해시켜 투명한 방사 도프를 제조한다.15% by weight of polysulfone resin (P-3500: manufactured by Amoco Co., Ltd.), 10% by weight of polyvinylpyrrolidone and 10% by weight of polyethylene glycol were added to 65% by weight of dimethylacetamide, followed by stirring and dissolution to provide a transparent spinning dope. Manufacture.
한편 물 20중량%에 디에틸렌글리콜 70중량%와 CaCl210중량%를 첨가하여 내부응고액을 제조한다. 상기 방사 도프와 내부응고액을 통상의 2중관형노즐로 방사하여 외경이 280㎛이고 내경이 200㎛인 중공사를 제조한다. 제조한 중공사를 10cm의 에어 갭으로 유도하여 통과시킨 후 물(외부응고액) 속에서 응고 / 수세하고 50m/분의 권취 속도로 권취하여 폴리설폰 중공사를 제조한다.Meanwhile, 70 wt% of diethylene glycol and 10 wt% of CaCl 2 were added to 20 wt% of water to prepare an internal coagulation solution. The spinning dope and the internal coagulating solution are spun with a conventional double tube nozzle to produce a hollow fiber having an outer diameter of 280 µm and an inner diameter of 200 µm. The prepared hollow fiber is guided through an air gap of 10 cm and then coagulated / washed in water (external coagulating solution) and wound at a winding speed of 50 m / min to produce polysulfone hollow fiber.
상기 폴리설폰 중공사를 모듈내에 설치하여 폴리설폰 중공사 막을 제조한다.The polysulfone hollow fiber is installed in a module to produce a polysulfone hollow fiber membrane.
제조한 폴리설폰 중공사 막의 분리능 및 투과능을 측정한 결과는 표 2와 같다.Table 2 shows the results of measuring the resolution and permeability of the prepared polysulfone hollow fiber membranes.
실시예 2Example 2
방사 도프 및 내부응고액 조성을 표1과 같이 변경한 것을 제외하고는 실시예1과 동일한 공정 및 조건으로 폴리설폰 중공사 막을 제조한다.A polysulfone hollow fiber membrane was prepared in the same process and conditions as in Example 1 except that the spinning dope and the internal coagulating solution were changed as shown in Table 1.
제조한 폴리설폰 중공사 막의 분리능 및 투과능을 측정한 결과는 표2와 같다.Table 2 shows the results of measuring the separation and permeability of the polysulfone hollow fiber membrane.
본 발명의 혈액투석용 중공사 막은 친수성, 분리능 및 투과능이 매우하다.The hollow fiber membrane for hemodialysis of the present invention has very high hydrophilicity, resolution and permeability.
아울러 본 발명은 간단하고 효율적인 방법으로 혈액투석용 중공사 막에 친수성을 부여하고, 사이즈가 크고 균일한 공경을 많이 형성할 수 있다.In addition, the present invention can impart hydrophilicity to the hollow fiber membrane for hemodialysis in a simple and efficient manner, and can form many large and uniform pore sizes.
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| WO2024096486A1 (en) * | 2022-10-31 | 2024-05-10 | 주식회사 이노셉 | Double-layer hollow fiber membrane for hemodialysis and method for manufacturing same |
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| KR930003739A (en) * | 1991-07-06 | 1993-02-24 | 황선두 | Swivel device |
| US5474680A (en) * | 1991-11-19 | 1995-12-12 | Kanegafuchi Kagaku Kogyo Kabushiki Kaisha | Polysulfone porous hollow fiber |
| WO1996035504A1 (en) * | 1995-05-09 | 1996-11-14 | Teijin Limited | Hollow-fiber membrane of polysulfone polymer and process for the production thereof |
| JPH0929078A (en) * | 1995-07-19 | 1997-02-04 | Kuraray Co Ltd | Production of hollow yarn membrane |
| JPH09206569A (en) * | 1996-02-05 | 1997-08-12 | Toray Ind Inc | Separation membrane and its production |
| JPH09308685A (en) * | 1996-03-21 | 1997-12-02 | Kanegafuchi Chem Ind Co Ltd | Hollow fiber membrane for blood purification and blood purifying device |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR930003739A (en) * | 1991-07-06 | 1993-02-24 | 황선두 | Swivel device |
| US5474680A (en) * | 1991-11-19 | 1995-12-12 | Kanegafuchi Kagaku Kogyo Kabushiki Kaisha | Polysulfone porous hollow fiber |
| WO1996035504A1 (en) * | 1995-05-09 | 1996-11-14 | Teijin Limited | Hollow-fiber membrane of polysulfone polymer and process for the production thereof |
| JPH0929078A (en) * | 1995-07-19 | 1997-02-04 | Kuraray Co Ltd | Production of hollow yarn membrane |
| JPH09206569A (en) * | 1996-02-05 | 1997-08-12 | Toray Ind Inc | Separation membrane and its production |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2024096486A1 (en) * | 2022-10-31 | 2024-05-10 | 주식회사 이노셉 | Double-layer hollow fiber membrane for hemodialysis and method for manufacturing same |
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