KR20140048458A - Method for manufacturing asymmetric hollow fiber membrane and asymmetric hollow fiber membrane manufactured using the same - Google Patents
Method for manufacturing asymmetric hollow fiber membrane and asymmetric hollow fiber membrane manufactured using the same Download PDFInfo
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- KR20140048458A KR20140048458A KR1020120114216A KR20120114216A KR20140048458A KR 20140048458 A KR20140048458 A KR 20140048458A KR 1020120114216 A KR1020120114216 A KR 1020120114216A KR 20120114216 A KR20120114216 A KR 20120114216A KR 20140048458 A KR20140048458 A KR 20140048458A
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- Prior art keywords
- hollow fiber
- fiber membrane
- asymmetric hollow
- polymer solution
- solvent
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- 239000012528 membrane Substances 0.000 title claims abstract description 75
- 239000012510 hollow fiber Substances 0.000 title claims abstract description 61
- 238000000034 method Methods 0.000 title claims abstract description 42
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 30
- 239000002904 solvent Substances 0.000 claims abstract description 53
- 239000010410 layer Substances 0.000 claims abstract description 50
- 229920000642 polymer Polymers 0.000 claims abstract description 46
- 239000011247 coating layer Substances 0.000 claims abstract description 34
- 239000002033 PVDF binder Substances 0.000 claims abstract description 25
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims abstract description 25
- 239000000654 additive Substances 0.000 claims abstract description 20
- 230000000996 additive effect Effects 0.000 claims abstract description 17
- 238000005191 phase separation Methods 0.000 claims abstract description 14
- 238000007599 discharging Methods 0.000 claims abstract description 9
- DQWPFSLDHJDLRL-UHFFFAOYSA-N triethyl phosphate Chemical compound CCOP(=O)(OCC)OCC DQWPFSLDHJDLRL-UHFFFAOYSA-N 0.000 claims description 10
- 239000003795 chemical substances by application Substances 0.000 claims description 7
- 238000001914 filtration Methods 0.000 claims description 6
- 229920002307 Dextran Polymers 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- 230000006698 induction Effects 0.000 claims 1
- 241000700605 Viruses Species 0.000 abstract description 19
- 238000002145 thermally induced phase separation Methods 0.000 abstract description 12
- 238000009987 spinning Methods 0.000 abstract description 10
- 238000002156 mixing Methods 0.000 abstract description 4
- 230000007704 transition Effects 0.000 abstract 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 14
- 239000011148 porous material Substances 0.000 description 12
- 239000000126 substance Substances 0.000 description 12
- 230000035699 permeability Effects 0.000 description 9
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical group O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 8
- 238000000926 separation method Methods 0.000 description 7
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 6
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 6
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 6
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 3
- 230000001112 coagulating effect Effects 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 238000007711 solidification Methods 0.000 description 3
- 230000008023 solidification Effects 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- NIQCNGHVCWTJSM-UHFFFAOYSA-N Dimethyl phthalate Chemical compound COC(=O)C1=CC=CC=C1C(=O)OC NIQCNGHVCWTJSM-UHFFFAOYSA-N 0.000 description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- 238000005345 coagulation Methods 0.000 description 2
- 230000015271 coagulation Effects 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- KQNPFQTWMSNSAP-UHFFFAOYSA-N isobutyric acid Chemical compound CC(C)C(O)=O KQNPFQTWMSNSAP-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 2
- 238000005374 membrane filtration Methods 0.000 description 2
- 229920000609 methyl cellulose Polymers 0.000 description 2
- 239000001923 methylcellulose Substances 0.000 description 2
- 235000010981 methylcellulose Nutrition 0.000 description 2
- 230000001717 pathogenic effect Effects 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000007790 solid phase Substances 0.000 description 2
- 230000001954 sterilising effect Effects 0.000 description 2
- 238000004659 sterilization and disinfection Methods 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 239000011800 void material Substances 0.000 description 2
- BCNBMSZKALBQEF-UHFFFAOYSA-N 1,3-dimethylpyrrolidin-2-one Chemical compound CC1CCN(C)C1=O BCNBMSZKALBQEF-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 description 1
- 206010059866 Drug resistance Diseases 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 235000013361 beverage Nutrition 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 239000013043 chemical agent Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- FBSAITBEAPNWJG-UHFFFAOYSA-N dimethyl phthalate Natural products CC(=O)OC1=CC=CC=C1OC(C)=O FBSAITBEAPNWJG-UHFFFAOYSA-N 0.000 description 1
- 229960001826 dimethylphthalate Drugs 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 230000008571 general function Effects 0.000 description 1
- 229920001477 hydrophilic polymer Polymers 0.000 description 1
- 238000001471 micro-filtration Methods 0.000 description 1
- 230000000269 nucleophilic effect Effects 0.000 description 1
- 239000006259 organic additive Substances 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 244000052769 pathogen Species 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920000131 polyvinylidene Polymers 0.000 description 1
- WVLBCYQITXONBZ-UHFFFAOYSA-N trimethyl phosphate Chemical compound COP(=O)(OC)OC WVLBCYQITXONBZ-UHFFFAOYSA-N 0.000 description 1
- 238000000108 ultra-filtration Methods 0.000 description 1
- 238000004065 wastewater treatment 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
- 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
- B01D69/088—Co-extrusion; Co-spinning
-
- 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
-
- 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
- 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
- B01D67/0018—Thermally induced processes [TIPS]
-
- 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
- B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
-
- 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
- B01D69/10—Supported membranes; Membrane supports
- B01D69/107—Organic support material
-
- 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
- B01D69/12—Composite membranes; Ultra-thin membranes
- B01D69/1213—Laminated layers
-
- 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
- B01D71/30—Polyalkenyl halides
- B01D71/32—Polyalkenyl halides containing fluorine atoms
- B01D71/34—Polyvinylidene fluoride
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/24—Formation of filaments, threads, or the like with a hollow structure; Spinnerette packs therefor
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/08—Addition of substances to the spinning solution or to the melt for forming hollow filaments
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2323/00—Details relating to membrane preparation
- B01D2323/219—Specific solvent system
-
- 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
- B01D2325/022—Asymmetric membranes
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- 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
- B01D2325/04—Characteristic thickness
Abstract
Description
본 발명은 비대칭성 중공사막의 제조방법 및 이에 의해 제조된 비대칭성 중공사막에 관한 것으로, 보다 상세하게는 삼중 구금을 사용하여 복합 중공사를 제막하는 방법으로 지지층은 열유도 상분리법(TIPS, thermally induced phase separation)을 이용하여 폴리비닐리덴플로라이드, 빈용매, 첨가제를 혼합하여 고분자 용액을 제조하고 코팅층은 비용매유도 상분리법(NIPS, non-solvent induced phase separation)을 이용하여 폴리비닐리덴플로라이드, 양용매, 빈용매, 첨가제를 혼합하여 고분자 용액을 제조한 후 삼중구금을 통해 두 종류의 고분자 용액을 동시에 토출하여 방사 공정 및 상전이 공정, 후처리 공정을 거쳐 비대칭성 중공사막을 제조하는 방법 및 이에 의해 제조된 바이러스 제거용으로 사용할 수 있는 비대칭성 중공사막에 관한 것이다.
The present invention relates to a method for producing an asymmetric hollow fiber membrane and an asymmetric hollow fiber membrane produced thereby. More particularly, the present invention relates to a method for forming a hollow fiber membrane using a triple sheathing method, induced phase separation. The polymer solution was prepared by mixing polyvinylidene fluoride, poor solvent, and additives, and the coating layer was formed using polyvinylidene fluoride (NPS) using non-solvent induced phase separation (NIPS) , A method of preparing an asymmetric hollow fiber membrane through a spinning process, a phase transfer process, and a post-treatment process by simultaneously discharging two kinds of polymer solutions through a triple inserting process after preparing a polymer solution by mixing a good solvent, a poor solvent and an additive, To an asymmetric hollow fiber membrane which can be used for removing viruses produced thereby.
최근에 에너지 절약 및 환경보호를 주목적으로 하여 여러 응용분야에 걸쳐 다양한 분리막 및 이를 이용한 막분리 공정이 활발히 전개되고 있다. 특히 한외여과막 및 정밀여과막 등의 분리막은 수백나노미터에서 수십마이크로 미터 크기의 기공을 가지기 때문에 오폐수처리, 용수제조, 식품 및 의료공업 등을 포함한 여러 분야에 적용되고 있으며, 최근 먹는 물에 대한 관심이 증가함에 따라 그 활용이 점차 증가하고 있는 추세이다. Recently, diverse membranes and membrane separation processes using these membranes have been actively developed in various application fields with the primary aim of energy saving and environmental protection. In particular, membranes such as ultrafiltration membranes and microfiltration membranes have pores ranging in size from several hundred nanometers to several tens of micrometers. Therefore, they are applied to various fields including wastewater treatment, water production, food and medical industry, etc. As it increases, its utilization is gradually increasing.
한편, 음료수 제조, 의약품 제조, 식품 공업 분야에서는 제조 공정 내에 바이러스 등의 병원체가 혼입되면 제조 라인이 오염되고, 제품 중에 바이러스 등의 병원체가 혼입되어 최종 소비자의 집단 감염을 야기할 위험이 있기 때문에, 제조 라인이나 제품에는 다양한 살균 기술이 적용되고 있다. 그 살균 방법으로서는 가열 처리나 염소 등의 화학 약품에 의한 처리를 들 수 있지만, 열 내성이나 약품 내성을 갖는 바이러스에는 효과가 희박하다. 따라서, 바이러스를 물리적으로 제거하는 방법으로서 분리막을 이용한 막 여과가 주목을 모으게 되었다. 막 여과에 의하면, 바이러스의 열적 성질이나 화학적 성질에 관계없이 바이러스를 크기에 따라 판별하여 분리 제거할 수 있다. On the other hand, in the fields of beverage manufacturing, pharmaceutical manufacturing, and food industry, when a pathogen such as a virus enters the manufacturing process, the production line is contaminated and there is a risk that a pathogenic substance such as a virus is mixed in the product, Various sterilization technologies are applied to manufacturing lines and products. Examples of the sterilization method include heat treatment and treatment with chemical agents such as chlorine, but the effect is insignificant for viruses having heat tolerance and drug resistance. Therefore, membrane filtration using a membrane has attracted attention as a method of physically removing the virus. According to the membrane filtration, the virus can be discriminated and separated according to the size irrespective of the thermal properties and the chemical properties of the virus.
이와 같은 분리막에는 우수한 분리 성능, 화학적 강도(특히 내약품성), 물리적 강도, 및 투과 성능이 요구된다. 따라서, 화학적 강도(특히 내약품성)와 물리적 강도를 겸비하는 폴리불화비닐리덴계 수지를 이용한 분리막이 많은 분야에서 사용되게 되었다.Such separation membranes require excellent separation performance, chemical strength (especially chemical resistance), physical strength, and permeability. Accordingly, a separator using a polyvinylidene fluoride resin having both chemical strength (in particular, chemical resistance) and physical strength has been used in many fields.
폴리불화비닐리덴계 수지를 이용하여 분리여과막을 제조하는 방법 중 열유도 상분리법(TIPS)은 고온에서 용해된 고분자 용액을 저온의 매체와 접촉시켜 액체-고체 상분리 및 고화가 발생함으로써 다공성 분리막을 달성하는 방법이며, 비용매유도 상분리법(NIPS)은 고분자를 용해시킬 수 있는 용매에 고분자를 용해시켜 용매와 비용매가 고분자 용액 내에서 상호교환이 이루어짐으로써 액체-고체 상분리 및 고화를 유도하여 다공성 분리막을 달성하는 방법이다. 비용매유도 상분리법은 보다 경제적으로 막을 제조할 수는 있으나, 기계적 강도가 충분하지 않은 문제가 있으며, 열유도 상 분리법은 균질한 고강도 막을 얻을 수 있지만, 매크로보이드가 형성되고 핀홀과 같은 결함이 생길 가능성이 있다.The thermally induced phase separation method (TIPS) of a method of producing a separation filtration membrane using a polyvinylidene fluoride resin is a method in which a polymer solution dissolved at a high temperature is contacted with a medium at a low temperature to cause liquid-solid phase separation and solidification, (NIPS) is a method in which a polymer is dissolved in a solvent capable of dissolving a polymer, and a solvent and a non-solvent are exchanged in a polymer solution to induce liquid-solid phase separation and solidification, It is a way to achieve. Although the non-solvent-based phase separation method can produce a more economical film, there is a problem in that the mechanical strength is not sufficient, and the thermally induced phase separation method can obtain a homogeneous high strength film, but macroboids are formed and defects such as pinholes are generated There is a possibility.
폴리불화비닐리덴계 수지를 이용하여 분리여과막으로 제조한 종래의 예로, 대한민국 특허공개 제10-2010-0007245호에는 중공사 제막시 삼중 구금을 이용하여 중공사 표면에 분리활성층을 도입하여 제조하는 방법이 개시되어 있다. 그러나 이러한 방법은 종래의 TIPS를 이용한 중공사막에 비하여 높은 저지율은 지닐 수 있으나 표면의 기공 사이즈 제어가 힘든 문제점과 순수투과수량이 적은 단점이 있다. As a conventional example in which a polyvinylidene fluoride resin is used as a separation filtration membrane, Korean Patent Laid-Open No. 10-2010-0007245 discloses a method in which a separating active layer is introduced into the surface of a hollow fiber by using a triple- . However, this method has a higher rejection ratio than the conventional hollow fiber membrane using TIPS, but has a disadvantage in that it is difficult to control the pore size of the surface and has a disadvantage in that the pure water permeation amount is small.
특히, 바이러스 제거의 경우에는 얇은 치밀층에 핀홀이나 균열과 같은 결점이 존재하면, 바이러스가 이 결점으로부터 거대 공극(macrovoid)을 통과하여 뒤로 빠지므로, 바이러스를 완전히 제거할 수 없다는 문제점이 있다. 따라서, 핀홀이나 균열이 생기더라도 바이러스가 뒤로 빠지지 않기 위해서는, 분리막이 거대 공극을 포함하지 않는 치밀층을 갖고 있거나, 또는 거대 공극을 갖고 있더라도 치밀층의 막 두께에 대하여 충분히 작은 거대 공극일 것이 요구된다.Particularly, in the case of virus removal, if a thin dense layer has defects such as pinholes or cracks, viruses can not completely remove the virus because they pass through macrovoids from the defect and come back. Therefore, in order to prevent the virus from falling back even if pinholes or cracks occur, it is required that the separation membrane has a dense layer not containing a large void or a macropore small enough to have a film thickness of the dense layer even if it has a large void .
또한 종래 기술에 있어서는, 바이러스 제거가 가능한 정도의 표면 공경 및 막 두께를 가지면서, 거대 공극을 포함하지 않는 치밀층을 형성시킨 분리막의 경우, 실용적인 물리적 강도가 되는 막 두께로 하면 투수 성능이 현저히 저하되고, 반대로 실용적인 투수성능으로 하면 물리적 강도가 현저히 저하된다는 문제점이 있어, 물리적 강도와 투수성능을 함께 실용화 가능한 수준으로 하는 것이 곤란한 문제점이 있었다.
Further, in the prior art, in the case of a separation membrane having a surface pore size and a film thickness enough to remove viruses and a dense layer not containing large pores, when the film thickness becomes practical physical strength, On the contrary, when the practical permeability is improved, there is a problem that the physical strength is remarkably lowered, and it is difficult to make the physical strength and the water permeability performance a practical level.
본 발명은 상기와 같은 종래 기술의 문제점을 해결하기 위한 것으로, 본 발명의 하나의 목적은 TIPS와 NIPS를 이용하여 화학적 강도와 물리적 강도를 겸비하고 내구성을 구비한 구상 구조층과 거대 공극을 함유하지 않는 스폰지 구조층을 가짐으로써 바이러스 제거용 여과막으로 사용할 수 있는 비대칭성 중공사막의 제조방법을 제공하는 것이다.DISCLOSURE Technical Problem Accordingly, the present invention has been made keeping in mind the above problems occurring in the prior art, and it is an object of the present invention to provide a cemented carbide structure having both chemical strength and physical strength using TIPS and NIPS, The present invention provides a method for producing an asymmetric hollow fiber membrane which can be used as a filter membrane for virus removal by having a spongy structure layer which is free from viruses.
본 발명의 또 하나의 목적은 상기와 같은 본 발명에 따른 비대칭성 중공사막의 제조방법을 이용하여 제조되는 비대칭성 중공사막을 제공하는 것이다.
It is still another object of the present invention to provide an asymmetric hollow fiber membrane produced using the asymmetric hollow fiber membrane manufacturing method according to the present invention.
상기와 같은 목적을 달성하기 위한 본 발명의 하나의 양상은, 삼중 구금을 사용하여 비대칭성 중공사막을 제조하는 방법으로서 상기 방법은 상중 구금의 내부 노즐로 중공형성제를 토출시키고, 외부 노즐로 코팅층을 형성하는 고분자 용액을 토출시키며, 내부와 외부 사이의 노즐로 지지층을 형성하는 고분자 용액을 토출시키는 비대칭성 중공사막의 제조방법에 관한 것이다.One aspect of the present invention for achieving the above object is a method of manufacturing an asymmetric hollow fiber membrane using triple detention, the method is to discharge the hollow former to the inner nozzle of the upper detention, the coating layer to the outer nozzle The present invention relates to a method for producing an asymmetric hollow fiber membrane for discharging a polymer solution for forming a polymer, and for discharging the polymer solution for forming a support layer with a nozzle between the inside and the outside.
본 발명의 일 구현예에 따른 비대칭성 중공사막의 제조방법에 있어서, 상기 방법은 지지층이 열유도 상분리법(TIPS)에 의해 상분리가 일어나며, 코팅층이 비용매유도 상분리법(NIPS)에 의해 상분리가 일어나는 것을 특징으로 한다.In the method for producing an asymmetric hollow fiber membrane according to an embodiment of the present invention, the method is a phase separation is performed by the thermally induced phase separation method (TIPS), the coating layer is a phase separation by the non-solvent induced phase separation method (NIPS) It is characterized by what happens.
본 발명의 일 구현예에 따른 비대칭성 중공사막의 제조방법에 있어서, 상기 지지층을 형성하는 고분자 용액은 폴리비닐리덴플로라이드, 빈용매 및 첨가제를 포함하며, 코팅층을 형성하는 고분자 용액은 폴리비닐리덴플로라이드, 양용매, 빈용매 및 첨가제를 포함하는 것을 특징으로 한다.In the method of manufacturing an asymmetric hollow fiber membrane according to an embodiment of the present invention, the polymer solution forming the support layer includes polyvinylidene fluoride, a poor solvent and an additive, and the polymer solution forming the coating layer is polyvinylidene It is characterized by containing a fluoride, a good solvent, a poor solvent and an additive.
본 발명의 일 구현예에 따른 비대칭성 중공사막의 제조방법에 있어서, 상기 지지층을 형성하는 고분자 용액은 폴리비닐리덴플로라이드 25~45 중량%, 빈용매 55~70 중량%, 첨가제 1~10 중량%를 포함하며, 코팅층을 형성하는 고분자 용액은 폴리비닐리덴플로라이드 10~20 중량%, 양용매 40~70 중량%, 빈용매 10~40 중량%, 첨가제 0.1~10 중량%를 포함하는 것을 특징으로 한다.In the method for producing an asymmetric hollow fiber membrane according to an embodiment of the present invention, the polymer solution forming the support layer is 25 to 45% by weight polyvinylidene fluoride, 55 to 70% by weight poor solvent, 1 to 10% by weight additive %, Wherein the polymer solution forming the coating layer comprises 10 to 20% by weight of polyvinylidene fluoride, 40 to 70% by weight of good solvent, 10 to 40% by weight of poor solvent, and 0.1 to 10% by weight of additive. It is done.
본 발명의 일 구현예에 따른 비대칭성 중공사막의 제조방법은, 코팅층을 형성하는 고분자 용액의 양용매로서 트리에틸포스페이트(TEP)를 사용하는 것을 특징으로 한다. The method for producing an asymmetric hollow fiber membrane according to an embodiment of the present invention is characterized by using triethyl phosphate (TEP) as a good solvent for a polymer solution forming a coating layer.
상기와 같은 목적을 달성하기 위한 본 발명의 또 하나의 양상은, 상기와 같은 본 발명의 방법에 의해 제조되는 비대칭성 중공사막에 관한 것이다.Another aspect of the present invention for achieving the above object relates to an asymmetric hollow fiber membrane produced by the method of the present invention as described above.
본 발명의 일 구현예에 따른 상기 비대칭성 중공사막은, 내부 지지층과 외부 코팅층을 가지는 중공사로 이루어지며, 상기 지지층은 평균직경 0.1 내지 5 ㎛ 범위의 구상형 고형분으로 이루어진 구상 구조의 층이며, 상기 코팅층은 직경 5 ㎛의 거대공극을 실질적으로 함유하지 않는 스폰지 구조층인 것을 특징으로 한다.The asymmetric hollow fiber membrane according to one embodiment of the present invention is made of a hollow fiber having an inner support layer and an outer coating layer, and the support layer is a spherical structure layer formed of a spherical solid component having an average diameter in the range of 0.1 to 5 μm, And the coating layer is a sponge structure layer substantially containing no large pores having a diameter of 5 탆.
본 발명의 일 구현예에 따른 상기 비대칭성 중공사막은, 상기 스폰지 구조층의 두께가 30 내지 100 ㎛ 범위인 것을 특징으로 한다.The asymmetric hollow fiber membrane according to an embodiment of the present invention is characterized in that the thickness of the sponge structure layer is in the range of 30 to 100 mu m.
본 발명의 일 구현예에 따른 상기 비대칭성 중공사막은, 분자량 7.5만의 덱스트란 제거율이 80% 이상으로 표시되는 여과성능을 갖는 것을 특징으로 한다.
The asymmetric hollow fiber membrane according to one embodiment of the present invention is characterized in that the dextran removal ratio of molecular weight of 750,000 is 80% or more.
본 발명에 따른 비대칭성 중공사막의 제조방법은 TIPS와 NIPS를 이용하여 고강도, 고투수성의 기공제어가 용이한 중공사막을 제막할 수 있으며 삼중구금을 통해 지지층과 코팅층 용액을 동시에 방사함으로써 중공사를 제막한 후에도 균일한 두께를 지니고 코팅층이 박리가 되지 않는 비대칭성 중공사막을 제조할 수 있는 효과가 있다.The asymmetric hollow fiber membrane manufacturing method according to the present invention can form a hollow fiber membrane having high strength and high water permeability and easy pore control using TIPS and NIPS and can produce a hollow fiber by simultaneously spinning the support layer and the coating layer solution through the triple- It is possible to produce an asymmetric hollow fiber membrane having a uniform thickness even after film formation and in which the coating layer is not peeled off.
특히 본 발명의 제조방법에 의해 제조된 비대칭성 중공사막은, 코팅층을 형성하는 고분자 용액의 양용매로서 트리메틸포스페이트(TEP)를 사용함으로써 코팅층이 거대 공극을 함유하지 않는 하는 스폰지 구조층으로 이루어지며, 지지층이 물리적 강도와 화학적 강도를 겸비하며 내구성을 구비한 구상 구조층으로 이루어짐으로서 바이러스 제거성, 투수 성능, 화학적 강도, 물리적 강도, 내오염성의 여러 성능이 우수하고, 신뢰성이 높은 바이러스 제거용 여과막으로서 장기간 사용이 가능한 효과가 있다.
In particular, the asymmetric hollow fiber membrane produced by the production method of the present invention comprises a sponge structure layer in which the coating layer does not contain large voids by using trimethyl phosphate (TEP) as a good solvent for the polymer solution forming the coating layer, The supporting layer is composed of a spherical structure layer having durability that combines physical strength and chemical strength, and is excellent in various performances of virus removal performance, water permeability, chemical strength, physical strength and stain resistance, and is a highly reliable filtration membrane for virus removal There is an effect that can be used for a long time.
이하, 본 발명의 바람직한 구현예에 대하여 실시예 등을 참조하여 더욱 상세히 설명한다. 또한, 본 발명을 설명함에 있어서, 관련된 공지의 범용적인 기능 또는 구성에 대한 상세한 설명은 생략한다.Hereinafter, preferred embodiments of the present invention will be described in more detail with reference to examples and the like. In the following description of the present invention, a detailed description of known general functions or configurations will be omitted.
본 발명은 삼중 구금을 사용하여 비대칭성 중공사막을 제조하는 방법으로서 상기 방법은 상중 구금의 내부 노즐로 중공형성제를 토출시키고, 외부 노즐로 코팅층을 형성하는 고분자 용액을 토출시키며, 내부와 외부 사이의 노즐로 지지층을 형성하는 고분자 용액을 토출시키는 비대칭성 중공사막의 제조방법에 관한 것이다.The present invention is a method of manufacturing an asymmetric hollow fiber membrane using triple detention, the method of discharging the hollow forming agent to the inner nozzle of the phase detention, discharge the polymer solution forming the coating layer with the outer nozzle, between the inside and the outside The manufacturing method of the asymmetric hollow fiber membrane which discharges the polymer solution which forms a support layer by the nozzle of this invention.
이하에서, 본 발명의 중공사 분리막의 제조공정을 더욱 상세하게 설명한다.
Hereinafter, the manufacturing process of the hollow fiber membrane of the present invention will be described in more detail.
지지층을 형성하는 고분자 용액의 제조공정 ; A process for producing a polymer solution forming a support layer ;
본 발명의 일 구현예에 따른 비대칭성 중공사막의 제조방법에 있어서, 지지층을 형성하는 고분자 용액은 폴리비닐리덴플로라이드, 빈용매 및 첨가제를 포함한다. 이때 각 성분의 함량비는 폴리비닐리덴플로라이드 25~45 중량%, 빈용매 55~70 중량%, 첨가제 1~10 중량%로 이루어지는 것이 바람직하다.In the method for producing an asymmetric hollow fiber membrane according to an embodiment of the present invention, the polymer solution forming the support layer includes polyvinylidene fluoride, a poor solvent, and an additive. In this case, the content ratio of each component is preferably 25 to 45% by weight of polyvinylidene fluoride, 55 to 70% by weight of a poor solvent, and 1 to 10% by weight of an additive.
본 발명에서 중공사막을 형성하는 폴리비닐리덴플루오라이드 고분자는 중량평균 분자량 100,000 달톤 내지 700,000만 달톤으로, 단독 혹은 2종이상 혼합물로 구성될 수 있다. 본 발명의 제조방법에서 빈용매로는 감마-부티로락톤(γ-butyrolactone), 디메틸프탈산(Dimethyl phthalate), 디부틸프탈산(Dibutyl phthalate), 디옥틸프탈산(Dioctyl phthalate), 사이클로헥사논(Cyclohexanone) 등을 사용할 수 있으며, 바람직하게는 감마-부티로락톤을 사용하는 것이 좋다. The polyvinylidene fluoride polymer forming the hollow fiber membrane in the present invention has a weight average molecular weight of 100,000 Daltons to 700,000 Daltons, it may be composed of a single or a mixture of two or more. In the preparation method of the present invention, the poor solvent is gamma-butyrolactone, dimethyl phthalate, dibutyl phthalate, dioctyl phthalate, cyclohexanone. And the like, and preferably gamma-butyrolactone is used.
첨가제의 구체적인 예로는 중량평균분자량 15,000달톤 내지 90,000달톤의 폴리비닐피롤리돈, 중량평균분자량이 200 내지 20,000 달톤의 폴리에틸렌글리콜, 폴리비닐알콜, 및 무수말레인산, 계면활성제 등 물에 쉽게 용해되는 친수성 고분자 혹은 유기물로서 단독 혹은 2종이상 혼합물로서 폴리비닐리덴플루오라이드 고분자 용액에 첨가하여 사용할 수 있으며, 바람직하게는 폴리비닐피롤리돈을 사용하는 것이 좋다. 이러한 폴리비닐피롤리돈, 폴리에틸렌글리콜, 폴리비닐알콜, 및 무수말레인산, 계면활성제는 기핵제로 작용하여 작은 기공을 다수 형성하여 강도 및 투수량을 향상시키는 역할을 한다. Specific examples of the additives include hydrophilic polymers which are easily soluble in water, such as polyvinyl pyrrolidone having a weight average molecular weight of 15,000 to 90,000 daltons, polyethylene glycol having a weight average molecular weight of 200 to 20,000 daltons, polyvinyl alcohol, maleic anhydride and a surfactant Or as an organic substance, or as a mixture of two or more thereof, to the polyvinylidene fluoride polymer solution, and it is preferable to use polyvinylpyrrolidone . Such Polyvinyl pyrrolidone, polyethylene glycol, polyvinyl alcohol, and maleic anhydride, and surfactants act as nucleophilic agents to form a large number of small pores to improve strength and permeability.
본 발명에서 지지층 형성용 고분자용액은 섭씨 120 내지 200도에서 제조되는 것이 바람직하고, 또한 용액 중에 존재하는 기포를 제거하기 위하여 반드시 탈포공정으로 거쳐야 한다. 일반적으로 섭씨 120도 이하의 온도에서 고화되어 중공사막을 형성하거나, 섭씨 120도 이하인 비용매와의 접촉시 상분리에 의하여 중공사 분리막이 형성된다. 따라서, 폴리비닐리덴플루오라이드 중공사막의 제조를 위해 적어도 섭씨 120 도 이상, 바람직하게는 섭씨 130 내지 180 도의 온도를 유지하는 방사 노즐을 통해 고분자용액을 응고액으로 토출시키는 것이 바람직하다. In the present invention, the polymer solution for forming the support layer is preferably prepared at a temperature of 120 to 200 degrees Celsius, and must be subjected to a defoaming process to remove bubbles present in the solution. Generally, a hollow fiber membrane is formed by solidification at a temperature of 120 DEG C or less, or when phase contact with a non-solvent having a temperature of 120 DEG C or less is performed. Therefore, for the production of the polyvinylidene fluoride hollow fiber membrane, it is preferable to discharge the polymer solution as a coagulating solution through a spinning nozzle maintaining a temperature of at least 120 degrees Celsius, preferably 130 to 180 degrees Celsius.
코팅층을 형성하는 고분자 용액의 제조공정 ; A process for preparing a polymer solution for forming a coating layer ;
본 발명의 일 구현예에 따른 비대칭성 중공사막의 제조방법에 있어서, 코팅층을 형성하는 고분자 용액은 폴리비닐리덴플로라이드, 양용매, 빈용매 및 첨가제를 포함한다. 이때 각 성분의 함량비는 폴리비닐리덴플로라이드 10~20 중량%, 양용매 40~70 중량%, 빈용매 10~40 중량%, 첨가제 0.1~10 중량%를 사용하는 것이 바람직하다.In the method for producing an asymmetric hollow fiber membrane according to an embodiment of the present invention, the polymer solution forming the coating layer includes polyvinylidene fluoride, a good solvent, a poor solvent and an additive. At this time, the content ratio of each component is preferably 10 to 20% by weight of polyvinylidene fluoride, 40 to 70% by weight of a good solvent, 10 to 40% by weight of a poor solvent, and 0.1 to 10% by weight of an additive.
일반적으로 폴리비닐리덴플로라이드 수지계 양용매로는 메틸피롤리돈(N,N-methyl-2-pyrrolidone), 디메틸술폭시드(Dimethylsulfoxide), 디메틸아세트아미드(Dimethylacetamide), 디메틸포름아미드(Dimethylformamide), 아세톤(Acetone) 등이 알려져 있다. 그러나 메틸피롤리돈 또는 디메틸아세트아미드를 코팅층의 양용매로 사용하는 경우에는 거대 공극이 발생하는 경우가 많다. 따라서 본 발명에 따른 제조방법에서는 거대 공극의 발생을 제어하기 위하여 코팅층의 양용매로서 트리에틸포스페이트(TEP)를 사용하는 것이 바람직하다.In general, examples of the polyvinylidene fluoride resin type solvents include N, N-methyl-2-pyrrolidone, dimethylsulfoxide, dimethylacetamide, dimethylformamide, (Acetone) are known. However, when methyl pyrrolidone or dimethylacetamide is used as a good solvent for the coating layer, large pores are often generated. Therefore, in the production method according to the present invention, it is preferable to use triethyl phosphate (TEP) as a good solvent for the coating layer in order to control the generation of large pores.
한편 빈용매에 대하여는 전술한 바와 같다.On the other hand, the poor solvent is as described above.
코팅층을 형성하는 고분자 용액은 첨가제로 리튬 클로라이드, 폴리비닐피롤리돈, 아세틸레이티드메틸셀룰로오스 등을 사용할 수 있으나 반드시 이에 한정되는 것은 아니며 목적에 따라 적절한 첨가제를 선택하여 사용할 수 있다.
As the polymer solution forming the coating layer, lithium chloride, polyvinyl pyrrolidone, acetylated methyl cellulose, etc. may be used as an additive, but not always limited thereto, and appropriate additives may be selected depending on the purpose.
중공형성제Hollow Forming Agent 제조공정; Manufacture process;
중공형성제는 비용매로서 물 또는 에틸렌글리콜을 주로 사용하고, 혼합시 혼합 양용매로서 디메틸 피롤리돈 혹은 디메틸아세테이트, 디메틸포름아미드, 디메틸설퍼옥사이드 등을 상온에서 비용매에 대한 양용매의 비를 2대 8 내지 8대 2로 상온에서 제조하여 탈포하고, 삼중방사노즐로 이송시 온도는 섭씨 1도 내지 80도를 유지한다.
The hollow formers are prepared by dissolving dimethylpyrrolidone, dimethyl acetate, dimethylformamide, dimethylsulfoxide and the like as a non-solvent in water or ethylene glycol as a non-solvent, and using a ratio of good solvent to non-solvent at room temperature 2 to 8 to 8 to 2 at normal temperature and defoamed, and the temperature is maintained at 1 to 80 degrees centigrade when transported to the triple spinning nozzle.
중공사막의 제조;Preparation of hollow fiber membranes;
본 발명에서는 상기에서 제조된 지지층을 형성하는 고분자 용액, 코팅층을 형성하는 고분자 용액 및 중공형성제를 삼중 구금을 이용하여 응고액으로 동시에 토출하여 구상 구조의 지지층 및 다수의 기공을 포함하는 코팅층을 갖는 중공사 막을 제조한다. 이때, 상중 구금의 내부 노즐로는 중공형성제를 토출시키고, 외부 노즐로는 코팅층을 형성하는 고분자 용액을 토출시키며, 내부와 외부 사이의 노즐로는 지지층을 형성하는 고분자 용액을 토출시키게 된다.In the present invention, the polymer solution forming the support layer, the polymer solution forming the coating layer, and the hollowing agent are simultaneously discharged into the coagulating solution by using the triple sheathing to have a support layer of a spherical structure and a coating layer containing a plurality of pores A hollow fiber membrane is prepared. At this time, the polymer solution for discharging the hollow polymer is discharged from the inner nozzle of the upper nozzle, the polymer solution for forming the coating layer is discharged from the outer nozzle, and the polymer solution for forming the supporting layer is discharged by the nozzle between the inside and the outside.
본 발명에서 사용하는 응고액은 비용매인 순수한 물 또는 일정량의 양용매를 함유한 비용매로 구성되며, 방사용액이 방사되면서 내부에서 접촉하는 중공형성제에 의해 내부에는 거대 기공을 갖는 내부 표면이 형성되기 시작한다.The coagulation liquid used in the present invention is composed of non-solvent pure water or a non-solvent containing a certain amount of a good solvent, the inner surface having a large pore formed by the hollow forming agent in contact with the inside as the spinning solution is spun It begins to be.
이와 같이 본 발명에 따른 비대칭성 중공사막의 제조방법은 지지층은 TIPS를 이용하고 코팅층은 NIPS를 이용하여 상분리를 시킴으로써, 고강도, 고투수성의 기공제어가 용이한 중공사막을 제막할 수 있다. 특히 삼중 구금을 통해 지지층과 코팅층 용액을 동시에 방사함으로써 중공사를 제막한 후에도 균일한 두께를 지니고 코팅층이 박리가 되지 않는 비대칭성 중공사막을 제조할 수 있게 된다.
As described above, in the method of manufacturing the asymmetric hollow fiber membrane according to the present invention, the support layer is formed of TIPS and the coating layer is subjected to phase separation using NIPS, whereby a hollow fiber membrane having high strength and high permeability and easy pore control can be formed. In particular, it is possible to produce an asymmetric hollow fiber membrane having a uniform thickness even after the hollow fiber membrane is formed by spinning the support layer and the coating layer solution simultaneously through the triple inserting process, and the coating layer is not peeled off.
세척과정;Washing process;
또한, 본 발명에서는 응고액으로부터 대기중으로 이송된 중공사막의 막내외에 잔존하는 용매를 포함한 유기물을 제거하기 위해 세척과정을 더욱 포함할 수 있다. 세척액으로 물의 사용이 바람직하며, 세척시간은 특별히 한정되지는 않으나, 적어도 1일 이상, 5일 이하가 바람직하다.
In addition, the present invention may further include a washing process to remove organic matter including solvent remaining in the membrane of the hollow fiber membrane transferred from the coagulating solution to the atmosphere. Water is preferably used as the washing liquid, and the washing time is not particularly limited, but at least one day or more and five days or less is preferable.
본 발명의 또 하나의 양상은, 상기와 같은 본 발명의 방법에 의해 제조되는 비대칭성 중공사막에 관한 것이다.Another aspect of the present invention relates to an asymmetric hollow fiber membrane produced by the method of the present invention as described above.
상기와 같은 본 발명의 제조방법에 의해 제조된 비대칭성 중공사막은, 코팅층을 형성하는 고분자 용액의 양용매로서 트리에틸포스페이트(TEP)를 사용함으로써 코팅층이 거대 공극을 함유하지 않는 하는 스폰지 구조층으로 이루어진다. 또한 지지층은 열유도 상분리법에 의해 물리적 강도와 화학적 강도를 겸비하며 내구성을 구비한 구상 구조층으로 이루어지게 된다. The asymmetric hollow fiber membrane produced by the method of the present invention as described above can be used as a sponge structure layer in which the coating layer does not contain large voids by using triethyl phosphate (TEP) as a good solvent for the polymer solution forming the coating layer . In addition, the support layer has a spherical structure layer having durability that combines physical strength and chemical strength by a heat-induced phase separation method.
본 발명에 따른 상기 비대칭성 중공사막에 있어서, 상기 구상 구조층은 평균직경 0.1 내지 5 ㎛ 범위의 구상형 고형분으로 이루어지며, 상기 스폰지 구조층은 직경 5 ㎛의 거대공극을 실질적으로 함유하지 않는 층으로 이루어질 수 있다. 상기 스폰지 구조층은 두께가 30 내지 100 ㎛ 범위인 것이 바람직하다. 스폰지 구조층의 두께가 30 ㎛ 이하이면 너무 얇아 벗겨지기 쉽고 스폰지 구조층의 두께가 100 ㎛ 이상이면 너무 두꺼워 투수량이 떨어지는 것이 단점이다. In the asymmetric hollow fiber membrane according to the present invention, the spherical structure layer is a spherical solid having an average diameter in the range of 0.1 to 5 mu m, and the sponge structure layer is a layer containing substantially no voids having a diameter of 5 mu m ≪ / RTI > The spongy structural layer preferably has a thickness in the range of 30 to 100 mu m. If the thickness of the sponge structure layer is 30 μm or less, it is too thin to be easily peeled off, and if the thickness of the sponge structure layer is 100 μm or more, it is too thick and the amount of water permeability is low.
본 발명의 일 구현예에 따른 상기 비대칭성 중공사막은, 분자량 7.5만의 덱스트란 제거율이 80% 이상으로 표시되는 여과성능을 가지며, 바이러스 제거성, 투수 성능, 화학적 강도, 물리적 강도, 내오염성의 여러 성능이 우수하고, 신뢰성이 높은 바이러스 제거용 여과막으로서 장기간 사용이 가능한 효과가 있다.
The asymmetric hollow fiber membrane according to one embodiment of the present invention has a filtering performance expressed by a dextran removal ratio of 80% or more with a molecular weight of 750,000, and is characterized in that the membrane has a virus removal performance, a water permeability performance, a chemical strength, There is an effect that it can be used for a long time as a filtration membrane for virus removal with high performance and high reliability.
이하에서 실시예를 통하여 본 발명을 구체적으로 설명하기로 한다. 그러나 하기의 실시예는 오로지 본 발명을 구체적으로 설명하기 위한 것으로 이들 실시예에 의해 본 발명의 범위를 한정하는 것은 아니다.
Hereinafter, the present invention will be described in detail by way of examples. However, the following examples are for illustrative purposes only and are not intended to limit the scope of the present invention.
실시예Example
폴리불화비닐리덴 비대칭 중공사막을 제조하기 위하여, 열유도 상분리법을 이용하여 지지층을 제조하고, 비용매 상분리법을 이용하여 코팅층을 제조하는데 있어서,In order to prepare a polyvinylidene fluoride asymmetric hollow fiber membrane, to prepare a support layer using a thermally induced phase separation method, and to prepare a coating layer using a non-solvent phase separation method,
상기 지지층은 빈용매인 감마-부티로락톤 57 중량%를 용해조에 장입하고 섭씨 50도로 가온한 후, 유기 첨가제인 무게 평균분자량이 19,000 달톤인 폴리비닐피롤리돈을 3 중량%를 첨가하여 섭씨 150도까지 가온한 후 40 중량%의 중량 평균 분자량 440,000 달톤인 폴리불화비닐리덴 고분자를 서서히 첨가한 후 섭씨 180도까지 승온하여 균일한 방사 용액을 제조하였다. The supporting layer was prepared by charging 57% by weight of gamma-butyrolactone, which is a poor solvent, into a dissolution tank, heating the mixture to 50 DEG C, adding 3% by weight of polyvinylpyrrolidone having a weight average molecular weight of 19,000 daltons as an organic additive, After the temperature was raised, a polyvinylidene fluoride polymer having a weight average molecular weight of 440,000 daltons of 40 wt% was slowly added thereto, and the temperature was raised to 180 ° C. to prepare a uniform spinning solution.
상기 코팅층은 양용매인 트리에틸포스페이트 45 중량%와 빈용매인 감마부티로락톤 30 중량%, 첨가제로 리튬 클로라이드 3 중량%와, 폴리비닐피롤리돈 4 중량%와 및 아세틸레이티드메틸셀룰로오스 1 중량%를 첨가한 후 섭씨 60 도로 가온한 후 17 중량%의 폴리불화비닐리덴 고분자를 서서히 첨가하여 방사용액을 제조하였다.The coating layer contained 45% by weight of triethyl phosphate as a two-component solvent and 30% by weight of gamma-butyrolactone as a poor solvent, 3% by weight of lithium chloride as an additive, 4% by weight of polyvinylpyrrolidone and 1% by weight of acetylated methylcellulose, Was added, and the mixture was heated to 60 degrees Celsius, and 17 wt% polyvinylidene fluoride polymer was gradually added to prepare a spinning solution.
이어서 지지층 형성용 방사용액은 섭씨 150도의 삼중 구금의 중간노즐로 흘려보내고, 내부에는 디메틸아세테이트와 물이 6대 4로 혼합된 상온의 중공형성제를 흘려서 중공이 형성되도록 하였으며, 바깥으로는 코팅층 형성용 방사용액을 섭씨 5도로 흘려보냈다. 상기 세 용액은 모두 섭씨 5도의 물로 이루어진 응고조로 방사되어 최종적으로 고화되었다. Subsequently, the spinning solution for forming the support layer was flowed to a middle nozzle of a triple cage at a temperature of 150 ° C, and a hollow forming agent mixed with dimethyl acetate and water at a temperature of 6 to 4 was flowed to form a hollow. I spent 5% of the water used. All three solutions were spun into a coagulation bath consisting of water at 5 degrees Celsius and finally solidified.
제조된 중공사막은 내경 0.7 밀리미터이고 외부직경이 1.3 밀리미터였으며, 인장강도가 단위 중공사막당 1,250 그램이었고, 신도는 45 퍼센트였다. 50 킬로 파스칼의 막투과 압력 및 섭씨 25도에서 투과수 플럭스는 단위시간 단위면적당 400 리터였다. 100 나노미터의 폴리스티렌 입자의 저지율은 99 퍼센트였다.
The hollow fiber membrane produced had an inner diameter of 0.7 millimeters, an outer diameter of 1.3 millimeters, a tensile strength of 1,250 grams per unit hollow fiber membrane, and an elongation of 45 percent. At a membrane permeation pressure of 50 kilopascals and at 25 degrees Celsius, the permeate flux was 400 liters per unit time unit area. The blocking rate of 100 nanometer polystyrene particles was 99 percent.
이상에서 본 발명의 바람직한 구현예를 들어 본 발명을 상세하게 설명하였으나 본 발명은 상술한 구현예에 한정되지 않으며, 본 발명의 기술적 사상의 범위 내에서 본 발명이 속하는 기술분야의 당업자에 의해 많은 변형이 가능함은 자명할 것이다.While the present invention has been particularly shown and described with reference to exemplary embodiments thereof, it is to be understood that the invention is not limited to the disclosed exemplary embodiments. This will be obvious.
Claims (7)
상기 방법은 상중 구금의 내부 노즐로 중공형성제를 토출시키고, 외부 노즐로 코팅층을 형성하는 고분자 용액을 토출시키며, 내부와 외부 사이의 노즐로 지지층을 형성하는 고분자 용액을 토출시키되,
상기 지지층을 형성하는 고분자 용액은 폴리비닐리덴플로라이드, 빈용매 및 첨가제를 포함하며, 코팅층을 형성하는 고분자 용액은 폴리비닐리덴플로라이드, 양용매, 빈용매 및 첨가제를 포함하며,
상기 코팅층을 형성하는 고분자 용액의 양용매로는 트리에틸포스페이트(TEP)를 사용하는 것을 특징으로 하는 비대칭성 중공사막의 제조방법.1. A method for producing an asymmetric hollow fiber membrane using a triple-
The method comprises discharging the hollow forming agent to the inner nozzle of the phase detention, discharging the polymer solution forming the coating layer with the outer nozzle, and discharging the polymer solution forming the support layer with the nozzle between the inside and the outside,
Wherein the polymer solution forming the support layer comprises polyvinylidene fluoride, a poor solvent, and an additive, and the polymer solution forming the coating layer comprises polyvinylidene fluoride, a good solvent, a poor solvent, and an additive,
Characterized in that triethyl phosphate (TEP) is used as a good solvent for the polymer solution forming the coating layer.
5. The asymmetric hollow fiber membrane according to claim 4, wherein the asymmetric hollow fiber membrane has a filtration performance represented by a dextran removal ratio of 80% or more with a molecular weight of 750,000.
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| CN112403289A (en) * | 2020-10-21 | 2021-02-26 | 清华大学 | Poly (4-methyl-1-pentene) hollow fiber membrane with gradient pore structure and preparation method thereof |
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| KR101026690B1 (en) * | 2010-02-25 | 2011-04-07 | 주식회사 디어포스 | Highly porous membrane using that and preparing method thereof |
| KR101381080B1 (en) * | 2011-12-14 | 2014-04-02 | 김백암 | Double layer hydrophilic hollow fiber membrane and its manufacturing method combined supported layer by Thermally Induced Phase Separation and active layer by Non-solvent Induced Phase Separation |
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| CN112403289A (en) * | 2020-10-21 | 2021-02-26 | 清华大学 | Poly (4-methyl-1-pentene) hollow fiber membrane with gradient pore structure and preparation method thereof |
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