KR101979567B1 - Thin Film Composite Membranes with Surface Pattern Structures for Excellent Antifouling Resistance - Google Patents
Thin Film Composite Membranes with Surface Pattern Structures for Excellent Antifouling Resistance Download PDFInfo
- Publication number
- KR101979567B1 KR101979567B1 KR1020170111761A KR20170111761A KR101979567B1 KR 101979567 B1 KR101979567 B1 KR 101979567B1 KR 1020170111761 A KR1020170111761 A KR 1020170111761A KR 20170111761 A KR20170111761 A KR 20170111761A KR 101979567 B1 KR101979567 B1 KR 101979567B1
- Authority
- KR
- South Korea
- Prior art keywords
- support
- pattern
- chloride
- layer
- thin film
- Prior art date
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- 239000000661 sodium alginate Substances 0.000 description 1
- 229940005550 sodium alginate Drugs 0.000 description 1
- 235000002639 sodium chloride Nutrition 0.000 description 1
- APSBXTVYXVQYAB-UHFFFAOYSA-M sodium docusate Chemical compound [Na+].CCCCC(CC)COC(=O)CC(S([O-])(=O)=O)C(=O)OCC(CC)CCCC APSBXTVYXVQYAB-UHFFFAOYSA-M 0.000 description 1
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 1
- RTVVXRKGQRRXFJ-UHFFFAOYSA-N sodium;2-sulfobutanedioic acid Chemical compound [Na].OC(=O)CC(C(O)=O)S(O)(=O)=O RTVVXRKGQRRXFJ-UHFFFAOYSA-N 0.000 description 1
- REFMEZARFCPESH-UHFFFAOYSA-M sodium;heptane-1-sulfonate Chemical compound [Na+].CCCCCCCS([O-])(=O)=O REFMEZARFCPESH-UHFFFAOYSA-M 0.000 description 1
- QWSZRRAAFHGKCH-UHFFFAOYSA-M sodium;hexane-1-sulfonate Chemical compound [Na+].CCCCCCS([O-])(=O)=O QWSZRRAAFHGKCH-UHFFFAOYSA-M 0.000 description 1
- 238000010186 staining Methods 0.000 description 1
- SFVFIFLLYFPGHH-UHFFFAOYSA-M stearalkonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCCCC[N+](C)(C)CC1=CC=CC=C1 SFVFIFLLYFPGHH-UHFFFAOYSA-M 0.000 description 1
- 229940057981 stearalkonium chloride Drugs 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 229940117986 sulfobetaine Drugs 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- WBWWGRHZICKQGZ-GIHLXUJPSA-N taurocholic acid Chemical compound C([C@@H]1C[C@H]2O)[C@@H](O)CC[C@]1(C)[C@@H]1[C@@H]2[C@@H]2CC[C@@H]([C@@H](CCC(=O)NCCS(O)(=O)=O)C)[C@@]2(C)[C@H](O)C1 WBWWGRHZICKQGZ-GIHLXUJPSA-N 0.000 description 1
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 235000010487 tragacanth Nutrition 0.000 description 1
- 239000000196 tragacanth Substances 0.000 description 1
- 229940116362 tragacanth Drugs 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 125000005208 trialkylammonium group Chemical group 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-O triethanolammonium Chemical compound OCC[NH+](CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-O 0.000 description 1
- FAGMGMRSURYROS-UHFFFAOYSA-M trihexadecyl(methyl)azanium;chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCC[N+](C)(CCCCCCCCCCCCCCCC)CCCCCCCCCCCCCCCC FAGMGMRSURYROS-UHFFFAOYSA-M 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Images
Classifications
-
- 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
- B01D69/122—Separate manufacturing of ultra-thin membranes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/002—Forward osmosis or direct osmosis
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/02—Reverse osmosis; Hyperfiltration ; Nanofiltration
- B01D61/025—Reverse osmosis; Hyperfiltration
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/02—Reverse osmosis; Hyperfiltration ; Nanofiltration
- B01D61/027—Nanofiltration
-
- 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
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A20/00—Water conservation; Efficient water supply; Efficient water use
- Y02A20/124—Water desalination
- Y02A20/131—Reverse-osmosis
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Water Supply & Treatment (AREA)
- Nanotechnology (AREA)
- Manufacturing & Machinery (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
본 발명은 내오염 특화 패턴 구조를 가지는 지지체를 이용한 박막 복합체 분리막 및 이의 제조방법에 관한 것으로, 내오염성이 극대화된 박막 복합체 분리막을 제공할 수 있다.The present invention relates to a thin film composite separator using a support having a contamination-specific pattern structure and a method of manufacturing the same, and can provide a thin film composite separator having the maximum stain resistance.
Description
본 발명은 내오염 특화 패턴 구조를 가지는 지지체를 이용한 박막 복합체 분리막의 제조방법에 관한 것이다. The present invention relates to a method for producing a thin film composite membrane using a support having a contamination-specific pattern structure.
박막 복합체 분리막(Thin Film Composite Membrane)이란 일반적으로 다공성 지지체와 박막 선택층으로 구성된 분리막을 지칭한다. 상기 박막 복합체 분리막은 해수담수화 및 탈염, 하·폐수처리 등의 수처리 분야를 비롯하여, 식품 및 바이오 생산물의 정제, 염분차 발전을 통한 에너지 생산 등 분리막을 사용하는 다양한 공정 분야에 널리 활용되고 있다. 상기 박막 복합체 분리막의 구조는 특히 고압력 및 고내구성을 요구하는 조건에 유리하기 때문에, 높은 구동 압력이 필요한 공정에서 선호되고 있다.Thin Film Composite Membrane generally refers to a membrane composed of a porous support and a thin film selective layer. The membrane composite membrane is widely used in various processing fields such as water treatment such as seawater desalination and desalination, underwater and wastewater treatment, purification of food and bio-products, and energy production through salinity generation. The structure of the thin film composite membrane is particularly favored in a process requiring high driving pressure because it is advantageous in conditions requiring high pressure and high durability.
현재 분리막 공정에서 분리막의 수명에 가장 큰 영향을 미치는 요소는 막 표면에서 일어나는 오염 현상이다. 분리막을 이용하여 분리하고자 하는 많은 종류의 오염원들이 존재하며, 이러한 오염물질들은 분리막을 투과하지는 못하지만 분리막 표면에 지속적으로 부착된 상태로 남게 된다. 이러한 막 오염 현상은 결과적으로 분리막의 투과도를 저하시키므로 막분리 공정 전체의 효율을 떨어뜨리는 문제를 유발한다.At present, the most important factor affecting membrane lifetime in separation membrane processes is contamination on membrane surface. There are many kinds of contaminants to be separated using a separator. These contaminants do not permeate the separator but remain attached to the separator surface continuously. This membrane contamination eventually lowers the permeability of the membrane, which results in a problem of reducing the efficiency of the entire membrane separation process.
이러한 문제를 해결하기 위해 기술적으로 다양한 시도들이 이루어져 왔으나, 분리막 표면에서의 막오염 현상을 저해하려는 이러한 시도들은 주로 선택층 표면에 친수성 또는 항균성 물질을 코팅 및 그라프팅 시키거나, 이러한 물질을 선택층 제조에 조합하여 화학적인 방식으로 내오염성을 구현시키고자 하였다.Various attempts have been made to solve this problem. However, attempts to inhibit membrane contamination on the surface of the separator have been mainly performed by coating and grafting a hydrophilic or antimicrobial substance on the surface of the selective layer, In order to realize the contamination resistance by a chemical method.
현재까지의 연구들은 막오염 현상이 근본적으로 표면 현상이라는 점 때문에 화학적 특성을 변화시키는 데에 주목해 왔으나, 근래에는 오염을 억제하는 방법에 대해 새로운 관점에서의 조망이 시도되고 있다.Studies to date have focused attention on changing chemical properties because membrane contamination is fundamentally a surface phenomenon. In recent years, however, attempts have been made to view a new perspective on how to prevent contamination.
이러한 관점에서 기존 해양생물오염 분야 등에서 실험적으로 보고된 바 있는 물리적 표면 구조에 의한 오염 방지 기술이 최근 분리막 연구 분야에서 각광받고 있다. 실제로 단순한 성형 패턴을 고분자 지지체에 나노임프린팅(nanoimprinting)하여 내오염성 효과를 관측한 논문이 콜로라도 대학의 Maruf 등에 의해 보고된 바 있다. 그러나 이는 사용한 공정의 한계로 인해 패턴의 높이가 나노미터 수준으로 매우 낮으며, 또한 패턴의 종류를 다양하게 이용할 수 없으며 가장 단순한 트렌치(trench) 형태의 패턴만을 사용한 데 그 한계가 있다. 한편 서울대학교 이정학 교수 연구팀에서는 마이크로패턴 형상을 가지는 몰드를 제조한 후 이를 상전이법에 적용하여 패턴 표면을 가지는 고분자 한외여과막을 제조하였다. 제조한 한외여과막은 실험 결과 박테리아에 대해 우수한 내오염성을 보여 주었으며 이러한 현상의 원인에 대해 다양한 방법으로 분석하여 제시하였다. From this point of view, the technique of preventing contamination by physical surface structure, which has been experimentally reported in the field of marine bio-pollution, has recently attracted attention in the field of separation membrane research. In fact, a paper by Maruf et al. Of the University of Colorado has been reported that nanoimprinting simple mold patterns on polymer scaffolds and observing stain resistance effects. However, this is because the height of the pattern is very low to the nanometer level due to the limit of the used process, and the pattern type can not be used variously, and there is a limit to using only the simplest pattern of the trench shape. Meanwhile, Professor Lee, Jeong-Hak of Seoul National University produced a polymer micropattern mold and applied it to the phase transition method to fabricate a polymer ultrafiltration membrane with a patterned surface. The ultrafiltration membranes produced by this study showed excellent stain resistance against bacteria. The causes of these phenomena were analyzed by various methods.
그러나 이러한 다공성 지지체에 대한 연구들은 지지체 기공 내에서의 오염현상으로 인해 표면패턴 구조에 따른 오염특성을 이해하는데 한계를 보이고 있으며, 지지체 구조에 대한 연구를 역삼투막 등의 비다공성 박막복합체 분리막에 적용하는 사례 또한 매우 드물게 보고되고 있다. 특히, 현재 상업적으로 제조되는 거의 모든 역삼투 분리막은 선택층 제조에서 계면 중합을 사용하는데, 다공성 지지체 위에서 계면 중합을 수행할 경우 공극 안에 함침된 용액이 반응 용액과 만나는 과정에서 모세관 현상에 의한 물질 전달 속도의 변화로 인해 결과적으로 나노스케일의 표면 요철을 형성한다. 이러한 공극의 존재는 패턴 형상 구현에 있어서도 단점으로 작용하는데, 공극 크기가 커질수록 패턴 형상의 구현도가 유의미하게 낮아지는 문제가 존재한다. 따라서 이러한 요소들은 패턴에 의한 표면 구조의 효과를 변질시키는 중요한 요인으로 작용하지만 현재까지 이를 완전히 해결한 역삼투 분리막에 대한 연구 및 특허는 알려진 바 없다.However, studies on such porous supports have been limited in understanding the contamination characteristics due to the surface pattern structure due to contamination in support pores, and studies on the support structure have been applied to nonporous thin film composite membranes such as reverse osmosis membranes It has also been reported very rarely. In particular, almost all currently commercially available reverse osmosis membranes use interfacial polymerization in the preparation of a selective layer. When interfacial polymerization is carried out on a porous support, the solution impregnated in the pores is subjected to mass transfer by capillary phenomenon As a result of the change of the speed, the nanoscale surface irregularities are formed. The existence of such voids is also a disadvantage in the pattern shape implementation. However, there is a problem that as the pore size increases, the degree of pattern shape implementation significantly decreases. Therefore, these factors play an important role in altering the effect of the surface structure by the pattern, but the research and patent on the reverse osmosis membrane completely solved to date are not known.
본 발명의 내오염 성능이 탁월한 박막 복합체 분리막 및 이의 제조방법을 제공하는 것을 목적으로 한다. It is an object of the present invention to provide a thin film composite membrane having excellent resistance to contamination and a method of manufacturing the same.
본 발명에서는 지지체; 및 In the present invention, And
상기 지지체 상에 형성된 선택층을 포함하며,And a selective layer formed on the support,
상기 선택층과 접하는 지지체의 표면에는 패턴이 형성되어 있는 박막 복합체 분리막을 제공한다. And a pattern is formed on the surface of the support contacting the selective layer.
또한, 본 발명에서는 (A) 표면에 패턴이 형성된 패턴 지지체를 제조하는 단계; 및 Further, the present invention provides a method for producing a pattern support, comprising the steps of: (A) preparing a pattern support on which a pattern is formed; And
(B) 상기 패턴 지지체 상에 선택층을 형성하는 단계를 포함하는 제 1 항에 따른 박막 복합체 분리막의 제조 방법을 제공한다. And (B) forming a selective layer on the pattern support. The thin film composite separator according to
본 발명에서는 내오염에 효과적인 패턴 구조를 적용한 패턴 지지체를 제공하며, 상기 패턴 지지체 상에 선택층을 형성하여, 내오염성이 극대화된 박막 복합체 분리막을 제조할 수 있다. In the present invention, a pattern support having a pattern structure effective for contamination resistance is provided, and a selective layer is formed on the pattern support to produce a thin film composite membrane having the maximum stain resistance.
또한, 본 발명에 따른 선택층은 conformal하고 표면이 매끈하므로 패턴 지지체 고유의 물리적 구조를 온전히 유지할 수 있으며, 지지체의 패턴 구조를 그대로 재현하여 표면 특성을 극대화할 수 있다. In addition, since the selective layer according to the present invention is conformal and smooth, the physical structure inherent to the pattern support can be completely maintained, and the pattern structure of the support can be reproduced to maximize the surface characteristics.
도 1은 패턴 지지체 및 이를 이용하여 제조한 박막 복합체 분리막의 표면 구조를 나타내는 사진이다.
도 2는 박테리아가 포함된 용액(P. aeruginosa 106 CFU, LB broth 1 g/L 농도)을 사용하여 수투과도를 측정한 결과를 나타낸다.
도 3은 패턴 구조를 포함한 박막 복합체 분리막 표면에서의 미생물 배양 결과를 나타내는 사진이다. 1 is a photograph showing the surface structure of a pattern support and a thin film composite separator manufactured using the same.
2 shows the results of measurement of water permeability using a solution containing bacteria (10 6 CFU of P. aeruginosa, 1 g / L concentration of LB broth).
3 is a photograph showing the result of microbial culture on the surface of a thin film composite membrane including a pattern structure.
이하, 본 발명의 박막 복합체 분리막을 구체적으로 설명한다.Hereinafter, the thin film composite separator of the present invention will be described in detail.
본 발명에 따른 박막 복합체 분리막은 지지체; 및 The thin film composite separator according to the present invention comprises a support; And
상기 지지체 상에 형성된 선택층을 포함한다. And a selective layer formed on the support.
본 발명에서 지지체는 선택층을 지지하고, 박막 복합체 분리막의 기계적 강도를 보강하여 안정적인 분리막 제조에 기여한다. 또한 상기 지지체는 박막 복합체 분리막의 표면 패턴 구현도를 결정한다. In the present invention, the support supports the selective layer and reinforces the mechanical strength of the thin film composite membrane, thereby contributing to the production of a stable membrane. The support also determines the surface pattern implementation of the thin film composite membrane.
이러한 지지체는 폴리에틸렌(polyethylene), 폴리프로필렌(Polypropylene), 폴리염화비닐(Polyvinyl Chloride), 폴리스티렌(Polystyrene), 폴리아미드(Polyamide), 폴리테트라플루오로에틸렌(Polytetrafluoroethylene), 폴리아크릴로니트릴(Polyacrylonitrile), 폴리이미드(Polyimide), 폴리아미드이미드 (polyamideimide), 폴리설폰(Polysulfone), 폴리이서설폰(Polyethersulfone) 및 폴리비닐리덴 플루오라이드(Polyvinyliden Fluoride)로 이루어진 그룹으로부터 선택된 수지로부터 형성될 수 있다. Such supports may be selected from the group consisting of polyethylene, polypropylene, polyvinyl chloride, polystyrene, polyamide, polytetrafluoroethylene, polyacrylonitrile, May be formed from a resin selected from the group consisting of polyimide, polyamideimide, polysulfone, polyethersulfone, and polyvinylidene fluoride.
상기 지지체는 선택층과 접하는 일면에 패턴이 형성된다. 본 발명에서는 이러한 지지체를 패턴 지지체 또는 패턴 다공성 지지체라 표현할 수 있다. The support has a pattern formed on one surface thereof in contact with the selective layer. In the present invention, such a support may be referred to as a pattern support or a pattern porous support.
최종 제조되는 박막 복합체 분리막은 패턴 지지체에 의해 피처리 유체와 접촉하는 일 면, 즉 선택층의 면에도 지지체의 패턴 형상이 나타나게 된다. 상기 피처리 유체와 접하는 표면에 형성된 반복적인 요철 모양의 패턴 구조로 인하여 막오염의 원인이 되는 케이크/층의 형성이 방지되어 분리막의 투과 성능이 현저하게 상승할 수 있다.The thin film composite separator to be finally produced exhibits a pattern shape of the support on one surface of the pattern support, which is in contact with the fluid to be treated, that is, on the surface of the selected layer. It is possible to prevent the formation of the cake / layer which causes the membrane contamination due to the repetitive irregular pattern structure formed on the surface in contact with the fluid to be treated, so that the permeability of the membrane can be remarkably increased.
이러한 패턴 구조는 돌기 부분을 가지는 요철 구조를 가진다. 돌기의 크기 및 돌기들 간의 간격은 0.1 내지 100 ㎛ 사이일 수 있다. 상기 돌기의 크기 및 돌기들 간의 간격은 돌기 상에 미생물 침전을 방지할 수 있을 만큼 작을 수 있다.Such a pattern structure has a concave-convex structure having a projection portion. The size of the protrusions and the distance between the protrusions may be between 0.1 and 100 mu m. The size of the protrusions and the distance between the protrusions may be small enough to prevent microbial precipitation on the protrusions.
본 발명에서는 돌기의 모양에 따라 패턴의 종류를 구분할 수 있으며, 상기 패턴은 연속 선형(line), 비연속 선형(discontinuous line), 샤크렛(sharklet), 지주형(pillar), 십자형(cross), 피라미드(pyramid), 엠보싱(embossing) 및 프리즘(prism)으로 이루어진 그룹으로부터 선택될 수 있다. 상기 패턴의 종류는 본 발명의 박막 복합체 분리막을 적용하는 공정 또는 모듈의 특성을 고려하여 결정할 수 있다.According to the present invention, the pattern can be classified according to the shape of the protrusions, and the pattern can be a continuous line, a discontinuous line, a sharklet, a pillar, a cross, And may be selected from the group consisting of pyramid, embossing, and prism. The kind of the pattern can be determined in consideration of the process of applying the thin film composite separator of the present invention or the characteristics of the module.
연속 선형은 하나 이상의 돌기가 일방향으로 정렬된 구조를 가지는 것을 나타낸다. 여기서 돌기의 단면은 삼각형, 사각형 또는 반원 형상을 가질 수 있다. 상기 돌기의 단면이 삼각형일 경우 프리즘이라 할 수 있다.The continuous linear shape indicates that one or more projections have a structure aligned in one direction. Here, the cross section of the projection may have a triangular, rectangular or semicircular shape. When the cross-section of the projection is triangular, it can be called a prism.
비연속 선형은 연속 선형 패턴에서 돌기가 연속적으로 연결된 구조를 가지지 않으며, 일정한 길이 간격으로 정렬되어 있는 것을 나타낸다.The noncontinuous linear shape indicates that the projections in the continuous linear pattern do not have a continuous structure and are arranged at regular intervals.
샤크렛은 상어의 피부에서 영감을 얻은 자연 모사형 복합 구조로서, 상기 패턴 구조에서는 박테리아, 미생물 등의 성장을 억제할 수 있다. 샤크렛 구조는 서로 다른 길이를 가진 일련의 비연속적 돌기가 마름모 형태로 배열된 패턴을 나타낸다. 돌기는 가장 긴 돌기를 중심으로 하여 길이가 짧아지는 순으로 좌우 동일하게 배열되며, 각 돌기는 규칙적인 간격으로 배치될 수 있다.Sharklet is a natural-mimetic composite structure inspired by the skin of a shark. In the pattern structure, growth of bacteria, microorganisms, etc. can be suppressed. The shaklet structure represents a pattern in which a series of discontinuous projections of different lengths are arranged in rhombic form. The protrusions are arranged in the left and right direction in the order of decreasing length around the longest protrusions, and the protrusions can be arranged at regular intervals.
지주형은 돌기의 높이보다 낮은 가로 길이 및 세로 길이를 가지는 하나 이상의 돌기가 일정한 간격으로 정렬된 것을 나타내고, 십자형은 하나 이상의 돌기가 십자 형상을 가진 것을 나타내며, 피라미드는 하나 이상의 돌기가 사면체의 형상을 가지는 것을 나타낸다. 또한, 엠보싱은 하나 이상의 돌기가 반구형의 형상을 가지는 것을 나타낸다. The column type indicates that one or more protrusions having a width and a length smaller than the height of the protrusions are aligned at regular intervals, and a cross indicates that one or more protrusions have a cross shape. The pyramid has one or more protrusions, . Also, embossing indicates that at least one projection has a hemispherical shape.
상기 패턴의 표면 조도(roughness)는 1.2 내지 20일 수 있다. 본 발명에서 표면조도는 패턴 지지체 표면에 형성된 패턴의 요철의 정도를 나타내는 인자로서, 각각의 패턴의 기하학적인 투영 면적에 대한 실제 표면적의 비로 정의되는 값이다. 본 발명에서 표면조도가 1.2 미만이면 유효 막면적 증대에 의한 막오염 방지 효과가 현저하게 감소할 우려가 있으며, 표면조도가 20을 초과하면 각 패턴 사이에 사영역이 발생되어 막오염이 심화될 우려가 있다. The surface roughness of the pattern may be 1.2-20. In the present invention, the surface roughness is a factor representing the degree of the unevenness of the pattern formed on the surface of the pattern support, and is a value defined by the ratio of the actual surface area to the geometrically projected area of each pattern. In the present invention, if the surface roughness is less than 1.2, there is a possibility that the effect of preventing the film fouling due to the increase of the effective film area is remarkably decreased. If the surface roughness exceeds 20, a yarn area is generated between each pattern, .
본 발명에서 패턴 지지체의 두께는 1 내지 100 ㎛일 수 있다. 이때 두께는 패턴 구조, 즉 돌기를 포함하는 두께를 의미한다. 상기 두께 범위 내에서 정삼투용, 압력지연삼투용, 가압식 정삼투용 또는 나노필트레이션, 역삼투 분리막으로 우수한 성능을 구현할 수 있다. 100 ㎛를 초과하는 두께에서도 분리막으로 사용 가능한 물성 및 성능을 가지나, 수투과도의 저감과 함께 제조 비용의 상승을 가져올 수 있으므로 두께를 1 내지 100 ㎛로 조절하는 것이 좋다. In the present invention, the thickness of the pattern support may be 1 to 100 mu m. At this time, the thickness means the pattern structure, that is, the thickness including the protrusions. It is possible to achieve excellent performance in the above-mentioned thickness range for positive osmosis, pressure delay osmosis, pressurized positive osmosis or nanofiltration and reverse osmosis membrane. Though the thickness exceeds 100 탆, the thickness and the performance can be adjusted to 1 to 100 탆, because the water permeability and the manufacturing cost may be increased.
또한, 패턴 지지체의 기공 크기는 1 내지 100 nm 또는 5 내지 50 nm일 수 있다. 또한, 기공도는 20 내지 90%, 30 내지 90%, 40 내지 90% 또는 50 내지 90%일 수 있다. 상기 기공 크기 및 기공도에서 우수한 수투과도를 가질 수 있으며, 매끈한 표면을 가지는 선택층을 제조할 수 있다.Also, the pore size of the patterned support may be 1 to 100 nm or 5 to 50 nm. The porosity may also be 20 to 90%, 30 to 90%, 40 to 90% or 50 to 90%. It is possible to have a good water permeability in the pore size and porosity and to produce a selective layer having a smooth surface.
본 발명에 따른 패턴 지지체는 친수화 처리된 패턴 지지체일 수 있다. 상기 친수화 처리에 의해 표면에너지가 높아지므로, 선택층과의 결합력을 높일 수 있다. The pattern support according to the present invention may be a hydrophilized pattern support. Since the surface energy is increased by the hydrophilization treatment, the coupling strength with the selective layer can be increased.
이러한 친수화 처리는 패턴 지지체의 단면 또는 양면에 처리될 수 있으며, 단면에 처리될 경우 선택층이 형성되는 면에 처리될 수 있다. Such hydrophilization treatment may be performed on a cross-section or on both sides of the pattern support, and when the cross-section is treated, it may be treated on the side where the selective layer is formed.
본 발명에 따른 박막 복합체 분리막은 지지체 및 선택층 사이에 중간층이 형성될 수 있다. In the thin film composite membrane according to the present invention, an intermediate layer may be formed between the support and the selective layer.
상기 중간층은 패턴 지지체과 선택층의 두 개의 층을 용이하게 접합시키기 위해 형성할 수 있다. 지지체는 다공성의 구조를 가지므로, 상기 지지체 상에 기공 크기보다 작은 원료(단량체) 물질을 이용하여 선택층을 형성할 경우 상기 지지체의 기공에 선택층의 원료 물질 용액이 함침되고, 상기 함침된 용액이 다른 반응 용액과 만나는 과정에서 모세관 현상 등에 의해 물질 전달 속도가 변화하여 결과적으로 매끈한 표면의 선택층이 아닌 나노스케일의 표면 미세 요철을 형성하게 된다. 따라서, 본 발명에서는 기공 크기보다 작은 원료 물질을 이용할 경우, 패턴 지지체 상에 중간층을 형성하고, 상기 중간층 상에 선택층을 형성하여 매끈한 표면의 선택층을 제조할 수 있다. 원료 물질이 지지체의 기공 크기보다 클 경우에는 상기 중간층의 형성을 생략할 수 있다.The intermediate layer can be formed to easily bond the two layers of the pattern support and the selective layer. Since the support has a porous structure, when a selective layer is formed using a material (monomer) material smaller than the pore size on the support, the pore of the support is impregnated with the raw material solution of the selective layer, During the process of contacting with the other reaction solution, the mass transfer rate is changed by the capillary phenomenon and the like, resulting in nanoscale surface fine irregularities rather than a smooth selective surface layer. Accordingly, in the present invention, when a raw material smaller than the pore size is used, a selective layer of a smooth surface can be produced by forming an intermediate layer on a pattern support and forming a selective layer on the intermediate layer. If the raw material is larger than the pore size of the support, the formation of the intermediate layer may be omitted.
이러한 중간층의 재질로는 폴리아크릴산, 폴리스타이렌 설포네이트, 폴리비닐술폰산, 폴리에틸렌이민, 폴리알릴아민, 폴리아크릴아미드 및 폴리피페라진아미드 등으로 이루어진 그룹에서 선택된 하나 이상을 사용할 수 있다. As the material of the intermediate layer, at least one selected from the group consisting of polyacrylic acid, polystyrene sulfonate, polyvinyl sulfonic acid, polyethyleneimine, polyallylamine, polyacrylamide and polypiperazine amide can be used.
본 발명에서 선택층은 패턴 지지체 상에 형성되며, 패턴 지지체 상에 중간층이 형성될 경우에는 상기 중간층 상에 형성될 수 있다. 상기 선택층은 고밀도의 얇은 박막이고 매끈한 표면을 가지므로, 패턴 지지체의 패턴 구조를 선택층에 그대로 재현 가능하다.In the present invention, the selection layer is formed on the pattern support, and may be formed on the intermediate layer when the intermediate layer is formed on the pattern support. Since the selective layer is a high-density thin film and has a smooth surface, the pattern structure of the pattern support can be reproduced in the selected layer as it is.
상기 선택층은 가교 또는 비가교된 폴리아마이드(polyamide), 폴리피페라진-아마이드(polypiperazine-amide), 폴리에스테르(polyester), 폴리우레탄(polyurethane), 폴리바이닐알코올(polyvinyl alcohol), 폴리이미드(polyimide) 또는 폴리이터이미드(polyetherimide)이거나, 전 방향족(fully aromatic) 화합물, 부분 방향족(semi-aromatic) 화합물 또는 전 지방족(fully aliphatic) 화합물을 포함할 수 있다. The optional layer may be selected from the group consisting of crosslinked or unmodified polyamide, polypiperazine-amide, polyester, polyurethane, polyvinyl alcohol, polyimide, ) Or polyetherimide, or may comprise a fully aromatic compound, a semi-aromatic compound or a fully aliphatic compound.
이러한 선택층의 두께는 1 내지 200 nm일 수 있다. The thickness of such a selective layer may be between 1 and 200 nm.
본 발명에 따른 박막 복합체 분리막은 나노필트레이션(nanofiltration, NF), 정삼투(forward osmosis, FO), 가압식 정삼투(pressure assisted osmosis, PAO), 압력지연삼투(pressure-retarded osmosis, PRO) 및 역삼투(reverse osmosis, RO) 공정에 사용될 수 있다. 특히, 본 발명에 따른 박막 복합체 분리막은 얇은 두께를 가지므로, 상기 공정에 용이하게 적용될 수 있다. The thin film composite membrane according to the present invention can be used for various applications such as nanofiltration (NF), forward osmosis (FO), pressure assisted osmosis (PAO), pressure-retarded osmosis Reverse osmosis (RO) process. Particularly, since the thin film composite separator according to the present invention has a small thickness, it can be easily applied to the above process.
또한, 본 발명에 따른 박막 복합체 분리막을 공정에 적용시, 상기 분리막의 패턴이 피처리 용액의 흐름 방향과 수직 방향이 되도록 위치시킬 수 있다.In addition, when the thin film composite membrane according to the present invention is applied to a process, the pattern of the separation membrane can be positioned so as to be perpendicular to the flow direction of the solution to be treated.
또한, 본 발명은 전술한 박막 복합체 분리막의 제조 방법에 관한 것이다. The present invention also relates to a method for producing the thin film composite membrane as described above.
상기 박막 복합체 분리막은 (A) 표면에 패턴이 형성된 패턴 지지체를 제조하는 단계; 및 (A) fabricating a patterned support having a pattern on its surface; And
(B) 상기 패턴 지지체 상에 선택층을 형성하는 단계를 통해 제조될 수 있다. (B) forming a selective layer on the pattern support.
단계 (A)는 표면에 패턴이 형성된 패턴 지지체를 제조하는 단계로서, 지지체 표면에 패턴을 형성하는 기술은 수 nm 내지 수백 μm 크기의 반복적인 패턴을 형성할 수 있는 기술이라면 특별하게 제한되지 않는다. 대표적으로 종래의 반도체 공정에서의 소자 표면 패턴화 기술인 소프트-리소그래피법을 적용할 수 있다.Step (A) is a step of producing a patterned support having a pattern on its surface, and the technique of forming a pattern on the surface of the support is not particularly limited as long as it is a technique capable of forming a repetitive pattern of a size of several nm to several hundreds of micrometers. Typically, a soft-lithography method which is a device surface patterning technique in a conventional semiconductor process can be applied.
소프트 리소그래피법은 마스터 몰드와 동일한 패턴을 가지며 PDMS (폴리디메틸실록산), 불소계 고분자 등과 같이 가요성(flexible)이며 연성의 재질의 복제 몰드(replica mold)를 반복하여 대량으로 제조한 후 이로부터 패턴을 형성하는 기술이다.The soft lithography method has the same pattern as that of the master mold, and a large number of replica molds made of flexible and flexible materials such as PDMS (polydimethylsiloxane) and fluorine-based polymers are repeatedly manufactured in large quantities, .
예를 들어, 본 발명의 단계 (A)는 한 쪽 표면에 음각의 패턴을 가지는 몰드에 지지체 원료 수지를 캐스팅하는 단계;For example, step (A) of the present invention comprises casting a support material resin to a mold having a pattern of engraved on one surface;
상기 지지체 원료 수지 상에 부직포를 덮어 몰드-원료 수지-부직포의 복합체를 제조하는 단계; Producing a composite of a mold-starting resin-nonwoven fabric by covering the nonwoven fabric on the support material resin;
상기 복합체를 비용매에 넣고 상전이시키는 단계; 및 Placing the composite in a non-solvent and phase transitions; And
상기 상전이된 복합체에서 몰드를 제거하여 패턴 지지체를 얻는 단계를 포함할 수 있다. And removing the mold from the phase-transformed composite to obtain a pattern support.
본 발명에서 사용되는 몰드는 일 표면에 수 nm 내지 수백 μm크기의 미세한 패턴이 음각으로 형성되어 있고 유기용매에 대한 내성이 높은 재질을 가진다면 특별히 제한되지 않는다. 예를들어, 실리콘, 석영 등과 같은 세라믹 재질의 마스터 몰드(master mold), 또는 전자빔 리소그래피, 포토 리소그래피 또는 소프트 리소그래피 기술 등의 반도체 공정용으로 활용되는 복제 몰드(replica mold)를 사용할 수 있다. 상대적으로 저렴한 비용으로 제작할 수 있는 복제 몰드의 원료로는, 폴리우레탄아크릴레이트 (polyurethan acrylate, PUA), 폴리디메틸실록산(PDMS) 또는 불소계 폴리머 등을 사용할 수 있다.The mold used in the present invention is not particularly limited as long as it has a fine pattern having a size of several nanometers to several hundreds of micrometers on a surface and has a high resistance to an organic solvent. For example, a master mold of a ceramic material such as silicon, quartz, or the like, or a replica mold utilized for semiconductor processing such as electron beam lithography, photolithography, or soft lithography can be used. Polyurethane acrylate (PUA), polydimethylsiloxane (PDMS), or a fluorine-based polymer can be used as a raw material of a replica mold that can be manufactured at a relatively low cost.
일 구체예에서 금속 등의 경성 재질로 원하는 패턴 형태를 양각으로 제조한 후, 이를 이용하여 음각의 패턴을 가지는 몰드를 제조할 수 있다. In one embodiment, a desired pattern may be embossed with a hard material such as a metal, and then a mold having an embossed pattern may be manufactured using the embossed pattern.
본 발명에서 몰드에 캐스팅되는 용액은 패턴이 형성되는 지지체의 원료 수지를 유기용매에 녹인 것이다. 상기 유기용매는 지지체 원료 수지를 균일하게 용해할 수 있는 것이라면 특별히 제한되지 않으며, 디메틸포름아미드, 메틸피롤리돈, 테트라하이드로퓨란 또는 디메틸설폭사이드 등을 사용할 수 있다. 또한, 지지체의 원료 수지는 전술한 수지를 제한없이 사용할 수 있다. In the present invention, the solution to be cast in the mold is obtained by dissolving the raw resin of the support on which the pattern is formed in an organic solvent. The organic solvent is not particularly limited as long as it can dissolve the support material resin uniformly, and dimethylformamide, methylpyrrolidone, tetrahydrofuran, dimethylsulfoxide and the like can be used. The above-mentioned resin can be used without limitation in the raw material resin of the support.
본 발명에서는 몰드에 지지체 원료 수지를 캐스팅한 후, 상기 지지체 원료 수지 상에 부직포를 덮어 몰드-원료 수지-부직포의 복합체를 제조할 수 있다. 상기 부직포를 통해 유동성이 있는 원료 수지의 이동을 방지할 수 있으며, 내구성을 보완할 수 있다. 상기 부직포의 재질로는 폴리에스터, 레이온, 폴리프로필렌, 폴리에틸렌, 폴리염화비닐, 폴리비닐알코올, 폴리스티렌, 폴리에틸렌 테레프탈레이트(PET) 또는 폴리아미드 등을 사용할 수 있다. In the present invention, a composite of a mold-raw resin-nonwoven fabric can be produced by casting a support raw material resin to a mold and then covering the nonwoven fabric on the support raw material resin. It is possible to prevent the movement of the raw resin having fluidity through the nonwoven fabric and to improve durability. As the material of the nonwoven fabric, polyester, rayon, polypropylene, polyethylene, polyvinyl chloride, polyvinyl alcohol, polystyrene, polyethylene terephthalate (PET) or polyamide can be used.
그 후, 상기 복합체를 비용매에 넣고 상전이시키는데, 비용매로는 물, 메탄올, 에탄올, 부탄올 또는 아이소프로판올 등을 사용할 수 있다. 상기 상전이를 통해 지지체 원료 수지는 패턴이 형성되며 다공성을 가지는 지지체로 제조될 수 있다. Thereafter, the complex is put into a non-solvent and phase transformation is carried out. Water, methanol, ethanol, butanol or isopropanol can be used as the non-solvent. Through the phase transition, the support material resin may be formed into a patterned and porous support.
상기 상전이가 완료된 후, 복합체에서 몰드를 제거하여 패턴 지지체를 얻을 수 있다. After the phase transition is completed, the mold can be removed from the composite to obtain a pattern support.
본 발명의 제조 방법에서는 패턴 지지체 상에 선택층을 형성하기 전에, 상기 패턴 지지체를 친수화 처리하는 단계를 추가로 포함할 수 있다. The production method of the present invention may further include a step of hydrophilizing the pattern support before forming the selective layer on the pattern support.
일반적으로, 지지체는 소수성 이므로, 상기 친수화 처리를 통해 선택층의 형성을 용이하게 수행할 수 있다. Generally, since the support is hydrophobic, the formation of the selective layer can be easily performed through the hydrophilization treatment.
이러한 친수화 처리는 화학적 산화, 플라즈마, UV 산화, 단원자층 증착(ALD), 화학기상 증착(CVD), 무기물 코팅 또는 고분자 코팅 처리일 수 있다. Such hydrophilization treatment may be chemical oxidation, plasma, UV oxidation, monolayer deposition (ALD), chemical vapor deposition (CVD), inorganic coating or polymer coating treatment.
상기 화학적 산화는 염산(hydrochloric acid), 황산(sulfuric acid), 질산(nitric acid), 과산화수소(hydrogen peroxide) 또는 차아염소산나트륨(sodium hypochlorite)을 포함하는 산성 용액이나, 수산화 나트륨(sodium hydroxide), 수산화 칼륨(potassium hydroxide) 또는 수산화 암모늄(ammonium hydroxide)을 포함하는 염기성 용액을 이용할 수 있고, 플라즈마 산화법을 이용할 경우 단면 및 양면을 처리할 수 있다. 무기물 코팅에서 무기물로는 구리(copper), 구리 산화물(copper oxide), 아연 산화물(zinc oxide), 티타늄 산화물(titanium oxide), 주석 산화물(tin oxide) 또는 알루미늄 산화물(aluminum oxide) 등을 이용할 수 있으며, 고분자 코팅에서 고분자로는 폴리하이드록시에틸렌메타크릴레이트(polyhydroxyethylenemethacrylate), 폴리아크릴산(polyacrylic acid), 폴리하이드록시메틸렌(polyhydroxymethylene), 폴리아릴아민(polyallyl- amine), 폴리아미노스틸렌(polyaminostyrene), 폴리아크릴아마드(polyacrylamide), 폴리에틸렌이민(polyethyleneimine), 폴리바이닐알코올(polyvinyl alcohol), 폴리도파민(polydopamine) 등의 친수 특성이 있는 화합물을 이용할 수 있다. The chemical oxidation may be an acidic solution containing hydrochloric acid, sulfuric acid, nitric acid, hydrogen peroxide or sodium hypochlorite, or an aqueous solution containing sodium hydroxide, A basic solution containing potassium hydroxide or ammonium hydroxide can be used, and when plasma oxidation is used, one side and both sides can be treated. As inorganic materials in the inorganic coating, copper, copper oxide, zinc oxide, titanium oxide, tin oxide or aluminum oxide can be used. In the polymer coating, the polymer may include polyhydroxyethylenemethacrylate, polyacrylic acid, polyhydroxymethylene, polyallyl-amine, polyaminostyrene, poly A compound having hydrophilic properties such as polyacrylamide, polyethyleneimine, polyvinyl alcohol and polydopamine can be used.
일 구체예에서 지지체의 재질이 폴리아크릴로니트릴(PAN)이면 강염기 처리를, 폴리설폰(PSF)이면 황산 처리를 수행할 수 있으며, 폴리비닐리덴 플루오라이드(PVDF)이면 건식 산소 플라즈마 처리를 수행하여 지지체의 친수성을 증가시킬 수 있다.In one embodiment, if the support is made of polyacrylonitrile (PAN), a strong base treatment may be applied, if polysulfone (PSF), sulfuric acid treatment may be performed, and if polyvinylidene fluoride (PVDF) The hydrophilicity of the support can be increased.
본 발명에서는 친수화 처리 후, 패턴 지지체를 세척하는 단계를 추가로 포함할 수 있다. 상기 세척 용매로는 아이소프로필 알코올(isopropyl alcohol), 물 또는 이의 혼합 용매를 사용할 수 있다. In the present invention, it is possible to further include a step of washing the pattern support after the hydrophilizing treatment. As the washing solvent, isopropyl alcohol, water or a mixed solvent thereof may be used.
본 발명에서는 패턴 지지체 상에 선택층을 형성하기 전에 상기 패턴 지지체 상에 중간층을 형성하는 단계를 추가로 수행할 수 있다. In the present invention, it is possible to further carry out a step of forming an intermediate layer on the pattern support before forming the selective layer on the pattern support.
본 발명에서는 패턴 지지체 상에 중간층을 형성한 후 선택층을 형성하여, 보다 안정된 선택층을 제조할 수 있다.In the present invention, a selective layer can be formed by forming an intermediate layer on a pattern support, and a more stable selective layer can be produced.
상기 중간층은 딥코팅법, 스프레이코팅법, 스핀코팅법, 계면중합법 또는 층상조립(layer-by-layer)법을 통해 형성할 수 있다. The intermediate layer may be formed by a dip coating method, a spray coating method, a spin coating method, an interfacial polymerization method, or a layer-by-layer method.
일 구체예에서, 중간층은 패턴 지지체 표면 전하와 상반되는 전하를 가지는 고분자 전해질 수용액에 패턴 지지체를 담지하여 고분자 전해질이 표면에 부착되도록 할 수 있다. 필요시 이후 상기 고분자 전해질과 반대 전하를 가지는 다른 고분자 전해질을 추가로 담지할 수 있다. 여기서, 양전하를 가지는 고분자로는 폴리아크릴산, 폴리스타이렌 설포네이트, 폴리비닐술폰산 등을 사용할 수 있으며, 음전하를 가지는 고분자로는 폴리에틸렌이민, 폴리알릴아민, 폴리아크릴아미드 등을 사용할 수 있다. In one embodiment, the intermediate layer can support the pattern support in an aqueous solution of the polymer electrolyte having charge opposite to the surface charge of the pattern support, so that the polymer electrolyte adheres to the surface. If necessary, another polymer electrolyte having an opposite charge to the polymer electrolyte may be further supported thereon. Examples of the polymer having a positive charge include polyacrylic acid, polystyrene sulfonate, polyvinyl sulfonic acid, and the like. Examples of the polymer having a negative charge include polyethyleneimine, polyallylamine, polyacrylamide, and the like.
본 발명에서 단계 (B)는 패턴 지지체 상에 선택층을 형성하는 단계이다. Step (B) in the present invention is a step of forming a selective layer on a patterned support.
이러한 선택층은 계면중합법, 딥코팅법, 스프레이코팅법, 스핀코팅법, 한계계면중합법 또는 층상조립(layer-by-layer)법을 통해 형성될 수 있으며, 본 발명에서는 한계계면중합법을 통해 형성될 수 있다. Such a selective layer can be formed through interface polymerization, dip coating, spray coating, spin coating, limiting interface polymerization or layer-by-layer method. As shown in FIG.
일 구체예에서 선택층은 한계계면중합을 이용하여 제조할 수 있다. In one embodiment, the selection layer can be prepared using limiting interface polymerization.
상기 한계계면중합은 패턴 지지체 상에 제 1 유기단량체를 포함하는 제 1 용액을 함침 또는 도포하는 단계;Impregnating or applying a first solution comprising a first organic monomer on a patterned support;
패턴 지지체 표면의 제 1 유기단량체의 함량을 조절하는 단계; Adjusting the content of the first organic monomer on the pattern support surface;
제 2 유기단량체를 포함하는 제 2 용액을 함침 또는 도포하는 단계;Impregnating or applying a second solution comprising a second organic monomer;
상기 제 1 용액 및 제 2 용액에 각각 용해되어 있는 제 1 유기단량체와 제 2 유기단량체 간의 계면중합을 통해 선택층을 형성하는 단계; 및Forming a selective layer by interfacial polymerization between a first organic monomer and a second organic monomer respectively dissolved in the first solution and the second solution; And
잔류 제 2 유기단량체를 제거하는 단계를 포함할 수 있다. And removing the residual second organic monomer.
이때, 제 1 용액은 제 1 유기단량체와 이를 용해하는 제 1 용매를 포함하며, 제 2 용액은 제 2 유기단량체와 이를 용해하는 제 2 용매를 포함한다. Wherein the first solution comprises a first organic monomer and a first solvent that dissolves the first organic monomer and the second solution comprises a second organic monomer and a second solvent that dissolves the second organic monomer.
일 구체예에서, 상기 제 1 유기단량체의 종류는 특별히 제한되지 않으며, 예를 들어, m-페닐렌 디아민(m-phenylene diamine, MPD), o-페닐렌 디아민(o-phenylene diamine, OPD), p-페닐렌 디아민(p-phenylene diamine, PPD), 피페라진(piperazine), m-자일렌 디아민(m-xylenediamine, MXDA), 에틸렌 디아민(ethylenediamine), 트리메틸렌디아민(trimethylenediamine), 헥사메틸렌 디아민(haxamethylenediamine), 디에틸렌 트리아민(diethylene triamine, DETA), 트리에틸렌 테트라민(triethylene tetramine, TETA), 메탄 디아민(methane diamine, MDA), 이소포론디아민(isophoroediamine, IPDA), 트리에탄올아민(triethanolamine), 폴리에틸렌이민(polyethyleneimine), 메틸 디에탄올아민(methyl diethanolamine), 하이드록시알킬아민(hydroxyakylamine), 하이드로퀴논(hydroquinone), 레소시놀(resorcinol), 카테콜(catechol), 에틸렌글리콜(ethylene glycol), 글리세린(glycerine), 폴리바이닐알코올(polyvinyl alcohol), 4,4'-비페놀(4,4'-biphenol), 메틸렌 디페닐 디이소시아네이트(methylene diphenyl diisocyanate), m-페닐렌 디이소시아네이트(m-phenylene diisocyanate), p-페닐렌 디이소시아네이트(p-phenylene diisocyanate) 및 톨루엔 디이소시아네이트(toluene diisocyanate)로 이루어진 그룹으로부터 선택된 하나 이상을 사용할 수 있다.In one embodiment, the first type of organic monomer is not particularly limited, for example, m - phenylenediamine (m -phenylene diamine, MPD), o - phenylenediamine (o -phenylene diamine, OPD), p - phenylenediamine (p -phenylene diamine, PPD), piperazine (piperazine), m - xylene diamine (m -xylenediamine, MXDA), ethylenediamine (ethylenediamine), trimethylenediamine (trimethylenediamine), hexamethylene diamine ( diethylene triamine (DETA), triethylene tetramine (TETA), methane diamine (MDA), isophoroediamine (IPDA), triethanolamine, polyethylene But are not limited to, polyethyleneimine, methyl diethanolamine, hydroxyakylamine, hydroquinone, resorcinol, catechol, ethylene glycol, glycerin, glycerine), Lee vinyl alcohol (polyvinyl alcohol), 4,4'- biphenol (4,4'-biphenol), methylene diphenyl diisocyanate (methylene diphenyl diisocyanate), m - phenylene diisocyanate (m -phenylene diisocyanate), p - At least one selected from the group consisting of p- phenylene diisocyanate and toluene diisocyanate can be used.
일 구체예에서, 제 1 용매의 종류는 특별히 제한되지 않으며, 예를 들어, 물, 메탄올, 에탄올, 프로판올, 부탄올, 이소프로판올, 에틸아세테이트, 아세톤, 클로로포름, 테트라하이드로퓨란, 디메틸설폭사이드, 디메틸포름아마이드 및 N-메틸-2-피롤리디온으로 이루어진 그룹으로부터 선택된 하나 이상을 사용할 수 있다.In one embodiment, the type of the first solvent is not particularly limited and includes, for example, water, methanol, ethanol, propanol, butanol, isopropanol, ethyl acetate, acetone, chloroform, tetrahydrofuran, dimethylsulfoxide, dimethylformamide And N -methyl-2-pyrrolidione can be used.
또한, 본 발명에서 제 1 용액은 계면활성제를 추가로 포함하여 지지체 내 제 1 용액의 젖음성을 향상시킬 수 있다. Further, in the present invention, the first solution may further include a surfactant to improve the wettability of the first solution in the support.
이러한 계면활성제로는 이온성 또는 비이온성 계면활성제를 사용할 수 있으며, 상기 이온성 계면활성제는 음이온성, 양이온성 또는 양쪽 이온성 계면활성제일 수 있다. As such a surfactant, an ionic or nonionic surfactant may be used, and the ionic surfactant may be an anionic, cationic or amphoteric surfactant.
일 구체예에서, 음이온성 계면활성제로는 암모늄 라우릴 설페이트, 소듐 1-헵탄설포네이트, 소듐 헥산설포네이트, 소듐 도데실설페이트, 트리에탄올암모늄도데실벤젠설페이트, 칼륨 라우레이트, 트리에탄올아민 스테아레이트, 리튬 도데실설페이트, 소듐 라우릴설페이트, 알킬 폴리옥시에틸렌 설페이트, 소듐 알기네이트, 디옥틸 소듐 술포숙시네이트, 포스파티딜 글리세롤, 포스파티딜 이노시톨, 포스파티딜세린, 포스파티드산 및 그의 염, 글리세릴 에스테르, 소듐 카르복시메틸셀룰로즈, 담즙산 및 그의 염, 콜산, 데옥시콜산, 글리코콜산, 타우로콜산, 글리코데옥시콜산, 알킬 술포네이트, 아릴 술포네이트, 알킬 포스페이트, 알킬 포스포네이트, 스테아르산 및 그의 염, 칼슘 스테아레이트, 포스페이트, 카르복시메틸셀룰로스 나트륨, 디옥틸술포숙시네이트, 소듐 술포숙신산의 디알킬에스테르, 인지질 및 칼슘 카르복시메틸셀룰로즈로 이루어진 그룹으로부터 선택된 하나 이상을 사용할 수 있고, 양이온성 계면활성제로는 4급(quaternary) 암모늄 화합물, 벤즈알코늄 클로라이드, 세틸트리메틸암모늄 브로마이드, 키토산, 라우릴디메틸벤질암모늄 클로라이드, 아실 카르니틴 히드로클로라이드, 알킬피리디늄 할라이드, 세틸 피리디늄 클로라이드, 양이온성 지질, 폴리메틸메타크릴레이트 트리메틸암모늄 브로마이드, 술포늄 화합물, 폴리비닐피롤리돈-2-디메틸아미노에틸 메타크릴레이트 디메틸 술페이트, 헥사데실트리메틸 암모늄 브로마이드, 포스포늄 화합물, 벤질-디(2-클로로에틸)에틸암모늄브로마이드, 코코넛 트리메틸 암모늄 클로라이드, 코코넛 트리메틸 암모늄 브로마이드, 코코넛 메틸 디히드록시에틸 암모늄 클로라이드, 코코넛 메틸 디히드록시에틸 암모늄 브로마이드, 데실 트리에틸 암모늄 클로라이드, 데실 디메틸 히드록시에틸 암모늄 클로라이드 브로마이드, (C12-C15)디메틸 히드록시에틸 암모늄 클로라이드, (C12-C15)디메틸 히드록시에틸 암모늄 클로라이드 브로마이드, 코코넛 디메틸 히드록시 에틸 암모늄 클로라이드, 코코넛 디메틸 히드록시에틸 암모늄 브로마이드, 미리스틸 트리메틸 암모늄 메틸술페이트, 라우릴 디메틸 벤질 암모늄 클로라이드, 라우릴디메틸 벤질 암모늄 브로마이드, 라우릴 디메틸 (에테녹시)4 암모늄 클로라이드, 라우릴 디메틸 (에테녹시)4 암모늄 브로마이드, N-알킬 (C12-C18)디메틸벤질 암모늄클로라이드, N-알킬 (C14-C18)디메틸-벤질 암모늄 클로라이드, N-테트라데실디메틸벤질 암모늄 클로라이드 일수화물, 디메틸 디데실 암모늄 클로라이드, N-알킬 (C12-C14)디메틸 1-나프틸메틸 암모늄 클로라이드, 트리메틸암모늄 할라이드 알킬-트리메틸암모늄 염, 디알킬-디메틸암모늄 염, 라우릴 트리메틸 암모늄 클로라이드, 에톡실화 알킬아미도알킬디알킬암모늄 염, 에톡실화 트리알킬 암모늄 염, 디알킬벤젠 디알킬암모늄 클로라이드, N-디데실디메틸 암모늄 클로라이드, N-테트라데실디메틸벤질 암모늄 클로라이드 일수화물, N-알킬(C12-C14) 디메틸 1-나프틸메틸 암모늄클로라이드, 도데실디메틸벤질 암모늄 클로라이드, 디알킬 벤젠알킬 암모늄클로라이드, 라우릴 트리메틸 암모늄 클로라이드, 알킬벤질 메틸 암모늄 클로라이드, 알킬 벤질 디메틸 암모늄브로마이드, C12 트리메틸 암모늄 브로마이드, C15 트리메틸암모늄 브로마이드, C17 트리메틸 암모늄 브로마이드, 도데실벤질 트리에틸 암모늄 클로라이드, 폴리디알릴디메틸암모늄 클로라이드, 디메틸 암모늄 클로라이드, 알킬디메틸암모늄 할로게니드, 트리세틸 메틸 암모늄 클로라이드, 데실트리메틸암모늄 브로마이드, 도데실트리에틸암모늄 브로마이드, 테트라데실트리메틸암모늄 브로마이드, 메틸 트리옥틸암모늄 클로라이드, 테트라부틸암모늄브로마이드, 벤질 트리메틸암모늄 브로마이드, 콜린 에스테르, 벤즈알코늄 클로라이드, 스테아르알코늄 클로라이드, 세틸 피리디늄 브로마이드, 세틸 피리디늄 클로라이드, 알킬 피리디늄 염, 아민, 아민 염, 이미드 아졸리늄 염, 양이온성 구아검, 벤즈알코늄 클로라이드, 도데실 트리메틸 암모늄 브로마이드, 트리에탄올아민 및 폴옥사민으로 이루어진 그룹으로부터 선택된 하나 이상을 사용할 수 있으며, 양쪽 이온성 계면활성제로 N-도데실-N,N-디메틸-3-암모니오-1-프로판설포네이트, 베타인, 알킬 베타인, 알킬아미도 베타인, 아미도 프로필 베타인, 코코암포카르복시글리시네이트, 사코시네이트 아미노프로피오네이트, 아미노글리시네이트, 이미다졸리늄 베타인, 양쪽성이미다졸린, N-알킬-N,N-디메틸암모니오-1-프로판술폰에이트, 3-콜아미도-1-프로필디메틸암모니오-1-프로판술폰에이트, 도데실포스포콜린 및 설포-베타인으로 이루어진 그룹으로부터 선택된 하나 이상을 사용할 수 있다. 또한, 비이온성 계면활성제로는 SPAN 60, 폴리옥시에틸렌 지방(fatty) 알코올 이터, 폴리옥시에틸렌 소르비탄 지방산 에스테르, 폴리옥시에틸렌 지방산 에스테르, 폴리옥시에틸렌 알킬이터, 폴리옥시에틸렌 피마자유 유도체, 소르비탄 에스테르, 글리세릴 에스테르, 글리세롤 모노스테아레이트, 폴리에틸렌 글리콜, 폴리프로필렌 글리콜, 폴리프로필렌 글리콜 에스테르, 세틸 알코올, 세토스테아릴 알코올, 스테아릴 알코올, 아릴알킬 폴리이터 알코올, 폴리옥시에틸렌폴리옥시프로필렌 공중합체, 폴록사머, 폴락사민, 메틸셀룰로즈, 히드록시셀룰로즈, 히드록시메틸셀룰로스, 히드록시에틸셀룰로스, 히드록시 프로필셀룰로즈, 히드록시 프로필메틸셀룰로즈, 히드록시프로필메틸셀룰로스 프탈레이트, 비결정성 셀룰로즈, 다당류, 전분, 전분 유도체, 히드록시에틸 전분, 폴리비닐 알코올, 트리에탄올아민 스테아레이트, 아민 옥시드, 덱스트란, 글리세롤, 아카시아 검, 콜레스테롤, 트래거캔스, 및 폴리비닐피롤리돈으로 이루어진 그룹으로부터 선택된 하나 이상을 사용할 수 있다. In one embodiment, the anionic surfactant includes ammonium lauryl sulfate, sodium 1-heptanesulfonate, sodium hexanesulfonate, sodium dodecyl sulfate, triethanolammonium dodecylbenzenesulfate, potassium laurate, triethanolamine stearate, lithium Phosphatidylserine, phosphatidylserine, phosphatidylserine and salts thereof, glyceryl ester, sodium carboxymethyl ester, sodium lauryl sulfate, alkyl polyoxyethylene sulfate, sodium alginate, dioctyl sodium sulfosuccinate, phosphatidylglycerol, phosphatidylinositol, phosphatidylserine, Cellulose, bile acid and salts thereof, cholic acid, deoxycholic acid, glycocholic acid, taurocholic acid, glycodeoxycholic acid, alkylsulfonate, arylsulfonate, alkylphosphate, alkylphosphonate, stearic acid and its salts, calcium stearate , Phosphate, carboxymethyl cellulose sodium, dioctyl sulfosuccinate A dialkyl ester of sodium sulfosuccinic acid, a phospholipid and calcium carboxymethyl cellulose, and examples of the cationic surfactant include a quaternary ammonium compound, benzalkonium chloride, cetyltrimethylammonium A cationic lipid, a polymethylmethacrylate trimethylammonium bromide, a sulfonium compound, a polyvinylpyrrolidone-2, a polyvinylpyrrolidone-2, a polyvinylpyrrolidone- (2-chloroethyl) ethyl ammonium bromide, coconut trimethyl ammonium chloride, coconut trimethyl ammonium bromide, coconut methyl di-hydrate Hydroxyethyl ammonium chloride, coconut methyl dihydroxyethyl ammonium bromide, decyl triethyl ammonium chloride, decyl dimethyl hydroxyethyl ammonium chloride bromide, (C 12 -C 15) dimethyl hydroxyethyl ammonium chloride, (C 12 -C 15) Dimethyldimethylbenzylammonium chloride, lauryldimethylbenzylammonium chloride, lauryldimethylbenzylammonium chloride, lauryldimethylbenzylammonium chloride, lauryldimethylbenzylammonium bromide, lauryldimethylammonium bromide, myristyltrimethylammonium bromide, N -alkyl (C 12 -C 18 ) dimethylbenzylammonium chloride, N -alkyl (C 14 -C 18 ) dimethyl-benzylammonium chloride , N - tetradecyl dimethyl benzyl ammonium chloride Lai Monohydrate, dimethyl didecyl ammonium chloride, N-alkyl (C 12 -C 14) dimethyl 1-naphthylmethyl ammonium chloride, trimethylammonium halide alkyl-trimethylammonium salts, dialkyl-dimethylammonium salts, lauryl trimethyl ammonium chloride, ethoxylated alkyl amido alkyl dialkyl ammonium salt, an ethoxylated trialkyl ammonium salt, dialkyl benzene dialkyl ammonium chloride, N - didecyl dimethyl ammonium chloride, N - tetradecyl dimethyl benzyl ammonium chloride monohydrate, N - alkyl (C 12 -C 14) dimethyl 1-naphthylmethyl ammonium chloride, dodecyl dimethyl benzyl ammonium chloride, dialkyl benzene alkyl ammonium chloride, lauryl trimethyl ammonium chloride, alkyl benzyl methyl ammonium chloride, alkyl benzyl dimethyl ammonium bromide, C 12 trimethyl ammonium bromide, C 15 trimethyl ammonium bromides, C 17 trimethyl Ammonium bromide, dodecylbenzyltriethylammonium chloride, polydiallyldimethylammonium chloride, dimethylammonium chloride, alkyldimethylammoniumhalogenide, tricetylmethylammonium chloride, decyltrimethylammonium bromide, dodecyltriethylammonium bromide, tetradecyltrimethyl Ammonium bromide, methyltrioctylammonium chloride, tetrabutylammonium bromide, benzyltrimethylammonium bromide, choline ester, benzalkonium chloride, stearalkonium chloride, cetylpyridinium bromide, cetylpyridinium chloride, alkylpyridinium salt, amine, amine At least one selected from the group consisting of a salt, an imidazolinium salt, a cationic guar gum, benzalkonium chloride, dodecyltrimethylammonium bromide, triethanolamine and poloxamine is used N -dodecyl- N, N -dimethyl-3-ammonio-1-propanesulfonate, betaine, alkyl betaine, alkylamido betaine, amidopropyl betaine, Aminopropionate, aminoglycinate, imidazolinium betaine, amphoteric imidazoline, N -alkyl- N, N -dimethylammonio-1-propanesulfonate , 3-coliamido-1-propyldimethylammonio-1-propanesulfonate, dodecylphosphocholine and sulfo-betaine may be used. Examples of the nonionic surfactant include
일 구체예에서, 제 2 유기단량체의 종류는 특별히 제한되지 않으며, 예를 들어, 트리메조일 클로라이드(trimesoyl chloride, TMC), 테레프탈로일 클로라이드(terephthaloyl chloride), 이소프탈로일 클로라이드(isophthaloyl chloride), 시클로헥산-1,3,5-트리카보닐 클로라이드(cyclohexane-1,3,5-tricarbonyl chloride), 5-이소시아네이토이소프탈로일 클로라이드(5-isocyanato-isophthaloyl chloride), 시아누릭 클로라이드(cyanuric chloride), 트리멜리토일 클로라이드(trimellitoyl chloride), 포스포릴 클로라이드(phosphoryl chloride) 및 글루타알데하이드(gluraraldehyde)로 이루어진 그룹으로부터 선택된 하나 이상을 사용할 수 있다. In one embodiment, the type of the second organic monomer is not particularly limited and includes, for example, trimesoyl chloride (TMC), terephthaloyl chloride, isophthaloyl chloride, Cyclohexane-1,3,5-tricarbonyl chloride, 5-isocyanato-isophthaloyl chloride, cyanuric chloride, cyanuric chloride, at least one selected from the group consisting of chloride, trimellitoyl chloride, phosphoryl chloride and glutaraldehyde can be used.
또한, 일 구체예에서, 제 2 용매의 종류는 특별히 제한되지 않으며, 예를 들어, n-헥산, 펜탄, 사이클로헥산, 헵탄, 옥탄, 사염화탄소, 벤젠, 자일렌, 톨루엔, 클로로폼, 테트라하이드로퓨란 및 아이소파라핀으로 이루어진 그룹으로부터 선택된 하나 이상을 사용할 수 있다. Also, in one embodiment, the kind of the second solvent is not particularly limited and may be, for example, n -hexane, pentane, cyclohexane, heptane, octane, carbon tetrachloride, benzene, xylene, toluene, chloroform, tetrahydrofuran And isoparaffin may be used.
본 발명에서 전술한 제 1 용액은 아민 단량체를 포함하고, 제 2 용액은 아실클로라이드 단량체를 포함하여 상기 단량체들 간의 계면중합을 통해 폴리아마이드 선택층을 합성할 수 있다. In the present invention, the first solution includes an amine monomer, and the second solution includes an acyl chloride monomer to synthesize a polyamide selective layer through interfacial polymerization between the monomers.
일 구체예에서, 제 1 용액을 도포한 후, 제 1 유기단량체의 함량을 조절하는 단계는 용매를 이용한 세척 또는 에어건 및 롤러를 사용 하여 조절할 수 있다. 또한, 계면중합을 통해 선택층을 형성한 후, 세척을 통해 선택층 상의 미반응 잔류 제 2 유기단량체를 제거할 수 있다. In one embodiment, the step of adjusting the content of the first organic monomer after application of the first solution can be controlled by washing with a solvent or using an air gun and a roller. In addition, after the selective layer is formed through interfacial polymerization, unreacted residual second organic monomer on the selected layer can be removed by washing.
실시예Example
실시예Example 1 내지 2 1 to 2
1) 폴리아크릴로니트릴 패턴 지지체 제작1) Production of polyacrylonitrile pattern support
(1) 고분자 용액 제조 (1) Preparation of polymer solution
1.4 g의 PAN(폴리아크릴로니트릴)을 8.6 g의 NMP(메틸피롤리돈)에 넣고 60℃로 가열하여 녹여주었다(고분자 용액 제조). 약 하루 정도 롤링 믹서(rolling mixer)에 보관하여 고분자 용액이 완벽하게 섞이도록 하였다. 상기 고분자 용액에 초음파 처리를 수행하여 고분자 용액 내에 존재하는 미세 기포를 제거하였다.1.4 g of PAN (polyacrylonitrile) was dissolved in 8.6 g of NMP (methylpyrrolidone) by heating at 60 DEG C (preparation of a polymer solution). The mixture was stored in a rolling mixer for about one day so that the polymer solution was completely mixed. The polymer solution was subjected to ultrasonic treatment to remove fine bubbles present in the polymer solution.
(2) 복제 몰드 제조(2) Replica Mold Manufacturing
마스터 몰드(양각)에 PUA(폴리우레탄아크릴레이트) 용액을 부어주었다. 여기에 양전하 코팅된 코팅지를 덮어 눌러 기포를 제거한 후, 253 nm 파장의 자외선에 15분간 경화시킨다. 이후 코팅지를 제거하고 경화된 PUA를 마스터 몰드로부터 분리시켜 복제 몰드(음각)를 완성하였다. PUA (polyurethane acrylate) solution was poured into the master mold (embossed). The coated paper is covered with positively-charged coated paper to remove bubbles, and then cured for 15 minutes in ultraviolet light of 253 nm wavelength. The coated paper was then removed and the cured PUA was separated from the master mold to complete the replica mold (engraved).
(3) 패턴 지지체의 제조(3) Production of pattern support
(2)에서 제조된 복제 몰드 위에 (1)에서 제조된 고분자 용액을 캐스팅하였다. 캐스팅 나이프를 이용해 미리 설정한 높이(100 μm)로 고분자 용액을 조절하였다. PET 재질의 부직포 (non-woven fabric)를 고분자 용액 위에 덮어주었다. 미리 준비한 비용매(IPA 100%) 수조에 상기의 PUA-고분자 용액-부직포 복합체를 넣어 상전이를 유도하였다. 약 4 내지 5 시간을 넣어 상전이를 완전하게 유도하였다. 상전이 과정이 완료 된 후, 부직포 위에 형성된 패턴 지지체를 PUA로부터 분리하였다. 분리된 패턴 지지체는 이후 실험에 사용할 때까지 증류수에 넣어 보관하였다.The polymer solution prepared in (1) was cast on the replica mold prepared in (2). The polymer solution was adjusted to a preset height (100 μm) using a casting knife. The non-woven fabric made of PET was covered on the polymer solution. The above-mentioned PUA-polymer solution-nonwoven fabric composite was placed in a water bath prepared in advance (IPA 100%) to induce phase transition. About 4 to 5 hours were added to completely induce the phase transition. After the phase transfer process was completed, the pattern support formed on the nonwoven fabric was separated from the PUA. The separated pattern supports were stored in distilled water until used for subsequent experiments.
이때, 각 실시예에서 사용된 패턴 형상은 하기 표 1과 같이 하였다. At this time, pattern shapes used in the examples were as shown in Table 1 below.
2) 패턴 지지체 친수화 처리2) Pattern support hydrophilization treatment
수산화나트륨 수용액(농도 1-2 M)에 폴리아크릴로니트릴 지지체를 담지하였다. 45℃ 및 10 분 동안 표면처리 하였다.A polyacrylonitrile support was supported on an aqueous sodium hydroxide solution (concentration 1-2 M). 45 < [deg.] ≫ C for 10 minutes.
3) 중간층 제조3) Preparation of intermediate layer
중간층 제조를 위해 폴리아크릴산 및 폴리에틸렌이민을 수용액 상태로 사용하였다.Polyacrylic acid and polyethyleneimine were used in aqueous solution for the preparation of the intermediate layer.
2)에서 친수화 처리된 패턴 지지체를 틀로 고정하고, 1 wt% 폴리에틸렌이민 수용액에 침지하여 고분자를 패턴 지지체에 흡착시킨 후 세척을 통해 과잉의 잔류물을 제거하였다. 이를 다시 1 wt% 폴리아크릴산 수용액에 침지하여 고분자를 패턴 지지체에 흡착시킨 후 세척을 통해 과잉의 잔류물을 제거하였다.2), the patterned support subjected to the hydrophilization treatment was fixed with a frame and immersed in a 1 wt% polyethyleneimine aqueous solution to adsorb the polymer on the pattern support, and then excess residues were removed by washing. The polymer was immersed in a 1 wt% aqueous solution of polyacrylic acid to adsorb the polymer on the pattern support, and excess residues were removed by washing.
4) 선택층 제조4) Manufacture of selective layer
제 1 유기 단량체 용액의 친수성 용매로 물을 사용하고, 이에 포함되는 단량체로 m-페닐렌 디아민(m-phenylene diamine: MPD)을 사용하였다. Water was used as a hydrophilic solvent of the first organic monomer solution, and m-phenylene diamine (MPD) was used as a monomer contained in the first organic monomer solution.
제 2 유기 단량체 용액의 유기 용매로 n-헥산(n-hexane)을 사용하고, 이에 포함되는 단량체로 트리메소일 클로라이드(trimesoyl chloride: TMC)를 사용하였다.N-hexane was used as an organic solvent for the second organic monomer solution, and trimesoyl chloride (TMC) was used as a monomer contained in the solution.
반응틀에 고정된 지지체(3)의 처리가 수행된 지지체를 1 wt% MPD를 포함한 제 1 유기 단량체 용액 안에 침지하여 지지체에 단량체를 흡착시켰다. 물을 이용한 세척으로 지지체 표면의 제 1 유기 단량체 용액을 필요 최소한만 남기고 제거한 후, 0.1 wt% TMC가 용해되어 있는 제 2 유기 단량체 용액에 침지하여, 계면에서 단량체 간의 계면중합을 통해 폴리아마이드 선택층을 합성하였다. 이후 미 반응한 TMC 단량체를 n-헥산을 이용하여 세척하고 건조한 후, 물속에 보관하였다.The support on which the support 3 fixed on the reaction frame was immersed was immersed in the first organic monomer solution containing 1 wt% MPD to adsorb the monomer on the support. After washing with water, the first organic monomer solution on the surface of the support was removed with minimum necessary amount, and then immersed in a solution of a second organic monomer in which 0.1 wt% TMC had been dissolved to perform interfacial polymerization between the monomers at the interface, Were synthesized. The unreacted TMC monomer was then washed with n-hexane, dried, and stored in water.
실시예Example 3 3
지지체의 패턴을 Sharklet AFTM으로하고, 중간층을 형성하지 않은 것을 제외하고는 실시예와 동일한 방법으로 박막 복합체 분리막을 제조하였다.Thin film composite membrane was prepared in the same manner as in Example except that the pattern of the support was Sharklet AF TM and no intermediate layer was formed.
비교예Comparative Example 1 One
지지체의 패턴을 무패턴으로 한 것을 제외하고는 실시예 1 및 2와 동일한 방법으로 박막 복합체 분리막을 제조하였다. A thin film composite membrane was prepared in the same manner as in Examples 1 and 2 except that the pattern of the support was patternless.
비교예Comparative Example 2 2
지지체로 폴리술폰 지지체(Nanostone 사, PS20)를 사용하였다. 상기 지지체를 아이소프로필 알코올(isopropyl alcohol) 및 물로 세척하였다.Polysulfone support (Nanostone, PS20) was used as a support. The support was washed with isopropyl alcohol and water.
상기 지지체를 반응틀에 고정하고, 3 wt% MPD를 포함한 제 1 유기 단량체 용액(수용액)을 부어 지지체 내부에 단량체를 담지 시켰다. 지지체 표면의 과잉의 제 1 유기 단량체 용액을 롤러를 사용하여 제거한 후, n-헥산에 0.3 wt% TMC가 용해되어 있는 제 2 유기 단량체 용액을 부어, 계면에서 단량체 간의 중합반응을 통해 폴리아마이드 선택층을 합성하였다. 미 반응한 아실 TMC 단량체를 n-헥산을 이용하여 세척하고 건조한 후, 물속에 넣어서 보관하였다.The support was fixed in a reaction frame, and a first organic monomer solution (aqueous solution) containing 3 wt% MPD was poured to carry the monomer into the support. After the excess first organic monomer solution on the surface of the support was removed using a roller, a solution of a second organic monomer in which 0.3 wt% TMC had been dissolved in n-hexane was poured to cause polymerization reaction between the monomers at the interface, Were synthesized. Unreacted acyl TMC monomer was washed with n-hexane, dried, and stored in water.
본 발명에서 도 1은 실시예 및 비교예에서 제조된 박막 복합체 분리막의 표면 구조를 나타내는 사진이다. 구체적으로, 도 1에서 무패턴은 비교예 1, 연속 선형은 실시예 1, Sharklet AFTM은 실시예 2 및 불균일형은 비교예 2에서 제조된 박막 복합체 분리막을 나타낸다. 1 is a photograph showing the surface structure of the thin film composite separator prepared in Examples and Comparative Examples. Specifically, FIG. 1 shows the thin film composite separator prepared in Comparative Example 1, the continuous linear type in Example 1, the Sharklet AF TM in Example 2, and the non-uniform type in Comparative Example 2.
상기 도에 나타난 바와 같이, 본 발명에 따른 방법으로 지지체를 제조하고, 한계계면중합을 통해 선택층을 제조할 경우 일정한 패턴 구조를 가지는 박막 복합체 분리막을 제조할 수 있다. 그러나, 일반 계면 중합을 사용하여 제조한 비교예 2의 경우 불균일한 표면 구조를 가지는 것을 확인할 수 있다. As shown in the figure, when a support is prepared by the method according to the present invention and a selective layer is produced through limiting interface polymerization, a thin film composite membrane having a constant pattern structure can be produced. However, in Comparative Example 2 produced using general interfacial polymerization, it can be confirmed that it has a nonuniform surface structure.
실험예Experimental Example . 성능 실험. Performance experiment
(1) 조건(1) Condition
실시예 1 내지 3 및 비교예 1 내지 2에서 제조된 박막 복합체 분리막을 유량 1 L/min, 압력 15.5 bar, 온도 25 ± 0.5℃ 공정조건에서 증류수를 사용하여 분리막의 순수 유량을 측정하였다. The pure membrane flow rate of the membrane composite membranes prepared in Examples 1 to 3 and Comparative Examples 1 and 2 was measured using distilled water at a flow rate of 1 L / min, a pressure of 15.5 bar, and a temperature of 25 ± 0.5 ° C.
또한, 동일 공정 조건에서 박테리아가 포함된 용액(P. aeruginosa 106 CFU, LB broth 1 g/L 농도)을 사용하여 오염수의 유량을 총 18시간 동안 측정하였으며, 매 시간 유량을 기록하여 오염수 유량의 감소 양상을 확인하였다.In addition, the flow rate of contaminated water was measured for 18 hours by using a solution containing bacteria (10 6 CFU of P. aeruginosa and 1 g / L of LB broth) under the same process conditions, and the flow rate was recorded every hour, The decrease of the flow rate was confirmed.
이후 최종 오염수 유량과 순수 유량을 각각 비교하여 이를 조정 유량으로 표시하였으며, 이 수치를 이용하여 오염으로 인한 유량의 감소폭, 즉 오염도를 계산하였다.Then, the final polluted water flow rate and the pure water flow rate are compared with each other, and the flow rate is indicated as the adjusted flow rate.
(2) 결과(2) Results
상기 분리막의 성능 평가 결과를 하기 표 2에 기재하였다. The results of the performance evaluation of the separator are shown in Table 2 below.
유량
(A, Lm-2h-1)pure
flux
(A, Lm -2 h -1 )
유량
(B, Lm-2h-1)Number of contaminants after 18 hours
flux
(B, Lm -2 h -1 )
(B/A)Adjustment flow
(B / A)
((1-B/A)*100)Pollution degree
((1-B / A) * 100)
본 발명에 따른 박막 복합체 분리막은 지지체 패턴의 2차원 배열 구조에 따라 확연한 내오염성 차이를 보였다. The thin film composite membrane according to the present invention showed distinct staining resistance according to the two-dimensional arrangement structure of the support pattern.
자연 모사형 패턴 구조(Sharklet AFTM)를 적용한 실시예 2는 0.871의 조정 유량을 기록하였는데, 이는 비교예 2의 0.478에 비해 1.8배 높은 값이다. 조정 유량이 1에 가까울수록 오염으로 인한 유량 감소가 적은 것을 나타내므로, 실시예 2의 분리막은 비교예 2의 분리막과 비교하여 비해 내오염성이 확연히 우수하다는 것을 알 수 있다.In Example 2 using the natural simulated pattern structure (Sharklet AF TM ), the adjusted flow rate of 0.871 was recorded, which is 1.8 times higher than 0.478 of Comparative Example 2. [ It can be seen that the separation membrane of Example 2 is significantly more excellent in stain resistance than the separation membrane of Comparative Example 2, since the closer the adjustment flow is to 1, the less the decrease in the flow rate due to the contamination.
이를 보다 구체적으로 수치화하기 위하여, 표면 오염으로 인한 유량 감소도인 오염도를 계산하였다. 실시예 2의 오염도는 12.9%로, 불균일형인 비교예 2가 기록한 값의 1/4에 불과한 확연히 낮은 수치이며, 무패턴인 비교예 1에 비해서도 37% 수준에 불과하다. 낮은 오염도 또한 높은 내오염성 효과를 가지는 것을 의미하는 것으로, 실시예 2는 비교군 대비 우수한 내오염성 효과를 가지는 것을 알 수 있다. In order to quantify this more specifically, the degree of contamination, which is a flow rate reduction due to surface contamination, was calculated. The pollution degree of Example 2 is 12.9%, which is a significantly lower value which is only 1/4 of the value recorded in Comparative Example 2 which is a non-uniform type, and is only 37% as compared with Comparative Example 1 which is non-patterned. It is understood that low pollution also means that it has a high stain resistance effect, and Example 2 has an excellent stain resistance effect compared with the comparison group.
한편 연속 선형 패턴을 가지는 실시예 1 또한 32.8%의 오염도를 기록하였다. 이는 불균일형인 비교예 2 대비 60%이고, 무패턴인 비교예 1 대비 5% 이상 낮은 값으로 실시예 2와 마찬가지로 내오염성 효과를 가지는 것을 알 수 있다. 추가로 패턴의 종류에 따라 내오염 특성을 조절할 수 있다는 사실도 확인할 수 있다.While Example 1 having a continuous linear pattern also recorded a pollution degree of 32.8%. This is 60% of the non-uniform type of Comparative Example 2 and 5% or more lower than that of the non-patterned Comparative Example 1, which shows that the same stain-resistant effect as in Example 2 is obtained. In addition, it can be confirmed that the pollution characteristics can be controlled depending on the kind of the pattern.
또한, Sharklet AFTM 패턴을 사용하였으나 일반 계면 중합을 사용하여 선택층을 제조한 실시예 3은 패턴을 사용하지 않고 동일한 중합 방식으로 제조된 비교예 2 대비 59%의 오염도를 기록하였다. 이는 패턴 지지체 자체만으로 높은 내오염성 효과가 있음을 증명하는 것이다. 그러나 실시예 3은 동일한 패턴 및 한계계면중합을 사용한 실시예 2에 비해서는 오염도가 2.4배에 달하여, 선택층의 제조 방식 또한 내오염성 효과 개선에 중요하게 작용한다는 사실도 확인되었다. In addition, Example 3 in which a Sharklet AF TM pattern was used but a selective layer was prepared using general interfacial polymerization showed a contamination level of 59% compared to Comparative Example 2 produced using the same polymerization method without using a pattern. This proves that the pattern support alone has a high stain resistance effect. However, in Example 3, the pollution degree reached 2.4 times as compared with Example 2 using the same pattern and limit interfacial polymerization, and it was also confirmed that the manufacturing method of the selective layer also plays an important role in improving the stain resistance effect.
도 2는 오염수 수투과도를 매 시간 측정하고 이를 초기 순수 수투과도로 각각 나누어 normalize한 결과를 나타낸다. 비교예 및 실시예에서 제시된 분리막의 패턴 종류에 따라 유량 감소폭이 달라지는 것을 그래프로 확인할 수 있으며, 미생물이 분리막 표면에서 생장하여 유량이 대폭 감소하는 4―12시간 사이 패턴 종류에 따라 감소 기울기가 다른 것을 알 수 있다. 이러한 감소 기울기의 차이는 패턴 표면에서 미생물의 부착 및 성장 양상에 따른 차이로 인해 나타나는 것으로, 도 3에서 이러한 차이를 보다 선명하게 확인할 수 있다.FIG. 2 shows the result of measuring the permeated water permeability every time and normalizing it by dividing it by the initial pure water permeability. It can be seen from the graph that the flow reduction width varies depending on the pattern type of the separation membrane proposed in the comparative example and the example. The microorganism grows on the surface of the separation membrane and the flow rate is greatly reduced. Able to know. This difference in the reduction slope is due to the difference in the adhesion and growth pattern of the microorganisms on the pattern surface, and this difference can be more clearly seen in Fig.
도 3은 패턴 구조를 포함한 박막 복합체 분리막 표면에서의 미생물 배양 결과를 나타내는 사진이다.3 is a photograph showing the result of microbial culture on the surface of a thin film composite membrane including a pattern structure.
도 3에 나타난 바와 같이, 실시예들은 비교예에 비해 표면에서 미생물이 차지하는 면적이 낮으며 특히 실시예 2에서는 극히 낮은 미생물 성장량을 보여 실시예에서 도입한 패턴이 효과적으로 기능하는 것을 확인할 수 있다.As shown in FIG. 3, the area occupied by the microorganisms on the surface was lower than those of the comparative examples, and in particular, the microorganism growth was extremely low in Example 2, confirming that the pattern introduced in the example effectively functions.
이 결과를 통해 본 발명에 따른 패턴 지지체를 사용하고, 또한 중간층을 형성한 박막 복합체 분리막은, 우수한 분리 성능과 함께 기존 분리막 대비 확연히 우수한 내오염성을 가지고 있어 충분히 상용화가 가능할 것이라 판단된다. 이러한 우수한 내구성을 활용하여 기존에 역삼투막 사용에 적합하지 않은 가혹한 수질조건에도 활용이 가능할 것으로 예상한다. As a result, the thin film composite separator using the pattern support according to the present invention and having the intermediate layer according to the present invention exhibits excellent separation performance and remarkably excellent stain resistance compared to the conventional separator, and thus it can be sufficiently commercialized. Utilizing this excellent durability, it is expected that it can be applied to harsh water quality conditions which are not suitable for the use of reverse osmosis membrane.
Claims (20)
상기 지지체 상에 형성된 선택층을 포함하며,
상기 선택층과 접하는 지지체의 표면에는 패턴이 형성되어 있으며,
상기 지지체의 표면에 형성된 패턴의 구조는 샤크렛(sharklet)이고,
상기 지지체 및 선택층 사이에 형성된 중간층을 추가로 포함하는 박막 복합체 분리막.
A support; And
And a selective layer formed on the support,
A pattern is formed on the surface of the support contacting the selective layer,
The structure of the pattern formed on the surface of the support is a sharklet,
Further comprising an intermediate layer formed between the support and the selective layer.
지지체는 폴리에틸렌(polyethylene), 폴리프로필렌(Polypropylene), 폴리염화비닐(Polyvinyl Chloride), 폴리스티렌(Polystyrene), 폴리아미드(Polyamide), 폴리테트라플루오로에틸렌(Polytetrafluoroethylene), 폴리아크릴로니트릴(Polyacrylonitrile), 폴리이미드(Polyimide), 폴리아미드이미드 (polyamideimide), 폴리설폰(Polysulfone), 폴리이서설폰(Polyethersulfone) 및 폴리비닐리덴 플루오라이드(Polyvinyliden Fluoride)로 이루어진 그룹으로부터 선택된 수지로부터 형성되는 박막 복합체 분리막.
The method according to claim 1,
The support may be selected from the group consisting of polyethylene, polypropylene, polyvinyl chloride, polystyrene, polyamide, polytetrafluoroethylene, polyacrylonitrile, A thin film composite separator formed from a resin selected from the group consisting of polyimide, polyamideimide, polysulfone, polyethersulfone, and polyvinylidene fluoride.
지지체의 기공 크기는 1 내지 100 nm인 박막 복합체 분리막.
The method according to claim 1,
Wherein the support has a pore size of 1 to 100 nm.
지지체는 친수화 처리된 것인 박막 복합체 분리막.
The method according to claim 1,
Wherein the support is hydrophilized.
선택층은 가교 또는 비가교된 폴리아마이드(polyamide), 폴리피페라진-아마이드(polypiperazine-amide), 폴리에스테르(polyester), 폴리우레탄(polyurethane), 폴리바이닐알코올(polyvinyl alcohol), 폴리이미드(polyimide) 또는 폴리이터이미드(polyetherimide)이거나, 전 방향족(fully aromatic) 화합물, 부분 방향족(semi-aromatic) 화합물 또는 전 지방족(fully aliphatic) 화합물을 포함하는 박막 복합체 분리막.
The method according to claim 1,
The optional layer may be selected from the group consisting of crosslinked or unmodified polyamide, polypiperazine-amide, polyester, polyurethane, polyvinyl alcohol, polyimide, Or a polyetherimide or a thin film composite separator comprising a fully aromatic compound, a semi-aromatic compound or a fully aliphatic compound.
나노필트레이션(nanofiltration, NF), 정삼투(forward osmosis, FO), 가압식 정삼투(pressure assisted osmosis, PAO), 압력지연삼투(pressure-retarded osmosis, PRO) 또는 역삼투(reverse osmosis, RO) 공정에 사용되는 박막 복합체 분리막.
The method according to claim 1,
(NF), forward osmosis (FO), pressure assisted osmosis (PAO), pressure-retarded osmosis (PRO) or reverse osmosis A thin film composite separator for use in the thin film composite separator.
(B) 상기 패턴 지지체 상에 선택층을 형성하는 단계를 포함하며,
상기 패턴 지지체 상에 선택층을 형성하기 전에, 상기 패턴 지지체 상에 중간층을 형성하는 단계를 추가로 포함하는 제 1 항에 따른 박막 복합체 분리막의 제조 방법.
(A) producing a patterned support having a pattern formed on its surface; And
(B) forming a selective layer on the patterned support,
The method of claim 1, further comprising forming an intermediate layer on the patterned support before forming the selective layer on the patterned support.
단계 (A)는 일 표면에 음각의 패턴을 가지는 몰드에 지지체 원료 수지를 캐스팅하는 단계;
상기 지지체 원료 수지 상에 부직포를 덮어 몰드-원료 수지-부직포의 복합체를 제조하는 단계;
상기 복합체를 비용매에 넣고 상전이시키는 단계; 및
상기 상전이된 복합체에서 몰드를 제거하여 패턴 지지체를 얻는 단계를 포함하는 박막 복합체 분리막의 제조 방법.
10. The method of claim 9,
Step (A) comprises casting a support raw resin to a mold having a pattern of engraved on one surface;
Producing a composite of a mold-starting resin-nonwoven fabric by covering the nonwoven fabric on the support material resin;
Placing the composite in a non-solvent and phase transitions; And
And removing the mold from the phase-transformed composite to obtain a patterned support.
패턴 지지체 상에 선택층을 형성하기 전에, 상기 패턴 지지체를 친수화 처리하는 단계를 추가로 포함하는 박막 복합체 분리막의 제조 방법.
10. The method of claim 9,
Further comprising the step of hydrophilizing the pattern support before forming the selective layer on the pattern support.
친수화 처리는 화학적 산화, 플라즈마, UV 산화, 단원자층 증착(atomic layer deposition, ALD), 화학기상 증착(chemical vapor deposition, CVD), 무기물 코팅 또는 고분자 코팅 처리인 박막 복합체 분리막의 제조 방법.
12. The method of claim 11,
Wherein the hydrophilization treatment is chemical oxidation, plasma, UV oxidation, atomic layer deposition (ALD), chemical vapor deposition (CVD), inorganic coating or polymer coating treatment.
중간층은 딥코팅법, 스프레이코팅법, 스핀코팅법, 계면중합법 또는 층상조립(layer-by-layer)법을 통해 형성하는 박막 복합체 분리막의 제조 방법.
10. The method of claim 9,
Wherein the intermediate layer is formed by a dip coating method, a spray coating method, a spin coating method, an interfacial polymerization method, or a layer-by-layer method.
선택층은 계면중합법, 딥코팅법, 스프레이코팅법, 스핀코팅법, 한계계면중합법 또는 층상조립(layer-by-layer)법을 통해 형성하는 박막 복합체 분리막의 제조 방법.
10. The method of claim 9,
Wherein the selective layer is formed through interface polymerization, dip coating, spray coating, spin coating, limiting interface polymerization or layer-by-layer method.
선택층은 패턴 지지체 상에 제 1 유기단량체를 포함하는 제 1 용액을 함침 또는 도포하는 단계;
패턴 지지체 상의 제 1 유기단량체의 함량을 조절하는 단계;
제 2 유기단량체를 포함하는 제 2 용액을 함침 또는 도포하는 단계;
상기 제 1 용액 및 제 2 용액에 각각 용해되어 있는 제 1 유기단량체와 제 2 유기단량체 간의 계면중합을 통해 선택층을 형성하는 단계; 및
잔류 제 2 유기단량체를 제거하는 단계를 포함하는 박막 복합체 분리막의 제조 방법.
10. The method of claim 9,
Impregnating or applying a first solution comprising a first organic monomer on a patterned support;
Adjusting the content of the first organic monomer on the pattern support;
Impregnating or applying a second solution comprising a second organic monomer;
Forming a selective layer by interfacial polymerization between a first organic monomer and a second organic monomer respectively dissolved in the first solution and the second solution; And
And removing the remaining second organic monomer.
제 1 유기단량체는 m-페닐렌 디아민(m-phenylene diamine, MPD), o-페닐렌 디아민(o-phenylene diamine, OPD), p-페닐렌 디아민(p-phenylene diamine, PPD), 피페라진(piperazine), m-자일렌 디아민(m-xylenediamine, MXDA), 에틸렌 디아민(ethylenediamine), 트리메틸렌디아민(trimethylenediamine), 헥사메틸렌 디아민(haxamethylenediamine), 디에틸렌 트리아민(diethylene triamine, DETA), 트리에틸렌 테트라민(triethylene tetramine, TETA), 메탄 디아민(methane diamine, MDA), 이소포론디아민(isophoroediamine, IPDA), 트리에탄올아민(triethanolamine), 폴리에틸렌이민(polyethyleneimine), 메틸 디에탄올아민(methyl diethanolamine), 하이드록시알킬아민(hydroxyakylamine), 하이드로퀴논(hydroquinone), 레소시놀(resorcinol), 카테콜(catechol), 에틸렌글리콜(ethylene glycol), 글리세린(glycerine), 폴리바이닐알코올(polyvinyl alcohol), 4,4'-비페놀(4,4'-biphenol), 메틸렌 디페닐 디이소시아네이트(methylene diphenyl diisocyanate), m-페닐렌 디이소시아네이트(m-phenylene diisocyanate), p-페닐렌 디이소시아네이트(p-phenylene diisocyanate) 및 톨루엔 디이소시아네이트(toluene diisocyanate)로 이루어진 그룹으로부터 선택된 하나 이상인 박막 복합체 분리막의 제조 방법.
16. The method of claim 15,
The first organic monomer is m - phenylenediamine (m -phenylene diamine, MPD), o - phenylenediamine (o -phenylene diamine, OPD), p - phenylenediamine (p -phenylene diamine, PPD), piperazine ( piperazine), m - xylene diamine (m -xylenediamine, MXDA), ethylenediamine (ethylenediamine), trimethylenediamine (trimethylenediamine), hexamethylene diamine (haxamethylenediamine), diethylenetriamine (diethylene triamine, DETA), triethylene tetramine And examples thereof include triethylene tetramine (TETA), methane diamine (MDA), isophoroediamine (IPDA), triethanolamine, polyethyleneimine, methyl diethanolamine, But are not limited to, hydroxyacylamine, hydroquinone, resorcinol, catechol, ethylene glycol, glycerine, polyvinyl alcohol, 4,4'- Phenol (4,4'-biphenol), methylene Diisocyanate (methylene diphenyl diisocyanate), m - phenylene diisocyanate (m -phenylene diisocyanate), p - phenylene diisocyanate (p -phenylene diisocyanate), toluene diisocyanate is at least one thin film selected from the group consisting of (toluene diisocyanate) A method for producing a composite membrane.
제 1 용액의 용매는 물, 메탄올, 에탄올, 프로판올, 부탄올, 이소프로판올, 에틸아세테이트, 아세톤, 클로로포름, 테트라하이드로퓨란(tetrahydrofuran, THF), 디메틸설폭사이드(dimethyl sulfoxide, DMSO), 디메틸포름아마이드(dimethylformamide, DMF) 및 N-메틸-2-피롤리디온(N-methyl-2-pyrrolidone, NMP)로 이루어진 그룹으로부터 선택된 하나 이상인 박막 복합체 분리막의 제조 방법.
16. The method of claim 15,
The solvent of the first solution may be water, methanol, ethanol, propanol, butanol, isopropanol, ethyl acetate, acetone, chloroform, tetrahydrofuran (THF), dimethyl sulfoxide (DMSO), dimethylformamide DMF) and N - methyl-2-pyrrolidine-dione (N -methyl-2-pyrrolidone, NMP) method for producing a thin film composite membrane is at least one selected from the group consisting of.
제 1 용액은 이온성 또는 비이온성 계면활성제를 추가로 포함하는 박막 복합체 분리막의 제조 방법.
18. The method of claim 17,
Wherein the first solution further comprises an ionic or nonionic surfactant.
제 2 유기단량체는 트리메조일 클로라이드(trimesoyl chloride, TMC), 테레프탈로일 클로라이드(terephthaloyl chloride), 이소프탈로일 클로라이드(isophthaloyl chloride), 시클로헥산-1,3,5-트리카보닐 클로라이드(cyclohexane-1,3,5-tricarbonyl chloride), 5-이소시아네이토이소프탈로일 클로라이드(5-isocyanato-isophthaloyl chloride), 시아누릭 클로라이드(cyanuric chloride), 트리멜리토일 클로라이드(trimellitoyl chloride), 포스포릴 클로라이드(phosphoryl chloride) 및 글루타알데하이드(gluraraldehyde)로 이루어진 그룹으로부터 선택된 하나 이상인 박막 복합체 분리막의 제조 방법.
16. The method of claim 15,
The second organic monomer is selected from the group consisting of trimesoyl chloride (TMC), terephthaloyl chloride, isophthaloyl chloride, cyclohexane-1,3,5-tricarbonyl chloride, 1,3,5-tricarbonyl chloride, 5-isocyanato-isophthaloyl chloride, cyanuric chloride, trimellitoyl chloride, phosphoryl chloride phosphoryl chloride, and glutaraldehyde. < Desc / Clms Page number 19 >
제 2 용액의 용매는 n-헥산, 펜탄, 사이클로헥산, 헵탄, 옥탄, 사염화탄소, 벤젠, 자일렌, 톨루엔, 클로로폼, 테트라하이드로퓨란 및 아이소파라핀으로 이루어진 그룹으로부터 선택된 하나 이상인 박막 복합체 분리막의 제조 방법.
16. The method of claim 15,
The solvent of the second solution is at least one selected from the group consisting of n -hexane, pentane, cyclohexane, heptane, octane, carbon tetrachloride, benzene, xylene, toluene, chloroform, tetrahydrofuran and isoparaffin .
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100459038B1 (en) | 2004-02-04 | 2004-12-03 | 주식회사 코레드 | Membrane module for water treatment |
| JP2010099590A (en) | 2008-10-23 | 2010-05-06 | Nitto Denko Corp | Sheet-like composite semi-permeable membrane and manufacturing method therefor |
| KR101519026B1 (en) * | 2014-02-17 | 2015-05-12 | 한국과학기술연구원 | Forward osmosis membranes based on multilayered thin films using a molecular layer-by-layer crosslinking assembly of organic monomers and method for fabricating the same |
| JP2017131794A (en) * | 2016-01-25 | 2017-08-03 | 東レ株式会社 | Composite semipermeable membrane |
| JP2017148771A (en) | 2016-02-26 | 2017-08-31 | 東レ株式会社 | Composite semipermeable membrane |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
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-
2017
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100459038B1 (en) | 2004-02-04 | 2004-12-03 | 주식회사 코레드 | Membrane module for water treatment |
| JP2010099590A (en) | 2008-10-23 | 2010-05-06 | Nitto Denko Corp | Sheet-like composite semi-permeable membrane and manufacturing method therefor |
| KR101519026B1 (en) * | 2014-02-17 | 2015-05-12 | 한국과학기술연구원 | Forward osmosis membranes based on multilayered thin films using a molecular layer-by-layer crosslinking assembly of organic monomers and method for fabricating the same |
| JP2017131794A (en) * | 2016-01-25 | 2017-08-03 | 東レ株式会社 | Composite semipermeable membrane |
| JP2017148771A (en) | 2016-02-26 | 2017-08-31 | 東レ株式会社 | Composite semipermeable membrane |
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