WO2016199951A1 - Water-treatment membrane having antibacterial and microbe-preventing function, and production method for same - Google Patents

Water-treatment membrane having antibacterial and microbe-preventing function, and production method for same Download PDF

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WO2016199951A1
WO2016199951A1 PCT/KR2015/005813 KR2015005813W WO2016199951A1 WO 2016199951 A1 WO2016199951 A1 WO 2016199951A1 KR 2015005813 W KR2015005813 W KR 2015005813W WO 2016199951 A1 WO2016199951 A1 WO 2016199951A1
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antimicrobial
membrane
water treatment
based polymer
weight
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PCT/KR2015/005813
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French (fr)
Korean (ko)
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최윤희
이현화
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㈜엔트리엘엔에이치
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    • 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
    • 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
    • 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

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  • the present invention relates to a membrane for water treatment and a method for producing the same, and more particularly, to a membrane for water treatment and a method for producing the same having an antibacterial and microbial protection function.
  • membranes used for water treatment filter the contaminated raw water and the contaminants are adsorbed and grown on the membrane surface, resulting in contamination of the membrane surface. If the membrane contamination is severe, the water permeation pressure during filtration increases and the production quantity is increased. Gradually decrease, ultimately degrading the filtration of the membrane.
  • PVDF polyvinylidene fluoride
  • PVDF polyvinylidene fluoride
  • An object of the present invention for solving the above problems is to provide a membrane for water treatment and a method for producing the same, which have antibacterial and antimicrobial functions to reduce hydrofouling by improving hydrophilicity and antibacterial properties.
  • Membrane method for water treatment having an antimicrobial and microbial protection function of one embodiment of the present invention is a polymer (30) to 61% by weight, organic solvent (solvent) 25 to 45% by weight, additive (additive) 12 to 22% by weight, And preparing the hollow fiber membrane raw material by stirring 1 to 5 wt% of the inorganic antimicrobial material, and discharging the hollow fiber membrane raw material to the cylinder of the extruder.
  • the polymer is preferably any one of a fluorine-based polymer, a sulfone-based polymer, and an olefin-based polymer.
  • the fluorine-based polymer is polyvinylidene fluoride or polytetrafluoroethylene
  • the sulfone-based polymer is polyethersulfone or polystyrene
  • the olefin-based polymer is polyethylene ( polyethylene) or polypropylene.
  • the organic solvent is preferably any one of dimethylformamide (DMF), n-methyl-2-pyrrolidone (NMP), dimethylacetamide (DMAC), dimethylsulfoxide (DMSO) and triethylphosphate (TEP).
  • DMF dimethylformamide
  • NMP n-methyl-2-pyrrolidone
  • DMAC dimethylacetamide
  • DMSO dimethylsulfoxide
  • TEP triethylphosphate
  • the additive is polyvinylpyrrolidone (PVPK30), ethylene glycol (EG), propylene glycol (PG), diethylene glycol (DEG), triethylene glycol (TEG), dipropylene glycol (DPG), polyethylene glycol (PEG) , Glycerol, maleic anhydride and propylene-1,2-carbonate (PC).
  • PVPK30 polyvinylpyrrolidone
  • EG ethylene glycol
  • PG propylene glycol
  • DEG diethylene glycol
  • TEG triethylene glycol
  • DPG dipropylene glycol
  • PEG polyethylene glycol
  • Glycerol maleic anhydride
  • PC propylene-1,2-carbonate
  • the inorganic antimicrobial material is preferably made of 0.0000005 to 10% by weight of silver colloid, 0.0000001 to 15% by weight of titanium dioxide nanoparticles, 0.00001 to 6% by weight of dispersion stabilizer, and 69 to 99% by weight of water based on 100% by weight of the total composition. Do.
  • the dispersion stabilizer is preferably any one of lysolecithin, flavonoid, tween 20, tween 40, tween 80, polyvinylpyrrolidone and polyvinylalcohol. .
  • the present invention has the effect of reducing the biofouling by adding an inorganic antimicrobial material is improved hydrophilicity and antimicrobial.
  • 1 is a graph showing the filtration flow rate with time of the membrane for water treatment according to an embodiment of the present invention.
  • the method for producing a membrane for water treatment of the present invention comprises 30 to 61 wt% of a polymer, 25 to 45 wt% of an organic solvent, 12 to 22 wt% of an additive, and 1 to 5 wt% of an inorganic antibacterial substance. It comprises a step of preparing a hollow fiber membrane raw material by stirring and discharging the hollow fiber membrane raw material to the cylinder of the extruder.
  • the polymer is preferably any one of a fluorine-based polymer, a sulfone-based polymer, and an olefin-based polymer.
  • the fluorine-based polymer is polyvinylidene fluoride or polytetrafluoroethylene
  • the sulfone-based polymer is polyethersulfone or polystyrene
  • the olefin-based polymer is polyethylene ( polyethylene) or polypropylene.
  • the organic solvent is preferably any one of dimethylformamide (DMF), n-methyl-2-pyrrolidone (NMP), dimethylacetamide (DMAC), dimethyl sulfoxide (DMSO), and triethylphosphate (TEP).
  • DMF dimethylformamide
  • NMP n-methyl-2-pyrrolidone
  • DMAC dimethylacetamide
  • DMSO dimethyl sulfoxide
  • TEP triethylphosphate
  • the additive is polyvinylpyrrolidone (PVPK30), ethylene glycol (EG), propylene glycol (PG), diethylene glycol (DEG), triethylene glycol (TEG), dipropylene glycol (DPG), polyethylene glycol (PEG) , Glycerol, maleic anhydride or propylene-1,2-carbonate (PC) is preferred.
  • PVPK30 polyvinylpyrrolidone
  • EG ethylene glycol
  • PG propylene glycol
  • DEG diethylene glycol
  • TEG triethylene glycol
  • DPG dipropylene glycol
  • PEG polyethylene glycol
  • PC propylene-1,2-carbonate
  • the inorganic antimicrobial material is composed of 0.0000005 to 10% by weight of silver colloid, 0.0000001 to 15% by weight of titanium dioxide nanoparticles, 0.00001 to 6% by weight of the dispersion stabilizer, and 69 to 99% by weight of water based on 100% by weight of the total composition.
  • the dispersion stabilizer is selected from the group consisting of lysolecithin (lysolecithin), flavonoid (flavonoid), Tween 20, Tween 40, Tween 80, polyvinylpyrrolidone, polyvinyl alcohol (polyvinylalcohol) It is preferable that it is at least one.
  • the method for preparing an inorganic antimicrobial agent includes preparing a silver colloidal solution by reacting a silver alcohol with a first alcohol containing a dispersion stabilizer, and a titanium precursor, a second alcohol, and an acid in a solution in which the silver colloidal solution is diluted with water. acid) is added to produce a titanium dioxide nanoparticles in the silver colloid solution.
  • the silver precursor is preferably silver nitrate (AgNO 3 ) or silver acetate (CH 3 COOAg).
  • the first alcohol is preferably any one of methanol, ethanol, isopropyl alcohol, butanol.
  • the titanium precursor is made of titanium tetraisopropoxide (TTIP), titaniumethoxyorthotitanate (TEOT), or titaniumbutoxyorthotitanate (TBOT).
  • TTIP titanium tetraisopropoxide
  • TEOT titaniumethoxyorthotitanate
  • TBOT titaniumbutoxyorthotitanate
  • the second alcohol is preferably any one of isopropyl alcohol, ethanol, butanol.
  • the acid catalyst is preferably any one of nitric acid, hydrochloric acid, sulfuric acid, and oxalic acid.
  • 1 is a graph showing the filtration flow rate with time of the membrane for water treatment according to an embodiment of the present invention.
  • the membrane prepared by stirring the polymer, the organic solvent and the additive (comparative example) and the membrane prepared by adding the inorganic antimicrobial material to the polymer, the organic solvent and the additive (Experimental Example 1, 2) It can be seen that the filtration flow rate is high when the change in the filtration flow rate adds an inorganic antimicrobial material. It can be seen that the hydrophilicity and antimicrobial properties are improved due to the inorganic antimicrobial material, so that bacteria on the surface of the membrane are killed so that the filtration flow rate does not drop.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Water Supply & Treatment (AREA)
  • Nanotechnology (AREA)
  • Separation Using Semi-Permeable Membranes (AREA)

Abstract

The present invention relates to a production method for a water-treatment membrane having an antibacterial and a microbe-preventing function, the method comprising: a step of preparing a hollow-fibre membrane raw material by mixing and stirring between 30 and 61 wt.% of a polymer, between 25 and 45 wt.% of a solvent, between 12 and 22 wt.% of an additive and between 1 and 5 wt.% of an inorganic antibacterial substance; and a step of introducing the hollow-fibre membrane raw material into the cylinder of an extruder.

Description

항균 및 미생물 방지 기능을 갖는 수처리용 멤브레인 및 그 제조방법Membrane for water treatment having antibacterial and microbial protection function and its manufacturing method
본 발명은 수처리용 멤브레인 및 그 제조방법에 관한 것으로, 더욱 상세하게는 항균 및 미생물 방지 기능을 갖는 수처리용 멤브레인 및 그 제조방법에 관한 것이다.The present invention relates to a membrane for water treatment and a method for producing the same, and more particularly, to a membrane for water treatment and a method for producing the same having an antibacterial and microbial protection function.
20세기 후반 이후 물부족을 해결하고자 하기 위해 이미 사용된 물을 재활용하거나 지하수 및 지표면 상의 담수를 식수로 사용하기 위한 수처리 연구가 활발히 진행되고 있다.Since the late twentieth century, there have been active researches on water treatment to recycle already used water or to use groundwater and fresh water on the ground for drinking water.
일반적으로 수처리에 사용되는 멤브레인은 오염된 원수를 여과시키면서 막 표면에 오염원이 흡착 및 성장하여 막표면에 오염이 발생하게 되는데, 이러한 멤브레인 오염이 심하게 되면 여과시 작용하는 수투과 압력을 상승시키고 생산수량을 점차 감소시켜 궁극적으로 멤브레인의 여과기능이 저하된다.In general, membranes used for water treatment filter the contaminated raw water and the contaminants are adsorbed and grown on the membrane surface, resulting in contamination of the membrane surface. If the membrane contamination is severe, the water permeation pressure during filtration increases and the production quantity is increased. Gradually decrease, ultimately degrading the filtration of the membrane.
이러한 멤브레인의 오염 제어를 위하여 염소계, 산, 알칼리를 사용하여 세정을 하는데, 이는 멤브레인의 수명을 단축시키는 문제가 있기 때문에, 최근에는 내화학성이 높은 소재인 폴리불화비닐리덴(PVDF)계 수지에 디메틸포름아마이드(DMF), n-메틸-2-피롤리돈(NMP), 디메틸아세트아마이드(DMAc), 디메틸설폭사이드(DMSO) 및 트리에틸포스페이트(TEP) 등의 양용매와 에틸렌글리콜(EG), 프로필렌 글리콜, 디에틸렌 글리콜(DEG), 트리에틸렌 글리콜(TEG), 디프로필렌 글리콜(DPG), 글리세롤, 말레인 무수물, 프로필렌-1,2-카보네이트(PC) 등의 빈용매를 혼합하여 멤브레인을 제조하고 있다.In order to control the contamination of the membrane, chlorine, acid, and alkali are used for cleaning, which has a problem of shortening the life of the membrane. In recent years, dimethyl propylene is used in polyvinylidene fluoride (PVDF) resin, which is a highly chemical resistant material. Good solvents such as formamide (DMF), n-methyl-2-pyrrolidone (NMP), dimethylacetamide (DMAc), dimethyl sulfoxide (DMSO) and triethylphosphate (TEP), and ethylene glycol (EG), Membrane was prepared by mixing poor solvents such as propylene glycol, diethylene glycol (DEG), triethylene glycol (TEG), dipropylene glycol (DPG), glycerol, maleic anhydride, and propylene-1,2-carbonate (PC). Doing.
그러나, 이러한 폴리불화비닐리덴(PVDF)계 수지에 양용매와 빈용매를 혼합하여 제조한 멤브레인은 기계적 강도가 약하고 바이오파울링(Biofouling)으로 인해 성능과 내구성이 떨어져 잦은 교체를 야기하는 문제점이 있다.However, a membrane prepared by mixing a good solvent and a poor solvent in such a polyvinylidene fluoride (PVDF) resin has a weak mechanical strength and poor performance and durability due to biofouling, causing frequent replacement. .
이러한 것에 대한 선행기술 문헌은 대한민국 공개특허공보 제10-2014-0081366호(2014.07.01)가 존재한다.Prior art literature on this is the Republic of Korea Patent Publication No. 10-2014-0081366 (2014.07.01) is present.
상기와 같은 문제점을 해결하기 위한 본 발명의 목적은 친수성과 항균성을 향상시켜 바이오파울링을 저감하는 항균 및 미생물 방지 기능을 갖는 수처리용 멤브레인 및 그 제조방법을 제공하는 데 있다.SUMMARY OF THE INVENTION An object of the present invention for solving the above problems is to provide a membrane for water treatment and a method for producing the same, which have antibacterial and antimicrobial functions to reduce hydrofouling by improving hydrophilicity and antibacterial properties.
본 발명의 일실시예인 항균 및 미생물 방지 기능을 갖는 수처리용 멤브레인 제조 방법은 고분자(polymer) 30~61중량%, 유기용매(solvent) 25~45중량%, 첨가제(additive) 12~22중량%, 및 무기 항균물질 1~5중량%을 교반하여 중공사막 원료를 준비하는 단계, 그리고 상기 중공사막 원료를 압출기의 실린더로 토출하는 단계를 포함하여 이루어진다.Membrane method for water treatment having an antimicrobial and microbial protection function of one embodiment of the present invention is a polymer (30) to 61% by weight, organic solvent (solvent) 25 to 45% by weight, additive (additive) 12 to 22% by weight, And preparing the hollow fiber membrane raw material by stirring 1 to 5 wt% of the inorganic antimicrobial material, and discharging the hollow fiber membrane raw material to the cylinder of the extruder.
상기 고분자는 불소계 고분자, 술폰계 고분자 및 올레핀계 고분자 중 어느 하나인 것이 바람직하다.The polymer is preferably any one of a fluorine-based polymer, a sulfone-based polymer, and an olefin-based polymer.
상기 불소계 고분자는 폴리비닐리덴플로라이드(polyvinylidene fluoride) 또는 폴리테트라플루오르에틸렌(polytetra fluoro ethylence)이고, 상기 술폰계 고분자는 폴리에테르설폰(polyetersulfone) 또는 폴리스타이렌(polystyrene)이며, 상기 올레핀계 고분자는 폴리에틸렌(polyethylene) 또는 폴리프로필렌(polypropylene)이다.The fluorine-based polymer is polyvinylidene fluoride or polytetrafluoroethylene, and the sulfone-based polymer is polyethersulfone or polystyrene, and the olefin-based polymer is polyethylene ( polyethylene) or polypropylene.
상기 유기용매는 디메틸포름아마이드(DMF), n-메틸-2-피롤리돈(NMP), 디메틸아세트아마이드(DMAC), 디메틸설폭사이드(DMSO) 및 트리에틸포스페이트(TEP) 중 어느 하나인 것이 바람직하다.The organic solvent is preferably any one of dimethylformamide (DMF), n-methyl-2-pyrrolidone (NMP), dimethylacetamide (DMAC), dimethylsulfoxide (DMSO) and triethylphosphate (TEP). Do.
상기 첨가제는 폴리비닐피롤리돈(PVPK30), 에틸렌글리콜(EG), 프로필렌 글리콜(PG), 디에틸렌 글리콜(DEG), 트리에틸렌 글리콜(TEG), 디프로필렌 글리콜(DPG), 폴리에틸렌 글리콜(PEG), 글리세롤, 말레인 무수물 및 프로필렌-1,2-카보네이트(PC) 중 어느 하나인 것이 바람직하다.The additive is polyvinylpyrrolidone (PVPK30), ethylene glycol (EG), propylene glycol (PG), diethylene glycol (DEG), triethylene glycol (TEG), dipropylene glycol (DPG), polyethylene glycol (PEG) , Glycerol, maleic anhydride and propylene-1,2-carbonate (PC).
상기 무기 항균물질은 전체 조성물 100 중량%를 기준으로, 은 콜로이드 0.0000005~10중량%, 이산화티탄 나노입자 0.0000001~15중량%, 분산안정제 0.00001~6중량% 및 물 69~99중량%로 이루어지는 것이 바람직하다.The inorganic antimicrobial material is preferably made of 0.0000005 to 10% by weight of silver colloid, 0.0000001 to 15% by weight of titanium dioxide nanoparticles, 0.00001 to 6% by weight of dispersion stabilizer, and 69 to 99% by weight of water based on 100% by weight of the total composition. Do.
상기 분산안정제는 리소레시틴(lysolecithin), 플라보노이드(flavonoid), 트윈 20(Tween 20), 트윈 40, 트윈 80, 폴리비닐피롤리돈(polyvinylpyrrolidone) 및 폴리비닐알콜(polyvinylalcohol) 중 어느 하나인 것이 바람직하다.The dispersion stabilizer is preferably any one of lysolecithin, flavonoid, tween 20, tween 40, tween 80, polyvinylpyrrolidone and polyvinylalcohol. .
이상에서 살펴본 바와 같이, 본 발명은 무기 항균물질을 첨가함으로써 친수성과 항균성이 향상되어 바이오파울링이 저감되는 효과가 있다.As described above, the present invention has the effect of reducing the biofouling by adding an inorganic antimicrobial material is improved hydrophilicity and antimicrobial.
도 1은 본 발명의 일실시예에 따른 수처리용 멤브레인의 시간에 따른 여과유량을 나타낸 그래프이다.1 is a graph showing the filtration flow rate with time of the membrane for water treatment according to an embodiment of the present invention.
아래에서는 첨부한 도면을 참고로 하여 본 발명의 실시예에 대하여 본 발명이 속하는 기술 분야에서 통상의 지식을 가진 자가 용이하게 실시할 수 있도록 상세히 설명한다. 그러나 본 발명은 여러 가지 상이한 형태로 구현될 수 있으며 여기에서 설명하는 실시 예에 한정되지 않는다.DETAILED DESCRIPTION Hereinafter, exemplary embodiments of the present invention will be described in detail with reference to the accompanying drawings so that those skilled in the art may easily implement the present invention. As those skilled in the art would realize, the described embodiments may be modified in various different ways, all without departing from the spirit or scope of the present invention.
본 발명의 일실시예에 따른 항균 및 미생물 방지 기능을 갖는 수처리용 멤브레인 제조방법에 대해 자세히 설명하면 다음과 같다.Referring to the method for producing a membrane for water treatment having an antibacterial and microbial protection function according to an embodiment of the present invention in detail.
본 발명의 수처리용 멤브레인 제조방법은, 고분자(polymer) 30~61중량%, 유기용매(solvent) 25~45중량%, 첨가제(additive) 12~22중량%, 및 무기항균물질 1~5중량%을 교반하여 중공사막 원료를 준비하는 단계와 상기 중공사막 원료를 압출기의 실린더로 토출하는 단계를 포함하여 이루어진다.The method for producing a membrane for water treatment of the present invention comprises 30 to 61 wt% of a polymer, 25 to 45 wt% of an organic solvent, 12 to 22 wt% of an additive, and 1 to 5 wt% of an inorganic antibacterial substance. It comprises a step of preparing a hollow fiber membrane raw material by stirring and discharging the hollow fiber membrane raw material to the cylinder of the extruder.
상기 고분자는 불소계 고분자, 술폰계 고분자, 올레핀계 고분자 중 어느 하나인 것이 바람직하다.The polymer is preferably any one of a fluorine-based polymer, a sulfone-based polymer, and an olefin-based polymer.
상기 불소계 고분자는 폴리비닐리덴플로라이드(polyvinylidene fluoride) 또는 폴리테트라플루오르에틸렌(polytetra fluoro ethylence)이고, 상기 술폰계 고분자는 폴리에테르설폰(polyetersulfone) 또는 폴리스타이렌(polystyrene)이며, 상기 올레핀계 고분자는 폴리에틸렌(polyethylene) 또는 폴리프로필렌(polypropylene)이다. The fluorine-based polymer is polyvinylidene fluoride or polytetrafluoroethylene, and the sulfone-based polymer is polyethersulfone or polystyrene, and the olefin-based polymer is polyethylene ( polyethylene) or polypropylene.
상기 유기용매는 디메틸포름아마이드(DMF), n-메틸-2-피롤리돈(NMP), 디메틸아세트아마이드(DMAC), 디메틸설폭사이드(DMSO), 트리에틸포스페이트(TEP) 중 어느 하나인 것을 바람직하다.The organic solvent is preferably any one of dimethylformamide (DMF), n-methyl-2-pyrrolidone (NMP), dimethylacetamide (DMAC), dimethyl sulfoxide (DMSO), and triethylphosphate (TEP). Do.
상기 첨가제는 폴리비닐피롤리돈(PVPK30), 에틸렌글리콜(EG), 프로필렌 글리콜(PG), 디에틸렌 글리콜(DEG), 트리에틸렌 글리콜(TEG), 디프로필렌 글리콜(DPG), 폴리에틸렌 글리콜(PEG), 글리세롤, 말레인 무수물, 프로필렌-1,2-카보네이트(PC) 중 어느 하나인 것이 바람직하다.The additive is polyvinylpyrrolidone (PVPK30), ethylene glycol (EG), propylene glycol (PG), diethylene glycol (DEG), triethylene glycol (TEG), dipropylene glycol (DPG), polyethylene glycol (PEG) , Glycerol, maleic anhydride or propylene-1,2-carbonate (PC) is preferred.
상기 무기 항균물질은 전체 조성물 100 중량%를 기준으로, 은 콜로이드 0.0000005~10중량%, 이산화티탄 나노입자 0.0000001~15중량%, 상기 분산안정제 0.00001~6중량%, 물 69~99중량%으로 이루어진다.The inorganic antimicrobial material is composed of 0.0000005 to 10% by weight of silver colloid, 0.0000001 to 15% by weight of titanium dioxide nanoparticles, 0.00001 to 6% by weight of the dispersion stabilizer, and 69 to 99% by weight of water based on 100% by weight of the total composition.
이때, 상기 분산안정제는 리소레시틴(lysolecithin), 플라보노이드(flavonoid), 트윈 20(Tween 20), 트윈 40, 트윈 80, 폴리비닐피롤리돈(polyvinylpyrrolidone), 폴리비닐알콜(polyvinylalcohol)로 이루어진 군에서 선택되는 어느 하나 이상인 것이 바람직하다.At this time, the dispersion stabilizer is selected from the group consisting of lysolecithin (lysolecithin), flavonoid (flavonoid), Tween 20, Tween 40, Tween 80, polyvinylpyrrolidone, polyvinyl alcohol (polyvinylalcohol) It is preferable that it is at least one.
상기 무기 항균물질 제조방법은, 분산안정제가 포함된 제1 알콜과 은 전구체를 반응시켜 은 콜로이드 용액을 제조하는 단계와, 상기 은 콜로이드 용액을 물로 희석한 용액에 티타늄 전구체, 제2 알콜 및 산(acid) 촉매를 가하여 상기 은 콜로이드 용액 내에 이산화티탄 나노입자를 생성시키는 단계로 이루어진다.The method for preparing an inorganic antimicrobial agent includes preparing a silver colloidal solution by reacting a silver alcohol with a first alcohol containing a dispersion stabilizer, and a titanium precursor, a second alcohol, and an acid in a solution in which the silver colloidal solution is diluted with water. acid) is added to produce a titanium dioxide nanoparticles in the silver colloid solution.
상기 은 전구체는 질산은(AgNO3) 또는 초산은(CH3COOAg)인 것이 바람직하다.The silver precursor is preferably silver nitrate (AgNO 3 ) or silver acetate (CH 3 COOAg).
상기 제1 알콜은 메탄올, 에탄올, 이소프로필알콜, 부탄올 중 어느 하나인 것이 바람직하다.The first alcohol is preferably any one of methanol, ethanol, isopropyl alcohol, butanol.
상기 티타늄 전구체는 TTIP(titaniumtetraisopropoxide), TEOT(titaniumethoxyorthotitanate) 또는 TBOT(titaniumbutoxyorthotitanate)로 이루어진다.The titanium precursor is made of titanium tetraisopropoxide (TTIP), titaniumethoxyorthotitanate (TEOT), or titaniumbutoxyorthotitanate (TBOT).
상기 제2 알콜은 이소프로필알콜, 에탄올, 부탄올 중 어느 하나인 것이 바람직하다.The second alcohol is preferably any one of isopropyl alcohol, ethanol, butanol.
상기 산 촉매는 질산, 염산, 황산, 옥살산 중 어느 하나인 것이 바람직하다.The acid catalyst is preferably any one of nitric acid, hydrochloric acid, sulfuric acid, and oxalic acid.
도 1은 본 발명의 일실시예에 따른 수처리용 멤브레인의 시간에 따른 여과유량을 나타낸 그래프이다.1 is a graph showing the filtration flow rate with time of the membrane for water treatment according to an embodiment of the present invention.
도 1에 나타낸 바와 같이, 고분자, 유기용매, 첨가제를 교반하여 제조한 멤브레인(비교예)과 고분자, 유기용매, 첨가제에 무기 항균물질을 추가하여 제조한 멤브레인(실험예1,2)의 시간에 따른 여과유량 변화가 무기 항균물질을 추가할 때 여과 유량이 많은 것은 알 수 있다. 이는 무기 항균물질로 인해 친수성과 항균성이 향상되어 멤브레인 표면의 세균이 사멸되어 여과 유량이 떨어지지 않은 것을 알 수 있다.As shown in FIG. 1, the membrane prepared by stirring the polymer, the organic solvent and the additive (comparative example) and the membrane prepared by adding the inorganic antimicrobial material to the polymer, the organic solvent and the additive (Experimental Example 1, 2) It can be seen that the filtration flow rate is high when the change in the filtration flow rate adds an inorganic antimicrobial material. It can be seen that the hydrophilicity and antimicrobial properties are improved due to the inorganic antimicrobial material, so that bacteria on the surface of the membrane are killed so that the filtration flow rate does not drop.
이상에서 본 발명은 기재된 실시예를 참조하여 상세히 설명되었으나,본 발명이 속하는 기술 분야에서 통상의 지식을 가진 자라면 상기에서 설명된 기술적 사상을 벗어나지 않는 범위 내에서 여러 가지 치환,부가 및 전용이 가능할 것임은 당연한 것으로, 이와 같은 변형된 실시 형태들 역시 아래에 첨부한 특허청구범위에 의하여 정해지는 본 발명의 보호 범위에 속하는 것으로 이해되어야 할 것이다.Although the present invention has been described in detail with reference to the described embodiments, it will be apparent to those skilled in the art that various substitutions, additions, and conversions may be made without departing from the spirit and scope described above. It is to be understood that such modified embodiments also fall within the protection scope of the present invention as defined by the appended claims below.

Claims (8)

  1. 고분자 30~61중량%, 유기용매 25~45중량%, 첨가제 12~22중량%, 및 무기 항균물질 1~5중량%을 교반하여 중공사막 원료를 준비하는 단계; 및Preparing a hollow fiber membrane raw material by stirring 30 to 61 wt% of a polymer, 25 to 45 wt% of an organic solvent, 12 to 22 wt% of an additive, and 1 to 5 wt% of an inorganic antibacterial material; And
    상기 중공사막 원료를 압출기의 실린더로 토출하는 단계Discharging the hollow fiber membrane raw material to the cylinder of the extruder
    를 포함하는 것을 특징으로 하는 항균 및 미생물 방지 기능을 갖는 수처리용 멤브레인 제조방법.Membrane for water treatment having an antimicrobial and microbial function, characterized in that it comprises a.
  2. 제1항에 있어서,The method of claim 1,
    상기 고분자는 불소계 고분자, 술폰계 고분자, 올레핀계 고분자 중 어느 하나인 것을 특징으로 하는 항균 및 미생물 방지 기능을 갖는 수처리용 멤브레인 제조방법.The polymer is a fluorine-based polymer, sulfone-based polymer, olefin-based polymer water treatment membrane having an antimicrobial and microbial protection function, characterized in that any one of.
  3. 제1항에 있어서,The method of claim 1,
    상기 불소계 고분자는 폴리비닐리덴플로라이드(polyvinylidene fluoride) 또는 폴리테트라플루오르에틸렌(polytetra fluoro ethylence)이고, 상기 술폰계 고분자는 폴리에테르설폰(polyetersulfone) 또는 폴리스타이렌(polystyrene)이며, 상기 올레핀계 고분자는 폴리에틸렌(polyethylene) 또는 폴리프로필렌(polypropylene)인 것을 특징으로 하는 항균 및 미생물 방지 기능을 갖는 수처리용 멤브레인 제조방법. The fluorine-based polymer is polyvinylidene fluoride or polytetrafluoroethylene, and the sulfone-based polymer is polyethersulfone or polystyrene, and the olefin-based polymer is polyethylene ( Method of producing a membrane for water treatment with antimicrobial and microbial protection, characterized in that the polyethylene) or polypropylene (polypropylene).
  4. 제1항에 있어서,The method of claim 1,
    상기 유기용매는 디메틸포름아마이드(DMF), n-메틸-2-피롤리돈(NMP), 디메틸아세트아마이드(DMAC), 디메틸설폭사이드(DMSO), 트리에틸포스페이트(TEP) 중 어느 하나인 것을 특징으로 하는 항균 및 미생물 방지 기능을 갖는 수처리용 멤브레인 제조방법.The organic solvent is any one of dimethylformamide (DMF), n-methyl-2-pyrrolidone (NMP), dimethylacetamide (DMAC), dimethyl sulfoxide (DMSO), triethyl phosphate (TEP) Membrane manufacturing method for water treatment having an antimicrobial and microbial protection function.
  5. 제1항에 있어서,The method of claim 1,
    상기 첨가제는 폴리비닐피롤리돈(PVPK30), 에틸렌글리콜(EG), 프로필렌 글리콜(PG), 디에틸렌 글리콜(DEG), 트리에틸렌 글리콜(TEG), 디프로필렌 글리콜(DPG), 폴리에틸렌 글리콜(PEG), 글리세롤, 말레인 무수물, 프로필렌-1,2-카보네이트(PC) 중 어느 하나인 것을 특징으로 하는 항균 및 미생물 방지 기능을 갖는 수처리용 멤브레인 제조방법.The additive is polyvinylpyrrolidone (PVPK30), ethylene glycol (EG), propylene glycol (PG), diethylene glycol (DEG), triethylene glycol (TEG), dipropylene glycol (DPG), polyethylene glycol (PEG) , Glycerol, maleic anhydride, propylene-1,2-carbonate (PC) any one of the membrane manufacturing method for water treatment having an antimicrobial and microbial protection function.
  6. 제1항에 있어서,The method of claim 1,
    상기 무기 항균물질은 전체 조성물 100 중량%를 기준으로, 은 콜로이드 0.0000005~10중량%, 이산화티탄 나노입자 0.0000001~15중량%, 분산안정제 0.00001~6중량%, 물 69~99중량%로 이루어진 것을 특징으로 하는 항균 및 미생물 방지 기능을 갖는 수처리용 멤브레인 제조방법.The inorganic antimicrobial material is composed of 0.0000005 to 10% by weight of silver colloid, 0.0000001 to 15% by weight of titanium dioxide nanoparticles, 0.00001 to 6% by weight of dispersion stabilizer, and 69 to 99% by weight of water based on 100% by weight of the total composition. Membrane manufacturing method for water treatment having an antimicrobial and microbial protection function.
  7. 제6항에 있어서,The method of claim 6,
    상기 분산안정제는 리소레시틴(lysolecithin), 플라보노이드(flavonoid), 트윈 20(Tween 20), 트윈 40, 트윈 80, 폴리비닐피롤리돈(polyvinylpyrrolidone), 폴리비닐알콜(polyvinylalcohol) 중 어느 하나인 것을 특징으로 하는 항균 및 미생물 방지 기능을 갖는 수처리용 멤브레인 제조방법.The dispersion stabilizer is characterized in that any one of lysolecithin (lysolecithin), flavonoid (flavonoid), Tween 20 (Tween 20), Tween 40, Tween 80, polyvinylpyrrolidone, polyvinyl alcohol (polyvinylalcohol) Membrane manufacturing method for water treatment having an antimicrobial and antimicrobial function.
  8. 상기 제1항 내지 제7항 중 어느 하나의 항으로 제조된 항균 및 미생물 방지 기능을 갖는 수처리용 멤브레인.Membrane for water treatment having an antimicrobial and microbial protection function of any one of claims 1 to 7.
PCT/KR2015/005813 2015-06-09 2015-06-10 Water-treatment membrane having antibacterial and microbe-preventing function, and production method for same WO2016199951A1 (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109718672A (en) * 2019-03-06 2019-05-07 长春工业大学 A kind of polysulfones/nano-titanium dioxide hybrid inorganic-organic hollow fiber ultrafiltration membrane and preparation method thereof

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20060069537A (en) * 2004-12-17 2006-06-21 양원동 Nano silver contain water purifier filter housing
KR20060089845A (en) * 2005-02-04 2006-08-09 (주) 인바이런먼트 리딩 테크놀러지 Structure of a filter for cleaning air
KR20060102420A (en) * 2005-03-23 2006-09-27 (주) 존인피니티 Porous nano particle titanium dioxide photocatalyst having nano sized pores and the method manufacturing pigment
WO2010024598A2 (en) * 2008-08-27 2010-03-04 주식회사 지피엔이 Method for preparing antimicrobial, antifungal, and antiviral compositions
KR20140081366A (en) * 2012-12-21 2014-07-01 엘지전자 주식회사 Hollow Fiber Membrane Having Novel Structure and Method of Preparing the Same

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20060069537A (en) * 2004-12-17 2006-06-21 양원동 Nano silver contain water purifier filter housing
KR20060089845A (en) * 2005-02-04 2006-08-09 (주) 인바이런먼트 리딩 테크놀러지 Structure of a filter for cleaning air
KR20060102420A (en) * 2005-03-23 2006-09-27 (주) 존인피니티 Porous nano particle titanium dioxide photocatalyst having nano sized pores and the method manufacturing pigment
WO2010024598A2 (en) * 2008-08-27 2010-03-04 주식회사 지피엔이 Method for preparing antimicrobial, antifungal, and antiviral compositions
KR20140081366A (en) * 2012-12-21 2014-07-01 엘지전자 주식회사 Hollow Fiber Membrane Having Novel Structure and Method of Preparing the Same

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109718672A (en) * 2019-03-06 2019-05-07 长春工业大学 A kind of polysulfones/nano-titanium dioxide hybrid inorganic-organic hollow fiber ultrafiltration membrane and preparation method thereof

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