WO2019022588A2 - Antimicrobial agent comprising mof and antimicrobial filter comprising same - Google Patents

Antimicrobial agent comprising mof and antimicrobial filter comprising same Download PDF

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Publication number
WO2019022588A2
WO2019022588A2 PCT/KR2018/008643 KR2018008643W WO2019022588A2 WO 2019022588 A2 WO2019022588 A2 WO 2019022588A2 KR 2018008643 W KR2018008643 W KR 2018008643W WO 2019022588 A2 WO2019022588 A2 WO 2019022588A2
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Prior art keywords
mof
antimicrobial
antibacterial
present
filter
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PCT/KR2018/008643
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French (fr)
Korean (ko)
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WO2019022588A3 (en
Inventor
박교성
Original Assignee
주식회사 엘지화학
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Priority claimed from KR1020180088204A external-priority patent/KR20190013629A/en
Application filed by 주식회사 엘지화학 filed Critical 주식회사 엘지화학
Publication of WO2019022588A2 publication Critical patent/WO2019022588A2/en
Publication of WO2019022588A3 publication Critical patent/WO2019022588A3/en

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Classifications

    • AHUMAN NECESSITIES
    • A01AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01NPRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N25/00Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
    • A01N25/34Shaped forms, e.g. sheets, not provided for in any other sub-group of this main group
    • AHUMAN NECESSITIES
    • A01AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01NPRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N59/00Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
    • A01N59/06Aluminium; Calcium; Magnesium; Compounds thereof
    • AHUMAN NECESSITIES
    • A01AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01NPRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N59/00Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
    • A01N59/16Heavy metals; Compounds thereof
    • AHUMAN NECESSITIES
    • A01AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01NPRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N59/00Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
    • A01N59/16Heavy metals; Compounds thereof
    • A01N59/20Copper
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07FACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F3/00Compounds containing elements of Groups 2 or 12 of the Periodic System
    • C07F3/06Zinc compounds

Definitions

  • Antimicrobial agents including MOF and antibacterial filters containing the same
  • the present invention relates to an antibacterial agent containing MOF and an antibacterial filter comprising the same.
  • microorganisms such as bacteria, bacteria and viruses are floating in the air, and these floating microorganisms cause infectious diseases and adversely affect health. Therefore, in general, automobile, air conditioner, air conditioner, air cleaner : clean room, etc. are equipped with an antibacterial filter capable of removing such microorganisms.
  • Antimicrobial agents used in antibacterial filters can be classified as organic antibacterial agents and inorganic antibacterial agents.
  • Organic antibacterial agents can be divided into antibacterial agents derived from natural materials and synthetic antibacterial agents.
  • the natural product-derived antimicrobial agent is safe for the human body but has a short persistence of the antibacterial property, and the synthetic compound antimicrobial agent is highly concerned about human safety.
  • Inorganic antimicrobial agents that can overcome such shortcomings is attracting attention.
  • Inorganic antimicrobial agents are characterized by long-lasting antimicrobial activity due to the loading of metal ions with excellent antimicrobial activity on inorganic carriers such as zeolite and silica alumina.
  • metal ions are toxic to humans and their application is limited.
  • Metal-organic framework is a hybrid organic / inorganic hybrid material that has recently been attracting attention as a metal organic structure with metal ions coordinating with organic ligands.
  • MOFs have antimicrobial activity against microorganisms It is known.
  • some of the MOFs It is difficult to apply it to an antibacterial air filter.
  • the present invention provides an antibacterial agent which is harmless to human body and exhibits excellent antibacterial activity and a filter using the antibacterial agent.
  • An antimicrobial agent comprising a metal-organic framework (MOF)
  • the present invention also provides an antimicrobial agent comprising at least one organic ligand.
  • An antibacterial filter comprising the antibacterial agent is provided.
  • the antibacterial agent and the antibacterial filter of the present invention it is possible to exhibit excellent antibacterial activity against harmful bacteria and / or bacteria such as Staphylococci and Escherichia coli present in the air.
  • the antimicrobial agent containing the MOF may be used as an antimicrobial agent by itself, or by co-mingling with other materials, or by coating or supporting on another substrate.
  • the antibacterial agent and the antibacterial filter of the present invention it is possible to replace the conventional antimicrobial agent which is non-toxic and harmful to the human body and has high persistency of antibacterial property.
  • 1 is a schematic diagram showing the three-dimensional structure of ZIF-8 contained in the antibacterial agent of the present invention.
  • FIG. 2 is a SEM photograph showing an antibacterial filter according to an embodiment of the present invention.
  • Fig. 3 is a photograph showing a photograph of the nonwoven fabric filter of the example of the present invention and the medium of the comparative example after 18 hours from inoculation with Staphylococcus aureus
  • FIG. 4 is a photograph showing a photograph of the nonwoven fabric filter of the example of the present invention and the comparative example medium after 18 hours from the inoculation with E. coli.
  • the MOF includes at least one metal ion selected from the group consisting of Zn, Co, Al, and Zr, and at least one metal ion selected from the group consisting of imidazole, At least one organic ligand selected from the group consisting of alkylimidazole, alkoxyimidazole, terephthalic acid, and aminoterephthajic acid.
  • Metal-organic framework also called metal organic structure, is an organic-inorganic hybrid material having a primary, secondary or tertiary structure for metal ion or ion clusters to feed organic ligands. Can make various MOF.
  • the MOF is characterized by a porous structure in which voids exist in the structure,
  • the pore size, porosity, three-dimensional structure, and surface area can be designed in various ways depending on the kind of metal ion and organic ligand and the manner of coupling of MOF. Due to such porosity, MOF has adsorbability to various organic compounds, and in particular, it has attracted attention as a next-generation functional adsorbent because it exhibits excellent adsorbability to various materials as compared with conventionally well known agents such as light or activated carbon. Also, the MOF does not easily deform at high temperature and has a rigid skeleton, so that it has excellent chemical stability and thermal stability. It is also known that some of the MOFs also have antimicrobial activity against microorganisms.
  • antimicrobial activity is only known to MOFs containing some metals among MOFs, for example, silver (Ag) ions or nickel (Ni) ions. Nickel (Ni) .
  • silver (Ag) has no problem in oral toxicity, but it is known to have serious adverse effects on human inhalation and aquatic ecosystems, and silver nanoparticles are prohibited in the United States in particular.
  • the inventors of the present invention have found that there is antimicrobial activity for inhibiting the propagation of various microorganisms of MO including metal ions known to have no antimicrobial activity.
  • the MOF may include at least one metal ion selected from the group consisting of Zn, Co, Al, and Zr and at least one metal ion selected from the group consisting of imidazole, alkylimidazole, And at least one organic ligand selected from the group consisting of alkoxyimidazole, terephthalic acid, and aminoterephthalic acid.
  • the MOF for example ZIF-8 (Zn 2+ + 2 -methylimidazole), ZIF-67 (Co + + 2-methylimidazole), NH 2 -UiO-66 (Zr 4+ + 2-aminoterephthalic acid, and NH 2 -MIL-101 (Al 3+ + 2-aminoterephthalic acid).
  • ZIF-8 Zn 2+ + 2 -methylimidazole
  • ZIF-67 Co + + 2-methylimidazole
  • NH 2 -UiO-66 Zr 4+ + 2-aminoterephthalic acid
  • NH 2 -MIL-101 Al 3+ + 2-aminoterephthalic acid
  • the MOF may be ZIF-8 (Zn 2+ + 2-methylimidazole).
  • 1 is a schematic diagram showing the three-dimensional structure of ZIF-8 contained in the antibacterial agent of the present invention.
  • ZIF-8 (Zn 2+ + 2-methylimidazole, C 8 H 10 N 4 Zn) exhibits a polyhedron structure and has a plane structure of ZIF-L (C 10 H 16 N 5 Zn).
  • ZIF-8 exhibits excellent antimicrobial activity unlike conventional antimicrobial activity, and has no toxicity to humans and thus can be effectively used as an antibacterial agent.
  • the MOF-containing antimicrobial agent may be used in various products such as automobiles, air conditioners, air conditioners, air cleaners, humidifiers, masks, filters, and the like.
  • an antibacterial filter comprising the antibacterial agent.
  • the MOF may be carried on a nonwoven fabric to exhibit efficient antibacterial properties.
  • the antibacterial filter of the present invention can be produced by a known nonwoven fabric manufacturing method such as electrospinning, melt spinning, wet spinning, application on a substrate, thermocompression bonding and the like.
  • the antibacterial filter may be prepared by electrospinning a polymer solution and a spinning solution in which the MOF is mixed, but the present invention is not limited thereto.
  • Electrospinning is a method of obtaining a fibrous aggregate in the form of a nonwoven fabric by spinning the polymer solution directly onto the substrate or directly without the substrate by a static force.
  • the polymer solution may include a polymer, a dispersion solvent, a dispersant, an additive, and the like, but the present invention is not limited thereto.
  • polyacrylonitrile PAN
  • PVDF polyvinylidene fluoride
  • PVVC polyvinyl chloride
  • polyethylene terephthalate PAN
  • PAN polyacrylonitrile
  • PVDF polyvinylidene fluoride
  • PVVC polyvinyl chloride
  • polyacrylonitrile PAN
  • PVDF polyvinylidene fluoride
  • PVVC polyvinyl chloride
  • polyethylene terephthalate and polyacrylonitrile may be preferably used, but the present invention is not limited thereto.
  • the dispersion solvent includes dimethylacetamide, diethylacetamide, dimethylmercaptacetamide, N-methylpyrrolidone, dimethylformamide, etc.
  • the dispersion solvent includes dimethylacetamide, diethylacetamide, dimethylmercaptacetamide, N-methylpyrrolidone, dimethylformamide, etc.
  • the nonwoven fabric may be produced by electrospinning a polymer solution containing a polymer and a spinning solution mixed with MOF, thereby producing a nonwoven fabric.
  • MOF can be obtained in the form of supported.
  • the MOF may comprise at least about 10 parts by weight, or at least about 30 parts by weight, or at least about 50 parts by weight and at most about 95 parts by weight of MOF, Parts by weight or less, or about 85 parts by weight or less. If the MOF is included in an excessively small amount, the antibacterial property may be deteriorated. If the MOF is included too much, the MOF particles may be desorbed in the external air amount.
  • the specific surface area of the nonwoven fabric before the MOF is supported is about 0.1 m 2 / g or more, or about 5 m 2 / g or more, or about 8 m 2 / 2 g or less, or about 30 m 2 / g or less, or about 20 m 2 / g or less. If the specific surface area of the nonwoven fabric is too small, the amount of MOF adhered to the surface of the nonwoven fabric may be reduced to lower the antibacterial property. If too large, the strength of the formed nonwoven fabric may decrease.
  • the specific surface area of the nonwoven fabric after the MOF is supported is much higher than that before being supported, for example, about 50 m 2 / g Or about 70 m 2 / g or more, or about 80 m 2 / g or more, about 200 m 2 / g or less, or about 180 m 2 / g or less, or about 150 m 2 / g or less. Since the porous MOF is supported as described above, the specific surface area is much increased, so that it can exhibit better antimicrobial activity.
  • the antibacterial filter in which the MOF of the present invention is supported on the nonwoven fabric is harmless to the human body and exhibits excellent antibacterial activity, and can exhibit more than 99.9% of antibacterial activity against Staphylococcus aureus and Escherichia coli.
  • a spinning solution is first prepared by mixing MOF with a polymer solution.
  • MOF MOF
  • polymer solution polymer solution
  • spinning solution are described in detail with reference to the antibacterial filter.
  • the spinning solution thus prepared may be electrospun on a substrate to produce an antibacterial filter having a MOF supported on a nonwoven fabric, but the present invention is not limited thereto.
  • the electrospinning can also be carried out using conventional methods and conditions known as nonwoven fabrication methods.
  • ZIF-8 Zn 2+ + 2-methylimidazole
  • FIG. 2 shows a photograph of the produced nonwoven filter with a scanning electron microscope (SEM). Referring to FIG. 2, it can be seen that a nonwoven fabric antibacterial filter having ZIF-8 supported on fibers was produced.
  • SEM scanning electron microscope
  • the antibacterial properties of the antibacterial filters of Examples 1 to 4 were measured by the following methods.
  • KS K 0693 2011, Escherichia coli ATCC 25922 inoculated with 0.05% of non-ionic surfactant TWEEN 80 and inoculum of staphylococcus aureus ATCC 6538 were inoculated into the medium, After the filters of Examples 1 to 4 were attached to the upper portion, bacteria were cultured for 18 hours.
  • Escherichia coli and Staphylococcus aureus were inoculated on the microorganism medium not treated with MOF, and the bacteria were cultured for 18 hours and used as Comparative Example 1.
  • FIG 3 is a photograph showing 18 hours after the inoculation of Staphylococcus aureus against the nonwoven fabric filter and the comparative example medium of Examples 1 to 4 of the present invention.

Abstract

The present invention relates to an antimicrobial agent comprising MOF and an antimicrobial filter comprising the same. The antimicrobial agent and the antimicrobial filter of the present invention may exhibit excellent antimicrobial activity against harmful microorganisms present in the air, and are non-toxic and thus may replace conventional antimicrobial agents which are harmful to humans.

Description

【발명의 명칭】  Title of the Invention
MOF를 포함하는 항균제 및 이를 포함하는 항균 필터  Antimicrobial agents including MOF and antibacterial filters containing the same
【기술분야】 TECHNICAL FIELD
관련 출원 (들)과의 상호 인용  Cross-reference with related application (s)
본 출원은 2017년 7월 28일자 한국 특허 출원 제 10-2017-0096509호 및 2018년 7월 27일자 한국 특허 출원 제 10-2018-0088204호에 기초한 우선권의 이익을 주장하며, 해당 한국 특허 출원들의 문헌에 개시된 모든 내용은 본 명세서의 일부로서 포함된다.  This application claims the benefit of priority based on Korean Patent Application No. 10-2017-0096509 filed on July 28, 2017, and Korean Patent Application No. 10-2018-0088204 filed on July 27, 2018, The entire contents of which are incorporated herein by reference.
본 발명은 MOF를 포함하는 항균제 및 이를 포함하는 항균 필터에 관한 것이다.  The present invention relates to an antibacterial agent containing MOF and an antibacterial filter comprising the same.
【발명의 배경이 되는 기술】 TECHNICAL BACKGROUND OF THE INVENTION
공기 중에는 박테리아, 세균, 바이러스와 같은 다양한 미생물이 부유하고 있으며, 이러한 부유 미생물은 감염성 질병을 유발하여 건강에 나쁜 영향을 미친다. 따라서, 일반적으로 자동차, 공조기, 에어컨, 공기청정기 : 클린룸 등에는 이러한 미생물을 제거할 수 있는 항균 필터가 장착된다. Various microorganisms such as bacteria, bacteria and viruses are floating in the air, and these floating microorganisms cause infectious diseases and adversely affect health. Therefore, in general, automobile, air conditioner, air conditioner, air cleaner : clean room, etc. are equipped with an antibacterial filter capable of removing such microorganisms.
항균 필터에 사용되는 항균제로는 크기 유기 항균제와 무기 항균제로 분류될 수 있으며, 유기 항균제는 다시 천연물 유래 항균제와 합성 화합물 항균제로 나눌 수 있다. 상기 천연물 유래 항균제는 인체에는 안전하지만 항균 특성의 지속성이 짧은 특성이 있고 합성 화합물 항균제는 인체 안전성에 대한우려가 크다.  Antimicrobial agents used in antibacterial filters can be classified as organic antibacterial agents and inorganic antibacterial agents. Organic antibacterial agents can be divided into antibacterial agents derived from natural materials and synthetic antibacterial agents. The natural product-derived antimicrobial agent is safe for the human body but has a short persistence of the antibacterial property, and the synthetic compound antimicrobial agent is highly concerned about human safety.
이러한 단점을 보완할 수 있는 무기 항균제가 주목받고 있다. 무기 항균제는 제올라이트, 실리카 알루미나 등의 무기 담체에 항균성이 뛰어난 금속 이온을 담지시킨 것으로 항균력의 지속성이 긴 특징이 있으나, 일부 금속은 인체에 독성이 있어 적용이 제한되고 있다.  An inorganic antimicrobial agent that can overcome such shortcomings is attracting attention. Inorganic antimicrobial agents are characterized by long-lasting antimicrobial activity due to the loading of metal ions with excellent antimicrobial activity on inorganic carriers such as zeolite and silica alumina. However, some metals are toxic to humans and their application is limited.
한편 금속 이온이 유기 리간드와 배위 결합을 이루며, 다공성의 금속 유기 구조체로 다양한 개발 가능성으로 최근 주목받는 유무기 하이브리드 재료로 MOF(Metal-organic framework)가 있는데 MOF 중 일부는 미생물에 대한 항균성 또한 갖는 것으로 알려져 있다. 그러나, MOF 중 일부는 인체 독성을 나타내어 항균성 공기 필터에 적용하는데 어려움이 있다. Metal-organic framework (MOF) is a hybrid organic / inorganic hybrid material that has recently been attracting attention as a metal organic structure with metal ions coordinating with organic ligands. Various MOFs have antimicrobial activity against microorganisms It is known. However, some of the MOFs It is difficult to apply it to an antibacterial air filter.
【발명의 내용】 DISCLOSURE OF THE INVENTION
【해결하고자 하는 과제】  [Problem to be solved]
상기와 같은 과제를 해결하기 위하여, 본 발명은 인체에 무해하면서 우수한 항균성을 나타내는 항균제 및 이를 이용하는 필터를 제공한다.  In order to solve the above-mentioned problems, the present invention provides an antibacterial agent which is harmless to human body and exhibits excellent antibacterial activity and a filter using the antibacterial agent.
【과제의 해결 수단】 MEANS FOR SOLVING THE PROBLEMS
상기와 같은 문제를 해결하기 위해서 본 발명의 일 측면은,  According to an aspect of the present invention,
MOF(Metal-organic framework)를 포함하는 항균제로, 상기 MOF는 Zn, An antimicrobial agent comprising a metal-organic framework (MOF)
Co, Al, 및 Zr로 이루어진 군으로부터 선택되는 1종 이상의 금속 이온과, 이미다졸 (imidazole), 알킬이미다졸 (alkylimidazole), 알콕시이미다졸 (alkoxyimidazole), 테레프탈산 (terephthalic acid), 및 아미노테레프탈산 (aminoterephthalic acid)으로 이루어진 군으로부터 선택되는 1종 이상의 유기 리간드를 포함하는 항균제를 제공한다. Co, Al, and Zr and at least one metal ion selected from the group consisting of imidazole, alkylimidazole, alkoxyimidazole, terephthalic acid, and aminoterephthalic acid ( aminoterephthalic acid). The present invention also provides an antimicrobial agent comprising at least one organic ligand.
또한, 본 발명의 다른 일 측면은,  According to another aspect of the present invention,
상기 항균제를 포함하는 항균 필터를 제공한다.  An antibacterial filter comprising the antibacterial agent is provided.
【발명의 효과】 【Effects of the Invention】
본 발명의 항균제 및 항균 필터에 따르면, 공기 중 존재하는 포도상구균, 대장균 등의 유해균 및 /또는 박테리아에 대해 우수한 항균성을 나타낼 수 있다. 상기 MOF를 포함하는 항균제는 그 자체로, 또는 다른 물질과 흔합하거나, 다른 기재에 코팅, 담지함으로써 항균제로 사용할 수 있다.  According to the antibacterial agent and the antibacterial filter of the present invention, it is possible to exhibit excellent antibacterial activity against harmful bacteria and / or bacteria such as Staphylococci and Escherichia coli present in the air. The antimicrobial agent containing the MOF may be used as an antimicrobial agent by itself, or by co-mingling with other materials, or by coating or supporting on another substrate.
또한 본 발명의 항균제 및 항균 필터에 의하면, 무독성으로 인체에 대한 유해성이 문제되는 종래의 항균제를 대체할 수 있으며 항균 특성의 지속성이 높다.  Further, according to the antibacterial agent and the antibacterial filter of the present invention, it is possible to replace the conventional antimicrobial agent which is non-toxic and harmful to the human body and has high persistency of antibacterial property.
또한, UV 램프, 광촉매, 플라즈마, 또는 오존 방식과 달리 별도의 전원 공급 장치를 필요로 하지 않으며, 장치가 간단하고 작은 부피만을 차지하여 설치가 용이하여 다양한 제품에 적용할 수 있다. 【도면의 간단한 설명】 In addition, unlike the UV lamp, photocatalyst, plasma, or ozone type, it does not require a separate power supply unit, and the apparatus is simple and easy to install because it occupies a small volume and can be applied to various products. BRIEF DESCRIPTION OF THE DRAWINGS
도 1은 본 발명의 항균제에 포함되는 ZIF-8의 3차원 구조를 보여주는 모식도이다.  1 is a schematic diagram showing the three-dimensional structure of ZIF-8 contained in the antibacterial agent of the present invention.
도 2는 본 발명의 일 실시예에 따른 항균 필터를 보여주는 SEM 사진이다.  2 is a SEM photograph showing an antibacterial filter according to an embodiment of the present invention.
도 3은 본 발명의 실시예의 부직포 필터 및 비교예의 배지에 대해 황색 포도상구균 접종 후 18시간후의 사진을 보여주는 도면이다ᅳ  Fig. 3 is a photograph showing a photograph of the nonwoven fabric filter of the example of the present invention and the medium of the comparative example after 18 hours from inoculation with Staphylococcus aureus
도 4는 본 발명의 실시예의 부직포 필터 및 비교예의 배지에 대해 대장균 접종 후 18시간후의 사진을 보여주는 도면이다.  4 is a photograph showing a photograph of the nonwoven fabric filter of the example of the present invention and the comparative example medium after 18 hours from the inoculation with E. coli.
【발명을 실시하기 위한 구체적인 내용】 DETAILED DESCRIPTION OF THE INVENTION
본 발명은 다양한 변경을 가할 수 있고 여러 가지 형태를 가질 수 있는 바, 특정 실시예들을 예시하고 하기에서 상세하게 설명하고자 한다. 그러나, 이는 본 발명을 특정한 개시 형태에 대해 한정하려는 것이 아니며, 본 발명의 사상 및 기술 범위에 포함되는 모든 변경, 균등물 내지 대체물을 포함하는 것으로 이해되어야 한다.  While the invention is susceptible to various modifications and alternative forms, specific embodiments thereof are shown by way of example in the drawings and will herein be described in detail. It should be understood, however, that the invention is not intended to be limited to the particular forms disclosed, but includes all modifications, equivalents, and alternatives falling within the spirit and scope of the invention.
이하, 본 발명의 항균제 및 항균 필터에 대해 보다 상세히 설명한다. 본 발명의 일 구현예에 따른 항균제는 MOF(Metal-organic framework)를 포함하며, 상기 MOF는 Zn, Co, A1, 및 Zr로 이루어진 군으로부터 선택되는 1종 이상의 금속 이온과, 이미다졸 (imidazole), 알킬이미다졸 (alkylimidazole), 알콕시이미다졸 (alkoxyimidazole), 테레프탈산 (terephthalic acid), 및 아미노테레프탈산 (aminoterephthajic acid)으로 이루어진 군으로부터 선택되는 1종 이상의 유기 리간드를 포함한다.  Hereinafter, the antibacterial agent and antibacterial filter of the present invention will be described in more detail. The MOF includes at least one metal ion selected from the group consisting of Zn, Co, Al, and Zr, and at least one metal ion selected from the group consisting of imidazole, At least one organic ligand selected from the group consisting of alkylimidazole, alkoxyimidazole, terephthalic acid, and aminoterephthajic acid.
MOF(Metal-organic framework)는 금속 유기 구조체라고도 불리며, 금속 이은 또는 이온 클러스트가 유기 리간드와 배위하여 1차, 2차 또는 3차 구조를 갖는 유기 -무기 하이브리드 물질로, 금속 이온과 유기 리간드의 선택에 따라 다양한 MOF를 만들 수 있다.  Metal-organic framework (MOF), also called metal organic structure, is an organic-inorganic hybrid material having a primary, secondary or tertiary structure for metal ion or ion clusters to feed organic ligands. Can make various MOF.
상기 MOF는 구조 내에 빈 공간이 존재하는 다공성인 특징이 있으며, MOF를 이루는 금속 이온 및 유기 리간드의 종류와 결합 방식에 따라 기공의 크기, 기공도 , 3차원 구조, 표면적 등이 다양하게 설계될 수 있다. 이러한 다공성으로 인해 MOF는 다양한 유기 화합물에 대해 흡착성을 가지며, 특히 종래에 널리 알려진 제을라이트나 활성탄과 비교하여 다양한 물질에 대해 우수한 흡착성을 나타내어 차세대 기능성 흡착제로 주목받고 있다. 또한 상기 MOF는 높은 온도에서 변형이 쉽게 일어나지 않으며 단단한 골격을 가지고 있어 화학적 안정성 및 열 안정성이 우수하다. 또한 MOF 중 일부는 미생물에 대한 항균성 또한 갖는 것으로 알려져 있다. The MOF is characterized by a porous structure in which voids exist in the structure, The pore size, porosity, three-dimensional structure, and surface area can be designed in various ways depending on the kind of metal ion and organic ligand and the manner of coupling of MOF. Due to such porosity, MOF has adsorbability to various organic compounds, and in particular, it has attracted attention as a next-generation functional adsorbent because it exhibits excellent adsorbability to various materials as compared with conventionally well known agents such as light or activated carbon. Also, the MOF does not easily deform at high temperature and has a rigid skeleton, so that it has excellent chemical stability and thermal stability. It is also known that some of the MOFs also have antimicrobial activity against microorganisms.
그러나, 이러한 MOF의 항균성을 이용하여 항균제 또는 항균 필터 (filter) 등으로 적용할 때 인체에 대한 독성 문제가 있다.  However, there is a toxicity problem to the human body when the antimicrobial agent or the antibacterial filter is applied using the antimicrobial property of such MOF.
예를 들어, 종래에는 MOF 중 일부 금속, 예를 들어 은 (Ag) 이온 또는 니켈 (Ni) 이온을 포함하는 MOF에 대해서만 항균성이 있다고 알려졌으나, 니켈 (Ni)은 흡입시 인체에 독성이 있어 사용에 제약이 있다. 또한, 은 (Ag)은 경구 독성은 문제 없으나 인체 흡입시나 수생 생태계에 심각한 악영향을 미치는 것으로 알려져 있고, 이 때문에 특히 은 나노 입자는 미국에서 사용이 금지되어 있다.  For example, it has been known in the past that antimicrobial activity is only known to MOFs containing some metals among MOFs, for example, silver (Ag) ions or nickel (Ni) ions. Nickel (Ni) . In addition, silver (Ag) has no problem in oral toxicity, but it is known to have serious adverse effects on human inhalation and aquatic ecosystems, and silver nanoparticles are prohibited in the United States in particular.
한편, 본 발명의 발명자들은 항균성이 없는 것으로 알려진 금속 이온을 포함하는 MO 각종 미생물의 번식을 억제하는 항균성이 있는 사실을 밝혀내어 본 발명에 이르게 되었다.  On the other hand, the inventors of the present invention have found that there is antimicrobial activity for inhibiting the propagation of various microorganisms of MO including metal ions known to have no antimicrobial activity.
이에, 본 발명의 일 실시예에 따르면, 상기 MOF는 Zn, Co, Al, 및 Zr로 이루어진 군으로부터 선택되는 1종 이상의 금속 이온과, 이미다졸 (imidazole), 알킬이미다졸 (alkylimidazole), 알콕시이미다졸 (alkoxyimidazole), 테레프탈산 (terephthalic acid), 및 아미노테레프탈산 (aminoterephthalic acid)으로 이루어진 군으로부터 선택되는 1종 이상의 유기 리간드를 포함하는 것일 수 있다.  According to an embodiment of the present invention, the MOF may include at least one metal ion selected from the group consisting of Zn, Co, Al, and Zr and at least one metal ion selected from the group consisting of imidazole, alkylimidazole, And at least one organic ligand selected from the group consisting of alkoxyimidazole, terephthalic acid, and aminoterephthalic acid.
본 발명의 일 실시예에 따르면, 상기 MOF는 예를 들어 ZIF-8(Zn2++2-methylimidazole), ZIF-67(Co ++2-methylimidazole), NH2-UiO-66(Zr4++2-aminoterephthalic acid), 및 NH2-MIL- 101 (Al3++2-aminoterephthalic acid)로 이루어진 군으로부터 선택되는 1종 이상을 포함할 수 있다. According to one embodiment, the MOF, for example ZIF-8 (Zn 2+ + 2 -methylimidazole), ZIF-67 (Co + + 2-methylimidazole), NH 2 -UiO-66 (Zr 4+ + 2-aminoterephthalic acid, and NH 2 -MIL-101 (Al 3+ + 2-aminoterephthalic acid). And may include one or more species.
보다 바람직하게, 상기 MOF는 ZIF-8(Zn2++2-methylimidazole)일 수 있다. More preferably, the MOF may be ZIF-8 (Zn 2+ + 2-methylimidazole).
도 1은 본 발명의 항균제에 포함되는 ZIF-8의 3차원 구조를 보여주는 모식도이다.  1 is a schematic diagram showing the three-dimensional structure of ZIF-8 contained in the antibacterial agent of the present invention.
도 1에 도시한 바와 같이, ZIF-8(Zn2++2-methylimidazole, C8H10N4Zn)는 다면체 (polyhedron) 구조를 나타내어, 평면 구조의 ZIF-L(C10H16N5Zn)과 구별된다. 본 발명에서는 특히, ZIF-8는 종래에 항균성이 없다고 알려진 바와 달리 우수한 항균성을 나타내고, 인체 독성이 없어 항균제로 유용하게 사용될 수 있음을 밝혀내었다. As shown in FIG. 1, ZIF-8 (Zn 2+ + 2-methylimidazole, C 8 H 10 N 4 Zn) exhibits a polyhedron structure and has a plane structure of ZIF-L (C 10 H 16 N 5 Zn). In the present invention, ZIF-8 exhibits excellent antimicrobial activity unlike conventional antimicrobial activity, and has no toxicity to humans and thus can be effectively used as an antibacterial agent.
상기 MOF를 포함하는 항균제는 항균성이 필요한 물품에 제한없이 사용될 수 있으며, 예를 들어, 자동차, 공조기, 에어컨, 공기청정기, 가습기, 마스크, 필터 등 다양한 제품에 적용될 수 있다.  The MOF-containing antimicrobial agent may be used in various products such as automobiles, air conditioners, air conditioners, air cleaners, humidifiers, masks, filters, and the like.
본 발명의 다른 일 구현예에 따르면, 상기 항균제를 포함하는 항균 필터를 제공한다.  According to another embodiment of the present invention, there is provided an antibacterial filter comprising the antibacterial agent.
상기 MOF에 대한 자세한 설명 및 구체적인 예시 물질 등은 상기 항균제에서 상술한 바와 같다.  A detailed description of the MOF and specific examples of the MOF are as described above for the antimicrobial agent.
상기 MOF는 부직포에 담지되어 효율적인 항균성을 나타낼 수 있다. 본 발명의 항균 필터는, 전기방사, 용융방사, 습식방사, 기재 상에 도포, 열압착 등 알려진 부직포 제조방법에 의해 제조될 수 있다.  The MOF may be carried on a nonwoven fabric to exhibit efficient antibacterial properties. The antibacterial filter of the present invention can be produced by a known nonwoven fabric manufacturing method such as electrospinning, melt spinning, wet spinning, application on a substrate, thermocompression bonding and the like.
본 발명의 일 실시예에 따르면, 항균 필터는 고분자 용액과 상기 MOF가 흔합된 방사 용액을 전기방사 (electrospinning)하여 제조한 것일 수 있으나, 본 발명이 이에 제한되는 것은 아니다.  According to an embodiment of the present invention, the antibacterial filter may be prepared by electrospinning a polymer solution and a spinning solution in which the MOF is mixed, but the present invention is not limited thereto.
전기방사는 정전기력에 의해 고분자 용액을 기재 (substrate) 위에 또는 기재없이 직접 섬유 형태로 방사하여 부직포 형태의 섬유 집합체를 얻는 방법이다.  Electrospinning is a method of obtaining a fibrous aggregate in the form of a nonwoven fabric by spinning the polymer solution directly onto the substrate or directly without the substrate by a static force.
본 발명의 일 실시예에 따르면, 상기 고분자 용액은, 고분자, 분산 용매, 분산제, 첨가제 등을포함할 수 있으나, 본 발명이 이에 제한되는 것은 아니다.  According to an embodiment of the present invention, the polymer solution may include a polymer, a dispersion solvent, a dispersant, an additive, and the like, but the present invention is not limited thereto.
본 발명의 일 실시예에 따르면, 상기 고분자는 폴리아크릴로니트릴 (poly acrylonitrile, PAN), 플루오르화 폴리비닐리덴 (polyvinylidene fluoride, PVDF), 폴리염화비닐 (polyvinyl chloride, PVC), 및 폴리에틸렌 테레프탈레이트 (polyethylene terephthalate, PET)로 이루어진 군으로부터 선택되는 1종 이상을 포함할 수 있으며, 바람직하게는 폴리아크릴로니트릴을 사용할 수 있으나 본 발명이 이에 제한되는 것은 아니다. According to one embodiment of the present invention, (1) selected from the group consisting of polyacrylonitrile (PAN), polyvinylidene fluoride (PVDF), polyvinyl chloride (PVC), and polyethylene terephthalate And polyacrylonitrile may be preferably used, but the present invention is not limited thereto.
또한, 본 발명의 일 실시예에 따르면, 상기 분산 용매로는 디메틸아세트아미드, 디에틸아세트아미드, 디메틸메특시아세트아미드, Nᅳ메틸피롤리돈, 디메틸포름아미드 등을 들 수 있으나, 본 발명이 이에 제한되는 것은 아니다.  In addition, according to one embodiment of the present invention, the dispersion solvent includes dimethylacetamide, diethylacetamide, dimethylmercaptacetamide, N-methylpyrrolidone, dimethylformamide, etc. However, But is not limited thereto.
한편, 본 발명의 일 실시예에 따르면, 상기 부직포는 고분자를 포함하는 고분자 용액과 MOF가 흔합된 방사 용액을 전기방사함으로써, 부직포를 제조함과 동시에 상기 부직포에. MOF가 담지된 형태로 수득될 수 있다.  According to an embodiment of the present invention, the nonwoven fabric may be produced by electrospinning a polymer solution containing a polymer and a spinning solution mixed with MOF, thereby producing a nonwoven fabric. MOF can be obtained in the form of supported.
본 발명의 일 실시예에 따르면, 상기 MOF는 부직포 100 중량부에 대하여, MOF를 약 10 중량부 이상, 또는 약 30 중량부 이상, 또는 약 50 중량부 이상이면서 약 95 중량부 이하, 또는 약 90 중량부 이하, 또는 약 85 중량부 이하로 포함할 수 있다. 상기 MOF가 너무 적게 포함되면 항균성이 저하될 수 있고, 너무 많이 포함될 경우 외부 풍량에 MOF 입자가 탈착될 수 있어, 이러한 관점에서 상기와 같은 중량부 범위로 포함되는 것이 바람직하다.  According to one embodiment of the present invention, the MOF may comprise at least about 10 parts by weight, or at least about 30 parts by weight, or at least about 50 parts by weight and at most about 95 parts by weight of MOF, Parts by weight or less, or about 85 parts by weight or less. If the MOF is included in an excessively small amount, the antibacterial property may be deteriorated. If the MOF is included too much, the MOF particles may be desorbed in the external air amount.
본 발명의 일 실시예에 따르면, 상기 MOF가 담지되기 전의 부직포의 비표면적은 약 0.1 m2/g 이상, 또는 약 5 m2/g 이상, 또는 약 8 m2/g 이상이면서, 약 50 m2/g 이하, 또는 약 30 m2/g 이하, 또는 약 20 m2/g 이하일 수 있다. 상기 부직포의 비표면적이 너무 적으면 표면에 부착되는 MOF의 양이 줄어들어 항균성이 저하될 수 있고, 너무 많으면 형성되는 부직포의 강도가 떨어질 수 있어 이러한 관점에서 상기 중량 범위를 갖는 것이 바람직하다. According to one embodiment of the present invention, the specific surface area of the nonwoven fabric before the MOF is supported is about 0.1 m 2 / g or more, or about 5 m 2 / g or more, or about 8 m 2 / 2 g or less, or about 30 m 2 / g or less, or about 20 m 2 / g or less. If the specific surface area of the nonwoven fabric is too small, the amount of MOF adhered to the surface of the nonwoven fabric may be reduced to lower the antibacterial property. If too large, the strength of the formed nonwoven fabric may decrease.
또한 본 발명의 일 실시예에 따르면, 상기 MOF가 담지된 후의 부직포의 비표면적은 담지되기 전보다 훨씬 증가하며, 예를 들어 약 50 m2/g 이상, 또는 약 70 m2/g 이상, 또는 약 80 m2/g 이상이면서, 약 200 m2/g 이하, 또는 약 180 m2/g 이하, 또는 약 150 m2/g 이하일 수 있다. 상기와 같이 다공성의 MOF가 담지되어 비표면적이 훨씬 증가함으로써 보다 우수한 항균성을 나타낼 수 있다. In addition, according to an embodiment of the present invention, the specific surface area of the nonwoven fabric after the MOF is supported is much higher than that before being supported, for example, about 50 m 2 / g Or about 70 m 2 / g or more, or about 80 m 2 / g or more, about 200 m 2 / g or less, or about 180 m 2 / g or less, or about 150 m 2 / g or less. Since the porous MOF is supported as described above, the specific surface area is much increased, so that it can exhibit better antimicrobial activity.
상기와 같은 본 발명의 MOF가 부직포에 담지된 항균 필터는, 인체에 무해하면서도 우수한 항균성을 나타내며, 특히 포도상구균, 대장균에 대해 99.9% 이상의 항균성을 나타낼 수 있다.  The antibacterial filter in which the MOF of the present invention is supported on the nonwoven fabric is harmless to the human body and exhibits excellent antibacterial activity, and can exhibit more than 99.9% of antibacterial activity against Staphylococcus aureus and Escherichia coli.
본 발명의 항균 필터의 제조방법에서, 먼저 MOF를 고분자 용액과 흔합하여 방사 용액을 제조한다. 이때 상기 MOF, 고분자 용액, 및 방사 용액에 대한 구체적인 설명 및 예시적인 물질은 앞서 항균 필터에서 설명한 바와 같다.  In the method for producing an antibacterial filter of the present invention, a spinning solution is first prepared by mixing MOF with a polymer solution. Here, the MOF, the polymer solution, and the spinning solution are described in detail with reference to the antibacterial filter.
이렇게 제조된 방사 용액을 기재 상에 전기방사하여 MOF가 부직포에 담지된 항균 필터를 제조할 수 있으나, 본 발명이 이에 제한되는 것은 아니다.  The spinning solution thus prepared may be electrospun on a substrate to produce an antibacterial filter having a MOF supported on a nonwoven fabric, but the present invention is not limited thereto.
또한 상기 전기방사는 부직포 제조방법으로 알려진 일반적인 방법 및 조건을 사용하여 수행할 수 있다.  The electrospinning can also be carried out using conventional methods and conditions known as nonwoven fabrication methods.
이하, 발명의 구체적안 실시예를 통해, 발명의 작용 및 효과를 보다 상술하기로, 한다. 다만, 이러한 실시예는 발명의 예시로 제시된 것에 불과하며, 이에 의해 발명의 권리범위가 정해지는 것은 아니다.  Best Mode for Carrying Out the Invention Hereinafter, the operation and effect of the present invention will be described in detail through specific embodiments of the present invention. It is to be understood, however, that these embodiments are merely illustrative of the invention and are not intended to limit the scope of the invention.
<실시예> <Examples>
실시예 1  Example 1
폴리아크릴로니트릴 (polyacrylonitrile, PAN), 32g, 디메틸아세트아미드 (dimethylacetamide) 30ml를 흔합하여 고분자 용액을 준비하였다.  32 mg of polyacrylonitrile (PAN) and 30 ml of dimethylacetamide were mixed to prepare a polymer solution.
ZIF-8(Zn2++2-methylimidazole) 20g을 상기 고분자 용액에 흔합하여 방사 용액을 준비하였다. 이를 전기방사법으로 방사하여 ZIF-8가 담지된 항균 필터 (비표면적 105 m2/g, 두께 500nm)를 제조하였다. 20 g of ZIF-8 (Zn 2+ + 2-methylimidazole) was added to the polymer solution to prepare a spinning solution. This was radiated by electrospinning to prepare an antibacterial filter (specific surface area 105 m 2 / g, thickness 500 nm) carrying ZIF-8.
제조된 부직포 필터를 주사전자현미경 (SEM)으로 관찰한 사진을 도 2에 나타내었다. 도 2를 참조하면, ZIF-8가 섬유에 담지된 형태인 부직포 항균 필터가 제조되었음을 확인할 수 있다. 실시예 2 FIG. 2 shows a photograph of the produced nonwoven filter with a scanning electron microscope (SEM). Referring to FIG. 2, it can be seen that a nonwoven fabric antibacterial filter having ZIF-8 supported on fibers was produced. Example 2
MOF로 ZIF-8(Zn2++2-methylimidazole) 20g 대신 ZIF-67Instead of 20 g of ZIF-8 (Zn 2+ + 2-methylimidazole) as MOF, ZIF-67
(Co2++2-methylimidazole) 20g을 사용한 것을 제외하고는 실시예 1과 동일한 방법으로 MOF가 담지된 항균 필터를 제조하였다. 실시예 3 (Co 2+ + 2-methylimidazole) was used in place of 20 g of CO 2 + 2-methylimidazole. Example 3
MOF로 ZIF-8(Zn2++2-methylimidazole) 20g 대신 NH2-UiO-66 Instead of 20 g of ZIF-8 (Zn 2+ + 2- methylimidazole) as MOF, NH 2 -UiO- 66
(Zr4++2-aminoterephthalic acid) 20g을 사용한 것을 제외하고는 실시예 1과 동일한 방법으로 MOF가 담지된 항균 필터를 제조하였다. 실시예 4 (Zr 4+ + 2-aminoterephthalic acid) was used as the antimicrobial filter. Example 4
MOF로 ZIF-8(Zn2++2-methylimidazole) 20g 대신 NH2-MIL-101ZIF-8 by MOF (Zn 2+ + 2-methylimidazole ) 20g instead NH 2 -MIL-101
(Al3++2-aminoterephthalic acid) 20g을 사용한 것을 제외하고는 실시예 1과 동일한 방법으로 MOF가 담지된 항균 필터를 제조하였다. (Al 3+ + 2-aminoterephthalic acid) was used as the antimicrobial filter.
<실험예 > <Experimental Example>
실시예 1 내지 4의 항균 필터에 대하여, 하기 방법으로 항균성을 측정하였다.  The antibacterial properties of the antibacterial filters of Examples 1 to 4 were measured by the following methods.
KS K 0693:2011법에 따라 각각 비이온 계면활성제 TWEEN 80을 0.05% 첨가한 대장균 (Escherichia coli ATCC 25922) 접종 균액과 황색포도상구균 (staphylococcus aureus ATCC 6538) 접종 균액을 각각 배지에 접종한 후, 배지 상부에 실시예 1 내지 4의 필터를 부착한 후 18시간 동안 세균을 배양하였다.  According to KS K 0693: 2011, Escherichia coli ATCC 25922 inoculated with 0.05% of non-ionic surfactant TWEEN 80 and inoculum of staphylococcus aureus ATCC 6538 were inoculated into the medium, After the filters of Examples 1 to 4 were attached to the upper portion, bacteria were cultured for 18 hours.
MOF 처리하지 않은 미생물 배지 위에 대장균과 황색포도상구균을 각각 접종한후, 18시간동안 세균을 배양하여 비교예 1로 사용하였다.  Escherichia coli and Staphylococcus aureus were inoculated on the microorganism medium not treated with MOF, and the bacteria were cultured for 18 hours and used as Comparative Example 1. [
18시간 경과 후, 남아있는 세균의 숫자를 미생물 배지와 비교하여 대장균과 황색포도상구균의 제거율을 측정한 결과, 본 발명의 실시예 1 내지 4의 부직포 필터는 대장균과 황색포도상구균을 99.9% 이상 제거한 것으로 확인하였다. After 18 hours, the number of the remaining bacteria was compared with the microbial culture medium, and the removal rates of E. coli and S. aureus were measured. As a result, 4 nonwoven filter was found to remove more than 99.9% of E. coli and S. aureus.
도 3은 본 발명의 실시예 1 내지 4의 부직포 필터 및 비교예의 배지에 대해 황색포도상구균 접종 후 18시간 후의 사진을 보여주는 도면이다.  3 is a photograph showing 18 hours after the inoculation of Staphylococcus aureus against the nonwoven fabric filter and the comparative example medium of Examples 1 to 4 of the present invention.
도 4는 본 발명의 실시예 1 내지 4의 부직포 필터 및 비교예의 배지에 대해 대장균 접종 후 18시간 후의 사진을 보여주는 도면이다.  4 is a photograph showing the photographs of the nonwoven fabric filters of Examples 1 to 4 and Comparative Example medium after 18 hours from inoculation with E. coli.
도 3 및 4를 참고하면, 비교예 1의 배지에는 황색포도상구균 및 대장균이 번식하였으나 실시예 1 내지 4의 부직포 필터는 대장균과 황색포도상구균의 번식을 억제하여 우수한 항균성이 있음을 확인할 수 있었다.  3 and 4, although Staphylococcus aureus and Escherichia coli were propagated in the medium of Comparative Example 1, the nonwoven fabric filters of Examples 1 to 4 suppressed the growth of Escherichia coli and Staphylococcus aureus, indicating excellent antimicrobial activity.

Claims

[특허청구범위] [Claims]
【청구항 1】  [Claim 1]
MOF(Metal-organic framework)를 포함하는 항균제로,  It is an antimicrobial agent containing MOF (Metal-organic framework)
상기 MOF는 Zn, Co, A1, 및 Zr로 이루어진 군으로부터 선택되는 1종 이상의 금속 이온과, 이미다졸 (imidazole), 알킬이미다졸 (alkylimidazole), 알콕시이미다졸 (alkoxyimidazole), 테레프탈산 (terephthalic acid), 및 아미노테레프탈산 (aminoterephthalic acid)으로 이루어진 군으로부터 선택되는 1종 이상의 유기 리간드를 포함하는, 항균제.  The MOF may include one or more metal ions selected from the group consisting of Zn, Co, Al, and Zr and at least one metal ion selected from the group consisting of imidazole, alkylimidazole, alkoxyimidazole, terephthalic acid, , And at least one organic ligand selected from the group consisting of aminoterephthalic acid.
【청구항 2】 [Claim 2]
제 1항에 있어서,  The method according to claim 1,
상기 MOF는 ZIF-8(Zn2++2-methylimidazole),The MOF is ZIF-8 (Zn 2+ + 2-methylimidazole),
ZIF-67(Co2++2-methylimidazole), NH2-UiO-66(Zr4++2-aminoterephthalic acid), 및 NH2-MIL- 101 (Al3++2-aminoterephthalic acid)로 이루어진 군으로부터 선택되는 1종 이상을 포함하는, 항균제. ZIF-67 (Co 2+ + 2-methylimidazole), NH 2 -UiO-66 (Zr 4+ + 2-aminoterephthalic acid), and NH 2 -MIL-101 (Al 3+ + 2-aminoterephthalic acid) Wherein the antimicrobial agent is at least one selected from the group consisting of:
【청구항 3】 [Claim 3]
제 1항의 항균제를 포함하는, 항균 필터.  An antibacterial filter comprising the antibacterial agent of claim 1.
【청구항 4】 Claim 4
게 3항에 있어서,  In Item 3,
상기 항균제는 부직포에 담지된, 항균 필터.  Wherein the antibacterial agent is supported on a nonwoven fabric.
【청구항 5】 [Claim 5]
제 4항에 있어서,  5. The method of claim 4,
상기 MOF는 상기 부직포 100 중량부에 대하여 10 내지 95 중량부로 포함되는, 항균 필터.  Wherein the MOF is contained in an amount of 10 to 95 parts by weight based on 100 parts by weight of the nonwoven fabric.
【청구항 6】 [Claim 6]
제 4항에 있어서, 상기 MOF가 담지된 부직포의 비표면적은, 50 내지 200 m2/g인, 항균 필터. 5. The method of claim 4, The specific surface area of the MOF-supported nonwoven fabric is 50 to 200 m 2 / g.
PCT/KR2018/008643 2017-07-28 2018-07-30 Antimicrobial agent comprising mof and antimicrobial filter comprising same WO2019022588A2 (en)

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