KR20220102204A - Antibacterial and antiviral CuBTC-PMF and its manufacturing method - Google Patents
Antibacterial and antiviral CuBTC-PMF and its manufacturing method Download PDFInfo
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- 230000000844 anti-bacterial effect Effects 0.000 title claims abstract description 19
- 230000000840 anti-viral effect Effects 0.000 title claims abstract description 18
- 238000004519 manufacturing process Methods 0.000 title claims description 8
- DHOBEDGRIOTEBA-UHFFFAOYSA-N benzene-1,3,5-tricarboxylic acid;copper Chemical compound [Cu].OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 DHOBEDGRIOTEBA-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000010949 copper Substances 0.000 claims description 31
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims description 16
- 229910001431 copper ion Inorganic materials 0.000 claims description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- WSFSSNUMVMOOMR-UHFFFAOYSA-N formaldehyde Substances O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 11
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- 238000000034 method Methods 0.000 claims description 8
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- 239000000126 substance Substances 0.000 claims description 5
- 239000002184 metal Substances 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 239000013148 Cu-BTC MOF Substances 0.000 claims 1
- NOSIKKRVQUQXEJ-UHFFFAOYSA-H tricopper;benzene-1,3,5-tricarboxylate Chemical compound [Cu+2].[Cu+2].[Cu+2].[O-]C(=O)C1=CC(C([O-])=O)=CC(C([O-])=O)=C1.[O-]C(=O)C1=CC(C([O-])=O)=CC(C([O-])=O)=C1 NOSIKKRVQUQXEJ-UHFFFAOYSA-H 0.000 claims 1
- 229920000877 Melamine resin Polymers 0.000 abstract 1
- 239000003443 antiviral agent Substances 0.000 abstract 1
- IVJISJACKSSFGE-UHFFFAOYSA-N formaldehyde;1,3,5-triazine-2,4,6-triamine Chemical compound O=C.NC1=NC(N)=NC(N)=N1 IVJISJACKSSFGE-UHFFFAOYSA-N 0.000 abstract 1
- 238000002360 preparation method Methods 0.000 abstract 1
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- 229910052802 copper Inorganic materials 0.000 description 17
- 241000894006 Bacteria Species 0.000 description 15
- 241000700605 Viruses Species 0.000 description 15
- QMKYBPDZANOJGF-UHFFFAOYSA-N benzene-1,3,5-tricarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 QMKYBPDZANOJGF-UHFFFAOYSA-N 0.000 description 11
- 239000012621 metal-organic framework Substances 0.000 description 10
- 230000000694 effects Effects 0.000 description 8
- 230000001954 sterilising effect Effects 0.000 description 7
- 238000004659 sterilization and disinfection Methods 0.000 description 7
- 241000588724 Escherichia coli Species 0.000 description 6
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- ZOQOMVWXXWHKGT-UHFFFAOYSA-N benzene-1,3,5-tricarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1.OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 ZOQOMVWXXWHKGT-UHFFFAOYSA-N 0.000 description 1
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION 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
- A01N59/00—Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
- A01N59/16—Heavy metals; Compounds thereof
- A01N59/20—Copper
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- F24—HEATING; RANGES; VENTILATING
- F24F—AIR-CONDITIONING; AIR-HUMIDIFICATION; VENTILATION; USE OF AIR CURRENTS FOR SCREENING
- F24F1/00—Room units for air-conditioning, e.g. separate or self-contained units or units receiving primary air from a central station
- F24F1/02—Self-contained room units for air-conditioning, i.e. with all apparatus for treatment installed in a common casing
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Abstract
Description
본 발명은 항균·항바이러스용 CuBTC-PMF 및 이의 제조방법에 관한 것으로, 상세하게는 폴리멜라민-포름알데히드(Polymelamine-formaldehyde, PMF) 표면에 코팅된 구리-1,3,5-벤젠트리카르복실산(Cu-1,3,5-Benzenetricarboxylic acid, Cu-BTC)을 포함하는 신규한 항균·항바이러스 물질과 PMF에 코팅하는 방법에 관한 것이다. The present invention relates to an antibacterial/antiviral CuBTC-PMF and a method for manufacturing the same, and more particularly, to a copper-1,3,5-benzenetricarboxyl coated on a polymelamine-formaldehyde (PMF) surface. It relates to a novel antibacterial and antiviral material containing acid (Cu-1,3,5-Benzenetricarboxylic acid, Cu-BTC) and a method for coating it on PMF.
최근 코로나바이러스로 인해 전 세계적으로 감염자와 사망자가 속출하면서 대유행으로 번지는 추세로서 실내 공기질에 대한 관심이 높아지고 있다. 현재 공기청정기는 바이러스와 세균을 처리할 수 있는 특화 공정이 없는 상황으로 항균 및 항바이러스 처리가 가능한 필터 또는 장치를 보유하고 있는 청정기 개발이 절실하다. Recently, as the number of infections and deaths worldwide due to the coronavirus has spread to a pandemic, interest in indoor air quality is increasing. Currently, there is no specialized process for treating viruses and bacteria in air purifiers, so it is urgent to develop a purifier with a filter or device capable of antibacterial and antiviral treatment.
일반적으로 구리의 항균·항바이러스 기능은 잘 알려져 있으며, 구리에 의한 세균 및 바이러스 살처분은 두 가지 메커니즘으로 설명하고 있다. 첫째, 구리와 병원균의 직접 접촉에 의한 살균(예, 세포막이 구리이온에 의해 비극성화되면서 파괴), 둘째, 구리에 의해 생성되는 반응성이 탁월한 산화제(예, 하이드록실 라디칼)에 의한 살균 효과를 꼽을 수 있다.In general, the antibacterial and antiviral functions of copper are well known, and the killing of bacteria and viruses by copper is explained by two mechanisms. First, sterilization by direct contact between copper and pathogens (e.g., cell membrane is depolarized and destroyed by copper ions), and secondly, sterilization effect by highly reactive oxidizing agents (e.g., hydroxyl radicals) generated by copper. can
하지만, 구리는 대기 중에 노출되면 산화되면서 기능을 상실하는 사례가 많고, 나노 형태의 구리는 뭉치는 현상이 발생하는 문제가 있어, 여전히 기술 개발이 요구되고 있는 실정이다. However, there are many cases where copper loses its function while being oxidized when exposed to the atmosphere, and there is a problem that nano-type copper has aggregation phenomenon, which is a situation in which technology development is still required.
따라서, 본 발명은 상기한 실정을 고려하여 종래 기술들에서 야기되는 여러 가지 결점 및 문제점들을 해결하고자 하는 것으로서, 구리이온(Cu2+)과 H3BTC를 반응시켜 금속 유기체(Metal-organic framework, MOF)인 CuBTC 적용하여 산화되는 문제와 뭉치는 문제를 해결하는 것을 목적으로 한다. Therefore, the present invention is to solve various drawbacks and problems caused by the prior art in consideration of the above circumstances, by reacting copper ions (Cu 2+ ) and H 3 BTC to form a metal-organic framework (Metal-organic framework, It aims to solve the problem of oxidation and agglomeration by applying CuBTC, which is MOF).
또한, CuBTC는 분말형태여서 직접 적용하기 어려운 문제를 기질인 PMF에 CuBTC를 코팅하여 분말형태 운영으로 인한 CuBTC의 손실을 줄이고 구리의 산화를 방지하여 세균 및 바이러스의 안정적 처리를 가능케 하는 것을 목적으로 한다. In addition, CuBTC is in powder form, so it is difficult to apply directly. By coating CuBTC on PMF, which is a substrate, the loss of CuBTC due to powder form operation is reduced and copper oxidation is prevented, thereby enabling stable treatment of bacteria and viruses. .
본 발명이 해결하고자 하는 과제들은 이상에서 언급된 과제로 제한되지 않으며, 언급되지 않은 또 다른 과제들은 아래의 기재로부터 통상의 기술자에게 명확하게 이해될 수 있을 것이다. The problems to be solved by the present invention are not limited to the problems mentioned above, and other problems not mentioned will be clearly understood by those skilled in the art from the following description.
상기와 같은 목적을 달성하기 위하여, 본 발명의 일 실시예에 따르면, 폴리멜라민-포름알데히드(Polymelamine-formaldehyde, PMF) 표면에 코팅된 구리-1,3,5-벤젠트리카르복실산(Cu-1,3,5-Benzenetricarboxylic acid, Cu-BTC)을 포함하는, 항균·항바이러스 물질이 제공된다. In order to achieve the above object, according to an embodiment of the present invention, copper-1,3,5-benzenetricarboxylic acid (Cu-) coated on the surface of polymelamine-formaldehyde (PMF) 1,3,5-Benzenetricarboxylic acid (Cu-BTC) containing, antibacterial and antiviral substances are provided.
본 발명의 일 실시예에 따르면, 상기 구리-1,3,5-벤젠트리카르복실산(Cu-1,3,5-Benzenetricarboxylic acid)는, 구리이온(Cu+2)과 H3BTC를 반응시켜 제조한 금속 유기체일 수 있다. According to an embodiment of the present invention, the copper-1,3,5-benzenetricarboxylic acid (Cu-1,3,5-Benzenetricarboxylic acid) is a copper ion (Cu +2 ) and H 3 BTC reaction It may be a metal organism prepared by
본 발명의 다른 일 실시예에 따르면, 전술한 항균·항바이러스 물질을 포함하는 공기청정기가 제공된다. According to another embodiment of the present invention, there is provided an air purifier comprising the above-described antibacterial/antiviral material.
본 발명의 또 다른 일 실시예에 따르면, 전구물질 Cu(NO3)2, H3BTC, 및 PEG-200를 폴리멜라민-포름알데히드에 반복적으로 도포하는 단계; 및 미반응물을 에탄올로 제거하는 단계;를 포함하는 항균·항바이러스용 CuBTC-PMF의 제조방법이 제공된다. According to another embodiment of the present invention, the precursor Cu(NO 3 ) 2, H 3 BTC, and repeatedly applying PEG-200 to polymelamine-formaldehyde; And there is provided a method for producing CuBTC-PMF for antibacterial and antiviral comprising; and removing the unreacted material with ethanol.
본 발명의 일 실시예에 따르면, 상기 도포하는 단계는 50 내지 100℃에서 수행되는 것일 수 있다.According to an embodiment of the present invention, the applying may be performed at 50 to 100 °C.
아울러, 본 발명의 또 다른 일 실시예에 따르면, 전술한 방법에 의해 제조된 항균·항바이러스용 CuBTC-PMF가 제공된다. In addition, according to another embodiment of the present invention, there is provided an antibacterial/antiviral CuBTC-PMF prepared by the above-described method.
본 발명은, 구리가 BTC MOF에서 분리되어 용출이 쉽게 일어나지 않아 구리의 독성 효과를 낮출 수 있는 효과가 있어 보다 광범위하고 융통성 있게 적용할 수 있는 이점이 있다. The present invention has the advantage that copper is separated from the BTC MOF and elution does not occur easily, thereby lowering the toxic effect of copper, so that it can be applied more broadly and flexibly.
또한, CuBTC는 표면적이 넓어, 대기 중의 세균과 바이러스의 흡착력이 높고, CuBTC MOF 구조 내부에 세균과 바이러스를 포획한 다음, CuBTC MOF에서 방출된 구리이온이 포획된 세균과 바이러스를 살처분할 수 있는 이점이 있다. In addition, CuBTC has a large surface area, so it has high adsorption capacity for bacteria and viruses in the atmosphere, and it is possible to trap bacteria and viruses inside the CuBTC MOF structure, and then the copper ions released from CuBTC MOF can sterilize the captured bacteria and viruses. There is an advantage.
또한, CuBTC는 구리이온의 저장소이며, 평형 상태를 유지하면서 지속적으로 소량의 구리이온을 방출하여 환경에 미치는 영향을 최소화하면서 지속적인 살균 효과를 제공할 수 있다. In addition, CuBTC is a storage of copper ions, and it can provide a continuous sterilization effect while maintaining an equilibrium state and continuously releasing a small amount of copper ions, minimizing the impact on the environment.
또한, CuBTC는 합성 조건에 따라 공극 크기 조절이 가능하여 처분 대상 세균과 바이러스에 적합한 공극으로 제조하여 선택적으로 세균과 바이러스 처분이 가능하다. In addition, CuBTC can control the pore size according to the synthesis conditions, so it is possible to selectively dispose of bacteria and viruses by preparing pores suitable for the bacteria and viruses to be disposed of.
본 발명의 효과들은 이상에서 언급된 효과로 제한되지 않으며, 언급되지 않은 또 다른 효과들은 아래의 기재로부터 통상의 기술자에게 명확하게 이해될 수 있을 것이다.Effects of the present invention are not limited to the effects mentioned above, and other effects not mentioned will be clearly understood by those skilled in the art from the following description.
도 1은 구리이온(Cu+2)과 H3BTC(1,3,5-Benzenetricarboxylic acid)가 결합하여 CuBTC 생성된 형태의 모식도이다.
도 2는 PMF 기질에 구리-1,3,5-벤젠트리카르복실산(Cu-1,3,5-Benzenetricarboxylic acid, Cu-BTC)를 도포하는 방식의 모식도이다.
도 3은 PMF, 구리, BTC를 합성하여 CuBTC/PMF를 제조하는 반응 메커니즘이다.
도 4는 본 발명의 일 실시예에 따른 CuBTC-PMF의 제조방법의 순서도이다.
도 5는 본 발명에 적용할 수 있는 롤링 기계의 실제 사진이다.
도 6은 CuBTC에 의한 세균 및 바이러스 살처분 메커니즘이다.
도 7은 수직형 플러그 흐름 반응기로서 시스템을 개략적으로 나타낸 도면이다.
도 8은 PMF와 Cu-BTC-PMF의 대장균 살균 효과를 비교 실험한 결과이다. 1 is a schematic diagram of CuBTC produced by combining copper ions (Cu+2) and H3BTC (1,3,5-Benzenetricarboxylic acid).
Figure 2 is a schematic diagram of a method of applying copper-1,3,5-benzenetricarboxylic acid (Cu-1,3,5-Benzenetricarboxylic acid, Cu-BTC) to the PMF substrate.
3 is a reaction mechanism for preparing CuBTC/PMF by synthesizing PMF, copper, and BTC.
4 is a flowchart of a method of manufacturing CuBTC-PMF according to an embodiment of the present invention.
5 is an actual photograph of a rolling machine applicable to the present invention.
6 is a bacterial and viral killing mechanism by CuBTC.
7 is a schematic representation of the system as a vertical plug flow reactor.
8 is a result of a comparative experiment on the E. coli sterilization effect of PMF and Cu-BTC-PMF.
이하, 본 발명에 대하여 상세히 설명하기로 한다. 이에 앞서, 본 명세서 및 특허청구범위에 사용된 용어 또는 단어는 통상적이거나 사전적인 의미로 한정해서 해석되어서는 아니되며, 발명자는 그 자신의 발명을 가장 최선의 방법으로 설명하기 위해 용어의 개념을 적절하게 정의할 수 있다는 원칙에 입각하여 본 발명의 기술적 사상에 부합하는 의미와 개념으로 해석되어야만 한다. 따라서, 본 명세서에 기재된 실시예에 기재된 구성은 본 발명의 가장 바람직한 일 실시예에 불과할 뿐이고 본 발명의 기술적 사상을 모두 대변하는 것은 아니므로, 본 출원시점에 있어서 이들을 대체할 수 있는 다양한 균등물과 변형예들이 있을 수 있음을 이해하여야 한다.Hereinafter, the present invention will be described in detail. Prior to this, the terms or words used in the present specification and claims are not to be construed as being limited to their ordinary or dictionary meanings, and the inventor must properly understand the concept of the term in order to best describe his invention. It should be interpreted as meaning and concept consistent with the technical idea of the present invention based on the principle that it can be defined in Therefore, the configuration described in the embodiment described in this specification is only the most preferred embodiment of the present invention and does not represent all of the technical idea of the present invention, so various equivalents and It should be understood that there may be variations.
본 명세서 전체에 걸쳐서 폴리멜라민-포름알데히드((Polymelamine-formaldehyde)는 폴리멜라민-포름알데히드 또는 PMF로 혼용하여 사용된다. Throughout this specification, polymelamine-formaldehyde (Polymelamine-formaldehyde) is used interchangeably with polymelamine-formaldehyde or PMF.
또한, 1,3,5-벤젠트리카르복실산(1,3,5-Benzenetricarboxylic acid)는 1,3,5-벤젠트리카르복실산 또는 BTC로 혼용되어 사용되며, 구리-1,3,5-벤젠트리카르복실산(Cu-1,3,5-Benzenetricarboxylic acid)는 구리-1,3,5-벤젠트리카르복실산, Cu-BTC 또는 CuBTC로 혼용되어 사용된다. In addition, 1,3,5-benzenetricarboxylic acid (1,3,5-Benzenetricarboxylic acid) is used in combination with 1,3,5-benzenetricarboxylic acid or BTC, copper-1,3,5 -Benzenetricarboxylic acid (Cu-1,3,5-Benzenetricarboxylic acid) is used in combination with copper-1,3,5-benzenetricarboxylic acid, Cu-BTC or CuBTC.
본 발명의 일 실시예에 따라, 폴리멜라민-포름알데히드(Polymelamine-formaldehyde, PMF) 표면에 코팅된 구리-1,3,5-벤젠트리카르복실산(Cu-1,3,5-Benzenetricarboxylic acid, Cu-BTC)을 포함하는, 항균·항바이러스 물질이 제공된다. 도 1은 구리이온(Cu+2)과 H3BTC(1,3,5-Benzenetricarboxylic acid)가 결합하여 CuBTC 생성된 형태의 모식도이다. 도 1을 참조하면, 구리-1,3,5-벤젠트리카르복실산(Cu-1,3,5-Benzenetricarboxylic acid)는, 구리이온(Cu+2)과 H3BTC를 반응시켜 제조한 금속 유기체로 MOF인 CuBTC를 적용하면, 종래 구리가 대기 중에 노출되면 산화되면서 기능을 상실하고, 나노 형태 구리는 뭉치는 현상을 해결할 수 있다. According to an embodiment of the present invention, polymelamine-formaldehyde (PMF) coated on the surface of copper-1,3,5-benzenetricarboxylic acid (Cu-1,3,5-Benzenetricarboxylic acid, Cu-BTC) containing, antibacterial and antiviral substances are provided. 1 is a schematic diagram of CuBTC produced by combining copper ions (Cu +2 ) and H 3 BTC (1,3,5-Benzenetricarboxylic acid). 1, copper-1,3,5-benzenetricarboxylic acid (Cu-1,3,5-Benzenetricarboxylic acid) is a metal prepared by reacting copper ions (Cu +2 ) and H 3 BTC When CuBTC, which is a MOF, is applied as an organism, copper loses its function as it oxidizes when exposed to the atmosphere, and nano-type copper can solve the aggregation phenomenon.
한편, 도 2는 PMF 기질에 구리-1,3,5-벤젠트리카르복실산(Cu-1,3,5-Benzenetricarboxylic acid, Cu-BTC)를 도포하는 방식의 모식도로, 도 2를 참조하면, 기질인 PMF에 CuBTC를 코팅하여 적용함으로써, 종래 분말형태 운영으로 인한 CuBTC의 손실을 줄이고 구리의 산화를 방지하여 세균 및 바이러스의 안정적 처리가 가능하다. On the other hand, FIG. 2 is a schematic diagram of a method of applying copper-1,3,5-benzenetricarboxylic acid (Cu-1,3,5-Benzenetricarboxylic acid, Cu-BTC) to a PMF substrate. Referring to FIG. , by coating CuBTC on PMF, a substrate, to reduce CuBTC loss due to conventional powder-type operation and prevent oxidation of copper, enabling stable treatment of bacteria and viruses.
도 3은 PMF, 구리, BTC를 합성하여 CuBTC/PMF를 제조하는 반응 메커니즘으로, 기질인 PMF에 구리이온(Cu+2)을 도포하면, PMF-구리이온(Cu+2) 복합체가 형성되고 이후, BTC(1,3,5-Benzenetricarboxylic acid)가 구리이온(Cu+2)과 결합하면서, 최종적으로 CuBTC-PMF가 형성된다. 3 is a reaction mechanism for preparing CuBTC/PMF by synthesizing PMF, copper, and BTC. When copper ions (Cu +2 ) are applied to PMF, which is a substrate, a PMF-copper ion (Cu +2 ) complex is formed and then , while BTC (1,3,5-Benzenetricarboxylic acid) is combined with copper ions (Cu +2 ), CuBTC-PMF is finally formed.
도 4는 본 발명의 일 실시예에 따른 CuBTC-PMF의 제조방법의 순서도이다. 도 4를 참조하면, 본 발명의 다른 일 실시예에 따라, 전구물질 Cu(NO3)2, H3BTC, 및 PEG-200를 폴리멜라민-포름알데히드에 반복적으로 도포하는 단계(S10) 및 미반응물을 에탄올로 제거하는 단계(S20)을 포함하는 항균·항바이러스용 CuBTC-PMF의 제조방법이 제공된다. 4 is a flowchart of a method of manufacturing CuBTC-PMF according to an embodiment of the present invention. Referring to Figure 4, according to another embodiment of the present invention, the precursor Cu(NO 3 ) 2, H 3 BTC, and repeatedly applying PEG-200 to polymelamine-formaldehyde (S10) and Mi There is provided a method for producing CuBTC-PMF for antibacterial and antiviral comprising the step (S20) of removing the reactant with ethanol.
이때, 전구물질 Cu(NO3)2, H3BTC, 및 PEG-200를 폴리멜라민-포름알데히드에 반복적으로 도포하는 단계(S10)는, 도 2와 같이 PMF를 롤링 기계에 연속적으로 투입하면서 CuBTC 전구물질을 PMF 도포하는 것으로, 이때 상기 CuBTC 전구물질은 Cu(NO3)2, H3BTC, PEG-200이며, 이를 PMF 폼(Foam)에 코팅하는 방식이다. 한편 도 5는 본 발명에 적용할 수 있는 롤링 기계의 실제 사진으로, PMF를 롤링 기계에 연속적으로 투입하면서 전구물질을 도포할 수 있으며, 이때, 속도는 10 내지 20 rpm 이거나 바람직하게는 15 rpm일 수 있으며 상기 속도 범위를 만족하는 경우 CuBTC 물질이 뭉치지 않고 PMF 폼에 균일하게 코팅될 수 있다. At this time, the step (S10) of repeatedly applying the precursor Cu(NO 3 ) 2, H 3 BTC, and PEG-200 to polymelamine-formaldehyde is CuBTC while continuously adding PMF to the rolling machine as shown in FIG. 2 . The precursor is applied to PMF, in which case the CuBTC precursor is Cu(NO 3 ) 2 , H 3 BTC, and PEG-200, which is coated on PMF foam. On the other hand, Figure 5 is an actual photograph of a rolling machine applicable to the present invention, it is possible to apply the precursor while continuously inputting PMF into the rolling machine, at this time, the speed is 10 to 20 rpm or preferably 15 rpm and if the speed range is satisfied, the CuBTC material may be uniformly coated on the PMF foam without agglomeration.
상기 도포하는 단계는 50 내지 100℃에서 수행될 수 있으며, 바람직하게는 80℃에서 수행될 수 있고, 상기 온도 범위를 만족하는 경우 전구물질의 변형되지 않으면서 PMF 폼에 균일하게 코팅될 수 있기 때문이다. The applying step may be performed at 50 to 100 ° C., preferably at 80 ° C., since it can be uniformly coated on the PMF foam without deformation of the precursor when the temperature range is satisfied. to be.
한편, 상기 PMF를 롤링 기계에 연속적으로 투입하면서 CuBTC 전구물질을 PMF 도포하는 단계는 반복적으로 수행될 수 있으며, 이는 CuBTC는 표면적이 넓혀 대기 중의 세균과 바이러스의 흡착력이 높히기 위함이다. On the other hand, the step of applying PMF to the CuBTC precursor while continuously introducing the PMF to the rolling machine may be repeatedly performed, in order to increase the surface area of CuBTC to increase the adsorption power of bacteria and viruses in the air.
도 6은 CuBTC에 의한 세균 및 바이러스 살처분 메커니즘으로, CuBTC MOF 구조 내부에 세균과 바이러스를 포획한 다음, CuBTC MOF에서 방출된 구리이온이 포획된 세균과 바이러스를 살처분할 수 있다. 6 is a mechanism for killing bacteria and viruses by CuBTC. After capturing bacteria and viruses in the CuBTC MOF structure, copper ions released from the CuBTC MOF can kill the captured bacteria and viruses.
일반적으로 구리는 독성이 있는 물질로서 금속 상태의 경우 수용액에서 농도를 0.05g/L 이하로 규정하고 있는 반면에 CuBTC는 10g/L 이하에서는 유해하지 않은 것으로 알려졌다. 즉 구리가 BTC MOF에서 분리되어 용출이 쉽게 일어나지 않음을 시사하고 있다. 그러므로 본 발명에 따른 CuBTC-PMF는 구리의 독성 효과를 낮출 수 있는 효과가 있어 보다 광범위하고 융통성 있게 적용할 수 있다.In general, copper is a toxic substance, and in the case of a metallic state, the concentration in aqueous solution is stipulated to be 0.05 g/L or less, whereas CuBTC is known not to be harmful if it is 10 g/L or less. That is, copper is separated from the BTC MOF, suggesting that elution does not occur easily. Therefore, CuBTC-PMF according to the present invention has the effect of lowering the toxic effect of copper, so it can be applied more widely and flexibly.
또한, CuBTC는 구리이온의 저장소이며, 평형 상태를 유지하면서 지속적으로 소량의 구리이온을 방출하여 환경에 미치는 영향을 최소화하면서 지속적인 살균 효과를 갖게 된다. In addition, CuBTC is a storage of copper ions, and while maintaining an equilibrium state, it continuously releases a small amount of copper ions to have a continuous sterilization effect while minimizing the impact on the environment.
한편, CuBTC는 합성 조건에 따라 공극 크기 조절이 가능하여 처분 대상 세균과 바이러스에 적합한 공극으로 제조하여 선택적으로 세균과 바이러스 처분이 가능하다.On the other hand, CuBTC can control the pore size according to the synthesis conditions, so it is possible to selectively dispose of bacteria and viruses by making pores suitable for the bacteria and viruses to be disposed of.
상기 미반응물을 에탄올로 제거하는 단계(S20)는, 반복적으로 도포 작업을 수행하여 CuBTC-PMF를 완성하고 미반응물은 에탄올로 제거하는 단계로 CuBTC-PMF의 순도를 높이는 단계이다. The step (S20) of removing the unreacted material with ethanol is a step of increasing the purity of CuBTC-PMF by repeatedly performing a coating operation to complete CuBTC-PMF and removing the unreacted material with ethanol.
도 7은 수직형 플러그 흐름 반응기로서 시스템을 개략적으로 나타낸 도면이다.7 is a schematic representation of the system as a vertical plug flow reactor.
한편, 본 발명의 다른 일 실시예에 따라 전술한 CuBTC-PMF를 포함하는 필터, 여과막, 여과기, 공기청정기, 에어컨 등이 제공될 수 있다. Meanwhile, according to another embodiment of the present invention, a filter, a filtration membrane, a filter, an air purifier, an air conditioner, etc. including the above-described CuBTC-PMF may be provided.
이하, 실시예를 통해 본 발명을 더욱 상술하나 하기 실시예에 의해 본 발명이 제한되지 아니함은 자명하다.Hereinafter, the present invention will be described in more detail by way of Examples, but it is obvious that the present invention is not limited by the Examples.
실시예Example
PMF를 80℃ 롤링 기계(Hot Rolling Machine MSK-HRP-01)에 15rpm 속도로 연속적으로 투입하면서, 전구물질(Cu(NO3)2(2.16g), H3BTC(2.16g), PEG-200(1㎖))을 도포하여 코팅하였다. 이후, 도포 작업을 5회 반복한 후, 미반응물을 에탄올로 제거하여 CuBTC-PMF을 제조하였다.Precursors (Cu(NO 3 ) 2 (2.16 g), H 3 BTC (2.16 g), PEG-200 while continuously adding PMF to an 80° C. rolling machine (Hot Rolling Machine MSK-HRP-01) at a speed of 15 rpm (1 mL)) was applied and coated. Then, after repeating the coating operation 5 times, the unreacted material was removed with ethanol to prepare CuBTC-PMF.
도 8은 PMF와 Cu-BTC-PMF의 대장균 살균 효과를 비교 실험한 결과로서 도 8은 에어로졸 상태로 대장균을 PMF와 CuBTC-PMF에 분사 접촉시킨 다음 시간별로 대장균 증식 상황을 관찰한 것으로 시간에 따라(접촉 이후 2, 17, 32, 47분 경과) 대장균 개체수가 감소하는 것을 도시하고 있다. 비교예인 PMF에서는 대장균 개체수 감소가 47분 경과한 경우 초기 개체 수 대비하여 49% 정도가 감소한 것으로 나타났다. 그러나 실제로는 이 감소도 대장균의 살균에 의한 것이라고 보다는 PMF에 의한 물리적 제거라고 추정된다. 실시예인 CuBTC-PMF의 경우는 2분만에 94%가 제거되고, 47분에는 100% 제거됨을 알 수 있다. 즉 PMF에 Cu-BTC를 코팅한 경우가 PMF 보다 대장균 처리 성능이 탁월함을 알 수 있다.8 is a result of a comparative experiment on the E. coli sterilization effect of PMF and Cu-BTC-PMF. (2, 17, 32, 47 minutes after contact) It shows the decrease in the E. coli population. In the comparative example, PMF, when the number of E. coli populations decreased after 47 minutes, about 49% decreased compared to the initial number. However, in reality, this reduction is also presumed to be physical removal by PMF rather than by sterilization of E. coli. In the case of CuBTC-PMF, which is an embodiment, it can be seen that 94% is removed in 2 minutes and 100% is removed in 47 minutes. In other words, it can be seen that the case of coating Cu-BTC on PMF has superior E. coli treatment performance than PMF.
이상으로 본 발명의 특정한 부분을 상세히 기술하였는 바, 당업계의 통상의 지식을 가진 자에게 있어서, 이러한 구체적 기술은 단지 바람직한 실시예일 뿐이며, 이에 의해 본 발명의 범위가 제한되는 것이 아닌 점은 명백할 것이다. 따라서, 본 발명의 실질적인 범위는 첨부된 청구항들과 그것들의 등가물에 의하여 정의된다고 할 것이다. As the specific parts of the present invention have been described in detail above, for those of ordinary skill in the art, it is clear that these specific descriptions are only preferred embodiments, and the scope of the present invention is not limited thereby. will be. Accordingly, it is intended that the substantial scope of the present invention be defined by the appended claims and their equivalents.
Claims (6)
Polymelamine-formaldehyde (Polymelamine-formaldehyde, PMF) containing copper-1,3,5-benzenetricarboxylic acid (Cu-1,3,5-Benzenetricarboxylic acid, Cu-BTC) coated on the surface, antibacterial ·Antiviral substances.
상기 구리-1,3,5-벤젠트리카르복실산(Cu-1,3,5-Benzenetricarboxylic acid)는, 구리이온(Cu+2)과 H3BTC를 반응시켜 제조한 금속 유기체인, 항균·항바이러스 물질.
The method of claim 1,
The copper-1,3,5-benzenetricarboxylic acid (Cu-1,3,5-Benzenetricarboxylic acid) is a metal organism prepared by reacting copper ions (Cu +2 ) and H 3 BTC, antibacterial · antiviral substances.
An air purifier comprising the antibacterial and antiviral material of claim 1 or 2.
미반응물을 에탄올로 제거하는 단계;를 포함하는 항균·항바이러스용 CuBTC-PMF의 제조방법. repeatedly applying the precursors Cu(NO 3 ) 2 , H 3 BTC, and PEG-200 to polymelamine-formaldehyde; and
Method for producing CuBTC-PMF for antibacterial and antiviral comprising; removing unreacted substances with ethanol.
상기 도포하는 단계는 50 내지 100℃에서 수행되는 것인, 항균·항바이러스용 CuBTC-PMF의 제조방법.
5. The method of claim 4,
The method for producing CuBTC-PMF for antibacterial and antiviral, wherein the applying step is performed at 50 to 100°C.
CuBTC-PMF for antibacterial and antiviral, prepared by any one of claims 4 or 5.
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KR20090129428A (en) * | 2007-03-12 | 2009-12-16 | 바스프 에스이 | Antimicrobially modified melamine/formaldehyde foam |
KR20140017316A (en) | 2012-07-31 | 2014-02-11 | 경희대학교 산학협력단 | Method of manufacturing ultrafiltration using metal organic frameworks |
KR20150051137A (en) * | 2013-10-29 | 2015-05-11 | 경희대학교 산학협력단 | Separation membrane for water treatment and method for manufacturing the same |
KR20160054086A (en) | 2014-11-05 | 2016-05-16 | 국방과학연구소 | A fluorinated metal organic framework powder surface-modified with amphiphilic molecules, a canister having the same and a gas mask having the canister |
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Publication number | Priority date | Publication date | Assignee | Title |
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KR20090129428A (en) * | 2007-03-12 | 2009-12-16 | 바스프 에스이 | Antimicrobially modified melamine/formaldehyde foam |
KR20140017316A (en) | 2012-07-31 | 2014-02-11 | 경희대학교 산학협력단 | Method of manufacturing ultrafiltration using metal organic frameworks |
KR20150051137A (en) * | 2013-10-29 | 2015-05-11 | 경희대학교 산학협력단 | Separation membrane for water treatment and method for manufacturing the same |
KR20160054086A (en) | 2014-11-05 | 2016-05-16 | 국방과학연구소 | A fluorinated metal organic framework powder surface-modified with amphiphilic molecules, a canister having the same and a gas mask having the canister |
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