KR20190013629A - Antimicrobial agent coomprising MOF and antimicrobial filter coomprising the same - Google Patents

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 human bodies.

Description

An antimicrobial agent containing MOF and an antimicrobial filter comprising the MOF and an antimicrobial filter coomprising the same

The present invention relates to an antibacterial agent containing MOF and an antibacterial filter comprising the same.

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, generally, an antibacterial filter capable of removing such microorganisms is installed in automobiles, air conditioners, air conditioners, air cleaners, clean rooms and the like.

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.

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.

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 MOFs are toxic to humans and are difficult to apply to antibacterial air filters.

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.

According to an aspect of the present invention,

Wherein the MOF comprises at least one metal ion selected from the group consisting of Zn, Co, Al, and Zr, an imidazole, an alkylimidazole, At least one organic ligand selected from the group consisting of alkoxyimidazole, terephthalic acid, and aminoterephthalic acid.

According to another aspect of the present invention,

An antibacterial filter comprising the antibacterial agent is provided.

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 can be used as an antimicrobial agent by itself or by mixing with other materials or by coating and supporting the same on other substrates.

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.

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.

1 is a schematic diagram showing the three-dimensional structure of ZIF-8 contained in the antibacterial agent of the present invention.
2 is a SEM photograph showing an antibacterial filter according to an embodiment of the present invention.
3 is a photograph showing 18 hours after the inoculation of Staphylococcus aureus against the nonwoven fabric filter of the example of the present invention and the medium of the comparative example.
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.

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.

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 aminoterephthalic acid.

Metal-organic framework (MOF), also called metal-organic structure, is an organic-inorganic hybrid material in which metal ions or ion clusters have primary, secondary or tertiary structure to feed organic ligands. Can make various MOF.

The MOF is characterized by the presence of voids in the structure, and the size, porosity, three-dimensional structure, and surface area of the pores can be designed in various ways depending on the type of the metal ion and the organic ligand that form the MOF, have.

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 zeolites and activated carbon which are well known in the art. 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.

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.

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.

On the other hand, the inventors of the present invention have found that MOF containing metal ions, which are known to have no antibacterial activity, have antimicrobial properties that inhibit the propagation of various microorganisms, leading to the present invention.

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.

According to one embodiment, the MOF, for example ^{ZIF-8 (Zn 2 + +} 2-methylimidazole), 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).

More preferably, 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.

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.

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.

According to another embodiment of the present invention, there is provided an antibacterial filter comprising the antibacterial agent.

A detailed description of the MOF and specific examples of the MOF are as described above for the antimicrobial 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.

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.

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.

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.

According to one embodiment of the present invention, the polymer is selected from the group consisting of polyacrylonitrile (PAN), polyvinylidene fluoride (PVDF), polyvinyl chloride (PVC), and polyethylene terephthalate polyethylene terephthalate (PET), and preferably polyacrylonitrile. However, the present invention is not limited thereto.

In addition, according to one embodiment of the present invention, the dispersion solvent includes dimethylacetamide, diethylacetamide, dimethylmethoxyacetamide, N-methylpyrrolidone, dimethylformamide, etc. However, But is not limited thereto.

Meanwhile, according to one embodiment of the present invention, the nonwoven fabric may be produced by electrospinning a spinning solution in which a polymer solution containing a polymer and a MOF are mixed, to obtain a nonwoven fabric and supporting the MOF in the nonwoven fabric have.

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.

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.

In addition, according to one embodiment of the present invention, the specific surface area of the nonwoven fabric after the MOF is supported is much greater than that before being supported, for example, about 50 m ² / g or more, or about 70 m ² / More preferably 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.

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.

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.

Best Mode for Carrying Out the Invention Hereinafter, the function and effect of the present invention will be described in more detail through specific examples 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.

<Examples>

Example 1

32 g of polyacrylonitrile (PAN), and 30 ml of dimethylacetamide were mixed to prepare a polymer solution.

20 g of ZIF-8 (Zn ^{2 +} + 2-methylimidazole) was mixed with 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.

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

Except that 20 g of ZIF-67 (Co ^{2 +} + 2-methylimidazole) was used instead of 20 g of ZIF-8 (Zn ^{2 +} + 2-methylimidazole) as MOF to prepare an MOF-supported antibacterial filter Respectively.

Example 3

Except that 20 g of NH ₂ -UiO-66 (Zr ^{4 +} + 2-aminoterephthalic acid) was used instead of 20 g of ZIF-8 (Zn ^{2 +} + 2-methylimidazole) as MOF. An antibacterial filter was prepared.

Example 4

Except that 20 g of NH ₂ -MIL-101 (Al ^{3 +} + 2-aminoterephthalic acid) was used instead of 20 g of ZIF-8 (Zn ^{2 +} + 2-methylimidazole) as MOF. An antibacterial filter was prepared.

<Experimental Example>

The antibacterial properties of the antibacterial filters of Examples 1 to 4 were measured by the following methods.

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.

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. [

After 18 hours, the number of remaining bacteria was compared with the microbial culture medium and the removal rate of E. coli and Staphylococcus aureus was measured. As a result, the nonwoven fabric filter of Examples 1 to 4 of the present invention was found to have 99.9% or more of E. coli and Staphylococcus aureus Respectively.

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.

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.

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 (6)

It is an antimicrobial agent containing MOF (Metal-organic framework)
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.
The method according to claim 1,
MOF is the ^{ZIF-8 (Zn 2 + +} 2-methylimidazole), 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).
An antibacterial filter comprising the antibacterial agent of claim 1.
The method of claim 3,
Wherein the antibacterial agent is supported on a nonwoven fabric.
5. The method of claim 4,
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.
5. The method of claim 4,
The specific surface area of the MOF-supported nonwoven fabric is 50 to 200 m ² / g.

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