KR102575876B1 - Antibacterial or antiviral filter having improved coating durability - Google Patents

Abstract

The present invention relates to an antibacterial or antiviral filter with improved coating durability. In more detail, the present invention relates to a polymer filter that optimizes coating thickness, improves coating durability, and simultaneously exhibits antibacterial or antiviral functions and a method of manufacturing the same.

Description

Antibacterial or antiviral filter having improved coating durability}

The present invention relates to an antibacterial or antiviral filter with improved coating durability. In more detail, the present invention relates to a polymer filter that can optimize coating thickness, improve coating durability, and simultaneously exhibit antibacterial or antiviral functions and a method of manufacturing the same.

Antibacterial filters are installed in air purifiers, air conditioners, water purifiers, masks, etc. and can remove microorganisms such as bacteria and fungi.

These antibacterial filters are equipped with antibacterial materials that can capture and remove bio-particles such as various microorganisms. Typically, antibacterial filters have been manufactured by coating fabrics with antibacterial agents such as activated carbon, metals, metal oxides, and artificial enzyme catalysts (Cu-phthalocyanine).

With these antibacterial filters, it is not easy to coat the antibacterial agent with adhesion to fibers, etc., and even when coated, the antibacterial agent easily falls off from the fiber, etc., and the coating durability is often not good.

Therefore, even if an expensive antibacterial filter is purchased, it is difficult to use for a long time and maintenance and/or management, such as having to replace the antibacterial filter periodically, is problematic.

In addition, in order to maintain a certain level of adhesion, a certain amount of antibacterial agent must be coated on the fiber, etc., so the thickness of the coating layer increases and the pressure loss of the filter increases. In addition, even when using an antibacterial filter, the durability of the coating is weak, which may make it difficult to use for a long time.

As background technology for the present invention, an antibacterial textile product and its manufacturing method are described in Japanese Patent Laid-Open No. 1997-049170.

The purpose of the present invention is to provide an antibacterial or antiviral polymer filter with improved coating durability.

Another object of the present invention is to provide an antibacterial or antiviral polymer filter capable of optimizing the coating thickness.

Another object of the present invention is to provide an antibacterial or antiviral polymer filter with excellent aesthetics.

Another object of the present invention is to provide a method for manufacturing an antibacterial or antiviral polymer filter that can efficiently manufacture an antibacterial or antiviral polymer filter with improved coating durability.

Other objects and advantages of the present invention will become more apparent from the following detailed description, claims, and drawings.

According to one aspect, a polymer filter in which a surface modification layer is formed by ion beam pretreatment so that the coating layer can bind to the polymer surface; An antibacterial or antiviral filter with improved coating durability is provided, including a metal or metal oxide coating layer coated on the polymer filter.

According to one embodiment, the ion beam pretreatment may be a gas ion beam pretreatment containing oxygen gas.

According to one embodiment, the polymer may be polypropylene (PP) or polyethylene terephthalate (PET).

According to one embodiment, the polymer may be manufactured by melt-blown polypropylene or polyethylene telephthalate.

According to one embodiment, the metal or metal oxide may be one or more of Cu, CuOx, ZnO, Ag, and Au.

According to one embodiment, the metal or metal oxide is one or more types of Cu, CuOx, and ZnO, and the filter is a Lab color method established by the CIE International Standard Color Measurement Organization, where L ^* is 30 to 60 and a ^* is - 2 to 2, and b ^* may be 0 to 10.

According to one embodiment, the filter may have antibacterial activity against one or more types of Staphylococcus aureus and Rods pneumoniae.

According to one embodiment, the filter may have antiviral activity against coronaviruses.

According to one embodiment, the filter may have antiviral activity against SARS-COV-2.

According to another aspect, a product comprising an antibacterial or antiviral filter with improved coating durability of the present application is provided.

According to another aspect, i) providing a polymer filter; ii) forming a surface modification layer by pre-treating the polymer filter with an ion beam; and iii) forming a metal coating layer of metal or metal oxide on the surface modification layer. A method of manufacturing an antibacterial or antiviral filter with improved coating durability is provided, including the step.

According to one embodiment, in step i), the polymer may be manufactured by melt-blown method by melt-spinning polypropylene or polyethylene telephthalate.

According to one embodiment, in step ii), the ion beam may be a gas ion beam containing oxygen gas.

According to one embodiment, in step ii) the ion beam may irradiate gas particles with an energy of 50 - 1,000 eV.

According to one embodiment, in step iii), a coating layer of metal or metal oxide may be formed by sputtering or evaporation.

According to one embodiment, the metal or metal oxide in step iii) may be one or more of Cu, CuOx, ZnO, Ag, and Au.

According to one embodiment, the coating durability of an antibacterial or antiviral polymer filter can be improved by adjusting the ion beam pretreatment.

According to one embodiment, the sputtering conditions of the antibacterial agent can be adjusted to optimize the coating thickness of the antibacterial or antiviral polymer filter to suit the product being used. In particular, it is possible to provide an antibacterial filter with excellent coating durability and antibacterial activity even if the coating thickness is thin.

According to one embodiment, an antibacterial or antiviral polymer filter with excellent aesthetics can be provided by controlling the sputtering conditions of the antibacterial agent.

According to one embodiment, an antibacterial or antiviral polymer filter with improved coating durability can be efficiently manufactured by controlling the ion beam pretreatment and sputtering conditions of the antibacterial agent.

Other objects and advantages of the present invention will become more apparent from the following detailed description, claims, and drawings.

Figure 1 is a diagram schematically showing a method of manufacturing an antibacterial or antiviral filter according to an embodiment.
Figure 2 is a photograph showing an antibacterial or antiviral filter according to one embodiment.
Figure 3 is a diagram showing the surface color of copper oxide according to sputtering conditions after ion beam pretreatment according to an embodiment.
Figure 4 is a diagram showing the results of evaluating the adhesion of a copper oxide deposited film according to the presence or absence of ion beam pretreatment and sputtering conditions after ion beam pretreatment.
Figure 5 is a FE-SEM photograph of the surface of a mask fiber on which CuOx metal oxide is deposited after ion beam pretreatment according to an embodiment.
Figure 6 is a diagram showing the results of XPS analysis showing the oxidation state of the CuOx thin film deposited on the disposable mask.
Figure 7 is a diagram showing the results of evaluating the antibacterial activity of an antibacterial or antiviral filter according to an embodiment.
Figure 8 is a photograph of an experiment evaluating the COVID-19 virus inactivation of an antibacterial or antiviral filter according to an embodiment.
Figure 9 is a graph showing the results of evaluating the COVID-19 virus inactivation of an antibacterial or antiviral filter according to an embodiment.

The terms used in this application are only used to describe specific embodiments and are not intended to limit the invention.

Singular expressions include plural expressions unless the context clearly dictates otherwise.

In this application, terms such as 'include' or 'have' are intended to designate the presence of features, numbers, steps, operations, components, parts, or combinations thereof described in the specification, but are not intended to indicate the presence of one or more other features. It should be understood that this does not exclude in advance the possibility of the existence or addition of elements, numbers, steps, operations, components, parts, or combinations thereof.

In this application, when a part “includes” a certain component, this means that it may further include other components rather than excluding other components unless specifically stated to the contrary. In addition, throughout the specification, “on” means located above or below the object part, and does not necessarily mean located above the direction of gravity.

Since the present invention can be modified in various ways and can have various embodiments, specific embodiments will be illustrated in the drawings and described in detail in the detailed description. However, this is not intended to limit the present invention to specific embodiments, and should be understood to include all transformations, equivalents, and substitutes included in the spirit and technical scope of the present invention. In describing the present invention, if it is determined that a detailed description of related known technologies may obscure the gist of the present invention, the detailed description will be omitted.

Terms such as first, second, etc. may be used to describe various components, but the components should not be limited by the terms. The above terms are used only for the purpose of distinguishing one component from another.

Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings. In the description with reference to the accompanying drawings, identical or corresponding components will be assigned the same drawing numbers and overlapping descriptions thereof will be omitted. do.

Figure 1 is a diagram schematically showing a method of manufacturing an antibacterial or antiviral filter according to an embodiment. Figure 2 is a photograph showing an antibacterial or antiviral filter according to one embodiment.

Referring to Figures 1 and 2. According to one aspect, the antibacterial or antiviral filter with improved coating durability of the present application includes a polymer filter pretreated with an ion beam to form a surface modification layer so that the coating layer can bind to the polymer surface; and a coating layer of metal or metal oxide coated on the polymer filter.

The ion beam pretreatment may be ion beam pretreatment of various gases. For example, ion beam pretreatment may use one or more of Ar, O ₂ , and N ₂ . Although not limited to this, ion beam pretreatment containing oxygen may be suitable for the ion beam pretreatment. The oxygen-containing ion beam pretreated polymer filter may have improved bonding between the surface modification layer and the metal coating layer.

There is no limitation to the structure of the surface modification layer as long as the polymer surface and the metal coating layer can be combined by ion beam pretreatment. Therefore, the surface modification layer may have various nano-holes, nano-wrinkles, nano-dimples, nano-protrusions, etc. formed.

There is no particular limitation on the type of the polymer as long as a surface modification layer can be formed. Although not limited thereto, polypropylene (PP) or polyethylene terephthalate (PET) may be suitable in terms of improving bonding between the polymer surface and the metal coating layer.

The polymer may be manufactured by melt-blown polypropylene or polyethylene telephthalate. Polymers, which are widely used as mask or air conditioning filter materials that require antibacterial and antiviral activity, are manufactured by melt-blown polypropylene or polyethylene telephthalate. However, the conventional coating mask had the problem of poor adhesion to the antibacterial agent, but the coating mask of the present invention can effectively solve this problem.

The metal or metal oxide may be one or more of Cu, CuOx, ZnO, Ag, and Au, which have antibacterial and/or antiviral activity. Although not limited to this, Cu, CuOx, and ZnO may be suitable metals or metal oxides in terms of antibacterial activity and economic efficiency.

The metal or metal oxide is one or more of Cu, CuOx, and ZnO, and the filter uses the Lab color method established by the CIE International Standard Color Measurement Organization, where L ^* is 30 to 60, a ^* is -2 to 2, and b. ^* can be 0 to 10. When observed with the naked eye, the filter can be implemented in a variety of colors, from copper or zinc to silver.

Although not limited thereto, our filter may have antibacterial activity against one or more of Staphylococcus aureus and Klebsiella pneumoniae . The Staphylococcus aureus is a type of pathogen that is difficult to kill because it causes skin disease and is resistant to food poisoning/some antibiotics, but can be eradicated by 99.9% using the antibacterial filter of the present invention. In addition, Klebsiella pneumoniae is a bacterium that causes opportunistic infections such as septicemia, pneumonia, urinary tract infection, and soft tissue infection in immunocompromised patients, but using the antibacterial filter of the present invention, 99.9 % eradication is possible.

Our filters may have antiviral activity against coronaviruses. In particular, the filter may have antiviral activity against SARS-COV-2. Therefore, when our filter is applied to a mask, it can effectively block droplets and prevent coronavirus infection. In addition, when our filter is applied to an air conditioner, it can effectively inactivate the coronavirus in multi-use facilities, closed spaces, etc., effectively preventing the spread of the coronavirus.

According to another aspect, a product comprising an antibacterial or antiviral filter with improved coating durability is provided. The products include all products requiring antibacterial and/or antiviral activity and may be, for example, masks or air conditioners.

Referring to Figure 1, according to another aspect, the method for manufacturing an antibacterial or antiviral filter with improved coating durability of the present application includes the steps of i) providing a polymer film; ii) forming a surface modification layer by pre-treating the polymer film with an ion beam; and iii) forming a metal coating layer of metal or metal oxide on the surface modification layer.

Step i) is a step of providing a polymer filter that requires antibacterial and antiviral activity. The polymer may include one manufactured by melt-blown method by melt-spinning polypropylene or polyethylene telephthalate.

Step ii) is a step of forming a surface modification layer on the polymer filter by performing ion beam pretreatment. The ion beam pretreatment may be ion beam pretreatment of various gases. Although not limited to this, oxygen ion beam pretreatment may be suitable for the ion beam pretreatment. The polymer filter subjected to oxygen ion beam pretreatment may have improved bonding strength with the metal coating layer through the surface modification layer.

In step ii), the ion beam may irradiate gas particles with an energy of 50 - 1,000 eV. When gas particles in the above energy range are irradiated, a surface modification layer of the polymer filter can be easily formed, thereby improving the bonding strength between the polymer filter surface and the metal coating layer.

Step iii) is a step of forming a metal coating layer made of metal or metal oxide on the surface modification layer. Although it is not limited to this, the metal or metal oxide coating layer can be formed uniformly and efficiently by sputtering or evaporation.

In step iii), there is no particular limitation as long as the metal or metal oxide has antibacterial activity and/or antiviral activity. The metal or metal oxide may be one or more of Cu, CuOx, ZnO, Ag, and Au.

Example

Hereinafter, the present invention will be described in more detail through specific examples and comparative examples of the present invention and their characteristic evaluation results.

1. After ion beam pretreatment sputtering Analysis of changes in copper oxide deposition film thickness and surface color according to conditions

1) Ion beam pretreatment

Ion beam pretreatment was performed on melt blown (MB) polypropylene (PP) fabric under the following fixed conditions.

- O ₂ / 600 V / 100 mA / 10 mm/s

2) Cu sputtering

As shown in Table 1 below, Cu sputtering was performed on the pretreated meltblown (MB) polypropylene (PP) fabric while changing the sputtering conditions.

As shown in Table 1, CuOx was found to be formed thinly as the oxygen gas flow rate increased during copper sputtering deposition. Therefore, the oxygen gas flow rate during copper sputtering deposition can optimize the thickness of the coating layer according to the purpose for which the filter is used.

Figure 3 is a diagram showing the surface color of copper oxide according to sputtering conditions after ion beam pretreatment according to an embodiment.

As shown in Table 1 and Figure 3, as the oxygen gas flow rate increased during copper sputtering deposition, the oxidation degree of copper increased, changing from copper color to silver. Therefore, by controlling the oxygen gas flow rate during copper sputtering deposition, the color of the coating layer can be optimized according to the purpose for which the filter is used and the aesthetics can be improved.

2. With or without ion beam pretreatment and after ion beam pretreatment sputtering Adhesion analysis of copper oxide deposited films according to conditions

The adhesion of the copper oxide deposited film was evaluated based on the degree of peeling of the coating layer when 3M tape (Scotch Magic Tape 810) was attached to the surface of the coated mask, rubbed, and then torn off.

The results are shown in Figure 4. That is, Figure 4 is a diagram showing the results of evaluating the adhesion of a copper oxide deposited film according to the presence or absence of ion beam pretreatment and sputtering conditions after ion beam pretreatment.

As shown in Figure 4, in the coated mask that was not treated with the ion beam, it was observed that the coating layer was peeled off from the mask fabric.

Meanwhile, in the case of a mask coated after ion beam pretreatment, it was observed that the mask fibers came off but the coating layer did not come off. This indicates that the adhesion of the coating is stronger than the durability of the mask fiber.

3. Cu after ion beam pretreatment sputtering after roll to roll Analysis of produced disposable mask fibers

After ion beam pretreatment, the disposable mask fiber produced by roll-to-roll after being coated to a thickness of 20 nm by Cu sputtering under the following conditions was analyzed by FE-SEM, and is shown in Figure 5.

- Cu sputtering (roll to roll) / Ar 200 sccm / 1kW / 562 V / 2.97 A / 1 mpm*1 time

That is, Figure 5 is a FE-SEM photograph of the surface of a mask fiber on which CuOx metal oxide is deposited after ion beam pretreatment according to an embodiment.

As shown in Figure 5, the surface of the mask fiber on which CuOx metal oxide was deposited after ion beam pretreatment by the present invention was found to be not damaged at all even during roll-to-roll production.

Figure 6 is an XPS analysis result showing the oxidation state of the CuOx thin film deposited on the disposable mask.

As shown in Figure 6, the sputtered Cu thin film deposited on the surface of the PP fiber was about 75% Cu ₂ O and about 25% CuO.

4. Cu after ion beam pretreatment sputtered Analysis of antibacterial activity of disposable masks

After ion beam pretreatment, the antibacterial activity against Staphylococcus aureus and K. pneumoniae by disposable mask fibers coated to a thickness of 20 nm by Cu sputtering was analyzed under the following conditions. The results are shown in Figure 7.

- Cu sputtering (surface treatment equipment) / Ar 75 sccm (chamber) / S#1 500V, 0.4A / S#2 465V, 0.4A / 16 mm/s*1 time

That is, Figure 7 is a diagram showing the results of evaluating the antibacterial activity of an antibacterial or antiviral filter according to one embodiment.

As shown in FIG. 7, unlike general masks, the mask according to the present invention is It showed 99.9% antibacterial activity against Staphylococcus aureus and Klebsiella pneumoniae.

5. Cu after ion beam pretreatment sputtered Analysis of antiviral activity of disposable masks

After ion beam pretreatment, COVID-19 virus inactivation by disposable mask fibers coated to a thickness of 20 nm by Cu sputtering was analyzed under the following conditions.

- Cu sputtering (roll to roll) / Ar 200 sccm / 1kW / 562 V / 2.97 A / 1 mpm*1 time

At this time, the materials and methods used for antiviral activity analysis are as follows.

- Vero cell

- SARS-COV-2: NCCP43328

virus 10 ^-5 200ul per well (2X10 ⁵ cells per 6 well plate)

- nCOVID19 Detection reagent: STANDARD M nCOV Real-Time PCR (SD BIOSCIENCE)

- Filter (Bare, copper deposited PP after ion beam treatment) 1 hour pretreatment

Verocells were infected with SARS-Cov 2 clinical isolate NCCP43328 at the designated time, 1 hour before the addition of the PP filter. Samples were taken 2 days after infection and viral load was determined using real-time PCR of cell-associated virus. Real-time analysis was performed on virus-infected cells using probes for RdRp genes and E genes.

The results are shown in Figures 8 and 9. That is, Figure 8 is a photograph of an experiment evaluating the COVID-19 virus inactivation of an antibacterial or antiviral filter according to an embodiment. Figure 9 is a graph showing the results of evaluating the COVID-19 virus inactivation of an antibacterial or antiviral filter according to an embodiment.

As shown in FIG. 9, the mask according to an embodiment of the present application can completely inactivate the COVID-19 virus.

Above, an embodiment of the present invention has been described, but those skilled in the art will be able to add, change, delete or add components without departing from the spirit of the present invention as set forth in the patent claims. The present invention may be modified and changed in various ways by addition, etc., and this will also be included within the scope of the rights of the present invention.

Claims (16)

A polymer filter that has been pretreated with an ion beam to form a surface modification layer so that the coating layer can bond to the polymer surface; and
A coating layer of CuOx, which is a thin film coated on the polymer filter by sputtering copper with a process gas containing oxygen; It consists of
The ion beam pretreatment is a gas ion beam pretreatment containing oxygen gas and having an energy of 50 - 1,000 eV,
The polymer is polypropylene (PP) or polyethylene terephthalate (PET), an antibacterial or antiviral filter with improved coating durability. delete delete According to paragraph 1,
The polymer is an antibacterial or antiviral filter with improved coating durability, which is manufactured by melt-blown method by melt-spinning polypropylene or polyethylene telephthalate. delete According to paragraph 1,
The filter is an antibacterial or antiviral filter with improved coating durability and aesthetics using the Lab color method established by the CIE International Standard Color Measurement Organization, where L ^* is 30 to 60, a ^* is -2 to 2, and b ^* is 0 to 10. . According to paragraph 1,
An antibacterial or antiviral filter with improved coating durability that has antibacterial activity against one or more types of Staphylococcus aureus and Klebsiella pneumoniae. According to paragraph 1,
Antibacterial or antiviral filter with improved coating durability, with antiviral activity against coronaviruses. According to paragraph 1,
Antibacterial or antiviral filters with improved coating durability that have antiviral activity against SARS-COV-2. A product comprising the antibacterial or antiviral filter with improved coating durability according to any one of claims 1 to 9. i) providing a polymer filter;
ii) forming a surface modification layer by pre-treating the polymer filter with an ion beam; and
iii) forming a thin metal coating layer of CuOx on the surface modification layer by sputtering copper with a process gas containing oxygen,
The polymer is polypropylene (PP) or polyethylene terephthalate (PET),
In step ii), the ion beam contains oxygen gas and is a gas ion beam with an energy of 50 - 1,000 eV. A method of manufacturing an antibacterial or antiviral filter with improved coating durability. According to clause 11,
In step i), the polymer is manufactured by melt-blown method by melt-spinning polypropylene or polyethylene telephthalate. A method of manufacturing an antibacterial or antiviral filter with improved coating durability. delete delete delete delete