KR102373319B1 - Medical antimicrobial sheets and preparation method thereof - Google Patents

Abstract

The present invention is a base resin; and an inorganic nanocomposite containing zinc oxide nanoparticles; to a medical antibacterial sheet including an antibacterial nonwoven fabric prepared by spinning a masterbatch composition containing a melt blown method, and a method for manufacturing the same.

Description

Medical antimicrobial sheets and preparation method thereof

The present invention relates to a medical antibacterial sheet and a method for manufacturing the same.

Nonwoven fabrics that we use on a daily basis often cause discomfort by causing disorders on human skin or alteration of fibers, deterioration and odor by microorganisms such as various bacteria and fungi present in the living environment. Appropriate measures have been required.

In the case of corona bias, which is a recent issue, as the survival period of the nonwoven fabric is longer than that of other articles of about 7 days, it is necessary to develop a nonwoven fabric with stronger antibacterial properties.

In particular, when an infected person with the virus visits the hospital, if the infected person cannot be systematically controlled, the virus may be spread through secretions such as saliva or sweat. In addition, long-term inpatients, patients with underlying diseases, and elderly patients have very weak safety due to reduced immunity, so measures to prevent nosocomial infection are more urgent.

As a similar prior document for this, Republic of Korea Patent Publication No. 10-1832073 is presented.

Republic of Korea Patent Publication No. 10-1832073 (2018.02.19)

In order to solve the above problems, an object of the present invention is to provide a medical antibacterial sheet having better antibacterial and antiviral properties and a manufacturing method thereof.

One aspect of the present invention for achieving the above object is a base resin; and an inorganic nanocomposite comprising zinc oxide nanoparticles; relates to a medical antibacterial sheet comprising an antibacterial nonwoven fabric prepared by spinning a masterbatch composition including a melt blown method.

In one aspect, the medical antibacterial sheet may be a medical antibacterial mask, medical antibacterial protective clothing, medical antibacterial sanitary clothing, medical antibacterial bedspread or medical antibacterial curtain.

In one aspect, the inorganic nanocomposite may be prepared by supporting zinc oxide nanoparticles through a solvothermal synthesis reaction on porous inorganic nanoparticles having an average particle size of 100 to 300 nm. Specifically, the porous inorganic nanoparticles The nanoparticles may be diatomaceous earth.

In one aspect, the masterbatch composition may include 5 to 30 parts by weight of the inorganic nanocomposite based on 100 parts by weight of the base resin.

In one aspect, the masterbatch composition may further include 5 to 30 parts by weight of zeolite nanoparticles based on 100 parts by weight of the base resin.

In another aspect of the present invention, there is provided a method for preparing porous inorganic nanoparticles, comprising: a) wet grinding the porous inorganic particles to have an average particle size of 100 to 300 nm; b) preparing an inorganic nanocomposite by supporting zinc oxide nanoparticles on the porous inorganic nanoparticles through a solvothermal synthesis reaction; c) preparing a masterbatch composition comprising the inorganic nanocomposite and a base resin; And d) spinning the masterbatch composition in a melt blown method to prepare an antibacterial nonwoven fabric; relates to a method of manufacturing an antibacterial sheet for medical use comprising a.

In another aspect, in step b), i) a first reaction solution obtained by adding porous inorganic nanoparticles and sodium hydroxide to a first alcohol solvent, and a second reaction solution obtained by dissolving zinc chloride in a second alcohol solvent preparing each; ii) preparing a reaction mixture by putting the first reaction liquid and the second reaction liquid in an ultrasonic stirrer and mixing them in an ice bath; iii) preparing an inorganic nanocomposite in which zinc oxide nanoparticles are supported on porous inorganic nanoparticles by applying a temperature of 80 to 150° C. to the reaction mixture and reacting it in a high-pressure reactor; and iv) calcining the inorganic nanocomposite.

The medical antibacterial sheet according to the present invention can significantly improve the antibacterial and antibacterial performance of the medical antibacterial sheet by supporting zinc oxide nanoparticles having the size of a primary particle on the porous inorganic nanoparticles through a solvothermal synthesis reaction, and the porous By using inorganic nanoparticles, deodorization performance can be greatly improved.

In addition, by using porous inorganic nanoparticles with an average particle size of 100 to 300 nm as a carrier, the masterbatch composition can be easily spun in a melt blown method, and microfibers with a diameter of 10 μm or less are interconnected to form a spider web-like structure. It is possible to effectively manufacture an antibacterial nonwoven fabric having a three-dimensional fiber aggregate. Through this, it is possible to effectively filter dust, dust, etc. while having excellent air permeability.

In addition, as a medical antibacterial sheet is prepared by spinning a masterbatch composition in which an inorganic nanocomposite is mixed with a base resin in a melt blown method, the washing fastness is very excellent, so that the inorganic nanocomposite can remain firmly in the sheet even after washing. It has the advantage of being washable and reusable.

Hereinafter, a medical antibacterial sheet and a manufacturing method thereof according to the present invention will be described in detail. The drawings introduced below are provided as examples so that the spirit of the present invention can be sufficiently conveyed to those skilled in the art. Accordingly, the present invention is not limited to the drawings presented below and may be embodied in other forms, and the drawings presented below may be exaggerated to clarify the spirit of the present invention. At this time, if there is no other definition in the technical terms and scientific terms used, it has the meaning commonly understood by those of ordinary skill in the art to which this invention belongs, and the gist of the present invention in the following description and accompanying drawings Descriptions of known functions and configurations that may be unnecessarily obscure will be omitted.

One aspect of the present invention is a base resin; And an inorganic nanocomposite comprising zinc oxide nanoparticles; relates to a medical antibacterial sheet comprising an antibacterial nonwoven fabric prepared by spinning the masterbatch composition comprising a melt blown method, preferably the inorganic nanocomposite may be prepared by supporting zinc oxide nanoparticles through a solvothermal synthesis reaction on porous inorganic nanoparticles having an average particle size of 100 to 300 nm.

As such, the medical antibacterial sheet according to the present invention can significantly improve the antibacterial and antibacterial performance of the medical antibacterial sheet by supporting zinc oxide nanoparticles having the size of a primary particle on the porous inorganic nanoparticles through a solvothermal synthesis reaction. , the deodorization performance can be greatly improved by using porous inorganic nanoparticles.

In addition, by using porous inorganic nanoparticles with an average particle size of 100 to 300 nm as a carrier, the masterbatch composition can be easily spun in a melt blown method, and microfibers with a diameter of 10 μm or less are interconnected to form a spider web-like structure. It is possible to effectively manufacture an antibacterial nonwoven fabric having a three-dimensional fiber aggregate. Through this, it is possible to effectively filter dust, dust, etc. while having excellent air permeability.

In addition, as a medical antibacterial sheet is prepared by spinning a masterbatch composition in which an inorganic nanocomposite is mixed with a base resin in a melt blown method, the washing fastness is very excellent, so that the inorganic nanocomposite can remain firmly in the sheet even after washing. It has the advantage of being washable and reusable.

As such, the medical antibacterial sheet according to the present invention has excellent antibacterial and antibacterial performance, and can be used for medical purposes as it has excellent deodorization performance, ventilation performance, dust filtration performance and washing fastness, specifically, a medical antibacterial mask, It can be used for medical antibacterial protective clothing, medical antibacterial sanitary clothes, medical antibacterial bedspreads, or medical antibacterial curtains.

Hereinafter, the medical antibacterial sheet according to the present invention will be described in more detail.

First, the base resin can be used without particular limitation as long as it is commonly used in the art, and as a specific example, it is selected from the group consisting of polypropylene fibers, polyolefin-based fibers, polyester-based fibers, and polyamide-based fibers. It may be any one or two or more.

The inorganic nanocomposite may include zinc oxide nanoparticles, and preferably, zinc oxide nanoparticles are supported on porous inorganic nanoparticles as a carrier, and zinc oxide nanoparticles are synthesized and supported through a solvothermal synthesis reaction. By using the method, zinc oxide nanoparticles can be made to have the size of primary particles. Usually, zinc oxide particles exist in the form of micron-sized secondary particles in which primary particles are aggregated. In this case, antibacterial activity is reduced due to aggregation, whereas the inorganic nanocomposite according to the present invention uses a porous carrier, and solvothermal synthesis reaction By synthesizing zinc oxide through aggregation of primary particles, it is possible to greatly improve antibacterial and antibacterial properties.

In this case, the average particle diameter of the zinc oxide nanoparticles in which the aggregation is suppressed may be 1 to 50 nm, and more preferably, 20 to 30 nm. In this range, the antibacterial performance may be the best.

The porous inorganic nanoparticles may be used without particular limitation as long as they have porosity, so that zinc oxide nanoparticles can be supported and pulverized to an average particle size of 100 to 300 nm. Specifically, for example, the porous inorganic nanoparticles are diatomaceous earth can As such, by having an average particle size of 100 to 300 nm, the masterbatch composition can be easily spun by a melt blown method, and the mechanical properties of the prepared antibacterial nonwoven fabric can be prevented from being deteriorated. In addition, by having porosity, zinc oxide nanoparticles can be supported at the level of primary particles, and through this, excellent antibacterial performance, antibacterial performance and deodorization performance can be secured.

On the other hand, in an example of the present invention, the antibacterial nonwoven fabric may be prepared by spinning the masterbatch composition in a melt blown method, in which case the melt blowing process may be performed by a method commonly used in the art. there is.

In addition, the masterbatch composition may include 5 to 30 parts by weight of the inorganic nanocomposite based on 100 parts by weight of the base resin. In such a range, the masterbatch composition may be easily spun in a melt blown manner, and may have excellent antibacterial and deodorizing performance. On the other hand, when the inorganic nanocomposite is added in an amount of less than 5 parts by weight, the antibacterial performance and deodorization performance may be reduced, and when the inorganic nanocomposite is added in an amount of more than 30 parts by weight, the mechanical properties of the antibacterial nonwoven fabric prepared by the melt blown method can be lowered

In addition, the masterbatch composition may further include 5 to 30 parts by weight of zeolite nanoparticles based on 100 parts by weight of the base resin. By further including zeolite nanoparticles having microporosity, the deodorization performance of the antibacterial nonwoven fabric can be further improved. In this case, the average particle size of the zeolite nanoparticles may be an average particle size of 100 to 300 nm, and may be wet-pulverized in the same manner as the porous inorganic nanoparticles.

In addition, another aspect of the present invention relates to a method for manufacturing an antibacterial sheet for medical use including the antibacterial nonwoven fabric described above, specifically a) wet-pulverizing porous inorganic particles to have an average particle size of 100 to 300 nm to obtain porous inorganic nanoparticles manufacturing a;

b) preparing an inorganic nanocomposite by supporting zinc oxide nanoparticles on the porous inorganic nanoparticles through a solvothermal synthesis reaction; c) preparing a masterbatch composition comprising the inorganic nanocomposite and a base resin; And d) spinning the masterbatch composition in a melt blown method to prepare an antibacterial nonwoven fabric; relates to a method of manufacturing an antibacterial sheet for medical use comprising a.

First, the step of a) wet-pulverizing the porous inorganic particles to have an average particle size of 100 to 300 nm to prepare the porous inorganic nanoparticles will be described.

In an example of the present invention, the porous inorganic nanoparticles can be used without particular limitation as long as they have porosity, so that zinc oxide nanoparticles can be supported and pulverized to an average particle size of 100 to 300 nm. Specifically, for example, The porous inorganic nanoparticles may be diatomaceous earth. As such, by having an average particle size of 100 to 300 nm, the masterbatch composition can be easily spun by a melt blown method, and the mechanical properties of the prepared antibacterial nonwoven fabric can be prevented from being deteriorated.

To this end, the porous inorganic particles may be wet-milled to an average particle size of 100 to 300 nm, and the wet grinding method is not particularly limited, but a method such as wet bead milling may be used, and as a specific example, a particle size of 0.5 to 3 mm Speed mill equipment using beads, nanoset mill equipment using beads having a particle size of 0.1 to 0.5 mm, or twin nanoset mill equipment using beads having a particle size of 0.03 to 0.5 mm may be used.

Next, b) preparing the inorganic nanocomposite by supporting the zinc oxide nanoparticles through a solvothermal synthesis reaction on the porous inorganic nanoparticles may be performed.

As described above, zinc oxide particles usually exist in the form of micron-sized secondary particles in which primary particles are aggregated. In this case, antibacterial activity is reduced due to agglomeration, whereas the inorganic nanocomposite according to the present invention contains porous inorganic nanoparticles. By synthesizing zinc oxide through a solvothermal synthesis reaction, the aggregation of primary particles can be suppressed, thereby greatly improving antibacterial and antibacterial properties.

As a more specific example, in step b), i) a first reaction solution obtained by adding porous inorganic nanoparticles and sodium hydroxide to a first alcohol solvent, and a second reaction solution obtained by dissolving zinc chloride in a second alcohol solvent. preparing each; ii) preparing a reaction mixture by putting the first reaction liquid and the second reaction liquid in an ultrasonic stirrer and mixing them in an ice bath; iii) preparing an inorganic nanocomposite in which zinc oxide nanoparticles are supported on porous inorganic nanoparticles by applying a temperature of 80 to 150° C. to the reaction mixture and reacting it in a high-pressure reactor; and iv) calcining the inorganic nanocomposite.

First, the steps of i) preparing a first reaction solution obtained by adding porous inorganic nanoparticles and sodium hydroxide to a first alcohol solvent and a second reaction solution obtained by dissolving zinc chloride in a second alcohol solvent, respectively, may be performed.

The concentration and ratio of each component can be important to perform well in a solvothermal synthesis reaction. As a specific example, the concentration of sodium hydroxide in the first reaction solution may be 0.1 to 2 M, more preferably 0.3 to 1 M, and the concentration of zinc chloride in the second reaction solution may be 0.01 to 0.5 M and, more preferably, it may be 0.05 to 0.2 M, and the molar ratio of zinc chloride to sodium hydroxide may be 1: 7 to 13, and more preferably 1: 9 to 11. In the following concentration and molar ratio ranges, zinc oxide nanoparticles can be effectively prepared.

In addition, the content of the porous inorganic nanoparticles added to the first reaction solution is also important. As a specific example, in the first reaction solution, 300 to 700 mg of the porous inorganic nanoparticles can be added to 1 mmol of zinc chloride, More preferably, 400 to 600 mg may be added. In this range, zinc oxide nanoparticles are not easily agglomerated and can be well dispersed and supported on porous inorganic nanoparticles, and since the surface of porous inorganic nanoparticles is not completely coated with zinc oxide nanoparticles, it has an adsorption effect on gases, etc. Deodorization performance can be secured. On the other hand, if too small amount of porous inorganic nanoparticles is added, the surface may be completely coated with zinc oxide nanoparticles, and open pores may be changed into completely closed pores, which may result in deterioration of deodorization performance. can Conversely, when the porous inorganic nanoparticles are added in too much excess, it is necessary to mix an excessive amount of the inorganic nanocomposite with the base resin in order to secure a similar level of antibacterial activity. The mechanical properties may deteriorate and the washing fastness may be deteriorated.

In this case, the first alcohol solvent and the second alcohol solvent may be, independently of each other, methanol, ethanol or ethylene glycol, but preferably methanol. By using methanol, zinc oxide nanoparticles having a spherical shape with a size of 20 to 30 nm can be effectively prepared.

Next, the step of ii) putting the first reaction solution and the second reaction solution into an ultrasonic stirrer and mixing them under an ice bath to prepare a reaction mixture may be performed. Since heat may be generated when the first reaction solution and the second reaction solution are mixed, it is recommended to mix them for at least 30 minutes, specifically for 1 to 3 hours under an ice bath, and through this, zinc hydroxide (Zn (OH) ₂ ) It is possible to prepare an inorganic nanocomposite precursor on which nanoparticles are supported.

In this way, zinc hydroxide (Zn(OH) ₂ ) nanoparticles synthesized by vigorously mixing the first reaction solution and the second reaction solution through ultrasonication effectively prevent agglomeration of the nanoparticles, while the hydroxide is well dispersed at the primary particle level. Zinc particles can be effectively supported and adsorbed on the porous inorganic nanoparticles. In this case, the ultrasonic treatment may be performed at a frequency of 1 kHz to 200 MHz to apply energy of 1 W to 200 kW.

Next, iii) applying a temperature of 80 to 150° C. to the reaction mixture and reacting it in a high-pressure reactor to prepare an inorganic nanocomposite in which zinc oxide nanoparticles are supported on porous inorganic nanoparticles may be performed.

This step is to oxidize the zinc oxide (Zn(OH) ₂ ) nanoparticles of the inorganic nanocomposite precursor on which the zinc hydroxide (Zn(OH) ₂ ) nanoparticles prepared in the previous step are supported to zinc oxide (ZnO) nanoparticles. As a step, zinc oxide (ZnO) nanoparticles can be effectively prepared by applying a temperature of 80 to 150° C. and performing a solvothermal synthesis reaction in a high-pressure reactor.

The reaction time is not particularly limited, but it is preferable to carry out for 6 hours or more, specifically, 12 to 24 hours, since most of the zinc oxide (Zn(OH) ₂ ) nanoparticles can be converted into zinc oxide (ZnO) nanoparticles.

Thereafter, of course, the process of removing excess sodium hydroxide and product sodium chloride and drying may be further performed.

Next, the step of iv) calcining the inorganic nanocomposite may be performed.

Through this step, zinc oxide (ZnO) can be firmly bound to the porous inorganic nanoparticles, and zinc oxide can be prevented from desorbing from the porous inorganic nanoparticles well even during washing.

As a preferred example, the sintering temperature may be 400 to 600 ℃. In this range, the zinc oxide nanoparticles can be well bound to the porous inorganic nanoparticles. In this case, the calcination time is preferably 1 hour or more, and may be specifically carried out for 2 to 6 hours.

When the inorganic nanocomposite is prepared through the above method, the step of c) preparing a masterbatch composition including the inorganic nanocomposite and the base resin may be performed.

In an example of the present invention, the masterbatch composition may be prepared by mixing 5 to 30 parts by weight of the inorganic nanocomposite with respect to 100 parts by weight of the base resin. In such a range, the masterbatch composition may be easily spun in a melt blown manner, and may have excellent antibacterial and deodorizing performance. On the other hand, when the inorganic nanocomposite is added in an amount of less than 5 parts by weight, the antibacterial performance and deodorization performance may be reduced, and when the inorganic nanocomposite is added in an amount of more than 30 parts by weight, the mechanical properties of the antibacterial nonwoven fabric prepared by the melt blown method can be lowered

In this case, the base resin may be used without particular limitation as long as it is commonly used in the art, and as a specific example, it is selected from the group consisting of polypropylene fibers, polyolefin-based fibers, polyester-based fibers, and polyamide-based fibers. It may be any one or two or more.

In addition, the masterbatch composition may further include 5 to 30 parts by weight of zeolite nanoparticles based on 100 parts by weight of the base resin. By further including zeolite nanoparticles having microporosity, the deodorization performance of the antibacterial nonwoven fabric can be further improved. In this case, the average particle size of the zeolite nanoparticles may be an average particle size of 100 to 300 nm, and may be wet-pulverized in the same manner as the porous inorganic nanoparticles.

Next, the step of d) spinning the masterbatch composition in a melt blown method to prepare an antibacterial nonwoven fabric may be performed, and the melt blown process of this step may be performed by a method commonly used in the art. Accordingly, a detailed description thereof will be omitted.

As described above, the antibacterial nonwoven fabric manufactured in this way can be utilized as a medical antibacterial sheet, and specifically, a medical antibacterial mask, medical antibacterial protective clothing, medical antibacterial sanitary clothing, medical antibacterial bedspread or medical antibacterial curtain. can As an example, the antibacterial nonwoven fabric may be utilized for both the endothelium, the outer skin, or the endothelial outer skin of the medical antibacterial sheet.

As a more specific example, a medical antibacterial mask will be described, which is only an example and does not exclude other uses.

When the medical antibacterial sheet is a medical antibacterial mask, the medical antibacterial mask may have a multilayer structure composed of several layers of nonwoven fabric, and as a specific example, the medical antibacterial mask may include an innermost layer made of a spunbond nonwoven fabric; a barrier layer made of a melt blown nonwoven fabric; and an outermost layer made of the antibacterial nonwoven fabric; or an innermost layer made of a spunbond nonwoven fabric having a triple layer structure comprising; a barrier layer made of a melt blown nonwoven fabric; an antibacterial layer made of the antibacterial nonwoven fabric; and an outermost layer made of a spunbond nonwoven fabric.

In an example of the present invention, the spunbond nonwoven fabric of the outermost layer or the innermost layer may have a filter role that blocks out dust or dust that can be observed with the naked eye while having excellent breathability, and when it comes into contact with the skin, the feeling and wearing comfort This can be excellent.

As an example, the spunbond nonwoven fabric of the outermost layer or innermost layer may be used without particular limitation as long as it is commonly used in the art, and as a specific example, polypropylene fibers, polyolefin-based fibers, polyester-based fibers, and polyamide-based fibers It may be a nonwoven fabric manufactured by spinning any one or two or more selected from the group consisting of fibers and the like in a spunbond method.

In an example of the present invention, the melt blown nonwoven fabric is electrostatically charged in the process of being manufactured through the melt blown method to effectively collect and filter fine dust or fine particles, and if it is commonly used in the art It can be used without particular limitation, and as a specific example, any one or two or more selected from the group consisting of polypropylene fibers, polyolefin-based fibers, polyester-based fibers, and polyamide-based fibers are spun in a melt blown method to generate static electricity. It may be a nonwoven fabric charged with

In addition, the medical antibacterial sheet may include: an inorganic nanocomposite prepared by supporting zinc oxide nanoparticles through a solvothermal synthesis reaction on porous inorganic nanoparticles having an average particle size of 100 to 300 nm in order to further improve antibacterial performance; and a water-soluble polymer binder; may be post-treated with an aqueous dispersion of inorganic nanocomposites prepared by dispersing in water. In this case, the post-treatment may be dried by spraying the inorganic nanocomposite aqueous dispersion onto a medical antibacterial sheet, and spraying may be repeated one or more times.

Since the inorganic nanocomposite prepared by supporting zinc oxide nanoparticles through a solvothermal synthesis reaction on the porous inorganic nanoparticles having an average particle size of 100 to 300 nm is the same as described above, redundant descriptions will be omitted.

The water-soluble polymer binder is to ensure that the inorganic nanocomposite is well attached to the medical antibacterial sheet during post-treatment, and it is preferable to use a water-soluble polymer binder that is well soluble in water and has excellent adhesion. A natural polymer, a urea-based binder or an acrylic binder may be used.

As a more specific example, the aqueous dispersion of the inorganic nanocomposite may include 1 to 10 parts by weight of the inorganic nanocomposite and 1 to 20 parts by weight of the water-soluble polymer binder based on 100 parts by weight of water. In this range, spraying is easy, and the inorganic nanocomposite may adhere well, but may not aggregate with each other.

In addition, the inorganic nanocomposite aqueous dispersion may further include zinc pyrithione, thereby further improving antibacterial and antibacterial performance. In this case, zinc pyrithione may be added in an amount of 0.1 to 3 parts by weight based on 100 parts by weight of water. In this range, zinc pyrithione is well dispersed in water, and it can have better antibacterial and antibacterial performance.

Hereinafter, the medical antibacterial sheet and the manufacturing method thereof according to the present invention will be described in more detail through examples. However, the following examples are only a reference for describing the present invention in detail, and the present invention is not limited thereto, and may be implemented in various forms.

Also, unless otherwise defined, all technical and scientific terms have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used herein is for the purpose of effectively describing particular embodiments only and is not intended to limit the invention. In addition, the unit of additives not specifically described in the specification may be weight %.

[Production Example 1]

Diatomaceous earth nanoparticles having an average particle size of 100 nm were obtained by wet grinding the diatomaceous earth using a nanoset mill (model name TNS010) equipment.

Next, an inorganic nanocomposite in which zinc oxide (ZnO) nanoparticles were supported on diatomaceous earth nanoparticles was prepared through the following solvothermal synthesis reaction.

First, sodium hydroxide was dissolved in 20 ml of methanol to prepare a 0.5 M sodium hydroxide solution, and 500 mg of diatomaceous earth nanoparticles were added to prepare a first reaction solution. At the same time, zinc chloride (ZnCl ₂ ) was dissolved in 10 ml of methanol to prepare a 0.1 M zinc chloride solution, which was prepared as a second reaction solution.

Under an ice bath, the first reaction solution and the second reaction solution were put into an ultrasonic reactor, and then ultrasonically stirred vigorously for 1 hour. Thereafter, the reaction mixture was put into a high-pressure reactor, and the temperature was raised to 120° C. to react for 12 hours. Thereafter, the resulting precipitate was filtered and washed with methanol to obtain an inorganic nanocomposite in which zinc oxide nanoparticles were supported on diatomaceous earth nanoparticles.

The inorganic nanocomposite was placed in a rotary kiln and calcined at 500° C. for 6 hours.

[Production Example 2]

Diatomaceous earth was wet pulverized with a nanoset mill (model name TNS010) equipment to obtain diatomaceous earth nanoparticles having an average particle size of 200 nm, and all processes were performed in the same manner as in Preparation Example 1 except for adding them to the first reaction solution. Thus, an inorganic nanocomposite in which zinc oxide (ZnO) nanoparticles were supported on diatomaceous earth nanoparticles was obtained.

[Production Example 3]

Diatomaceous earth was wet pulverized with a nanoset mill (model name TNS010) equipment to obtain diatomaceous earth nanoparticles having an average particle size of 300 nm, and all processes were performed in the same manner as in Preparation Example 1 except that these were added to the first reaction solution. Thus, an inorganic nanocomposite in which zinc oxide (ZnO) nanoparticles were supported on diatomaceous earth nanoparticles was obtained.

[Production Example 4]

Inorganic nanocomposites in which zinc oxide (ZnO) nanoparticles are supported on diatomite nanoparticles were prepared in the same manner as in Preparation Example 1 except that 100 mg of diatomaceous earth nanoparticles having an average particle size of 200 nm were added to the first reaction solution. obtained.

[Production Example 5]

All processes were performed in the same manner as in Preparation Example 1 except that 300 mg of diatomaceous earth nanoparticles having an average particle size of 200 nm were added to the first reaction solution to prepare an inorganic nanocomposite in which zinc oxide (ZnO) nanoparticles were supported on the diatomaceous earth nanoparticles. obtained.

[Production Example 6]

Inorganic nanocomposites in which zinc oxide (ZnO) nanoparticles are supported on diatomite nanoparticles were prepared in the same manner as in Preparation Example 1 except that 700 mg of diatomaceous earth nanoparticles having an average particle size of 200 nm were added to the first reaction solution. obtained.

[Production Example 7]

Inorganic nanocomposite in which zinc oxide (ZnO) nanoparticles are supported on diatomaceous earth nanoparticles was prepared in the same manner as in Preparation Example 1 except that 1000 mg of diatomaceous earth nanoparticles having an average particle size of 200 nm were added to the first reaction solution. obtained.

[Production Example 8]

Without using an ultrasonic reactor, the first reaction solution and the second reaction solution were put into a general stirred reactor, and all processes were performed in the same manner as in Preparation Example 2 except that the mixture was stirred at a speed of 500 rpm to add zinc oxide to diatomaceous earth nanoparticles. An inorganic nanocomposite on which (ZnO) nanoparticles were supported was obtained.

[Comparative Preparation Example 1]

Diatomaceous earth nanoparticles having an average particle size of 200 nm were prepared by wet grinding diatomaceous earth with a nanoset mill (model name TNS010) equipment.

[Comparative Preparation Example 2]

Diatomaceous earth nanoparticles having an average particle size of 200 nm were obtained by wet grinding diatomaceous earth using a nanoset mill (model name TNS010) equipment.

Next, sodium hydroxide was dissolved in 20 ml of methanol to prepare a 0.5 M sodium hydroxide solution to prepare a first reaction solution. At the same time, zinc chloride (ZnCl ₂ ) was dissolved in 10 ml of methanol to prepare a 0.1 M zinc chloride solution, which was prepared as a second reaction solution. Under an ice bath, the first reaction solution and the second reaction solution were put into an ultrasonic reactor, and then ultrasonically stirred vigorously for 1 hour. Thereafter, the reaction mixture was put into a high-pressure reactor, and the temperature was raised to 120° C. to react for 12 hours. Thereafter, the resulting precipitate was filtered and washed with methanol to obtain an inorganic nanocomposite in which zinc oxide nanoparticles were supported on diatomaceous earth nanoparticles. The inorganic nanocomposite was placed in a rotary kiln and calcined at 500° C. for 6 hours.

An inorganic mixture was prepared by mixing 500 mg of each of the prepared diatomaceous earth nanoparticles and 80 mg of zinc oxide (ZnO) nanoparticles.

[Comparative Preparation Example 3]

Diatomaceous earth was wet pulverized with a nanoset mill (model name TNS010) equipment to obtain diatomaceous earth nanoparticles having an average particle size of 500 nm, and all processes were performed in the same manner as in Preparation Example 1 except for adding them to the first reaction solution Thus, an inorganic nanocomposite in which zinc oxide (ZnO) nanoparticles were supported on diatomaceous earth nanoparticles was obtained.

[Example 1]

Based on 100 parts by weight of the polypropylene chip, 15 parts by weight of the inorganic nanocomposite prepared in Preparation Example 1 and 15 parts by weight of zeolite nanoparticles (average particle size of 150 nm) were mixed to prepare a masterbatch composition, and a conventional melt blown method An antibacterial nonwoven fabric was prepared.

[Examples 2 to 6]

Based on 100 parts by weight of the polypropylene chip, 1 part by weight (Example 2), 5 parts by weight (Example 3), 15 parts by weight (Example 4), 30 parts by weight of the inorganic nanocomposite prepared in Preparation Example 2, respectively (Example 5), 50 parts by weight (Example 6), except that the master batch was prepared, all processes were performed in the same manner as in Example 1 to prepare an antibacterial nonwoven fabric.

[Examples 7 to 12]

With respect to 100 parts by weight of the polypropylene chip, 15 parts by weight of the inorganic nanocomposites prepared in Preparation Examples 3 to 8 were mixed, respectively, and all processes were performed in the same manner as in Example 1 except for preparing each masterbatch of Examples 7 to 12. Thus, an antibacterial nonwoven fabric was prepared. (Example 7-Preparation Example 3, Example 8-Preparation Example 4, Example 9-Preparation Example 5, Example 10-Preparation Example 6, Example 11-Preparation Example 7, Example 12-Preparation Example 8)

[Comparative Example 1]

With respect to 100 parts by weight of the polypropylene chip, instead of the inorganic nanocomposite, only 15 parts by weight of the diatomaceous earth nanoparticles prepared in Comparative Preparation Example 1 were mixed to prepare a master batch. prepared.

[Comparative Example 2]

With respect to 100 parts by weight of the polypropylene chip, 15 parts by weight of the inorganic mixture prepared in Comparative Preparation Example 2 was mixed to prepare a master batch, and all processes were performed in the same manner as in Example 1 to prepare an antibacterial nonwoven fabric.

[Comparative Example 3]

With respect to 100 parts by weight of the polypropylene chip, 15 parts by weight of the inorganic nanocomposite prepared in Comparative Preparation Example 3 was mixed to prepare a master batch, and all processes were performed in the same manner as in Example 1 to prepare an antibacterial nonwoven fabric.

[Characteristic evaluation]

1) Antibacterial performance test: The antibacterial performance was tested by the method of KS K 0693:2016.

Specifically, on the antibacterial nonwoven fabric prepared in Examples 1 to 15 and Comparative Examples 1 and 2 E. coli ( Escherichia coli ) 9.2 × 10 ⁴ CFU / ㎖, Staphylococos aureus ) 8.9 × 10 ⁴ CFU / ㎖, Typhoid murine Salmonella typhimurium 7.4×10 ⁴ CFU/ml and Klebsiella pneumoniae 9.1×10 ⁴ CFU/ml were inoculated at initial concentrations (A ₀ , CFU/ml), respectively, and inoculated at 37.0±0.2° C. for 24 hours. The concentration (A ₁ , CFU/ml) after standing was confirmed, and the bacteriostatic reduction rate (%) was calculated therefrom, and the results are shown in Table 1 below. As a control group, an untreated group was prepared. In addition, the bacteriostatic reduction rate was calculated as (A ₀ -A ₁ )/A ₀ ×100.

2) Deodorization performance test: The deodorization performance was tested according to the FITI test guideline FTM-5-2:2004.

In detail, each of the antibacterial nonwoven fabrics prepared in Examples 1 to 15 and Comparative Examples 1 and 2 was cut into 10 cm × 10 cm to prepare a test piece, inserted into an ammonia gas test gas pack having an initial concentration of 100 ppm, and then the gas detection tube method (KICM-FIR-1004) was used to measure the deodorization rate (%), and the results are shown in Table 1 below. At this time, the deodorization rate was calculated as (C _b -C _s )/C _b × 100, where C _b is the concentration (ppm) of ammonia gas remaining in the test gas pack after 2 hours without an antibacterial nonwoven fabric test piece (blank), C _s is the concentration (ppm) of ammonia gas remaining in the test gas pack after 2 hours have elapsed after placing the antibacterial nonwoven test piece.

bacteriostatic reduction rate (%) deodorization rate
(%) E. coli S. aureus S. typhimurium K. pneumoniae initial concentration 9.2×10 ⁴ 8.9×10 ⁴ 7.4×10 ⁴ 9.1×10 ⁴ - control 7.1×10 ⁵ 6.7×10 ⁵ 6.5×10 ⁵ 1.6×10 ⁶ Example 1 99.9 99.9 99.9 99.9 99.8 Example 2 97.2 98.0 98.3 97.7 94.2 Example 3 99.9 99.9 99.9 99.9 99.8 Example 4 99.9 99.9 99.9 99.9 99.8 Example 5 99.9 99.9 99.9 99.9 99.8 Example 6 99.9 99.9 99.9 99.9 99.9 Example 7 99.9 99.9 99.9 99.9 99.8 Example 8 99.9 99.9 99.9 99.9 85.9 Example 9 99.9 99.9 99.9 99.9 99.8 Example 10 99.9 99.9 99.9 99.9 99.8 Example 11 97.1 97.6 98.0 97.3 99.9 Example 12 95.9 96.3 96.8 96.1 99.9 Comparative Example 1 66.1 73.9 54.4 69.0 99.9 Comparative Example 2 95.5 95.8 96.0 95.7 99.9 Comparative Example 3 99.9 99.9 99.9 99.9 99.9

As shown in Table 1, it was confirmed that the antibacterial nonwoven fabric according to the present invention had superior antibacterial performance compared to the comparative example.

However, in the case of Example 2 in which a small amount of the inorganic nanocomposite was added, the antibacterial performance was somewhat deteriorated, and in the case of Example 6 in which the inorganic nanocomposite was added in too much, the mechanical properties of the antibacterial nonwoven were somewhat poor, so it was impossible to reuse it during washing. did

In the case of Example 8, in which a small amount of diatomaceous earth nanoparticles were added during solvothermal synthesis, as the surface of the diatomaceous earth nanoparticles was coated with zinc oxide and some of the pores disappeared, the gas adsorption capacity was somewhat lowered, and the deodorization performance was lowered, and the diatomaceous earth nanoparticles In the case of Example 11 in which was added in excess, as the ratio of zinc oxide in the inorganic nanocomposite decreased, the antibacterial performance was somewhat decreased.

On the other hand, in Comparative Example 1 in which only diatomaceous earth nanoparticles were added, the antibacterial performance was very significantly reduced, and in the case of Comparative Example 2, in which zinc oxide was prepared without adding diatomaceous earth nanoparticles during solvothermal synthesis, and then added as a mixture, also oxidized The aggregation of zinc occurred and the antibacterial performance was somewhat lowered. In the case of Comparative Example 3, since diatomaceous earth nanoparticles having a rather large particle size were used, the mechanical properties of the sheet were somewhat poor, making it impossible to reuse during washing.

[Production Example 9]

All processes were performed in the same manner as in Preparation Example 2 except that the calcination temperature was changed to 200° C. to obtain an inorganic nanocomposite in which zinc oxide (ZnO) nanoparticles were supported on diatomaceous earth nanoparticles.

[Production Example 10]

All processes were performed in the same manner as in Preparation Example 2 except that the calcination temperature was changed to 400° C. to obtain an inorganic nanocomposite in which zinc oxide (ZnO) nanoparticles were supported on diatomaceous earth nanoparticles.

[Production Example 11]

All processes were performed in the same manner as in Preparation Example 2 except that the calcination temperature was changed to 800° C. to obtain an inorganic nanocomposite in which zinc oxide (ZnO) nanoparticles were supported on diatomaceous earth nanoparticles.

[Examples 13 to 15]

With respect to 100 parts by weight of the polypropylene chip, 15 parts by weight of the inorganic nanocomposite prepared in Preparation Examples 9 to 11 were mixed, respectively, and all processes were performed in the same manner as in Example 1 except for preparing each masterbatch of Examples 13 to 15 to prepare an antibacterial nonwoven fabric. (Example 13-Preparation Example 9, Example 14-Preparation Example 10, Example 15-Preparation Example 11)

[Evaluation of fastness to washing properties]

After washing the antibacterial nonwoven fabric prepared in Example 2, Examples 13 to 15, and Comparative Example 2 5 times with standard washing, the antibacterial performance was tested according to the above method, and the results are shown in Table 2 below.

Bacteriostatic reduction rate after washing 5 times (%) E. coli S. aureus S. typhimurium K. pneumoniae initial concentration 9.2×10 ⁴ 8.9×10 ⁴ 7.4×10 ⁴ 9.1×10 ⁴ Example 4 99.9 99.9 99.9 99.9 Example 13 84.6 89.5 86.4 90.1 Example 14 99.9 99.9 99.9 99.9 Example 15 96.3 96.4 97.0 96.1 Comparative Example 2 71.2 76.5 73.7 75.8

As shown in Table 2, in the case of Examples 4 and 14, where the firing temperature satisfies 400 to 600° C., the zinc oxide nanoparticles are well supported on the porous inorganic nanoparticles even after washing, so that very excellent antibacterial performance is maintained. was able to confirm

On the other hand, in the case of Example 13, in which the firing temperature was too low, the washing fastness was not good, so the desorption of zinc oxide nanoparticles from the porous inorganic nanoparticles occurred after washing, and it was confirmed that the antibacterial performance was greatly reduced.

In addition, in the case of Example 15, in which the firing temperature was too high, a phenomenon in which the zinc oxide nanoparticles were partially agglomerated due to the high temperature occurred, so that the antibacterial performance was somewhat deteriorated.

On the other hand, in the case of Comparative Example 2, since the diatomaceous earth nanoparticles and the zinc oxide nanoparticles were mixed and added, the washing fastness was not as good as in Example 13, and thus the antibacterial performance was greatly reduced.

Although the present invention has been described with reference to specific matters and limited examples as described above, these are only provided to help a more general understanding of the present invention, and the present invention is not limited to the above examples, and the present invention belongs to Various modifications and variations are possible from these descriptions by those of ordinary skill in the art.

Therefore, the spirit of the present invention should not be limited to the described embodiments, and not only the claims to be described later, but also all those with equivalent or equivalent modifications to the claims will be said to belong to the scope of the spirit of the present invention. .

Claims (8)

base resin; and an inorganic nanocomposite comprising zinc oxide nanoparticles; a medical antibacterial sheet comprising an antibacterial nonwoven fabric prepared by spinning a masterbatch composition containing a melt blown method,
The inorganic nanocomposite is a medical antibacterial sheet prepared by supporting zinc oxide nanoparticles through a solvothermal synthesis reaction on porous inorganic nanoparticles having an average particle size of 100 to 300 nm.
The method of claim 1,
The medical antibacterial sheet is a medical antibacterial mask, medical antibacterial protective clothing, medical antibacterial sanitary clothing, medical antibacterial bedspread or medical antibacterial curtain, medical antibacterial sheet.
delete The method of claim 1,
The porous inorganic nanoparticles are diatomaceous earth, a medical antibacterial sheet.
The method of claim 1,
The masterbatch composition is a medical antibacterial sheet comprising 5 to 30 parts by weight of the inorganic nanocomposite based on 100 parts by weight of the base resin.
The method of claim 1,
The masterbatch composition further comprises 5 to 30 parts by weight of zeolite nanoparticles based on 100 parts by weight of the base resin, medical antibacterial sheet.
a) preparing porous inorganic nanoparticles by wet grinding the porous inorganic particles to have an average particle size of 100 to 300 nm;
b) preparing an inorganic nanocomposite by supporting zinc oxide nanoparticles on the porous inorganic nanoparticles through a solvothermal synthesis reaction;
c) preparing a masterbatch composition comprising the inorganic nanocomposite and a base resin; and
d) preparing an antibacterial nonwoven fabric by spinning the masterbatch composition in a melt blown method;
A method of manufacturing an antibacterial sheet for medical use comprising a.
8. The method of claim 7,
Step b) is,
i) preparing a first reaction solution obtained by adding porous inorganic nanoparticles and sodium hydroxide to a first alcohol solvent, and a second reaction solution obtained by dissolving zinc chloride in a second alcohol solvent;
ii) preparing a reaction mixture by putting the first reaction liquid and the second reaction liquid in an ultrasonic stirrer and mixing them in an ice bath;
iii) preparing an inorganic nanocomposite in which zinc oxide nanoparticles are supported on porous inorganic nanoparticles by applying a temperature of 80 to 150° C. to the reaction mixture and reacting it in a high-pressure reactor; and
iv) calcining the inorganic nanocomposite;
A method of manufacturing an antibacterial sheet for medical use, comprising a.