KR102182774B1 - Breathable antimicrobial sheet and preparation method thereof, and antimicrobial mask comprising the same - Google Patents

Abstract

The present invention relates to an air permeable antibacterial fiber sheet, a production method thereof, and an antibacterial mask comprising the same. The air permeable antibacterial fiber sheet is produced by spinning, through a melt blown scheme, a master batch composition comprising: a base resin; and an inorganic nanocomposite produced by dipping zinc oxide nanoparticles through a solvothermal synthetic reaction in porous inorganic nanoparticles having an average particle size of 100 to 300 nm.

Description

Breathable antimicrobial sheet and preparation method thereof, and antimicrobial mask comprising the same}

The present invention relates to a breathable antibacterial fiber sheet, a method for manufacturing the same, and an antibacterial mask comprising the same.

Conventionally, for the purpose of preventing airborne dust, pollen, bacteria, viruses, etc. from invading the human bronchi through breathing, a breathable sheet is cut into a predetermined shape, and is used for earrings. Masks that are worn by attaching rubber or the like and covering the mouth or nose are widely known.

Such a mask has a certain degree of effect when it is intended to prevent inhalation of house dust or dust that can be observed with the naked eye, to prevent splashing of secretions such as saliva due to coughing and sneezing of the wearer, and to keep the throat or nose warm. Could get

Therefore, a mask with improved antimicrobial and antiviral properties is required due to the recent expansion of new influenza virus infections such as highly pathogenic avian influenza virus (H5N1 type) and severe acute respiratory syndrome (SARS) virus.

Korean Patent Publication No. 10-1884670 is proposed as a similar prior document for this.

Korean Patent Publication No. 10-1884670 (2018.07.27)

In order to solve the above problems, an object of the present invention is to provide a breathable antibacterial fiber sheet having superior antimicrobial and antiviral properties, a method of manufacturing the same, and an antibacterial mask including the same.

One aspect of the present invention for achieving the above object is a base resin; And an inorganic nanocomposite prepared by supporting zinc oxide nanoparticles through a solvent heat synthesis reaction on porous inorganic nanoparticles having an average particle size of 100 to 300 nm; a master batch composition comprising a melt blown method It relates to a breathable antibacterial fiber sheet, characterized in that produced by spinning.

In the above aspect, the porous inorganic nanoparticles may be diatomaceous earth.

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

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

In addition, another aspect of the present invention is a) preparing porous inorganic nanoparticles by wet grinding the porous inorganic particles to an average particle size of 100 to 300 ㎚; b) preparing an inorganic nanocomposite by supporting zinc oxide nanoparticles on the porous inorganic nanoparticles through a solvent heat synthesis reaction; c) preparing a masterbatch composition comprising the inorganic nanocomposite and a base resin; And d) producing a breathable antibacterial fiber sheet by spinning the masterbatch composition in a melt blown method. It relates to a method of manufacturing a breathable antibacterial fiber sheet comprising.

In the other aspect, the step b) comprises: i) a first reaction solution in which porous inorganic nanoparticles and sodium hydroxide are added to a first alcohol solvent, and a second reaction solution in which zinc chloride is dissolved in a second alcohol solvent. Preparing each; Ii) preparing a reaction mixture by putting the first reaction solution and the second reaction solution into 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 reacting in a high-pressure reactor by applying a temperature of 80 to 150°C to the reaction mixture; And iv) firing the inorganic nanocomposite.

In addition, another aspect of the present invention relates to an antibacterial mask comprising the above-described breathable antibacterial fiber sheet.

In another aspect, the antibacterial mask includes an innermost layer made of a spunbond nonwoven fabric; A barrier layer made of a melt blown nonwoven fabric; And the outermost layer made of the breathable antimicrobial fiber sheet layer.

In another aspect, the antibacterial mask includes an innermost layer made of a spunbond nonwoven fabric; A barrier layer made of a melt blown nonwoven fabric; The breathable antibacterial fiber sheet layer; And it may have a four-layer structure including; the outermost layer made of a spunbond nonwoven fabric.

In another aspect, the antimicrobial mask comprises: an inorganic nanocomposite prepared by supporting zinc oxide nanoparticles through a solvent heat synthesis reaction on porous inorganic nanoparticles having an average particle size of 100 to 300 nm; And a water-soluble polymer binder; may be post-treated with an aqueous dispersion of an inorganic nanocomposite prepared by dispersing in water.

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

In addition, by using porous inorganic nanoparticles having 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 having a diameter of 10 µm or less are mutually bonded to form a spider web. It is possible to effectively manufacture a nonwoven fabric sheet, which is a three-dimensional fiber aggregate having Through this, it is possible to effectively filter dust or dust while having excellent ventilation.

In addition, as the masterbatch composition in which the inorganic nanocomposite is mixed with the base resin is spun in a melt blown method to produce a breathable antibacterial fiber sheet, the washing fastness is very excellent, so that the inorganic nanocomposite can remain firmly in the sheet even after washing. It has the advantage that it can be washed and reused.

Hereinafter, a breathable antibacterial fiber sheet according to the present invention, a manufacturing method thereof, and an antibacterial mask including the same 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, unless there are other definitions in the technical terms and scientific terms used, they have the meanings commonly understood by those of ordinary skill in the technical field to which this invention belongs, and the gist of the present invention in the following description and accompanying drawings Description 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 prepared by supporting zinc oxide nanoparticles through a solvent heat synthesis reaction on porous inorganic nanoparticles having an average particle size of 100 to 300 nm; a master batch composition comprising a melt blown method It relates to a breathable antibacterial fiber sheet, characterized in that produced by spinning.

In this way, by supporting zinc oxide nanoparticles having the size of the primary particles on the porous inorganic nanoparticles through a solvent heat synthesis reaction, the antibacterial and antibacterial performance of the breathable antibacterial fiber sheet can be greatly improved, and porous inorganic nanoparticles are used. By doing so, the deodorizing performance can be greatly improved.

In addition, by using porous inorganic nanoparticles having 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 having a diameter of 10 µm or less are mutually bonded to form a spider web. It is possible to effectively manufacture a nonwoven fabric sheet, which is a three-dimensional fiber aggregate having Through this, it is possible to effectively filter dust or dust while having excellent ventilation.

In addition, as the masterbatch composition in which the inorganic nanocomposite is mixed with the base resin is spun in a melt blown method to produce a breathable antibacterial fiber sheet, the washing fastness is very excellent, so that the inorganic nanocomposite can remain firmly in the sheet even after washing. It has the advantage that it can be washed and reused.

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

In the inorganic nanocomposite, zinc oxide nanoparticles are supported on porous inorganic nanoparticles as a carrier, and zinc oxide nanoparticles are at the level of primary particles by using a method of synthesizing and supporting zinc oxide nanoparticles through a solvent heat synthesis reaction. You can make it have a size. In general, zinc oxide particles exist in the form of micron-sized secondary particles in which primary particles are aggregated.In this case, the antimicrobial activity is lowered by aggregation, whereas the inorganic nanocomposite according to the present invention uses a porous carrier, and a solvent heat synthesis reaction By synthesizing zinc oxide through the method, it is possible to significantly improve antibacterial and antibacterial properties by suppressing aggregation of primary particles.

At this time, the average particle diameter of the zinc oxide nanoparticles in which aggregation is inhibited may be 1 to 50 nm, 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. I can. As such, by having an average particle size of 100 to 300 nm, the master batch composition can be easily spun in a melt blown method, and mechanical properties of the manufactured fiber sheet can be prevented from deteriorating. In addition, by having porosity, zinc oxide nanoparticles can be supported at the level of primary particles, and excellent antibacterial performance, antibacterial performance, and deodorization performance can be secured through this.

On the other hand, in an example of the present invention, the breathable antibacterial fiber sheet may be produced by spinning a master batch composition in a melt blown method, and at this time, the melt blown process is performed by a method commonly used in the art. Can be.

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 this range, the masterbatch composition can be easily spun in a melt blown manner, while having excellent antibacterial performance 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 deteriorated, and when the inorganic nanocomposite is added in an amount of more than 30 parts by weight, the mechanical properties of the fiber sheet manufactured by the melt blown method It can be degraded.

In addition, the master batch 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 microporous properties, the deodorizing performance of the breathable antibacterial fiber sheet may be further improved. In this case, the zeolite nanoparticles may have an average particle size of 100 to 300 nm, and may be wet-milled in the same manner as the porous inorganic nanoparticles.

Hereinafter, a method of manufacturing the above-described breathable antibacterial fiber sheet will be described.

As a specific example, the method of manufacturing a breathable antibacterial fiber sheet according to the present invention comprises the steps of: a) preparing porous inorganic nanoparticles by wet grinding the porous inorganic particles to 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 solvent heat synthesis reaction; c) preparing a masterbatch composition comprising the inorganic nanocomposite and a base resin; And d) preparing a breathable antibacterial fiber sheet by spinning the master batch composition in a melt blown manner.

First, a) a step of preparing porous inorganic nanoparticles by wet grinding the porous inorganic particles to a size having an average particle size of 100 to 300 nm will be described.

In one example of the present invention, the porous inorganic nanoparticles may be used without particular limitation as long as they have porosity and thus can support zinc oxide nanoparticles, and can be pulverized to an average particle size of 100 to 300 nm, and 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 master batch composition can be easily spun in a melt blown method, and mechanical properties of the manufactured fiber sheet can be prevented from deteriorating.

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

Next, b) the step of preparing an inorganic nanocomposite by supporting zinc oxide nanoparticles through a solvent heat 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 lowered by aggregation, whereas the inorganic nanocomposite according to the present invention contains porous inorganic nanoparticles. In addition, by synthesizing zinc oxide through a solvent heat synthesis reaction, the aggregation of primary particles is suppressed, and antibacterial and antibacterial properties can be greatly improved.

In a more specific example, step b) comprises: i) a first reaction solution in which porous inorganic nanoparticles and sodium hydroxide are added to a first alcohol solvent, and a second reaction solution in which zinc chloride is dissolved in a second alcohol solvent. Preparing each; Ii) preparing a reaction mixture by putting the first reaction solution and the second reaction solution into 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 reacting in a high-pressure reactor by applying a temperature of 80 to 150°C to the reaction mixture; And iv) firing the inorganic nanocomposite.

First, i) preparing a first reaction solution in which porous inorganic nanoparticles and sodium hydroxide are added to a first alcohol solvent, and a second reaction solution in which zinc chloride is dissolved in a second alcohol solvent may be prepared.

In order to perform the solvothermal synthesis reaction well, the concentration and ratio of each component may be important. 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 zinc chloride: sodium hydroxide molar ratio may be 1: 7 to 13, more preferably 1: 9 to 11. Zinc oxide nanoparticles can be effectively prepared in the following concentration and molar ratio range.

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 porous inorganic nanoparticles may be added to 1 mmol of zinc chloride, More preferably, 400 to 600 mg may be added. In this range, the zinc oxide nanoparticles are not easily aggregated and can be well dispersed and supported on the porous inorganic nanoparticles, and as the surface of the porous inorganic nanoparticles is not completely coated with the zinc oxide nanoparticles, it has an adsorption effect on gases, etc. Deodorization performance can be secured. On the other hand, if too small amounts of porous inorganic nanoparticles are added, the surface of the zinc oxide nanoparticles is completely coated and the open pores may change into completely closed pores, resulting in a decrease in deodorization performance. I can. Conversely, when too much porous inorganic nanoparticles are added, an excess of inorganic nanocomposites must be mixed with the base resin to secure similar levels of antimicrobial activity. In this case, melt blown spinning is not easy or the mechanical Due to poor physical properties, the fastness to washing may decrease.

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

Next, ii) the step of preparing a reaction mixture by putting the first reaction solution and the second reaction solution into an ultrasonic stirrer and mixing them in an ice bath 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 for 30 minutes or more, specifically 1 to 3 hours, in an ice bath, through which zinc hydroxide (Zn (OH) ₂ ) It is possible to prepare an inorganic nanocomposite precursor on which nanoparticles are supported.

Zinc hydroxide (Zn(OH) ₂ ) synthesized by vigorous mixing of the first reaction solution and the second reaction solution through ultrasonic treatment as described above effectively prevents the agglomeration of nanoparticles, while being well-dispersed at the level of primary particles. 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) reacting in a high-pressure reactor by applying a temperature of 80 to 150°C to the reaction mixture to prepare an inorganic nanocomposite in which zinc oxide nanoparticles are supported on the porous inorganic nanoparticles.

This step is for oxidizing the zinc hydroxide (Zn(OH) ₂ ) nanoparticles supported in the inorganic nanocomposite precursor to zinc oxide (Zn(OH) ₂ ) nanoparticles into 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 solvent heat synthesis reaction in a high-pressure reactor.

The reaction time is not particularly limited, but it is good to perform most of the zinc oxide (Zn(OH) ₂ ) nanoparticles into zinc oxide (ZnO) nanoparticles by performing it for 6 hours or more, specifically 12 to 24 hours.

After that, the process of removing excess sodium hydroxide and sodium chloride as a product, and drying may be further performed.

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

Through this step, zinc oxide (ZnO) can be tightly bound to the porous inorganic nanoparticles, and zinc oxide can be prevented from being easily desorbed from the porous inorganic nanoparticles even during washing.

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

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

In one example of the present invention, the masterbatch composition may be prepared by mixing 5 to 30 parts by weight of the inorganic nanocomposite based on 100 parts by weight of the base resin. In this range, the masterbatch composition can be easily spun in a melt blown manner, while having excellent antibacterial performance 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 deteriorated, and when the inorganic nanocomposite is added in an amount of more than 30 parts by weight, the mechanical properties of the fiber sheet manufactured by the melt blown method It can be degraded.

At this time, the base resin may be used without particular limitation as long as it is commonly used in the art, and as a specific example, selected from the group consisting of polypropylene fibers, polyolefin fibers, polyester fibers and polyamide fibers, etc. 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 microporous properties, the deodorizing performance of the breathable antibacterial fiber sheet may be further improved. In this case, the zeolite nanoparticles may have an average particle size of 100 to 300 nm, and may be wet-milled in the same manner as the porous inorganic nanoparticles.

Next, d) the master batch composition may be spun in a melt blown method to prepare a breathable antibacterial fiber sheet, and the melt blown process of this step is performed by a method commonly used in the art. As it may be, a detailed description will be omitted.

On the other hand, another aspect of the present invention relates to an antibacterial mask comprising the above-described breathable antibacterial fiber sheet, specifically, a base resin; And an inorganic nanocomposite prepared by supporting zinc oxide nanoparticles through a solvent heat synthesis reaction on porous inorganic nanoparticles having an average particle size of 100 to 300 nm; a master batch composition comprising a melt blown method It may be an antibacterial mask comprising a breathable antibacterial fiber sheet, characterized in that it is produced by spinning. At this time, since the breathable antibacterial fiber sheet is the same as described above, a redundant description will be omitted.

More specifically, the antibacterial mask according to an example of the present invention may be a multilayer antibacterial mask composed of a plurality of layers of nonwoven fabric, and as a specific example, the antibacterial mask may include an innermost layer composed of a spunbond nonwoven fabric; A barrier layer made of a melt blown nonwoven fabric; And an outermost layer made of the breathable antimicrobial fiber sheet layer; an innermost layer made of a spunbond nonwoven fabric or having a three-layer structure including; A barrier layer made of a melt blown nonwoven fabric; The breathable antibacterial fiber sheet layer; And it may have a four-layer structure including; the 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 excellent breathability and may have a filter role to block dust or dust that can be observed with the naked eye. This can be an excellent one.

For example, the outermost layer or the innermost layer of the spunbond nonwoven fabric may be used without particular limitation as long as it is commonly used in the art, and as a specific example, polypropylene fibers, polyolefin fibers, polyester fibers and polyamide 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 charged with static electricity in the process of being manufactured through a melt blown method to effectively collect and filter fine dust or fine particles, etc., 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 fibers, polyester fibers, and polyamide fibers are spun in a melt blown method to prevent static electricity. It may be a nonwoven fabric charged with.

In addition, the antimicrobial mask includes an inorganic nanocomposite prepared by supporting zinc oxide nanoparticles through a solvent heat 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 an inorganic nanocomposite prepared by dispersing in water. In this case, the post-treatment may be dried by spraying the aqueous dispersion of the inorganic nanocomposite onto an antibacterial mask, and spraying may be repeatedly performed at least once.

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

The water-soluble polymer binder is intended to allow the inorganic nanocomposite to adhere well to the antibacterial mask during post-treatment, and it is preferable to use a water-soluble polymer binder that is well soluble in water and has excellent adhesion, and a specific example is natural such as alginic acid and chitosan. A polymer, a urea 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. Spray spraying is easy in this range, and while the inorganic nanocomposite can be adhered well, it may not clump together.

In addition, the aqueous dispersion of the inorganic nanocomposite may further include zinc pyrithione, thereby further improving antibacterial performance and antibacterial performance. At this time, 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 may have more excellent antibacterial performance and antibacterial performance.

Hereinafter, a breathable antibacterial fiber sheet according to the present invention, a method of manufacturing the same, and an antibacterial mask including the same will be described in more detail through examples. However, the following examples are only one reference for describing the present invention in detail, and the present invention is not limited thereto, and may be implemented in various forms.

Further, 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 the present invention belongs. The terms used in the description herein are merely to effectively describe specific embodiments and are not intended to limit the invention. In addition, the unit of the additive not specifically described in the specification may be a weight %.

[Production Example 1]

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

Next, an inorganic nanocomposite was prepared in which zinc oxide (ZnO) nanoparticles were supported on diatomaceous earth nanoparticles through the following solvent heat (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. In addition, zinc chloride (ZnCl ₂ ) was dissolved in 10 ml of methanol to prepare a 0.1 M zinc chloride solution to prepare a second reaction solution.

Under an ice bath, the first reaction solution and the second reaction solution were placed in an ultrasonic reactor, followed by vigorous ultrasonic agitation for 1 hour. Thereafter, the reaction mixture was put into a high-pressure reactor, and the temperature was raised to 120° C. and reacted for 12 hours. 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 put in a rotary kiln and fired at 500°C for 6 hours.

[Production Example 2]

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

[Production Example 3]

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

[Production Example 4]

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, an inorganic nanocomposite in which zinc oxide (ZnO) nanoparticles were supported on the diatomaceous earth nanoparticles was prepared. Obtained.

[Production Example 5]

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, an inorganic nanocomposite in which zinc oxide (ZnO) nanoparticles were supported on the diatomaceous earth nanoparticles was prepared. Obtained.

[Production Example 6]

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, an inorganic nanocomposite in which zinc oxide (ZnO) nanoparticles were supported on the diatomaceous earth nanoparticles was prepared. Obtained.

[Production Example 7]

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, the inorganic nanocomposite in which zinc oxide (ZnO) nanoparticles were supported on the diatomaceous earth nanoparticles was prepared. Obtained.

[Production Example 8]

Zinc oxide in diatomaceous earth nanoparticles was carried out in the same manner as in Preparation Example 2 except that the first reaction solution and the second reaction solution were added to a general stirred reactor without using an ultrasonic reactor and then stirred at a speed of 500 rpm. 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 pulverizing diatomaceous earth with a nanoset mill (model name TNS010).

[Comparative Preparation Example 2]

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

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. In addition, zinc chloride (ZnCl ₂ ) was dissolved in 10 ml of methanol to prepare a 0.1 M zinc chloride solution to prepare a second reaction solution. Under an ice bath, the first reaction solution and the second reaction solution were placed in an ultrasonic reactor, followed by vigorous ultrasonic agitation for 1 hour. Thereafter, the reaction mixture was put into a high-pressure reactor, and the temperature was raised to 120° C. and reacted for 12 hours. 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 put in a rotary kiln and fired 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 nanoparticles having an average particle size of 500 nm were obtained by wet grinding with a nanoset mill (model name TNS010) equipment, and all processes were performed in the same manner as in Preparation Example 1 except for adding this to the first reaction solution. Thus, an inorganic nanocomposite was obtained in which zinc oxide (ZnO) nanoparticles were supported on diatomaceous earth nanoparticles.

[Example 1]

With respect to 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 150 nm) were mixed to prepare a masterbatch composition, and in a conventional melt blown method An antibacterial fiber sheet (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, respectively, of the inorganic nanocomposite prepared in Preparation Example 2 (Example 5), 50 parts by weight (Example 6) were mixed to prepare a master batch, and all processes were performed in the same manner as in Example 1 to prepare an antibacterial fiber sheet.

[Examples 7 to 12]

With respect to 100 parts by weight of the polypropylene chip, 15 parts by weight of the inorganic nanocomposite prepared in Preparation Examples 3 to 8 were each mixed to prepare each master batch of Examples 7 to 12, and all processes were performed in the same manner as in Example 1. Thus, an antibacterial fiber sheet 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, all the processes were carried out in the same manner as in Example 1, except that only the diatomaceous earth nanoparticles prepared in Comparative Preparation Example 1 were mixed in 15 parts by weight instead of the inorganic nanocomposite. Was 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 fiber sheet.

[Comparative Example 2]

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 fiber sheet.

[Characteristic evaluation]

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

Specifically, Examples 1 to 15 and Comparative Examples 1 and E. coli in the antimicrobial fiber sheet prepared in 2 (Escherichia coli) 9.2 × 10 4 CFU / ㎖, Staphylococcus aureus ^{(staphylococos aureus) 8.9 × 10 4} CFU / ㎖, rat typhoid bacteria ^{(Salmonella typhimurium) 7.4 × 10 4} CFU / ㎖ and Klebsiella pneumoniae ^{(Klebsiella pneumoniae) 9.1 × 10 4} CFU / ㎖ each inoculated to an initial density (a _0, CFU / ㎖) and, 24 hours at 37.0 ± 0.2 ℃ After leaving for a while, the concentration (A ₁ , CFU/ml) was checked, 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: Deodorization performance was tested by the method of FTM-5-2:2004 in the FITI test guideline.

In detail, the antimicrobial fiber sheets prepared in Examples 1 to 15 and Comparative Examples 1 and 2 were cut into 10 cm×10 cm, respectively, to prepare a test piece, and after inserting it into a test gas pack of ammonia gas having an initial concentration of 100 ppm, gas detection Deodorization rate (%) was measured using a conventional method (KICM-FIR-1004), 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, and C _b is the concentration (ppm) of ammonia gas remaining in the test gas pack after 2 hours without adding the antibacterial fiber sheet test piece (blank). , C _s is the concentration (ppm) of ammonia gas remaining in the test gas pack after 2 hours have elapsed after putting the antibacterial fiber sheet 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 described in Table 1, it was confirmed that the antibacterial fiber sheet according to the present invention has excellent 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 antimicrobial performance was slightly inferior, and in the case of Example 6 in which the inorganic nanocomposite was added too much, the mechanical properties of the sheet were somewhat poor, so that reuse during washing was not possible. .

In the case of Example 8, in which a small amount of diatomaceous earth nanoparticles were added during the solvent heat synthesis, the surface of the diatomaceous earth nanoparticles was coated with zinc oxide, and as the pores partially disappeared, the gas adsorption capacity was slightly lowered and the deodorizing performance was lowered. In the case of Example 11 in which an excess of was added, the antimicrobial performance was slightly lowered as the ratio of zinc oxide in the inorganic nanocomposite decreased.

On the other hand, in the case of Comparative Example 1 in which only diatomaceous earth nanoparticles were added, the antimicrobial performance was very poor, and in the case of Comparative Example 2 in which zinc oxide was prepared without adding diatomaceous earth nanoparticles during solvent heat synthesis, and then added as a mixture, also oxidation Due to the occurrence of zinc aggregation, the antibacterial performance was slightly lowered. In the case of Comparative Example 3, as diatomaceous earth nanoparticles having a somewhat larger particle size were used, the mechanical properties of the sheet were somewhat poor, so that reuse during washing was not possible.

[Production Example 9]

All processes were performed in the same manner as in Preparation Example 2, except that the sintering 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 firing 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 firing 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 each mixed to prepare each master batch of Examples 13 to 15, and all processes were performed in the same manner as in Example 1. Thus, an antimicrobial fiber sheet was prepared. (Example 13-Preparation Example 9, Example 14-Preparation Example 10, Example 15-Preparation Example 11)

[Evaluation of washing fastness characteristics]

The antibacterial fiber sheets prepared in Example 2, Examples 13 to 15, and Comparative Example 2 were washed 5 times by standard washing, and then 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 in which 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. Could be confirmed.

On the other hand, in the case of Example 13 in which the sintering temperature was too low, it was confirmed that the antibacterial performance was greatly degraded due to the occurrence of desorption of the zinc oxide nanoparticles from the porous inorganic nanoparticles after washing due to poor washing fastness.

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

On the other hand, in the case of Comparative Example 2, as diatomaceous earth nanoparticles and zinc oxide nanoparticles were added by mixing, respectively, the washing fastness was poorer than that of Example 13, and accordingly, the antibacterial performance was greatly reduced.

Although the present invention has been described through the above-specified matters and limited embodiments, this is only provided to help a more general understanding of the present invention, and the present invention is not limited to the above embodiments, and the present invention pertains to Those of ordinary skill in the field can make various modifications and variations from this description.

Therefore, the spirit of the present invention is limited to the described embodiments and should not be defined, and all things that are equivalent or equivalent to the claims as well as the claims to be described later fall within the scope of the spirit of the present invention. .

Claims (10)

Base resin; And
An inorganic nanocomposite prepared by supporting zinc oxide nanoparticles through a solvent heat synthesis reaction on porous inorganic nanoparticles having an average particle size of 100 to 300 nm;
Breathable antibacterial fiber sheet, characterized in that the master batch composition comprising a melt blown (melt blown) is produced by spinning. The method of claim 1,
The porous inorganic nanoparticles are diatomaceous earth, breathable antibacterial fiber sheet. The method of claim 1,
The masterbatch composition will contain 5 to 30 parts by weight of the inorganic nanocomposite based on 100 parts by weight of the base resin, breathable antibacterial fiber sheet. 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, breathable antibacterial fiber sheet. a) preparing porous inorganic nanoparticles by wet grinding the porous inorganic particles to 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 solvent heat synthesis reaction;
c) preparing a masterbatch composition comprising the inorganic nanocomposite and a base resin; And
d) manufacturing a breathable antibacterial fiber sheet by spinning the master batch composition in a melt blown method;
Method for producing a breathable antibacterial fiber sheet comprising a. The method of claim 5,
Step b),
I) preparing a first reaction solution in which porous inorganic nanoparticles and sodium hydroxide are added to a first alcohol solvent, and a second reaction solution in which zinc chloride is dissolved in a second alcohol solvent;
Ii) preparing a reaction mixture by putting the first reaction solution and the second reaction solution into 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 reacting in a high-pressure reactor by applying a temperature of 80 to 150°C to the reaction mixture; And
Iv) firing the inorganic nanocomposite;
Containing, a method for producing a breathable antibacterial fiber sheet. An antibacterial mask comprising the breathable antibacterial fiber sheet of any one of claims 1 to 4. The method of claim 7,
The antibacterial mask includes 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 breathable antibacterial fiber sheet layer. The method of claim 7,
The antibacterial mask includes an innermost layer made of a spunbond nonwoven fabric; A barrier layer made of a melt blown nonwoven fabric; The breathable antibacterial fiber sheet layer; And an outermost layer made of a spunbond nonwoven fabric, which has a four-layer structure including. The method of claim 7,
The antimicrobial mask may include an inorganic nanocomposite prepared by supporting zinc oxide nanoparticles through a solvent heat synthesis reaction on porous inorganic nanoparticles having an average particle size of 100 to 300 nm; And a water-soluble polymeric binder; which is post-treated with an aqueous dispersion of an inorganic nanocomposite prepared by dispersing in water.