KR102139710B1 - Method for manufacturing nanofiber membrane, nanofiber membrane and mask filter comprising the same - Google Patents

Abstract

The present invention relates to a method for manufacturing a nanofiber membrane, a nanofiber membrane and a mask filter comprising the same, comprising: preparing a spinning solution comprising a polymer resin and an adhesive material; And spinning the spinning solution to form a nano-fiber film; provides a method for producing a nano-fiber film comprising a. In addition, a nano-fiber film prepared by the above manufacturing method and a mask filter including the same are provided.

Description

Method for manufacturing nanofiber membrane, and mask filter comprising the same{Method for manufacturing nanofiber membrane, nanofiber membrane and mask filter comprising the same}

The present invention relates to a method for manufacturing a nanofiber membrane, a nanofiber membrane and a mask filter comprising the same.

In general, it is well known that fine dust has a very harmful effect on the human body to the extent that it is designated as a primary carcinogen by the World Health Organization (WHO). When the concentration of fine dust is very high, such as smog or yellow sand, which frequently occurs recently, wearing a yellow dust mask to protect your health from fine dust is the only way to protect your health. However, various types of yellow dust masks have limitations in improving the removal performance of fine dust as well as limitations in effectively blocking dust because the mask body itself acts as a filter for filtering fine dust contained in the air. I had.

Accordingly, it is necessary to develop a mask that can be easily carried and worn even when going out by combining a technology that blocks fine dust with a very high removal performance through a high performance filter.

Many conventional mask filters often use a hepa filter. At this time, there are problems in that breathing is not smooth due to a high differential pressure and a problem of air leakage, and there are attempts to solve it in various physical methods.

As a way to solve the shortcomings of these existing filters and masks, recently, attempts to use a mask filter including the same by using the characteristics of the electrospinning micro or nanofibers having a large surface area and porosity compared to the volume have been published in various patents. In addition, there have been attempts to filter bio-microorganisms and viruses by adding antibacterial agents. These polymer micro or nanofiber membranes have been recently studied for their efficiency in filtering particulate matter (PM), which is a problem in recent years, but have limitations in filtration of bio-float and hydrocarbon-based fine dust. Research to solve is being actively conducted. In addition, above all, there is no solution to the inhalation of toxic substances from the polymer fiber membrane itself, which is a component of the fine dust mask, and the solution to the toxicity of the components of the mask itself.

It is an object of the present invention to provide a nanofiber membrane that is safe for the human body by being made of a biodegradable material having excellent collection efficiency for fine dust and bio-float, and excellent biocompatibility.

In order to achieve the above object, the present invention comprises the steps of preparing a spinning solution comprising a polymer resin and an adhesive material; And spinning the spinning solution to form a nanofiber film; and the adhesive material provides a method of manufacturing at least one nanofiber film selected from the group consisting of an adhesive protein, an adhesive polysaccharide, and an adhesive polymer.

In addition, the present invention provides a nanofiber membrane manufactured by the method for manufacturing the nanofiber membrane.

In addition, the present invention provides a mask filter comprising the nano-fiber film.

Since the nanofiber membrane of the present invention contains an adhesive material, not only the dust collection efficiency for fine dust having polarity is much improved, but also the collection efficiency for non-polar materials (hydrocarbons, biomaterials such as bacteria and fungi, suspended solids, etc.) It has a very good effect.

In addition, polymer resins such as PVA and PEO are biodegradable materials that have excellent biocompatibility and are environmentally friendly because they have a property of dissolving in water, and adhesive materials are biomaterials such as natural materials. It has an excellent effect.

In addition, since it can be manufactured by a simple spinning method without requiring additional auxiliary equipment (ionization equipment, plasma equipment, etc.) for improving the dust collection rate of the nanofiber membrane, productivity can be improved and manufacturing costs can be reduced.

1 is a photograph confirming the structure of the nanofiber membrane by SEM after collecting fine dust on the nanofiber membranes of Examples 1 to 4 using the adhesive material and the nanofiber membranes of Comparative Example 1 without using the adhesive material.
Figure 2 is a nanofiber film of Examples 1 to 4 using the adhesive material and the nanofiber film of Comparative Example 1 that does not use the adhesive material, the comparison of the results before (a) and after (b) dust collection experiment It is a picture.
3 is a photograph of a total of 25 samples of the spinning solution prepared in Example 5.
FIG. 4 is a photograph showing the results of an adhesion test on the nanofiber film of Example 2 using an adhesive material and the nanofiber film of Comparative Example 1 without using an adhesive material.

Hereinafter, the present invention will be described in detail.

The present invention provides a method for manufacturing a nanofiber membrane.

The manufacturing method of the nano-fiber film includes preparing a spinning solution containing a polymer resin and an adhesive material, and forming a nano-fiber film by electrospinning the spinning solution.

A spinning solution is prepared by dissolving a polymer resin and an adhesive substance in a solvent. At this time, the polymer resin may be first dissolved in a solvent, the adhesive material may be dissolved first, or the two may be mixed and then dissolved together, but unless otherwise specified, the polymer resin is first dissolved and then the adhesive material is dissolved. Prepare a spinning solution.

The polymer resin is dissolved in a solvent. At this time, it is preferable to dissolve the polymer resin in a solvent at a temperature of room temperature to 100°C, for example, 40°C to 90°C, and when dissolved at a temperature below room temperature, the polymer resin may not be dissolved in the solvent, and 100°C When dissolved at an excess temperature, the inherent properties of the polymer resin may be denatured.

The polymer resin may be electrospinned to form fibers, that is, a spinning polymer resin may be used without limitation, for example, polycaprolactone (poly(e-caprolactone)); PCL], polylactic acid [(poly)lactic acid; PLA], polyglycolic acid [(poly)glycolic acid; PGA], poly(hydroxy valerate); PHV], poly(lactic-co-glycolic acid) PLGA, poly-hydroxy butyrate (PHB), polyhydroxybutylate cobalerate [poly(hydroxy butyrate-co-valerate); PHBV], polyanhydride, polyorthoester, poly(vinyl alchol); PVA], polyethylene oxide (PEO), polyurethane (polyurethane), polyacrylic acid (PAA), poly-N-isopropylacrylamide [poly(N-isopropylacrylamide)], diol/diacid aliphatic Polyester, polyester-amide/polyester-urethane, polypropylene (PP), polyethylene terephthalate (PET), polyvinylidene fluoride ( poly vinylidene fluoride), nylon, and poly(vinyl acetate); PVAc], polymethyl methacrylate [Poly(methyl methacrylate); PMMA], polyacrylonitrile (PAN), poly(butyleneterephthalate); PBT], Poly vinyl butyral, Poly vinyl chloride (PVC), Polyethyleneimine (PEI), Polyolefin, Polyethylene naphthalate (PEN), Polyamide ( Polyamide; PA), silk, cellulose, and the like, specifically, polyvinyl alcohol, polycaprolactone, polyethylene glycol, polyacrylic acid, polymethyl methacrylate, and the like.

The solvent is phenol, formic acid, sulfuric acid, m-cresol, thifluoroacetand hydride/dichloromethane, water, N-methylmorpholine N-oxide, chloroform, tetrahydrofuran, and methyl iso, a group of aliphatic ketones. Butyl ketone, methyl ethyl ketone, aliphatic hydroxyl group m-butyl alcohol, isobutyl alcohol, isopropyl alcohol, methyl alcohol, ethanol, aliphatic compounds hexane, tetrachloroethylene, acetone, glycol group, propylene glycol, diethylene glycol, ethylene Trichloroethylene, dichloromethane, aromatic compound group toluene, xylene, and cyclohexanone, cyclohexane and ester groups of n-butyl acetate, ethyl acetate, and aliphatic ether groups as a group of aliphatic cyclic compounds. As butyl cellosolve, acetic acid 2-ethoxyethanol, 2-ethoxyethanol, amide, dimethylformamide, dimethylacetamide, and the like can be used, and a mixture of a plurality of solvents can be used.

On the other hand, in terms of biocompatibility, it is preferable to use water (eg, distilled water), a pH buffer solution, etc., and these may be used alone or in combination. Specifically, as the pH buffer solution, a phosphate buffer solution, a phosphate buffered saline solution, or an acetic acid buffer solution may be used. In this case, when a buffer solution is used as a solvent, the salt contained in the buffer solution may be included in a concentration of 0.1 to 15% (w/w).

The polymer resin may be dissolved in the spinning solution at a concentration of 1 to 15% (w/w), preferably 3 to 10% (w/w). When the concentration of the polymer resin is less than 1% (w/w), it is spun in the form of beads due to the low viscosity of the spinning solution, and the diameter of the fibers increases, so that the dust collection efficiency may decrease. When the concentration of the polymer resin exceeds 15% (w/w), the viscosity of the spinning solution becomes too high, so that the nanofiber film may be difficult to manufacture because it is not spinning.

Next, a spinning solution is prepared by dissolving an adhesive substance in a solution in which the polymer resin is dissolved. At this time, the temperature at which the adhesive material is dissolved is preferably 80° C. at room temperature, and when the temperature is lower than room temperature, the adhesive material may not be dispersed in the spinning solution, and when the temperature is higher than 80° C., the adhesive material is denatured and denatured. There may be problems with reliability and reproducibility.

The adhesive material is for simultaneously improving the dust collection efficiency for polar materials such as fine dust and the collection efficiency for non-polar materials such as bio-float, since the adhesive material itself has adhesive strength, it may be easier to collect fine dust. have. The adhesive material may be an adhesive protein, an adhesive polysaccharide, an adhesive polymer, or the like. Specifically, the adhesive material may be mucin, mucoid, gelatin, chitin, chitosan, amylopectin, and the like.

The adhesive material may be dissolved in the spinning solution at a concentration of 0.01 to 15% (w/w), preferably 0.01 to 10% (w/w). If the concentration of the adhesive material is less than 0.01% (w/w), the proportion of the adhesive material is relatively small, and thus the adhesive strength of the spun fiber film may be lowered, and the concentration of the adhesive material exceeds 15% (w/w). If the dispersion of the spinning solution is not perfect, the workability may be poor when manufacturing a fiber membrane through electrospinning.

On the other hand, the polymer resin and the adhesive material dissolved in the spinning solution may be included in a weight ratio of 1: 0.01 to 1, specifically 1: may be included in a weight ratio of 0.1 to 0.5. When the content ratio of the adhesive material to the polymer resin 1 is less than 0.01, dust collection efficiency may be substantially deteriorated, and if it exceeds 1, workability may be deteriorated, such as dispersion degree dropping.

The nanofiber membrane is prepared by spinning the spinning solution prepared as described above.

The spinning may use a non-woven fabric, a mesh material, etc. as a substrate, the non-woven fabric may be used in a thickness of 0.1 mm to 5.0 mm, and the mesh material may be used in a thickness of 0.1 mm to 1.0 mm, but is not limited thereto. Commercialized products can also be used.

The material of the nonwoven fabric and the mesh material is poly(e-caprolactone); PCL], polylactic acid [(poly)lactic acid; PLA], polyglycolic acid [(poly)glycolic acid; PGA], poly(hydroxy valerate); PHV], poly(lactic-co-glycolic acid) PLGA, poly-hydroxy butyrate (PHB), polyhydroxybutylate cobalerate [poly(hydroxy butyrate-co-valerate); PHBV], polyanhydride, polyorthoester, poly(vinyl alchol); PVA], polyethylene oxide (PEO), polyurethane (polyurethane), polyacrylic acid (PAA), poly-N-isopropylacrylamide [poly(N-isopropylacrylamide)], diol/diacid aliphatic Polyester, polyester-amide/polyester-urethane, polyethylene (PE), polypropylene (PP), polyethylene terephthalate (PET) , Polyvinylidene fluoride, nylon, poly(vinyl acetate); PVAc], polymethyl methacrylate [Poly(methyl methacrylate); PMMA], polyacrylonitrile (PAN), poly(butyleneterephthalate); PBT], Poly vinyl butyral, Poly vinyl chloride (PVC), Polyethyleneimine (PEI), Polyolefin, Polyethylene naphthalate (PEN), Polyamide ( Polyamide; PA), silk, cellulose, and the like, specifically, polyethylene, polypropylene, polyethylene oxide, polyethylene terephthalate, and the like.

The spinning may be compound spinning, melt blown spinning, flash spinning, electrospinning, etc., and it is preferable to perform electrospinning in consideration of polymer diversity, simplicity of manufacturing process, commercialization potential, and applicability to various technologies. At this time, the voltage of the electric radiation is adjusted to 10 to 25 kV, and the flow rate is preferably adjusted to 0.1 to 1.5 ml/h. When the voltage is less than 10 kV, there is a problem of spraying in a particle form, not a fiber form, and when it exceeds 25 kV, there may be a safety problem. In addition, if the flow rate is less than 0.1 ml/h, there is a problem that the spinning takes too long because the speed is too slow, and when it exceeds 1.5 ml/h, there is a problem that the loss of the spinning solution increases during spinning.

In addition, it is preferable to adjust the distance between the syringe needle and the spun fiber collection plate during the spinning to 10 to 25 cm, and when the distance between the syringe needle and the spun fiber collection plate is closer than 10 cm, the fiber is too small area The whole spun fiber may be uneven, and when it is farther than 25 cm, the voltage may not be properly applied to both the syringe needle and the spun fiber collection plate, so that spun may not be properly performed.

The nanofibrous film obtained under the above conditions has a structure in which nanofibers having a uniform thickness are entangled with each other in the form of a nonwoven fabric.

On the other hand, the nano-fiber membrane obtained as described above may be further performed by immersing in a solution in which the adhesive material is dissolved in order to further improve dust collection.

As the solution in which the adhesive substance is dissolved, it is preferable to use water (eg, distilled water), a pH buffer solution, etc. from the viewpoint of biocompatibility, and these may be used alone or in combination. Specifically, the pH buffer solution may be a phosphate buffer (Phosphate buffer), phosphate buffered saline (Phosphate buffered saline), acetic acid buffer (Acetic acid buffer) and the like.

The adhesive material in the solution may be dissolved at a concentration of 0.05 to 30% (w/w), preferably 0.1 to 20% (w/w), and the concentration of the adhesive material is less than 0.05% (w/w) The dust collection efficiency can be remarkably reduced, and if it exceeds 30% (w/w), the viscosity of the solution becomes too high, making it difficult to manufacture the nanofiber film because it is not spun.

The nanofiber membrane prepared as described above may be used to manufacture a mask filter. The mask filter made of the nanofiber membrane manufactured according to the present invention can improve the dust collection efficiency of the mask filter for polar substances such as fine dust and non-polar substances such as bio-floats due to the adhesive material contained in the nanofiber membrane.

Hereinafter, the present invention will be described in detail by examples.

However, the following examples specifically illustrate the present invention, and the contents of the present invention are not limited by the following examples.

Example One

5 g of polyethylene oxide (Mw: ~1,000,000, sigma) was dissolved in 100 g of acetic acid buffer solution at a concentration of 7% (w/w). Dissolve 0.1 g of mucin (Mucin from porcine stomach, Type II, sigma) in the solution prepared as above to prepare a spinning solution. The spinning solution was fixed at a distance of 15 cm from the distal end of the spinneret of the electrospinning device to 15 cm, and the voltage was 15 kV, and at a flow rate of 1.0 ml/h through a single nozzle, the spinning solution prepared as above. A nanofiber membrane was prepared by electrospinning. After collecting the fine dust on the nanofiber membrane prepared as described above, it was confirmed by SEM, and the results are shown in FIG. 1(a).

Example 2

5 g of polyethylene oxide (Mw: ~1,000,000, sigma) was dissolved in 100 g of acetic acid buffer solution at a concentration of 7% (w/w). In the solution prepared as above, 0.5 g of mucin (Mucin from porcine stomach, Type II, sigma) was dissolved to prepare a spinning solution. The spinning solution was fixed at a distance of 15 cm from the distal end of the spinneret of the electrospinning device to 15 cm, and the voltage was 15 kV, and at a flow rate of 1.0 ml/h through a single nozzle, the spinning solution prepared as above. A nanofiber membrane was prepared by electrospinning. After collecting the fine dust on the nanofiber membrane thus prepared, it was confirmed by SEM and the results are shown in FIG. 1(b).

Example 3

5 g of polyethylene oxide (Mw: ~1,000,000, sigma) was dissolved in 100 g of acetic acid buffer solution at a concentration of 7% (w/w). A spinning solution is prepared by dissolving 1.0 g of mucin from porcine stomach (Type II, sigma) in the solution prepared as described above. The spinning solution is fixed at a distance of 15 cm from the distal end of the spinneret of the electrospinning device to 15 cm, and the voltage is fixed at 15 kV, at a flow rate of 1.0 ml/h through a single nozzle, and the spinning prepared as above. The nanofiber membrane was prepared by electrospinning the solution. After collecting the fine dust on the nanofiber membrane prepared as described above, it was confirmed by SEM, and the results are shown in FIG. 1(c).

Example 4

5 g of polyethylene oxide (Mw: ~1,000,000, sigma) was dissolved in 100 g of acetic acid buffer solution at a concentration of 7% (w/w). Here, 3.0 g of mucin (Mucin from porcine stomach, Type II, sigma) was dissolved to prepare a spinning solution. The spinning solution was fixed at a distance of 15 cm from the distal end of the spinneret of the electrospinning device to 15 cm, and the voltage was 15 kV, and at a flow rate of 1.0 ml/h through a single nozzle, the spinning solution prepared as above. A nanofiber membrane was prepared by electrospinning. After collecting the fine dust on the nanofiber membrane thus prepared, it was confirmed by SEM and the results are shown in FIG. 1(d).

Comparative example One

5 g of polyethylene oxide (Mw: ~1,000,000, sigma) is dissolved in 100 g of acetic acid buffer solution at a concentration of 7% (w/w). Using the electrospinning device, the distance from the distal end of the spinneret to the integrated plate was fixed at 7 cm and the voltage was 17 kV, and then electrospun at a flow rate of 0.3 ml/h through a single nozzle to prepare a nanofiber membrane. After collecting the fine dust on the nanofiber membrane thus prepared, it was confirmed by SEM and the results are shown in FIG. 1(e).

Example 5

0, 1, 3, 5 and 7% (w/w) acetic acid buffer solution (distilled water if the concentration of acetic acid is 0% (w/w)) to 10 g, 0.45 g polyethylene oxide (Mw: ~1,000,000, sigma). In each of the five types of solutions prepared as above, 0, 7, 12, 50 or 100 g of mucin (Mucin from porcine stomach, Type II, sigma) was dissolved, respectively, to prepare a total of 25 types of spinning solution samples. The names of the 25 samples prepared as described above were respectively designated in the form of'AD # ₁ -# ₂ ', # ₁ represents the concentration [% (w/w)] of acetic acid buffer solution, and # ₂ represents the amount of mucin (g ). 3 is a photograph of a total of 25 samples of the spinning solution prepared as described above.

The distance from the distal end of the spinneret of the electrospinning device to the integrated plate was fixed at 15 cm, and the voltage was 10-18 kV, at a flow rate of 1.0 ml/h through a single nozzle, 25 spinning solutions prepared as above. A total of 25 nanofiber membranes were respectively produced by electrospinning the sample.

Experimental Example

For the nanofiber membranes prepared in the above Examples and Comparative Examples, the dust collection rate and adhesion were confirmed by the following method.

<dust collection rate>

In the test jig equipped with the nanofiber membranes of Examples 1 to 4 and Comparative Example 1, the fragrance generating PM2.5 fine dust was burned and flowed using a fan or a vacuum pump, and the fine dust concentration before and after passing through the nanofiber membrane By comparing it was calculated as the dust collection rate. And the difference in pressure (differential pressure) before and after passing through the nanofiber membrane was measured by a differential pressure sensor and is shown in Table 1 below. In Table 1 below, E is the dust collection rate and ΔP is the differential pressure. And the photo of the nanofibrous film of Examples 1 to 4 and Comparative Example 1, before and after passing through the fine dust as shown above is shown in FIG. 2.

Example 1 Example 2 Example 3 Example 4 Comparative Example 1 △P [Pa]
(Differential pressure) 85-115 85-114 80-107 108- 151 105-160 E [%]
(Dust collection rate) 91.45-92.56 95.45-97.60 74.44-76.45 66.50- 68.72 62.54-64.29

In Example 5, a total of 25 nanofiber membranes, prepared using a total of 25 different spinning solution samples, were measured for dust collection and differential pressure in the same manner as above, and the results are shown in Table 2.

AD 0-0 AD 0-7 AD 0-12 AD 0-50 AD 0-100 △P [Pa]
(Differential pressure) 65±10 65±10 65±10 65±10 65±10 E [%]
(Dust collection rate) 51-53 61-65 58-62 50-54 42-45 AD 1-0 AD 1-7 AD 1-12 AD 1-50 AD 1-100 △P [Pa]
(Differential pressure) 65±10 65±10 65±10 65±10 65±10 E [%]
(Dust collection rate) 66-71 84-87 81-84 74-78 69-72 AD 3-0 AD 3-7 AD 3-12 AD 3-50 AD 3-100 △P [Pa]
(Differential pressure) 65±10 65±10 65±10 65±10 65±10 E [%]
(Dust collection rate) 57-60 67-69 65-68 59-63 52-55 AD 5-0 AD 5-7 AD 5-12 AD 5-50 AD 5-100 △P [Pa]
(Differential pressure) 65±10 65±10 65±10 65±10 65±10 E [%]
(Dust collection rate) 51-54 62-67 59-64 52-55 42-44 AD 07-0 AD 7-7 AD 7-12 AD 7-50 AD 7-100 △P [Pa]
(Differential pressure) 65±10 65±10 65±10 65±10 65±10 E [%]
(Dust collection rate) 41-45 50-52 48-51 42-44 39-42

Among the total of 25 samples of Example 5, the nanofiber membranes prepared from the AD 1-7 samples, which were found to be the most effective, were compared with other nanofiber membrane products commercially available in the same manner as above. Table 3 shows the results.

Nano fiber membrane type Differential pressure (Pa) Dust collection efficiency (%) Thickness(mm) Nanofiber membrane made from AD 1-7 sample 150-250 89-97 - H10 grade HEPA filter 35-70 50-60 0.72-0.85 W mask products 221-289 KF 80 grade - W mask products 176-233 KF 94 grade - T mask products 179-236 KF 94 grade -

<Adhesive force>

In order to visually confirm the difference in adhesive strength depending on whether an adhesive material is used, cut the nanofiber membranes prepared in Example 2 and Comparative Example 1 into a circle shape having a diameter of 5 cm, and evenly distribute 1 g of graphite previously ground thereon. Sprinkled. Then, after inverting the nanofiber membrane upside down to remove unadhered graphite, the nanofiber membrane was photographed and shown in FIG. 4.

Claims (8)

Preparing a spinning solution containing a polymer resin and an adhesive material; And
It includes; spinning the spinning solution to form a nano-fiber film;
The adhesive material is a method of manufacturing a nano-fiber membrane containing mucin. The method according to claim 1,
The spinning solution contains the polymer resin and the adhesive material in a weight ratio of 1: 0.01 to 1, the method of manufacturing a nanofiber membrane. The method according to claim 1,
The method of manufacturing a nano-fiber membrane further comprising the step of dipping the nanofiber membrane formed by spinning in a solution in which an adhesive substance is dissolved. The method according to claim 1,
The polymer resin may include poly(e-caprolactone); PCL], polylactic acid [(poly)lactic acid; PLA], polyglycolic acid [(poly)glycolic acid; PGA], poly(hydroxy valerate); PHV], poly(lactic-co-glycolic acid) PLGA, poly-hydroxy butyrate (PHB), poly(hydroxy butyrate-co -valerate); PHBV], polyanhydride, polyorthoester, poly(vinyl alchol); PVA], polyethylene oxide (PEO), polyurethane (polyurethane), polyacrylic acid (PAA), poly-N-isopropylacrylamide [poly(N-isopropylacrylamide)], diol/diacid aliphatic Polyester, polyester-amide/polyester-urethane, polypropylene (PP), polyethylene terephthalate (PET), polyvinylidene fluoride ( poly vinylidene fluoride), nylon, and poly(vinyl acetate); PVAc], polymethyl methacrylate [Poly(methyl methacrylate); PMMA], polyacrylonitrile (PAN), poly(butyleneterephthalate); PBT], Poly vinyl butyral, Poly vinyl chloride (PVC), Polyethyleneimine (PEI), Polyolefin, Polyethylene naphthalate (PEN), Polyamide ( Polyamide; PA), a method for producing a nano-fiber membrane comprising at least one selected from the group consisting of silk and cellulose. delete It contains a polymer resin and an adhesive material,
The adhesive material is a nano-fiber membrane containing mucin. Nanofiber membrane produced by the method of any one of claims 1 to 4. Mask filter comprising the nanofiber film of claim 6.

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