KR102211659B1 - Good with Antiviral and antibacterial Filter cartridgeand method of manufacturing them - Google Patents

Abstract

The present invention relates to a filter cartridge having excellent antiviral and sterilization, and a method of manufacturing the same, and more particularly, has the advantage of being capable of removing viruses while having removal efficiency of bacteria and bacteria.
Furthermore, the present invention as described above makes it possible to provide a filter cartridge that solves the problem of bacterial growth and thus a decrease in use cycle occurring in the core while maintaining a high flow rate.

Description

Good with Antiviral and antibacterial Filter cartridge and method of manufacturing them}

The present invention relates to a filter cartridge having excellent antiviral and sterilization, and a method for manufacturing the same, and more particularly, to a filter cartridge having excellent antiviral and sterilization excellent antiviral and sterilization efficiency while having removal efficiency of bacteria and bacteria and the like, and manufacturing the same. It's about how.

In general, many ionic substances and chemical substances, including natural organic matter (NOM), exist in water, and they are not removed in the water treatment process and act as a causative substance that generates new pollutants. In addition, in recent years, the existence of pathogenic microorganisms that have not been removed by chlorine disinfection has been controversial. Pathogenic microorganisms classified as viruses, Cryptosphoridium, and Giardia are discharged into the environment through human and animal feces and are present in not only sewage but also surface water and groundwater. Viruses have a size of 0.02 ~ 0.09㎛, bacteria are 0.4 ~ 14㎛, width 0.2 ~ 1.2㎛. Protozoa such as Cryptosporidium and Xyaldia are relatively larger than viruses or bacteria. Viruses are very small in size, so they are hardly treated by general filtration, and they form a highly resistant cyst, and live stably in water for several months or longer. Currently, in order to remove trace pollutants from water, advanced coagulation treatment, activated carbon adsorption, and membrane filtration are being suggested in the water treatment process. Recently, large-scale research on water treatment processes using membranes is underway.

In particular, a lot of research has been conducted on membrane filtration in recent years, and practical use in advanced water treatment is being investigated, but it is still not widely used due to economical cost and technical problems. Existing filters, including membranes classified as reverse osmosis membranes (RO), nanofiltration membranes (NF), ultrafiltration membranes (UF), and microfiltration membranes (MF), use the size of pores to remove contaminants in water based on a physical mechanism. It is a system to remove.

The main mechanism for removing contaminants from the membrane is to remove bacteria, viruses and organic contaminants floating in the water by applying the sieve effect, that is, removal by particle size. In addition to the removal by the particle size, microorganisms in water are also filtered by electrostatic adsorption according to the surface charge of the separator, and this method is being studied in the spotlight for its high water permeability and high particle removal performance compared to a small operating pressure.

Conventional microfiber filters widely used for water treatment have a disadvantage in that the filtration area is small and there is no electrostatic force, so the efficiency is low. The membrane filter has a disadvantage in that the filtration efficiency is high but the pressure loss is large. Accordingly, research is being conducted to increase the filtration efficiency of the fiber filter and reduce the pressure loss by imposing an electrostatic force on the fiber filter having nano-sized pores to compensate for the disadvantages of the micro fiber filter and the membrane filter.

For example, in the prior art, glass fiber is used as a basic filter for the manufacture of antiviral media, and a positively charged filter is manufactured by adding an inorganic compound having a positive charge during the production of glass fiber, and the virus is adsorbed and removed using it. (Korean Patent Publication No. 10-2004-0101723). However, since this technology uses glass fibers, there is a problem that the suitability of the water treatment process is concerned due to the controversy of harmfulness such as carcinogenesis, and there is a problem that it cannot be diversified in the product line by the compounds added during manufacture using glass fibers.

As another conventional technique, positive charge was used as an organic compound, and the stability of the filter medium was improved by using a polypropylene filter material instead of glass fiber, and a positive charge filter filter material was manufactured by a post-treatment coating method (Japanese Patent Laid-Open Patent No. 1994-015167). . However, this technology has a problem that not only virus can be removed, but also bacteria and bacteria cannot be removed, and flow rate and filtration pressure are significantly lowered.

In addition, the filter of the prior art has a problem that bacteria proliferate in the core, and the use cycle is short, and thereby there is also an economic problem due to frequent replacement.

The present invention was conceived to solve the above problems, and an object of the present invention is that it is possible to remove nano-sized viruses while maintaining the ability to remove bacteria and bacteria, thereby having excellent filtration efficiency and improved use cycle To provide a cartridge.

In order to solve the above problems, the present invention is a composite filter including a polysulfone-based separator; And an antibacterial core; providing a filter cartridge having excellent antiviral and antibacterial properties.

According to a preferred embodiment of the present invention, in the composite filter, the polysulfone-based separator is laminated on one surface of an antiviral nonwoven fabric in a filtering direction, and the antiviral nonwoven fabric may be a single layer or a multilayer. In addition, the antibacterial core is an inorganic compound containing at least one selected from silver (Ag), aluminum (Al), copper (Cu), zinc (Zn), iron (Fe) and manganese (Mn); And an amine compound containing at least one selected from polyethyleneimine, diethylenetriamine, piperazine, dimethylene piperazine, and diphenylamine; It may be a polypropylene antibacterial core containing at least one selected from among.

According to a preferred embodiment of the present invention, the polysulfone separator comprises a polysulfone polymer containing at least one selected from polyethersulfone, polysulfone, polyallylethersulfone, polyphenylsulfone and polyetheretherketone. The polysulfone-based separator may have an average pore diameter of 0.1 to 5 μm and an average thickness of 50 to 200 μm.

According to a preferred embodiment of the present invention, the antibacterial core can increase the service life of the filter by inhibiting the propagation of microorganisms such as bacteria and bacteria in water, and preventing pore clogging by bacteria.

According to a preferred embodiment of the present invention, the antiviral nonwoven fabric includes an amine-based coating layer, and the surface charge of the antiviral nonwoven fabric may have a surface charge of 15 to 80 mV, and the amine-based coating layer contains a multifunctional amine compound. Including, the multifunctional amine compound may include an amine-based compound containing at least one selected from polyethyleneimine, diethylenetriamine, piperazine, dimethylene piperazine and diphenylamine.

According to a preferred embodiment of the present invention, the antiviral nonwoven fabric includes at least one selected from polypropylene, polyethylene terephthalate, polyethylene, polyester, nylon and cellulose, and the antiviral nonwoven fabric has an average fineness of 1 to 10 ㎛ and the average pore diameter may be 1 ㎛ ~ 20 ㎛, the antiviral nonwoven fabric may have an average thickness of 0.1 ~ 2㎜.

According to a preferred embodiment of the present invention, the composite filter may have an average weight of 50 to 500 g/m2, an average pore diameter of 0.5 to 2.0 μm, and a water permeation of 40 to 80 ml/cm ² ·min·bar. have.

Another aspect of the present invention provides a filter cartridge having excellent antiviral and sterilization performance of 6log or more and 3log or more of virus removal performance.

Another aspect of the present invention provides a method of manufacturing a filter cartridge having excellent antiviral and antibacterial properties in which a composite filter including a polysulfone separator is bent and bonded to a cylindrical shape, and then an antibacterial core is thermally bonded to the composite filter.

According to a preferred embodiment of the present invention, in the composite filter, the polysulfone separator is laminated on one side of the antiviral nonwoven fabric in the filtering direction, and the antiviral nonwoven fabric may be a single layer or a multilayer, and the antiviral Pre-treating the surface and interior of the nonwoven fabric; And electrostatically treating the pretreated nonwoven fabric. It can be manufactured through a process including.

According to a preferred embodiment of the present invention, the electrostatic treatment may include coating the pretreated nonwoven fabric with an amine-based polymer solution; And immobilizing an amine compound on the nonwoven fabric through crosslinking treatment of the coated nonwoven fabric, and the pretreatment of the pretreatment step is corona, plasma, hydro-charging , Sputtering, primer, flame treatment and acid treatment can be performed by one or more methods selected from.

According to a preferred embodiment of the present invention, the amine-based polymer solution includes a polyfunctional amine compound, and the polyfunctional amine compound is selected from polyethyleneimine, diethylenetriamine, piperazine, dimethylene piperazine and diphenylamine. Amine-based polymer resin containing at least one selected; A solvent containing at least one of C1-C3 alcohol, acetone, and purified water; and the amine-based polymer solution may contain 0.1 to 5% by weight of the amine-based polymer resin.

According to a preferred embodiment of the present invention, the crosslinking treatment is a polyfunctional halogen compound containing at least one selected from xylene dichloride, trimethylbenzoyl chloride, and benzene disulfonyl chloride; And a solvent containing at least one selected from toluene, acetone, N,N-dimethylacetamido, and N-formdimethylamine; a nonwoven fabric coated with an organic solution containing a coating-treated nonwoven fabric at 20°C to 80°C for 30 minutes to 2 This can be done by immersion for hours.

The filter cartridge having excellent anti-virus and sterilization of the present invention has the ability to remove microorganisms such as bacteria and bacteria, while also adsorbing and removing nano-sized viruses.

Further, the filter cartridge having excellent antiviral and sterilization of the present invention solves the problem of bacterial growth occurring in the core and a decrease in use cycle accordingly, and enables more effective removal of bacteria and aquatic microorganisms.

1 is a schematic cross-sectional view of a filter cartridge according to a preferred embodiment of the present invention.
Each of FIGS. 2 and 3 is a schematic diagram of a filter cartridge according to a preferred embodiment of the present invention, and is a cross-sectional view taken along AA of FIG. 3.
4 is a schematic cross-sectional view of a composite filter material according to a preferred embodiment of the present invention.
5 is a schematic cross-sectional view of a composite filter material according to another preferred embodiment of the present invention.

The filtering direction of the present invention indicates the direction of arrows in FIGS. 4 and 5, and indicates a direction out of which a material to be separated flows in.

Hereinafter, the present invention will be described in more detail with reference to the drawings.

As described above, conventionally, since the composite material is made of glass fiber, there is a controversy about harmfulness such as carcinogenesis, and there is a problem that the suitability for use in the water treatment process is concerned, and the product group is diversified by the compound added during manufacture using glass fiber. There was a problem that could not be done. In addition, there is a problem that the life cycle of the filter cartridge is short, which is uneconomical.

Accordingly, according to an aspect of the present invention, a composite filter comprising a polysulfone-based separator; And an antibacterial core; by providing a filter cartridge having excellent antiviral and sterilization, as well as solving the conventional problems, a filter cartridge having excellent antiviral and sterilization performance is provided.

In the filter cartridge of the present invention, the composite filter material is bent and bonded in a cylindrical shape, and then the antibacterial core is thermally bonded by a conventional method, or the antibacterial core and the composite filter material are thermally bonded and then bent to form the antibacterial core and the composite filter material. In this way, by manufacturing the integrated filter cartridge in which the composite filter material and the antibacterial core are integrated, not only the flow rate is high, but also antiviral and sterilization are possible, and a filter cartridge having excellent performance with a long life cycle is produced. Can provide.

Specifically, FIG. 1 is a cross-sectional view of a filter cartridge according to a preferred embodiment of the present invention, in which an antibacterial core having a hollow inside is installed, and a composite filter including a polysulfone separator is wrapped around the outside thereof. Consists of. Each of FIGS. 2 and 3 is a schematic cross-sectional view in the AA direction of the cross-sectional view of FIG. 1 as a cross-sectional schematic view of a filter cartridge according to a preferred embodiment of the present invention, and FIG. 3 is a form in which only a part of the composite filter and the antibacterial core are thermally bonded. And Figure 2 is a form in which the composite filter material and the antibacterial core are entirely bonded.

Conventional filter cartridges have a problem that they are uneconomical due to short use cycles due to the proliferation of bacteria in the core, whereas in the present invention, by using an antibacterial core, the growth of bacteria in the core is suppressed and biofouling is removed. , It is possible to provide a filter cartridge excellent in antiviral and sterilization with improved use cycle, preferably 15% or more increase in use cycle, and more preferably 20% or more use cycle.

In addition, the filter cartridge of the present invention can simultaneously remove microorganisms such as nano-sized viruses and bacteria, unlike conventional filter cartridges that can only remove bacteria or viruses, and also removes viruses and bacteria with high removal performance. can do. The filter cartridge of the present invention may have a bacteria removal performance of 6 log or more and a virus removal performance of 3 log or more, preferably a bacteria removal performance of 6.5 log or more and a virus removal performance of 3.5 log or more, more preferably removal of bacteria Since the performance may be 7log or more and the virus removal performance may be 4.0log or more, it is possible to provide a filter cartridge having excellent antiviral and sterilization that can simultaneously remove bacteria and viruses.

An antibacterial core 303, which is one of the configurations of the present invention, will be described.

The antibacterial core of the present invention inhibits the growth of bacteria to reproduce and develop in water, removes odor, and inhibits biofouling.

The antibacterial core of the present invention is an antimicrobial material, comprising: an inorganic compound containing at least one selected from silver (Ag), aluminum (Al), copper (Cu), zinc (Zn), iron (Fe), and manganese (Mn); And an amine compound containing at least one selected from polyethyleneimine, diethylenetriamine, piperazine, dimethylene piperazine, and diphenylamine; It may contain at least one selected from among, and preferably, it is good to include at least one of silver and aluminum in consideration of antibacterial properties. In addition, the antibacterial core may be a polypropylene antibacterial core based on polypropylene.

Further, the antibacterial core of the present invention may have a disinfecting performance of 98% or more, preferably 99.99%.

Next, a detailed description of the composite filter material 300 is as follows.

The composite filter material constituting the filter cartridge of the present invention is a form in which the polysulfone separator 301 is stacked on one side of the antiviral nonwoven fabric 302 in the filtering direction, and the antiviral nonwoven fabric may be a single layer or a multilayer. In the case of a multilayer, the antiviral nonwoven fabric may preferably include 2 to 5 layers, and as the number of layers increases, the water permeability may be slightly lowered, but filtration efficiency may be improved.

In the present invention, the composite filter may have an average weight of 50 to 500 g/m2, preferably an average weight of 100 to 300 g/m2, and an average pore diameter of 0.5 to 2.0 μm, preferably In this case, if the average weight of the composite filter is less than 50 g/m2, there may be a problem of reducing virus removal performance due to the small amount of virus adsorption. If it exceeds 500 g/m2, pretreatment There may be a problem that the inside of the nonwoven fabric cannot be processed well. In addition, if the average pore diameter is less than 0.5 μm, there may be a problem of decreasing the flow rate, and if it exceeds 2.0 μm, there may be a problem of decreasing virus removal performance.

The polysulfone-based separation membrane 301 constituting the composite filter material as a component of the present invention will be described in detail as follows.

In the present invention, the polysulfone-based separation membrane 301 serves to remove bacteria and germs, and to remove particles having a micro size, and preferably can remove microbes of 0.2 µm to 20 µm. have.

The polysulfone-based separator of the present invention may be a polysulfone-based separator manufactured through a conventional manufacturing method, and the manufacturing method is also irrelevant as long as it is a method that can be manufactured by those skilled in the art. In addition, the thickness of the polysulfone separator may be 50 µm to 200 µm, and if the average thickness is less than 50 µm, there is a problem of decreasing the use cycle, and if the average thickness exceeds 200 µm, the problem of reducing the efficiency due to the occurrence of differential pressure There may be. In addition, the polysulfone-based separator may include all of a symmetric membrane, an asymmetric membrane, and the like, and may include a flat membrane or a hollow fiber.

And, in the present invention, the polysulfone-based separator may be made of a polysulfone-based polymer containing at least one selected from polyethersulfone, polysulfone, polyallylethersulfone, polyphenylsulfone and polyetheretherketone. have.

The polysulfone-based separation membrane may be a polysulfone-based separation membrane manufactured through a conventional manufacturing method, and preferably may be manufactured by the following method.

The pullisulfone separator of the present invention comprises a first step of casting a polymer solution consisting of a polysulfone polymer, a hydrophilic pore control agent, and a residual amount of a solvent on a support to form a film; A second step of forming pores in the upper layer of the film by spraying air maintained at a temperature of 20°C to 60°C and a humidity of 30% to 80% in the formed film; And a third step of peeling the film from the support by immersing in a coagulation bath after the second step.

The support used in the first process is a metal material, and due to the characteristics of the metal material, the surface temperature may be 8° C. to 12° C., and a preferable example of the support may be stainless steel, aluminum, or copper alloy.

In addition, the polymer solution may consist of 8 to 40% by weight of a polysulfone-based polymer, 10 to 20% by weight of a hydrophilic pore control agent, and a residual amount of a solvent, and the hydrophilic pore control agent of the polymer solution serves to form internal pores, The hydrophilic porosity control agent may be used as long as it is well mixed with a solvent, and preferably at least one selected from the group consisting of polyvinylpyrrolidone, polyethylene glycol and silica may be used, and more preferably, a weight average molecular weight of 10,000 to Polyvinylpyrrolidone having 100,000 can be used as a hydrophilic pore control agent.

In addition, the solvent may be one or more selected from N-methyl-2-pyrrolidone, dimethylformamide, dimethyl sulfoxide, and dimethylacetamide, wherein the content of the solvent is 100% by weight of the total composition. The remaining amount except for can be used. In addition, the polymer solution includes glycols including ethylene glycol and glycerol; Alcohols including ethanol and methanol; And ketones including acetone; at least one hydrophilic additive selected from the furnace may be further mixed.

On the other hand, when casting the polymer solution, it is preferable to cast the film so that the thickness is 100 μm to 130 μm.

In addition, the second process is a step of forming pores in the formed film, and the pore size of the upper layer of the film formed in the second process has an average diameter of 0.01 μm to 1.0 μm, and the pore size of the lower layer of the membrane excluding the upper layer is average It may have a diameter of 0.45 μm to 10 μm.

Specifically, the conditions for forming pores in the upper layer can be formed by spraying air at a speed of 1 to 20 m/min under conditions maintained at an air injection temperature of 20°C to 60°C and humidity of 30% to 80%, At this time, the air exposure time may be performed for 5 seconds to 10 minutes.If the air injection speed is less than 1 m/min, there is a problem of process control, and if it is performed at a speed exceeding 20 m/min, the membrane surface It is not preferable because it causes scratches and affects pore formation.

In addition, if the air exposure time during air injection is less than 5 seconds, pore formation on the surface is insufficient, so it is preferable to sufficiently control the residence time for coagulation. If the air exposure time exceeds 10 minutes, the appearance of the film This is not good and is not desirable.

The pore size of the upper layer of the polysulfone separator formed by the air injection may have an average diameter of 0.01 μm to 1.0 μm, the pore size of the lower layer of the polysulfone separator may be 0.45 μm to 10 μm of the average diameter, and the pore formation of the lower layer may be When casting a polymer solution on a support, pores may be formed due to a temperature difference between the support and the polymer solution. At this time, the surface temperature of the support is 8℃ ~ 12℃ due to the characteristics of the metal material. At this time, if the temperature of the support is too low below 8℃, the temperature difference between the contacting polymer solutions increases, making it difficult to form a film because uniform application is difficult. On the other hand, if it is kept high at 12°C, the temperature difference between the polymer solutions decreases, making it inefficient to control the pore structure by the heat-induced phase transfer method. Therefore, the temperature of the polymer solution cast on the support is maintained at a temperature higher than the temperature of the support, preferably, it can be maintained at 35 ℃ to 60 ℃.

That is, according to the preferred method of manufacturing a polysulfone-based separator of the present invention, the pore size of the upper layer is 0.01 µm to 1.0 µm on the average, and the pore size of the lower layer is 0.45 µm to 10 µm, and a polysulfone-based separator having an asymmetric structure Can provide.

Next, the antiviral nonwoven fabric 302 constituting the composite filter will be described in detail.

In the present invention, the antiviral nonwoven fabric plays a role of adsorbing and removing viruses, and can adsorb and remove viruses having a size of preferably 20 nm to 90 nm, and biofouling by adsorbing and controlling organic pollutants such as humic acid. Can be removed.

Antiviral nonwoven fabric can be applied as long as it is commonly used, and preferably chemical bonding nonwoven fabric, thermal bonding nonwoven fabric, air ray nonwoven fabric, wet nonwoven fabric wet ray, needle punching nonwoven fabric (Needle Punching), spanless (water bonded method-Water zet), spun bond (Spun Bond), melt blown (Melt Blown) and may be any one type selected from stitch bond (Stitch Bond).

The fibers constituting the antiviral nonwoven fabric of the present invention may include one or more selected from polypropylene, polyethylene terephthalate, polyethylene, polyester, nylon, and cellulose, and the average fineness of the fibers constituting the nonwoven fabric is 1 to 10 Μm and an average pore diameter of 1 µm to 20 µm. If the average fineness of the fibers constituting the nonwoven fabric is less than 1 µm, there may be a problem of reducing the flow rate due to the occurrence of differential pressure during filtration, and if it exceeds 10 µm, there may be a problem that the porosity decreases and filtration efficiency decreases. . In addition, when the average pore diameter is less than 1 μm, there may be a problem in that the flow rate decreases, and when it exceeds 20 μm, there may be a problem that the virus removal performance decreases.

In the present invention, the antiviral nonwoven fabric may include an amine-based coating layer, preferably may include an amine-based coating layer inside and outside the antiviral nonwoven fabric, and more preferably fibers constituting the antiviral nonwoven fabric An amine-based coating layer may be formed on. The antiviral nonwoven fabric formed with the amine-based coating layer as described above can have an electrostatic property showing positive charges inside and outside the pores of the nonwoven fabric, thereby greatly improving the virus removal rate. In addition, the amine-based coating layer includes a multifunctional amine compound, and the polyfunctional amine compound is an amine containing at least one selected from polyethyleneimine, diethylenetriamine, piperazine, dimethylene piperazine and diphenylamine. It may contain a compound.

The surface charge of the antiviral nonwoven fabric of the present invention may exhibit a positive charge, and preferably, the surface charge may be 15 mV to 80 mV. This is because the surface charge of the nonwoven fabric represents a positive charge, so that viruses with negative charges of -10 mV to -40 mV can be adsorbed and collected.If the surface charge of the nonwoven fabric is less than 15 mV, the virus adsorption ability may be lowered. In addition, even if it exceeds 80 mV, the virus adsorption capacity is similar, but there may be a problem of an increase in production cost due to an increase in the reaction time and concentration to show a high surface charge during the process.

In addition, the surface charge can be measured based on the method calculated by Equation 1 below by measuring the flow potential using the Surpass model of Anton Parr, but the present invention is not limited thereto.

[Equation 1]

??

In Equation 1, ζ: zeta potential (mV), dU: streaming potential change, dp: pressure change, η: electrolyte viscosity, ε: basic dielectric constant of electrolyte, ε ₀ : Dielectric constant of electrolyte, K _b : It is the electrical conductivity of the electrolyte.

In addition, the antiviral nonwoven fabric may have an average thickness of 0.1 mm to 2 mm, and if the average thickness is less than 0.1 mm, there is a problem that the removal efficiency is reduced due to a short virus adsorption path. If it exceeds 2 mm, the differential pressure during filtration There may be a problem that the flow rate has decreased due to occurrence.

A description will be given of a method of manufacturing such an antiviral nonwoven fabric as follows.

Antiviral nonwoven fabric constituting the composite filter of the present invention comprises the steps of pre-treating the surface and the inside of the nonwoven fabric; And electrostatically treating the pretreated nonwoven fabric. It may be manufactured through a process including.

The pretreatment step serves to perform a hydrophilic treatment for coating, and may be performed by at least one method selected from corona, plasma, hydro-charging, sputtering, primer, flame treatment, and acid treatment. The pretreatment step of the present invention may pretreat not only the surface of the nonwoven fabric but also the fibers constituting the nonwoven fabric, that is, the inside of the nonwoven fabric. And, the nonwoven fabric in the pretreatment step is the same as described above.

In the electrostatic treatment, the antiviral nonwoven fabric is treated to exhibit a positive charge on the surface and inside of the antiviral nonwoven fabric so as to adsorb and remove a virus having a negative charge.The electrostatic treatment comprises an amine-based treatment of the pretreated nonwoven fabric. Coating with a polymer solution; And immobilizing the amine-based compound on the nonwoven fabric by crosslinking the coated nonwoven fabric.

The amine-based polymer solution of the coating treatment may include an amine-based polymer resin; And a solvent; and the amine-based polymer solution may contain 0.1 to 5% by weight of the amine-based polymer resin. If the amine-based polymer resin is less than 0.1% by weight, there is a problem that the virus removal effect is reduced. If it exceeds 5% by weight, there may be a problem that the nonwoven fiber is not evenly coated and formed into a film to reduce porosity. In addition, the amine-based polymer resin may be a polyfunctional amine compound including at least one selected from polyethyleneimine, diethylenetriamine, piperazine, dimethylene piperazine, and diphenylamine. In addition, the solvent may include a commonly used one, preferably one containing one or more of C1 ~ C3 alcohol, acetone, and purified water may be used.

In addition, the coating in the step of coating treatment may be performed by any one method selected from dip coating, sperray coating, bar coating, and roll coating, preferably dip coating, and the dip coating is temperature Can be performed by immersing the pretreated nonwoven fabric under 50°C to 60°C in an amine-based polymer solution for 1 minute to 60 minutes.

Next, the step of immobilizing is to immobilize the amine-based compound by crosslinking the coated nonwoven fabric, which is performed to prevent the amine-based compound from being desorbed when water treatment and/or contact with water. As such, it is possible to extend the life of the filter cartridge of the present invention and maintain stable positive charge characteristics through such immobilization.

According to a preferred embodiment of the present invention, the crosslinking treatment is a polyfunctional halogen compound containing at least one selected from xylene dichloride, trimethylbenzoyl chloride, and benzene disulfonyl chloride; And a solvent containing at least one selected from toluene, acetone, N,N-dimethylacetamido, and N-formdimethylamine; a nonwoven fabric coated with an organic solution containing a coating treatment at 20°C to 80°C for 30 minutes to 2 This can be done by immersion for hours. At this time, if the temperature is less than 20℃, the crosslinking reaction does not occur well, so there may be a problem that the amine compound is desorbed. If it exceeds 80℃, the risk of evaporation of the solvent increases and additional reaction equipment is installed to install additional production equipment. There may be a problem of increased cost. And, if the immersion time is less than 30 minutes, there may be a problem in that the crosslinking reaction does not occur well and the amine-based compound is desorbed, and if it exceeds 2 hours, there may be a problem of decreased productivity.

On the other hand, after the step of crosslinking the nonwoven fabric, any one or more steps selected from neutralization, washing, and drying may be further performed, and neutralization, washing and drying may be performed in a conventional manner.

Next, a description will be given of a method of manufacturing the composite filter material constituting the filter cartridge of the present invention, as a method of laminating an antiviral nonwoven fabric on one side of the polysulfone-based separation membrane described above, it is possible in a conventionally available method, preferably Alternatively, it can be manufactured by laminating by one or more methods selected from cross lamination (horizontal lamination) and vertical lamination (vertical lamination).

In addition, the antiviral nonwoven fabric may be laminated in a single layer or multiple layers, and a method of stacking an antiviral nonwoven fabric in a multilayered manner is also possible by a conventionally available method, preferably by a cross-lamination method, and after lamination The process of compressing can be further performed

Hereinafter, the present invention will be described in more detail through examples, but the following examples do not limit the scope of the present invention, which should be construed to aid understanding of the present invention.

[ Example ]

Example One

(1) Manufacture of polysulfone separator

After dissolving 13% by weight of polysulfone polymer in 65% by weight of dimethylacetamide, 12% by weight of polyethylene glycol (weight average molecular weight 200) and 10% by weight of polyvinylpyrrolidone were added, followed by 50°C water bath A polymer solution was prepared by stirring for at least 12 hours.

Next, the polymer solution was uniformly coated at a rate of 1.5 m/min to a thickness of 110 μm on a stainless steel support at 10°C. Next, by using a temperature range of 20 ℃ ~ 65 ℃, humidity range of 30% ~ 80% gradient device exposed to air to treat the coated polymer solution to form pores in the surface layer (upper layer), and the composition ratio of isopropyl alcohol and water It was solidified by immersing in a coagulation bath containing the mixed solution maintained at a constant weight ratio of 10:90.

Next, the membrane was peeled from the support, the residual solvent component contained in the membrane was extracted in a water washing tank, and dried with air at 80° C. to prepare a weakly asymmetric polysulfone separator.

The prepared polysulfone-based separator has an average pore diameter of 0.5 μm (upper layer: 0.45 μm, lower layer 0.65 μm), thickness 110 μm, water permeability is 55 ml/cm ² ·min·bar, and surface charge is -5 mV. .

(2) Antiviral nonwoven fabric manufacturing

Polypropylene melt blown nonwoven fabric (manufacture, Woongjin Chemical, weight 30g/㎡, thickness 100㎛, fineness 2.5㎛, pore diameter 20㎛) using a water jet to adjust the spray pressure to 35bar and spray water at a speed of 2m/min. And the inside was pretreated. And the pretreated nonwoven fabric was immersed in an aqueous solution containing 0.5% by weight of a polyethyleneamine polymer (weight average molecular weight of 70,000) at 25°C for 1 hour (: electrostatic treatment step). Thereafter, the residual solvent of the filter medium was removed using a niproll, and then immersed in a 0.5% by weight xylenedichloride organic solution (toluene was used as a solvent) for 1 hour (a crosslinking treatment step), followed by washing and drying.

(3) Composite filter Produce

A composite filter including a polysulfone-based separator was prepared in the form as shown in FIG. 4 by laminating one layer of the antiviral nonwoven fabric on one side of the polysulfone-based separator using a cross method.

(4) Manufacture of filter cartridge

The composite filter prepared above was bent and bonded to a cylindrical shape, and then thermally bonded to a polypropylene antibacterial core containing silver (Ag) to mount a filter cartridge in the shape as shown in FIG. 3.

Example 2

A filter cartridge was manufactured in the same manner as in Example 1, except that a polypropylene antibacterial core containing alumina (Al) was used instead of a polypropylene antibacterial core containing silver (Ag).

Example 3

A filter cartridge was manufactured in the same manner as in Example 1, except that a polypropylene antibacterial core containing polyethyleneimine was used instead of a polypropylene antibacterial core containing silver (Ag).

Example 4

A filter cartridge was manufactured in the same manner as in Example 1, except that a polypropylene antibacterial core containing zinc (Zn) was used instead of a polypropylene antibacterial core containing silver (Ag).

Example 5

When manufacturing the antiviral nonwoven fabric, a filter cartridge was manufactured in the same manner as in Example 1, except that the pretreatment step was performed in the corona.

At this time, the corona was treated by maintaining the distance between the electrode and the non-woven fabric (surface filter) at 5 mm and setting the input volt 215V, output load 4.5A, and pulse 286 m/min.

Example 6

When manufacturing the antiviral nonwoven fabric, a filter cartridge was manufactured in the same manner as in Example 1, except that the pretreatment step was performed with plasma.

At this time, the plasma conditions were injected at a flow rate of 4 L/min of helium gas and 20 L/min of oxygen gas, and discharge treatment was performed by performing low-temperature induction plasma treatment in the plasma apparatus, and the discharge treatment speed was performed at 30 mm/sec.

Example 7

When preparing the antiviral nonwoven fabric, a filter cartridge was manufactured in the same manner as in Example 1, except that the crosslinking treatment step was performed at 50°C for 30 minutes.

Example 8

When manufacturing the antiviral nonwoven fabric, a filter cartridge was manufactured in the same manner as in Example 1, except that a polyethylene terephthalate melt brown nonwoven fabric was used instead of the polypropylene melt brown nonwoven fabric.

Example 9

A filter cartridge was manufactured in the same manner as in Example 1, except that two antiviral nonwoven fabrics were laminated in a cross manner and then laminated on one side of a polysulfone separator, and a cross-sectional view of the composite filter was shown in FIG. Done.

Comparative example One

A filter cartridge was manufactured in the same manner as in Example 1, except that a general polypropylene core was used instead of a polypropylene antibacterial core containing silver (Ag).

Comparative example 2

When manufacturing the antiviral nonwoven fabric, a filter cartridge was manufactured in the same manner as in Example 1, except that electrostatic treatment was not performed.

Comparative example 3

A filter cartridge was manufactured in the same manner as in Example 1 without preparing a polysulfone-based separator, and only a polypropylene melt blown nonwoven fabric.

Comparative example 4

A filter cartridge composed of an antibacterial core and a polysulfone separator was prepared in the same manner as in Example 1, except that the antiviral nonwoven fabric was not used.

Experimental example : Performance experiment

The performance of the filter cartridges prepared in Examples 1 to 9 and Comparative Examples 1 to 4 was measured.

(1) Bacteria removal performance

The filter cartridge was passed through a solution of Pseudomonas diminuta diluted with 8.2×10 ⁷ CFU/ml at 1 bar positive pressure to evaluate the removal performance.

(2) Virus removal performance

The filter cartridge was permeated with a virus (MS2 phage) solution diluted with 6×10 ⁵ PFU/ml in PFU/ml (PFU: plaque forming units) unit at a positive pressure of 1 bar to evaluate the removal performance.

(3) Cumulative constant quantity

While passing the filter cartridge through tap water at an initial rate of 2 L/min for 24 hours, while injecting 1 L of bacteria at a concentration of 10 ⁷ to 10 ⁸ CFU/ml and virus preparation at a concentration of 10 ⁴ to 10 ⁵ PFU/ml every 6 hours , The accumulated amount of purified water was measured.

The cumulative water quantity is a measurement of the total water purification quantity at the same time and hydraulic pressure, and an increase in the processing flow rate of the filter cartridge means an increase in the filter usage cycle.

division Bacteria removal performance (log) Virus removal performance (log) Initial flow
(LPM) Cumulative constant quantity (L) Example 1 7.0 4.0 2.2 2,400 Example 2 7.5 4.3 2.2 2,490 Example 3 7.0 4.4 2.4 2,670 Example 4 6.8 3.5 2.2 2,230 Example 5 6.6 3.9 2.5 2,380 Example 6 6.9 3.2 2.2 2,280 Example 7 7.5 4.8 2.5 2,720 Example 8 6.5 3.3 2.5 2,800 Example 9 7.5 4.8 1.8 2,100 Comparative Example 1 6.3 3.4 2.2 2,100 Comparative Example 2 6.5 0 2.2 2,100 Comparative Example 3 1.7 3.8 2.4 2,300 Comparative Example 4 7.0 0.2 2.8 2,700

As can be seen from Table 1, the filter cartridges of Examples 1 to 4 differ in removal performance and flow rate, etc., depending on the material of the antibacterial core, but when compared with Comparative Example 1 in which the antibacterial core is not used, It was confirmed that the cumulative flow rate was increased from as little as 6% to as much as 27%, and the overall bacteria and virus removal performance tended to be better in the Examples.

In addition, in Example 3 using an antibacterial core containing an organic material, unlike the use of the antibacterial core containing the inorganic material of Examples 1, 2, and 4, the initial flow rate, cumulative water quantity, and virus removal performance It can be seen that this appears high. In addition, in Examples 5 to 8, when the antiviral nonwoven fabric was manufactured, the effects were analyzed by different conditions, but in Examples 5 and 6, corona and plasma electrostatic treatments were each performed differently from the conventional electrostatic treatment. , Initial flow rate equals or increases, but bacteria and virus removal performance and cumulative water content decrease. As the electrostatic treatment efficiency decreases, the removal performance decreases, and accordingly, the cumulative flow rate seems to decrease. On the other hand, when the electrostatic treatment was not performed in Comparative Example 2, it can be seen that the positively charged material was not properly coated, so that the virus removal performance was little. It can be seen that electrostatic treatment is a necessary process for manufacturing antiviral nonwoven fabric.

In the case of Example 8 using the PET melt brown nonwoven fabric as the material of the nonwoven fabric, the virus removal performance slightly decreased compared to Example 1 using the PP melt brown nonwoven fabric, but the flow rate and cumulative flow rate tended to increase. In addition, as the two antiviral nonwovens were stacked in Example 9, the initial flow rate and the accumulated flow rate decreased, but it was confirmed that there is an effect of improving the removal performance.

And, in the case of Comparative Example 4 in which the antiviral nonwoven fabric was not used, the flow rate was greatly increased, but the virus removal performance was very largely decreased, and there was practically no virus removal effect. And, in the case of Comparative Example 3 in which the polysulfone-based separator was not used, as opposed to Comparative Example 4, the virus removal performance was excellent, but there was a problem that the bacteria removal performance was very significantly reduced.

300: porous composite filter 301: polysulfone separator
302: antiviral nonwoven fabric 401: antibacterial core
500: filter cartridge

Claims (19)

delete A composite filter comprising a polysulfone-based separator having an average pore diameter of 0.1 to 5 μm and an average thickness of 50 to 200 μm; And a polypropylene antibacterial core; and
In the composite filter, the polysulfone-based separator is laminated on one surface of a single-layer or multi-layer antiviral nonwoven fabric in a filtering direction,
The antiviral nonwoven fabric is formed by forming an amine-based coating layer on the inside and outside of the pretreated nonwoven fabric,
The amine-based coating layer includes a multifunctional amine compound,
The polypropylene antibacterial core is an inorganic compound containing at least one selected from silver (Ag), aluminum (Al), copper (Cu), zinc (Zn), iron (Fe), and manganese (Mn); And an amine compound containing at least one selected from polyethyleneimine, diethylenetriamine, piperazine, dimethylene piperazine, and diphenylamine; Including one or more selected from among,
The composite filter has an average weight of 50 to 500 g/㎡, an average pore diameter of 0.5 to 2.0 µm, and a water permeation amount of 40 to 80 ㎖/cm ² ·min·bar,
The composite filter has a cylindrical shape with a bent cross section, and is a filter cartridge in which the bent portion of the composite filter and the antibacterial core are thermally bonded, and the antiviral and disinfectant, characterized in that the bacteria removal performance is 6log or more and the virus removal performance 3log or more. This excellent filter cartridge for water treatment.
delete The method of claim 2, wherein the polysulfone separator comprises a polysulfone polymer containing at least one selected from polyethersulfone, polysulfone, polyallylethersulfone, polyphenylsulfone and polyetheretherketone. Filter cartridge for water treatment with excellent antiviral and sterilization.
delete delete The method of claim 2, wherein the amine-based coating layer comprises a multifunctional amine compound,
The multifunctional amine compound contains an amine-based compound containing at least one selected from polyethyleneimine, diethylenetriamine, piperazine, dimethylene piperazine and diphenylamine. Excellent antiviral and antibacterial water treatment Filter cartridge.
The method of claim 2,
The antiviral nonwoven fabric includes at least one selected from polypropylene, polyethylene terephthalate, polyethylene, polyester, nylon, and cellulose,
The antiviral nonwoven fabric has an average fineness of 1 to 10 µm and an average pore diameter of 1 to 20 µm.
The method of claim 2, wherein the antiviral nonwoven fabric
Filter cartridge for water treatment excellent in anti-virus and sterilization, characterized in that the average thickness of 0.1 ~ 2㎜.
delete delete A composite filter material containing a polysulfone separator having an average pore diameter of 0.1 to 5 μm and an average thickness of 50 to 200 μm is bent and bonded to a cylindrical shape, and then the bent portion of the composite filter and a polypropylene antibacterial core are thermally bonded to each other,
In the composite filter, the polysulfone-based separator is laminated on one surface of a single-layer or multi-layer antiviral nonwoven fabric in a filtering direction,
Pre-treating the surface and the interior of the antiviral nonwoven fabric; And electrostatically treating the pre-treated nonwoven fabric; it is manufactured through a process including,
The electrostatic treatment may include coating the pretreated nonwoven fabric with an amine-based polymer solution; And immobilizing an amine-based compound including a multifunctional amine compound on the nonwoven fabric through crosslinking treatment of the coated nonwoven fabric,
The polypropylene antibacterial core is an inorganic compound containing at least one selected from silver (Ag), aluminum (Al), copper (Cu), zinc (Zn), iron (Fe), and manganese (Mn); And an amine compound containing at least one selected from polyethyleneimine, diethylenetriamine, piperazine, dimethylene piperazine, and diphenylamine; Including one or more selected from among,
The composite filter has an average weight of 50 to 500 g/m2, an average pore diameter of 0.5 to 2.0 µm, and a water permeation amount of 40 to 80 ㎖/cm ² ·min·bar. .
delete delete delete The method of claim 12,
The pretreatment of the pretreatment step is performed by at least one method selected from corona, plasma, hydro-charging, sputtering, primer, flame treatment, and acid treatment. Cartridge manufacturing method.
The method of claim 12, wherein the amine-based polymer solution is
Amine-based polymer resins containing at least one selected from polyethyleneimine, diethylenetriamine, piperazine, dimethylene piperazine, and diphenylamine; And
A solvent containing at least one of C1 to C3 alcohol, acetone, and purified water;
A method of manufacturing a filter cartridge for water treatment having excellent antiviral and sterilization, comprising a.
The method of claim 12,
The amine-based polymer solution is a method for producing a filter cartridge for water treatment excellent in antiviral and sterilization, characterized in that it contains 0.1 to 5% by weight of an amine-based polymer resin.
The method of claim 12, wherein the crosslinking treatment is
A polyfunctional halogen compound containing at least one selected from xylene dichloride, trimethylbenzoyl chloride, and benzene disulfonyl chloride; And a solvent containing at least one selected from toluene, acetone, N,N-dimethylacetamido, and N-formdimethylamine; a nonwoven fabric coated with an organic solution containing a coating-treated nonwoven fabric at 20°C to 80°C for 30 minutes to 2 A method of manufacturing a filter cartridge for water treatment having excellent antiviral and antibacterial properties, characterized in that it is immersed for a period of time.

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