JP2022189818A - Antibacterial hollow fiber membrane, method for producing the same, and water purification mechanism - Google Patents

Abstract

To provide a method for producing an antibacterial hollow fiber membrane which achieves drinking water contamination suppression and cost reduction, an antibacterial hollow fiber membrane having sufficient antibacterial property and excellent water permeation capability, and having characteristics as to purify water even by a natural pressure (gravity), and an air purification mechanism having antibacterial characteristics even for drinking water to be stored.SOLUTION: A method for producing an antibacterial hollow fiber membrane includes the steps of: melting a polymer resin on which copper nano-particles are vapor-deposited, a polymer resin on which copper nano-particles are not vapor-deposited, and an additive in an organic solvent and producing a polymer solution; mixing the organic solvent and the additive and producing an internal coagulating agent; charging the polymer solution and the internal coagulating agent into a double nozzle and emitting the polymer solution and the internal coagulating agent to an air gap, then immersing the polymer solution and the internal coagulating agent passing through the air gap in an external coagulating agent; and producing a hollow fiber membrane through a phase transition process, wherein the polymer resin on which the copper nano-particles are vapor-deposited is 5 wt.% to 9 wt.% with respect to the total weight of the polymer resin on which the copper nano-particles are vapor-deposited and the polymer resin on which the copper nano-particles are not vapor-deposited.SELECTED DRAWING: None

Description

TECHNICAL FIELD The present invention relates to an antibacterial hollow fiber membrane, a method for producing the same, and a water purification mechanism.

It is known to use antibacterial metals such as silver and copper in the form of fine particles against bacteria in drinking water. In particular, in the water purification mechanism for purifying drinking water, existing hollow fiber membranes, activated carbon, etc. are made to support these metal particles, and antibacterial effects are attempted by the metal ions eluted in the drinking water.

On the other hand, for example, copper has long been used as a raw material for pipes, pipes, valves, and joints for conveying drinking water due to its workability and cost, but it is indispensable when evaluating the quality of drinking water. It is a nutritive element in water as well as a contaminant of drinking water. The WHO Guidelines for Drinking Water Quality also have provisions regarding this.

In addition, the water purification mechanism that purifies water using antibacterial materials is excreted only by the primary intake of raw water. If the time is long, there is a risk of bacterial growth.

BACKGROUND ART Conventionally, a water purifier is known in which activated carbon impregnated with copper is placed near a hollow fiber membrane filter to exhibit an antibacterial function (Patent Document 1). Also, there is known a technique of a fiber coated with nano-sized copper oxide (Patent Document 2).

JP-A-05-293473 International Publication No. 2008-027530

The present invention provides a method for producing an antibacterial hollow fiber membrane that can exhibit sufficient antibacterial properties while minimizing the proportion of polymer resin on which copper nanoparticles are vapor-deposited, in terms of preventing contamination of drinking water and reducing costs. Its purpose is to provide Another object of the present invention is to provide an antibacterial hollow fiber membrane which is excellent in sufficient antibacterial properties and water permeation ability, and has characteristics capable of purifying water even under natural pressure (gravity). A further object of the present invention is to provide a water purifying mechanism having antibacterial properties even for stored drinking water.

In order to solve the above problems, the present invention provides the following.

(1) a first step of depositing copper (Cu) nanoparticles on a polymeric resin;
a second step of preparing a polymer solution by melting the polymer resin deposited with the copper nanoparticles, the polymer resin not deposited with the copper nanoparticles, and the additive in an organic solvent;
A third step of mixing the organic solvent and additives to produce an internal coagulant;
After the polymer solution and the internal coagulant are injected into a double nozzle and radiated into the air gap, the polymer solution and the internal coagulant that have passed through the air gap are immersed in the external coagulant, and undergo a phase transition process. , a fourth step of manufacturing a hollow fiber membrane;
Based on the total weight of the polymer resin deposited with the copper nanoparticles and the polymer resin not deposited with the copper nanoparticles, the polymer resin deposited with the copper nanoparticles is 5 wt% to 9 wt%. A method for producing an antibacterial hollow fiber membrane.

(2) In (1), the polymer resin is selected from the group consisting of polysulfone resin, polyethersulfone resin, polyacrylonitrile resin, polyvinylidene fluoride resin and polytetrafluoroethane resin. A method for producing a thread membrane.

(3) The method for producing an antibacterial hollow fiber membrane in (1), wherein the polymer resin is a polysulfone resin.

(4) In (1), the polymer solution contains 10 to 20% by weight of polymer resin on which copper nanoparticles are deposited and polymer resin on which copper nanoparticles are not deposited, and 10 to 20% of polyvinylpyrrolidone (PVP). A method for producing an antibacterial hollow fiber membrane comprising 5 to 15% by weight of polyethylene glycol (PEG), 50 to 70% by weight of N,N-dimethylacetamide (DMAc) and 10% by weight or less of water.

(5) An antibacterial hollow fiber membrane produced by the production method of any one of (1) to (4).

(6) An antibacterial hollow fiber membrane formed to carry 0.5 ppm to 50 ppm of copper nanoparticles in the hollow fiber membrane.

(7) a container body capable of storing water therein; and a hollow fiber membrane-carrying module disposed in the container body and containing an antibacterial hollow fiber membrane on which copper nanoparticles are carried, the hollow fiber membrane-carrying module A water purification mechanism configured such that at least a portion of the is immersed in water.

(8) In (7), the water purification mechanism further includes a sensor unit for detecting the amount of water stored inside the container body, and a control unit for controlling the immersion amount of the hollow fiber membrane-supported module in water, and the hollow fiber A water purification mechanism in which the membrane support module includes a drive unit configured to be movable according to the water level inside the container body, and the control unit drives the drive unit based on the amount of water detected by the sensor unit. .

(9) In (7) or (8), the water purification mechanism further includes an opening formed at the upper end of the container body, and a cover that is detachable from the opening and has a discharge part for discharging water. A water purification mechanism, wherein the hollow fiber membrane supporting module is vertically movable with respect to the container body.

(10) In (7) or (8), the water purifying mechanism includes an opening formed at one end of the container body in the lateral direction with respect to the horizontal surface, and a discharge part that is detachable from the opening and is used to discharge water. The water purification mechanism further comprising a cover with the hollow fiber membrane carrying module laterally movable relative to the container body.

(11) A water purification mechanism manufactured by the method for manufacturing an antibacterial hollow fiber membrane according to item (1).

(12) A water purification mechanism in which the antibacterial hollow fiber membrane manufactured by the method for manufacturing an antibacterial hollow fiber membrane according to item 1 is provided at a position where the water to be filtered comes into contact with the lowest level of the water to be filtered.

Since the hollow fiber membrane according to the present invention has copper (Cu) nanoparticles vapor-deposited inside and outside, it is excellent in sterilization performance, stain resistance, and the like.

The antibacterial hollow fiber membrane, the method for producing the same, and the water purification mechanism according to the present invention have a copper nanoparticle concentration of 99% or more in the aspect of suppressing contamination of drinking water, even though the concentration of copper nanoparticles contained in the antibacterial hollow fiber membrane is minimal. Sufficient antibacterial performance can be shown.

The water purification mechanism to which the antibacterial hollow fiber membrane according to the present invention is applied includes a hollow fiber membrane-carrying module containing an antibacterial hollow fiber membrane on which copper nanoparticles are carried. You can do fungi.

In addition, the water purification mechanism to which the antibacterial hollow fiber membrane according to the present invention is applied can adjust the amount of copper nanoparticles present in water per unit volume of water stored inside the container main body according to changes in the amount of water. Therefore, contamination of water due to elution of copper nanoparticles can be effectively prevented.

A water purification mechanism in which an antibacterial hollow fiber membrane manufactured by inserting a polymer resin in which 5 to 9% by weight of copper nanoparticles are vapor-deposited with respect to the total weight of the polymer resin is placed at a position where it contacts with the water to be filtered from the lowest water level. Even if the liquid level of the raw water is at the lowest level or the highest level (full tank), the antibacterial properties can be exhibited, so if left for a long time, various bacteria in the stored water will grow. Also, it is possible to prevent the antibacterial action from being lost due to the water level becoming low.

FIG. 1 shows a portable water purification bottle (trade name: Super Delios) as a specific example of the water purification mechanism. FIG. 2 shows a household water purifier as a specific example of the water purification mechanism. FIG. 3 shows a pitcher-type water purifier as a specific example of the water purification mechanism. FIG. 4 shows another pitcher-type water purifier as a specific example of the water purifying mechanism. (a) and (b) of FIG. 5 are enlarged operation diagrams of the manual pump of FIG. FIG. 6 is one embodiment of a water purification mechanism according to the present invention. FIG. 7 is another embodiment of a water purification mechanism according to the invention.

The invention is described in more detail below. However, the present invention can be modified and embodied in various forms, and is not limited to the embodiments described herein.

Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. In general, the nomenclature used herein and the experimental procedures described below are those well known and commonly used in the art.

The present invention provides an antibacterial hollow fiber membrane in which copper nanoparticles are vapor-deposited on the inside and outside of the hollow fiber membrane and has excellent sterilization performance and contamination resistance, a method for producing the same, and a water purification mechanism.

The method for producing the antibacterial hollow fiber membrane includes a first step of depositing copper nanoparticles on a polymer resin; a second step of dissolving the agent in an organic solvent to prepare a polymer solution; a third step of mixing an organic solvent and an additive to prepare an internal coagulant; A fourth step of manufacturing a hollow fiber membrane after passing through a heavy nozzle and radiating into an air gap and then immersing the polymer solution and the internal coagulant that have passed through the air gap in an external coagulant to undergo a phase transition process. 5% to 9% by weight of the polymer resin on which the copper nanoparticles are deposited, based on the total weight of the polymer resin on which the copper nanoparticles are deposited and the polymer resin on which the copper nanoparticles are not deposited. %.

The first step may deposit copper nanoparticles on the polymer resin. The polymeric resin can be selected from the group consisting of polysulfone resins, polyethersulfone resins, polyacrylonitrile resins, polyvinylidene fluoride resins and polytetrafluoroethane resins. Preferably, the polymer resin may be polysulfone resin or polyethersulfone resin. More preferably, the polymer resin may be polysulfone resin.

The polymer resin deposited with the copper nanoparticles can be prepared by a vacuum deposition method in a vacuum deposition tank.

The polymer resin on which the copper nanoparticles are deposited is prepared by putting the polymer resin, which is the radiation material for the hollow fiber membrane, into a vacuum deposition tank, stirring it, and applying the antibacterial metal by DC sputtering. It is performed by a physical vapor deposition method in which atoms are separated to form uniform copper nanoparticles with a purity of 99.99% without agglomeration with a particle size of 1 to 20 nm in a plasma state and directly and uniformly deposited on the polymer resin. .

The second step is to prepare a polymer solution by melting the polymer resin on which the copper nanoparticles are deposited, the polymer resin on which the copper nanoparticles are not deposited, and the additive in an organic solvent. The polymer solution is a solution that forms a hollow fiber membrane after phase conversion, and can influence the structure and water permeability of the hollow fiber membrane.

The polymer resin on which the metal nanoparticles are deposited is evenly distributed in the polymer solution, and is evenly distributed in the hollow fiber membrane even after the hollow fiber membrane is manufactured. Due to the characteristics of the hollow fiber membrane, the hollow fiber membrane has a sponge structure with many pores, and at this time, the nanoparticles present on the surface of the numerous pores inside and outside the hollow fiber membrane have an antibacterial effect.

The polymer resin deposited with the copper nanoparticles may be 5 wt% to 9 wt% of the total weight of the polymer resin deposited with the copper nanoparticles and the polymer resin not deposited with the copper nanoparticles. . By controlling the content of the polymer resin on which the copper nanoparticles of the hollow fiber membrane are vapor-deposited within the range of 5% to 9% by weight, the antibacterial effect of the hollow fiber membrane is excellent and the contamination of drinking water is minimized. It is advantageous in that it can In particular, from 5%, the nanoparticles are distributed in the hollow fiber membrane to such an extent that the antibacterial performance can be 99% or more. When the content of the polymer resin on which the copper nanoparticles are deposited is less than 5% by weight, the absolute content of the nanoparticles distributed in the hollow fiber membrane is small, the antibacterial performance is 99% or less, and the antibacterial performance varies. It is not preferable in that it is necessary to maintain stable antibacterial performance.

Moreover, if the polymer resin on which the copper nanoparticles are vapor-deposited exceeds 9% by weight, the price of the copper nanoparticle-deposited polymer resin is high, which is not preferable in terms of cost.

On the other hand, South Korea and the World Health Organization set the copper ion concentration standard for drinkable water at 1 ppm or less. The applicant produced a hollow fiber membrane using 100% by weight of copper nanoparticle-deposited polysulfone, left the hollow fiber membrane in 350 ml of water for 24 hours, and then measured the copper ion content in water with a result of 1.46 ppm. was issued. From the above results, when using 60% by weight of copper nanoparticle-deposited polysulfone, the copper ion content is expected to be about 0.9 ppm. The ion content is expected to be 1 ppm or less. Therefore, the maximum content of polymer resin deposited with copper nanoparticles is expected to be 30% by weight. In addition, since the price of the copper nanoparticle-deposited polymer resin is about eight times higher than that of the polymer resin on which the copper nanoparticles are not deposited, the cost can be reduced by using less copper nanoparticle polysulfone. It is preferable because it can be done.

In the second step, the polymer resin on which the copper nanoparticles are deposited, the polymer resin, and the additive are melted and stirred in an organic solvent to prepare a polymer solution, and the stirring time is 8 hours to 8 hours. 24 hours.

The organic solvent is selected from n-methylpyrrolidone (NNMP), dimethylformamide (DMF), dimethylsulfoxide (DMSO), chlorobenzene, m-cresol, tetrahydrofuran and N,N-dimethylacetamide (DMAc) alone or It is preferable to use a mixed solvent of two or more kinds, and N,N-dimethylacetamide (DMAc) is more preferable.

The above additives are polyethylene, polypropylene, polyvinyl alcohol, polyvinylpyrrolidone, glycerin, polyethylene glycol, polypropylene glycol, methyl alcohol, ethyl alcohol, water, calcium chloride, lithium chloride, etc., and may be used alone or in combination of two or more. are preferred, and polyvinylpyrrolidone (PVP) and polyethylene glycol (PEG) are more preferred. The additive may play a role in forming pores and imparting hydrophilicity to the hollow fiber membrane.

The viscosity of the polymer solution is preferably 10 to 30,000 cp or less, more preferably 1,000 to 30,000 cp or less, and even more preferably 1,000 to 10,000 cp or less. . At this time, the viscosity of the polymer solution is preferably low in terms of fluidity, but if it is too low, there is a problem that the polymer may absorb and swell.

The polymer solution includes 10 to 20% by weight of polymer resin deposited with copper nanoparticles and polymer resin not deposited with copper nanoparticles, 10 to 20% by weight of polyvinylpyrrolidone (PVP), and polyethylene glycol (PEG). 5 to 15% by weight, 50 to 70% by weight of N,N-dimethylacetamide (DMAc) and up to 10% by weight of water.

The third step above is to produce an internal coagulant, which is for forming the hollow portion of the hollow fiber membrane. Ingredients used, which can in part affect the membrane structure and pore size, consist of additives and organic solvents used in the preparation of the polymer solution and mixtures thereof. Among the additives, the internal coagulant contains a large amount of a non-solvent having a large difference in solubility parameter from that of the polysulfone resin and having a strong coagulation power, forming an active layer inside the hollow fiber membrane, The pores become smaller and the removal performance improves, but the water permeability may decrease. If an organic solvent with weak coagulation power is used, an active layer is formed on the outside of the hollow fiber membrane and the pores become larger. , the removal performance is lowered, but the permeability is improved. In addition, if a large amount of organic solvent with weak coagulation power is used, the hollow portion inside the hollow fiber membrane may not be able to form a circular shape, or the hollow fiber membrane may not be formed. It is preferable to use a non-solvent and an organic solvent in an appropriate ratio.

In the fourth step, the polymer solution and the internal coagulant are injected into the double nozzle and radiated into the air gap, and then the polymer solution and the internal coagulant passed through the air gap are immersed in the external coagulant. After undergoing a phase transition process, a hollow fiber membrane can be manufactured. At this time, by spraying the polymer solution and the internal coagulant into the air gap, the phase transition of the hollow fiber membrane can be delayed and the pore size can be partially controlled.

An external coagulant can serve to completely phase-transform the polymer solution into the solid phase. The external coagulant can be produced by using only water, or by using water as a main component and adding the above organic solvent, additives, or a mixture thereof.

In the fourth step, the air gap is supplied with constant humidity and temperature, and the humidity causes the hydrophilizing additive to migrate toward the surface of the hollow fiber membrane to increase the water permeability of the membrane. and temperature can partly control the size of the pores.

The polymer solution and the internal coagulant sprayed into the air gap are coagulated by the external coagulant, resulting in a complete phase transition and manufacturing a hollow fiber membrane.

The present invention also relates to an antibacterial hollow fiber membrane produced by the above production method. The antibacterial hollow fiber membrane may have various removal performances and water permeation performances.

The present invention also relates to antimicrobial hollow fiber membranes formed to carry 0.5 ppm to 50 ppm of copper nanoparticles within the hollow fiber membrane.

The measured copper content in the antibacterial hollow fiber membrane manufactured by adding the polysulfone resin vapor-deposited with copper nanoparticles at 5 wt% to 9 wt% is 2.8 ppm to 5.3 ppm, but the polymer solution solidifies. There should be some variation in the amount of copper nanoparticles lost during the phase transition process due to the agent, and since it is a small amount in the ppm unit, it is considered that there is a measurement error. preferably 0.5 to 50 ppm, more preferably 1 to 10 ppm of copper nanoparticles.

The cross section of the hollow fiber membrane has a network sponge structure, and the cross section shows a structure in which pores gradually increase from the outer surface to the inner surface. The outer surface of the hollow fiber membrane is formed with a network structure. The inner surface of the hollow fiber membrane has a structure in which oval pores with a diameter of about 30 μm are formed, and the pore size in the hollow fiber membrane may be 5 to 60 μm. By forming 0.5 ppm to 50 ppm of copper nanoparticles in the hollow fiber membrane, it is advantageous in terms of cost and sufficient antibacterial properties. or it is not preferable because it increases the cost.

Also, the antibacterial hollow fiber membrane produced in the present invention can be applied and used in a water purification system.

The present invention also relates to a water purification mechanism including a hollow fiber membrane-carrying module containing an antibacterial hollow fiber membrane on which copper nanoparticles are carried.

Specifically, FIG. 1 shows a portable water purification bottle (trade name: Super Delios) as a specific example of the water purification mechanism. Inside the cartridge, an antibacterial hollow fiber membrane is arranged at the discharge port (secondary side), and activated carbon is arranged at the bottle side. Conventionally, the bottle is placed so that the cartridge faces upward, as is the case at present, but in this embodiment, a base cap is provided on the top of the cartridge, and the cap also serves as a counter seat to support the bottle body. By doing so, the antibacterial hollow fiber membrane inside the cartridge is always in contact with the raw water (water to be filtered), so that the antibacterial power is exerted.

FIG. 2 shows a household water purifier as a specific example of the water purification mechanism. The protrusions on the top are an inlet for filtered water and an outlet for ejecting filtered drinking water (filtered water). Inside the water purifier, activated carbon absorbs chlorinated odors, musty odors, chlorine and trihalomethane from the water to be filtered that flows into the water purifier, and then the hollow fiber membrane removes various germs. Conventionally, there is a technique for imparting an antibacterial function to activated carbon, but in this example, copper nanoparticles are supported on the hollow fiber membrane side. With the conventional technology, when the water purifier is not used, residual water from which chlorine has been removed remains inside the hollow fiber membrane, making it difficult to exert the antibacterial effect of activated carbon, but in this embodiment. Since the copper nanoparticles supported by the hollow fiber membranes are in direct contact with the stagnant water in the hollow fiber membranes and the stagnant water around the activated carbon, the antibacterial action can be sufficiently exhibited.

FIG. 3 shows a pitcher-type water purifier as a specific example of the water purification mechanism. Conventionally, a water purification cartridge consisting mainly of a pre-filter and activated carbon is placed at the inflow port (primary side) where the lid of the water purifier is opened and the water to be filtered flows into the pitcher, and the filtered water is stored in the pitcher. It was something that made In addition, the water purifier never used activated carbon and hollow fiber membranes. The reason for this is that hollow fiber membrane filtration requires water pressure to facilitate filtration, and although the conventional pitcher type can take into account the head pressure of a full tank of filtered water, if the volume decreases due to use, This is because it cannot be filtered. For the same reason, if a water purification cartridge that uses a hollow fiber membrane is installed on the discharge side (secondary side), it will take time to filter the filtered water when it is discharged from the water purifier. The ability to supply is lost.

However, if a water purification cartridge is installed on the primary side, it will be easier to secure the water pressure for filtering, but since chlorine has already been removed from the filtered water by the water purification cartridge, the longer the standing (storage) time, the more bacteria will grow. Increased risk of breeding.

Therefore, in this embodiment, the pitcher has a structure in which the flow path from the inflow port of the water to be filtered to the discharge port is divided into two regions by a partition wall, and the antibacterial property is obtained even if the water stored in the pitcher is at the minimum water level used. By detachably fixing the cartridge to a portion of the partition wall at or near the bottom of the pitcher where the hollow fiber membrane can be submerged in or in contact with the pooled water, the primary pooled water can filter the cartridge. A flow path is formed to connect the two areas so that the water is stored on the secondary side. As a result, it is possible to replace the water purification cartridge with a new water purification cartridge according to the degree of use, and the water purification cartridge always maintains an antibacterial state because the water purification cartridge is in contact with the primary side stored water before filtration and the secondary side stored water after filtration. can be done.

With such a structure, when the opening/closing cover is opened and the water to be treated is put in, the water is stored as the primary side water, the water pressure is applied to the cartridge, and the water to be treated is filtered and stored as the secondary side water. Then, when the filtered water is discharged, the secondary-side stored water is quickly supplied from the discharge port.

In addition, the ratio of the primary-side stored water to the secondary-side stored water amount is determined by balancing the required amount of filtered water discharged at one time and the speed at which the cartridge filters with the head pressure of the primary-side stored water. For example, in order to secure 400 cc of water for two cups of water within several minutes as secondary water, 800 cc or more is required as the primary water storage, and the practical size of the pitcher as a whole is taken into account. For example, the ratio of the amount of water stored on the primary side to the amount of water stored on the secondary side is preferably in the range of about 1:2 to 1:4.

FIG. 4 shows another pitcher-type water purifier as a specific example of the water purifying mechanism. The difference from FIG. 3 is that the open/close lid is provided with a manual pump, and a detachable water purification cartridge composed of activated carbon and antibacterial hollow fiber membrane is provided on a part of the partition and on the secondary side of the stored water. ing.

(a) and (b) of FIG. 5 are enlarged operation diagrams of the manual pump of FIG. (A) is a state in which the manual pusher is pressed down (a state in which pressure is applied to the primary side stored water), and the air in the bottle is released while the vent valves 1 and 2 are biased to close by a coil spring or the like (not shown). The primary-side water to be compressed downward is forcibly filtered by the water purification cartridge and stored as secondary-side water.

When the manual pusher is released, the pushing force of the pusher coil in the direction of the arrow raises the manual pusher and returns to the standby state (b) (state of taking in outside air). The valves 1 and 2 are opened to draw outside air into the bottle through the vent holes 1 and 2. By manually operating the pump as described above, it is possible to purify the water with the urging pressure while taking in the outside air, so that a large area of the secondary side water can be secured without taking a large area of the primary side water. be able to.

FIG. 6 illustrates a water purification mechanism (1) according to one embodiment of the present invention. The water purification mechanism (1) includes a container body (10) capable of storing water therein, and a hollow fiber membrane containing an antibacterial hollow fiber membrane that is disposed in the container body (1) and supports copper nanoparticles. It includes a carrier module (20). Such an antibacterial hollow fiber membrane can be configured as the antibacterial hollow fiber membrane characterized by the present invention as described above. In addition, the hollow fiber membrane carrying module (20) may include a module housing that covers the antibacterial hollow fiber membranes, and the module housing may contain water in which the antibacterial hollow fiber membranes are stored inside the container body (10). configured to be accessible. For example, the module housing may include a number of micro-apertures on the water contact surface or the water contact surface may be constructed in the form of a permeable membrane.

In FIG. 6, the water purifying mechanism (1) includes an opening (30) formed at the upper end of the container body (10) and a discharge part (41) detachable from the opening (30) for discharging water. ), before drinking water is stored in the container body (1) in proper amount through the opening (30) and discharged into a cup or the like through the outlet (41) of the cover (40). You can drink it by discharging an appropriate amount.

Thus, the amount of water stored inside the container body (10) is variable depending on use.

Therefore, the water purification mechanism (1) according to the present invention is configured such that at least part of the hollow fiber membrane-supported module is immersed in water.

In addition, the water purification mechanism (1) according to the present invention includes a sensor unit (not shown) for detecting the amount of water stored inside the container body (10), and the immersion amount of the hollow fiber membrane supporting module (20) in water. (not shown). In addition, the hollow fiber membrane supporting module (20) includes a driving part (21) configured to be movable inside the container body (10) depending on the water level.

The sensor unit may be a known sensor capable of detecting the amount of water, and its type is not particularly limited. Also, the type of control unit is not particularly limited as long as it can receive a detected value from the sensor unit and transmit a control signal to the driving unit (21).

The control section drives the drive section (21) based on the amount of water detected by the sensor section. For example, as shown in FIG. 6, the drive unit (21) may be an elevating member configured to vertically elevate the hollow fiber membrane supporting module (20) from the interior of the container body (10). Alternatively, the drive unit (21) adjusts the buoyancy of the hollow fiber membrane-supporting module (20) such that part of the water is accommodated in the hollow fiber membrane-supporting module (20), thereby allowing the hollow fibers to react with water. The immersion amount of the membrane support module (20) can be configured to be adjustable. However, the drive unit (21) is not limited to the above example, as long as it is capable of adjusting the immersion amount of the hollow fiber membrane supporting module (20).

As described above, according to the water purification mechanism (1) of the present invention, at least a part of the hollow fiber membrane-supported module (20) is configured to be immersed in water. Antibacterial or sterilization of water stored inside can be performed.

In addition, the water purification mechanism (1) according to the present invention can adjust the amount of copper nanoparticles present in water per unit volume of water stored inside the container body (10) according to changes in the amount of water. Therefore, contamination of water due to elution of copper nanoparticles can be effectively prevented.

Next, another embodiment of the water purification mechanism according to the present invention will be described with reference to FIG.

The water purification mechanism (1) of FIG. 6 stores water vertically, whereas the water purification mechanism (100) shown in FIG. 7 stores water horizontally. Technical features for achieving the object of the invention are common to the water purification mechanism (1) of FIG.

Specifically, the water purification mechanism (100) of FIG. 7 includes a container body (110) capable of storing water therein, and an antibacterial hollow fiber carrying copper nanoparticles disposed in the container body (110). It includes a hollow fiber membrane carrier module (120) containing membranes.

In addition, the water purification mechanism (100) is detachable from the opening (130) formed at one end of the container body (110) in the lateral direction with respect to the horizontal surface, and is detachable from the opening (130). It further includes a cover (140) with a portion (141).

The water purification mechanism (100) also includes a sensor unit (not shown) that detects the amount of water stored inside the container body (110), and controls the amount of immersion of the hollow fiber membrane supporting module (120) in water. Further includes a controller (not shown). In addition, the hollow fiber membrane supporting module (120) includes a driving part (121) configured to be laterally movable inside the container body (110) depending on the water level.

That is, in the water purification mechanism (100) according to FIG. 7, the hollow fiber membrane-supporting module (20) is capable of moving laterally from the interior of the container body (110). It differs from the water purification mechanism (1) according to FIG. 6, which is vertically displaceable from inside the body (10).

In addition, in the water purification mechanism (100) shown in FIG. 7, the outer periphery of the hollow fiber membrane supporting module (120) is located on the container body (110) so that water is stored on the opposite side of the opening (130). It can be configured to contact the inner periphery. Also, in order to store water in the container body (110) through the opening (130), the hollow fiber membrane carrying module (120) is detachably configured, or a separate module is provided at the other lateral end of the container body. An inlet can be formed.

In the water purification mechanism (100) shown in FIG. 7, the control unit drives the drive unit (121) based on the amount of water detected by the sensor unit, similar to the water purification mechanism (1).

Therefore, according to the water purification mechanism (100), since at least a part of the hollow fiber membrane supporting module (120) is configured to be immersed in water, the copper nanoparticles are stored inside the container body (110). It is possible to effectively prevent contamination of water due to elution of copper nanoparticles while antibacterially or sterilizing water.

The present invention also relates to a water purification mechanism provided with an antibacterial hollow fiber membrane produced by the method for producing an antibacterial hollow fiber membrane according to the invention. The present invention also relates to a water purification mechanism in which the antibacterial hollow fiber membrane manufactured by the method for manufacturing an antibacterial hollow fiber membrane according to the present invention is provided at a position where the water to be filtered comes into contact with the lowest water level.

Preferred examples are presented below to aid understanding of the present invention. However, the following examples are only provided for easier understanding of the present invention, and the present invention is not limited to the following examples.

In order to confirm the antibacterial properties depending on the copper ion concentration, the following hollow fiber membranes were produced and the following experiments were conducted.

Example 1 (copper ion concentration 5% by weight)
0.75% by weight of polysulfone resin vapor-deposited with copper nanoparticles, 14.25% by weight of polysulfone resin, and 30% by weight of a mixed solution of polyvinylpyrrolidone (PVP) and polyethylene glycol (PEG) were dissolved in N,N-dimethylacetamide. to prepare a polymer solution (5% by weight of the polysulfone resin vapor-deposited with copper nanoparticles to the polysulfone resin vapor-deposited with all copper nanoparticles and the polysulfone resin not vapor-deposited with copper nanoparticles). The internal coagulant was prepared by mixing 10% by weight of water, 20% by weight of polyethylene glycol and 70% by weight of N,N-dimethylacetamide. The polymer solution was radiated through a double nozzle with a diameter of 1,000 μm, and the internal coagulant was radiated through a double nozzle with a diameter of 400 μm at an air gap humidity of 95% and a temperature of 35° C., with an air gap distance of 10 cm. After radiating at a speed of 20 m/min, it was immersed in an external coagulant to undergo a phase transition process, and then a hollow fiber membrane was manufactured.

*Copper ion concentration (% by weight) = polysulfone resin vapor-deposited with copper nanoparticles / (polysulfone resin vapor-deposited with copper nanoparticles + polysulfone resin not vapor-deposited with copper nanoparticles) × 100

Examples 2 and 3 (copper ion concentration 7% by weight, 9% by weight) and Comparative Examples 1 to 3
A hollow fiber membrane was prepared in the same manner as in Example 1, except that a polysulfone resin deposited with copper nanoparticles and a polysulfone resin not deposited with copper nanoparticles were used in the preparation of the polymer solution.

(1) Water immersion antibacterial test Inject sterilized distilled water into the water purifier filter to which the hollow fiber membranes of Examples 1 to 3 and Comparative Examples 1 to 3 are applied. was sealed. Immediately after injection of the bacterial culture solution and 24 hours later, the bacterial culture solution was collected. 1 mL of the collected bacterial culture was inoculated into a dry film medium Sanita-kun (general aerobic bacteria, Japan), and one day later, bright red colonies were counted to measure the number of bacteria.

* Bacteria reduction rate = [(number of bacteria after 24 hours) - (number of bacteria immediately after inoculation)] / (number of bacteria after 24 hours) x 100 (%)

As shown in Table 2, in Examples 1 to 3, the bacteria reduction rate was 99.2% or more, and the copper ion concentration range was 5% to 9% by weight. We were able to confirm that it satisfies the water purification performance required for water.

(2) Antibacterial Hollow Fiber Membrane The hollow fiber membranes of Examples 1 to 3 were formed so as to support 0.5 ppm to 50 ppm of copper nanoparticles in the hollow fiber membrane.

As can be seen from the above water immersion antibacterial test, the hollow fiber membrane formed to support 0.5 ppm to 50 ppm of copper nanoparticles in the hollow fiber membrane has less than 0.5 ppm of copper nanoparticles in the hollow fiber membrane. It was confirmed that the antibacterial effect was superior to that of the hollow fiber membrane formed to support the That is, it was confirmed that the antibacterial hollow fiber membrane formed to support 0.5 ppm to 50 ppm of copper nanoparticles in the hollow fiber membrane according to the present invention has an excellent antibacterial effect.

Claims (8)

A first step of depositing copper (Cu) nanoparticles on a polymer resin;
a second step of preparing a polymer solution by melting the polymer resin deposited with the copper nanoparticles, the polymer resin not deposited with the copper nanoparticles, and the additive in an organic solvent;
A third step of mixing the organic solvent and additives to produce an internal coagulant;
After the polymer solution and the internal coagulant are injected into a double nozzle and radiated into the air gap, the polymer solution and the internal coagulant that have passed through the air gap are immersed in the external coagulant, and undergo a phase transition process. , a fourth step of manufacturing a hollow fiber membrane;
Based on the total weight of the polymer resin deposited with the copper nanoparticles and the polymer resin not deposited with the copper nanoparticles, the polymer resin deposited with the copper nanoparticles is 5 wt% to 9 wt%. A method for producing an antibacterial hollow fiber membrane. The antibacterial hollow fiber membrane according to claim 1, wherein the polymer resin is selected from the group consisting of polysulfone resin, polyethersulfone resin, polyacrylonitrile resin, polyvinylidene fluoride resin and polytetrafluoroethane resin. Production method. The method for producing an antibacterial hollow fiber membrane according to claim 1, wherein the polymer resin is a polysulfone resin. The polymer solution includes 10 to 20% by weight of polymer resin deposited with copper nanoparticles and polymer resin not deposited with copper nanoparticles, 10 to 20% by weight of polyvinylpyrrolidone (PVP), and polyethylene glycol (PEG). The method for producing an antibacterial hollow fiber membrane according to claim 1, comprising 5 to 15% by weight, 50 to 70% by weight of N,N-dimethylacetamide (DMAc), and 10% by weight or less of water. An antibacterial hollow fiber membrane produced by the production method according to any one of claims 1 to 4. An antibacterial hollow fiber membrane formed to carry 0.5 ppm to 50 ppm of copper nanoparticles in the hollow fiber membrane. A water purification mechanism provided with an antibacterial hollow fiber membrane manufactured by the method for manufacturing an antibacterial hollow fiber membrane according to claim 1. A water purifying mechanism in which the antibacterial hollow fiber membrane manufactured by the method for manufacturing an antibacterial hollow fiber membrane according to claim 1 is provided at a position where the water to be filtered comes into contact with the water to be filtered from the lowest water level.

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