JP2008095266A - Conjugate fiber filter using nano material, production equipment of conjugate fiber filter using nano material and production method of conjugate fiber filter using nano material - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a production equipment and production method of a conjugate fiber filter having high efficiency, high functionality and antibacterial property. <P>SOLUTION: The conjugate fiber filter is produced by forming a microfiber layer comprising microfiber threads on a molding rod by melt-spinning with a melt spinning machine, which molding rod comprises an electroconductive material and is grounded at one end thereof and driven to rotate, then laminating to form a nanofiber layer on the microfiber layer to produce a highly efficient and highly functional conjugate fiber filter, which nanofiber layer comprises nanofiber obtained by electric field spinning with an electric field spinning machine a polymer resin solution having certain dielectric constant capable of being spun by electric field spinning, and further, antibacterial function is imparted by adding a silver nanocomponent to the microfiber of the microfiber layer and the nanofiber of the nanofiber layer. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a composite fiber filter using a nanomaterial, a manufacturing apparatus for a composite fiber filter using a nanomaterial, and a method for manufacturing a composite fiber filter using a nanomaterial, in particular, by combining nanofibers and microfibers. The present invention relates to an apparatus and method for producing a composite fiber filter having high efficiency, high functionality and antibacterial properties.

  Most of the microfibers that are usually manufactured are made by spinning methods such as melt spinning, dry spinning, wet spinning, etc., that is, polymer solution is microporous by mechanical force. Manufactured by forced extrusion spinning through. However, the diameter of the microfiber manufactured by such a method is about 5 to 500 μm, and it is not easy to manufacture a nano-order fiber having a diameter of 1 μm or less. Therefore, such a microfiber filter can filter micro-size contaminant particles, but it is virtually impossible to filter nano-size fine contaminant particles.

  For this reason, various methods for producing nano-sized fibers (nonwoven fabrics) are currently being developed and used. Examples of methods for forming organic nanofibers include nanostructured material formation by block segments, nanostructured material formation by self-assembly, nanofiber formation by polymerization under a silica catalyst, and carbonization after melt spinning. Examples thereof include nanofiber formation by a process and nanofiber formation by electrospinning of a polymer solution or a melt.

  When a nanofiber filter is realized using nanofibers manufactured in this manner, the non-target is extremely large and the flexibility with respect to the surface functional groups is superior to the microfiber filter. Since it has nano-level pores, harmful particles and gases can be efficiently removed.

  However, a filter using nanofibers has a disadvantage that production costs are extremely high, and it is difficult to match various conditions for production, so that production and diffusion cannot be performed at a relatively low cost.

  When realizing a filter using nanofibers, not only the high cost described above, but also problems relating to differential pressure and filtration efficiency may occur. Therefore, by combining conventional microfiber manufacturing technology and nanofiber manufacturing technology, there is a need for a functional filter that can solve problems related to differential pressure and filtration efficiency as well as cost competitiveness, and can guarantee high efficiency and high functionality. ing. Such a functional filter is considered to be extremely effective in the entire industrial field.

  Therefore, the present invention has been made in view of such a problem, and the object thereof is a novel and capable of combining nanofibers and microfibers to achieve high efficiency, high functionality and antibacterial properties. An object of the present invention is to provide a composite fiber filter using the improved nanomaterial, a composite fiber filter manufacturing apparatus using the nanomaterial, and a composite fiber filter manufacturing method using the nanomaterial.

  As described above, an object of the present invention is to provide a composite fiber filter having a high efficiency, a high functionality, and an antibacterial property by combining nanofibers and microfibers, and a manufacturing apparatus and method therefor.

  Another object of the present invention is to provide a composite fiber filter manufacturing apparatus and method capable of manufacturing a composite fiber filter in which nanofibers and microfibers are combined with high productivity.

  Still another object of the present invention is to provide a composite fiber filter having high efficiency, high functionality, and antibacterial properties, and an apparatus and method for producing the same for a water purification filter.

  Accordingly, in order to solve the above-described problems, according to one aspect of the present invention, in a method for manufacturing a composite fiber filter, a melt spinning machine melts a conductive rod formed on a conductive rod that is rotationally driven with one end grounded. A microfiber layer made of microfiber yarn is formed by spinning, and a polymer resin solution having a predetermined dielectric constant capable of electrospinning is electrospun on the microfiber layer by an electrospinning machine, There is provided a method for producing a composite fiber filter using nanofibers, characterized by laminating and forming nanofiber layers made of fiber yarns.

  The microfiber layer and the nanofiber layer may be alternately and continuously laminated using the melt spinning machine and the electrospinning machine to form a multilayer.

  In the polymer resin solution, 0.1 mass% to 1.0 mass% of dispersant-containing silver nanoparticles may be mixed with respect to the mass of the polymer resin.

The nanofiber layer may have a porosity of 30 to 70%, and the nanofiber layer may have a pure density of 0.1 to 0.22 g / cm ³ .

  The polymer resin contained in the nanofiber yarn may be formed from either a polyacrylonitrile resin or a polyamide resin (nylon resin such as nylon 6).

  The polymer resin contained in the nanofiber yarn is polyvinyl alcohol, polystyrene, polycaprolactone, polyethylene terephthalate, polyvinylidene fluoride, nylon, polyvinyl acetate, polymethyl methacrylate, polyacrylonitrile, polyurethane, polybutylene terephthalate, polyvinyl butyral, It may be formed from any one selected from the group consisting of polyvinyl chloride, polyethyleneimine, polysulfone and nitrocellulose.

  The microfiber yarn to be melt-spun may include a polypropylene component, and 0.1 mass% to 1.0 mass% of a self-dispersing agent-containing silver nanoparticle may be mixed with respect to the mass of the polypropylene.

  The forming rod may be rotationally driven at 30 to 50 rpm.

In the melt spinning conditions of the melt spinning machine, the spinning nozzle diameter is 0.1 to 0.3 mm,
The spinning distance may be 80 to 230 mm.

  The electrospinning parameter of the electrospinning machine may include a polymer resin concentration in the polymer resin solution, a spinning speed of the polymer resin solution, an applied voltage, and a spinning distance.

  The electrospinning parameter of the electrospinning machine may further include silver concentration.

  In order to solve the above problems, according to another aspect of the present invention, a composite fiber filter manufactured by the above-described manufacturing method is provided.

  In order to solve the above-mentioned problem, according to another aspect of the present invention, in a method for manufacturing a composite fiber filter, a first melt spinning machine is formed on a forming rod made of a conductive material that is grounded at one end and is driven to rotate. A first microfiber layer composed of the first microfiber yarn is formed by melt spinning with a polymer resin solution having a constant dielectric constant that can be electrospun on the first microfiber layer using an electric field spinning machine. Spinning to form a nanofiber layer composed of nanofiber yarns, and melt spinning on the nanofiber layer with a second melt spinning machine to have a second microfiber yarn having a diameter different from that of the first microfiber yarn A method for producing a composite fiber filter using nanofibers is provided, wherein a second microfiber layer is formed, and each of the fiber layers is continuously laminated on the forming rod. .

  In order to solve the above-described problem, according to another aspect of the present invention, in the composite fiber filter manufacturing apparatus, a conductive material formed rod having one end grounded is configured to be rotationally driven by a drive unit, One or more melt spinning machines and an electrospinning machine are installed in the vicinity of the forming rod, and a microfiber made of microfiber yarn is formed on the forming rod by melt spinning of the melt spinning machine and electrospinning of the electrospinning machine. An apparatus for producing a composite fiber filter using nanofibers is provided, wherein the fiber layers and nanofiber layers made of nanofiber yarns are alternately and continuously laminated.

  A cold rolling roll that can be pressed and rotated with the forming rod may be provided at each corresponding position of the first melt spinning machine and the electrospinning machine.

  The apparatus for producing a composite fiber filter using the nanofibers may further include a cutting machine that cuts the cylindrical fiber layers that are alternately and continuously laminated to a predetermined effective length.

  In order to solve the above problems, according to still another aspect of the present invention, in a method for producing a composite fiber filter, a first microfiber is obtained by melt spinning on a rotationally driven forming rod with a first melt spinning machine. A first microfiber layer made of yarn was formed, and 0.1 mass% to 1.0 mass% of the self-dispersing agent-containing silver nanoparticles were mixed on the first microfiber layer with respect to the mass of the polymer resin. A nanofiber layer in which a planar nanofiber nonwoven fabric made of nanofiber yarn is wound to a certain thickness is laminated, and melt spinning is performed on the nanofiber layer by a second melt spinning machine. A second microfiber layer composed of second microfiber yarns having different diameters is laminated and each fiber layer is continuously laminated on the forming rod, and nanofibers are used. How to make composite fiber filters There is provided.

In order to solve the above problems, according to still another aspect of the present invention, a nanofiber nonwoven fabric is formed on a microfiber nonwoven fabric by an electrospinning method and laminated, and then the microfiber nonwoven fabric and the nanofiber are formed. A nanocomposite water purification filter is manufactured by winding a nonwoven fabric into a cylindrical shape until a certain thickness is obtained, and the nanofiber constituting the nanofiber nonwoven fabric is 0.1 mass% to 1.0 mass relative to the mass of the polymer resin. % Of the self-dispersing agent-containing silver nanoparticles, the porosity of the nanofiber nonwoven fabric is 30 to 70%, and the pure density of the nanofiber nonwoven fabric is 0.1 to 0.22 g / cm ³ . A method for producing a composite fiber filter using nanofibers is provided.

In order to solve the above-mentioned problem, according to still another aspect of the present invention, nanofibers in which 0.1 mass% to 1.0 mass% of self-dispersing agent-containing silver nanoparticles are mixed with respect to the mass of the polymer resin. After the planar nanofiber nonwoven fabric having a porosity of 30 to 70% and a pure density of 0.1 to 0.22 g / cm ³ is alternately stacked with the planar microfiber nonwoven fabric, A method for producing a composite fiber filter is provided, which is produced by bending to produce a cylindrical nanocomposite fiber filter.

  According to the present invention, a composite fiber filter having high efficiency, high functionality, and antibacterial properties can be realized by combining nanofibers and microfibers, and the composite fiber filter can be used as a filter for water purification and others. It can also be used for other applications.

  Exemplary embodiments of the present invention will be described below in detail with reference to the accompanying drawings. In addition, in this specification and drawing, about the component which has the substantially same function structure, duplication description is abbreviate | omitted by attaching | subjecting the same code | symbol.

  In the present invention, a nanofiber nonwoven fabric and microfiber are hybridized to realize a new type of highly efficient and highly functional composite fiber filter that has fine pores but does not increase pressure.

  FIG. 1 is a configuration diagram of a composite fiber filter manufacturing apparatus 100 according to an embodiment of the present invention, and FIG. 2 is a cylindrical composite fiber filter manufactured by the composite fiber filter manufacturing apparatus 100 according to the embodiment. FIG.

  The composite fiber filter manufacturing apparatus 100 according to the present embodiment includes a drive unit 4 having a forming rod 2, first and second melt spinning machines 6, 10, an electrospinning machine 8, cold rolling as shown in FIG. The rolls 12a and 12b and the cutting machine 14 are provided, and continuous production by an automated process is possible.

  The drive unit 4 rotates the forming rod 2 under the control of the control unit in the composite fiber filter manufacturing apparatus 100. In addition, when the horizontal transfer with respect to the fiber layer already formed on the forming rod 2 is required, the driving unit 4 projects a recessed piece (recessed piece) in the forming rod 2 under the control of the control unit, and The fiber layer formed on the forming rod 2 is gradually and horizontally transferred to one side by the action of the blowing force from the intermediate rolling roll 12a.

  The forming rod 2 takes a role as a collector of the first and second melt spinning machines 6 and 10 and a role as a collector of the electrospinning machine 8. For this purpose, the rod is made of a conductive material and one end is grounded. Moreover, the surface of the forming rod 2 is smooth so that the fiber layer formed on the forming rod 2 can be horizontally transferred to one side.

  The forming rod 2 has a rotational speed, preferably 30 so that both the melt spinning by the first and second melt spinning machines 6 and 10 and the electrospinning by the electrospinning machine 8 can be accommodated under the control of the drive unit 4. Rotate at a low speed of ~ 50 rpm. Further, when it is necessary to further increase the production speed of the filter, the rotational speed of the forming rod 2 when the first and second melt spinning machines 6 and 10 are operated is set to the rotational speed of the forming rod 2 when the electrospinning machine 8 is operated. Compared to the rotational speed, increase it relatively.

  The first and second melt spinning machines 6 and 10 are apparatuses for melt spinning fiber yarns in micrometer units (micrometer order) by an air blow method, and the electrospinning machine 8 is a nanometer unit (nanometer). This is an apparatus for electrospinning fiber yarns (on the order of meters). The second melt-spinning machine 10 melt-spins the fiber yarn in the micrometer unit similarly to the first melt-spinning machine 6, but melt-spins the fiber yarn having a relatively larger diameter than the first melt-spinning machine 6. It is preferable to configure.

  The electrospinning machine 8 includes a syringe pump including a syringe having a metal needle spinneret, a collector portion as a forming rod 2 having one end grounded, and a high piezoelectric field of 0 to 40 kV. It is comprised with the high voltage power supply device applied to. The nanofiber is obtained by drawing and spinning a positive (+) charged polymer solution from the electrospinning machine 8 with a high piezoelectric field applied between the metal injection needle spinning port of the syringe and the forming rod 2 of the collector part. Is formed on the forming rod 2.

  At the corresponding positions of the first melt spinning machine 6 and the electrospinning machine 8, cold rolling rolls 12a and 12b that can be pressed and rotated (contact rotation) with the forming rod 2 are provided. These cold rolling rolls 12a and 12b have a function of pressurizing the surface of the fiber layer formed on the forming rod 2 with a predetermined pressure to make the density dense and uniform, and a function of cooling by blowing. In particular, among the cold rolling rolls 12a and 12b, the cold rolling roll 12a corresponding to the first melt spinning machine 6 is constituted by a bobbin having a tapered portion, and the fiber layer formed on the forming rod 2 is formed by the forming rod 2. The fiber layer is pushed out by being inclined and blown when it is lifted by the protrusion of the inner concave piece, and gradually transferred horizontally. The cold rolling roll 12b is a cylindrical roll.

  The cutting machine 14 is laminated on the forming rod 2 and cuts the fiber filter layer, which is continuously pushed and transferred, into a predetermined effective length by an internal cutter, thereby completing the cylindrical composite fiber filter 200 shown in FIG. Let

  The control unit of the composite fiber filter manufacturing apparatus 100 controls the drive unit 4 to rotate the forming rod 2 at a predetermined rotational speed in the range of 30 to 50 rpm, and first operates only the first melt spinning machine 6 to perform the air bronze. The inner microfiber layer 20 shown in FIG. 2 is formed by spinning fiber yarns in micrometer units on the forming rod 2 by melt spinning. At this time, the cold rolling roll 12 a presses the inner microfiber layer 20 being formed while rotating in contact with the forming rod 2.

  When the inner microfiber layer 20 is formed to a predetermined thickness (thickness that shifts to transfer control), the control unit controls the drive unit 4 to project the concave piece in the forming rod 2 to the outside. The inner microfiber layer 20 inside is finely raised. At this time, the inner microfiber layer 20 formed on the forming rod 2 is gradually transferred horizontally to one side by the inclined air blowing force from the tapered cold rolling roll 12a. At this time, the first melt spinning machine 6 continues to melt and spin the fiber yarn in the micrometer unit, while the electrospinning machine 8 and the second melt spinning machine 10 start to operate under the control of the control unit. And melt spinning.

  As shown in FIG. 2, the nanofiber layer 22 and the outer microfiber layer 20 are sequentially stacked on the inner microfiber layer 20 by the electrospinning of the electrospinning machine 8 and the melt spinning of the second melt spinning machine 10. . When this fiber layer is gradually transferred horizontally and enters the cutting machine 14, an internal cutter in the cutting machine 14 cuts the cylindrical fiber layer into a predetermined effective length, and the cylindrical composite fiber shown in FIG. A filter 200 is obtained.

  In the present embodiment, the composite fiber filter manufacturing apparatus 100 shown in FIG. 1 employs two melt spinning machines and an electrospinning machine to manufacture the cylindrical composite fiber filter 200. On the other hand, manufacturing the composite fiber filter It will be apparent to those skilled in the art that the apparatus 100 employs a large number of melt spinning machines and electrospinning machines, and the microfiber layers 20 and the nanofiber layers 22 can be alternately laminated as shown in FIG. It is a thing.

  In particular, in FIGS. 2 and 3, the nanofiber according to the present embodiment constituting the nanofiber layer 22 has a fiber thread diameter of several nm to several hundred nm, preferably 50 nm to 800 nm. Such nanofiber yarns are extremely fine, have a large surface area and excellent flexibility, are easy to be crimped, and are suitable for filter materials. Therefore, since the nanofiber layer 22 made of nanofiber yarn has a large number of pores, most of the fine particles can be removed with a low pressure.

  The thickness of the nanofiber layer 22 according to the present embodiment is in the range of several μm to several hundred μm, and the manufacturer may appropriately set the thickness within the above range in consideration of the filter efficiency of the corresponding filter. it can.

Further, when the nanofiber layer 22 according to the present embodiment is used as a filter for water purification, the average pore diameter is 1 to 3.5 μm, the porosity is 30 to 70%, and the pure density is 0.1 to 0. 0.22 g / cm ³ and an apparent density of 0.18 to 0.35 g / cm ³ are preferable.

  In the present invention, in realizing a filter using nanofibers, the problem relating to differential pressure and filtration efficiency is solved while fusing the microfiber manufacturing technology and nanofiber manufacturing technology while having cost competitiveness. In order to realize a functional filter that ensures high functionality and has antibacterial properties, it is necessary to consider the following raw material and various parameters of the spinning machine.

  For the microfiber layer 20, synthetic resin materials that can be melt-spun from a melt spinning machine include, for example, polypropylene (PP), polyethylene terephthalate, polyvinylidene fluoride, nylon, polyvinyl acetate, polymethyl methacrylate, and polyacrylonitrile. Polyurethane, polybutylene terephthalate, polyvinyl butyral, polyvinyl chloride, polyethyleneimine, polysulfone, polyolefin and the like can be used, and among these, polypropylene (PP) is preferably used.

  The nanofiber layer 22 is preferably made of a polymer resin having a certain dielectric constant (dielectric constant greater than a predetermined value) that enables electrospinning.

  For the polymer resin having a certain dielectric constant or more constituting the nanofiber layer 22, for example, polyacrylonitrile (PAN) resin or polyamide (nylon 6 or the like) is used as a polymer resin that can be dissolved in an organic solvent containing water. Nylon fiber) is preferably used.

  Other examples of the polymer resin that can be dissolved in an organic solvent containing water include, for example, polyvinyl alcohol, polystyrene, polycaprolactone, polyethylene terephthalate, polyvinylidene fluoride, nylon, polyvinyl acetate, polymethyl methacrylate, polyacrylonitrile, Examples include polyurethane, polybutylene terephthalate, polyvinyl butyral, polyvinyl chloride, polyethyleneimine, polysulfone, and nitrocellulose. Among the above examples, polystyrene, polyvinylidene fluoride, polymethyl methacrylate, polyacrylonitrile, polyurethane, polyvinyl butyral, polyvinyl chloride, polysulfone, and nitrocellulose are excellent in water resistance and chemical resistance (alkali resistance, acid resistance, etc.). Therefore, it can be suitably applied to the nanofiber layer 22 of the filter for water purification.

  Further, in forming the microfiber layer 20 and the nanofiber layer 22, in order to ensure high efficiency and high function and to provide antibacterial properties, it is preferable to mix nanosilver particles in this embodiment. That is, a polypropylene chip is charged into a melt spinning machine for melting microfiber yarn and melted. In this embodiment, nano silver particles are included in the polypropylene chip. The nanosilver particles melt at a temperature much lower than the melting point of the polypropylene chip.

  Further, nano silver particles are also contained in a polymer resin solution in an injection machine for electrospinning nanofiber yarn. That is, it is extremely important that the nano silver particles are dispersed and distributed when they are mixed in the melt spinning machine and the injection machine. For this purpose, it is necessary to add a solvent such as alcohol. However, since a solvent such as alcohol causes partial precipitation of silver particles, nanosilver particles that can be dispersed and distributed without using a solvent such as alcohol are used in this embodiment. The nano silver particles are nano silver particles having a dispersant (containing a dispersant).

  On the other hand, conventionally, when an alcohol solvent is used to disperse the nanosilver particles, the silver content is only about 0.1 mass% with respect to the mass of the polymer resin, and thus the antibacterial property is inferior. If nano silver particles far exceeding 0.1 mass% were mixed in order to enhance antibacterial properties, precipitation occurred.

  On the other hand, when the self-dispersing agent-containing nano silver particles according to the present embodiment are used, they can be mixed up to 1 mass% with respect to the mass of the polymer resin. It does not make sense to mix more nanosilver particles. This is because an antibacterial property close to 100% can be exhibited only by mixing about 0.5 mass% of nano silver particles with respect to the mass of the polymer resin.

  Therefore, the self-dispersing agent-containing nano silver particles according to this embodiment are preferably mixed in the range of 0.1 mass% to 1.0 mass%, more preferably the mass of the polymer resin, with respect to the mass of the polymer resin. Is mixed in the range of 0.3 mass% to 0.6 mass%.

  In mixing nano silver particles for imparting antibacterial properties, the mixing ratio can be applied to both microfiber yarns and nanofiber yarns, and either microfiber yarns or nanofibers are used as necessary. It can also be applied to only. Moreover, when applying only to either one, it is preferable to apply to the nanofiber yarn which has a relatively high surface area and porosity.

  In forming the microfiber layer 20 and the nanofiber layer 22, in order to fully exhibit the various functions of the filter, it is extremely important to produce the fiber yarn uniformly and to make it as thin as possible.

  First, in forming the microfiber layer 20, in order to make the polypropylene microfiber yarn uniform and thinner than the conventional one, parameters such as the diameter of the spinning nozzles of the melt spinning machines 6 and 10, the spinning temperature, and the spinning distance are taken into consideration. There is a need to. The inventors of the present application changed these parameters to establish optimum melt spinning conditions.

  The inventors of the present application conducted an experiment for realizing the cylindrical composite fiber filter 200 as a filter for water purification. It is preferable that the water purification filter has a strength that can withstand the pressure applied during water purification work and has a uniform average diameter.

  Of the parameters considered for the realization of the filter for water purification, the spinning temperature is preferably 280 ° C. to 300 ° C., and it was confirmed that the spinning distance is not a variable required for ensuring the uniformity of the microfibers.

  However, it was confirmed that the diameter of the spinning nozzle is a very important variable required for ensuring the uniformity of the microfibers. At this time, the diameter of the spinning nozzle is preferably 0.1 to 0.3 mm, and it has been confirmed that even in the range of 0.1 to 0.3 mm, the lower the diameter, the more advantageous for ensuring uniformity. It was.

  As an experimental example, melt spinning was performed while the spinning nozzle diameter was 0.2 mm and the spinning distance was adjusted little by little. As a result, uniform microfibers having an average diameter of 12 to 17 μm could be obtained. At this time, it was confirmed that the diameter of the microfiber yarn became thinner as the spinning distance increased, and it was confirmed that it is preferable to relatively shorten the spinning distance in order to optimize the production efficiency. The range of the spinning distance is, for example, about 80 mm to 230 mm.

  The microfiber yarn constituting the microfiber layer 20 according to the present embodiment can be made uniform while having the average diameter of 12 to 17 μm, and the normal diameter of the microfiber yarn constituting the conventional water purification filter. For example, it is much thinner than 23 to 50 μm, and has a relatively large surface area and excellent flexibility as compared with the prior art.

  Next, in forming the nanofiber layer 22 according to the present embodiment, the electric field of the electrospinning machine 8 for uniformly spinning the nanofiber yarn of the polymer resin having a certain dielectric constant or more and improving the reproducibility is obtained. The parameters that make up the spinning conditions must be taken into account. Parameters include voltage, spinning distance, spinning speed, polymer resin solution concentration, and the like.

  In the embodiment of the present invention, among polyacrylonitrile (PAN) resin or polyamide (nylon resin such as nylon 6), which is a preferable example of a polymer resin having a certain dielectric constant or higher, polyacrylonitrile (PAN) is used. ) N, N-dimethylformamide (DMF) was used as the solvent for dissolving the resin, and formic acid (formic acid) was used as the solvent for dissolving the polyamide (nylon 6).

  The inventors of the present application conducted a nanofiber formation experiment for realizing the cylindrical composite fiber filter 200 as a filter for water purification. The experiment was performed separately for the case of using polyacrylonitrile resin and the case of using polyamide (nylon 6) as the polymer resin for forming the nanofiber layer 22 of the filter for water purification.

  First, an experimental example in the case of using a polyacrylonitrile resin as the polymer resin will be described.

  The polyacrylonitrile PAN resin is dissolved in an N, N-dimethylformamide (DMF) solvent to obtain a PAN / DMF solution (polymer solution). At this time, it was experimentally confirmed that important parameters to be considered in electrospinning the PAN / DMF solution were the concentration in the PAN / DMF solution, the spinning speed of the PAN / DMF solution, the applied voltage, the spinning distance, and the like. It was.

  At this time, the diameter of the nanofibers decreased as the concentration in the solution and the spinning speed of the solution decreased, and decreased as the applied voltage and the spinning distance increased.

  Examples of nanofibers optimized as a water purification filter are as follows.

(1) PAN nanofiber having an average diameter of 600 nm In the parameters of electrospinning conditions, the concentration in the solution is 12 mass%, the spinning speed of the solution is 1.2 mL / h, the applied voltage is 15 kV, and the spinning distance is 15 cm.

(2) PAN nanofiber with an average diameter of 300 nm In the parameters of electrospinning conditions, the concentration in the solution is 10 mass%, the spinning speed of the solution is 1.2 mL / h, the applied voltage is 15 kV, and the spinning distance is 13 cm.

  Among the optimized PAN nanofibers, PAN nanofibers having an average diameter of about 300 nm have an advantage that the fiber shape is uniform, beads are not mixed, and the reproducibility is excellent. In addition, a sheet of PAN nanofibers having an average diameter of about 600 nm is easy to operate and easy to adjust the thickness, and can be most suitably applied to a nano / micro composite fiber filter. The PAN nanofiber can be easily applied to a carbon nanofiber manufacturing process.

  Next, an experimental example when the polymer resin is polyamide (nylon 6) will be described.

  Polyamide (nylon 6) was dissolved in a formic acid solvent to obtain a polymer solution, and electrospinning was performed under various conditions. As a result of the experiment, in order to obtain uniform nanofibers having excellent reproducibility, among the parameters of electrospinning conditions, the voltage is 10 to 19 kV, the spinning distance is 8 to 20 cm, and the spinning speed is 0.1 to 0. It was confirmed that the polymer concentration was preferably 15 to 26 mass% of the solvent at 3 mL / h.

  Electrospinning was performed under the above electrospinning conditions, and polyamide (nylon 6) nanofibers having an average diameter of about 200 nm could be produced.

  In this embodiment, in order to impart antibacterial properties to the microfiber layer 20 and the nanofiber layer 22, nanosilver was added to perform spinning.

  When nano silver is added, it is necessary to check whether the fiber yarn is smoothly spun and whether the obtained fiber yarn has antibacterial properties even if the spinning is performed smoothly.

  The present inventors have been able to produce antibacterial nanofibers using an electrospinning machine, for example, by adding nanosilver having a particle size of 10 to 20 nm to polyamide (nylon 6). As a result of the experiment, it was confirmed that the thickness of the nanofiber yarn became thinner as the applied voltage of the electrospinning machine became higher, and on the other hand, there was no change in the shape of the nanofiber due to the change in silver concentration, so it was confirmed that there was no problem It was done.

  Thereafter, an experiment for confirming the presence / absence of the silver component and the presence / absence of antibacterial action was performed on the obtained polyamide (nylon 6) / silver nanofiber yarn nonwoven fabric.

  4A and 4B are diagrams showing a TEM analysis image of polyamide (nylon 6) / silver nanofiber yarn, and FIG. 5 is an EDS (Energy Dispersive Spectroscopy) analysis image of polyamide (nylon 6) / silver nanofiber yarn. FIG. In FIG. 4A and FIG. 4B, it can be confirmed that silver particles having a particle diameter of 10 to 20 nm are permeated and dispersed on the surface of the polyamide (nylon 6) / silver nanofiber yarn and inside thereof. In FIG. It can be confirmed from the spectrum that the silver component is contained in.

  The inventors of the present application conducted antibacterial experiments using Staphylococcus aureus and Klebsiella pneumonia. S. aureus is an example of a positive bacterium, and K. pneumoniae is an example of a negative bacterium.

  FIG. 6A is a bar graph showing antibacterial experimental results using Staphylococcus aureus, and FIG. 6B is a bar graph showing antibacterial experimental results using Klebsiella pneumoniae.

  Referring to the graphs of FIG. 6A and FIG. 6B, in an antibacterial experiment using Staphylococcus aureus and Klebsiella pneumoniae, if the silver content is 1000 ppm or more, 90% or more of the antibacterial activity (Growth inhibition rate) is shown. I can confirm that. At this time, antibacterial [%] is calculated by the formula (A−B / A) * 100 (where A is the number of viable bacteria cultured and calculated in a general nonwoven fabric, and B is a silver-containing nanofiber nonwoven fabric. Is the number of viable bacteria calculated in culture). The silver content of 1000 ppm is a value corresponding to about 0.3 mass% with respect to the mass of the polymer resin.

  In the antibacterial effect, if the antibacterial property is about 20 to 30%, the effect is not so much, and if it is 90% or more, the effect is very good. Therefore, it can be seen that the silver-containing nanofiber nonwoven fabric of the present invention has an excellent antibacterial effect when the silver content is 1000 ppm or more.

  7A and 7B are diagrams showing the antibacterial zone test results of nanofibers using Staphylococcus aureus and Klebsiella pneumoniae. FIG. 7A is a photograph showing the antibacterial zone test results of nanofibers using Staphylococcus aureus, and FIG. 7B is a photograph showing the antibacterial zone test results of nanofibers using Klebsiella pneumoniae.

  In FIG. 7A and FIG. 7B, the sample nonwoven fabric labeled “N” is a general nanofiber nonwoven fabric (left side), and the sample nonwoven fabric (right side) without labeling is a silver-containing nanofiber nonwoven fabric containing about 1500 ppm of silver. .

  From FIG. 7A and FIG. 7B, it is confirmed that the silver-containing nanofiber nonwoven fabric (right side) cannot inhabit and multiply in the vicinity thereof.

  FIG. 8 is an SEM image showing that nanofibers 22 are formed by electrospinning nanofibers on the microfiber layer 20 according to the present embodiment, and FIGS. 9A to 9C are inner microfiber layers. 2 is a partial cross-sectional photograph showing that a nanofiber layer 22 and an outer microfiber layer 20 are sequentially laminated on 20.

  The inventors of the present application determined the filtration rate based on the particle diameter by experiments using the conventional microfilter and the cylindrical composite fiber filter 200 of FIG. 2, and the results are shown in FIGS. 10A and 10B.

  In the table of FIG. 10A and the graph of FIG. 10B, “Dejein microfilter” is a conventional microfilter, and “Dejin nanofilter” is the cylindrical composite fiber filter 200 of FIG. It is a sample. Comparing both, the sample of the cylindrical composite fiber filter 200 “Daejin nanofilter” is a conventional microfilter, whereas almost 99% or more of 0.1 μm particles are filtered. It is confirmed that only about 80% of the “Dejin microfilter” can be filtered even for particles of 3 μm or more.

  From such a comparison, the excellent filtration efficiency of the cylindrical composite fiber filter 200 according to the present embodiment is proved.

  Further, the inventors of the present application experimentally determined the pressure loss due to the flow rate (flow velocity) of the conventional microfilter and the pressure loss due to the flow rate (flow velocity) of the cylindrical composite fiber filter 200 of FIG. 2, and the results are shown in FIG. 11A. And shown in FIG. 11B. The pressure loss means the difference between the pressure of the flow rate entering the filter and the pressure of the flow rate discharged from the filter, and the lower the value, the better.

  Referring to FIGS. 11A and 11B, the pressure loss due to the flow rate (flow velocity) of the conventional microfilter “Dejin microfilter” and the composite fiber filter “Daejin nanofilter” according to the present embodiment. The pressure loss due to the flow rate (flow velocity) is not significantly different at a flow rate (flow velocity) of 12 to 18 L / min. In particular, the flow rate (flow velocity) in general tap water is about 12 L / min. Here, the pressure loss of the conventional microfilter “Daejin microfilter” is 0.015, and the composite of the present invention The pressure loss (differential pressure) of the fiber filter “Daejin nano filter” is 0.021.

  Therefore, in the case of general tap water, the composite fiber filter according to the present embodiment has a differential pressure similar to that of a conventional microfilter, and thus has good performance. Considering that the differential pressure of the reverse osmotic pressure filter in general tap water is several tens of L / min, it can be seen that the differential pressure performance of the composite fiber filter according to the present embodiment is greatly improved.

  When the cylindrical composite fiber filter according to the present embodiment is opened by cutting the cylindrical surface in the length direction, a planar composite fiber filter is obtained.

  In addition, the composite fiber filter according to the present embodiment can be applied directly or applied to not only for water purification but also for air purification and other filter media, which is for those who have ordinary knowledge in this technical field. Is obvious.

  As mentioned above, although preferred embodiment of this invention was described referring an accompanying drawing, it cannot be overemphasized that this invention is not limited to this example. It will be apparent to those skilled in the art that various changes and modifications can be made within the scope of the claims, and these are naturally within the technical scope of the present invention. Understood.

  For example, in the present invention, as a method for combining a microfiber nonwoven fabric and nanofibers, other examples than the method for producing a composite fiber filter by the above-described continuous process will be described. After being produced and wound to a certain thickness on the microfiber layer 20 formed on the forming rod 2 of FIG. 1, the microfiber layers are alternately laminated using the microfiber melt spinning machine of FIG. A composite fiber filter can also be manufactured by this method.

At this time, the forming rod 2 is not necessarily made of a conductive material, and the nanofibers constituting the separately produced planar nanofiber nonwoven fabric are 0% relative to the mass of the polymer resin according to the present invention. 0.1 mass% to 1.0 mass% of the self-dispersing agent-containing silver nanoparticles are mixed, and the planar nanofiber nonwoven fabric has a porosity of 30 to 70% and a pure density of 0.1 to 0.00. It is preferably 22 g / cm ³ .

In addition, according to another embodiment of the present invention, after the nanofiber nonwoven fabric of the present invention is formed by electrospinning on a microfiber nonwoven fabric such as a spunbond, These can be rolled into a cylindrical shape to a certain thickness to produce a nano composite water purification filter. At this time, the nanofiber constituting the nanofiber nonwoven fabric is a fiber in which 0.1 mass% to 1.0 mass% of a self-dispersing agent-containing silver nanoparticle is mixed with respect to the mass of the polymer resin, and the nanofiber The non-woven fabric has a porosity of 30 to 70% and a pure density of 0.1 to 0.22 g / cm ³ .

Furthermore, in the present invention, it is possible to produce a cylindrical nanocomposite fiber filter in which planar nanofiber nonwoven fabrics and planar microfiber nonwoven fabrics are alternately stacked to be multilayered and then bent into a bellows shape. At this time, the nanofiber constituting the nanofiber nonwoven fabric is a nanofiber yarn in which 0.1 mass% to 1.0 mass% of the self-dispersing agent-containing silver nanoparticles are mixed with respect to the mass of the polymer resin. The porosity of the fiber nonwoven fabric is 30 to 70%, and the pure density is 0.1 to 0.22 g / cm ³ .

It is a block diagram of the manufacturing apparatus of the composite fiber filter which concerns on one Embodiment of this invention. It is a perspective view of the cylindrical composite fiber filter which concerns on one Embodiment of this invention. It is sectional drawing of the cylindrical composite fiber filter which shows an example by which the nanofiber layer was multilayered. It is a figure which shows the TEM analysis image with respect to a polyamide (nylon 6) / silver nanofiber yarn. It is a figure which shows the TEM analysis image with respect to a polyamide (nylon 6) / silver nanofiber yarn. It is a figure which shows the EDS analysis image with respect to a polyamide (nylon 6) / silver nanofiber yarn. It is a bar graph which shows the antibacterial experiment result using Staphylococcus aureus and Klebsiella pneumoniae. It is a bar graph which shows the antibacterial experiment result using Staphylococcus aureus and Klebsiella pneumoniae. It is a figure which shows the antimicrobial zone test result of the nanofiber using Staphylococcus aureus and Klebsiella pneumoniae. It is a figure which shows the antimicrobial zone test result of the nanofiber using Staphylococcus aureus and Klebsiella pneumoniae. It is a SEM image photograph which shows that the nanofiber layer was laminated | stacked and formed on the inner microfiber layer. It is a SEM image partial cross-section photograph which shows that the nanofiber layer and the outer microfiber layer were laminated in order on the inner microfiber layer. It is a SEM image partial cross-section photograph which shows that the nanofiber layer and the outer microfiber layer were laminated in order on the inner microfiber layer. It is a SEM image partial cross-section photograph which shows that the nanofiber layer and the outer microfiber layer were laminated in order on the inner microfiber layer. It is a figure which calculates | requires experimentally the filtration rate by the particle size of the conventional filter, and the filtration rate by the particle size of the composite fiber filter which concerns on the same embodiment, and shows the result. It is a figure which calculates | requires experimentally the filtration rate by the particle size of the conventional filter, and the filtration rate by the particle size of the composite fiber filter which concerns on the same embodiment, and shows the result. It is a figure which shows the pressure loss by the flow volume (flow velocity) of the conventional filter, and the pressure loss by the flow volume (flow velocity) of the composite fiber filter which concerns on the same embodiment by experiment, and shows the result. It is a figure which shows the pressure loss by the flow volume (flow velocity) of the conventional filter, and the pressure loss by the flow volume (flow velocity) of the composite fiber filter which concerns on the same embodiment by experiment, and shows the result.

Claims (19)

In the method for producing a composite fiber filter,
A microfiber layer composed of microfiber yarns is formed by melt spinning with a melt spinning machine on a forming rod of a conductive material that is grounded at one end and driven to rotate,
A nanofiber layer composed of nanofiber yarns is laminated on the microfiber layer by electrospinning a polymer resin solution having a predetermined dielectric constant that can be electrospun with an electrospinning machine. A method for producing a composite fiber filter using fibers. 2. The nanofiber according to claim 1, wherein the microfiber layer and the nanofiber layer are alternately and continuously laminated using the melt spinning machine and the electrospinning machine to form a multilayer. Manufacturing method of used composite fiber filter. In the polymer resin solution,
The composite fiber filter using nanofiber according to claim 1, wherein 0.1 mass% to 1.0 mass% of dispersant-containing silver nanoparticles are mixed with respect to the mass of the polymer resin. Manufacturing method. The porosity of the nanofiber layer is 30 to 70%,
The pure density of the nanofiber layer, characterized in that the 0.1~0.22g / cm ^3, method for manufacturing a composite fiber filter using nanofibers according to claim 1 or 3. The polymer resin contained in the nanofiber yarn is
The method for producing a composite fiber filter using nanofibers according to claim 1 or 3, wherein the method comprises any one of a polyacrylonitrile resin and a polyamide resin. The polymer resin contained in the nanofiber yarn is
Polyvinyl alcohol, polystyrene, polycaprolactone, polyethylene terephthalate, polyvinylidene fluoride, nylon, polyvinyl acetate, polymethyl methacrylate, polyacrylonitrile, polyurethane, polybutylene terephthalate, polyvinyl butyral, polyvinyl chloride, polyethyleneimine, polysulfone and nitrocellulose 4. The method for producing a composite fiber filter using nanofibers according to claim 1, wherein the composite fiber filter comprises any one selected from the group consisting of: The melt-spun microfiber yarn includes a polypropylene component,
The composite fiber filter using nanofibers according to claim 1, wherein 0.1 mass% to 1.0 mass% of the self-dispersing agent-containing silver nanoparticles are mixed with respect to the mass of the polypropylene. Production method. The method for producing a composite fiber filter using nanofiber according to claim 1, wherein the forming rod is driven to rotate at 30 to 50 rpm. In the melt spinning conditions of the melt spinning machine,
The spinning nozzle diameter is 0.1 to 0.3 mm,
The method for producing a composite fiber filter using nanofibers according to claim 1, wherein the spinning distance is 80 to 230 mm. For the parameters of the electrospinning conditions of the electrospinning machine,
The method for producing a composite fiber filter using nanofibers according to claim 1, wherein the polymer resin concentration in the polymer resin solution, the spinning speed of the polymer resin solution, the applied voltage, and the spinning distance are included. The method for producing a composite fiber filter using nanofiber according to claim 10, wherein the parameter of the electrospinning condition of the electrospinning machine further includes silver concentration.   A composite fiber filter manufactured by the manufacturing method according to claim 1. In the method for producing a composite fiber filter,
Forming a first microfiber layer composed of the first microfiber yarn by melt spinning with a first melt spinning machine on a forming rod made of a conductive material grounded at one end and driven to rotate;
On the first microfiber layer, a polymer resin solution having a constant dielectric constant capable of electrospinning is electrospun with an electrospinning machine, and a nanofiber layer composed of nanofiber yarns is laminated and formed.
On the nanofiber layer, a second microfiber layer composed of a second microfiber yarn having a diameter different from that of the first microfiber yarn is formed by melt spinning with a second melt spinning machine,
Each of the fiber layers is continuously laminated on the forming rod, and the method for producing a composite fiber filter using nanofibers. In production equipment for composite fiber filters,
A conductive rod with one end grounded is configured to be rotationally driven by the drive unit,
Install one or more melt spinning machines and electrospinning machines in the vicinity of the forming rod,
By the melt spinning of the melt spinning machine and the electrospinning of the electrospinning machine, microfiber layers made of microfiber yarns and nanofiber layers made of nanofiber yarns are alternately and continuously formed on the forming rod. An apparatus for producing a composite fiber filter using nanofibers. In the corresponding positions of the first melt spinning machine and the electrospinning machine,
15. The apparatus for producing a composite fiber filter using nanofibers according to claim 14, wherein the forming rod and a cold rolling roll capable of being crimped and rotated are provided. [Claim 16] The composite fiber filter using nanofiber according to claim 14 or 15, further comprising a cutting machine that cuts the cylindrical fiber layers alternately and continuously laminated to a predetermined effective length. Manufacturing equipment. In the method for producing a composite fiber filter,
Forming a first microfiber layer composed of a first microfiber yarn on a rotationally driven forming rod by melt spinning with a first melt spinning machine;
On the first microfiber layer, a planar nanofiber nonwoven fabric composed of nanofiber yarns mixed with 0.1 mass% to 1.0 mass% of a self-dispersing agent-containing silver nanoparticle with respect to the mass of the polymer resin is constant. Layered nanofiber layers wound to a thickness of
On the nanofiber layer, a second microfiber layer made of a second microfiber yarn having a diameter different from that of the first microfiber yarn by laminating with a second melt spinning machine is laminated and formed.
Each of the fiber layers is continuously laminated on the forming rod, and the method for producing a composite fiber filter using nanofibers. After forming a nanofiber nonwoven fabric by electrospinning on a microfiber nonwoven fabric and laminating it, the nanofiber nonwoven fabric and the nanofiber nonwoven fabric are wound into a cylindrical shape until a predetermined thickness is produced to produce a nano composite water purification filter,
The nanofibers constituting the nanofiber nonwoven fabric are fibers in which 0.1 mass% to 1.0 mass% of the self-dispersing agent-containing silver nanoparticles are mixed with respect to the mass of the polymer resin,
The nanofiber nonwoven fabric has a porosity of 30 to 70%, and the nanofiber nonwoven fabric has a pure density of 0.1 to 0.22 g / cm ³ , thereby producing a composite fiber filter using nanofibers. Method. It consists of nanofibers mixed with 0.1 mass% to 1.0 mass% of self-dispersing agent-containing silver nanoparticles based on the mass of the polymer resin
A planar nanofiber nonwoven fabric having a porosity of 30 to 70% and a pure density of 0.1 to 0.22 g / cm ³ is layered alternately with a planar microfiber nonwoven fabric, and then folded into a cylinder. A method for producing a composite fiber filter using nanofibers, characterized by producing a nanocomposite fiber filter in the form of a tube.