KR20180000215A - Manufacturing method for filter for blocking fine and yellow dust containing nanofiber web and manufacturing apparatus thereof - Google Patents

Abstract

The present invention relates to a method for producing a fine dust-blocking filter, and an apparatus therefor. To this end, a nanofiber web is continuously produced by an upflow-downflow electrospinning device on the same plane by rotating a support where the nanofiber web is laminated, thereby making production processes for the fine dust-blocking filter simple and reducing production times.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention [0001] The present invention relates to a method and an apparatus for forming a fine dust-blocking filter including a nanofiber web,

The present invention relates to a method and an apparatus for forming a fine dust barrier filter including a nanofiber web. More particularly, the present invention relates to a fine dust barrier filter comprising a nanofiber web and a mesh or a carrier for blocking fine dust, To a manufacturing apparatus capable of mass production.

In the windows and doors installed in various buildings such as offices including ordinary households, an integrated insect screening network is installed in a frame made separately so that various kinds of insects such as mosquitoes and flies in summer can not fly into the room.

These insect screens are usually installed in a frame made of synthetic resin net made of synthetic resin in dense net shape or metal net made of dense woven wire or aluminum to prevent insects from entering the room. As well as ventilation can be done smoothly.

In the prior art for insect screen structure, Korean Utility Model Application Publication No. 1999-0035011 or Registered Utility Model No. 0382472 discloses a method for inspecting a damaged area by a simple and easy repair operation without replacing the insect screen entirely, The present invention provides a maintenance structure for an insect net that can reduce work time and economical cost, and discloses a repair structure for a screen net, which is disclosed in Korean Utility Model Publication No. 2010-3529, The double-sided tape in the form of strips provided with the releasing paper is integrally adhered to the back edge of the repaired retention net formed repeatedly, and the repair net is directly attached to the damaged area of the double- The present invention relates to an insect-proof sheet which is easy to repair.

Korean Patent Laid-Open Publication No. 2010-32078 discloses a double-sided tape which is provided adjacent to a window or a door, a double-sided tape adhered to the side surfaces of the frame, one side of the double-sided tape adhered to one side, Wherein the first and second velcro integrally formed by extrusion molding on the same surface of the binding member are folded and folded together to form a pair of first and second velcro fasteners, So that the insect net can be fixed by being fitted to the insect netting structure.

However, the above-described technique is for facilitating the repair of the insect-proof net, or for tightening the binding, and is not related to the object of the present invention for blocking fine dust or dust. Dust, fine dust, or soot are rapidly increasing every year and have a direct impact on public health, but no screening has yet been disclosed to effectively solve this problem.

Accordingly, the present invention has developed an apparatus for manufacturing a filter for blocking fine dust that can be manufactured using a nanofiber web.

Disclosure of the Invention The present invention has been conceived to solve the problems as described above, and it is an object of the present invention to provide a method and a device for forming a mesh, which is used as a support by providing spin- The present invention provides a method and apparatus for manufacturing a fine dust-blocking filter capable of mass production of a high-quality nanofiber web production and a top-down electrospinning apparatus, which are capable of continuously stacking nanofiber webs on one surface, .

According to a preferred embodiment of the present invention, Forming a first nanofiber web on the upper surface of the support by electrospinning the first polymer spinning solution with a top-down electrospinning device; The support having the first nanofiber web laminated thereon passes through the rotating device and the upper surface is rotated 180 degrees to the lower surface; A step of continuously laminating a second nanofiber web by electrospinning a second polymer spinning solution with a bottom-up electrospinning device on a first nanofiber web laminated on the support; And a step of winding a support on which the first and second nanofiber webs are continuously laminated.

Herein, the first and second polymer spinning solutions are electrospun through a temperature controller at a temperature of 50 to 200 ° C, and the first and second polymer spinning solutions are polyurethane, polyvinylidene fluoride, Wherein the support is at least one member selected from the group consisting of polyacrylonitrile, nylon, polyethersulfone, polyamic acid, and polyimide, wherein the support is a mesh or a carrier, The support is composed of one layer or two or more layers, and the fine dust barrier filter has a fine dust light transmittance of 30 to 80%, an air permeability (cfm) of 10 to 500, and an efficiency of 80% or more . The basis weight of the first and second nanofiber webs is 0.001 to 2.0 g / m < 2 >. The step of laminating the first and second nanofiber webs on the support may include ultrasonic bonding, applying a chemical or thermal adhesive, or electrospinning the adhesive directly.

According to another preferred embodiment of the present invention, there is provided a top-down electrospinning device for producing a first nanofiber web by electrospinning a polymer spinning solution on a support, the nozzle being directed from top to bottom; A rotating device for rotating the upper surface of the support 180 degrees to the lower surface; And a bottom-up electrospinning device in which the nozzles are directed from the bottom to the top and the same polymer spinning solution used in the top-down electrospinning device is electrospun on the first nanofiber web to laminate the second nanofiber web, An electrospinning device, the rotating device, and the bottom-up electrospinning device in this order.

Here, the rotating device is characterized in that the supporting body is rotated by 180 degrees by a flip device or rotated in a U-turn direction vertically, wherein the bottom-up electrospinning device and the top-down type electrospinning device are provided for controlling the temperature of the polymer spinning solution Characterized in that the apparatus further comprises a top-down type electrospinning device or a bottom-up type electrospinning device, in addition to the temperature control device do.

As described above, the present invention having the above-described structure can be achieved by rotating a mesh or carrier, which is a supporting member on which a nanofiber web is laminated, by rotating a mesh or carrier on a surface of the nanofiber web So that the manufacturing process of the filter for blocking fine dust can be simplified and the manufacturing time can be reduced.

In addition, the present invention can be installed as a floor layer arranged horizontally or vertically on a plane by installing a mesh or a rotating device for rotating the carrier between the electrospinning apparatuses in the installation of the electrospinning apparatus Accordingly, it is easy to use the space, and at the same time, there is a margin in the installation space. In other words, it is possible to install and operate the electrospinning device in a narrow space, and it is possible to mass-produce the filter.

The filter manufactured by the manufacturing apparatus of the present invention has a 2-layer structure, and after the mass production thereof, there is an advantageous effect that it can be used as a user-customized product (D.I.Y).

1 is a side view schematically showing an apparatus for manufacturing a filter for blocking fine dust used in a filter manufacturing apparatus of the present invention,
FIG. 2 is a plan view schematically showing a nozzle block installed in each electrospinning device of the fine dust-blocking filter manufacturing apparatus of the present invention,
3 is a front sectional view schematically showing a state in which a heating wire for temperature control is installed in a nozzle block installed in each electrospinning device of the fine dust blocking filter manufacturing apparatus of the present invention,
4 is a sectional view taken along the line A-A 'in Fig. 3,
5 and 6 are cross-sectional views schematically showing a flip device used as an embodiment of a rotating device of an apparatus for producing a fine dust-blocking filter according to the present invention,
7 is a plan view showing a state in which the tube body of the nozzle block of the present invention is turned on and off in the CD direction,
FIG. 8 is a plan view showing a process of electrospinning of the nozzles in the nozzle block, as shown in FIG. 7,
FIG. 9 is a plan view showing a process of electrospinning of a nozzle in a nozzle block in the nozzle block according to an embodiment of the present invention,
Fig. 10 is a side view schematically showing a layout in the case where the apparatus for manufacturing a fine dust-blocking filter of the present invention is arranged in a vertical direction; Fig.
Fig. 11 is a bird's-eye view schematically showing a layout in the case where the device for producing fine dust-blocking filters according to the present invention is arranged in U-shape with respect to the horizontal direction.

Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the accompanying drawings. The present invention is not limited to the scope of the present invention, but is merely an example, and various modifications can be made without departing from the technical spirit of the present invention.

FIG. 1 is a side view schematically showing an apparatus for manufacturing a fine dust-blocking filter used in the apparatus for manufacturing a filter of the present invention, and FIG. 2 is a cross-sectional view of a nozzle block provided in each electrospinning apparatus of the fine dust- 3 is a front sectional view schematically showing a state in which a heating wire for temperature control is installed in a nozzle block provided in each electrospinning device of the apparatus for manufacturing a fine dust-blocking filter according to the present invention, and Fig. 4 is a cross- 5 and 6 are cross-sectional views schematically showing a flip device 20-1, which is one embodiment of the rotating device 20 used in the apparatus for producing a fine dust-blocking filter according to the present invention. Fig. 7 is a plan view showing a state in which the tubular body of the nozzle block according to the present invention is turned on and off in the CD direction, and Fig. 8 is a cross- And FIG. 9 is a plan view showing a process in which the electrospinning process is performed on the nozzles in the nozzle block in the nozzle block according to the present invention, And Fig. 10 is a side view schematically showing the arrangement of the apparatus for producing a fine dust-blocking filter according to the present invention in a vertical direction. Fig. 11 is a cross- And FIG. 7 is a bird's-eye view schematically showing a layout in the case of disposition.

As shown in the figure, an apparatus 1 for manufacturing a fine dust-blocking filter according to the present invention includes a top-down or bottom-up electrospinning apparatus 10 and a top-down or top- (30), wherein the top-down or bottom-up electrospinning device (10) and the bottom-up or top-down electrospinning device (30) are arranged at regular intervals. In the present invention, the bottom-up electrospinning apparatus 10 is located at the front end, and thereafter, the bottom-up electrospinning apparatus 30 is located at the rear end, but it is also possible that the bottoms electrospinning apparatus comes to the front end. In addition, although the electrospinning apparatus is composed of two in the present invention, it is also possible that three or more top-down and bottom-up electrospinning apparatuses are arranged alternately.

The top-down or bottom-up electrospinning device 10 and the bottom-up or top-down electrospinning device 30 are used for discharging the polymer solution in the spinning solution main tanks 11 and 31 in which a polymer spinning solution (not shown) A nozzle block 13, 33 in which a plurality of nozzles 15, 35 in the form of a pin are arranged, and an upper end of the nozzles 15, 35 (in the case of a bottom-up electrospinning device) The collectors 17 and 37 are spaced apart from the nozzles 15 and 35 by a predetermined distance in order to collect the polymer spinning solution injected from the nozzles 15 and 35 and a voltage generator 14 ).

According to the structure as described above, the fine dust blocking filter manufacturing apparatus 1 according to the present invention can be applied to the spinning liquid main tanks 11 and 12 of the top-down or bottom-up electrospinning apparatus 10 and the bottom- 31 are continuously supplied in a fixed quantity in a plurality of nozzles 15, 35 to which a high voltage is applied through the metering pump, and the polymer spinning solution supplied to the nozzles 15, 35 is supplied to the nozzles 15, And then the nanofibers are formed by embossing or needle-punching the formed nanofibers into a nonwoven fabric.

On the other hand, the nozzle blocks 13 and 33 in which the nozzles 15 and 35 are disposed in the respective electrospinning devices are provided with a temperature control device 60 in each tube 112. That is, in order to adjust the temperature of the polymer solution in the tubular body of the nozzle block 13, 33 provided in each of the electrospinning devices 10, 30 and supplied with the polymer solution by the plurality of nozzles 15, A temperature control device is provided. Here, the flow of the polymer spinning solution in the nozzle blocks 13 and 33 is supplied from the spinning liquid main tanks 11 and 31 in which the polymer spinning solution is stored to each tube through a spinning solution flow pipe (not shown). The polymer spinning solution supplied to each tube is radiated and discharged through a plurality of nozzles 15 and 35, and is accumulated on the support 3 in the form of a nanofiber web. At this time, the plurality of nozzles (15, 35), which are spaced apart from each other at a predetermined interval in the longitudinal direction, are mounted on the tubular body in a state of being electrically connected and electrically connected. Here, the temperature controller 60 is provided in the shape of a heat ray 113 on the inner circumference of the tube to control the temperature control of the polymer solution for supplying and flowing into the tubes. 3 to 5, a temperature regulating device 60 composed of a hot wire is formed on the periphery of the inside of the tubular body of the nozzle blocks 13 and 33 in a spiral manner on the inner circumference of the tubular body of the nozzle blocks 13 and 33 Thereby controlling the temperature of the polymer spinning solution supplied and introduced into the tubular body. In the present invention, it is common to spin at room temperature, but it is also possible to spin at a high temperature, preferably 50 to 200 ° C.

In an embodiment of the present invention, a temperature regulating device 60 consisting of a hot line is spirally arranged on the inner circumference of the tubular body of the nozzle block 13, 33. However, the temperature regulating device 60 is formed in a hot line shape, The temperature regulating device 60 may be formed in a substantially C-shaped plate-like shape. The temperature regulating device 60 may be formed in a substantially C-shaped plate shape, To control the temperature of the polymer spinning solution. The temperature control device 60 can control the temperature of the polymer solution in the nozzle block, and it is possible to electrospray the polymer solution in the temperature range of 50 to 200 ° C. The basis weight of the nanofiber web is 0.001 to 2.0 g / m < 2 >. At this time, the basis weight of the nanofiber web is preferably 0.001 to 0.2 g / m < 2 >. If the basis weight is less than 0.001 g / m < 2 >, mechanical properties are deteriorated. If 2.0 g / m < 2 >

On the other hand, the down-type electrospinning device 10 is disposed at the front end of the fine dust-blocking filter manufacturing apparatus 1, the bottom-up electrospinning device 30 is disposed at the rear end, A feed roller 5 for feeding a support 3 on which a fiber web is laminated and a feed roller 5 for feeding a support 3 on which nanofibers are laminated are provided at the rearmost end of the fine dust- Up roller 9 is provided.

 In the present invention, the bottom-up electrospinning apparatus 10 is located at the front end, and thereafter, the bottom-up electrospinning apparatus 30 is located at the rear end, but it is also possible that the bottoms electrospinning apparatus comes to the front end. In addition, although the electrospinning apparatus is composed of two in the present invention, it is also possible that three or more top-down and bottom-up electrospinning apparatuses are arranged alternately.

It is preferable that the support 3 on which the polymer spinning solution of the top-down or bottom-up electrospinning apparatus 10 and the bottom-up or bottom-down electrospinning apparatus 30 are laminated is made of a nonwoven fabric or a fabric. However, in the present invention, It is preferable to use a carrier.

The mesh which can be used as the support is preferably one selected from the group consisting of a polyester mesh, a bicomponent substrate, a fiberglass mesh or a nylon mesh. The basis weight is preferably 30 to 150 g / m < 2 >. If the basis weight is less than 30 g / m < 2 >, the physical properties of the base material of the nanoscreen filter medium deteriorate. If the basis weight exceeds 150 g / m & There was a problem of falling. These meshes are composed of monofilaments. Also, as a generally preferred mesh used, 100% of polyester mono and generally 20 to 35 mesh are preferably used.

The carrier is generally used as a substrate and is preferably one selected from the group consisting of a polyester carrier, a polyurethane carrier, and a nylon carrier. , Monofilaments or multifilaments, and it is also possible to use a low melting point nonwoven fabric. In the present invention, the basis weight of the carrier is preferably 10 to 50 g / m < 2 >. If the basis weight is less than 10 g / m < 2 >, the physical properties of the base material are poor. When the basis weight exceeds 50 g / m < 2 >, the stiffness is high, . The carrier preferably used in the present invention is a 100% polyester woven fabric (WOVEN FABRIC).

On the other hand, the mesh and carrier can be flame retarded with a flame retardant agent. In an environment requiring high temperature, it is also possible to directly use the flame retarded mesh or carrier by treating the mesh and carrier with a phosphorus flame retardant agent. In detail, in the present invention, a flame-retardant coating agent is applied to each mesh. The flame-retardant coating agent is prepared by adding 5-50 wt% of an inorganic flame retardant, 5-20 wt% of a cationic urethane, 1-70 wt% of water, Are mixed with each other and then mixed for 5-10 minutes so that the mixture becomes uniform. A process such as polyethylene (PE) or polypropylene (PP) is supplied in the state where the flame-retardant coating agent is produced, the container is filled with the coating agent mixture, The packed container is packed. Therefore, the flame retardant coating agent is more effective than the conventional flame retardant agent in protecting the product effectively and continuously from the fire, thereby enhancing the flame resistance and physically and chemically improving the flammable product so that the product is burned by the flame, To minimize it.

Therefore, the flame retardant coating agent is excellent in flame retardant performance by promoting carbonization and formation of a protective film by using a polyol containing phosphorus (P) or a halogen component, and the flame retardant coating agent is a water-soluble emulsion type environmentally friendly and non- Therefore, it is possible to manufacture a flame retardant coating agent suitable for application to a fine screening net or a mesh or a carrier woven with a monofilament yarn with an excellent flame retardant durability superior to that of the conventional flame retardant agent.

The top-down or bottom-down electrospinning apparatus 10 and the bottom-up or top-down electrospinning apparatus 30 of the present invention are arranged symmetrically with respect to the collectors 17 and 37 in the upward and downward directions, respectively. That is, in the top-down or bottom-up electrospinning apparatus 10, the collector 17 is located at the top of the nozzle 15, and the bottom-up or top-down electrospinning apparatus 30 is arranged such that the collector 37 is located at the bottom of the nozzle 35 Located.

On both sides of the collectors 17 and 37, conveying rollers 7 are provided and the nano-fibers are stacked on the respective collectors 17 and 37 via the conveying rollers 7, (3) is transported in the horizontal direction. That is, nanofibers prepared by laminating the polymer spinning solution injected from the nozzles 15 of the top-down or bottom-up electrospinning device 10 on the support 3 of the collector 17 can be used as a bottom- 30 on the collector 37 and conveying rollers 7 for repeatedly and continuously advancing the above-described process are provided at both ends of the respective collectors 17, 37, respectively.

In the meantime, the present invention is characterized in that a rotary device 20 is provided between a top-down or bottom-up electrospinning device 10 and a bottom-up or top-down electrospinning device 30. The rotating device 20 is disposed between the electrospinning devices and rotates the supporting body 3 by 180 degrees so that the upper surface of the support body is rotated to the lower surface and the lower surface is rotated to the upper surface to be.

5 and 6 are cross-sectional views schematically showing a flip device 20-1 used as an embodiment of a rotating device. 5 is a cross-sectional view showing an initial operation of the flip device 20-1, and FIG. 6 is a cross-sectional view showing a process of the flip device 20-1 in the latter stage of operation.

The flip device 20-1 used as an embodiment of the rotating device is formed as a cylindrical body having a hollow inside and is provided at its central portion with both ends of the support 3 inserted in the horizontal both- Left and right guide members 21 and 21 having guide grooves are formed so as to protrude inwardly. The left guide member 21 of the left and right guide members 21 and 21 formed to protrude inwardly from the inner periphery of the flip device 20-1 is formed to extend upward along the inner periphery, So that the right guide member 21 is extended in the downward direction along the inner periphery and then spirally rotated so as to extend upward in the upward direction And is located at the initial position and direction of the left guide member 21. [

The one end and the other end of the support inserted into the guide grooves 22 and 22 of the left and right guide members protruding inwardly from the inner periphery of the flip device 20-1 by the above- The upper and lower surfaces of the support body 3 are reversed by rotating the inner periphery of the flip device 20-1 in a spiral manner so as to face each other while being guided by the right guide members 21 and 21.

In the present invention, the flip device 20-1 is used as the rotating device 20 for rotating the electrospun nanofibers 180 degrees between the electrospinning devices. However, the present invention is not limited to this, and a device having a twist roller It is also possible to use an apparatus that rotates by 90 degrees in the advancing direction of the support by the torsion roller.

The polymeric spinning solution filled in the spinning liquid main tank 11 of the top-down or bottom-up electric device 10 is injected through the nozzle 15 onto the support 3 of the collector 17 or onto the base material The support (3) or the substrate on which nanofiber webs are laminated to form nanofiber filter media after lamination of nanofiber webs are stacked on the support (3) of the collector (17) The lower surface of the support 3 on which the nanofibers are laminated by the top-down or top-down electrospinning is rotated 180 degrees by the rotation device 20 to the upper surface. And then transferred onto the collector 37 of the bottom-up or top-down electrospinning device 30 via the transport roller 7 and the support 3, on which the nanofibers transferred onto the collector 37 are laminated, The polymer spinning solution filled in the spinning liquid main tank 31 of the top-down electrospinning device 30 is electrospun through the nozzle 35, and the above-mentioned process is continuously and repeatedly performed to produce the final product.

The nano-fiber manufacturing apparatus 1 according to the present invention has the structure as described above. The nano-fiber manufacturing apparatus 1 includes a top-down or bottom-up electrospinning apparatus 10, a rotating apparatus 20, and a nano- The fibrous web is injected into the support 3 through the nozzles 15 and 35 of the top-down or bottom-up electrospinning apparatus 10 and the bottom-up or top-down electrospinning apparatus 30, The polymer spinning solution which is sprayed from the nozzles 15 and 35 of the top-down or bottom-up electrospinning apparatus 10 and the bottom-up or top-down electrospinning apparatus 30 such that the nanofibers are continuously laminated on one surface of the support 3 And the nanofibers are formed in multiple layers.

According to an embodiment of the present invention, the voltage of the top-down or bottom-up electrospinning apparatus is higher than the voltage of the bottom-up or top-down electrospinning apparatus so that the diameter of the nanofibers produced by the top- It is possible to fabricate the nanofibrous web with a diameter smaller than the diameter of the nanofiber web produced by the top-down electrospinning device 30.

In the meantime, it is possible to fill the spinning liquid main tanks 11 and 31 of the top-down or bottom-up electrospinning apparatus 10 and the bottom-up or top-down electrospinning apparatus 30 with the same type of polymer spinning solution, The nanofibers produced through the nanofiber manufacturing apparatus 1 can be variously manufactured according to the characteristics by filling the polymer spinning solution.

In the present invention, the polymer spinning solution injected from the top-down or bottom-up electrospinning device 10 and the polymer solution injected from the bottom-up or top-down electrospinning device 30 can be made of the same or different kinds of polymer spinning solution.

Here, the polymer spinning solution is not particularly limited, and examples thereof include polypropylene (PP), polyethylene terephthalate (PET), polyvinylidene fluoride, nylon, polyvinylacetate, polymethylmethacrylate, (PBA), polyvinyl butyral, polyvinyl chloride, polyethyleneimine, polyolefin, polylactic acid (PLA), polyacrylic acid, ), Polyvinyl acetate (PVAc), polyethylene naphthalate (PEN), polyamide (PA), polyvinyl alcohol (PVA), polyethylene imide (PEI), polycaprolactone (PCL) Silicate, cellulose, and chitosan. Among them, polypropylene (PP) materials and heat-resistant polymer materials such as polyamide, polyimide, polyamideimide, poly (meta- Aromatic polyesters such as polyethylene terephthalate, polyethylene terephthalate and the like, polytetrafluoroethylene, polydiphenoxaphospazene, polybis [poly (ethylene terephthalate), poly Polyphosphates such as polyphosphazenes such as 2- (2-methoxyethoxy) phosphazene, polyurethane copolymers including polyurethanes and polyetherurethanes, polymers such as cellulose acetate, cellulose acetate butyrate, cellulose acetate propionate and the like Are preferably used in a commercial manner.

Examples of the polymer that can be preferably used in the present invention include polyacrylonitrile (PAN), polyvinylidene fluoride (PVDF), polyethersulfone (PES), polyimide (PI) One or two selected from the group consisting of polyamic acid (PAA), nylon, polyurethane (PU), meta-aramid, inorganic polymer and polyetherimide (PEI) It is desirable to be species.

Hereinafter, preferred polymers will be described.

First, polyacrylonitrile (PAN) refers to a polymer of acrylonitrile (CH2 = CHCN), and polyacrylonitrile resin is a copolymer made from a mixture of acrylonitrile and a monomer, which constitutes the majority. Frequently used monomers include butadiene styrene vinylidene chloride or other vinyl compounds. The acrylic fiber contains at least 85% acrylonitrile, and the mode acrylic contains 35 to 85% acrylonitrile. When other monomers are included, the fiber has the property of increasing the affinity to the dye. More specifically, in the production of an acrylonitrile-based copolymer and spinning solution, in the case of producing an acrylonitrile-based copolymer, there is little contamination of nozzles in the course of manufacturing ultrafine fibers by electrospinning, Thereby increasing the solubility in the solvent and imparting better mechanical properties. In addition, polyacrylonitrile has a softening point of 300 ° C or more and is excellent in heat resistance.

The degree of polymerization of the polyacrylonitrile is preferably 1,000 to 1,000,000, and more preferably 2,000 to 1,000,000.

The polyacrylonitrile is preferably used within a range that satisfies the use amount of the acrylonitrile monomer, the hydrophobic monomer and the hydrophilic monomer. When the polymer is polymerized, the weight% of the acrylonitrile monomer is too low to be electrospun when the weight% of the hydrophilic monomer and the weight% of the hydrophobic monomer are 3: 4 and the total monomer is less than 60, It is difficult to form a stable jet (JET) at the time of electrospinning as well as to cause contamination of the nozzle. If the ratio is more than 99, the spinning viscosity is too high to spin, and even if an additive capable of lowering the viscosity is added, the diameter of the microfine fibers becomes too large and the productivity of electrospray is too low to achieve the object of the present invention.

In addition, as much amount of comonomer is added to the acrylic polymer, the amount of crosslinking agent must be increased to secure the stability of electrospinning and to prevent deterioration of the mechanical properties of the nanofiber.

The hydrophobic monomer may be an ethylene-based compound such as methacrylate, ethyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, vinyl acetate, vinyl pyrrolidone, vinylidene chloride or vinyl chloride, It is preferable to use at least one selected.

Wherein the hydrophilic monomer is selected from the group consisting of acrylic acid, allyl alcohol, methallyl alcohol, hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, butanediol monoacrylate, dimethylaminoethyl acrylate, butent ricarboxylic acid, vinyl It is preferable to use at least one selected from ethylene-based compounds such as sulfonic acid, allylsulfonic acid, methallylsulfonic acid, and para-styrenesulfonic acid and polyvalent acids or derivatives thereof.

As the initiator to be used for preparing the acrylonitrile-based polymer, an azo-based compound or a sulfate compound may be used, but it is generally preferable to use a radical initiator used for the oxidation-reduction reaction.

 On the other hand, polyvinylidene fluoride (PVDF) is one of the fluorine-based polymers, and the fluororesin contains fluorine, which is excellent in thermal and chemical properties.

(Preparation of polyvinylidene fluoride)

The polyvinylidene fluoride is prepared in the same manner as in the above Reaction Scheme 1, and the vinylidene chloride monomer is prepared by free radical vinyl polymerization to produce polyvinylidene fluoride.

In addition, polyvinylidene fluoride has lower melting point, lower density, lower cost, and more chemical stability than other fluorinated resins, and is used for electric insulators and high-grade paints applied to the exterior walls of buildings.

Polyvinylidene fluoride is a representative organic material exhibiting piezoelectricity, and many studies have been conducted since the 1960s. In the polyvinylidene fluoride polymer, four kinds of crystals are mixed, and it is divided into at least four types of α, β, γ and δ type depending on crystal form. Among them, the? -Form crystal of polyvinylidene fluoride has a trans-type molecular chain filled in parallel, and all the permanent dipoles of the monomers are aligned in one direction, and exhibit large spontaneous polarization. This means that the polyvinylidene fluoride molecules can be regularly arranged through stretching to give piezoelectricity by giving anisotropy to the aggregated state. In order to improve such piezoelectric characteristics, various methods for increasing the? -Form crystal in the polyvinylidene fluoride fiber have been studied. In general, melt spinning systems have been applied to produce polyvinylidene fluoride fibers. However, it is expensive to construct melt spinning equipment, and the size of fibers produced by melt spinning is limited.

Due to the coagulation mechanism of wet spinning, fibers prepared by wet spinning have a significantly higher β-form crystal ratio in the fiber at the initial stage of spinning than the α-form crystal ratio, and the spinning speed is slower than the melt spinning. However, It also has the advantage of reducing fiber size. In addition, wet spinning has the advantage of improving physical properties through continuous post-treatment processes (stretching, crimping, etc.).

For wet spinning, the polymer is dissolved in a solvent to make a spinning solution, and the spinning solution is discharged through a gear pump and spinning nozzle into a coagulation bath containing an aqueous solution containing a solvent. As the discharged spinning liquid phase and the co-diffusion with the solvent and the precipitating agent in the coagulating bath occur, the precipitating agent penetrates into the spinning liquid phase and phase separation and precipitation occur in the three-component system of the polymer-solvent-precipitating agent, Is obtained. Such a wet spinning system has the advantage of enhancing the mechanical properties of fibers by orienting the polymer in a fiber direction by stretching and tensioning in a spinning bath.

The polyvinylidene fluoride may be a homopolymer of vinylidene fluoride or a copolymerized polymer containing vinylidene fluoride in a molar ratio of 50% or more in preparing a spinning liquid in which the polyvinylidene fluoride is dissolved in an appropriate organic solvent It is more preferable that the homopolymer is excellent in strength of the polyvinylidene fluoride resin. When the polyvinylidene fluoride resin is a copolymer polymer, as the other copolymerizable monomer copolymerized with the vinylidene fluoride monomer, And a fluorine-based monomer, a chlorine-based monomer, and the like can be suitably used. The weight average molecular weight (Mw) of the polyvinylidene fluoride resin is not particularly limited, but is preferably 10,000 to 500,000, more preferably 50,000 to 500,000.

When the weight average molecular weight of the polyvinylidene fluoride resin is less than 10,000, sufficient physical properties for forming a nonwoven fabric can not be obtained. When the weight average molecular weight exceeds 500,000, the solution is not easily handled, It is difficult to obtain a nonwoven fabric.

 Polyethersulfone (PES) is an amber transparent, non-crystalline resin having the following repeating units, and is generally produced by condensation polymerization of dichlorodiphenylsulfone.

(A unit of polyethersulfone)

Polyethersulfone is a super heat resistant engineering plastic developed by ICI in the UK. It is a highly heat resistant polymer among thermoplastic plastics. Since the polyethersulfone is amorphous, the physical properties of the polyether sulfone are not lowered by temperature rise, and the temperature dependency of the flexural modulus is small, so that it hardly changes at -100 to 200 캜. The load-strain temperature is 200 to 220 占 폚, and the glass transition temperature is 225 占 폚. In addition, the creep resistance of up to 180 is the most excellent among the thermoplastic resins, and has the property of enduring resistance to hot water and steam of 150 to 160 ° C. Due to the above characteristics, polyethersulfone is used in optical disks, magnetic disks, electric and electronic fields, hydrothermal fields, automobile fields, and heat resistant paints.

The molecular weight of the polyethersulfone is preferably from 8,000 to 200,000, and more preferably from 10,000 to 100,000, in terms of the viscosity average molecular weight. Examples of the solvent include dichloromethane, chloroform, tetrahydrofuran, methanol, ethanol, butanol, toluene, xylene, acetone, ethyl acetate, dimethylformamide, N- But are not limited to these.

On the other hand, polyimide is a polymer containing an imide group in a repeating unit and has a characteristic that the physical properties do not change even in a temperature range from -273 DEG C to 400 DEG C, and has excellent mechanical strength and heat resistance. However, most of the polyimides are insoluble and have poor physical properties and are difficult to process by conventional techniques, so it is common to process them in the form of its precursor poly (amic acid) (PAA). Therefore, the polyimide is prepared by first polymerizing a polyamic acid and then carrying out an imidation process.

Generally, polyimides are prepared by a two step reaction.

The first step is a step of synthesizing polyamic acid. The polyamic acid is polymerized by adding a dianhydride to a reaction solution in which diamine is dissolved. In order to increase the degree of polymerization, the reaction temperature, the water content of the solvent, Purity control is required. Organic polar solvents such as dimethylacetamide (DMAc), dimethylformamide (DMF) and en-methyl-2-pyrrolidone (NMP) are mainly used as the solvent used in this step. Examples of the diamine include 4,4'-oxydianiline (ODA), para-phenylene diamine (p-PDA), and o-phenylene diamine diamine, o-PDA) may be used. Examples of the anhydride include pyromellitic dianhydride (PMDA), benzophenonetetracarboxylic dianhydride (BTDA), 4-4'-oxydiphthalic anhydride (4-4 ' bisdiphthalic anhydride (ODPA), biphenyl-tetracarboxylic acid dianhydride (BPDA), and bis (3,4'-dicarboxyphenyl) dimethylsilanedianhydride. dimethylsilane dianhydride, SIDA).

(Preparation of polyamic acid)

The weight average molecular weight (Mw) of the polyamic acid prepared by the above method is preferably 10,000 to 500,000. If the molecular weight of the polyamic acid is less than 10,000, sufficient physical properties for forming the nanofiber nonwoven fabric can not be obtained. If the molecular weight exceeds 500,000, the handling of the solution is not easy and the processability is degraded.

The second step is the dehydration and ring-closing reaction step of producing the polyimide from polyamic acid as the following four methods.

In the re-impregnation method, a polyamic acid solution is added to an excess amount of a poor solvent to obtain a solid polyamic acid. As the re-precipitation solvent, water is mainly used, but toluene or ether is used as a co-solvent.

The chemical imidization method is a method in which a imidization reaction is chemically performed using a dehydration catalyst such as acetic anhydride / pyridine, and is useful for producing a polyimide film.

The thermal imidization method is a method in which the polyamic acid solution is heated to 150 to 350 ° C to thermally imidize it. In the simplest process and the crystallization degree is high, the amine exchange reaction occurs when the amine type solvent is used. have.

Finally, the isocyanate method uses a diisocyanate instead of a diamine as a monomer. When the monomer mixture is heated to a temperature of 120 ° C or higher, a polyimide is produced while CO 2 gas is generated.

(Production of polyimide)

The following describes nylon.

Generally, a polyamide refers to a generic term of a polymer linked by an amide bond (-CONH-), which can be obtained by condensation polymerization of a diamine and a dicarboxylic acid. Polyamides are characterized by amide bonds in the molecular structure, and their physical properties vary depending on the ratio of amide groups. For example, when the ratio of amide groups in the molecule is increased, specific gravity, melting point, absorbency, rigidity and the like are increased.

In addition, polyamide is a material used in a wide range of fields such as clothing, tire cord, carpet, rope, computer ribbon, parachute, plastic and adhesive due to its excellent resistance to corrosion, abrasion resistance, chemical resistance and insulation.

Generally, polyamides are classified into aromatic polyamides and aliphatic polyamides. Representative aliphatic polyamides include nylon. Nylon is originally a trademark of DuPont, Inc., but is now used as a generic name.

Nylon is a hygroscopic polymer and is sensitive to temperature. Representative nylons include nylon 6, nylon 66, and nylon 46.

First, nylon 6 is characterized by excellent heat resistance, moldability and chemical resistance, and is produced by ring-opening polymerization of ε-caprolactam in order to produce it. Nylon 6 means that caprolactam has 6 carbon atoms.

(Nylon 6 polymerization of caprolactam)

On the other hand, nylon 66 is generally similar in properties to nylon 6, but is superior in heat resistance to nylon 6 and superior in self-extinguishing and abrasion resistance. Nylon 66 is prepared by dehydration condensation polymerization of hexamethylenediamine and adipic acid.

(Nylon 66 polymerization by dehydration condensation polymerization reaction of hexamethylenediamine and adipic acid)

Nylon 46 is also excellent in heat resistance, mechanical properties and impact resistance, and has a high processing temperature. Nylon 46 is prepared by polycondensation of tetramethylenediamine and adipic acid. Diaminobutane (DAB), a raw material, is prepared from the reaction of acrylonitrile with hydrogen cyanide. In the first stage of the polymerization operation, a salt is formed from diaminobutane and adipic acid, and the mixture is polymerized under appropriate pressure The prepolymer is converted into a prepolymer and the solid of the prepolymer is polymerized at a solid state by treatment at about 250 ° C in the presence of nitrogen and water vapor.

In particular, nylon 46 exhibits excellent properties with a high amide concentration and a regular arrangement between the methylene and amide groups. The melting point of nylon 46 is about 295 ° C, which is higher than that of other types of nylon, and has attracted attention as a resin having excellent heat resistance due to the above characteristics.

On the other hand, polyurethane is not a thermosetting resin but a plastic having a similar three-dimensional structure. It has good quality and good resistance to chemicals. It is used for electric insulators, structural materials, bubble insulation, bubble cushion, elastic fiber, etc. It is also used as a substitute material of rubber because of its good elasticity. The isocyanate group (-N = C = O) readily bonds with the hydroxyl group (-OH) (urethane bond). When a molecule having two hydroxyl groups is reacted with diisocyanate using this reaction, a linear polymer is obtained. This polymer is polyurethane. Generally, toluene diisocyanate is used as the diisocyanate, and polyether or polyester is used as the molecule having the hydroxyl group (polyol). Using a polyether makes it smoother, and using polyester makes it harder. The polyurethane made by using a molecule having three or more hydroxyl groups as a polyol is three-dimensionally bonded.

The polyurethane having such a structure has a characteristic that it does not deform against heat.

(Polyurethane synthesis)

The meta-aramid is the first high heat resistant aramid fiber that can be used at 350 ° C for a short time and 210 ° C for continuous use. When exposed to temperatures above this temperature, it is carbonized without melting or burning like other fibers . Above all, unlike other products that are flame retarded or refractory treated, they do not emit toxic gases or harmful substances even when carbonized, and thus they have excellent properties as eco-friendly fibers.

In addition, the meta-aramid has a very strong molecular structure of the fiber itself, so it has strong inherent strength as well as easy orientation of molecules in the fiber axis direction in the spinning stage to increase the strength of the fiber .

The specific gravity of the meta-aramid is 1.3 to 1.4, and the weight average molecular weight is preferably 300,000 to 1,000,000. The most preferred weight average molecular weight is 3,000 to 500,000. And a meta-oriented synthetic aromatic polyamide. The polymer should have a fiber-forming molecular weight, and may comprise a polyamide homopolymer, a copolymer and mixtures thereof, which are predominantly aromatic, wherein at least 85% of the amide (-CONH-) bonds are attached directly to the two aromatic rings . The ring may be unsubstituted or substituted. The polymer becomes a meta-aramid when the two rings or radicals are meta-oriented along the molecular chain with respect to each other. Preferably, the copolymer contains up to 10% other diamines substituted for the primary diamine used to form the polymer, or up to 10% other diacids substituted for the primary diacid chloride used to form the polymer It has a diacid chloride. Preferred meta-aramids are poly (meta-phenylene isophthalamide) (MPD-I) and copolymers thereof. One such meta-aramid fiber is < RTI ID = 0.0 > a < / RTI > children. Aramid fibers available from EI du Pont de Nemours and Company, but the meta-aramid fibers are available from Teijin Ltd., Tokyo, Japan. ≪ RTI ID = 0.0 > Possible trade names Tejinconex (R); New Star (TM) meta-aramid available from Yantai Spandex Co. Ltd, Shandong, China; And Chinfunex (registered trademark) Aramid 1313, available from Guangdong Charming Chemical Co., Ltd., Shinduo, Guangdong, China.

The inorganic polymer may be a single polymer containing a silane group or a siloxane group, or may be a silane group or a siloxane group and monomethacrylate, vinyl, hydride, distearate, bis (12 -Hydroxy-stearate), methoxy, ethoxylate, propoxylate, diglycidyl ether, monoglycidyl ether, monohydroxy, bis (hydroxyalkyl) ) And bis ((aminoethyl-aminopropyl) dimethoxysilyl) ether can be used.

On the other hand, the inorganic polymer of the spinning solution used in the present invention will be described.

The inorganic polymer refers to a polymer containing an inorganic element in a polymer main chain or a side chain. Herein, the inorganic element is narrowly defined as an internal transition such as a metal such as aluminum or magnesium that fills s and p orbitals, a transition metal such as titanium, zirconium, or tungsten that fills the d orbit, or a lanthanide- Metal), but broadly includes elements constituting the skeleton of elements such as Si, Ge, P, and B which are non-metallic inorganic elements.

The inorganic polymers are divided into the following four types.

First, when the inorganic component is contained in the side chain of the organic polymer, the organic polymer is maintained substantially in the nature and the inorganic component contained in the side chain is also represented. Second, the inorganic element is bonded to the skeleton of the polymer main chain with carbon Thirdly, in the case of an organic-inorganic hybrid polymer designed to serve as a precursor for the production of ceramics, fourthly, in the case of an ionic compound having a net-like structure or a lattice structure composed purely of inorganic components.

Interest in inorganic polymers began to emerge from the commercialization of silicon carbide (SiC) fibers (trade name: NICALON) synthesized by Polycarbosilane (PCS) by Yajima of Nippon Carbon in the mid 1980's It became an occasion. Until now, it is not so much utilized, but it is expected to be applied in the field of heat resistance in general industries as well as aerospace and nuclear fields in the future. Polymer impregnation and pyrolysis (PIP) is a method of applying an inorganic polymer to a composite. This is a method in which an organic compound such as PCS is mixed with a silicon carbide powder to prepare a slurry, Is impregnated into a fiber preform and pyrolyzed to obtain a silicon carbide base. Recently, attention has been paid to the development of a fiber having excellent heat resistance. Thus, by developing a new organic compound having excellent characteristics and improving the PIP method, a pyrolysis temperature can be increased to produce a silicon carbide base matrix having excellent crystallinity and stoichiometric ratio.

Polyetherimide (PEI) is also a transparent amber amorphous thermoplastic resin having the following chemical structure. It is a resin with an imide bond showing excellent heat resistance and mechanical properties and an ether bond with good processability. It has excellent heat resistance, mechanical properties, flame retardancy, and electrical properties, and is used in electrical and electronic parts, automobile parts, and machine parts.

(Polyetherimide)

It is characterized by excellent heat resistance. The load-distortion temperature is 200 ° C or more, and the long-term service temperature of UL is 170 ° C or more. It also shows excellent hydrolysis resistance (tensile strength retention after immersion in hot water for 10,000 hours is high). The dielectric constant and dielectric tangent are wide and stable in temperature range and frequency band. In addition, not only the dielectric breakdown voltage is high but also excellent flame retardancy is exhibited. An oxygen index of 47 or higher, UL94-V0 (thickness: 0.41 mm) / 5 VA (thickness 1.9 mm). The combustion amount (NBS test) at the time of combustion is extremely low, which is among the lowest among engineering plastics, and is excellent in resistance to ultraviolet rays and radiation.

On the other hand, the polymer spinning solution containing a polymer as described above is a solution prepared by dissolving a polymer, which is a synthetic resin material capable of electrospinning, in a suitable solvent, and the type of the solvent is not limited as long as it can dissolve the polymer. For example, methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, isopropyl, n-butyl, isobutyl, sec-butyl, Isobutyl alcohol, isopropyl alcohol, methyl alcohol, ethanol, aliphatic compounds such as hexane, tetrachlorethylene, acetone, and glycol groups such as propylene glycol, diethylene glycol, isobutyl ketone, methyl ethyl ketone, aliphatic hydroxyl group, m- Ethylene glycol, and halogen compounds such as trichlorethylene, dichloromethane, aromatic compounds toluene, xylene, alicyclic compounds such as cyclohexanone, cyclohexane and esters such as n-butyl acetate, ethyl acetate, aliphatic ether Butyl cellosolve, acetic acid 2-ethoxy ethanol, 2-ethoxy ethanol, amide dimethyl formamide, dimethylacetamide, etc. And, it is possible to use a mixture of a plurality kinds of solvents. The polymer spinning solution preferably contains, but is not limited to, an additive such as a conductivity improver.

In the present invention, the polymer spinning solution filled in the spinning solution main tank 11 of the top-down or bottom-up electrospinning device 10 and the spinning solution main tank 31 of the bottom-up or down spinning electrospinning device 30 The polymeric spinning solution can be of the same or different kinds.

Basis Weight or Grammage, on the other hand, is defined as the mass per unit area, that is, the preferred unit, grams per square meter (g / m 2). The basis weight of the nanofiber web prepared on the mesh used as the support according to the present invention is preferably 0.001 to 0.2 g / m < 2 >. If the basis weight is less than 0.001 g / m < 2 >, mechanical properties are deteriorated. If 2.0 g / m < 2 >

Thereafter, a laminate of a base material and a nano-fiber web manufactured through the top-down or bottom-up electrospinning apparatus 10 and the bottom-up or top-down electrospinning apparatus 30 constituting the apparatus for manufacturing nanofibers according to an embodiment of the present invention is laminated The laminating apparatus 50 is further provided at the rear end of the apparatus 1 for manufacturing nanofibers according to the present invention and performs a post-process.

The top-down or bottom-up electrospinning apparatus 10 and the bottom-up or bottom-down electrospinning apparatus 30 constituting the nanofiber manufacturing apparatus 1 may be arranged in parallel to one another in the horizontal direction, And the respective electrospinning devices are arranged in the U direction in the same layer. The fact that they can be arranged in the vertical direction for each layer or in the U direction in the same layer has the advantage that the productivity can be increased in a limited area.

Each of the nozzle blocks 13 and 33 of the present invention includes a tubular body 112a, 112b, 112c, 112d, 112e, 112f, 112g, 112h and 112i having a plurality of nozzles 15, 112b, 112c, 112d, 112e, 112f, 112g, 112h, 112i are connected to the spinning liquid main tanks 11, 31 And the polymer spinning solution filled in the spinning solution main tanks 11 and 31 is supplied.

Here, the tubes 112a, 112b, 112c, 112d, 112e, 112f, 112g, 112h, 112i are connected to the spinning liquid main tanks 11, 31 by a supply pipe (not shown) Is branched into a plurality of tubes to connect the tubular bodies 112a, 112b, 112c, 112d, 112e, 112f, 112g, 112h, 112i and the spinning liquid main tanks 11,

At this time, a supply pipe adjusting means (not shown) is provided in the supply piping which is communicated to the tubes 112a, 112b, 112c, 112d, 112e, 112f, 112g, 112h, 112i in the spinning liquid main tanks 11, Wherein the supply amount adjusting means is constituted by a valve.

In this way, valves are respectively provided in the supply liquid piping leading to the tubular bodies 112a, 112b, 112c, 112d, 112e, 112f, 112g, 112h, 112i in the spinning liquid main tanks 11, 31, By the on-off system in which supply of the polymer solution to be supplied to the tubes 112a, 112b, 112c, 112d, 112e, 112f, 112g, 112h, 112i in the spinning liquid main tanks 11, Respectively.

That is, when the polymer solution is supplied from the spinning solution main tanks 11 and 31 to the tubes 112a, 112b, 112c, 112d, 112e, 112f, 112g, 112h and 112i through the supply pipe, The nozzle blocks 13 and 33 are opened and closed by the valves provided in the supply pipes for supplying the tubes 11 and 31 and the tubes 112a, 112b, 112c, 112d, 112e, 112f, 112g, 112h and 112i. 112b, 112d, 112f, 112g, 112h, and 112i of the tubular bodies 112a, 112b, 112c, 112d, 112e, 112f, 112g, 112h, 112b, 112c, 112d, 112e, 112f, 112g, 112h, 112i in the spinning liquid main tanks 11, 13 by opening and closing of the valves 212, 213, 214, The supply of the polymer spinning solution to be supplied is controlled and controlled.

By using the structure as described above, the waste liquid main tanks 11 and 31 and the tubes 112a, 112b, 112c, 112d, 112e, 112f, 112g, 112h and 112i are provided, Valves are provided for supplying the polymer solution to the tubes 112a, 112b, 112c, 112d, 112e, 112f, 112g, 112h, 112i in the spinning liquid main tanks 11, 112d, 112f, 112g, 112h, 112i, 112f, 112g, 112h, 112i of the tubes 112a, 112b, 112c, 112d, 112e, 112f, 112g, 112h, 112i arranged in the nozzle blocks 13, The supply of the polymer spinning solution is only supplied to the tubes 112a, 112c and 112e at specific positions in the tubular body arranged in the nozzle blocks 13 and 33 by closing the specific valve, 112b, 112c, 112d, 112e, 112f, 112g, 112h, 112i from the spinning liquid main tanks 11, Is regulated and controlled.

That is, each of the nozzles 15 and 35 provided in the supply pipe and the pipes 112a, 112b, 112c, 112d, 112e, 112f, 112g, 112h and 112i is spoken, As shown in FIG.

The radiation amount regulating means is constituted by a valve. In this way, the supply of the polymer spinning solution supplied to the nozzles 15 and 35 from the supply pipe by the opening and closing of the valve is individually controlled by the valve being provided as the radiation amount adjusting means, Preferably, the opening and closing of the valve is automatically controlled by the control unit, but it is also possible that the opening and closing of the valve are manually controlled according to the situation of the field and the operator's request.

In the present invention, if the amount of the spinning solution of the polymer spinning solution is easily controlled and controlled after the spinning amount control means is provided as a valve but is supplied to the nozzles 15 and 35 in the supply pipe, But is not limited thereto.

In the present invention, a valve is provided in the supply piping so that the tubes 112, 112b, 112c, 112d, 112e, 112f, 112g, 112h, 112i of the nozzle blocks 13, 33 in the spinning liquid main tanks 11, And a valve is provided in the supply pipe to supply a supply amount of the polymer solution for the respective nozzles supplied from the tubes 112a, 112b, 112c, 112d, 112e, 112f, 112g, 112h, 112i, 112b, 112c, 112d, 112e, 112f, 112g, 112h, 112i of the tubular body 112a, 112b, 112c, 112d, 112h, 112i by controlling and controlling the radiation amount of the polymer solution, A nano-fiber web having different polymer types or basis weights is laminated in the width direction or the longitudinal direction of the support 3 by an electrospinning polymer spinning solution.

The concentration of the polymer spinning solution is generally preferably from 5 to 30% by weight.

The nanofiber web produced according to the present invention is characterized in that it has a different basis weight in the width direction, that is, in the CD direction or in the transverse direction, or is electrospun and laminated in the longitudinal direction, that is, in the MD direction. The CD direction is the cross direction, which means the direction perpendicular to the MD direction (Machine Direction). The MD direction is the longitudinal direction / longitudinal direction, and the CD direction is the width direction / transverse direction.

Basis Weight or Grammage, on the other hand, is defined as the mass per unit area, that is, the preferred unit, grams per square meter (g / m 2).

7 is a plan view showing a state in which the nozzles 15 and 35 in the electrospinning apparatus according to the present invention are turned on and off in the CD direction and Fig. 8 is a cross- As described above, the operation of the nozzle in the electrospinning device is electrically turned on and off so that the nanofiber web having a different type or basis weight of the polymer spinning solution in the CD direction . 9 is a plan view showing a state in which the nozzles in each electrospinning apparatus of the present invention are turned on and off in the MD direction. As described above, the operation of the nozzles in the electrospinning apparatus is electrically turned on and off, It is possible to form a nanofiber web different in kind or basis weight.

Generally, the diameters of the nanofibers produced are different from polymer to polymer, but on the average, they range from 50 to 500 nm.

Meanwhile, the nanofiber web produced through the top-down or bottom-up electrospinning apparatus 10 and the bottom-up or top-down electrospinning apparatus 30 constituting the apparatus for manufacturing a fine dust-blocking filter according to the present invention and the support 3 are laminated The laminating device 50 is located at the rear end of the device 1 for producing a fine dust-blocking filter according to the present invention, and performs a post-process.

The top-down or bottom-up electrospinning apparatus 10 and the bottom-up or bottom-down electrospinning apparatus 30 constituting the fine dust-blocking filter manufacturing apparatus 1 may be arranged in parallel to one another in the horizontal direction, And the electrospinning devices are arranged in the U direction in the same layer. The fact that they can be arranged in the vertical direction for each layer or in the U direction in the same layer has the advantage that the productivity can be increased in a limited area.

That is, the rotary device is characterized in that the support rotates 180 degrees or vertically rotates in the U-turn direction by the flip device.

Meanwhile, in one embodiment of the present invention, the laminating device 50 is provided at the rear end of the fine dust-blocking filter manufacturing apparatus 1 and is manufactured through the bottom-up electrospinning device 10 and the top-down electrospinning device 30, (Not shown) for supplying a base material (not shown) is provided on the lower side of the laminating device 50, and the supply roller (not shown) is provided through the supply roller And the nano-fiber web is directly electrolized on the support or substrate to laminate and laminate the multilayered laminate through the laminating device 50.

The laminating device 50 is provided with a supply roller for supplying another substrate (not shown) on the upper side of the laminating device 50 to laminate the base material on the support 3 on which the nano- Layer laminate.

The filter for blocking fine dust as described above has a DOP filtration efficiency of 80% or more for particles having a light transmittance of 30 to 80%, an air permeability of 10 to 500 and a size of 2.5 μm, and excellent visibility, air permeability and filtration efficiency Therefore, when the filter for blocking fine dust of the present invention is installed in a window of a home or an office, it is effective to effectively block the inflow of polluted air from outside into the room while securing visibility. When the light transmittance is 30% and the air permeability is less than 10, visibility and air permeability are not good, which is not suitable for use in ventilated windows.

Hereinafter, a method for manufacturing a filter for blocking fine dust according to the present invention will be described.

First, the support 3 is supplied to the top-down type or bottom-up type electrospinning device 10 through the feed roller 5 provided at the tip of the fine dust blocking filter manufacturing apparatus 1 according to the present invention. At this time, the support 3 is preferably made of a nonwoven fabric or a fabric, but is not limited thereto. In the present invention, a mesh or a carrier is used as the support 3. The mesh is preferably one selected from the group consisting of a polyester mesh, a bicomponent substrate, a fiberglass mesh or a nylon mesh, If the basis weight is less than 30 g / m < 2 >, the mechanical properties are deteriorated. If the basis weight exceeds 150 g / m < 2 >, the stiffness is high. These meshes are composed of monofilaments, and it is generally preferable to use 20 to 35 mesh.

The carrier is generally used as a substrate and is preferably one selected from the group consisting of a polyester carrier, a polyurethane carrier and a nylon carrier, Monofilaments or multifilaments. It is also possible to use a low melting point nonwoven fabric. In the present invention, the basis weight of the carrier is preferably 10 to 50 g / m < 2 >. If the basis weight is less than 10 g / m < 2 >, the physical properties of the base material are poor. When the basis weight exceeds 50 g / m < 2 >, the stiffness is high, .

On the other hand, the support 3 fed to the bottom-up electrospinning apparatus 10 through the feed roller 5 is positioned on the lower surface of the collector 17. At this time, a high voltage of the voltage generator (not shown) is generated on the nozzle 15 and the collector 17, and the polymer spinning solution filled in the spinning liquid main tank 11 on the collector 17 flows into the nozzle block 13 via a nozzle 15.

Here, the spinning liquid to be filled in the spinning liquid main tank 11 is continuously supplied in a constant amount into a plurality of nozzles 15 to which a high voltage is applied through a metering pump (not shown) The spinning solution is radiated and focused on the collector 17 with a high voltage applied thereto through the nozzle 15 and the first nanofiber web is laminated on the lower surface of the support 3.

In this case, the mesh or carrier and the nanofiber web preferably used as the support 3 are preferably bonded by a chemical or thermal adhesive according to an embodiment of the present invention, but they may be bonded through ultrasonic bonding .

According to an embodiment of the present invention, an adhesive may be applied and adhered also between the support and the nanofiber web. After the adhesive is electrospun on the support to form an adhesive layer, the polymer spinning solution is applied to the adhesive layer by electrospinning To form a nanofiber web.

As the adhesive, a commercially available adhesive can be used. However, a low melting point polymer solution can be used. As the low melting point polymer solution, a low melting point polyvinylidene fluoride, a low melting point polyurethane or a low melting point nylon Is preferably used. The low-melting-point polymer solution preferably has a weight average molecular weight of 5000 to 15000 and a melting point of 80 to 160 ° C. When the molecular weight is less than 5,000, there is a problem that the adhesive strength is lowered. When the molecular weight is more than 15,000, it is not easily melted by heat and thus it is difficult to serve as an adhesive. When the melting point is lower than 80 ° C, it is difficult to use because of poor handling property. When the melting point is higher than 160 ° C, it is not easily melted at the laminating temperature and it is difficult to serve as an adhesive.

On the other hand, examples of the adhesive include an epoxy resin, a curing agent solution, and the like.

At this time, the epoxy resin is an intermediate of a thermosetting resin and forms a three-dimensional network structure insoluble / infusible by reaction with a curing agent to exhibit physical properties inherent to epoxy, and the epoxy resin is adhered It has an advantage of being excellent in properties, mechanical strength, heat resistance, chemical resistance, water resistance, electric insulation property, moldability and impregnation property, easy production of a composite material, and realizing various properties according to the selection of a curing agent.

Nonlimiting examples of such epoxy resins include bisphenol A type epoxy resins, bisphenol F type epoxy resins, and bisphenol S type epoxy resins.

The above-mentioned bisphenol A type epoxy resin is represented by the following general formula (1), and the most commonly used epoxy resin is produced by a direct method or indirect method.

[Chemical Formula 1]

The bisphenol F type epoxy resin is represented by the following general formula (2) and is produced by the reaction of bisphenol F with ECH. The bisphenol F type epoxy resin has a lower viscosity than the bisphenol A type epoxy resin and theoretically has a somewhat lower mechanical and physical properties. And the like.

 (2)

The bisphenol S type epoxy resin is represented by the following general formula (3), and is generally used for rapidly curing an epoxy adhesive and used as a reactant in a polymer reaction.

(3)

 On the other hand, the curing agent is preferably one selected from the group consisting of an amine curing agent, an acid anhydride curing agent and an imidazole curing agent, but is not limited thereto.

Non-limiting examples of the amine-based curing agent include aliphatic polyamines, modified aliphatic polyamines, aromatic amines, tertiary amines, and secondary amines.

Examples of the aliphatic polyamines include diethylene triamine (DETA), triethylene tetramine (TETA), diethylamino propyl amine (DEAPA), Menthane diamine (MDA), N-aminoethyl piperazine Isophorone diamine (IPDA), but is not limited thereto.

Examples of the modified aliphatic polyamines include, but are not limited to, Epoxy Polyamine Adduct, Ethylene or Propylene Oxide, Polyamine Adduct, Cyanoethylated Polyamine, and Ketone-blocked Poylamine (Ketimine).

Examples of the aromatic amine include, but are not limited to, Meta phenylene diene (MPD), 4.4 'Dimethyl aniline (DAM or DDM), Diamino diphenyl sulfone (DDS), and Aromatic amine adduct.

Examples of the acid anhydride-based curing agent include polyamide (PA), tetrahydrophthalic anhydride (THPA), methyl tetrahydrophthalic anhydride (MTHPA), hexahydrophthalic anhydride (HHPA), and MNA.

Nonlimiting examples of the imidazole-based curing agent include 2MZ and 2E4MZ.

In addition, the curing agent solution may further include a curing accelerator.

The curing accelerator used in the present invention is not particularly limited as long as it is a curing accelerator generally used for accelerating the curing of the epoxy compound. Examples thereof include tertiary amines, tertiary amine salts, imidazoles, Quaternary ammonium salts, quaternary phosphonium salts, organic metal salts, and boron compounds. The curing accelerator may be used alone or in combination of two or more.

Examples of tertiary amines include lauryldimethylamino, N, N-dimethylcyclohexylamine, N, N-dimethylbenzylamine, N, N-dimethylaniline, (N, N- dimethylaminomethyl) , 4,6-tris (N, N-dimethylaminomethyl) phenol, 1,8-diazabicyclo [5.4.0] undecene-7 (DBU), 1,5-diazabicyclo [4.3.0] -5 (DBN).

Examples of the tertiary amine salt include a carboxylate, a sulfonate, and an inorganic acid salt of the above-mentioned tertiary amine. Examples of the carboxylate include salts of carboxylic acids having 1 to 30 carbon atoms (especially 1 to 10 carbon atoms) such as octylate (particularly fatty acid salts). Examples of the sulfonate include p-toluenesulfonate, benzenesulfonate, methanesulfonate and ethanesulfonate. Representative examples of tertiary amine salts include salts of 1,8-diazabicyclo [5.4.0] undecene-7 (DBU) (for example, p-toluenesulfonic acid salt and octylic acid salt).

Examples of the metal-based curing accelerator include organic metal complexes or organic metal salts of metals such as cobalt, copper, zinc, iron, nickel, manganese and tin. Specific examples of the organometallic complexes include organic cobalt complexes such as cobalt (II) acetylacetonate and cobalt (III) acetylacetonate, organic copper complexes such as copper (II) acetylacetonate, zinc (II) acetylacetonate Organic iron complexes such as iron (III) acetylacetonate, organic nickel complexes such as nickel (II) acetylacetonate, and organic manganese complexes such as manganese (II) acetylacetonate. Examples of the organic metal salt include zinc octylate, tin octylate, zinc naphthenate, cobalt naphthenate, stannous stearate and zinc stearate. As the metal curing accelerator, cobalt (II) acetylacetonate, cobalt (III) acetylacetonate, zinc (II) acetylacetonate, zinc naphthenate and iron (III) acetylacetonate are preferable from the viewpoints of curability and solvent solubility Cobalt (II) acetylacetonate, and zinc naphthenate are particularly preferred. The metal-based curing accelerator may be used singly or in combination of two or more.

 The addition amount of the metal-based curing accelerator is preferably in the range of from 25 to 500 ppm, more preferably from 40 to 200 ppm, of the metal based on the metal-based curing accelerator when the non-volatile content in the resin composition is 100 mass% Do. If it is less than 25 ppm, it tends to make it difficult to form a conductor layer having a low roughness with good adhesion to the surface of the insulating layer. When it exceeds 500 ppm, the storage stability and insulating property of the resin composition tend to be lowered.

Examples of the quaternary ammonium salt include tetraethylammonium bromide and tetrabutylammonium bromide.

 As the quaternary phosphonium salt, for example, the following formula (1)

(Wherein R1, R2, R3 and R4 are the same or different and each represents a hydrocarbon group of 1 to 16 carbon atoms, and X represents an anion residue of a carboxylic acid or an organic sulfonic acid).

 Examples of the hydrocarbon group having 1 to 16 carbon atoms include a linear or branched hydrocarbon group such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, s-butyl, t-butyl, pentyl, A branched alkyl group; Straight or branched alkenyl groups such as vinyl, allyl, and crotyl; Aryl groups such as phenyl, toluyl, xylyl, naphthyl, anthryl, phenanthryl groups; And aralkyl groups such as benzyl and phenethyl groups. Of these, a straight or branched alkyl group having 1 to 6 carbon atoms, particularly a butyl group, is preferred.

 Examples of the "carboxylic acid" in the "anion residue of a carboxylic acid or an organic sulfonic acid" include aliphatic alcohols having 1 to 20 carbon atoms such as octanoic acid, decanoic acid, lauric acid, myristic acid and palmitic acid Monocarboxylic acids; Cyclohexanetetracarboxylic acid, bicyclo [2.2.1] heptane-2,3-dicarboxylic acid, methylbicyclo [2.2.1] heptane-2,3-dicarboxylic acid Alicyclic carboxylic acids (monocyclic alicyclic mono- or polycarboxylic acids, crosslinked cyclic mono- or polycarboxylic acids), and the like. The alicyclic carboxylic acid may have a substituent such as a linear or branched alkyl group having 1 to 4 carbon atoms such as a methyl group, an alkoxy group having 1 to 4 carbon atoms such as a methoxy group, or a halogen atom such as a chlorine atom It is possible. Among them, an aliphatic monocarboxylic acid having 10 to 18 carbon atoms and an alicyclic polycarboxylic acid having 8 to 18 carbon atoms are preferable as the carboxylic acid.

Examples of the "organic sulfonic acid" in the "anion residue of a carboxylic acid or an organic sulfonic acid" include methanesulfonic acid, ethanesulfonic acid, 1-propanesulfonic acid, 2-propanesulfonic acid, Aliphatic sulfonic acids such as 1-pentanesulfonic acid, 1-hexanesulfonic acid, 1-octanesulfonic acid, 1-decanesulfonic acid and 1-dodecanesulfonic acid (for example, aliphatic sulfonic acids having 1 to 16 carbon atoms); Benzene sulfonic acid, p- toluenesulfonic acid, 4-ethylbenzenesulfonic acid, 3- (straight or branched octyl) benzenesulfonic acid, 4- (straight or branched octyl) benzenesulfonic acid, 3- (linear or branched dodecyl Benzene sulfonic acid, 4-methoxybenzenesulfonic acid, 4-ethoxybenzenesulfonic acid, 4-methoxybenzenesulfonic acid, 4-methoxybenzenesulfonic acid, -Chlorobenzenesulfonic acid, and the like.

Typical examples of the quaternary phosphonium salts include tetrabutylphosphonium decanoate, tetrabutylphosphonium laurate, tetrabutylphosphonium myristate, tetrabutylphosphoniumpolate, tetrabutylphosphonium cation and bicyclor [2.2 .1] heptane-2,3-dicarboxylic acid and / or methyl bicyclo [2.2.1] heptane-2,3-dicarboxylic acid, a salt of an anion of tetrabutylphosphonium cation, Salts of anions of 4,5-cyclohexanetetracarboxylic acid, salts of anions of tetrabutylphosphonium cation and methanesulfonic acid, salts of anions of tetrabutylphosphonium cation and benzenesulfonic acid, salts of tetrabutylphosphonium cation and p- Salts of anions of toluenesulfonic acid, salts of anions of tetrabutylphosphonium cation and 4-chlorobenzenesulfonic acid, salts of anions of tetrabutylphosphonium cation and dodecylbenzenesulfonic acid, and the like.

Examples of the boron compound include boron trifluoride, triphenylborate, and the like.

 Examples of the imidazole-based curing accelerator include 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, 2-methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-methylimidazole, -Benzyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl- 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazolium trimellitate, 1-cyanoethyl-2-phenylimidazolium trimellitate , 2,4-diamino-6- [2'-methylimidazolyl- (1 ')] -ethyl-s-triazine, 2,4- diamino-6- [ (1 ')] - ethyl-s-triazine, 2,4-diamino-6- [2'-ethyl-4'-methylimidazolyl- , 2,4-diamino-6- [2'-methylimidazolyl- (1 ')] -ethyl-s-triazine as an isocyanuric acid adduct, 2- 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2,3-dihydro-imidazole, Imidazole compounds such as 1H-pyrrolo [1,2-a] benzimidazole, 1-dodecyl-2-methyl-3-benzylimidazolium chloride, 2-methylimidazoline and 2-phenylimidazoline And adducts of an imidazole compound and an epoxy resin.

Examples of amine curing accelerators include trialkylamines such as triethylamine and tributylamine; amines such as 4-dimethylaminopyridine, benzyldimethylamine, 2,4,6-tris (dimethylaminomethyl) phenol, 1,8-diazabicyclo (5,4,0) -undecene (hereinafter abbreviated as DBU), and the like.

As described above, the support 3, on which the first nanofiber webs are laminated, is moved to the rotating device 20 through the top-down or bottom-up electrospinning device 10.

The support 3, on which the first nanofiber web is laminated on the lower surface, passes through the rotating device 20, and as the upper surface is rotated 180 degrees to the lower surface, Is reversed in the lower surface direction.

As described above, the support 3, whose upper surface is rotated to the lower surface through the rotary device 20, is then fed to the bottom-up or top-down electrospinning device 30 by the conveying roller 7, The support 3 supplied to the electrospinning device 30 is located on the upper surface of the collector 37.

The high voltage of the voltage generator is generated in the nozzle 35 and the collector 37 and the polymer spinning solution filled in the spinning liquid main tank 31 on the collector 37 generating the high voltage is supplied to the nozzle block 33 Through the nozzle 35 of the spray nozzle.

Each of the voltage generators has a structure similar to that of a general electrospinning device and generates a high voltage in the collectors 17 and 37 through the nozzles 15 and 35 and a nozzle 15 and 35 and the collector located below or above the nozzle blocks 13 and 33, preferably a voltage of 1 kV or more, more preferably 20 kV or more.

On the other hand, the spinning liquid to be filled in the spinning liquid main tank 31 is continuously and constantly supplied in a plurality of nozzles 35 to which a high voltage is applied through the metering pump, and the spinning solution supplied from the nozzle 35 is supplied to the nozzle On a first nanofiber web laminated by a top-down or bottom-down electrospinning on the underside of the support 3 while being radiated and focused on a collector 37 with a high voltage applied by a top-down or top-down electrospinning A second nanofiber web is laminated.

At this time, the conveying of the support 3 to the top-down or bottom-up electrospinning apparatus 10, the conveyance to the rotary apparatus 20 and the conveyance to the bottom-up or top-down electrospinning apparatus 30 are performed by the conveying roller 7.

In the present invention, it is preferable that the top-down or bottom-down electrospinning apparatus 10 and the bottom-up or top-down electrospinning apparatus 30 are arranged in a straight line in the horizontal direction, but they may be arranged in a vertical direction, And the respective electrospinning devices are arranged in the U direction in the same layer. The fact that they can be arranged in the vertical direction for each layer or in the U direction in the same layer has the advantage that the productivity can be increased in a limited area.

That is, the rotary device is characterized in that the support rotates 180 degrees or vertically rotates in the U-turn direction by the flip device.

In addition, the spinning liquid main tank 11 and the spinning liquid main tank 31 may be the same.

As described above, the process of continuously laminating the nanofibers on one surface of the support 3 while the support 3 is transferred to the top-down or bottom-up electrospinning apparatus 10 and the bottom-up or top-down electrospinning apparatus 30 Repeatedly, the nanofiber web is laminated on the support 3 in multiple layers.

In the present invention, the spinning liquid main tanks 11 and 31 of the top-down or bottom-up electrospinning apparatus 10 and the bottom-up or top-down electrospinning apparatus 30 are filled with the same type of polymer spinning solution.

That is, the polymer spinning solution injected from the top-down or bottom-up electrospinning apparatus 10 and the polymer solution injected from the bottom-up or top-down electrospinning apparatus 30 are made of the same or different kinds of polymer spinning solution.

As described above, the nanofibers are arranged on one surface through the fine dust-blocking filter manufacturing apparatus 1 having the top-down or bottom-up electrospinning apparatus 10 and the bottom-up or down-top electrospinning apparatus 30, The support 3, which is formed in a multilayer structure, is wound up through a take-up roller 7 and used as a fine dust barrier filter.

Here, the support 3, on which the nanofiber webs prepared through the top-down or bottom-up electrospinning apparatus 10 and the bottom-up or top-down electrospinning apparatus 30 are laminated, is laminated with the laminating apparatus 50, Process.

In the present invention, the bottom-up electrospinning apparatus 10 is located at the front end, and thereafter, the bottom-up electrospinning apparatus 30 is located at the rear end, but it is also possible that the bottoms electrospinning apparatus comes to the front end. In addition, although the electrospinning apparatus is composed of two in the present invention, it is also possible that three or more top-down and bottom-up electrospinning apparatuses are arranged alternately.

Also, it is possible to further include an air permeability measuring device 70 for measuring an abnormality such as air permeability of the manufactured nanofiber web, and other process devices for other post-processes.

While the present invention has been particularly shown and described with reference to specific embodiments thereof, it will be understood by those skilled in the art that various changes and modifications may be made without departing from the spirit and scope of the invention as defined in the appended claims. Anyone with it will know easily.

[Example 1]

15% by weight of polyurethane (Pellethane 2363-80AE) of DOW (USA)) and 85% by weight of a solvent of NN-dimethylacetamide (DMF) to prepare a polymer spinning solution having a concentration of 15% Respectively. Thereafter, the polymer spinning solution was moved to a nozzle block, and then a polyester mesh was used as a support under the conditions of a distance between the nozzle block and collector of 20 cm, an applied voltage of 15 kV, and a spinning solution flow rate of 0.1 mL / h. % Is the mesh. The polyester 100% mesh was composed of 25 denier monofilaments and had a basis weight of 91 g / m 2 and a width of 1620 mm. The polyester was electrospun on a polyester mesh having a density of 25.5 x 25 to prepare a polyurethane nanofiber having a basis weight of 0.1 g / The web was laminated. Thus, a filter for blocking fine dust was prepared by attaching the nanofiber web and the polyester mesh. The average diameter of the polyurethane nanofiber web was 400 nm.

[Example 2]

As in the case of Example 1 except that the nylon 6 spinning solution containing 15% by weight of nylon 6 and 85% by weight of formic acid was used as the polymer spinning solution and that the basis weight of the nanofiber web was changed to 0.2 g / A filter for blocking fine dust was produced. At this time, the average diameter of the nylon 6 nanofiber web was 130 nm.

[Example 3]

Using a polyester carrier instead of the polyester mesh and using a PVDF spinning solution having a concentration of 15% consisting of 15% by weight of PVDF and 85% by weight of dimethylacetamide (DMAc) as a polymer spinning solution, Was changed to 0.3 g / m < 2 >. The average diameter of the PVDF nanofiber web was 150 nm. As a polyester carrier, the yarn used as the WP slope is 20 denier polyester, the yarn used as WT weft is 60 denier, the warp density per WP 1 inch is 12.93 g / yd, and the weft density per WI weft 1 inch is 31.80 g / yd And the fabric length was 59 ~ 60 '' and the basis weight was 44.73g / yd.

 [Example 4]

A 15% by weight PES spinning solution consisting of 15% by weight of polyethersulfone (PES) and 85% by weight of dimethylacetamide (DMAc) was used as the polymer spinning solution, and the basis weight of the nanofiber web was changed to 0.4 g / A filter for blocking fine dust was prepared in the same manner as in Example 3. [ At this time, the average diameter of the PES nanofiber web was 150 nm.

[Example 5]

The use of a 15% polyacrylonitrile spinning solution consisting of 15% by weight of polyacrylonitrile (PAN) and 85% by weight of dimethylformamide as the polymer spinning solution, and a basis weight of the nanofiber web of 0.5 g / m2 , A filter for blocking fine dusts was prepared in the same manner as in Example 1. The average diameter of the PAN nanofiber web was 200 nm.

[Example 6]

15 wt% of polyamic acid and 85 wt% of N-N-dimethylacetamide (DMAc) solvent were dissolved to prepare a polyamic acid (PAA) polymer spinning solution having a concentration of 15% and provided in a raw material tank. Thereafter, the polymer spinning solution was moved to a nozzle block, and a polyester mesh was used as a support for a distance between the nozzle block and the collector of 20 cm, an applied voltage of 15 kV, and a spinning solution flow rate of 0.1 mL / h. It is 100% mesh. The polyester 100% mesh was composed of 25 denier monofilaments and had a basis weight of 91 g / m 2 and a width of 1620 mm and was electrospun on a polyester mesh having a density of 25.5 x 25 to obtain a polyamic acid nanofiber having a basis weight of 0.1 g / The web was laminated. The nanofiber web and the polyester mesh were attached using ultrasonic bonding. The polyester mesh and the polyamic acid nanofiber web were attached in this manner to prepare a filter for blocking fine dust. The polyimide nanofibers were converted to polyimide nanofiber webs by imidizing polyamic acid through heat treatment. The average diameter of the polyimide nanofiber web was 400 nm.

[Example 7]

15% by weight of polyurethane (Pellethane 2363-80AE by DOW, USA) was dissolved in 85% by weight of NN-dimethylacetamide (DMAc) to prepare a spinning solution having a concentration of 15% and a viscosity of 1000 cps. Lt; / RTI > Thereafter, the spinning liquid was moved to the nozzle block, and the distance between the nozzle block and the collector was set to 20 cm, the applied voltage was 15 kV, the spinning liquid flow rate was 0.1 mL / h, the temperature was 60 ° C, Lt; / RTI > Thereafter, the concentration of the spinning solution in the raw material tank was changed to 20% in the course of providing the raw material tank, which is one of the storage tanks, overflowed by the spinning process, and the viscosity was changed to 2000 cps. Thereafter, the temperature of the raw material tank was raised to 80 ° C in order to lower the viscosity to 1000 cps by the sensor of the temperature control device, and the nanofiber web was laminated by electrospinning on a polyester mesh. By attaching the nanofiber web and the polyester mesh in this way, a filter for blocking fine dust was manufactured. The average diameter of the polyurethane nanofiber web was 300 nm.

[Example 8]

15% by weight of polyurethane (Pellethane 2363-80AE) from DOW (USA)) was dissolved in 85% by weight of NN-dimethylacetamide (DMAc) solvent to prepare a spinning solution having a concentration of 15% Respectively. Thereafter, the spinning solution was moved to each nozzle block of the top-down electrospinning device and the bottom-up electrospinning device, and the distance between the nozzle block and the collector was 20 cm, the applied voltage was 15 kV, the spinning solution flow rate was 0.1 mL / The nanofiber web was laminated by electrospinning on a polyester mesh. That is, on the top-down electrospinning device located at the front end, the spinning solution is electrospun on the polyester mesh to form a first nanofiber web. After that, the laminate composed of the polyester mesh and the first nanofiber web was rotated 180 degrees by the rotating device (after up-down reversing), and in the bottom-up electrospinning device located at the rear end, the spinning solution was applied to the first nanofiber web And the second nanofiber web was laminated to form the second nanofiber web. By attaching the nanofiber web and the polyester mesh in this way, a filter for blocking fine dust was manufactured. The average diameter of the polyurethane nanofiber web was 400 nm.

[Comparative Example 1]

A filter composed of a nanofiber web prepared by electrospinning the same polymer spinning solution as in Example 1 was prepared between two low melting point nonwoven fabrics (LM nonwoven fabric, POA40V6) composed of two sheets and having a basis weight of 60 g / m 2.

- Efficiency measurement

A DOP efficiency of 2.5 mu m was measured at a speed of 5.33 cm / s using ASTM D2986.

- Ventilation measurement

Air permeability at 125 Pa was measured using ASTM D737-96 (Frazier).

- Visibility of light transmittance (visibility)

ASTM E 424-71: 2007, METHOD A 6. 5 2 The light transmittance was measured with SELECTED ORDINATES METHOD (%).

Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Comparative Example 1 efficiency (%) 84 90 94 99.9 96 98 40 Air permeability (cfm) 450 260 150 30 25 24 5 Light transmittance (%) 80 61 45 30 30 30 0

Thus, in the embodiment of the present invention, since the efficiency as a filter is higher than that of Comparative Example 1, the air permeability is higher and the air flow resistance is lower than that of the Comparative Example, fine dust and the like are effectively filtered out, .

In Example 7, the production process using the existing thinner was simplified, the risk of explosion of the diluent was reduced, and the high-temperature radiation was enabled, thereby increasing the concentration of the spinning solution to increase the productivity of the nanofiber nonwoven fabric. 8, there is an advantage that the productivity of manufacturing the nanofiber nonwoven fabric can be improved by using the bottom-up and top-down electrospinning device together.

As described above, the filter and the method for fabricating the fine dust filter according to the present invention are not limited to the configurations and the methods of the embodiments described above, but the embodiments may be modified in various ways, All or some of the embodiments may be selectively combined.

1: Manufacturing device for filter for blocking fine dust, 3: Support,
5: feed roller, 7: feed roller,
9: take-up roller, 10: top-down electrospinning device,
11: tank main tank, 13: nozzle block,
14: voltage generating device, 15: nozzle,
17: collector, 20: rotating device,
20-1: flip device, 21, 21 ': left and right guide member,
22, 22 ': left and right guide grooves,
30: bottom-up electrospinning device, 31: spinning liquid main tank,
33: nozzle block, 35: nozzle
37: collector, 50: laminating device,
60: Temperature control device,
70: air permeability measuring device,
112, 112a, 112b, 112c, 112d, 112e, 112f, 112g, 112h, 112i:
113: Heat line.

Claims (13)

Preparing a support;
Forming a first nanofiber web on the upper surface of the support by electrospinning a first polymer spinning solution with a top-down electrospinning device in a top-down manner;
The support having the first nanofiber web laminated thereon passes through the rotating device and the upper surface is rotated 180 degrees to the lower surface;
A step of continuously laminating a second nanofiber web by electrospinning a second polymer spinning solution with a bottom-up electrospinning device on a first nanofiber web laminated on the support; And
And winding a support on which the first and second nanofiber webs are continuously laminated. ≪ RTI ID = 0.0 > 21. < / RTI >
The method according to claim 1,
Wherein the first and second polymer spinning solutions are electrospun through a temperature controller at a temperature of 50 to 200 ° C.
The method according to claim 1,
Wherein the first and second polymer spinning solution are one or more selected from the group consisting of polyurethane, polyvinylidene fluoride, polyacrylonitrile, nylon, polyethersulfone, meta-aramid, polyetherimide, polyamic acid and polyimide, or The method of manufacturing a filter for blocking fine dust according to claim 1,
The method according to claim 1,
Wherein the support is a mesh or a carrier. ≪ RTI ID = 0.0 > 21. < / RTI >
The method according to claim 1,
Wherein the support is composed of one layer or two or more layers.
The method according to claim 1,
Wherein the fine dust-blocking filter has a fine dust light transmittance of 30 to 80% and an air permeability (cfm) of 10 to 500.
The method according to claim 1,
Wherein the fine dust blocking filter has an efficiency of 80% or more.
The method according to claim 1,
Wherein the basis weight of the first and second nanofibrous webs is 0.001 to 2.0 g / m < 2 >.
The method according to claim 1,
The step of forming the first and second nanofiber webs on the support includes ultrasonic bonding, applying a chemical or thermal adhesive, or electrospinning the adhesive directly. ≪ / RTI >
A top-down electrospinning device in which the nozzles are directed from the top to the bottom, and a polymeric spinning solution is electrospun on a support to produce a first nanofiber web;
A rotating device for rotating the upper surface of the support 180 degrees to the lower surface; And
And a bottom-up electrospinning apparatus in which the nozzles are directed from the bottom to the top, and the same polymer spinning solution used in the top-down electrospinning apparatus is electrospun on the first nanofibrous web to laminate the second nanofibrous web
And the bottom-up electrospinning device, the rotating device, and the bottom-up electrospinning device are arranged in this order.
11. The method of claim 10,
Wherein the rotating device rotates the supporting body 180 degrees or vertically rotates in the U-turn direction by the flip device.
11. The method of claim 10,
Wherein the bottom-up electrospinning device and the bottom-up electrospinning device each further comprise a temperature regulating device for regulating the temperature of the polymer solution.
11. The method of claim 10,
Wherein the fine dust blocking filter manufacturing apparatus further comprises a bottom-up electrospinning device or a top-down electrospinning device alternately.

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