KR101484510B1 - Both sides substrate nanofiber filter for excellent heat-resisting property and its manufacturing method - Google Patents

Abstract

The present invention aims to resolve low thermal stability, which is a flaw of an existing nanofiber filter. To this end, a double-sided nanofiber filter having enhanced thermal resistance is manufactured by electrospinning thermal resistant fiber on both sides of a base material. The double-sided nanofiber filter is manufactured by the steps of: stacking inorganic nanofibers on the base material; manufacturing double-sided nanofiber by continuously electrospinning thermal resistant polymer nanofibers on a side of the base material, on which the inorganic nanofibers are not stacked; and arranging thick nanofibers in the direction of air introduction and thin nanofibers in the direction of air discharge during an air filter process. Therefore, a functional filter, which has filter efficiency, price competitiveness, high efficiency, and thermal resistance is manufactured.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a two-sided substrate nanofiber filter having improved heat resistance,

The present invention relates to a base material double-sided nanofiber filter material having improved heat resistance, and a method of manufacturing the same. The nanofiber filter material is produced by electrospinning an inorganic polymer on a base material to laminate nanofibers having a large fiber diameter, Surface nanofiber filter material having improved heat resistance, comprising the step of forming a thin film of electrospinning having a small fiber diameter by selecting one of polyimide, polyvinylidene fluoride, meta-aramid or polyamide, and a method for producing the same.

Generally, a gas turbine used in a thermal power plant sucks and compresses purified air from the outside, injects compressed air into the combustor together with the fuel, mixes the mixed air and fuel, And then the high-temperature and high-pressure combustion gas is injected into the vanes of the turbine to obtain a rotational force.

Since these gas turbines are made up of very precise parts, they are subjected to periodic planned preventive maintenance and air filters are used for the pretreatment to purify the air in the compressor.

The air filter removes foreign substances such as dust and dust contained in the air when the combustion air sucked into the gas turbine is taken in the air and purifies the purified air to supply it to the gas turbine. Is weak at high temperature, and there is a problem that the foreign matter is not removed well.

In addition, most microfibers that are conventionally produced are prepared by spinning, such as melt spinning, dry spinning, wet spinning or the like, in which the polymer solution is forcedly extruded and spun through fine holes by mechanical force. However, the diameter of nanofibers produced in this manner is in the range of about 5 to 500 mu m, and it is difficult to produce nanofiber fibers of 1 mu m or less. Therefore, a filter composed of such a large-diameter fiber can filter contaminant particles having a large diameter, but it is practically impossible to filter nano-sized contaminant particles.

In order to solve the above problems, various methods for fabricating nano-sized fibers (nonwoven fabric) have been developed and used. Among them, a method for forming organic nanofibers includes forming nanostructured materials by block segments, Formation of nanofibers by polymerization using silica catalyst, nanofiber formation by carbonization process after melt spinning, and nanofiber formation by electrospinning of polymer solution or melt.

When a nanofiber filter is fabricated using the nanofibers thus produced, the nanofiber filter has a larger specific surface area than the nanofiber filter having a larger diameter, has flexibility for surface functional groups, and has nano-sized pore size. It can be efficiently removed.

However, the implementation of the filter using the nanofibers is not easy to control the various conditions for the production because the production cost is low and the production of the filter using the nanofiber is not available at a low price. The present gas turbine, Filters used in furnaces and the like require heat resistance.

In addition, conventional techniques for spinning nanofibers are limited to small-scale operation lines focused on laboratories, so that there is no unit or block concept in the spinning section. In this case, only nanofibers having a uniform fiber diameter are emitted. This is a limitation that has limitations in ventilation and service life when used as a filter.

In general, a filter is a filtration device for filtering foreign matters in a fluid, and is divided into a liquid filter and an air filter. Among them, the air filter has been developed as a clean room where the biologically harmful substances such as particulate matter, germs and molds, bacteria and the like are completely removed from the air in order to prevent the deterioration of the high- Demand is gradually increasing as the usage area spreads day by day. Cleanroom applications are widely used in semiconductor manufacturing, computer equipment assembly, tape manufacturing, printing painting, hospitals, pharmaceutical manufacturing, food processing plants, agriculture, forestry and fisheries.

The air filter forms a porous layer of microporous structure on the surface of the filter media so that the dust does not penetrate into the filter media and performs filtration. However, the large particles are formed by the filter cake on the surface of the filter material, and the fine particles pass through the primary surface layer and gradually accumulate in the filter material, thereby blocking the pores of the filter. As a result, large particles and fine particles, which trap the pores of the filter, increase the pressure loss of the filter and deteriorate the life of the filter. In addition, conventional filter media have difficulties in filtering fine particles having a size of 1 μm or less .

On the other hand, the efficiency of the conventional air filter is measured by the principle that the static electricity is given to the fibrous aggregate constituting the filter filter material and the particles are collected by the electrostatic force. However, the European air filter classification standard EN779 recently decided to exclude the efficiency of the filter due to the electrostatic effect in 2012, so that the actual efficiency of the conventional filter was lowered by more than 20%. In addition, due to the adverse effect of glass fiber, which has been used as a material of conventional heat resistant filter, on the environment, in Europe and the United States, the use of glass fiber is regulated for environmental stability.

In order to solve the above-mentioned problems, various methods of manufacturing nano-sized fibers and applying them to filters have been developed. When nanofibers are implemented in a filter, they have a large specific surface area compared to conventional filter media having a large diameter, good flexibility for surface functional groups, and nanoparticle pore size, so that harmful fine particles and gas can be efficiently removed It was.

However, since the production cost of the filter using the nanofibers is large, and it is difficult to control the various conditions for production, it is difficult to mass-produce the filter. Therefore, the filter using the nanofiber is produced at a relatively low cost I can not. Furthermore, filters used in gas turbines, blast furnaces and the like are demanding heat resistance.

In addition, since the nanofiber having a small fiber diameter has a disadvantage that the filter life is shortened due to a high pressure loss when the filter is used, a gradient is applied to the diameter of the nanofiber to effectively filter the fine particles, can do.

The present invention relates to a method for producing a polymeric nanofiber, comprising the steps of: (a) preparing an inorganic polymer nanofiber laminated on a surface of a substrate by electrospinning; and (2) heat-resisting polymer nanofiber laminated on the back surface of the substrate on which the inorganic polymer nanofiber is not laminated Wherein the inorganic polymer nanofiber is a silanol group or a siloxane group alone polymer or a copolymer polymer of a silane group or a siloxane group, and the heat-resistant polymer nanofiber is a polyacrylate Rhenitrile, polyethersulfone, polyimide, meta-aramid or polyamide, and polyvinylidene fluoride. The substrate double-sided nanofiber filter having improved heat resistance is characterized in that nanofibers having a larger diameter of the nanofibers are arranged in the air inlet direction and nanofibers having a smaller diameter of the nanofibers are arranged in the air discharge direction Thereby producing a substrate double-sided nanofiber filter material material having improved heat resistance.

The present invention uses a heat-resistant polymer and thus has excellent heat resistance. By using a continuous electrospinning method, not only the manufacturing process is efficient and cost-competitive, but also nanofibers are used, it can be used as a high efficiency filter.

Further, by providing a thickness gradient of the nanofiber layer, filter damage due to pressure loss can be mitigated.

Fig. 1 is a schematic view of a nanofiber filter media on both sides of a substrate having improved heat resistance.
2 is a schematic diagram of a hybrid electrospinning apparatus.
3 is a schematic view of the process of the electrospinning apparatus.
Fig. 4 is a schematic process diagram of a block of an electrospinning device. Fig.
5 is a schematic view of an apparatus for measuring thickness of an electrospinning device.
6 is a schematic view of a nozzle block and a nozzle of an electrospinning device.

Preferred embodiments of the present invention will be described in detail with reference to the accompanying drawings. It is to be noted that like elements in the drawings denote like elements wherever possible. In the following description, well-known functions or constructions are not described in detail since they would obscure the invention in unnecessary detail.

The present invention relates to a method for producing a nanofibrous nanofiber by electrospinning an inorganic polymer in an air inflow direction of a substrate with a filter having nanofibers on both sides of the substrate to laminate nanofibers having a large fiber diameter, A two-sided nano-fiber filter material having improved heat resistance by electrospinning a polymer selected from polyacrylonitrile, polyethersulfone, polyimide, polyamide, meta-aramid and polyvinylidene fluoride to laminate nanofiber layers having a small fiber diameter .

In the present invention, the base material of the filter media uses a meta-aramid or cellulose base material having excellent heat resistance.

The meta-aramid is bonded to the amide group at the meta-position. Its strength and elongation are similar to ordinary nylon, but it is very stable against heat. It has the advantages of being light and absorbing somewhat compared with other heat-resistant materials. This can be suitably used as a filter substrate since the filter stability can be ensured at higher operating conditions.

Cellulose is produced by plant photosynthesis. Cellulose fibers such as cotton, hemp, and rayon are typical examples of cell membranes of higher plants. In the case of the surface first, it has a large specific gravity, and is a material which is relatively heat stable because of heat resistance and flame resistance. It has good hygroscopicity, strong acidity but strong alkali. Hygroscopicity and durability, and thus it is widely used as a wide range of coating materials, and many studies have been conducted to overcome the disadvantages through functional processing. Flax fiber is composed of 5-6 square, thick shell and small hollow fiber yarn. It has high strength and heat resistance and can be used stably at high temperature. In addition, there are cellulosic fibers such as ramie, hemp, and jute. The common feature is that it is made of a material with high heat resistance. It can be used as a heat-resistant filter base material that can operate stably at high temperatures.

The electrospinning apparatus of the present invention can be seen in FIG. 2, FIG. 3 and FIG.

2, the combined electrosupply apparatus 100 includes a bottom-up electrospinning apparatus 110 and a top-down electrospinning apparatus 130. The bottoms electrospinning apparatus 110 and the top- The electrospinning apparatuses 130 are arranged alternately and continuously in the horizontal direction.

The bottom-up electrospinning device 110 and the top-down electrospinning device 130 are connected to the spinning liquid main tanks 111 and 131 and the spinning liquid main tanks 111 and 131 in which a polymer spinning solution (not shown) (Not shown) for supplying a polymeric spinning liquid filled in the main spinning liquid main tanks 111 and 131 and a polymer spinning solution in the spinning liquid main tanks 111 and 131, And collectors 117 and 137 spaced apart from the nozzles 115 and 135 by a predetermined distance in order to accumulate the polymer solution for spraying located at the lower ends of the nozzles 115 and 135, And a voltage generator (not shown) for generating a voltage to the collectors 117 and 137.

The mixed electrospinning apparatus 100 according to the present invention has a structure in which the spinning liquid filled in the spinning liquid main tank 111 of the bottom-up electrospinning apparatus 110 is supplied with a high voltage through the metering pump And the polymer spinning solution supplied to the nozzle 115 is radiated and focused on the collector 117 with a high voltage applied thereto through the nozzle 115 to form a nanofiber web And the formed nanofiber is embossed or needle punched to produce the nanofiber.

A polymeric spinning solution is sprayed from a bottom-up electrospinning device 110 and a top-down electrospinning device 130 to the front end of the mixing electrospinning device 100 to form a support 121 on which nanofibers (not shown) And a winding roller 118 for winding the support 121 on which nanofibers are laminated is provided at the rear end.

Here, the support 121, on which the polymer spinning solution of the bottom-up electrospinning device 110 and the top-down electrospinning device 130 are laminated, is preferably made of nonwoven fabric or fabric, but is not limited thereto.

At this time, the bottom-up electrospinning device 110 and the top-down electrospinning device 130 are arranged symmetrically with respect to the collectors 117 and 137, respectively. That is, in the bottom-up electrospinning device 110, the collector 117 is located at the top of the nozzle 115, and the top-down electrospinning device 130 is located at the bottom of the nozzle 135.

Electrode directions of the collectors 117 and 137 provided in the bottom-up electrospinning device 110 and the top-down electrospinning device 130 are opposite to each other. That is, the direction of the electrodes of each collector 117 provided in each of the bottom-up electrospinning devices 110 and 110 'is set such that the top surface of the collector 117 faces the nozzle block 113 having the plurality of nozzles 115 And the direction of the electrodes of each collector 137 provided in each of the down-type electrospinning devices 130 and 130 'is the same as that of the lower part of the collector 137 so as to face the nozzle block 133 having the plurality of nozzles 135. [ Plane.

On both ends of each of the collectors 117 and 137 are provided conveyance rollers 119 and are stacked on the collectors 117 and 137 via the conveyance rollers 119 to form nano- (13) is transported in the horizontal direction. That is, the polymer spinning solution injected from the nozzle 115 of the bottom-up electrospinning device 110 is laminated on the support 121 of the collector 117, and the nanofibers produced by the collector 115 of the bottom- And a transfer roller 119 for moving the transfer roller 119 horizontally onto the transfer rollers 137 and for moving the process repeatedly and continuously are provided at both ends of the collectors 117 and 137, respectively.

The polymer spinning liquid filled in the spinning liquid main tank 111 of the bottom-up electrospinning apparatus 110 is sprayed onto the support 121 of the collector 117 through the nozzle 115, The nanofibers are formed on the supporter 121 of the collector 117 and the nanofibers are stacked on the supporter 121. The nanofibers are stacked on the supporter 121 through the transport rollers 119, The polymer solution is transferred to the collector 137 of the top-down electrospinning device 130 and the polymer solution is injected into the polymer solution tank 130, which is filled in the spinning solution main tank 131 of the top-down electrospinning device 130, The bottom-up electrospinning apparatus 110, 110 'and the top-down electrospinning apparatus 130, 130' are alternately arranged in succession such that the use liquid is sprayed through the nozzle 135, and the above- The final product is produced.

In the embodiment of the present invention, a bottom-up electrospinning device 110 is provided at the front end of the composite electrospinning device 100 and a top-down electrospinning device 130 is provided at a rear end of the bottoms electrospinning device 110 The bottom-up type electrospinning device 110 and the bottom-up type electrospinning device 130 and 130 'are sequentially arranged in this order. However, the bottom type electrospinning device 130 is installed at the end of the combined type electrospinning device 100 And a bottom-up electrospinning device 110 is provided at a rear end of the bottom-up electrospinning device 130. The bottom-up electrospinning device 130 and the bottom-up electrospinning device 110, 110 ' It is also possible to arrange them in such a manner.

In addition, two or more bottom-up electrospinning apparatuses 110 are continuously arranged at the tip of the composite electrospinning apparatus 100, and two or more top-down electrospinning apparatuses 130 are continuously arranged Or two or more top-down electrospinning apparatuses 130 may be successively arranged at the front end, and two or more bottom-up electrospinning apparatuses 110 may be continuously arranged at the rear end thereof.

The nanofibers produced while passing through the bottom-up electrospinning apparatus 110 and the top-down electrospinning apparatus 130 of the composite electrospinning apparatus 100 according to the present invention have the above- The polymeric spinning solution is injected through the nozzles 115 and 135 of the spinning device 110 and the top-down electrospinning device 130 so that the nanofibers are stacked on the lower surface and the upper surface of the support 121 on the collectors 117 and 37, The polymer spinning solution injected from the nozzles 115 and 235 of the bottom-up electrospinning device 110 and the top-down electrospinning device 130 is laminated on the support 121 to form a plurality of nanofibers, Fiber products are produced.

A polymeric spinning solution is sprayed from a bottom-up electrospinning device 110 and a top-down electrospinning device 130 to the front end of the mixing electrospinning device 100 to form a support 121 on which nanofibers (not shown) And a winding roller 118 for winding the support 121 on which nanofibers are laminated is provided at the rear end.

According to a preferred embodiment of the present invention, there is provided a method of fabricating a semiconductor device, comprising: forming a first nanofiber by electrospinning a solution prepared by dissolving a first polymer packed in a first supply device in an organic solvent onto a film surface of a substrate; And laminating the second nanofibers by electrospinning a solution prepared by dissolving the second polymer filled in the second supply device in an organic solvent on the lower surface of the substrate.

The filled solution of the first feeding device may or may not be the same solution in the second feeding device. In addition, two or more feeding devices are possible.

As shown in the other drawings, FIG. 3 is a schematic diagram of a general continuous electrospinning apparatus, which is a schematic diagram of a general continuous electrospinning apparatus, in which a spinning liquid main tank (not shown) in which spinning liquid is filled and a polymer spinning solution filled in the spinning liquid main tank (3) in which a plurality of nozzles (2) in the form of a pin are arranged and which discharges the polymer spinning liquid in the spinning liquid main tank and a metering pump (not shown) for spraying the spinning liquid, (20) and a block (20) accommodating therein a collector (4) spaced apart from the nozzle (2) by a predetermined distance and a voltage generating device (1) And a case 8 made of a conductor or a nonconductive conductor.

In the present invention, one spinning liquid main tank (not shown) is provided. However, in the case where the spinning liquid is composed of two or more spinning liquids, two or more main spinning liquid main tanks may be provided, or one spinning liquid main tanks It is also possible to divide into two or more spaces and supply two or more polymer spinning solution filled in each divided space.

Herein, in the present invention, the electrospinning device 10 uses a bottom-up electrospinning device for spraying the spinning liquid in the upward direction.

Meanwhile, in the embodiment of the present invention, a bottom-up electrospinning device for spraying the spinning solution in the upward direction with the electrospinning device is used, but a top-down electrospinning device for spraying the spinning solution in the downward direction can be used. A combined electrospinning device in which the device is used together may be used, but is not limited thereto.

With the above structure, the electrospinning apparatus 10 is configured such that the spinning liquid filled in the spinning liquid main tank in the block 20 continuously flows into the plurality of nozzles 2 to which a high voltage is applied through the metering pump And the spinning solution of the polymer supplied to the nozzle 2 is radiated and focused on the collector 13 having a high voltage through the nozzle 2 to form nanofibers (not shown) The fibers are laminated (19) to produce a filter.

In the front end of the electrospinning device 10, there is provided a feed roller 11 for feeding a long sheet on which nanofibers are laminated by spraying a polymer spinning solution in each block 20, Up roller 12 for winding the sheet.

In the present invention, the filter sheet 5 is used as a long sheet and the polymer spinning solution is sprayed on the filter substrate 5 to form nanofibers .

In the embodiment of the present invention, the filter substrate 5 is used as a long sheet, but a release or nonwoven fabric may be used, but the present invention is not limited thereto.

That is, one side and the other side of the filter base 5 used as a long sheet in the present invention are wound around a feeding roller 11 provided at the front end of the electrospinning apparatus 10 and a winding roller 12 provided at the rear end .

On the other hand, the electrospinning device of each block 20 is installed in the advancing direction (a) of the radiation with respect to the collector 4. An auxiliary belt 6 is provided between each of the collectors 4 and the filter substrate 5 and is integrated with each of the collectors 4 through the auxiliary belts 6 to form nano- (5) is transported in the horizontal direction. That is, the auxiliary belt 6 rotates in synchronization with the feed speed V of the filter base material, and has the auxiliary belt roller 7 for driving the auxiliary belt 6. The auxiliary belt roller 7 is an automatic roller having at least two frictional forces. Since the auxiliary belt 6 is provided between the collector and the filter substrate 5, the filter substrate 5 is smoothly conveyed without being attracted to the collector to which the high voltage is applied.

The spinning liquid filled in the spinning liquid main tank in the block 20 of the electrospinning device 10 is sprayed onto the filter substrate 5 located on the collector 4 through the nozzle 2 And the spraying liquid sprayed on the filter substrate 5 is accumulated to form a laminate of nanofibers. The auxiliary belt 6 is driven by the rotation of the auxiliary belt rollers 7 provided on both sides of the collector 4 to transfer the filter base material 5 to the blocks 20 at the rear end of the electrospinning device 10 ) So as to repeatedly perform the above-described process.

5, the nozzle block 3 includes a plurality of nozzles 2 arranged upward from the discharge port, a tube 43 formed of a row of nozzles 2, a spinning solution storage tank 44, And a spinning liquid circulating pipe (45).

First, the spinning liquid storage tank 44 connected to the spinning liquid main tank to receive and store the spinning solution is connected to the nozzle 2 through the spinning liquid circulating pipe 45 by the metering pump (not shown) And the spinning solution is supplied to the spinning solution. Here, the tube 43 having a plurality of nozzles 2 in a row is supplied with the same spinning solution from the spinning solution storage tank 44, but a plurality of spinning solution storage tanks are provided, It is also possible to supply different kinds of spinning liquids to the tubular bodies 43 and radiate them.

When radiated from the discharge port of the plurality of nozzles 2, the overflowed solution is moved to the overflow solution storage tank 41. The overflow solution storage tank 41 is connected to a spinning solution main tank (not shown) so that the overflow solution can be reused for spinning.

The main controller 30 controls the amount of spinning solution supplied to the nozzle block 3 and controls the voltage of the voltage supply device 1 for each block 20 And the conveying speed V of each block can be controlled according to the thickness of the nanofiber and the filter substrate measured by the thickness measuring device 9. [

The thickness measuring device 9 of the present invention is disposed opposite the filter substrate 5 located at the front end and the rear end of the block 20 and having the nanofibers stacked therebetween. The thickness measuring device 9 is connected to the main controller 30 for adjusting the radiation conditions of the electrospinning device 10 so that the thickness measuring device 9 measures the thickness of the nanofiber and the filter substrate 5 The main controller 30 controls the conveying speed V of each block 20 on the basis of one value. For example, if the thickness of the discharged nanofibers in each block 20 in the electrospinning is measured to be thinner, the feeding speed V of the block 20 located at the rear end is decreased, . Further, the main controller 30 increases the discharge amount of the nozzle block 3 and adjusts the intensity of the voltage of the voltage generator 1 to increase the discharge amount of the nanofibers per unit area to uniformly control the thickness of the nanofibers It is possible.

The thickness measuring device 9 is provided with a thickness measuring part consisting of a pair of ultrasonic longitudinal waves and a transverse wave measuring method for measuring the distance from the nanofiber on which the nanofibers are laminated to the filter base 5 by an ultrasonic measuring method , And the thickness of the nanofiber and the filter substrate 5 is calculated on the basis of the distance measured by the pair of ultrasonic measuring devices, as shown in FIG. More specifically, the ultrasonic longitudinal wave and the transverse wave are projected to the filter substrate 5 on which the nanofibers are laminated, and the time during which each ultrasonic signal of the longitudinal wave and the transverse wave reciprocates on the filter base 5, From the predetermined arithmetic expression using the propagation time of the measured longitudinal waves and transverse waves and the temperature constants of longitudinal and transverse wave propagation speeds and propagation speeds at the reference temperature of the filter substrate 5 on which the nanofibers are stacked, It is a thickness measuring device that calculates the thickness of a dead body.

The electrospinning device 10 used in the present invention is configured such that when the thickness deviation P of the nanofiber is less than a predetermined value, the feed velocity V is not changed from the initial value, , It is possible to control the feed speed V to be changed from the initial value, so that it becomes possible to simplify the control of the feed speed V by the feed speed V control device. In addition to the control of the conveying speed V, the discharge amount and the voltage intensity of the nozzle block 3 can be adjusted. When the thickness deviation P is less than the predetermined value, the discharge amount of the nozzle block 3 and the intensity of the voltage It is possible to control the amount of discharge and the intensity of the voltage of the nozzle block 3 to be changed from the initial value when the deviation amount P is equal to or larger than the predetermined value without changing the initial value, It becomes possible to simplify control of the discharge amount and the intensity of the voltage.

The block 20 of the electrospinning device 10 is divided into a front end block 20a located at the front end portion and a rear end block 20b located at the rear end portion according to the radiation position. In the embodiment of the present invention, the number of blocks is limited to two, but it is also possible to have two or more blocks.

In the present invention, the same polymeric spinning solution is radiated in each of the blocks 20a and 20b, but it is also possible to spin different kinds of polymer spinning solutions for each block, and two or more different It is also possible that the polymer spinning solution is radiated. When at least two different kinds of spinning solutions are supplied and radiated for each block 20, it is possible that the polymer nanofibers of different kinds are successively laminated.

In addition, it is also possible to manufacture hybrid nanofibers by constituting two or more polymer types of the spinning solution to be used.

It is also possible to continuously laminate nanofibers having different fiber diameters by varying the intensity of the voltage applied to each block 20, and even in one block 20, the nozzles 2 It is also possible to form a hybrid nanofiber in which two or more polymers are electrospun and laminated.

On the other hand, a laminating device 19 is provided at the rear end of the electrospinning device 10 of the present invention. The laminating device 19 applies heat and pressure to the filter base material on which the nanofibers are laminated, that is, the nanofiber filter material is wound on the winding roller 12 to form a nanofiber filter material.

The nanofibers produced as shown in FIG. 1 by electrospinning by the electrospinning method have a different lamination of nanofibers according to the direction of air flow.

In the case of implementing the filter using the nanofibers of the present invention, the inorganic polymer is electrospun with nanofibers having a large fiber diameter in the air inlet direction of the base material, and polyacrylonitrile, polyether sulfone, polyimide, Vinylidene fluoride, or meta-aramid is elected and electrospun nanofiber having a fine fiber diameter to laminate.

More simply stated, when the upper surface of the substrate is in the air inflow direction, the inorganic polymer is electrospun with the nanofibers having a large fiber diameter on the upper surface of the substrate, and the lower surface of the substrate is in the air discharge direction. Therefore, polyacrylonitrile, polyethersulfone, Refers to the formation of nanofibers on both sides of a substrate by electrospinning with fine nanofibers having a fiber diameter selected from one or more of meso, polyamide, meta-aramid, and polyvinylidene fluoride.

Hereinafter, a method for producing nanofibers of an inorganic polymer and a heat-resistant polymer, polyacrylonitrile, polyethersulfone, polyimide, meta-aramid, polyamide, and polyvinylidene fluoride used in the present invention will be described.

First, an 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.

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 in the mid-1980s when Yajima of Nippon Carbon sold silicon carbide (SiC) fiber (trade name: NICALON) synthesized using Polycarbosilane (PCS) 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.

A method of preparing an inorganic polymer nanofiber by electrospinning the inorganic polymer of the present invention will be described.

First, a spinning solution is prepared by dissolving an inorganic polymer (Meta aramide) in an acetone solvent. The spinning solution containing the inorganic polymer is stored in the spinning liquid main tank, metered by a separate metering pump, and supplied to the spinning solution dropping device in a fixed amount.

When the nanocomposite is made of an inorganic polymer or used in the production of an active layer of a composite membrane, the number average molecular weight of the inorganic polymer is 5,000 to 100,000. When the nanofiber is prepared by mixing or adding to other polymer or inorganic material, To 100,000.

The inorganic polymer may be a siloxane group or a siloxane group alone or may be a copolymer of a silane group or a siloxane group with a polymer of monomethacrylate, vinyl, hydride, distearate, bis (12-hydroxy-stearate) (Aminopropyl-aminopropyl) aminopropyl, mono- and di (aminopropyl) mono-, di-, tri-, and tetra- ) Dimethoxysilyl) ether may be used.

The heat-resistant polymer resin is composed of a polymer having a melting point of 180 ° C or higher so that the nanofiber layer does not collapse due to melting even when the temperature is continuously increased. For example, the heat-resistant polymer resin constituting the heat-resistant polymer microfine fiber layer may be selected from the group consisting of polyamide, polyimide, polyamideimide, poly (meta-phenylene isophthalamide), polysulfone, polyetherketone, polyetherimide, , Aromatic polyesters such as polytrimethylene terephthalate and polyethylene naphthalate, polytetrafluoroethylene such as polytetrafluoroethylene, polydiphenoxaphospazene and polybis [2- (2-methoxyethoxy) phosphazene] Such as polyurethane copolymers including polyglycerol, polyglycerol, polyglycerol, polyglycerol, polyglycerol, polyglycerol, polyetherketone, polyglycerol, polyglycerol, polyglycerol, polyglycerol and polyetherurethane; cellulose acetate, cellulose acetate butyrate, cellulose acetate propionate and the like. A resin with no melting point refers to a resin that burns without experiencing a melting process even when the temperature rises above 180 ° C. The heat-resistant polymer resin used in the present invention is preferably soluble in an organic solvent for ultra-fine fiberization such as electrospinning.

Among the heat-resistant polymer resins, the most preferable heat-resistant polymer resin in the present invention is meta-aramid, polyacrylonitrile, polyethersulfone, polyimide, polyamide, and polyvinylidene fluoride.

The meta-aramid is the first high heat-resisting aramid fiber that can be used at 350 in a short time and 210 at continuous use. It is carbonized without melting or burning like other fibers when exposed to temperatures above this range. 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 is not only strong in its original strength but also easily oriented in the fiber axis direction in the spinning stage to improve the crystallinity, .

 In general, 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 300,000 to 500,000. Meta-oriented aromatic polyamides. The polymer should have a fiber forming molecular weight, and may comprise a polyamide homopolymer, a copolymer and mixtures thereof, which are mainly 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); NewStar TM meta-aramid available from Yantai Spandex Co. Ltd, Shandong, China; And Chinfunex (registered trademark) Aramid 1313, available from Guangdong Charming Chemical Co., Ltd., Shinshu, Guangdong, China.

The organic solvent is not particularly limited as long as it can sufficiently dissolve the polymer and is applicable to the charge induction spinning method. In addition, when the porous polymer nanofiber is produced by the charge-induced spinning method, since the organic solvent is almost removed, Anything that affects the characteristics may also be used. For example, propylene carbonate, butylene carbonate, 1,4-butyrolactone, diethyl carbonate, dimethyl carbonate, 1,2-dimethoxyethane, 1,3-dimethyl-2-imidazolidinone, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, polyethylene sulfolane, tetraethylene glycol dimethyl ether, acetone, alcohol or mixtures thereof Can be selected and used.

A method of preparing a porous nanofiber by electrospinning a heat-resistant polymer polyacrylonitrile of the present invention and coating inorganic particles on the polyacrylonitrile (PAN) nanofiber will be described.

A spinning solution is prepared which is dissolved in dimethylformamide (DMF) and dimethylacetamide (DMAc), which are solvents mainly used for polyacrylonitrile.

Polyacrylonitrile resins are copolymers made from mixtures of acrylonitrile and monomers. Frequently used monomers are vinyl compounds including butadiene styrene vinylidene chloride. Of course, the same acrylic fiber contains at least 85% acrylonitrile, and the mode acrylic contains 35-85% acrylonitrile. If other monomer units are included, desired properties such as increasing the affinity of the fiber to the dye can be obtained.

More particularly, in the production of acrylonitrile-based copolymers and spinning solutions. Acrylonitrile-based copolymer is used, it is possible to produce a nanofiber by electrospinning with little contamination of the nozzle, excellent electrospinning property, increase in solubility in a solvent and good mechanical properties have.

It is preferable to use it in a range that satisfies the usage amount of the acrylonitrile monomer, the hydrophobic monomer and the hydrophilic monomer. When the polymer is polymerized, the weight% of the acrylonitrile monolith 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% Even if a cross-linking agent is added thereto, it is difficult to form a stable jet (JET) in the case of electrospinning as well as inducing contamination of the nozzle. If the content is more than 99%, the spinning viscosity is too high to spin, and even if an additive capable of lowering the viscosity is added thereto, the diameter of the superfine fiber becomes too large and the productivity of electrospinning 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 the crosslinking agent must be increased so that the stability of electrospinning can be secured and deterioration of the mechanical properties of the nanofiber can be prevented.

The polymerization degree of the polyacrylonitrile is 1,000 to 1,000,000, preferably 2,000 to 1,000,000. When the polymerization degree is lower than 1,000, the efficiency of the battery tends to decrease due to dissolution or swelling in the carbonate-based electrolyte and progress of the cycle, leading to desorption of the electrode from the collector. When the polymerization degree is higher than 1,000,000, , The viscosity of the electrode mixture is increased and it is difficult to handle.

The hydrophobic monomer may be at least one selected from the group consisting of ethylenic compounds such as methyl acrylate, ethyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, vinyl acetate, vinyl pyrrolidone, vinylidene chloride, vinyl chloride, It is preferable to use at least one selected.

In the present invention, the hydrophilic monomer may be selected from the group consisting of acrylic acid, allyl alcohol, methallyl alcohol, hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, butanediol monoacrylate, dimethylaminoethyl acrylate, It is preferable to use any one or more selected from ethylene-based compounds such as acid, vinylsulfonic acid, allylsulfonic acid, methallylsulfonic acid, and para styrenesulfonic acid, and polyvalent acids or derivatives thereof.

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

Polyethersulfone (PES) is a transparent amorphous resin.

That is, since the polyether sulfone (PES) is amorphous, there is little deterioration of physical properties due to temperature rise, and the temperature dependence of the flexural modulus is very small, so that it hardly changes at 100 to 200 ° C. The load-strain temperature is 200 to 220 占 폚, and the glass transition temperature is 225 占 폚. In addition, the creep resistance up to 180 占 폚 is the most excellent among the thermoplastic resins, and has the characteristic of being resistant to hot water and steam at 150 to 160 占 폚. Therefore, due to the above characteristics of polyethersulfone, it is used for optical disks, magnetic disks, electric and electronic fields, hot water fields, automobile fields, heat resistant paints and the like.

Polyethersulfone has properties of improving heat resistance and thermal dimensional stability, and is not difficult to dissolve in a solvent. The molecular weight of the polyethersulfone is in the range of 8,000 to 200,000 in viscosity average molecular weight. When the viscosity average molecular weight is less than 8,000, the strength of the molded product is weak, which is easily undesirable. On the other hand, if it exceeds 200,000, the melt flowability tends to deteriorate, and it is difficult to obtain a good molded article. More preferably, the viscosity ranges from 400 to 1,200 cps. Examples of the solvent include dichloromethane, chloroform, tetorohydrofuran, methanol, ethanol, butanol, toluene, xylene, acetone, ethyl acetate, dimethylformamide, N-methyl-2-pyrrolidinone, dimethylacetamide But are not limited to these.

The polyvinylidene fluoride (PVDF) resin is one of the fluoro-based polymers, and the fluororesin contains fluorine, which is excellent in thermal and chemical properties. In producing a spinning solution in which polyvinylidene fluoride is dissolved in an appropriate organic solvent, the polyvinylidene fluoride includes a homopolymer of vinylidene fluoride or a copolymerized polymer containing vinylidene fluoride in a molar ratio of 50% or more , A homopolymer is more preferable from the viewpoint of excellent strength of the polyvinylidene fluoride resin. When the polyvinylidene fluoride resin is a copolymer polymer, known copolymerizable monomers copolymerized with vinylidene fluoride monomers may be suitably used For example, fluorine-based monomers and chlorine-based monomers can be suitably used.

The weight average molecular weight (Mw) is not particularly limited, but is preferably 10,000 to 500,000, more preferably 50,000 to 500,000, and when the weight average molecular weight of the polyvinylidene fluoride resin is less than 10,000, The fibers can not obtain sufficient strength. When the number average molecular weight exceeds 500,000, the handling of the solution is not easy, and the processability is deteriorated, making it difficult to obtain uniform nanofibers.

Polyimide is dissolved in a mixed solvent of tetrahydrofuran (THF) / dimethylacetamide (DMAc) (THF / DMAc) to prepare a spinning solution.

In the present invention, poly (amic acid) (PAA) was synthesized and dissolved in a THF / DMAc mixed solvent of tetrahydrofuran (THF) and dimethylacetamide (DMAc) to prepare polyamic acid , Polyimide nanofibers using electrospinning, and polyimide (PI) nanofibers through imidization can be prepared.

The polyimide is prepared by a two-step reaction.

In the first step, polyamic acid is prepared by adding 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, And purity control. As the solvent used in this step, organic polar solvents such as dimethylacetamide (DMAc), dimethylformamide (DMF) and N-methyl-2-pyrrolidone (NMP) are mainly used. Examples of the anhydride include pyromellitic dianhydride (PMDA), benzophenonetetracarboxylic dianhydride (BTDA), 4,4'-oxydiphthalic anhydride (4,4'-oxydiphthalic anhydride) ODPA), biphenyltetracarboxylic dianhydride (BPDA), and bis (3,4'-dicarboxyphenyl) dimethylsilane dianhydride (SIDA). One can be used. Examples of the diamine include 4,4'-oxydianiline (ODA), p-penylene diamine (p-PDA) and o-penylenediamine o-PDA) may be used.

Reaction 1. Preparation of polyamic acid

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

In the re-impregnation method, a polyamic acid solution is added to an excessive 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 imidation method is a method in which the polyamic acid solution is heated to 150 to 200 ° C to thermally imidize the resin. In the simplest process or crystallization degree, the amine exchange reaction occurs when the amine type solvent is used, have.

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

Reaction formula 2. Preparation of polyimide

The polyamide is selected from the group consisting of polyamide 6, polyamide 66 and polyamide 46, and is divided into aromatic polyamide and aliphatic polyamide. Representative aliphatic polyamide is nylon. Nylon was originally a trademark of DuPont, 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 it is produced by ring-opening polymerization of caprolactam in order to produce it. Nylon 6 means that caprolactam has 6 carbon atoms.

Nylon 66 has excellent heat resistance, excellent self-extinguishing properties and abrasion resistance, and has very similar properties to nylon 6 as a whole. Nylon 66 is made by dehydration condensation polymerization of hexamethylenediamine and adipic acid.

 Nylon 46 is prepared by polycondensation of tetramethylenediamine and adipic acid. The raw material diaminobutane (DAB) is prepared from the reaction of acrylonitrile with hydrogen cyanide. In the first stage of the polymerization operation, a salt is formed from DAB and adipic acid, and the polymerization reaction is carried out under appropriate pressure to convert it into a prepolymer And the solid of Prepolymer is treated at about 250 in the presence of nitrogen and steam to polymerize at high temperature to produce nylon 46.

Hereinafter, a method for producing a filter material using the heat-resistant polymer resin will be described in detail.

First, an inorganic polymer is dissolved in an organic solvent to prepare a first spinning solution. The first spinning liquid is supplied to the spinning liquid main tank of the electrospinning device 10 and is supplied to the spinning liquid main tank. The first spinning liquid is supplied to a plurality of nozzle blocks 3 In a constant amount in the nozzle 2 of the nozzle.

The inorganic polymer solution supplied to each of the nozzles 2 is injected onto the substrate 5 while being radiated and focused on the collector 4 with a high voltage applied thereto through the nozzle 2 to form the inorganic polymer nanofibers. The inside of the unit in which the inorganic polymer nanofibers are stacked in the front end block 20a of the electrospinning apparatus 10 is provided with a feed roller 11 operated by driving of a motor (not shown) And is transferred from the front end block 20a into the rear end block 20b by rotation of the auxiliary belt 6 driven by rotation.

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The base material having the top and bottom portions reversed in position is a base material in which the solution of one selected from polyacrylonitrile, polyethersulfone, polyimide, polyamide, meta-aramid, and polyvinylidene fluoride is injected into the rear end block 20b The second spinning liquid supplied to the tank is continuously supplied in a constant amount into the plurality of nozzles 2 of the nozzle block 3 to which a high voltage is applied through the metering pump.

At this time, the front end block 20a is referred to as a first feeding device and the rear end block 20b is referred to as a second feeding device.

More specifically, in the first main tank for storing the electrospinning liquid of the present invention, the inorganic polymer spinning solution is added to the second main tank. The second main tank contains polyacrylonitrile, methaaramide, polyethersulfone, polyimide, Vinylidene fluoride, and the first and second supply devices are designed to have a generally closed cylindrical shape so that the spinning solution continuously injected from the spinning liquid tank is divided into sections Respectively. The nozzle block is divided into two sections, and the first and second feeding devices are provided in the respective sections. The spinning liquids each contain an inorganic polymer solution for the first feeding device and polyacrylonitrile, polyethersulfone, poly A solution of a polymer resin selected from a polyamide, a polyamide, a meta-aramid, and a polyvinylidene fluoride is used.

The inorganic polymer and the heat-resistant polymer nanofiber filter on both sides of the fabricated substrate are produced by the air filter process, and the inorganic polymer and the heat-resistant polymer nanofiber filter on both sides of the substrate are arranged in the direction of air inflow with the side of the nanofiber of the inorganic polymer resin, A nanofiber selected from polyacrylonitrile, polyethersulfone, polyimide, polyamide, meta-aramid, and polyvinylidene fluoride, which is another heat-resistant polymer, is disposed. Since the gas turbine air filter introduces high temperature air into the air inlet direction when using the air filter, it can extend the life of the filter because it uses a polymer resin with good heat resistance.

In addition, the life of the filter can be extended by disposing nanofibers having a larger diameter of nanofibers in the air inlet direction and nanofibers having a smaller diameter of the nanofibers in the air discharge direction.

In the present invention, the voltage of the front end block 20a of the electrospinning device 10 is lowered to form laminated nanofibers having a large fiber diameter on the base material, the voltage of the rear end block 20b is increased, The thin nanofiber is formed into a double-sided nanofiber filter on the backside of a substrate having no nanofibers having a large fiber diameter. However, it is also possible that the nanofibers having a small fiber diameter are radiated from the front end block 20a and the nanofibers having a large fiber diameter are radiated from the rear end block 20b.

Alternatively, in the present invention, the bottom-up electrospinning can be fabricated by using a hybrid electrospinning device in which nanofibers having a small fiber diameter are top down and fibers having a large fiber diameter are top down.

The length of the section defined by the nozzle block can be adjusted according to the thickness of each layer constituting the filter media.

Further, the collector of the grounded collector can be controlled to be moved in one direction, and a continuous process of forming a continuous nanofiber layer can be performed. The present invention can simplify the manufacturing process of the double-sided filter material through such a process, .

The thickness of the polymer film, the diameter of the fiber, and the mechanical characteristics of the shape of the fiber can be arbitrarily controlled by controlling the electrospinning process conditions such as the intensity of the applied voltage, the kind of the polymer solution, the viscosity of the polymer solution, have.

The preferred electrospinning process conditions are that the spinning liquid transferred to the spinning liquid supply tube is discharged to the collector through the multiple tubular nozzles to form fibers, and the nanofibers electrospun from the tubular nozzle are discharged by the air injected from the air supply nozzle It spreads widely and is collected on the collector to widen the collecting area and to make the density of the particles uniform. The excess flushing solution which is not fibrous in the tubular nozzle is sucked in the overflow removing nozzle and then moved back to the flushing solution supply plate through the temporary storage plate of the overflow liquid.

When manufacturing nanofibers, it is preferable that the speed of air in the air supply nozzle is 0.05 m to 50 m / sec, more preferably 1 to 30 m / sec. If the velocity of the air is less than 0.05 m / sec, the collecting area of the nanofibers is low and the collecting area is not greatly improved. If the velocity of the air exceeds 50 m / sec, the velocity of the air is too fast, The more serious problem is attached to the collector in the form of a thick thread rather than the nanofiber, thereby causing a serious problem that the capability of forming the nanofiber is remarkably lowered.

In addition, the spinning solution which is excessively supplied to the top of the nozzle block is forcibly transferred to the spinning liquid main tank by the spinning solution discharging device.

At this time, in order to promote the formation of the fiber by the electric force, a voltage of 1 kV or more, more preferably 20 kV or more, generated by the voltage generator is applied to the conductive plate and collector provided at the lower end of the nozzle block. It is more advantageous in terms of productivity to use an endless belt as the collector. The collector preferably reciprocates a predetermined distance in the left and right directions to uniform the density of the nanofibers.

When the nanofibers formed on the collector are wound on the winding roller through the web supporting roller, the manufacturing process of the nanofibers is completed.

The manufacturing apparatus can increase the collecting area to uniform the density of the nanofibers and effectively prevent the droplet phenomenon, thereby improving the quality of the nanofibers and enhancing the fiber-forming effect by the electric force, And nanofibers thereof can be mass-produced. In addition, the width and thickness of the nonwoven fabric and the filament can be freely changed and adjusted by arranging the nozzles composed of a plurality of pins in block form.

In addition, when the heat-resistant polymer is spun as described above, it is most preferable to spin the polymer under environmental conditions of a temperature range of 30 to 40 DEG C and a humidity of 40 to 70% depending on the polymer material.

In the present invention, the diameter of the nanofiber forming the multi-layer filter media is preferably 30 to 1000 nm, more preferably 50 to 500 nm.

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail with reference to examples. However, the embodiments according to the present invention can be modified into various other forms, and the scope of the present invention should not be construed as being limited to the embodiments described below. The embodiments of the present invention are provided to enable those skilled in the art to more fully understand the present invention.

[Example 1]

In the first section, polysiloxane (DOW CORNINGMB50-010) having a number average molecular weight of 50,000, which is one of the inorganic polymers, was dissolved in acetone solvent to prepare 20 mass% polysiloxane dope. In the second section, polyamic acid having a weight average molecular weight of 100,000 (Dope) is prepared by dissolving poly (amic acid) (PAA) in a mixed solvent (THF / DMAc) of tetrahydrofuran (THF) and dimethylacetamide (DMAc). Polysiloxane nanofibers having a thickness of 3 탆 and an average diameter of 500 nm under a condition of a distance between the electrode and the collector of 40 cm, an applied voltage of 15 kV, a spinning liquid flow rate of 0.1 mL / h, a temperature of 22 캜 and a humidity of 20% A nanofiber layer was formed by spinning polyamic acid nanofibers such that the collector had a thickness of 3 탆 and an average diameter of 200 nm on the back surface of the substrate on which the polysiloxane nanofibers were not stacked in the second section after being formed on the meta-aramid base material Thereafter, the polyamic acid nanofibers are imidized with polyimide nanofibers by heating at 200 DEG C to form a filter material in which nanofibers are laminated on both sides of the substrate.

[Example 2]

In the first section, polysiloxane (DOW CORNING MB50-010) having a number average molecular weight of 50,000, which is one of the inorganic polymers, was dissolved in an acetone solvent to prepare 20 mass% polysiloxane dope. In the second section, a viscosity of 50,000 cps and a solid content of 20 weight% The meta-aramid is dissolved in dimethylacetamide (DMAc) to produce meta-aramid dope. A polysiloxane solution having a thickness of 3 mu m and an average diameter of 500 nm in an electrospinning condition of a distance of 40 cm, an applied voltage of 15 kV, a spinning liquid flow rate of 0.1 mL / h, a temperature of 22 DEG C and a humidity of 20% A nanofiber layer is formed by radiating meta-aramid nanofibers so that the collector has a thickness of 3 탆 and an average diameter of 200 nm on the back surface of the substrate on which the polysiloxane nanofibers are not laminated in the second section.

[Example 3]

In the first section, polysiloxane (DOW CORNINGMB50-010) having a number average molecular weight of 50,000, which is one of the inorganic polymers, was dissolved in acetone solvent to prepare 20 mass% polysiloxane dope. In the second section, a viscosity of 1,200 cps and a solid content of 20 wt% Of polyether sulfone is dissolved in dimethylacetamide (DMAc), and polyethersulfone electrospinning solution (Dope) is dissolved to prepare spinning solution. Polysiloxane nanofibers having an average diameter of 500 nm and a thickness of 3 mu m were subjected to electrospinning at a distance of 40 cm from the electrode, an applied voltage of 15 kV, a spinning solution flow rate of 0.1 mL / h, a temperature of 22 DEG C and a humidity of 20% A polyether sulfone was spun on the back surface of the substrate on which the polysiloxane nanofibers were not laminated in the second section so as to have a thickness of 3 m and an average diameter of 200 nm to form nanofibers, Thereby forming a filter material in which nanofibers are laminated on both sides.

[Example 4]

In the first section, a polysiloxane (DOW CORNINGMB50-010) having a number average molecular weight of 50,000, which is one of the inorganic polymers, was dissolved in an acetone solvent to prepare a 20 mass% polysiloxane dope. In the second section, polyacryloyl Nitrile (Korea-Japan synthesis) is dissolved in dimethylformamide (DMF) to prepare a spinning solution. Polysiloxane nanofibers having a thickness of 3 mu m and an average diameter of 500 nm in an electrospinning condition having a distance of 40 cm from the electrode and an applied voltage of 15 kV, a spinning solution flow rate of 0.1 mL / h, a temperature of 22 DEG C and a humidity of 20% And the collector was moved at a constant speed, polyacrylonitrile was spun in such a manner that the thickness of the substrate was 3 μm and the average diameter was 200 nm on the back surface of the substrate on which the polysiloxane nanofibers were not laminated in the two sections to laminate the nanofibers, To form a filter material in which nanofibers are laminated.

[Example 5]

In the first section, polysiloxane (DOW CORNING MB50-010) having a number average molecular weight of 50,000, which is one of the inorganic polymers, was dissolved in acetone solvent to prepare 20 mass% polysiloxane dope. In the second section, a weight average molecular weight (Mw) (KYNAR 741) was dissolved in dimethylacetamide (DMAc) solvent to prepare a spinning liquid. The distance between the electrode and the collector was set to 40 cm, the applied voltage was 15 kV, the spinning liquid flow rate was 0.1 mL / h, the temperature was 22 ° C , And a humidity of 20% on a meta-aramid base having a basis weight of 30 gsm and a collector moved at a constant rate to form polysiloxane nanofibers stacked in two sections Polyvinylidene fluoride was spun in such a manner that the thickness thereof was 3 占 퐉 and the average diameter was 200 nm on the backside of the base material, and the nanofibers were laminated to form a laminate of nanofibers It is formed in the filter media.

[Example 6]

In the first section, polysiloxane (DOW CORNING MB50-010) having a number average molecular weight of 50,000, which is one of the inorganic polymers, was dissolved in acetone solvent to prepare 20 mass% polysiloxane dope. In the second section, 100% A nylon 6 homopolymer was dissolved in a solvent of tetrafluoroacetate (TFA) and dichloromethane (Dcm) in a weight ratio of 5: 5 to prepare an electroblastic spinning solution. The distance between the electrode and the collector was 40 cm, Polysilox nanofibers having a thickness of 3 mu m and an average diameter of 500 nm were formed on a meta-aramid base having a basis weight of 30 gsm under electrospinning conditions of 15 kV, spinning liquid flow rate of 0.1 mL / h, temperature of 22 DEG C and humidity of 20% The nanofibers were laminated by irradiating meta-aramid so that the thickness was 3 mu m and the average diameter was 200 nm on the back surface of the substrate where the polysiloxane nanofibers were not laminated in the two sections, It forms a nanofiber filter media are stacked.

[Comparative Example 1]

In the first section, a meta-aramid dope is prepared by dissolving meta-aramid having a viscosity of 50,000 cps and a solid content of 20% by weight in dimethylacetamide (DMAc). A 6-μm-thick meta-aramid nanofiber was laminated on a meta-aramid substrate having a basis weight of 30 gsm under the conditions of a distance of 40 cm from the electrode, an applied voltage of 15 kV, a spinning liquid flow rate of 0.1 mL / h, a temperature of 22 ° C. and a humidity of 20% Thereby forming a filter medium.

- Evaluation of heat shrinkage

The filters of the examples and comparative examples were cut into 3 cm x 3 cm and stored at 190 ° C for 30 minutes, and the heat shrinkage ratio was evaluated and shown in Table 1.

- Filtration efficiency measurement -

The DOP test method was used to measure the efficiency of the fabricated nanofiber filter. The DOP test method measures the dioctyl phthalate (DOP) efficiency with an automated filter analyzer (AFT) of TSI 3160 from TSI Incorporated and measures the permeability, filter efficiency and differential pressure of the filter media material .

The automation analyzer is a device that automatically measures the velocity of air, DOP filtration efficiency, air permeability (permeability), etc. by passing DOP through the filter sheet by making particles of desired size and is a very important device for high efficiency filter.

The DOP filtration efficiency (%) is defined as:

DOP transmittance (%) = 1 - 100 (DOP concentration downstream / DOP concentration upstream)

The filtration efficiencies of Examples and Comparative Examples were measured by the above-mentioned method and shown in Table 3.

Example 1 Example 2 Example 3 Example 4 Example 5 Example 6  Comparative Example 1 Heat shrinkage
(%) 2.6 2.8 2.7 2.8 2.9 2.8 5.0

Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Comparative Example 1 0.35um DOP% 98 97 98 98 98 97 85

As described above, the multi-layered nanofiber filter manufactured by the embodiment of the present invention has higher heat shrinkage and filtration efficiency than the comparative example.

1, 1a, 1b: voltage generating device 2, 115, 135: nozzle
3, 113, 133: nozzle block 4, 137, 117: collector
5: substrate 6: auxiliary belt
7: Auxiliary belt roller 8: Case
9: thickness measuring device 10: electrospinning device
11, 120: feed roller 12, 118: take-up roller
19: laminating apparatus 20, 20a, 20b: block
30: main control device 41: overflow solution storage tank
43: tubular body 44: spinning liquid storage tank
45: Fluid distribution pipe
200: Inorganic polymer nanofiber with large fiber diameter
300: Heat-resistant polymer nanofibers having a small fiber diameter
100: Combined electrospinning device 121: Support
119: Feed roller
110, 110 ': bottom-up electrospinning device 111, 131: main tank
130, 130 ': Top-down electrospinning device

Claims (11)

An inorganic polymer nanofiber that is a silane group or a siloxane group alone polymer laminated by electrospinning on one surface of a substrate, or a copolymer polymer of a silane group or a siloxane group; And
Wherein the inorganic polymer nanofibers are selected from polyacrylonitrile, polyethersulfone, polyimide, meta-aramid or polyamide laminated by electrospinning on the back surface of a substrate on which the inorganic polymer nanofibers are not laminated, one selected from polyvinylidene fluoride Heat-resistant polymer nanofibers;
Wherein the heat-resistant high-heat-resistant double-sided nanofiber filter material is a thermosetting resin.
delete delete The method according to claim 1,
The substrate double-sided nanofiber filter material having improved heat resistance is characterized in that nanofibers having a larger diameter of the nanofibers are arranged in the air inlet direction and nanofibers having a smaller diameter of the nanofibers are disposed in the air discharge direction Two-sided nanofiber filter media with improved heat resistance.
The method according to claim 1,
Wherein the base material is a cellulose or a meta-aramid base material.
A manufacturing method of a filter material for electrospinning a polymer on both sides of a substrate,
A solution prepared by dissolving an inorganic polymer, which is a silane group- or siloxane-group-only polymer, or a copolymeric polymer of a silane group or a siloxane group, in an organic solvent is added to the first block in the form of polyacrylonitrile, polyether sulfone, polyimide, Supplying a solution prepared by dissolving one heat-resistant polymer selected from polyvinylidene fluoride or polyamide in an organic solvent to a nozzle connected to the second block;
Forming a laminate by electrospinning the inorganic polymer nanofibers on a substrate in a nozzle connected to the block located in the first block;
In the nozzle connected to the block located in the second block, the heat-resistant polymer is continuously electrospun on the back surface of the substrate on which the inorganic polymer nonwoven fabric is not laminated to form a laminate;
Surface nanofiber filter material having improved heat resistance.
delete delete The method according to claim 6,
Wherein the base material is a cellulose or a meta-aramid base material.
The method according to claim 6,
In the manufacturing method of the substrate double-sided nanofiber filter material with improved heat resistance, nanofibers having a large fiber diameter are arranged in the air inlet direction and nanofibers having a small fiber diameter are arranged in the air discharge direction Wherein the method comprises the steps of:
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