WO2016171329A1 - Electrospinning device comprising temperature adjustment device, method for manufacturing nanofiber filter using same, and nanofiber filter manufactured thereby - Google Patents

Abstract

The present invention relates to an electrospinning device comprising a temperature adjustment device, a method for manufacturing a nanofiber filter using the same, and a nanofiber filter manufactured thereby. The electrospinning device comprises: an overflow system for reusing a spinning solution that has not become nanofibers; and a temperature adjustment device for maintaining the viscosity of the spinning solution that is electrospun, instead of maintaining the concentration thereof, such that no diluent is used. In addition, the present invention relates to a method for manufacturing a nanofiber filter using electrospinning, wherein an upward electrospinning device, which comprises a plurality of nozzle tube bodies inside the upward electrospinning device, is used such that the basis weight of a nanofiber differs in the longitudinal direction (MD) or in the transverse direction (CD), the method being characterized in that a nozzle block is designed to comprise two, three, or nine parts in the longitudinal direction (MD) or in the transverse direction (CD), and the basis weight of a specific part of the same nanofiber can be adjusted differently such that the basis weight of the nanofiber differs in the longitudinal direction (MD) or in the transverse direction (CD).

Description

[Correction 24.07.2015 by Rule 26] 전기 Electrospinning apparatus including temperature control device, method of manufacturing nanofiber filter using the same, and nanofiber filter manufactured by the method

The present invention relates to an electrospinning apparatus including a temperature control device, a method of manufacturing a nanofiber filter using the same, and a nanofiber filter manufactured by the method, and more specifically, to a temperature higher than that of a conventional electrospinning temperature. The present invention relates to a manufacturing apparatus and method for producing a nanofiber filter by electrospinning a spinning solution containing a polymer of high concentration at a temperature, and a nanofiber filter manufactured by the manufacturing method.

In addition, an overflow system for reusing non-nanofiber spinning solutions is available.

Compared to maintaining the concentration of the electrospinning spinning solution, by including a temperature control device for maintaining the viscosity of the spinning solution, an electrospinning device comprising a temperature control device, characterized in that a diluent is not used, nanofibers using the same A method for producing a filter and a nanofiber filter produced by the method.

In addition, the nozzle body provided with a plurality of pin-shaped nozzles is arranged in the MD direction or the CD direction on the substrate provided in the unit of the electrospinning apparatus, and each nozzle body and nozzles are controlled to control the MD or CD direction of the substrate. Electrospinning apparatus comprising a temperature control device for adjusting the basis weight of the nanofiber filter laminated on the substrate by controlling the radiation amount of the polymer spinning solution electrospun, a method of manufacturing a nanofiber filter using the same, and as a manufacturing method It relates to a manufactured nanofiber filter.

In general, nanofiber refers to a microfiber having a diameter of only tens to hundreds of nanometers, and the products such as nonwoven fabric, membrane, and braid composed of nanofibers are used for household goods, agriculture, clothing, and industrial use. Widely used.

In addition, it is used in various fields such as applied to defense materials such as artificial leather, artificial suede, sanitary napkins, garments, diapers, packaging materials, miscellaneous materials, various filter materials, medical materials of the gene carrier and bulletproof vest.

Nanofibers as described above are produced by electric fields. In other words, the nanofibers are subjected to a high voltage electric field to the polymer material as a raw material to generate an electric repulsive force inside the polymer material as a raw material, whereby the molecules are agglomerated into nano-sized yarns to produce and produce the nanofibers.

In this case, the stronger the electric field, the thinner the tearing of the polymer material as a raw material, and thus, the nanofibers having a fine diameter of 10 to 1000 nm can be obtained.

Electrospinning apparatus for manufacturing and producing such thin nanofibers is provided with a spinning solution main tank filled with spinning solution, a metering pump for quantitative supply of spinning solution, and a plurality of nozzles for ejecting spinning solution. It is configured to include a nozzle block that is located at the bottom of the nozzle, a collector for accumulating the fibers to be emitted and a voltage generator for generating a voltage.

The electrospinning device having the structure as described above comprises a metering pump for quantitative supply of the spinning solution main tank filled with the spinning solution and the polymer spinning solution filled in the spinning solution main tank and the polymer spinning solution in the spinning solution main tank. Discharge, but collectors are spaced apart from the nozzle and a high voltage to the collector in order to accumulate a nozzle block in which a plurality of nozzles in the form of pins are arranged and the polymer spinning solution to be injected is located on the top of the nozzle It consists of a unit containing the device.

In the method of manufacturing nanofibers using the electrospinning method, the spinning solution in the spinning solution filled with the spinning solution is quantitatively supplied to a plurality of nozzles to which a high voltage is applied through a metering pump, and the spinning solution is supplied to the nozzle. The nanofiber is spun and focused through a nozzle on a collector where high voltage is applied to form a nanofiber web, and a nanofiber web is formed on a long sheet conveyed to the units of the electrospinning apparatus, and the nanofibers are laminated. The elongated sheet is passed through each unit, and the nanofibers are repeatedly stacked and then laminated, embossed, heat and pressed, and needle punched to produce a nonwoven fabric.

  Here, the electrospinning device is divided into a bottom-up electrospinning device, a top-down electrospinning device, and a horizontal electrospinning device according to the direction of the position on the collector. That is, the electrospinning device is made of a configuration in which the collector is located at the top of the nozzle, a bottom-up electrospinning apparatus capable of producing uniform and relatively thin nanofibers, and the collector is configured in the bottom of the nozzle, It is possible to produce a thick nanofiber, it is divided into a top-down electrospinning device that can increase the production of nanofibers per unit time and a horizontal electrospinning device consisting of a collector and a nozzle arranged in a horizontal direction.

Upward electrospinning device is composed of a configuration in which the spinning solution is injected through the nozzle of the upward nozzle block, the spinning solution is sprayed is laminated on the lower surface of the support to form nanofibers.

According to the configuration described above, the long sheet of nanofiber web is laminated by spraying the spinning solution through a nozzle in one unit of the bottom-up electrospinning apparatus is transferred into another unit, and transferred into another unit. The nanofiber web is manufactured by repeatedly performing the above-described process, such as spraying the spinning solution through a nozzle on a long sheet, and stacking nanofibers again.

Here, the spinning solution injected through the nozzle of the nozzle block comprises a polymer polymer and a solvent.

  At this time, the polymer included in the spinning solution is laminated on the polymer long sheet to form nanofibers when spinning the spinning solution through the nozzle of the nozzle unit of the electrospinning apparatus, but the polymer polymer discharged to the end of the nozzle during the spinning process is not fibrous. If you do not fall into the nozzle block. In conventional electrospinning, the polymer polymer that is spun through the nozzle but is not fibrous and overflows is 70 to 90% by weight of the total polymer of the electrospun, and is fed back to the storage tank through the overflow system and from the storage tank. It has a structure that is supplied for electrospinning back to the nozzle block, so that the overflowed spinning solution can be recovered and reused as a raw material of nanofibers, thus saving raw materials and reducing raw material usage costs, thereby reducing nanofiber manufacturing costs. can do.

On the other hand, the prior literature related to electrospinning was carried out after fixing the concentration of the polymer solution for electrospinning. However, in order to fix the concentration of the polymer solution, devices for fixing the concentration and technical processes are required. In particular, in the case of electrospinning including an overflow system that reuses a polymer solution that is not fibrous and falls into the nozzle block, a diluent is used. This is necessary, and the addition of a diluent causes a decrease in production speed, a risk of explosion, and problems in production cost.

In addition, due to the characteristics of electrospinning rather than melt spinning, in the field of manufacturing nanofibers using existing electrospinning technology, the concentration is maintained using a predetermined level of solvent. At this time, the electrospinning is usually performed with a low concentration of polymer solution, and the productivity is low due to the relative reduction of the solid content accumulated in the collector due to the use of the electrospinning solvent, which requires a lot of time to achieve the target yield.

In addition, a problem caused by the use of a low concentration of the polymer solution is a relatively high level of the remaining solvent other than the polymer polymer in the nanofibrous layer integrated in the collector, causing a problem of poor quality of the nanofibers.

When applying the nanofiber filter produced by electrospinning the polymer spinning solution through the electrospinning as described above as the filter material used in the industrial field, the basis weight of the entire nanofiber filter used as the filter material must be constant and uniform. It was possible to produce and sell the product by satisfying the standard. In the case of the filter used for the gas turbine of a thermal power plant, depending on the direction of air inflow, the position of the air inlet, the direction of the air exhaust, and the position of the exhaust In some cases, the basis weight of the nanofiber filter constituting the filter material does not need to be constant. On the contrary, the filter portion with active air filtration must adjust the basis weight of the nanofiber filter to increase the air filtration efficiency, while the air filtration is active. The filter part that is not used does not have a lot of air flow rate, so it is possible to adjust the The situation is required to design more durable than the side.

Thus, the basis weight of the nanofiber filter is a situation that requires a nanofiber filter material having a different basis weight on the same nanofiber filter depending on the position of the air inlet and outlet.

Accordingly, the present invention has been made to solve the above problems, in the electrospinning apparatus including the overflow system, the polymer solution that is not electrospun and falls to the nozzle block is recovered and reused as an electrospinning, as well as a viscosity control system. An object of the present invention is to provide a device capable of manufacturing a nanofiber filter comprising a.

It is another object of the present invention to provide an apparatus for manufacturing a nanofiber filter, wherein the adhesion between the substrate and the nanofiber layer and the nanofiber layer is adhered through an adhesive layer formed by electrospinning a low melting polymer solution.

In addition, the present invention has been made to solve the above problems, in order to increase the wear resistance and productivity when manufacturing the nanofiber filter, the basis weight in the longitudinal direction (MD) or width direction (CD) of the planar direction of the nanofiber filter layer It is an object to provide these different nanofiber filters and methods for their preparation.

According to a preferred embodiment of the present invention for achieving the above object, the main storage tank for storing the polymer solution, the nozzle block for discharging the polymer solution, the collector for integrating the nano-membrane, high voltage between the collector and the nozzle block An apparatus for manufacturing a nanofiber filter including a power supply device and an overflow system, wherein the low melting point polymer unit for forming an adhesive layer for adhesion between the substrate, the nanofiber layer, and the nanofiber layer, and the viscosity of the polymer solution to be emitted are fixed. It includes a temperature control device that can be adjusted to, wherein the adhesive layer provides an apparatus for producing a nanofiber filter, characterized in that formed by electrospinning a low melting polymer solution.

Here, the low melting point polymer solution is preferably one selected from the group consisting of low melting point polyester, low melting point polyurethane, low melting point polyvinylidene fluoride, and the temperature control device is a polymer solution recovered through an overflow system It is preferable to include a heating device and a cooling device capable of constantly adjusting the viscosity of.

In addition, the viscosity of the polymer solution is preferably controlled to be constant from 1,000 cps to 3,000 cps, the heating device is preferably selected from one or more of the heat transfer heater, hot water circulation device and hot air circulation device, the cooling device is chilling It is preferable to be a (chilling) device.

In addition, the temperature control device is preferably installed in any one or more of the storage tank, the nozzle block and the overflow system.

According to another suitable embodiment of the present invention, there is provided an article comprising: a substrate; At least one nanofiber layer laminated on the substrate by electrospinning; In the method of manufacturing a nanofiber filter composed of an adhesive layer formed between the substrate and the nanofiber layer and the nanofiber layer, the nanofiber layer is different in the basis weight of the nanofiber in the longitudinal direction (MD), the adhesive layer is a low melting point polymer It provides a method for producing a nanofiber filter characterized in that the solution is electrospun.

According to another suitable embodiment of the present invention, there is provided an article comprising: a substrate; At least one nanofiber layer laminated on the substrate by electrospinning; In the method of manufacturing a nanofiber filter comprising an adhesive layer formed between the substrate and the nanofiber layer and the nanofiber layer, the nanofiber layer is different in basis weight of the nanofiber in the width direction (CD), the adhesive layer is a low melting point poly Provided is a method for producing a nanofiber filter comprising electrospinning a low melting polymer solution selected from vinylidene fluoride, low melting polyurethane, and low melting polyester.

In this case, the basis weight of the nanofibers is characterized in that to operate a plurality of nozzle tube in the on-off system, the on-off system in the longitudinal direction (MD) or width direction (CD) of the nanofibers are integrated It characterized in that the gradient of basis weight is designed to increase, the on-off system is characterized in that the gradient of the basis weight is designed to increase or decrease in both directions in the longitudinal direction (MD) or width direction (CD) in which the nanofibers are integrated Provided is a method of manufacturing a fiber filter.

In addition, the on-off system is characterized in that the basis weight alternately designed in the longitudinal direction (MD) or width direction (CD) in which the nanofibers are integrated, the basis weight is in the range of 0.1 to 0.5g / m ² It provides a method for producing a nanofiber filter, characterized in that different in the longitudinal direction (MD) or the width direction (CD).

In addition, it provides a nanofiber filter produced by the above production method.

The present invention provides a device for manufacturing a nanofiber filter including a temperature control device, by maintaining a constant concentration of the polymer solution to suppress the use of a diluent and to form an adhesive layer electrospun a low melting polymer solution between the substrate and the nanofiber layer There is an advantage in providing a more robust nanofiber filter.

In addition, by providing a nanofiber filter having a different basis weight in the longitudinal direction or the width direction, it is possible to improve the durability and productivity of nanofiber production.

1 is a view schematically showing an electrospinning device according to the prior art,

2 is a view of a nanofiber filter manufacturing method having an overflow system and a temperature control device and a viscosity control system according to the present invention;

3 is a front sectional view showing a tubular body equipped with a coiled heating wire in an electrospinning apparatus having a temperature adjusting apparatus according to the present invention;

4 is a side cross-sectional view taken along line AA ′ of FIG. 3;

5 is a front sectional view showing a tubular body equipped with a heating wire in a linear form in the electrospinning apparatus having a temperature adjusting device according to the present invention;

6 is a side cross-sectional view taken along line B-B 'of FIG. 5;

7 is a front sectional view showing a tubular body equipped with a U-shaped pipe in an electrospinning apparatus having a temperature regulating apparatus according to the present invention;

8 is a side cross-sectional view taken along line CC ′ of FIG. 7;

9 and 10 are graphs showing the viscosity value of the polyurethane and polyvinylidene fluoride for each temperature;

FIG. 11 is a side view schematically showing an electrofiber spinneret of FIG. 1.

13 and 13 are a plan view schematically showing a nozzle body arranged in the nozzle block of the electrospinning apparatus according to the present invention;

14 and 15 are side views schematically showing a nozzle tube arranged in the nozzle block of the electrospinning apparatus according to the present invention;

16 is a perspective view schematically showing a nozzle tube arranged in a nozzle block of the electrospinning apparatus according to the present invention;

17 to 20 is an operation process of the polymer spinning solution is electrospun on the same plane of the substrate through the nozzle of each nozzle tube of the nanofiber filter electrospinning apparatus according to the present invention (nozzle indicated by broken lines in Figs. 17 and 18) A plan view schematically showing this closed nozzle, and a nozzle indicated by broken lines in FIGS. 19 and 20 indicates that it is located below the substrate),

21 to 23 is a plan view of the basis weight nanofiber filter in the CD direction produced by the present invention,

24 to 25 are plan views of nanofiber filters different in basis weight in the MD method produced by the present invention.

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

1. Electrospinning method with overflow system

Nanofiber manufacturing method according to the present invention is configured to include an overflow system (200) for recycling the spinning solution spun from the electrospinning apparatus (1) nozzle block 110, but not nanofiberized.

Here, the electrospinning apparatus 1 includes a case 102, a nozzle block 110, a collector 150, a power supply device 160, an auxiliary belt device 170, and a unit 100, 100 ′ therein. ), The main storage tank 210, the second transfer pipe 216, the second transfer control device 218 and the regeneration tank 230 and the overflow system 200 consisting of these.

In this case, the case 102 is preferably made of a conductor, but the case 102 may be made of an insulator, or the case 102 may be applied by mixing a conductor and an insulator, and made of various other materials. It is also possible.

The nozzle 42 of the nozzle block 110 can be a bottom-up, a top-down, and a horizontal type, and in particular, in the electrospinning apparatus to which the overflow system 200 is applied, bottom-up electrospinning is preferable. A plurality of nozzles 42 are installed in a bottom-up, top-down or horizontal manner, and receives the spinning solution from the main storage tank 210 or the regeneration tank 230. Hereinafter, the invention will be described based on bottom-up electrospinning, and the following bottom-up radiation is not intended to limit the scope of the present invention, but is merely presented as an example, and various modifications may be made without departing from the technical scope of the present invention. .

The tip of the nozzle 42 of the bottom-up electrospinning is preferably formed in a shape cut along the plane that crosses the cylinder at an angle to the axis of the cylinder, but the tip of the nozzle 42 of the portion of the nozzle block 110 is shaped like a fallopian tube. It is also possible to have a shape.

The collector 150 is disposed above the nozzle block 110, is made of a conductor, and is attached to the case 102 through the insulating member 152. At this time, when the case 102 is made of an insulator, or the upper portion of the case 102 is used as an insulator, and the lower portion is used as a conductor, the insulating member 152 may be deleted.

The power supply device 160 applies a high voltage between the collector 42 and the nozzles 42 arranged in a plurality of nozzle blocks 110 upwardly. The positive electrode of the power supply device 160 is connected to the collector 150, and the negative electrode of the power supply device 160 is connected to the nozzle block 110 through the case 102.

The nanofibers produced through the nozzle 42 for discharging the nanofibers from the discharge port toward the collector 150 upward from the discharge port are deposited on the long sheet and move while maintaining a uniform thickness.

At this time, the electrospun nanofibers are fibers of an average diameter of 50 ~ 1000nm prepared by spinning the electrospun synthetic resin material, the synthetic resin material capable of electrospinning is not limited separately, for example, polypropylene (PP) , Polyethylene terephthalate (PET), polyvinylidene fluoride, nylon, polyvinylacetate, polymethyl methacrylate, polyacrylonitrile (PAN), polyurethane (PUR), polybutylene terephthalate (PBT), poly Vinyl butyral, polyvinyl chloride, polyethyleneimine, polyolefin, polylactic acid (PLA), polyvinyl acetate (PVAc), polyethylene naphthalate (PEN), polyamide (PA), polyvinyl alcohol (PVA), polyethyleneimide ( PEI), polycaprolactone (PCL), polylactic acid glycolic acid (PLGA), silk, cellulose, chitosan, etc. Among them, polypropylene (PP) material and heat-resistant polymer polyamide, Aromatic polyesters such as polyimide, polyamideimide, poly (meth-phenylene isophthalamide), polysulfone, polyetherketone, polyetherimide, polyethylene terephthalate, polytrimethylene terephthalate, polyethylene naphthalate and the like Polyphosphazenes such as tetrafluoroethylene, polydiphenoxyphosphazene, polybis [2- (2-methoxyethoxy) phosphazene], polyurethane copolymers including polyurethane and polyetherurethane, cellulose Groups of polymers such as acetate, cellulose acetate butyrate and cellulose acetate propionate are widely used commercially.

In addition, the spinning solution supplied through the nozzle 42 in the unit 100, 100 ′ is a solution in which the polymer, which is the electrospinable synthetic resin material, is dissolved in a suitable solvent, and the kind of solvent may also dissolve the polymer. If present, there is no limitation, for example phenol, formic acid, sulfuric acid, m-cresol, thifluoroacetide & hydride / dichloromethane, water, N-methylmorpholine N-oxide, chloroform, tetrahydro Furan and aliphatic ketone groups methyl isobutyl ketone, methyl ethyl ketone, aliphatic hydroxyl group m-butyl alcohol, isobutyl alcohol, isopropyl alcohol, methyl alcohol, ethanol, aliphatic compounds hexane, tetrachloroethylene, acetone, propylene as glycol group In the glycol, diethylene glycol, ethylene glycol, halogen compound group, trichloroethylene, dichloromethane, aromatic compound, toluene, xylene, aliphatic ring Cyclohexanone as the compound group, n-butyl acetate as the cyclohexane and ester group, ethyl acetate, butyl cellosalbu as the aliphatic ether group, 2-ethoxyethanol acetate, 2-ethoxyethanol, amide form dimethyl formamide, dimethyl Acetamide and the like can be used, and a plurality of solvents can be mixed and used. The spinning solution may contain additives such as conductivity improvers.

On the other hand, the outer side of the collector 150 is provided with an auxiliary belt device, the auxiliary belt device 170 is to rotate the auxiliary belt 172 and the auxiliary belt 172 to rotate in synchronization with the feed rate of the long sheet. The auxiliary belt roller 174 and the auxiliary belt driving device for driving the auxiliary belt 172 are provided.

At this time, the auxiliary belt roller 174 preferably rotates the auxiliary belt 172 by the auxiliary belt driving device, but also by using a roller with a low coefficient of friction to assist the transfer of the long sheet without a separate driving device. It is possible.

The main storage tank 210 stores the spinning solution that is a raw material of the nanofibers. The main storage tank 210 is provided with a stirring device 211 to prevent separation or solidification of the spinning solution therein.

The second transfer pipe 216 is composed of a pipe and a valve 233 connected to the main storage tank 210 or the regeneration tank 230, and intermediate from the main storage tank 210 or the regeneration tank 230. The spinning solution is transferred to the tank 220.

The second transfer control device 218 controls the transfer operation of the second transfer pipe 216 by controlling the valves 212, 213, 214 of the second transfer pipe 216. The valves 212, 213, 214 control the transfer of the spinning solution from the main storage tank 210 to the intermediate tank 220, and control the transfer of the spinning solution from the regeneration tank 230 to the intermediate tank 220. The amount of the spinning solution flowing into the intermediate tank 220 from the main storage tank 210 and the regeneration tank 230 is controlled.

The control method as described above is controlled according to the liquid level of the spinning solution measured by the second sensor 222 of the intermediate tank 220 to be described later.

The intermediate tank 220 stores the spinning solution supplied from the main storage tank 210 or the regeneration tank 230, supplies the spinning solution to the nozzle block 110, and measures the liquid level of the supplied spinning solution. The second sensor 222 is provided.

The second sensor 222 may be a sensor capable of measuring the liquid level, and is preferably made of, for example, an optical sensor or an infrared sensor.

The lower portion of the intermediate tank 220 is provided with a supply pipe 24 and a supply control valve 242 for supplying the spinning solution to the nozzle block 110, the supply control valve 242 is the supply pipe 240 Control the supply operation.

The regeneration tank 230 has a stirring device 231 for storing the spinning solution recovered due to overflow and preventing separation or coagulation of the spinning solution, and a first sensor for measuring the liquid level of the recovered spinning solution ( 232).

The first sensor 232 may be a sensor capable of measuring the liquid level, and for example, it is preferable that the first sensor 232 is formed of an optical sensor or an infrared sensor.

On the other hand, the spinning solution overflowed from the nozzle block 110 is recovered through the spinning solution recovery path 250 provided below the nozzle block 110. The spinning solution recovery path 250 recovers spinning solution to the regeneration tank 230 through the first transfer pipe 251.

On the other hand, the first transfer pipe 251 is provided with a pipe and a pump connected to the regeneration tank 230, and transfers the spinning solution from the spinning solution recovery path 250 to the regeneration tank 230 by the power of the pump. .

At this time, the regeneration tank 230 is preferably at least one, in the case of two or more may be provided with a plurality of the first sensor 232 and the valve 233.

Subsequently, when there are two or more regeneration tanks 230, a plurality of valves 233 positioned above the regeneration tank 230 are also provided, so that a first transfer control device (not shown) is provided in the regeneration tank 230. Two or more valves located above are controlled according to the liquid level of the first sensor 232 to control which one of the plurality of regeneration tanks 230 of the regeneration tank 230 is transferred.

2. Temperature control system of polymer solution (polymer)

Polymer solution is used for electrospinning. Generally, existing inventions include diluents and concentration adjusting devices to maintain a constant concentration of the polymer solution. As such a diluent, MEK (methyl ether ketone), THF (tetra hydrofuran), and alcohol are used. In addition to the polymer solution electrospun through the nozzle block 110 and integrated in the collector 150, the concentration of the polymer solution recovered through the overflow system 200 is the concentration of the polymer solution initially supplied from the main storage tank 210. It will have a higher concentration. In the conventional electrospinning, a diluent was added to maintain a certain level of the polymer solution. In addition, MEK or THF, which is used as a diluent, has a low boiling point (b.p) (about 60 ° C.) and is easier to disperse nanofibers than the case of using DMAc alone as a solvent during electrospinning.

However, the present invention is to increase the efficiency of electrospinning by using a high concentration of the polymer solution to be reused after the overflow instead of maintaining a constant concentration, but by constantly adjusting the viscosity of the polymer solution using the temperature control controller 60 It provides a means and excellent scattering properties at high temperature conditions to control high viscosity without the use of diluents to facilitate nanofiber formation of polymer solutions.

Viscosity refers to the ratio of the skew stress and skew rate of the solute and solvent in the flowing liquid. It is usually expressed in terms of viscoelasticity per cut area and the unit is dynscm-2gcm-1s-1 or poise (P). The viscosity decreases in inverse proportion to the temperature rise. The viscosity of the solution is higher than that of the solvent because the flow of the liquid is skewed depending on the solute and the flow rate of the liquid is reduced by that amount.

The viscosity of the solution was measured at various concentrations of the solution, and extrapolated to the concentration 0, the relationship between the intrinsic viscosity (η) and the molecular weight M of the substance can be expressed as (η) = KMa. K and a at this time are integers which depend on a kind of a solute or a solvent, and temperature. Therefore, the viscosity value is affected by temperature and the degree of change depends on the type of fluid. Therefore, when talking about viscosity, you must specify the values of temperature and viscosity.

When manufacturing the nanofibers by the electrospinning apparatus 1, the fiber diameter and radioactivity of the nanofibers in which the type of polymer and solvent used, the concentration of the polymer solution, the temperature and humidity of the spinning room, etc. are manufactured. It is known to affect. That is, the physical properties of the polymer (polymer solution) radiated by electrospinning is important. In general, the viscosity of the polymer during electrospinning has been considered necessary to maintain a certain viscosity or less. This is due to the characteristic that the higher the viscosity, the spinning of the nano-thickness fiber is not achieved through the nozzle 42, and the higher the viscosity is not suitable for fiberization through electrospinning.

The present invention is characterized in that it comprises a temperature control controller 60 for adjusting the viscosity with the temperature control controller 60 to maintain the fiber viscosity suitable for electrospinning as described above.

The thermostat control device 60 may include both a heating device capable of maintaining a low viscosity of a high viscosity polymer solution reused through an overflow and a cooling device capable of maintaining a high viscosity of a relatively low viscosity polymer solution. It can be provided.

In the temperature of the electrospinning region, the temperature of the region where electrospinning occurs (hereinafter referred to as the 'spinning region') changes the surface tension of the spinning solution by changing the viscosity of the spinning solution, so that the diameter of the nanofibers spun Will affect.

That is, when the viscosity of the solution is low because the temperature of the radiation region is relatively high, the fiber becomes thinner than the fiber diameter, and when the viscosity of the solution is high because the temperature is relatively low, the fiber diameter is relatively thick.

In particular, in the case of the polymer solution, the concentration of the polymer solution re-supplied through the overflow tends to increase. By measuring the concentration of the polymer solution in the intermediate tank 220, the temperature is controlled using a temperature-viscosity graph according to the corresponding concentration. The viscosity can be kept constant (see FIG. 9).

The concentration measuring device for measuring the concentration may be a contact type and a non-contact type directly contacting the solution, and the contact type may be a capillary concentration measuring device or a disc (DISC) concentration measuring device. Concentration measuring apparatus or concentration measuring apparatus using infrared light can be used.

The heating apparatus of the present invention may be made of a heat transfer heater, a hot water circulation device or a warm air circulation device, etc., in addition to the devices that can increase the temperature in an equivalent range with the above devices can be borrowed.

As an example of the heating device, the electric heating heater may be used in the form of a hot wire, and the coil wires 62a and 62b may be mounted inside the tubular body 43 of the nozzle block 110, which may be transformed into a jacket ( 3 to 8).

In addition, it is also possible to have a configuration of the hot wires (62a, 62b) of the linear form and the pipe 63 of the U-shape.

Such a heating apparatus includes a nozzle block 110 in which the polymer solution is radiated, a tank (main storage tank, an intermediate tank or a regeneration tank) in which the polymer solution is stored, and an overflow system 200, in particular, transferred from the recovery part to the regeneration tank. It may be provided in any one or more of the transfer piping).

As the cooling device of the present invention, a cooling means including a chilling device may be used, and a means for maintaining a constant viscosity of the polymer solution is generally applicable. The cooling device may be provided in any one or more of the nozzle block 110, the tank, and the overflow system 200 in the same manner as the heating device, and is used to maintain a constant viscosity of the polymer solution.

In addition, the temperature control controller 60 of the present invention includes a sensor for measuring the concentration and thus a temperature control controller (not shown) for controlling the temperature.

The sensor is installed in the main storage tank 210, the intermediate tank 220, the regeneration tank 230, the nozzle block 110 or the overflow system 200 and the like to measure the concentration of the spinning solution in real time to control the temperature control In the device 60, the heating and / or cooling device is operated so that the viscosity is kept constant.

The concentration of the polymer solution re-supplied through the overflow system 200 of the present invention is 20 to 40%, which is a higher concentration of solution than the concentration of 10 to 18% of the polymer solution used in conventional electrospinning.

In addition, in order to keep the viscosity of the polymer solution resupply of the present invention, the temperature of the polymer solution according to the concentration of the polymer solution is characterized in that it is adjusted to 45 to 120 ℃, not room temperature.

Meanwhile, the polymer solution of the present invention preferably has a viscosity of 1,000 to 5,000 cps, more preferably 1,000 to 3,000 cps. If the viscosity is 1,000 cps or less, the quality of the nanofibers laminated by electrospinning is poor, and if the viscosity is 3,000 cps or more, the discharge of the polymer solution from the nozzle 42 is not easy during electrospinning, and thus the production speed is slowed.

In addition, the present invention, as the electrospinning proceeds, the viscosity of the polymer solution is constant, so that it is excellent in the easiness of spinning during electrospinning and the concentration of the polymer solution is increased, thereby increasing productivity by increasing the amount of solids excluding the solvent in the nanofibers concentrated on the collector. This has the effect of increasing.

In addition, the amount of the remaining solvent of the nanofibers using the electrospinning is less than when using the conventional electrospinning it can be produced a nanofiber of excellent quality.

In addition, the temperature control control device 60 of the present invention to measure the concentration of the intermediate tank 220 by the operator offline to adjust the viscosity of the polymer solution through the temperature control of the nozzle block 110 or the main storage tank 210. In addition to being able to control manually, the automatic control system online includes automatic control of the temperature of the solution according to the concentration measurement.

Hereinafter, a method of manufacturing a nanofiber filter using electrospinning electrospinning, which includes a temperature control controller 60 and maintains a constant viscosity, will be described. However, the following manufacturing method is only one manufacturing method of the present invention, and the scope of the present invention is not limited thereto.

The manufacturing method of the nanofibers constituting the nanofiber filter includes a supply step of supplying the polymer solution to the nozzle block 110 from the main storage tank 210 in which the polymer solution is stored. In this case, the polymer solution introduced into the main storage tank 210 may be variously used as described above.

The polymer solution supplied from the main storage tank 210 to the nozzle block 110 includes an electrospinning step of electrospinning the collector 150 through the nozzle 42 to stack the nanofiber layer. In the electrospinning step, the distance between the nozzle block 110 and the collector 150 is adjusted to 20 to 50 cm on average, the applied voltage is adjusted to 10 to 40 kV, and the flow rate, temperature and humidity of the polymer solution It can be set in a normal range.

In the electrospinning step, only 30 to 10% of the polymer solution electrospun from the nozzle block 110 is nanofiberized, and the remaining 70 to 90% of the polymer solution is not nanofiberized. The polymer solution that is not nanofiberized is subjected to a recovery step of collecting and collecting the regeneration tank 230 through the overflow system 200.

Thereafter, the polymer solution stored in the regeneration tank 230 may be directly supplied to the nozzle block 110. In addition, the polymer solution may be introduced into the regeneration tank 230 from the main storage tank 210 to the regeneration tank 230. Through the storage step to be stored may be supplied back to the nozzle block (110).

Thereafter, the regeneration tank 230 undergoes a resupply step in which the polymer solution is resupplied to the nozzle block 110. In this case, the temperature control controller 60 is provided in the nozzle block 110 to constantly adjust the viscosity of the polymer solution. Is installed. In addition, the temperature control controller 60, as well as the nozzle block 110 may be installed in any one of the overflow system 200, the regeneration tank 230 or the main storage tank (210).

3. Method of controlling radiation dose of polymer solution (polymer).

Referring to Figure 11, as shown in the figure, the electrospinning apparatus 100 according to the present invention is composed of a bottom-up electrospinning device, consisting of at least one unit (110, 110 '). In one embodiment of the present invention, the electrospinning apparatus 100 is composed of a bottom-up electrospinning apparatus, it may be made of a top-down electrospinning apparatus.

Here, the unit (110, 110 ') is a metering pump for supplying the quantitative supply of the polymer spinning solution filled in the spinning solution main tank 120 and the spinning solution main tank 120 filled with the polymer spinning solution (not shown) And a nozzle block for discharging the polymer spinning solution in the spinning solution main tank 120, wherein a plurality of nozzle pipes 112 having a plurality of nozzles 111a having a pin shape are arranged in a lateral direction of the collector ( In order to accumulate the 111 and the polymer spinning solution sprayed from the nozzle 111a, the collector 113 and the voltage generator 114 for generating a high voltage to the collector 113 are spaced apart at a predetermined interval from the nozzle 111a. It is configured to include).

As described above, the nanofiber filter electrospinning apparatus 1 is continuously supplied to the nozzle block 111 in which the polymer spinning solution filled in the spinning solution main tank 120 is applied with a high voltage through a metering pump, The polymer spinning solution supplied to the nozzle block 111 is spun and focused on the collector transported in the electrospinning apparatus through the nozzle 111a on the collector 113 on which the high voltage is applied to form a nanofiber filter. .

At this time, at least one or more units (110, 110 ') provided in the nanofiber filter electrospinning apparatus (1) are sequentially spaced at a predetermined interval, the polymer spinning solution through the unit (110, 110') Spinning to produce a nanofiber filter.

On the other hand, the nozzle block 111 of the electrospinning apparatus 100 has a plurality of nozzle pipes 112 are arranged in the transverse direction, the spinning liquid main tank for supplying a polymer spinning solution to the nozzle pipe (112) ( 120 is provided with at least one connection.

That is, the nozzle body (112a, 112b, 112c, 112d, 112e, 112f, 112g, 112h, 112i) is formed in a rectangular parallelepiped, a plurality of nozzles (111a) are provided linearly on the upper surface of the nozzle block 111 And a plurality of nozzle pipes 112a, 112b, 112c, 112d, 112e, 112f, 112g, 112h, 112i are arranged in the transverse direction of the collector in the spinneret main tank 120 The polymer spinning solution filled in the tank 120 is supplied.

Here, each nozzle pipe (112a, 112b, 112c, 112d, 112e, 112f, 112g, 112h, 112i) is connected to the spinning solution main tank 120 as a solution supply pipe 121, the solution supply pipe 121 is A plurality of branching bodies are connected to connect the nozzle bodies 112a, 112b, 112c, 112d, 112e, 112f, 112g, 112h, 112i and the spinning solution main tank 120.

At this time, the supply amount adjusting means (not shown) to the solution supply pipe 121 that is addressed to each nozzle pipe (112a, 112b, 112c, 112d, 112e, 112f, 112g, 112h, 112i) in the spinning solution main tank 120 Is provided, the supply amount adjusting means is made of a supply valve (122).

In this way, the supply valve 122 is provided in each of the solution supply pipes 121 extending from the spinning solution main tank 120 to the nozzle pipes 112a, 112b, 112c, 112d, 112e, 112f, 112g, 112h, and 112i. The supply of the polymer spinning solution supplied from the spinning solution main tank 120 to each nozzle tube 112a, 112b, 112c, 112d, 112e, 112f, 112g, 112h, and 112i by the respective supply valves 122 is controlled. And controlled.

That is, the spinning solution when the polymer spinning solution is supplied from the spinning solution main tank 120 to each nozzle tube 112a, 112b, 112c, 112d, 112e, 112f, 112g, 112h, and 112i through the solution supply pipe 121. The nozzle is opened and closed by the supply valve 122 provided in the solution supply pipe 121 extending the main tank 120 and the nozzle pipe bodies 112a, 112b, 112c, 112d, 112e, 112f, 112g, 112h, and 112i. It is optional only for the nozzle pipes 112b, 112d, 112f, 112g, 112h, 112i at a specific position among the nozzle pipes 112a, 112b, 112c, 112d, 112e, 112f, 112g, 112h, and 112i arranged in the block 111. Each nozzle pipe 112a, 112b, 112c, 112d, 112e, 112f, 112g, 112h, 112i in the spinning solution main tank 120 by opening and closing the supply valve 122, etc. The supply of the polymer spinning solution to be controlled is controlled.

To this end, the supply valve 122 is controllably connected to the control unit (not shown), it is preferable that the opening and closing of the supply valve 122 is automatically controlled by the control unit, according to the site situation and the needs of the operator It is also possible that the opening and closing of the supply valve 122 is controlled manually.

In one embodiment of the present invention, the supply amount adjusting means is composed of a supply valve 122, but in the spinning solution main tank 120, each nozzle pipe (112a, 112b, 112c, 112d, 112e, 112f, 112g, 112h, 112i) Control and control of the supply amount of the polymer spinning solution to be supplied to the) If available, the supply amount adjusting means may be made of various other structures and means, but is not limited thereto.

By the structure as described above, the solution supply pipe 121 is to branch, while the spinning solution main tank 120 and each nozzle pipe (112a, 112b, 112c, 112d, 112e, 112f, 112g, 112h, 112i) to be addressed Each of the supply valves 122 is provided in each of the plurality of nozzles 112a, 112b, 112c, 112d, 112e, 112f, 112g, 112h, 112i from the spinning solution main tank 120 to supply a plurality of polymer spinning solutions. The nozzle at a specific position among the nozzle pipes 112a, 112b, 112c, 112d, 112e, 112f, 112g, 112h, 112i, which is opened to the nozzle block 111 by opening a specific supply valve 122 among the supply valves 122. Supply the polymer spinning solution only to the pipe bodies 112b, 112d, 112f, 112g, 112h, 112i, or close the specific supply valve 122, and the nozzle pipe 112a at a specific position among the nozzle pipes arranged in the nozzle block 111. And nozzles 1 in the spinning solution main tank 120 by opening and closing the supply valve 122, for example, blocking the supply of the polymer spinning solution only to 112c and 112e. The supply of the polymer spinning solution to 12a, 112b, 112c, 112d, 112e, 112f, 112g, 112h, 112i) is regulated and controlled.

On the other hand, the polymer spinning solution supplied to each nozzle pipe (112a, 112b, 112c, 112d, 112e, 112f, 112g, 112h, 112i) through the solution supply pipe 121 in the spinning solution main tank 120 is the solution supply pipe It is supplied to each nozzle 111a provided in the nozzle pipe bodies 112a, 112b, 112c, 112d, 112e, 112f, 112g, 112h, 112i through the nozzle supply pipe 125 extended to 121. As shown in FIG.

That is, each nozzle 111a provided in the solution supply pipe 121 and the nozzle pipes 112a, 112b, 112c, 112d, 112e, 112f, 112g, 112h, and 112i is addressed to the nozzle supply pipe 125, and The nozzle supply pipe 125 is branched to correspond to the number of nozzles 111a.

Here, the nozzle supply pipe 125 is provided with a radiation dose adjusting means (not shown), the radiation dose adjusting means is composed of a nozzle valve (126).

Thus, the nozzle valve 126 is provided as the radiation amount adjusting means to individually control the supply of the polymer spinning solution supplied from the nozzle supply pipe 125 to each nozzle 111a by opening and closing the nozzle valve 126. The nozzle valve 126 is controllably connected to a control unit (not shown), but the opening and closing of the nozzle valve 126 are preferably controlled automatically by the control unit. Opening and closing of the nozzle valve 126 may be controlled manually.

In one embodiment of the present invention, the radiation dose adjusting means is composed of a nozzle valve 126, the radiation dose adjusting means if it is easy to control and control the radiation dose of the polymer spinning solution that is emitted after being supplied to the nozzle 111a from the nozzle tube May be made of various other structures and means, but is not limited thereto.

By the above structure, the solution supply pipe 121 and the nozzles 111a are connected and installed, and the nozzle valve 126 is provided in the nozzle supply pipe 125 which is branched, respectively, and the spinning solution main tank 120 is provided. When the supply of the polymer spinning solution to each nozzle (111a) through each nozzle pipe (112a, 112b, 112c, 112d, 112e, 112f, 112g, 112h, 112i) in the nozzle nozzle 126 of the plurality of nozzle valve 126 ), The polymer spinning solution is electrospun selectively in the nozzle 111a at a specific position among the nozzles 111a provided in the nozzle bodies 112a, 112b, 112c, 112d, 112e, 112f, 112g, 112h, and 112i. Or a specific nozzle valve 126 to close the nozzle body 112a, 112b, 112c, 112d, 112e, 112f, 112g, 112h, 112i of each of the nozzles (111a) provided in the nozzle 111a at a specific position Selectively block the electrospinning of the spinning solution, such as the nozzle valve 126 in the spinning solution main tank 120 in the nozzle pipe (112a, 1) The supply of the polymer spinning solution supplied to each nozzle 111a through 12b, 112c, 112d, 112e, 112f, 112g, 112h, 112i is individually controlled and controlled.

In an embodiment of the present invention, the supply valve 122 is provided in the solution supply pipe 121 so that each nozzle pipe 112a, 112b, 112c, 112d, 112e of the nozzle block 111 in the spinning solution main tank 120 is provided. , 112f, 112g, 112h, and 112i, and control the supply amount of the polymer spinning solution supplied to the nozzle and the nozzle supply pipe 125 is provided with a nozzle pipe 112a, 112b, 112c, 112d , 112e, 112f, 112g, 112h, 112i and the nozzle pipe 112a, 112b, 112c, 112d, 112e, 112f, by adjusting and controlling the radiation amount of the polymer spinning solution electrospun through each nozzle (111a) Nanofiber filters having different basis weights in the width direction of the collector are formed by stacking the polymer spinning solution electrospun from the nozzles 111a of 112g, 112h, and 112i, but the nozzles 111a are formed on the nozzle block 111. After installing and installing each nozzle, each nozzle 111a is directly adjusted and controlled individually. By through the respective nozzles (111a) adjusting and controlling the amount of radiation of the polymer spinning solution to be electrospun can be made to form a laminate having different nanofiber filter having a basis weight in the widthwise direction of the collector, and shall not be limited thereto.

Thus, through the supply valve 122 of the solution supply pipe 121 and the nozzle valve 126 of the nozzle supply pipe 125 in the spinning solution main tank 120 nozzle nozzles 112a, 112b, 112c, 112d, 112e, 112f, Supply amount of the polymer spinning solution supplied to 112g, 112h, 112i and of the polymer spinning solution electrospun through the nozzle 111a of the nozzle body (112a, 112b, 112c, 112d, 112e, 112f, 112g, 112h, 112i) By adjusting and controlling the amount of radiation, the nozzle pipes 112a, 112b, 112c, 112d, 112e, 112f, 112g, 112h, and 112i provided on one side of the collector in the horizontal direction and the nozzle pipes 112a, 112b, 112c, 112d, 112e, By controlling the nozzles 111a of 112f, 112g, 112h, and 112i, the nanofiber filter 115a having a basis weight of 50 to 150 nm is laminated on one side of the collector in the transverse direction, and on the side of the collector in the transverse center side. Laminating a nanofiber filter 115b having a basis weight of 150 to 300 nm, the basis weight of 300 to 500 nm on the other transverse plane of the collector The nanofiber filter nanofiber filter (115a, 115b, 115c) having a (115c) of different basis weight, such as in the same longitudinal or lateral direction of the collector to form a lamination plane of may form various laminated.

As described above, the length of the collector is controlled by controlling the nozzle body of the nozzle block 111 and the nozzle 111a of the nozzle body 112a, 112b, 112c, 112d, 112e, 112f, 112g, 112h, 112i. A nanofiber filter having three kinds of basis weights having different basis weights on the same plane in the transverse direction is laminated.

Meanwhile, in one embodiment of the present invention, nanofiber filters having three kinds of different basis weights are formed on the same plane in the longitudinal or transverse direction of the collector, but the nozzle bodies 112a, 112b, 112c, 112d, 112e, 112f, 112g, 112h, 112i) and each nozzle 111a of the nozzle body 112a, 112b, 112c, 112d, 112e, 112f, 112g, 112h, 112i to control the collector. It is also possible to simultaneously form a nanofiber filter having two different basis weights on the same plane in the longitudinal or transverse direction, and the nozzle pipe bodies 112a, 112b, 112c, 112d, 112e, and 112f of the nozzle block 111 can be formed at the same time. , 112g, 112h, 112i) and the nozzles 111a of the nozzle bodies 112a, 112b, 112c, 112d, 112e, 112f, 112g, 112h, 112i to control the collector in the longitudinal or transverse coplanar direction. It is also possible to simultaneously laminate four or more types of nanofiber filters having different basis weights. It is not limited.

Here, the material of the polymer spinning solution to be filled in the spinning solution main tank 120 is not limited, for example, polypropylene (PP), polyethylene terephthalate (PET), polyvinylidene fluoride, nylon, poly Vinyl acetate, polymethyl methacrylate, polyacrylonitrile (PAN), polyurethane (PUR), polybutylene terephthalate (PBT), polyvinyl butyral, polyvinyl chloride, polyethyleneimine, polyolefin, polylactic acid (PLA) ), Polyvinyl acetate (PVAc), polyethylene naphthalate (PEN), polyamide (PA), polyvinyl alcohol (PVA), polyethyleneimide (PEI), polycaprolactone (PCL), polylactic acid glycolic acid (PLGA) , Silk, cellulose, chitosan, etc. Among them, polypropylene (PP) material and polyamide, polyimide, polyamideimide, poly (meth-phenylene isophthalamide), polysulfone, Poly Aromatic polyesters such as ether ketones, polyetherimide, polyethylene terephthalate, polytrimethylene terephthalate, polyethylene naphthalate, and the like, polytetrafluoroethylene, polydiphenoxyphosphazene, poly bis [2- (2-methoxy to Methoxy) phosphazene], a polyurethane copolymer including polyurethanes and polyetherurethanes, polymers such as cellulose acetate, cellulose acetate butylate, cellulose acetate propionate, etc. It is preferred to be used.

Hereinafter, an operation process of the nanofiber filter electrospinning apparatus according to the present invention will be described with reference to FIGS. 17 to 20.

First, the collector is introduced and supplied into the units 110 and 110 'of the electrospinning apparatus 100 through a supply roller (not shown) provided at the tip of the electrospinning apparatus 100 according to the present invention. The polymer spinning solution is electrospun within (110, 110 ') to form a nanofiber filter.

At this time, the collector is conveyed by the conveying belt 116a is rotated between the conveying rollers (116b).

Thus, the high voltage of the voltage generator 114 is generated on the collector 113 through the nozzle 111a provided in each nozzle tube of the nozzle block 111, and the spinning solution main on the collector 113 where the high voltage is generated. Electrospinning the polymer spinning solution supplied from the tank 120.

As described above, the polymer spinning solution supplied from the spinning solution main tank 120 to the nozzle block 111 may be formed in each nozzle tube 112a, 112b, 112c, of the spinning solution main tank 120 and the nozzle block 111. Each nozzle tube 112a, 112b, 112c, 112d, 112e, 112f, 112g, 112h, in the spinning solution main tank 120 through the solution supply pipe 121 delivered to 112d, 112e, 112f, 112g, 112h, 112i, 112i, the spinning solution main tank 120 supplied to the nozzle pipe (112a, 112b, 112c, 112d, 112e, 112f, 112g, 112h, 112i) is a nozzle supply pipe to the solution supply pipe 121 After being supplied to the nozzle 111a through the 125, the electrospinning is performed through the nozzle 111a to form a nanofiber filter on the collector.

Here, the nozzle pipe (112a, 112b, 112c, 112d, 112e, 112f, 112g, 112h, 112i) arranged in the longitudinal direction or transverse direction of the collector through the solution supply pipe 121 in the spinning solution main tank 120 The supply amount of the polymer spinning solution to be supplied is controlled by the opening and closing of the supply valve 122 respectively provided in the solution supply pipe 121 branched from the spinning solution main tank 120, and the nozzle pipes 112a and 112b. , 112c, 112d, 112e, 112f, 112g, 112h, 112i, the amount of radiation of the polymer spinning solution electrospun through the nozzles 111a is the nozzle tube 112a, 112b, 112c, 112d, 112e, 112f, 112g, 112h, It is controlled by the opening and closing of the nozzle valve 126 provided in the nozzle supply pipe 125 branched from the solution supply pipe 121 of 112i), respectively.

Thus, the supply amount of the polymer spinning solution and the nozzle 111a supplied to the nozzle pipes 112a, 112b, 112c, 112d, 112e, 112f, 112g, 112h, and 112i by the supply valve 122 and the nozzle valve 126. The radiation amount of the electrospinning polymer spinning solution is controlled through this, thereby allowing stacking of nanofiber filters having different basis weights on the same plane in the longitudinal or transverse direction of the collector.

For example, among the nozzle bodies 112a, 112b, 112c, 112d, 112e, 112f, 112g, 112h, 112i, which are arranged in a plurality in the longitudinal direction or the transverse direction of the collector, in one longitudinal direction or the transverse direction of the collector. The solution supply pipe 121 connected to the nozzle pipe bodies 112a and 112c provided at both sides of the supply valve 122 provided in the solution supply pipe 121 of the three nozzle pipes 112a, 112b and 112c located at one side. To close the supply valve 122 and open the supply valve 122 of the solution supply pipe 121 connected to the one nozzle pipe 112b provided at the center side thereof, and supply it from the spinning solution main tank 120. Each nozzle valve of the nozzle supply pipe 125 is branched to the solution supply pipe 121 for supplying the polymer spinning solution to be supplied to one nozzle pipe 112b, and to supply the polymer spinning solution to the one nozzle pipe 112b ( 126) to open the polymer spinning solution supplied to the one nozzle body 121b all nozzles After supplying to 111a, the polymer spinning solution is electrospun on the collector to form a nanofiber filter 115a having a low basis weight of 50 to 150 nm.

And three nozzles located in the transverse center side of the collector among the nozzle bodies 112a, 112b, 112c, 112d, 112e, 112f, 112g, 112h, and 112i arranged in plural in the longitudinal or transverse direction of the collector. The supply valve 122 of the solution supply pipe 121 connected to the nozzle pipe 112e provided at the center of the supply valve 122 provided in the solution supply pipe 121 of the pipe bodies 112d, 112e, and 112f is closed. The polymer spinning solution supplied from the spinning solution main tank 120 was opened by opening the supply valve 122 of the solution supply pipe 121 connected to the two nozzle pipes 112d and 112f respectively provided at both sides thereof. Each nozzle valve 126 of the nozzle supply pipe 125 which is supplied to the nozzle pipes 112d and 112f and is branched to the solution supply pipe 121 that supplies the polymer spinning solution to the two nozzle pipes 112d and 112f. Open the polymer spinning solution supplied to the two nozzle bodies (112d, 112f) to all the nozzles (111a) To form a laminated electrospinning to 150 nm membrane (115b) having a basis weight of 300nm to the polymer spinning solution onto a collector after.

Further, among the nozzle tubes 112a, 112b, 112c, 112d, 112e, 112f, 112g, 112h, and 112i arranged in plural in the longitudinal direction or the transverse direction of the collector, located on the other side in the longitudinal or transverse direction of the collector. All of the supply valves 122 provided in the solution supply pipes 121 of the two nozzle pipes 112g, 112h, and 112i are opened to supply the polymer spinning solution supplied from the spinning solution main tank 120 to the three nozzle pipes 112g and 112h. , 112i) and each nozzle valve 126 of the nozzle supply pipe 125 branched from the solution supply pipe 121 for supplying the polymer spinning solution to the three nozzle pipes 112g, 112h and 112i. The nanofiber filter having a high basis weight of 300 to 500 nm by supplying the polymer spinning solution supplied to each nozzle tube 112g, 112h, 112i to all the nozzles 111a and then electrospinning the polymer spinning solution on the collector ( 115c) is laminated.

In one embodiment of the present invention, each of the solution supply pipe 121 for supplying the polymer spinning solution from the spinning solution main tank 120 to the nozzle pipe (112a, 112b, 112c, 112d, 112e, 112f, 112g, 112h, 112i) By controlling the supply valve 122, the nanofiber filters 115a, 115b, and 115c having different basis weights are formed on the same plane in the longitudinal or transverse direction of the collector, but the nozzles are branched to the solution supply pipe 121. It is also possible to stack the nanofiber filters 115a, 115b and 115c having different basis weights on the same plane in the longitudinal or transverse direction of the collector by controlling the nozzle valve 126 of the supply pipe 125.

For example, one of the nozzle tubes 112a, 112b, 112c, 112d, 112e, 112f, 112g, 112h, and 112i arranged in a plurality in the longitudinal or transverse direction of the collector is located on one side in the longitudinal or transverse direction of the collector. Opening the supply valve 122 provided in the solution supply pipe 121 of the three nozzle pipe (112a, 112b, 112c) to the three nozzle pipe 112a to supply the polymer spinning solution supplied from the spinning solution main tank 120 , 112b and 112c of the nozzle supply pipe 125 which is branched to the solution supply pipe 121 of the nozzle pipe bodies 112a and 112c provided on both sides of the three nozzle pipes 112a, 112b and 112c. All the nozzle valves 126 are closed, and the nozzle valve 126 of the nozzle supply pipe 125 which is branched to the solution supply pipe 121 of the one nozzle pipe 112b provided at the center side thereof is opened to open the one. For spinning the polymer on the collector which supplied the polymer spinning solution to each nozzle 111a provided in the nozzle pipe 112b The liquid is electrospun to form a nanofiber filter 115a having a low basis weight of 50 to 150 nm.

And three nozzles located in the transverse center side of the collector among the nozzle bodies 112a, 112b, 112c, 112d, 112e, 112f, 112g, 112h, and 112i arranged in plural in the longitudinal or transverse direction of the collector. Open the supply valve 122 provided in the solution supply pipe 121 of the pipe bodies 112d, 112e, and 112f to supply the polymer spinning solution supplied from the spinning solution main tank 120 to the three nozzle pipes 112d, 112e, and 112f. All of the nozzle valves 126 of the nozzle supply pipe 125 is branched to the solution supply pipe 121 of the nozzle pipe 112e provided in the center of the three nozzle pipe (112d, 112e, 112f) to supply all And the nozzle valve 126 of the nozzle supply pipe 125 branched to the solution supply pipe 121 of the two nozzle pipe bodies 112d and 112f respectively provided on both sides thereof to open the two nozzle pipe bodies ( After supplying the polymer spinning solution to each of the nozzles 111a provided at 112d and 112f, the polymer spinning on the collector To form the electrospun nanofibers to filter having a basis weight of 150 to 300nm (115b) the liquid deposition.

Further, among the nozzle tubes 112a, 112b, 112c, 112d, 112e, 112f, 112g, 112h, and 112i, which are arranged in plural in the longitudinal or transverse direction of the collector, located at one side of the collector in the longitudinal or transverse direction. All of the supply valves 122 provided in the solution supply pipes 121 of the two nozzle pipes 112g, 112h, and 112i are opened to supply the polymer spinning solution supplied from the spinning solution main tank 120 to the three nozzle pipes 112g and 112h. , 112i) and each nozzle valve 126 of the nozzle supply pipe 125 branched from the solution supply pipe 121 for supplying the polymer spinning solution to the three nozzle pipes 112g, 112h and 112i. The nanofiber filter having a high basis weight of 300 to 500 nm by supplying the polymer spinning solution supplied to the nozzle bodies 112g, 112h and 112i to all the nozzles 111a and then electrospinning the polymer spinning solution onto the collector. 115c) is laminated.

As described above, by controlling the respective supply valves 122 of the solution supply pipe 121 for supplying the polymer spinning solution from the spinning solution main tank 120 to the nozzle pipe 112, the same lengthwise or transverse direction of the collector In addition to stacking the nanofiber filters having different basis weights on the phase, the nozzle valve 126 of the nozzle supply pipe 125 branched to the solution supply pipe 121 is controlled to be equal in the longitudinal or transverse direction of the collector. The nanofiber filters 115a, 115b, and 115c having different basis weights may be stacked on a plane.

In one embodiment of the present invention by controlling the respective supply valves 122 of the solution supply pipe 121 for supplying the polymer spinning solution from the spinning solution main tank 120 to the nozzle pipe 112, the collector in the longitudinal or transverse direction The length of the collector is formed by stacking the nanofiber filters 115a, 115b, and 115c having different basis weights on the same plane or by controlling the nozzle valve 126 of the nozzle supply pipe 125 branched to the solution supply pipe 121. Nanofiber filters 115a, 115b, and 115c having different basis weights are stacked on the same plane in the lateral or transverse directions, but a solution for supplying the polymer spinning solution from the spinning solution main tank 120 to the nozzle tube 112. While controlling the respective supply valves 122 of the supply pipe 121 and the nozzle valve 126 of the nozzle supply pipe 125 branched to the solution supply pipe 121 to control the collector in the longitudinal or transverse coplanar direction Having different basis weight It is also preferable that the nanofiber filters 115a, 115b, and 115c are laminated, and the nanofiber filters 115a, 115b, and 115c vary in basis weight in specific regions and specific portions on the same plane in the longitudinal or transverse direction of the collector. It is also possible to stack the nanofiber filters 115a, 115b, and 115c that vary in basis weight in a specific shape and a specific shape on the same plane in the longitudinal or transverse direction of the collector, but are not limited thereto.

As described above, each of the supply valve 122 of the solution supply pipe 121 or the nozzle valve 126 of the nozzle supply pipe 125 is individually controlled, or each of the supply valve 122 of the solution supply pipe 121 and By simultaneously controlling the nozzle valve 126 of the nozzle supply pipe 125 it is possible to manufacture a nanofiber filter having a variety of different basis weight.

In addition, the nozzle pipes 112a, 112b, 112c, 112d, 112e, and 112f arranged in the longitudinal or transverse direction of the collector by individually controlling the opening and closing of the nozzle valve 126 of the nozzle supply pipe 125. , The polymer spinning solution is supplied to only one of the nozzles 111a of the plurality of nozzles 111a provided in the 112g, 112h, and 112i, and the polymer spinning solution is blocked to the other specific nozzles 111a, thereby preventing the supply of the polymer spinning solution. It is also possible to laminate the nanofiber filters having different basis weights on the same plane in the transverse direction.

At this time, the polymer spinning solution is supplied among the nozzles 111a provided in the nozzle tubes 112a, 112b, 112c, 112d, 112e, 112f, 112g, 112h, and 112i arranged in the longitudinal direction or the transverse direction of the collector. The number and shape of the specific nozzles (111a) and the specific nozzles (111a) for blocking the supply of the polymer spinning solution can be changed in various ways, it is made variable and controllable.

On the other hand, in one embodiment of the present invention, the nozzle body 112a, 112b, 112c, 112d, 112e, 112f, 112g, 112h, 112i arranged in the longitudinal or transverse direction of the collector is controlled by one group of three It is possible to connect the nanofiber filter having three kinds of basis weights differently on the same plane in the longitudinal or transverse direction of the collector, but the nozzle body (112a, 112b, 112c, 112d, 112e, 112f, 112g, 112h, 112i are controllably connected in groups of two, or the nozzle bodies 112a, 112b, 112c, 112d, 112e, 112f, 112g, 112h, 112i are grouped in four It is also possible to have a structure that is controllably connected so as to stack nanofiber filters having different basis weights on the same plane in the longitudinal or transverse direction of the collector, but is not limited thereto.

In addition, in one embodiment of the present invention, the nozzle block (112a, 112b, 112c, 112d, 112e, 112f, 112g, 112h, 112i) arranged in the nozzle block 111, but the nozzle pipe 112a , 112b, 112c, 112d, 112e, 112f, 112g, 112h, 112i and the number of nozzles 111a provided in the nozzle pipe bodies 112a, 112b, 112c, 112d, 112e, 112f, 112g, 112h, 112i. The number can be changed in various ways, but is not limited thereto.

Meanwhile, in one embodiment of the present invention, the nozzle block is controlled by controlling the opening and closing of the supply valve 122 of the solution supply pipe 121 or by controlling the opening and closing of the nozzle valve 126 of the nozzle supply pipe 125. Each nozzle body 112a, 112b, 112c, 112d, 112e, 112f, 112g, 112h, 112i of (111) and the operation of each nozzle 111a by controlling the nozzle body 112a, 112b, 112c, 112d, 112e. , 112f, 112g, 112h, 112i) by controlling the supply amount of the polymer spinning solution and the spinning amount of the electrospinning polymer spinning solution through the nozzle (111a) to form a stack of nanofiber filters of different basis weights at the same time, By controlling the opening and closing of the nozzle bodies 112a, 112b, 112c, 112d, 112e, 112f, 112g, 112h, 112i and the nozzle 111a, it is preferable to variably adjust the width of the nanofiber filter having different basis weights. It is not limited to this.

In this way, the supply amount of the polymer spinning solution supplied to the nozzle bodies 112a, 112b, 112c, 112d, 112e, 112f, 112g, 112h, and 112i and the radiation amount of the polymer spinning solution electrospun from the nozzle 111a are controlled and controlled. As a result, the width of the nanofiber filters having different basis weights in the longitudinal direction or the transverse direction on the same plane of the collector or the radiation region and the radiating portion of the nanofiber filters having the different basis weights can be adjusted through the nozzle 111a.

In an embodiment of the present invention, the electrospinning apparatus 100 shows an example in which it is applied to a bottom-up electrospinning apparatus. However, the electrospinning apparatus 100 according to the present invention may be applied to a top-down electrospinning apparatus. It is also possible to be applied to the electrospinning apparatus in the up and down composite.

By the structure as described above, by controlling and controlling the radiation amount of the polymer spinning solution electrospun on the collector through the electrospinning apparatus 100 according to the present invention to the specific region and the specific portion in the transverse direction on the same plane of the collector Nano membranes having different basis weights can be stacked to facilitate manufacturing of various nanofiber filters.

The MD direction used in the present invention means Machine Direction, which means the longitudinal direction corresponding to the advancing direction in the case of continuous production of fibers such as film or nonwoven fabric, and the CD direction means the cross direction perpendicular to the MD direction. . MD may also be referred to as machine direction / longitudinal direction, and CD as width direction / lateral direction.

Basis Weight or Grammage is defined as mass per unit area, ie grams per square meter (often referred to as gsm rather than g / m 2) as preferred units.

Hereinafter will be described in more detail through embodiments of the present invention. However, the embodiments are only examples of the present invention, and the scope of the present invention is not limited thereto.

The physical property value in an Example was measured by the following method.

Basis weight [g / m ² ]

Six test pieces of 200 mm (MD) x 50 mm (CD) were taken from the nanofiber layer. In addition, the collection place was made into arbitrary three places in each part in which a basis weight differs by an on-off control system. Subsequently, the mass (g) of each sample collected was measured using the upper plate electronic balance. The average value of the mass of each test piece was calculated | required. It converted into mass (g) per 1m <^2> from the calculated | required average value, rounded off the 1st decimal point, and it was set as the basis weight of the nanofiber layer sample of a part.

Example 1

A low melting point polyurethane solution having a softening temperature of 80-100 ° C. was dissolved in 15% by weight of a solvent of DMAc (N, N-dimethylaceticamide) to prepare a low melting point polymer solution. It was put in a tank. In addition, polyvinylidene fluoride having a weight average molecular weight of 50,000 was dissolved in dimethylacetamide (N, N-Dimethylacetamide, DMAc) to prepare respective spinning solutions, which were added to the main tank connected to the spinning solution unit 110 '. It was.

In the low melting point polymer unit 110, the distance between the electrode and the collector was electrospun at 40 cm, an applied voltage of 25 kV, and 70 ° C. to form an adhesive layer having a basis weight of 0.1 g / m ² on the cellulose substrate, and then in the spinning solution unit 110 ′. When the distance between the electrode and the collector is 40 cm, applied voltage 20 kV, and 70 ° C., the basis weight of the polyvinylidene fluoride nanofibers in one direction in the width direction (CD) is 0.2 g / m ² and the remaining weight in one direction is 1 m in the other direction. A nanofiber filter having a CD width of 0.5 m / m ² having a width of 2 m was prepared.

Example 2

A polyurethane solution is prepared by dissolving a polyurethane having a weight average molecular weight of 157,000 in dimethylformamide (DMF). Applying the polyurethane solution to each of the spinning solution main tanks and applying an applied voltage of 20 kV to a nozzle block including an on-off system designed to separate the nozzle block into three parts in one direction of the width direction (CD). Electrospun on 3 g / m ² popular material. In the middle of the width direction (CD) on the electrospun collector, 1m of the polyurethane nanofiber has a basis weight of 0.5 / m ² , and 50cm of the other edge has a basis weight of 0.2g / m ² and a CD width of 2m. Was formed to prepare a polyurethane nanofiber filter. At this time, the bottom-up electrospinning was performed under the condition that the distance between the electrode and the collector was 40 cm and the temperature was 22 ° C.

Example 3

A polyurethane solution is prepared by dissolving a polyurethane having a weight average molecular weight of 157,000 in dimethylformamide (DMF). Applying the polyurethane solution to the spinning solution main tank and applying an applied voltage of 20 kV to the nozzle block including the on-off system designed to separate the nozzle block into nine parts in one direction of the width direction (CD), the basis weight 0.3 It was electrospun on a substrate of g / m ² . Polyurethane nanofibers having a CD width of 2 m with a basis weight of 0.2 g / m ² and a basis weight of 0.5 g / m ² alternately in the width direction (CD) on the electrospun cellulose substrate It was formed to prepare a polyurethane nanofiber filter. At this time, the bottom-up electrospinning was performed under the condition that the distance between the electrode and the collector was 40 cm and the temperature was 22 ° C.

Example 4

A low melting point polyurethane solution having a softening temperature of 80-100 ° C. was dissolved in 15% by weight of a solvent of DMAc (N, N-dimethylaceticamide) to prepare a low melting point polymer solution. It was put in a tank. In addition, polyvinylidene fluoride having a weight average molecular weight of 50,000 was dissolved in dimethylacetamide (N, N-Dimethylacetamide, DMAc) to prepare respective spinning solutions, which were added to the main tank connected to the spinning solution unit 110 '. It was.

In the low melting point polymer unit 110, the distance between the electrode and the collector was electrospun at 40 cm, an applied voltage of 25 kV, and 70 ° C. to form an adhesive layer having a basis weight of 0.1 g / m ² on the cellulose substrate, and then in the spinning solution unit 110 ′. The distance between the electrode and the collector is 40 cm, the applied voltage is 20 kV, and 1 m in one direction of the longitudinal direction (MD) at 70 ° C. is 0.2 g / m ² of basis weight of polyvinylidene fluoride nanofibers, and 1 m in the other direction. A nanofiber filter having a MD width of 2 m having a width of 0.5 g / m ² was prepared.

Example 5

A polyurethane solution is prepared by dissolving a polyurethane having a weight average molecular weight of 157,000 in dimethylformamide (DMF). Applying the polyurethane solution to each of the spinning solution main tanks and applying an applied voltage of 20 kV to a nozzle block including an on-off system designed to separate the nozzle block into three parts in one direction of the longitudinal direction (MD). It was electrospun on a substrate of 3 g / m ² . On the electrospun collector, 1m of the middle part of the longitudinal direction (MD) is a polyurethane nanofiber having a basis weight of 0.5 / m ² , and 50cm of the remaining edge is a polyurethane nanofiber having a basis weight of 0.2g / m ² and a MD width of 2m. Was formed to prepare a polyurethane nanofiber filter. At this time, the bottom-up electrospinning was performed on the conditions of 40 cm and 22 degreeC of distances between an electrode and a collector.

Example 6

A polyurethane solution is prepared by dissolving a polyurethane having a weight average molecular weight of 157,000 in dimethylformamide (DMF). Applying the polyurethane solution to the spinning solution main tank and applying an applied voltage of 20 kV to a nozzle block including an on-off system designed to separate the nozzle block into nine parts in one direction of the longitudinal direction (MD), the basis weight 0.3 It was electrospun on a substrate of g / m ² . Polyurethane nanofibers having an MD width of 2 m having a basis weight of 0.2 g / m ² and a basis weight of 0.5 g / m ² alternately in the longitudinal direction (MD) on the electrospun cellulose substrate It was formed to prepare a polyurethane nanofiber filter. At this time, the bottom-up electrospinning was performed under the condition that the distance between the electrode and the collector was 40 cm and the temperature was 22 ° C.

Claims (15)

1. Main storage tank for storing the polymer solution, nozzle block from which the polymer solution is discharged, b.

   In the apparatus for manufacturing a nanofiber filter comprising a collector for integrating the furnace membrane, a power supply for applying a high voltage between the collector and the nozzle block and an overflow system,

   A low melting polymer unit for forming an adhesive layer for adhesion between the substrate and the nanofiber layer and the nanofiber layer,

   It includes a thermostat that can constantly adjust the viscosity of the polymer solution to be spun,

   The adhesive layer is a nanofiber filter manufacturing apparatus, characterized in that formed by electrospinning a low melting polymer solution.
2. The method of claim 1,

   The low melting point polymer solution is a low melting point polyester, low melting point polyurethane, low melting point polyvinylidene fluoride is one selected from the group consisting of nanofiber filter manufacturing apparatus.
3. The method of claim 1,

   The temperature control device is a device for manufacturing a nanofiber filter, characterized in that it comprises a heating device and a cooling device that can constantly adjust the viscosity of the polymer solution recovered through the overflow system.
4. The method of claim 3, wherein

   The viscosity of the polymer solution is a device for producing a nanofiber filter, characterized in that it is constantly adjusted to 1,000 cps to 3,000 cps.
5. The method of claim 3, wherein

   The heating device is a manufacturing apparatus of the nanofiber filter, characterized in that at least one of the electric heater, hot water circulation device and hot air circulation device is selected.
6. The method of claim 3, wherein

   The cooling device is a device for producing a nanofiber filter, characterized in that the chilling (Chilling) device.
7. The method according to claim 1 or 3,

   The temperature control device is a manufacturing apparatus of the nanofiber filter, characterized in that installed in any one or more of the storage tank, nozzle block and overflow system.
8. A base material;

   At least one nanofiber layer laminated on the substrate by electrospinning; In the method of manufacturing a nanofiber filter composed of an adhesive layer formed between the substrate and the nanofiber layer and nanofiber layer,

   The nanofiber layer is different in the basis weight of the nanofibers in the longitudinal direction (MD),

   The adhesive layer is a method of manufacturing a nanofiber filter, characterized in that the electrospun low-melting polymer solution.
9. A base material;

   At least one nanofiber layer laminated on the substrate by electrospinning; In the method of manufacturing a nanofiber filter composed of an adhesive layer formed between the substrate and the nanofiber layer and nanofiber layer,

   The nanofiber layer has a basis weight of nanofibers different in the width direction (CD),

   Wherein the adhesive layer is a low-melting polyvinylidene fluoride, a low melting point polyurethane, a method of manufacturing a nanofiber filter, characterized in that the low-melting point polymer solution selected from low-polyester polyester.
10. The method according to claim 8 or 9,

    The basis weight of the nanofibers is a method of manufacturing a nanofiber filter, characterized in that for operating a plurality of nozzle tube on-off system.
11. The method of claim 10,

    The on-off system is a manufacturing method of the nanofiber filter, characterized in that the gradient of the basis weight is designed to increase in one direction of the longitudinal direction (MD) or the width direction (CD) in which the nanofibers are integrated.
12. The method of claim 10,

    The on-off system is a manufacturing method of the nanofiber filter, characterized in that the gradient of the basis weight is designed to increase or decrease in both directions in the longitudinal direction (MD) or the width direction (CD) in which the nanofibers are integrated.
13. The method of claim 10,

    The on-off system is a method for producing a nanofiber filter, characterized in that the basis weight alternately designed in the longitudinal direction (MD) or width direction (CD) in which the nanofibers are integrated.
14. The method of claim 10,

    The basis weight of the nanofiber filter manufacturing method, characterized in that different in the longitudinal direction (MD) or the width direction (CD) in the range of 0.1 to 0.5g / m ² .
15. The nanofiber filter manufactured by the manufacturing method according to any one of claims 8 to 14.

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