JP2009510272A - Composite electrospinning apparatus, composite nanofiber nonwoven fabric and composite nanofiber filament manufactured using the same - Google Patents

Abstract

The present invention relates to a composite electrospinning apparatus for producing a fiber (nanofiber) having a nano-level fineness and a nanofiber produced using the same. The composite electrospinning apparatus according to the present invention includes a spinning solution main tank (1); a metering pump (2); a nozzle block (4); a nozzle (5) installed in the nozzle block; a fiber spun from the nozzle block, and the like. In an electrospinning apparatus comprising a collector (7) for accumulating pressure and a voltage generating apparatus (9) for applying a voltage to the nozzle block (4) and the collector (7), [I] the nozzle block (4) The nozzles for spinning two or more kinds of spinning solutions are regularly or randomly arranged in the same or different ratios in a certain repeating unit, and [II] the spinning solution main tank (1) is two or more. [III] A spinning solution drop device (3) is provided between the spinning solution main tank (1) and the nozzle block (4). In the present invention, since two or more spinning solutions can be electrospun simultaneously in a composite manner, the physical properties (characteristics) of the nonwoven fabric and the filament can be easily managed by a simple process, and the fiber forming effect is maximized. Thus, mass production of nanofibers and non-woven fabrics thereof is possible.
[Selection] Figure 1

Description

In the present invention, two or more kinds of polymer spinning solutions are simultaneously electrospun through nozzles arranged on one nozzle block, and two or more kinds of fibers having nano-level fineness (hereinafter referred to as “nanofibers”) are simultaneously obtained. The present invention relates to a composite electrospinning apparatus that can be mass-produced.

The present invention also relates to a non-woven fabric (hereinafter referred to as “composite nanofiber non-woven fabric”) in which two or more types of nanofibers are produced by the composite electrospinning apparatus.

The present invention also relates to a continuous filament (hereinafter referred to as “composite nanofiber filament”) produced by mixing the two or more types of nanofibers produced by the composite electrospinning apparatus.

Nonwoven fabrics composed of nanofibers, membranes, braids, and other products are widely used for daily necessities, agriculture, clothing, and industrial use. Specifically, artificial leather, artificial suede, sanitary napkins, clothes, diapers, packaging materials, miscellaneous materials, various filter materials, medical materials such as gene carriers, and defense materials such as bulletproof clothing Used in various fields.

A conventional electrospinning apparatus described in US Pat. No. 4,044,404 and a method for producing nanofibers using this apparatus are as follows. A conventional electrospinning apparatus includes a spinning solution main tank for storing a spinning solution, a metering pump for quantitatively supplying the spinning solution, a nozzle block in which a plurality of nozzles for discharging the spinning solution are arranged, It is comprised from the collector which accumulate | stores the fiber etc. which are located in the lower stage, and the voltage generation apparatus which generates a voltage.

More specifically, the conventional method for producing nanofibers using the electrospinning apparatus will be described. The spinning solution in the spinning solution main tank is continuously fed into a large number of nozzles to which a high voltage is applied by a metering pump. Quantitative supply.

Next, the spinning solution supplied to the nozzle or the like is spun and focused on a collector to which a high voltage is applied through the nozzle, thereby forming a single fiber web.

The single fiber web is then embossed or needle-punched to produce a nonwoven fabric.

In such a conventional electrospinning apparatus and a method for producing a nonwoven fabric using the same, since the spinning solution is continuously supplied to the nozzle to which a high voltage is applied, the applied electric force effect is reduced. was there.

More specifically, since the electric force applied to the nozzle is dispersed throughout the spinning solution, the electric force cannot overcome the interfacial tension of the spinning solution. As a result, the fiber formation effect by the electric force is reduced, and the spinning is performed. There is a problem that the solution is dropped in the form of water droplets as it is (hereinafter referred to as “droplet”), which deteriorates the quality of the product and makes mass production difficult.

Further, the conventional technology as described above has a problem that it is difficult to commercialize because spinning is almost performed to the level of one hole and mass production is impossible.

In addition, since the conventional electrospinning apparatus can electrospin only one kind of polymer spinning solution through nozzles arranged in one nozzle block, various physical properties (characteristics) of the nanofiber nonwoven fabric required by the application are effectively improved. There were disadvantages that could not be satisfied.

In order to solve such problems, several conventional electrospinning apparatuses are provided in parallel, and two or more polymer spinning solutions are electrospun in each electrospinning apparatus to produce a composite nanofiber nonwoven fabric. There has been proposed a method for producing a composite nanofiber nonwoven fabric by laminating two or more types of nanofiber nonwoven fabrics each produced by a separate electrospinning apparatus during needle punching.

However, the above method has a problem that the manufacturing equipment and the manufacturing process are complicated and the manufacturing cost increases.

The purpose of the present invention is to maximize the electric force effect imparted to the electrospinning nozzle block (4), in other words, to increase the electric force higher than the interfacial tension of the spinning solution, thereby enhancing the fiber-forming effect. It is to provide a composite electrospinning apparatus capable of producing a large amount of nanofibers, effectively preventing the current state of droplets and producing high-quality nanofibers.

Another object of the present invention is that since two or more polymer spinning solutions can be simultaneously electrospun through nozzles arranged in one nozzle block, the composite nanofiber nonwoven fabric and the composite nanofiber filament can be easily installed and processed. It is providing the composite electrospinning apparatus which can be manufactured by.

The present invention produces composite nanofiber nonwoven fabric and composite nanofiber filaments having physical properties suitable for the application by simple equipment and processes by electrospinning two or more polymer spinning solutions through nozzles arranged in one nozzle block. try to.

Furthermore, the present invention seeks to simultaneously mass produce two or more types of high-quality nanofibers by maximizing the electric force effect during electrospinning and effectively preventing the current state of droplets.

The composite electrospinning apparatus according to the present invention for achieving the above-mentioned problems is as follows: [I] Nozzles for spinning two or more kinds of spinning solutions in the nozzle block (4), etc., at a constant repetition rate at the same or different ratios. Points that are regularly or randomly arranged in units, or are randomly arranged in a fixed ratio, [II] The number of spinning solution main tanks (1) is two or more, [III] Spinning solution A spinning solution drop device (3) is provided between the main tank (1) and the nozzle block (4).

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

As shown in FIGS. 1 and 2, the composite electrospinning apparatus according to the present invention includes two or more spinning solution main tanks (1) for storing each spinning solution, and a metering pump (2) for quantitatively supplying the spinning solution. ) And a nozzle (5) composed of a large number of pins are combined in a block form, and the nozzle block (4) for discharging the spinning solution into a fiber form is positioned above or below the nozzle block and is spun. A collector (7) for accumulating single fibers, a voltage generator (9) for generating a high voltage, and a spinning solution discharging device (12) connected to the uppermost part of the nozzle block.

FIG. 1 is a process schematic diagram for producing a composite nanofiber nonwoven fabric using the composite electrospinning apparatus according to the present invention, and FIG. 2 is a process schematic diagram for producing a composite nanofiber filament using the composite electrospinning apparatus according to the present invention. It is.

In the present invention, nozzles for spinning two or more kinds of spinning solutions in the nozzle block (4) are regularly or randomly arranged in the same or different ratios in a certain repeating unit. Preferably, the nozzle block (4) is arranged such that the nozzles and the like are alternately arranged one by one in any direction selected from the horizontal direction, the vertical direction, and the diagonal direction.

FIG. 3 is a schematic diagram showing a state in which nozzles for spinning two or more kinds of polymer spinning solutions on the nozzle block (4) are alternately arranged in a row in a diagonal direction. FIG. 4 is a schematic view showing a state in which nozzles for spinning two or more kinds of polymer spinning solutions on a nozzle block according to the present invention are regularly arranged in a certain repeating unit at a different ratio. is there. FIG. 5 is a schematic diagram showing a state in which nozzles for spinning two or more kinds of polymer spinning solutions on the nozzle block are alternately arranged in a row in the longitudinal direction and a solution supply state.

In addition, as shown in FIGS. 1 and 2, the present invention includes two or more spinning solution main tanks (1, 1 ′) for storing and supplying different polymer spinning solutions, A spinning solution drop device (3) is provided between the nozzle blocks (4).

In the present invention, the outlet of the nozzle (5) provided in the nozzle block (4) is formed in the upper direction, the lower direction or the horizontal direction. The collector (7) is provided at the upper part, the lower part or the horizontal position of the nozzle block (4), but is preferably provided at the upper part from the viewpoint of mass production.

Hereinafter, in the composite electrospinning apparatus of the present invention, the outlet of the nozzle (5) provided in the nozzle block (4) is formed in the upper direction, and the collector (7) is located in the upper part of the nozzle block (4). An explanation will be made focusing on an up-spinning type electrospinning apparatus. However, the present invention is not limited only to the upward electrospinning apparatus. As shown in FIG. 6, the nozzle block (4) of the present invention has [I] nozzles (5) for spinning different spinning solutions, etc. regularly or randomly by a certain repeating unit at the same or different ratio. A nozzle plate (4f) arranged on the nozzle plate, two or more spinning solution supply plates (4h, 4h ′), which are positioned below the nozzle plate (4f) and supply the spinning solution to the nozzle, [II] nozzle ( 5) an overflow removal nozzle (4a) enclosing and an overflow liquid temporary storage plate (4g) which is connected to the overflow removal nozzle and is located immediately above the nozzle plate, and the overflow liquid temporary storage plate Overflow removal nozzle support plate (4e) located on the upper stage and supporting the overflow removal nozzle; [III] Nozzle (5) and overflow removal nozzle An air supply nozzle (4b) enclosing (4a), an air supply nozzle support plate (4c) located at the uppermost stage of the nozzle block and supporting the air supply nozzle, and an air supply nozzle support plate An air storage plate (4d) that is located immediately below and supplies air to the air supply nozzle; [IV] A conductor plate that has pins arranged in the same manner as the nozzle arrangement method and is located immediately below the nozzle plate (4i); and [V] A heating plate (4j) located immediately below the spinning solution supply plate is preferable.

As shown in FIG. 6, an overflow removal nozzle (4a) for removing the spinning solution that has not been spun around the nozzle (5) for electrospinning the spinning solution onto the collector, and the accumulation distribution of the nanofibers. An air supply nozzle (4b) for supplying air for spreading is installed in order to form a triple tube.

In the nozzle block (4) of FIG. 6, nozzles (5) for spinning different spinning solutions are alternately arranged in a row in a diagonal direction.

As shown in FIGS. 8 and 10, the outlet of the nozzle (5) for electrospinning the spinning solution onto the collector has a shape in which the outlet portion is expanded into one or more soot tubes. At this time, the angle (θ) is set to 90 to 175 °, more preferably 95 to 150 °, in order to stably form spinning solution drops of the same form at the outlet of the nozzle (5). preferable.

When the exit angle (θ) of the nozzle exceeds 175 °, a large droplet is formed at the nozzle portion, and the surface tension increases. As a result, in order to form nanofibers, a higher voltage is required, and by spinning from the outer peripheral part instead of the central part of the droplet, the phenomenon that the central part of the droplet is solidified and the nozzle is clogged. Problems can occur.

On the other hand, when the nozzle exit angle (θ) is less than 90 °, the droplets formed at the nozzle exit site are considerably small, and the electric field becomes instantaneously non-uniform or supplied at the nozzle exit site. As a result, the droplets are formed abnormally, the fibers cannot be formed, and a droplet phenomenon can occur.

In the present invention, the length of the nozzle (L, L ₁ , L ₂ ) is not particularly limited.

However, the nozzle inner diameter (Di) is preferably 0.01 to 5 mm, and the nozzle outer diameter (Do) is preferably 0.01 to 5 mm. When the inner diameter or outer diameter of the nozzle is less than 0.01 mm, droplet phenomenon frequently occurs, and when it exceeds 5 mm, fibers cannot be formed.

8 and 9 show a side surface and a plane of the nozzle where one enlarged portion (angle) is formed at the nozzle outlet, and FIGS. 10 and 11 show two enlarged portions (angle) formed at the nozzle outlet. The side and the plane of the nozzle are shown. That is, θ ₁ shown in FIG. 10 is an exit angle of the first nozzle that is a portion where the spinning solution is spun, and θ ₂ is an exit angle of the second nozzle that is a portion where the spinning solution is supplied. is there.

A number of nozzles (5) in the nozzle block (4) are arranged in a nozzle plate (4f), and an overflow removal nozzle (4a) enclosing the nozzle (5) is provided outside the nozzle (5). An air supply nozzle (4b) and the like are sequentially installed.

The overflow removal nozzle (4a) not only prevents the droplet phenomenon that occurs when the excessive amount of spinning solution formed at the outlet of the nozzle (5) is not fiberized, but also recovers the overflowing spinning solution. The spinning solution that is not fiberized at the nozzle outlet is collected and transferred to an overflow liquid temporary storage plate (4g) located immediately below the nozzle plate (4f).

The diameter of the overflow removing nozzle (4a) is naturally larger than that of the nozzle (5), and is preferably made of an insulator.

The overflow liquid temporary storage plate (4g) is made of an insulator, temporarily stores the remaining spinning solution flowing in through the overflow removing nozzle (4a), and then transfers it to the spinning solution supply plate (4h). Play a role.

An air supply plate (4d) for supplying air is located on the upper stage of the overflow liquid temporary storage plate (4g) and includes a nozzle (5) and an overflow removal nozzle (4a). To supply air. An air supply nozzle support plate (4c) is installed on the uppermost layer of the nozzle block (4) in which the air supply nozzles (4b) are arranged, and the air supply nozzle support plate (4c). ) Is made of a non-conductive material. The support plate (4c) for the air supply nozzle is located in the nozzle block, and the electric force applied to the collector (7) and the nozzle (5) is concentrated only on the nozzle (5), so that the nozzle (5) site So that it can be spun smoothly.

The distance (h) from the upper tip of the nozzle (5) to the upper tip of the air supply nozzle (4b) is 1 to 20 mm, preferably 2 to 15 mm. That is, the height of the air supply nozzle (4b) is set to be 1 to 20 mm, preferably about 2 to 15 mm higher than the height of the nanofiber spinning nozzle (5). When h is 0, that is, when the air supply nozzle (4b) is positioned at the same height as the nozzle (5), a jet stream is not effectively formed in the nozzle (5) portion, and the nanofibers are collected by the collector ( 7) Less area deposited on top. On the other hand, if h exceeds 20 mm, the electric force is weakened by the high voltage applied between the collector and the nozzle, not only the ability to form nanofibers by electrospinning is reduced, but also the length and formation pattern of the jet stream It becomes unstable. Specifically, the stability of the jet stream forming portion is hindered by a Taylor cone. Therefore, smooth spinning of nanofibers is difficult.

The air velocity at the air supply nozzle (4b) is 0.05 to 50 m / sec, more preferably 1 to 30 m / sec. When the air velocity is less than 0.05 m / sec, the spreading property of the nanofibers collected in the collector is low and the collection area is not improved so much, and the air velocity is 50 m / sec. If it exceeds 2 seconds, the air velocity will be too high and the collection area where the nanofibers will be collected by the collector will be reduced, reducing the uniformity of nanofiber collection.

A conductor plate (4i) in which pins are arranged in the same manner as the nozzle arrangement method is installed immediately below the nozzle plate (4f), and a voltage generator (9) is connected to the conductor plate (4i). Is done.

Further, an indirect heating type heating apparatus (not shown) is provided immediately below the spinning solution supply plate (4h).

The conductor plate (4i) serves to apply a high voltage to the nozzle (5), and the spinning solution supply plate (4h) is spun into the nozzle block (4) from the spinning solution drop device (3). After storing the solution, it serves to supply the nozzle (5). At this time, the spinning solution supply plate (4h) is preferably manufactured so as to occupy a minimum space so that the storage amount of the spinning solution can be minimized.

On the other hand, the spinning solution drop device (3) of the present invention is designed to have a sealed cylindrical shape as shown in FIGS. 12 (a) and 12 (b) as a whole. The spinning solution continuously flowing from the tank (1) serves to supply the nozzle block (4) in droplet form.

The spinning solution drop device (3) has a generally sealed cylindrical shape as shown in FIGS. 12 (a) and 12 (b). 12A is a cross-sectional view of the spinning solution drop device, and FIG. 12B is a perspective view of the spinning solution drop device. At the upper end of the spinning solution drop device (3), a spinning solution guide tube (3c) for guiding the spinning solution to the nozzle block and a gas inflow tube (3b) are arranged side by side. At this time, it is preferable to form the spinning solution guide tube (3c) slightly longer than the gas inflow tube (3b).

The gas is introduced from the lower end of the gas inlet pipe, and the portion where the gas is introduced for the first time is connected to the filter (3a). A spinning solution discharge pipe (3d) for guiding the dropped spinning solution to the nozzle block (4) is formed at the lower end of the spinning solution drop device (3). The intermediate portion of the spinning solution drop device (3) is formed in a hollow state so that the spinning solution is dropped from the end portion of the spinning solution guide tube (3c).

The spinning solution that has flowed into the spinning solution drop device (3) flows along the spinning solution guide tube (3c) and is dropped from the end thereof, thereby interrupting the spinning solution flow one or more times.

The principle by which the spinning solution is dropped will be described in detail. When gas flows into the upper end of the spinning solution drop device (3) sealed along the filter (3a) and the gas inflow tube (3b), the pressure of the spinning solution guide tube (3c) is caused by gas overflow or the like. Will be naturally irregular, and the spinning solution will drop due to the pressure difference generated at this time.

In the present invention, an inert gas such as air or nitrogen can be used as the inflowing gas.

The entire nozzle block (4) of the present invention is perpendicular to the traveling direction of the nanofibers to be electrospun by the left and right reciprocating movement (10) of the nozzle block in order to make the distribution of the nanofibers to be electrospun uniform. Reciprocates left and right.

Further, in the nozzle block (4), more specifically, in the spinning solution supply plate (4h), the spinning solution is prevented from being gelled in the nozzle block (4). For this purpose, a stirrer (11c) for stirring the spinning solution stored in the nozzle block (4) is installed.

The agitator (11c) is connected to the agitator motor (11a) by a non-conductive insulating rod (11b).

When the stirrer (11c) is installed in the nozzle block (4), when the solution containing the inorganic metal is electrospun or the spinning solution dissolved using a mixed solvent for a long time is electrospun, the nozzle block (4) It is possible to effectively prevent gelation of the spinning solution.

A spinning solution discharge device (12) for forcibly transferring the spinning solution supplied excessively to the nozzle block to the spinning solution main tank (1) is connected to the uppermost part of the nozzle block (4).

The spinning solution discharge device (12) forcibly transports the spinning solution excessively supplied into the nozzle block to the spinning solution main tank (1) by suction or the like.

The collector (7) of the present invention is provided (attached) with a direct heating or indirect heating heating device (not shown), and the collector (7) is fixed or continuously rotated.

Next, a method for producing a composite nanofiber nonwoven fabric using the composite electrospinning apparatus of the present invention will be described with reference to FIG.

First, the two spinning solutions of thermoplastic resins or thermosetting resins stored in the two spinning solution main tanks (1, 1 ') are measured by the respective metering pumps (2, 2'). Then, it is quantitatively supplied to the spinning solution drop device (3, 3 ′). At this time, as the thermoplastic or thermosetting resin used to produce the spinning solution, polyester resin, acrylic resin, phenol resin, epoxy resin, nylon resin, poly (glycolide / L-lactide) Copolymers, poly (L-lactide) resins, polyvinyl alcohol resins, polyvinyl chloride resins and the like are included. As the spinning solution, a melt of the above resin may be used, or another resin solution may be used.

Thus, the spinning solution supplied into each spinning solution drop device (3, 3 ') discontinuously passes through the spinning solution drop device (3, 3'), that is, the flow of the spinning solution. Is supplied to the spinning solution supply plate (4h) of the nozzle block (4) to which the stirrer (11c) is installed while the high voltage according to the present invention is applied. The spinning solution drop device (3, 3 ') also serves to block the flow of the spinning solution and prevent electricity from passing through the spinning solution main tank (1, 1').

Next, in the nozzle block (4), each spinning solution is discharged upwardly to the upper collector (7) to which a high voltage is applied through nozzles and the like that are alternately arranged in a row in a diagonal direction. A web is produced.

The spinning solution transferred to the spinning solution supply plate (4h) is discharged to the upper collector (7) through the nozzle (5) to form fibers. At this time, the nanofibers electrospun from the nozzle (5) are collected by the collector (7) while being widely spread by the air jetted from the air supply nozzle (4b), thereby increasing the collection area and the integration density. Becomes uniform. Excess spinning solution that could not be fibrillated by the nozzle (5) gathers at the overflow removal nozzle (4a) and moves again to the spinning solution supply plate (4h) through the overflow liquid temporary storage plate (4g). Become.

Further, the spinning solution excessively supplied to the uppermost part of the nozzle block is forcibly transferred to the spinning solution main tank (1, 1 ') by the spinning solution discharge device (12, 12').

At this time, in order to promote fiber formation by electric force, the voltage was generated in the voltage generating device (6) on the conductor plate (4i) and the collector (7) installed in the lower part of the nozzle block (4). A voltage of 1 kV or higher, more preferably, 20 kV or higher is applied. As the collector (7), it is more advantageous from the viewpoint of productivity to use an endless belt. The collector (7) preferably reciprocates a certain distance from side to side in order to make the density of the nonwoven fabric uniform.

In this way, the nanofiber web (15) formed on the collector (7) passes through the web support roller (14) and is wound around the take-up roller (16), thereby completing the non-woven fabric manufacturing process. .

The composite nanofiber nonwoven fabric produced by the production apparatus of the present invention can easily satisfy physical properties suitable for various applications by adjusting the type and ratio of the spinning solution. As a result, the composite nanofiber nonwoven fabric according to the present invention is used in various applications such as artificial leather, sanitary napkins, filters, medical materials such as artificial blood vessels, winter clothes, semiconductor wipers, and battery nonwoven fabrics.

Next, a method for producing a composite nanofiber filament using the composite electrospinning apparatus of the present invention will be described with reference to FIG.

As shown in FIG. 2, the composite nanofiber filament is manufactured by manufacturing the nanofiber web (15) in the same manner as the composite nanofiber nonwoven fabric described above, and then manufacturing the nanofiber web (15). Is passed through the air twisting device (18) and twisted, and subsequently passed through the first roller (19), the second roller (20) and the third roller (22) in order and stretched. It is manufactured by a method of winding on a take-up roller (16).

Optionally, a stretching process can be performed by the heat setting device (21) between the stretching process and the winding process.

At this time, the nanofiber web (15) is in the form of a ribbon. In order to produce a ribbon-shaped nanofiber web (15), (I) the nanofiber web (15) is electrospun into the same width as the entire width of the collector (7), Either a method of cutting the web (15) with a web cutting device is used, or (II) a method of electrospinning by dividing the width of the nanofiber web (15) into the same small width as that of one nozzle.

The present invention can mass-produce two or more kinds of high-quality nanofibers, and can produce composite nanononwoven fabrics and composite nanofilaments suitable for physical properties required for each application by simple equipment and processes.

Hereinafter, the present invention will be described in more detail through examples and comparative examples. However, the present invention is not limited to these examples.

A poly (ε-caprolactone) polymer (manufactured by Aldrich, USA) having a number average molecular weight of 80,000 is mixed with methylene chloride / N, N-dimethylformamide (volume ratio: 75/25) in a mixed solvent to a concentration of 13% by weight. To prepare a spinning solution. The polymer spinning solution had a surface tension of 35 mN / m, a solution viscosity of 35 centipoise (cPS) at room temperature, an electric conductivity of 0.02 mS / m, and a dielectric constant of 90.

On the other hand, a polyurethane resin having a number average molecular weight of 80,000 (PEllethane 2103-80AE manufactured by Dow Chemical Co.) was dissolved in N, N-dimethylformamide so as to have a concentration of 8% by weight to produce another spinning solution.

The two kinds of spinning solutions stored in the spinning solution main tank (1, 1 ′) of the composite electrospinning apparatus according to the present invention shown in FIG. The flow of the spinning solution was discontinuously changed by feeding to the apparatus (3, 3 ′). Subsequently, two kinds of the above spinning solutions are supplied to the nozzle (5) in the nozzle block (4) shown in FIG. 6, and the upper part of the collector (7) located at the upper part through this nozzle (5) is supplied. Then, the nanofiber web (15) was produced by electrospinning upward in the form of a fiber, and then the composite nanofiber nonwoven fabric was produced by winding on the take-up roller (16) through the web support roller (14). At this time, as the nozzle block (4) used, the nozzles for spinning the above two kinds of spinning solutions are arranged as shown in FIG. 4, and the poly (ε-caprolactone) spinning solution is used in the whole nozzles. The ratio of the number of nozzles for spinning is 66.7%, the ratio of the number of nozzles for spinning the polyurethane resin spinning solution is 33.3%, and four nozzle blocks having 9,720 nozzles per nozzle block are used. The total number of nozzles is 38,880, the spinning distance is 15 cm, the reciprocating motion of the nozzle block (4) is 2 m / min, an electric heater is installed in the collector (7), and the surface temperature of the collector (7) is 35. Electrospinning was performed at 0 ° C. During spinning, the spinning solution overflowing from the top of the nozzle block (4) was forcibly transferred to the spinning solution main tank (1) using the spinning solution discharge device (12) using suction air. At this time, a nozzle having a nozzle outlet angle (θ) of 120 °, a nozzle inner diameter (Di) of 0.9 mm, and an outer diameter of 1 mm was used. As the air supply nozzle, an air supply nozzle having an inner diameter (Di) of 20 mm, an outer diameter of 23 m, and a distance (h) from the upper tip of the nozzle (5) to the upper tip of the air supply nozzle (4b) is 8 mm. The air velocity was 10 m / sec. A model CH50 manufactured by Simco Company was used as a voltage generating apparatus. The graph of strength-elongation for the composite nanofiber nonwoven fabric (W) produced in this way is as shown in FIG. 13, and the graph of tear strength is as shown in FIG.

A poly (ε-caprolactone) polymer (manufactured by Aldrich, USA) having a number average molecular weight of 80,000 is mixed with methylene chloride / N, N-dimethylformamide (volume ratio: 75/25) in a mixed solvent to a concentration of 13% by weight. To prepare a spinning solution. The polymer spinning solution had a surface tension of 35 mN / m, a solution viscosity of 35 centipoise (cPS) at room temperature, an electric conductivity of 0.02 mS / m, and a dielectric constant of 90.

On the other hand, a polyurethane resin having a number average molecular weight of 80,000 (PEllethane 2103-80AE manufactured by Dow Chemical Co.) was dissolved in N, N-dimethylformamide so as to have a concentration of 8% by weight to produce another spinning solution.

The two kinds of spinning solutions stored in the spinning solution main tank (1, 1 ′) of the composite electrospinning apparatus according to the present invention shown in FIG. The flow of the spinning solution was discontinuously changed by feeding to the apparatus (3, 3 ′). Subsequently, two kinds of the above spinning solutions are supplied to the nozzle (5) in the nozzle block (4) shown in FIG. 6, and the upper part of the collector (7) located at the upper part through this nozzle (5) is supplied. Then, the nanofiber web (15) was produced by electrospinning upward in the form of a fiber, and then the composite nanofiber nonwoven fabric was produced by winding on the take-up roller (16) through the web support roller (14). At this time, as the used nozzle block (4), the nozzles for spinning the above two kinds of spinning solutions are arranged as shown in FIG. 4, and poly (ε-or prolactone) spinning is performed in the whole nozzles. The ratio of the number of nozzles for spinning the solution is 33.3%, the ratio of the number of nozzles for spinning the polyurethane resin spinning solution is 66.7%, and four nozzle blocks having 9,720 nozzles per nozzle block are used. The total number of nozzles is 38,880, the spinning distance is 15 cm, the reciprocating motion of the nozzle block (4) is 2 m / min, an electric heater is installed in the collector (7), and the surface temperature of the collector (7) Was electrospun at 35 ° C. During spinning, the spinning solution overflowing from the top of the nozzle block (4) was forcibly transferred to the spinning solution main tank (1) using the spinning solution discharge device (12) using suction air. At this time, a nozzle having a nozzle outlet angle (θ) of 120 °, a nozzle inner diameter (Di) of 0.9 mm, and an outer diameter of 1 mm was used. As the air supply nozzle, an air supply nozzle having an inner diameter (Di) of 20 mm, an outer diameter of 23 m, and a distance (h) from the upper tip of the nozzle (5) to the upper tip of the air supply nozzle (4b) is 8 mm. The air velocity was 10 m / sec. A model CH50 manufactured by Simco Company was used as a voltage generating apparatus. The graph of strength-elongation for the composite nanofiber nonwoven fabric (X) thus produced is as shown in FIG. 13, and the graph of tear strength is as shown in FIG.

Comparative Example 1

A poly (ε-caprolactone) polymer (manufactured by Aldrich, USA) having a number average molecular weight of 80,000 is mixed with methylene chloride / N, N-dimethylformamide (volume ratio: 75/25) in a mixed solvent to a concentration of 13% by weight. To prepare a spinning solution. The polymer spinning solution had a surface tension of 35 mN / m, a solution viscosity of 35 centipoise (cPS) at room temperature, an electric conductivity of 0.02 mS / m, and a dielectric constant of 90.

The polymer spinning solution stored in the spinning solution main tank (1) of the normal upward electrospinning apparatus is metered by the metering pump (2), and then the nozzle block (4) to which a voltage of 35 kV is applied. After the nanofiber web (15) is manufactured by feeding the nozzle (5) in the inside (5) and electrospinning upward on the collector (7) located above through the nozzle (5). The nanofiber nonwoven fabric was manufactured by winding on a winding roller (16) through a web support roller (14). At this time, as the used nozzle block (4), all the nozzles for spinning the above-mentioned one kind of spinning solution are arranged diagonally, and four nozzle blocks having 9,720 nozzles per nozzle block are arranged. The total number of nozzles used is 38,880, the spinning distance is 15 cm, the discharge amount per nozzle is 1.2 mg / min, the reciprocating motion of the nozzle block (4) is 2 m / min, and the collector (7) An electric heater was installed in the collector, and the surface temperature of the collector was set to 35 ° C. to perform electrospinning. During the spinning process, the spinning solution overflowing from the top of the nozzle block (4) was forcibly transferred to the spinning solution main tank (1) by the spinning solution discharge device (12) using suction air. Here, a nozzle having a nozzle outlet angle (θ) of 120 °, an inner diameter (Di) of 0.9 mm, and an outer diameter of 1 mm was used. As the air supply nozzle, an air supply nozzle having an inner diameter (Di) of 20 mm, an outer diameter of 23 m, and a distance (h) from the upper tip of the nozzle (5) to the upper tip of the air supply nozzle (4b) is 8 mm. The air velocity was 10 m / sec. A model CH50 manufactured by Simco Company was used as a voltage generating apparatus. The graph of strength-elongation for the nanofiber nonwoven fabric (Y) produced in this way is as shown in FIG. 13, and the graph of tear strength is as shown in FIG.
Comparative Example 2

A spinning solution was prepared by dissolving polyurethane resin having a number average molecular weight of 80,000 (PElletane 2103-80AE manufactured by Dow Chemical Co.) in N, N-dimethylformamide to a concentration of 8% by weight.

The polymer spinning solution stored in the spinning solution main tank (1) of the normal upward electrospinning apparatus is metered by the metering pump (2), and then the nozzle block (4) to which a voltage of 35 kV is applied. After the nanofiber web (15) is manufactured by feeding the nozzle (5) in the inside (5) and electrospinning upward on the collector (7) located above through the nozzle (5). The nanofiber nonwoven fabric was manufactured by winding on a winding roller (16) through a web support roller (14). At this time, as the nozzle block (4) used, all nozzles for spinning the above-mentioned one kind of spinning solution are arranged diagonally, and four nozzle blocks having 9,720 nozzles per nozzle block are used. The total number of nozzles is 38,880, the spinning distance is 15 cm, the discharge amount per nozzle is 1.2 mg / min, the reciprocating motion of the nozzle block (4) is 2 m / min, and the collector (7) An electric heater was installed, and the surface temperature of the collector was set to 35 ° C. to perform electrospinning. During the spinning process, the spinning solution overflowing from the top of the nozzle block (4) was forcibly transferred to the spinning solution main tank (1) by the spinning solution discharge device (12) using suction air. Here, a nozzle having a nozzle outlet angle (θ) of 120 °, an inner diameter (Di) of 0.9 mm, and an outer diameter of 1 mm was used. As the air supply nozzle, an air supply nozzle having an inner diameter (Di) of 20 mm, an outer diameter of 23 m, and a distance (h) from the upper tip of the nozzle (5) to the upper tip of the air supply nozzle (4b) is 8 mm. The air velocity was 10 m / sec. A model CH50 manufactured by Simco Company was used as a voltage generating apparatus. The graph of strength-elongation with respect to the nanofiber nonwoven fabric (Z) manufactured as described above is as shown in FIG. 13, and the graph of tear strength is as shown in FIG.

Since the present invention has the required physical properties for each application, it includes not only daily products such as artificial leather, air cleaning filters, wiping cloth, golf gloves, wigs, but also filters for artificial dialysis, artificial blood vessels, anti-adhesion agents, artificial It can be used to produce composite nanofiber nonwoven fabrics and composite nanofilaments that are used as materials in various industrial fields such as bone.

It is the process schematic which manufactures a composite nanofiber nonwoven fabric using the composite electrospinning apparatus of this invention. It is the process schematic which manufactures the continuous filament comprised from the composite nanofiber using the composite electrospinning apparatus of this invention. FIG. 2 is a schematic diagram showing a state in which nozzles for spinning two or more kinds of polymer spinning solutions on a nozzle block according to the present invention are alternately arranged in a diagonal direction in a row (◯: first spinning solution component; Two spinning solution components). FIG. 3 is a schematic diagram showing a state in which nozzles for spinning two or more kinds of polymer spinning solutions on a nozzle block according to the present invention are regularly arranged in a constant repeating unit at a different ratio from each other (◯: first Spinning solution component, ●: second spinning solution component). FIG. 3 is a schematic diagram showing a state in which nozzles for spinning two or more kinds of polymer spinning solutions on a nozzle block according to the present invention are alternately arranged in a longitudinal direction and a solution supply state (◯: first spinning solution component) , ●: Second spinning solution component). It is a schematic diagram of the nozzle block (4) by this invention. FIG. 4 is a cross-sectional view of a nozzle block (4) according to the present invention. It is a schematic diagram which shows the side surface of a nozzle (5). It is a plane illustration figure of a nozzle (5). It is a schematic diagram which shows the side surface of a nozzle (5). It is a plane illustration figure of a nozzle (5). It is sectional drawing of the spinning dope drop apparatus (3) in this invention. It is a perspective view of the spinning dope drop device (3) in the present invention. It is a graph of the strength-elongation with respect to the kind (type) of each nanofiber nonwoven fabric. It is a graph of the tear strength with respect to the kind (type) of each nanofiber nonwoven fabric.

Explanation of symbols

1, 1 ': Spinning solution main tank 2, 2': Metering pump 3, 3 ': Spinning solution drop device 3a: Spinning solution drop device filter 3b: Gas inflow tube 3c: Spinning solution guide tube 3d: Spinning solution discharge tube 4: Nozzle block 4a: Overflow removal nozzle 4b: Air supply nozzle 4c: Air supply nozzle support plate (non-conductor)
4d: Air storage plate 4e: Overflow removal nozzle support plate 4f: Nozzle plate 4g: Overflow liquid temporary storage plate 4h, 4h ': Spinning solution supply plate 4i: Conductor plate 4j: Heating plate 5: Nozzle 6: Nanofiber 7: Collector (conveyor belt)
8a, 8b: Collector support roller 9: Voltage generating device 10: Left-right reciprocating device for nozzle block 11a: Stirrer motor 11b: Non-conductive insulating rod 11c: Stirrer 12, 12 ': Spinning solution discharge device 13: Transfer tube 14 : Web support roller 15: nanofiber web 16: web winding roller 17: web transfer roller 18: air twisting machine 19: first roller 20: second roller 21: heat fixing device (heater)
22: Third roller W: Composite nanofiber non-woven fabric manufactured from Example 1 X: Composite nanofiber non-woven fabric manufactured from Example 2 Y: Nanofiber non-woven fabric manufactured from Comparative Example 1 Z: Comparative Example 2 Nanofiber nonwoven fabric manufactured from: θ: Nozzle outlet angle L: Nozzle length Di: Nozzle inner diameter Do: Nozzle outer diameter h: Distance from the upper tip of the nozzle to the upper tip of the air supply nozzle

Claims (13)

Spinning solution main tank (1); Metering pump (2); Nozzle block (4); Nozzle (5) installed in the nozzle block; Collector (7) for collecting fibers spun from the nozzle block; and In an electrospinning apparatus comprising a voltage generating apparatus (9) for applying a voltage to a nozzle block (4) and a collector (7), [I] two or more spinning solutions are respectively added to the nozzle block (4). The spinning nozzles and the like are regularly or randomly arranged in the same or different ratios in a certain repeating unit, and [II] two or more spinning solution main tanks (1), and [III] the spinning solution main A composite electrospinning apparatus, wherein a spinning solution drop device (3) is provided between the tank (1) and the nozzle block (4). Nozzles for spinning two or more kinds of polymer spinning solutions in the nozzle block (4) are alternately arranged in a row in any direction selected from the horizontal direction, the vertical direction and the diagonal direction. The composite electrospinning apparatus according to claim 1, characterized in that it is characterized in that: The outlet of a nozzle (5) provided in the nozzle block (4) is formed in an upper direction, and the collector (7) is provided in an upper part of the nozzle block (4). 2. The composite electrospinning apparatus according to item 1. The composite electrospinning apparatus according to claim 1, wherein the entire nozzle block (4) reciprocates left and right. The composite electrospinning apparatus according to claim 1, wherein a heating device is installed in the collector (7). The composite electrospinning apparatus according to claim 1, wherein a stirrer (11c) is installed in the nozzle block (4). A spinning solution discharge device (12) for forcibly transferring the spinning solution that has not been spun at the nozzle portion to the spinning solution main tank (1) is formed in the upper stage of the nozzle block (4). The composite electrospinning apparatus according to claim 1, wherein The composite electrospinning device according to claim 1, wherein the collector (7) is fixed or continuously rotated. The composite electrospinning according to claim 1, characterized in that the outlet of the nozzle (5) is formed into one or more rods having an angle (θ) of 90 to 175 °. apparatus. In the nozzle block (4), nozzles for spinning two or more kinds of spinning solutions in the nozzle block (4) are arranged regularly or randomly in the same or different ratios in a certain repeating unit. Nozzle plate (4f) and two or more spinning solution supply plates (4h, h ') for supplying the spinning solution to the nozzle located at the lower stage of the nozzle plate; [II] Overflow removal surrounding nozzle (5) Nozzle (4a), connected to the above-mentioned overflow removal nozzle, and an overflow liquid temporary storage plate (4g) located immediately above the nozzle plate and an overflow removal located directly above the overflow liquid temporary storage plate Nozzle support plate (4e) for overflow removal supporting the nozzle; [III] The nozzle (5) and the overflow removal nozzle (4a) are wrapped. The air supply nozzle (4b), the air supply nozzle support plate (4c) positioned at the uppermost stage of the nozzle block and supporting the air supply nozzle, and the air positioned immediately below the air supply nozzle support plate Air storage plate (4d) for supplying air to the supply nozzle; [IV] Conductor plate (4i) arranged in the same stage as the nozzle plate and positioned immediately below the nozzle plate; and [V The composite electrospinning device according to claim 1, characterized by comprising a heating plate (4j) positioned immediately below the spinning solution supply plate. Nozzles for spinning two or more kinds of polymer spinning solutions in the nozzle block (4) are alternately arranged in a row in any direction selected from the horizontal direction, the vertical direction and the diagonal direction. The composite electrospinning apparatus according to claim 10, characterized in that it is characterized in that: A composite nanofiber nonwoven fabric produced using the composite electrospinning apparatus according to claim 1. A continuous composite nanofiber filament produced using the composite electrospinning apparatus according to claim 1.

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