KR101834408B1 - Nanofiber composite fiber having excellent adhesive ability between substrate and nanofiber nonwoven and a separator containing thereof - Google Patents

Abstract

The present invention relates to a method for producing a conjugate fiber having improved adhesion between nanofiber nonwoven fabrics, comprising the steps of: preparing a thermoplastic polyurethane base; Moving the thermoplastic polyurethane base material to an electrospinning device and electrospinning a polymer spinning liquid on one side of the thermoplastic polyurethane base material to laminate the nanofiber nonwoven fabric; And thermally fusing a laminate having the nanofiber nonwoven fabric laminated on the thermoplastic polyurethane base material, wherein the total basis weight of the nanofiber nonwoven fabric is 1 g / m ² or more and 50 g / m ² or less The present invention also provides a method for producing a composite fiber having improved adhesion between a nonwoven fabric and a nanofiber nonwoven fabric.
According to the present invention, there is provided a method for producing a fiber in which a nanofiber is laminated by electrospinning a nanofiber nonwoven fabric on a thermoplastic polyurethane base material followed by thermal fusion bonding, so that the adhesion force between the base fiber and the nanofiber nonwoven fabric It is possible to provide an improved nanofiber laminated composite fiber.

Description

TECHNICAL FIELD [0001] The present invention relates to a nanofiber laminated composite fiber having improved adhesion between a base fiber and a nanofiber nonwoven fabric, and a separator containing the nanofiber composite fiber and an excellent adhesive ability between the nanofiber nonwoven and a separator,

The present invention relates to a composite fiber having improved adhesion between a substrate and a nanofiber nonwoven fabric, a separation membrane containing the same, and a method of manufacturing the same.

Nanofibers refer to microfibers having a diameter of only a few tens to several hundreds of nanometers. Nonwoven fabrics, membranes, filaments and braids composed of nanofibers are widely used for daily necessities, agriculture, clothing, and industrial applications.

In addition, it is used in a variety of fields such as artificial leather, artificial suede, sanitary napkin, clothes, diaper, packaging materials, various kinds of materials for use in general merchandise, various filter materials, medical materials for gene delivery materials and anti-

Nanofibers are produced by electric fields. That is, nanofibers generate electrical repulsive force inside the polymer material by applying a high voltage electric field to the polymer material, which is the raw material, and the nanofibers are manufactured and produced by breaking the molecules into a nano-sized yarn shape. At this time, as the electric field becomes stronger, the polymer material as the raw material is finely torn, so that a nanofiber having a thinning of 10 to 1000 nm can be obtained.

Meanwhile, a method of laminating the produced nanofibers with other base fibers includes a method of coating the nanofibers with different kinds of nanofibers when they are produced, and a method of separately producing nanofibers and bonding them to the different types of textiles. In the case of directly spinning the nanofibers on the base fiber in the production of the nanofiber, the adhesion between the nanofiber and the base fiber is weak, resulting in frequent peeling. In order to solve this problem, there is a method of enhancing the adhesion by adding a hot-melt layer between the nanofiber and the base fiber. However, there is a disadvantage in that the manufacturing cost is increased by addition of the process.

Disclosure of the Invention The present invention has been accomplished to solve the problems described above, and it is an object of the present invention to provide a thermoplastic polyurethane base material in which the first and second nanofiber nonwoven fabric layers are bonded to base fiber It is possible to provide a composite fiber in which a nanofiber nonwoven fabric strongly adhered and not peeled off even after multiple washing is laminated.

An embodiment of the present invention provides a method of manufacturing a nanofiber, comprising: preparing a thermoplastic polyurethane base material with base fiber to which nanofibers are radiated; Moving the thermoplastic polyurethane base material to the electrospinning unit 1 of the electrospinning apparatus and electrospinning the polymer spinning solution on one side of the base material to form a first nanofiber nonwoven fabric layer; Forming a second nanofiber nonwoven fabric layer on the first nanofiber nonwoven fabric layer by moving the laminate having the first nanofiber nonwoven fabric layer to the electrospinning unit 2; And thermally fusing a laminate having two layers of the nanofiber nonwoven fabric layer laminated on the base material,

And the total basis weight of each of the nanofiber nonwoven fabric layers is 1 g / m ² or more and 50 g / m ² or less. The object of the present invention is to provide a method for producing a conjugated fiber having improved adhesion between the substrate and the nanofiber nonwoven fabric.

Wherein a step of laminating at least one support selected from the group consisting of a polyethylene terephthalate base material, a cellulose base material, a synthetic base material and a binary material base to the other surface of the thermoplastic polyurethane base material may be added before the heat fusion step.

Wherein the polymer is one or two selected from the group consisting of polyimide (PI), polyacrylonitrile (PAN), polyethersulfone (PES), polyamide (PA), meta-aramid, PVDF, polyurethane It can be more than a species.

According to another embodiment of the present invention, there is provided a method of manufacturing a composite fiber having improved adhesion between a substrate and a nanofiber nonwoven fabric, wherein the first nanofiber nonwoven fabric layer and the second nanofiber nonwoven fabric layer have different fiber diameters or different polymer types .

According to another embodiment of the present invention, the first nanofiber nonwoven fabric layer is polyurethane (PU) and the second nanofiber nonwoven fabric layer is polyvinylidene fluoride (PVDF) or polyimide (PI) Provided is a method for producing a conjugated fiber having improved adhesion between a substrate and a nanofiber nonwoven fabric.

According to another embodiment of the present invention, in the method for producing a conjugate fiber having improved adhesion between a substrate and a nanofiber nonwoven fabric, the total basis weight of the nanofiber nonwoven fabric may be 1 g / m ² or more and 20 g / m ² or less.

According to another embodiment of the present invention, the electrospinning device used in the above-described manufacturing method controls the diameter range of the nanofibers by allowing the polymer spinning solution to be electrospun through a nozzle at a high temperature of 45 to 120 ° C .

According to another embodiment of the present invention, the first and second nanofiber nonwoven fabric layers are formed by electrospinning the polymer spinning solution with different basis weights in the transverse direction or longitudinal direction, so that the adhesion between the substrate and the nanofiber non- Thereby providing an improved method of producing a fiber.

According to an embodiment of the present invention, there is provided a method for producing a fiber in which a nanofiber is laminated by electrospinning a nanofiber nonwoven fabric on a thermoplastic polyurethane base followed by thermal fusion, It is possible to provide a nano-fiber laminated composite fiber having improved adhesion between non-woven fabrics.

According to another embodiment of the present invention, in fabricating the fiber having improved adhesion between the base material and the nanofiber nonwoven fabric, the polymer spinning solution is electrospun through the nozzle at a high temperature of 45 to 120 DEG C using a temperature controller, The diameter range of the fibers can be controlled.

According to another embodiment of the present invention, it is possible to provide a method of manufacturing a composite fiber including nanofibers having different basis weights on a planar surface by electrospinning the polymer spinning solution with different weights in the transverse or longitudinal direction.

Also, the composite fiber of the present invention is preferably usable as a separator. Since the separator made of the nanofibers produced through electrospinning has porosity, the separator prepared from the separator is preferably used as a separator because of its excellent cell performance, and desorption occurs between the substrate and the nanofibers Therefore, it is possible to use a stable separation membrane.

1 is a side view schematically showing an electrospinning apparatus according to the present invention,
2 is a side sectional view schematically showing a nozzle of a nozzle block installed in each unit of the electrospinning apparatus according to the present invention,
3 is a side cross-sectional view schematically showing another embodiment according to a nozzle of a nozzle block installed in each unit of the electrospinning apparatus according to the present invention,
4 is a front sectional view schematically showing a state in which an electric heater is installed in a nozzle block installed in each unit of the electrospinning apparatus according to the present invention,
5 is a sectional view taken along line A-A '
6 is a front sectional view schematically showing another embodiment in which an electric heater is installed in a nozzle block installed in each unit of the electrospinning apparatus according to the present invention,
7 is a sectional view taken along the line B-B '
FIG. 8 is a front sectional view schematically showing another embodiment of a state in which an electric heater is installed in a nozzle block installed in each unit of the electrospinning apparatus according to the present invention,
9 is a sectional view taken along line C-C '
10 is a view schematically showing an auxiliary transfer device of an electrospinning device according to the present invention,
11 is a view schematically showing another embodiment of the auxiliary belt roller of the auxiliary transfer device of the electrospinning apparatus according to the present invention,
FIGS. 12 to 15 are side views schematically showing the operation of the long sheet conveying speed adjusting apparatus of the electrospinning apparatus according to the present invention,
16 is a layout diagram of a nozzle block installed in the unit of the present invention,
17 is a plan view showing a process of electrospinning work according to the arrangement of the nozzle blocks as shown in FIG. 16,
18 is a plan view showing a state in which the nozzle in the spinning solution unit of the present invention is turned on and off in the CD direction,
FIG. 19 is a plan view showing a work process in which the basis weight of the polymer is electrospun in the CD direction according to the operation of the nozzle in the spinning solution unit as shown in FIG. 18;
20 is a plan view showing a state in which the nozzle in the spinning solution unit of the present invention is turned on and off in the MD direction,
21 is a structure of a composite fiber prepared by laminating a first nanofiber nonwoven fabric and a second nanofiber nonwoven fabric on a thermoplastic polyurethane base fabricated according to an embodiment of the present invention, and a support on the bottom of the thermoplastic polyurethane base fabric .

1. Description of Electrospinning Apparatus Used in the Present Invention

The electrospinning apparatus 1 according to the present invention comprises a bottom-up electrospinning apparatus 1 or a top-down electrospinning apparatus (not shown), wherein at least one unit 10a or 10b is sequentially arranged at a predetermined interval, Each of the units 10a and 10b emits the same polymer spinning solution individually, or the polymer spinning solution having different materials is separately electrospun to produce a nanofiber web.

Each of the units 10a and 10b has therein a spinning liquid main tank 8 in which a polymer spinning solution is filled therein and a metering pump for supplying a polymer spinning solution filled in the spinning solution main tank 8 in a fixed amount A nozzle block 11 for discharging the polymer solution for filling the spinning solution main tank 8 with a plurality of nozzles 12 arranged in a pin shape, And a voltage generator 14a, 14b for generating a voltage in the collector 13, the collector 13 being spaced apart from the nozzle 12 by a predetermined distance in order to accumulate the polymer spinning solution.

The electrospinning device 1 according to the present invention has a structure in which the polymeric spinning liquid filled in the spinning liquid main tank 8 is supplied to a plurality of nozzles 12 formed in the nozzle block 11 through the metering pump, And the supplied polymer spinning solution is radiated and focused on the collector 13 having a high voltage applied thereto through the nozzle 12 to form nanofibers on the long sheet 15 which is moved on the collector 13, Thereby forming a nonwoven fabric.

In the unit 10a of the units 10a and 10b of the electrospinning device 1 in front of the unit 10a positioned at the tip end of the unit 10a, nanofiber nonwoven fabrics are laminated by spraying the polymer spinning solution A feeding roller 3 for feeding the long sheet 15 is provided and a long sheet 15 in which a nano fiber nonwoven fabric is laminated is provided at the rear of the unit 10b located at the rear end of each unit 10a and 10b Up roller 5 for winding is provided.

On the other hand, it is preferable that the elongated sheet 15 in which the polymer solution is laminated while passing through the units 10a and 10b is made of nonwoven fabric or fabric, but is not limited thereto.

The material of the polymer solution to be radiated through each of the units 10a and 10b of the electrospinning device 1 is not particularly limited. For example, polyimide (PI), polyacrylonitrile (PAN) Polyether sulfone (PES), polyamide (PA), meta-aramid, polyvinylidene fluoride (PVDF), polyurethane (PU) and the like are preferable. Of these polyurethanes having properties similar to those of thermoplastic polyurethane Is most preferably used.

The spinning solution supplied through the nozzles 12 in the units 10a and 10b is a solution in which a polymer as a synthetic resin material capable of electrospinning is dissolved in a suitable solvent, But are not limited to, for example, phenol, formic acid, sulfuric acid, m-cresol, thifluoroacetone hydride / dichloromethane, water, N-methylmorpholine N-oxide, chloroform, tetrahydrofuran And aliphatic ketone groups such as methyl isobutyl ketone, methyl ethyl ketone, aliphatic hydroxyl group m-butyl alcohol, isobutyl alcohol, isopropyl alcohol, methyl alcohol, ethanol, aliphatic compounds such as hexane, tetrachlorethylene, acetone, , Diethylene glycol, ethylene glycol, halogen compounds such as trichlorethylene, dichloromethane, aromatic compounds such as toluene, xylene, aliphatic Cyclohexanone and cyclohexane as ester group and n-butyl acetate, ethyl acetate, butyl cellosolve as aliphatic ether group, acetic acid 2-ethoxyethanol, 2-ethoxyethanol, amide dimethylformamide, Dimethylacetamide, and the like, or a mixture of plural kinds of solvents may be used. The spinning solution preferably contains an additive such as a conductivity improver.

2, the nozzle 12 provided in the nozzle block 11 of the electrospinning device 1 according to the present invention comprises a multi-tubular nozzle 500, And two or more inner and outer tubes 501 and 502 are combined in a sheath-core form so that the use solution can be electrospun at the same time.

The nozzle block 11 includes a nozzle plate 405 in which a sheath-core type multi-tubular nozzle 500 is arranged and a multi-tubular nozzle 500 positioned at a lower end of the nozzle plate 405 (Not shown) for supplying a polymer solution (not shown) to the overflow removing nozzles 415 and the overflow removing nozzles 415 surrounding the multi-tubular nozzles 500, The overflow liquid temporary storage plate 410 and the overflow liquid temporary storage plate 410 located at the upper right end of the nozzle plate 405 and the overflow removing nozzle 415 And an overflow removing nozzle support plate 416 for supporting the overflow removing nozzle 416.

An air supply nozzle 404 surrounding the multi-tubular nozzle 500 and the overflow removing nozzles 415 and an air supply nozzle 404 located at the uppermost end of the nozzle block 11 to support the air supply nozzle 404 An air inlet 413 located at the lower end of the support plate 414 of the supply nozzle and directly below the support plate 414 of the air supply nozzle for supplying air to the air supply nozzle 404 and an air storage 413 for storing the supplied air And a plate 411.

Further, an overflow outlet 412 for discharging the overflow liquid to the outside through the overflow removing nozzle 415 is provided.

On the other hand, the electrospinning device 1 according to the present invention is provided with an overflow device 200. That is, each of the units 10a and 10b of the electrospinning device 1 is provided with a spinning liquid main tank 8, a second transfer pipe 216, a second transfer control device 218, an intermediate tank 220, And an overflow device 200 including a tank 230 are respectively provided.

Although the overflow device 200 is provided in each unit 10a and 10b of the electrospinning device 1 according to the embodiment of the present invention, any one of the units 10a and 10b, And the unit 10b located at the rear end of the overflow device 200 may be integrally connected to the overflow device 200. In this case,

According to the structure as described above, the spinning liquid main tank 8 stores spinning solution to be a raw material of the nanofibers. The spinning liquid main tank 8 is provided therein with an agitating device 211 for preventing separation or coagulation of the spinning solution.

The second transfer pipe 216 is composed of a pipe connected to the spinning liquid main tank 8 or the regeneration tank 230 and valves 212 213 and 214, The spinning liquid is transferred from the tank 230 to the intermediate tank 220.

The second conveyance control device 218 controls the conveyance operation of the second conveyance pipe 216 by controlling the valves 212, 213 and 214 of the second conveyance pipe 216. The valve 212 controls the transfer of the spinning liquid from the spinning liquid main tank 8 to the intermediate tank 220 and the valve 213 is used to transfer the spinning liquid from the regeneration tank 230 to the intermediate tank 220. [ . The valve 214 controls the amount of the polymer spinning solution flowing into the intermediate tank 220 from the spinning liquid main tank 8 and the regeneration tank 230.

The control method as described above is controlled according to the liquid surface height of the spinning liquid measured by the second sensor 222 provided in the intermediate tank 230 to be described later.

The intermediate tank 220 stores the spinning solution supplied from the spinning liquid main tank 8 or the regeneration tank 230 and supplies the spinning solution to the nozzle block 11 and adjusts the liquid surface height of the spinning solution And a second sensor 222 for measuring the temperature.

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

A supply pipe 240 and a supply control valve 242 for supplying a spinning solution to the nozzle block 11 are provided in the lower part of the intermediate tank 220. The supply control valve 242 is connected to the supply pipe 240 And the like.

The regeneration tank 230 has an agitating device 231 therein for storing the recovered circulating fluid and preventing separation or coagulation of the circulating fluid, and a first sensor 231 for measuring the liquid level of the recovered circulating fluid, (Not shown).

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

On the other hand, the spinning liquid overflowed in the nozzle block 11 is recovered through the spinning liquid recovery path 250 provided below the nozzle block 11. [ The spinning solution recovery path 250 recovers the spinning solution to the regeneration tank 230 through the first transfer pipe 251.

The first transfer pipe 251 is provided with a pipe and a pump connected to the regeneration tank 230 and the spinning liquid is transferred from the spinning liquid recovery path 250 to the regeneration tank 230 by the power of the pump .

At this time, it is preferable that at least one of the regeneration tanks 230 is provided, and when there are two or more, the first sensor 232 and the valve 233 may be provided in plurality.

When the number of the regeneration tanks 230 is two or more, a plurality of valves 233 located above the regeneration tank 230 are also provided, so that a first transfer control device (not shown) It is possible to control the two or more valves 233 located at the upper part in accordance with the height of the liquid level of the first sensor 232 to control whether the spinning liquid is to be transferred to one of the plurality of regeneration tanks 230 do.

Meanwhile, the VOC recycling apparatus 300 is provided in the electrospinning apparatus 1. That is, a condenser (not shown) for condensing and liquefying VOC (Volatile Organic Compounds) generated during spinning of the polymer spinning solution through the nozzles 12 to the units 10a and 10b of the electrospinning device 1, (320) for distilling and liquefying the condensed VOC through the condenser (310) and the condenser (310), and a solvent storage device (330) for storing the liquefied solvent through the distillation device A VOC recycling apparatus 300 is provided.

Here, the condenser 310 is preferably a water-cooled, evaporative or air-cooled condenser, but is not limited thereto.

The vaporized VOC generated in each of the units 10a and 10b is introduced into the condenser 310 and the vaporized VOC generated in the condenser 310 is stored in the solvent storage unit 330 The pipes 311 and 331 are connected to each other.

That is, pipes 311 and 331 for interconnecting the units 10a and 10b and the condenser 310, the condenser 310, and the solvent storage unit 330 are connected to each other.

In an embodiment of the present invention, the VOC is condensed through the condenser 310, and the condensed and liquefied VOC is supplied to the solvent storage device 330. However, the condenser 310 and the solvent storage It is also possible that a distillation apparatus 320 is provided between the apparatuses 330 so as to separate and sort each solvent when more than one solvent is applied.

Here, the distillation apparatus 320 is connected to the condenser 310 to vaporize the VOC in the liquefied state by the high-temperature heat and to cool it again to supply the liquefied VOC to the solvent storage apparatus 330.

In this case, the VOC recycling apparatus 300 includes a condenser 310 for supplying air and cooling water to the vaporized VOC discharged through the units 10a and 10b and condensing and liquefying the same, A distillation apparatus 320 for converting the condensed VOC to heat to form a vaporized state and then cooling it to a liquefied state and a solvent storage apparatus 330 for storing the liquefied VOC through the distillation apparatus 320 .

Here, the distillation apparatus 320 is preferably a fractionation apparatus, but it is not limited thereto.

That is, the piping for interconnecting the units 10a and 10b and the condensing unit 310, the condensing unit 310 and the distillation unit 320, and the distillation unit 320 and the solvent storage unit 330 311, 321, and 331 are connected to each other.

Then, the content of the solvent in the spinning liquid overflowed and recovered in the recovery tank 230 is measured. The measurement can be performed by extracting a part of the spinning solution as a sample in the recovery tank 230 and analyzing the sample. Analysis of the spinning solution can be carried out by a known method.

Based on the measurement results, the required amount of the solvent is supplied to the regeneration tank 230 through the pipe 332 in the liquefied state, which is supplied to the solvent storage device 330. That is, the liquefied VOC is supplied to the regeneration tank 230 by a required amount according to the measurement result, and can be reused and recycled as a solvent.

The case 18 constituting each unit 10a and 10b of the electrospinning device 1 is preferably made of a conductor but the case 18 may be made of an insulator or the case 18 may be made of a conductive material, A body and an insulator may be used in combination, or may be made of various other materials.

It is also possible to eliminate the insulating member 19 when the upper portion of the case 18 is made of an insulator and the lower portion thereof is used in combination as a conductor. To this end, the case 18 is preferably formed as a case 18 by being coupled with a lower part formed of a conductor and an upper part formed of an insulator, but the present invention is not limited thereto.

As described above, the case 18 is formed of a conductor and an insulator, and the upper part of the case 18 is formed of an insulator so that the collector 18 is separately provided for mounting the collector 13 on the inner surface of the upper part of the case 18 It is possible to eliminate the insulating member 19, which can simplify the structure of the apparatus.

It is also possible to optimize the insulation between the collector 13 and the case 18 so that when 35 kV is applied between the nozzle block 11 and the collector 13 for electrospinning, It is possible to prevent the breakdown of the insulation that may occur between the electrode 18 and other members.

In addition, the leakage current can be stopped within a predetermined range, the current supplied from the voltage generators 14a and 14b can be monitored, and the abnormality of the electrospinning device 1 can be detected early, (1) can be continuously operated for a long time, and the production of nanofibers having required performance is stable and mass production of nanofibers is possible.

Here, the thickness a of the case 18 formed of an insulator is made to satisfy "a = 8 mm".

Therefore, when 40 kV is applied between the nozzle block 11 and the collector 13 to perform electrospinning, an insulation breakdown that may occur between the collector 13 and the case 18 and other members And the leakage current can be limited within a predetermined range.

The distance between the inner surface of the case 18 formed of an insulator and the outer surface of the collector 13 is smaller than the thickness a of the case 18 and the distance between the inner surface of the case 18 and the outer surface of the collector 13 The distance "b" is made to satisfy "a + b = 80 mm".

Therefore, when 40 kV is applied between the nozzle block 11 and the collector 13 to perform electrospinning, an insulation breakdown that may occur between the collector 13 and the case 18 and other members And the leakage current can be limited within a predetermined range.

On the other hand, the temperature control device 60 is provided in each tube 40 of the nozzle block 11 provided in each unit 10a, 10b of the electrospinning device 1 according to the present invention, And 14b, respectively.

4, the tubular body 40 of the nozzle block 11, which is provided in each of the units 10a and 10b and to which the polymer solution is supplied by the plurality of nozzles 12 provided on the unit, ) Is provided with a temperature control device (60).

Here, the flow of the polymer spinning solution in the nozzle block 11 is supplied to each tube 40 from the spinning liquid main tank 8 in which the polymer spinning solution is stored, through the solution flow pipe.

The polymer spinning solution supplied to each tube 40 is discharged and injected through a plurality of nozzles 12 and accumulated on the long sheet 15 in the form of nanofibers.

A plurality of nozzles 12 are mounted at predetermined intervals in the longitudinal direction on each of the tubes 40. The nozzles 12 and the tubes 40 are electrically connected to the tube 40 .

In order to control the temperature control of the polymer spinning solution supplied to and introduced into the respective tubes 40, the temperature control device 60 is connected to the heating wires 41 and 42 or pipes 43).

In order to control the temperature of the plurality of tubes 40, a temperature control device 60 is provided.

4 to 5, a temperature control device 60 in the form of a heat line 41 is formed in a spiral shape around the inner periphery of the tubular body 40 of the nozzle block 11 to form a tubular body 40, And the temperature of the polymer spinning solution supplied to and introduced into the polymer spinning solution is controlled.

In the embodiment of the present invention, the temperature control device 60 in the form of a heat ray 41 is spirally provided on the inner periphery of the tube 40 of the nozzle block 11, but as shown in FIGS. 6 to 7 8 to 9, it is also possible that a plurality of temperature control devices 60 in the form of a heat line 42 are radially provided on the inner circumference of the tube 40, ) Type temperature control device 60 may be provided in the form of a "C"

As shown in Fig. 10, an auxiliary conveying device (not shown) for regulating the conveying speed of the long sheet 15 which is drawn into and supplied into each unit 10a, 10b of the electrospinning device 1 according to the present invention 16 are provided.

The auxiliary conveying device 16 is provided for controlling the conveying speed of the long sheet 15 so as to facilitate detachment and conveyance of the long sheet 15 attached by the electrostatic attraction to the collector 13 provided in each unit 10a, An auxiliary belt 16a rotating synchronously and an auxiliary belt roller 16b supporting and rotating the auxiliary belt 16a.

The auxiliary belt 16a is rotated by the rotation of the auxiliary belt roller 16b by the above structure and the long sheet 15 is rotated by the rotation of the auxiliary belt 16a to the units 10a and 10b And one auxiliary belt roller 16b of the auxiliary belt roller 16b is rotatably connected to the motor for this purpose.

In the embodiment of the present invention, five auxiliary belt rollers 16b are provided on the auxiliary belt 16a, and one of the auxiliary belt rollers 16b is rotated by the operation of the motor to rotate the auxiliary belt 16a At the same time, the remaining auxiliary belt rollers 16b are rotated. However, the auxiliary belt 16a is provided with two or more auxiliary belt rollers 16b, and one of the auxiliary belt rollers 16b is rotated by the operation of the motor , So that the auxiliary belt 16a and the remaining auxiliary belt roller 16b are rotated.

Meanwhile, in the embodiment of the present invention, the auxiliary transfer device 16 is composed of the auxiliary belt roller 16b and the auxiliary belt 16a that can be driven by a motor. However, as shown in FIG. 11, The roller 16b may be made of a roller having a low coefficient of friction.

At this time, the auxiliary belt roller 16b preferably comprises a roller including a bearing having a low friction coefficient.

The auxiliary conveying device 16 is composed of the auxiliary belt 16a and the auxiliary belt roller 16b having a low coefficient of friction but only the roller having a low friction coefficient excluding the auxiliary belt 16a So that the long sheet 15 is transported.

In addition, in the embodiment of the present invention, the auxiliary belt roller 16b is applied with a roller having a low coefficient of friction. However, any roller having a low coefficient of friction is not limited in its shape and configuration, It is also possible to apply rollers including bearings such as roller bearings, sliding bearings, sleeve bearings, fluid pressure journal bearings, hydrostatic journal bearings, pneumatic bearings, air bearing bearings, air static bearings and air bearings, It is also possible to apply a roller having a reduced coefficient of friction by including a material and an additive.

On the other hand, the thickness measuring device 70 is provided in the electrospinning device 1 according to the present invention. That is, as shown in Fig. 1, a thickness measuring device 70 is provided between each unit 10a, 10b of the electrospinning device 1, and the thickness measured by the thickness measuring device 70 And controls the feed velocity V and the nozzle block 11. [

When the thickness of the nanofiber nonwoven fabric discharged from the unit 10a located at the distal end portion of the electrospinning device 1 is measured to be thinner than the deviation amount by the above structure, the conveyance speed V of the next unit 10b, The discharge amount of the nozzle block 11 is increased and the voltage intensity of the voltage generating devices 14a and 14b is adjusted to increase the discharge amount of the nanofiber nonwoven fabric per unit area to increase the thickness.

When the thickness of the nanofiber nonwoven fabric discharged from the unit 10a located at the front end of the electrospinning device 1 is measured to be thicker than the amount of deviation, the feeding speed V of the next unit 10b is increased, It is possible to reduce the thickness by reducing the discharge amount of the block 11 and adjusting the intensity of the voltage of the voltage generating devices 14a and 14b to reduce the discharge amount of the nanofiber nonwoven fabric per unit area to reduce the amount of lamination, A nanofiber nonwoven fabric having a uniform thickness can be produced.

Here, the thickness measuring device 70 is disposed so as to face upward and downward with a long sheet 15 interposed therebetween, and measures the distance to the upper or lower portion of the long sheet 15 by an ultrasonic measuring method, And a thickness measuring unit including a pair of ultrasonic longitudinal wave measuring systems for measuring the ultrasonic longitudinal wave.

Thus, the thickness of the long sheet 15 can be calculated on the basis of the distance measured by the pair of ultrasonic measuring devices. That is, the ultrasonic longitudinal wave and the transverse wave are projected to the long sheet 15 laminated with the nanofiber nonwoven fabric so that the propagation time of the longitudinal wave and the transverse wave, that is, the time during which the ultrasonic signals of the longitudinal wave and the transverse wave reciprocate on the longitudinal sheet 15 A predetermined calculation using the propagation time of longitudinal waves and transverse waves and the propagation speed of longitudinal waves and transverse waves at the reference temperature of the elongated sheet 15 in which the nanofiber nonwoven fabric is laminated and the temperature constants of longitudinal waves and transverse wave propagation velocities Is a thickness measuring apparatus using an ultrasonic longitudinal wave and a transverse wave to calculate the thickness of the object from the equation.

In other words, the thickness measuring device 70 measures the propagation time of the longitudinal wave and the transverse wave, and the propagation time of the longitudinal wave and the transverse wave at the reference temperature of the elongate sheet 15, The thickness of the elongate sheet 15 in which the nanofiber nonwoven fabric is laminated is calculated from a predetermined equation using a propagation velocity and a temperature constant of the longitudinal wave and the transverse wave propagation velocity to determine the propagation velocity It is possible to precisely measure the thickness by self-compensating for the error due to the change, and it is possible to measure the thickness accurately even if there is any type of temperature distribution in the nanofiber nonwoven fabric.

Meanwhile, the thickness of the nanofiber nonwoven fabric of the long sheet 15 to be transported after the polymer spinning solution is sprayed and laminated to the electrospinning device 1 according to the present invention is measured to determine the feeding speed of the long sheet 15 and the thickness The elongated sheet conveying speed regulating device 30 for controlling the conveying speed of the long sheet 15 is further provided on the electrospinning device 1. The thickness measuring device 70 controls the thickness of the long sheet 15,

The elongated sheet conveying speed regulator 30 includes a buffer zone 31 formed between each unit 10a and 10b of the electrospinning device 1 and a buffer zone 31 provided on the buffer zone 31, A pair of support rollers 33 and 33 'for supporting the support rollers 15 and an adjustment roller 35 provided between the pair of support rollers 33 and 33'.

At this time, the support rollers 33 and 33 'are provided so that when the long sheet 15, in which the nanofiber nonwoven fabric is laminated by the spinning solution injected by the nozzles 12 in the respective units 10a and 10b, For supporting the conveyance of the sheet 15 and provided at the line and the rear end of the buffer zone 31 formed between the units 10a and 10b.

The adjustment roller 35 is provided between the pair of support rollers 33 and 33 'so that the long sheet 15 is wound and moved up and down by the adjustment roller 35, The feeding speed and the moving time of the long sheets 15a and 15b for each unit 10a and 10b are adjusted.

To this end, a sensing sensor (not shown) for sensing the feeding speed of the long sheets 15a, 15b in each of the units 10a, 10b is provided. In each unit 10a, 10b sensed by the sensing sensor, And a main controller 7 for controlling the movement of the adjusting roller 35 in accordance with the feeding speed of the long sheets 15a and 15b.

In one embodiment of the present invention, the conveying speed of the long sheets 15a and 15b is sensed in each of the units 10a and 10b and the control unit controls the conveying speed of the adjusting rollers 15a and 15b according to the conveying speed of the long sheets 15a and 15b. The auxiliary belt 16a provided on the outer side of the collector 13 or the auxiliary belt 16a for driving the auxiliary belt 16a for transferring the long sheets 15a and 15b, The control unit may detect the driving speed of the roller 16b or the motor (not shown), and thereby control the movement of the adjusting roller 35. [

With the above structure, the detection sensor can detect the length of the long sheet (15a) in the unit (10b) in which the conveying speed of the long sheet (15a) in the unit (10a) 15b, it is possible to prevent the elongated sheet 15a fed in the unit 10a located at the leading end from sagging, as shown in Figs. 13 to 14, The unit 10b positioned at the rear end in the unit 10a positioned at the front end while the regulating roller 35 wound around the long sheet 15 is moved downward and provided between the supporting rollers 33 and 33 ' The elongated sheet 15a which is conveyed to the outside of the unit 10a located at the front end among the elongated sheets 15 to be conveyed to the buffering section 31 is conveyed to the buffer section 31 located between the units 10a and 10b, The conveying speed of the long sheet 15a in the unit 10a located at While the unit (10b) within the elongated sheet correction controlled to be equal to the feed rate of (15b) positioned to prevent the deflection and wrinkling of the elongated sheet (15a).

On the other hand, if the conveyance speed of the long sheet 15a in the unit 10a located at the front end of each unit 10a, 10b is smaller than the conveyance speed of the long sheet 15b in the unit 10b positioned at the rear end, 15 to 16, in order to prevent the long sheet 15b conveyed in the unit 10b located at the rear end from tearing, the pair of support rollers 33 The unit 10b positioned at the front end of the adjustment roller 35 and the unit 10b positioned at the rear end of the unit 10b are moved in the upward direction, The elongated sheet 15a wound on the regulating roller 35 is guided to the buffering zone 31 which is conveyed outside the unit 10a located at the front end of the sheet 15 and located between the units 10a and 10b To the unit 10b located at the rear end, The feed rate of the root (15a) unit (10b) within the elongated sheet (15b) which is located in the transfer speed and the rear end of the year, while the correction control such that the same prevents the dead of the elongated sheet (15b).

By adjusting the feeding speed of the long sheet 15b to be fed into the unit 10b located at the rear end of each of the units 10a and 10b by the above described structure, It is possible to obtain the effect that the conveying speed of the long sheet 15b in the first unit 10b becomes equal to the conveying speed of the long sheet 15a in the unit 10a located at the leading end thereof.

On the other hand, the electrospinning device 1 according to the present invention is provided with the air permeability measuring device 80. That is, the air permeability measurement for measuring the air permeability of the nanofiber nonwoven fabric manufactured through the electrospinning device 1 at the rear of the unit 10b positioned at the rear end of each unit 10a, 10b of the electrospinning device 1 Device 80 is provided.

As described above, the feeding speed of the long sheet 15 and the nozzle block 11 are controlled on the basis of the air permeability of the nanofiber nonwoven fabric measured through the air permeability measuring device 80.

When the air permeability of the nanofiber nonwoven fabric discharged through each of the units 10a and 10b of the electrospinning device 1 is measured largely, the feeding speed V of the unit 10b positioned at the rear end portion is delayed, The discharge amount of the nozzle block 11 is increased and the intensity of the voltage of the voltage generating devices 14a and 14b is regulated to increase the discharge amount of the nanofibers per unit area to thereby reduce the air permeability.

When the air permeability of the nanofiber nonwoven fabric discharged through the units 10a and 10b of the electrospinning device 1 is measured to be small, the feeding speed V of the unit 10b positioned at the rear end is increased, The discharge amount of the nozzle block 11 is reduced and the discharge amount of the nanofibers per unit area is reduced by controlling the intensity of the voltage of the voltage generating devices 14a and 14b to reduce the amount of lamination to increase the air permeability.

As described above, it is possible to manufacture a nanofiber nonwoven fabric having a uniform air permeability by controlling the feeding speed of each unit 10a, 10b and the nozzle block 11 according to the degree of air permeability after measuring the air permeability of the nonwoven fabric .

Here, if the air entrainment amount P of the nonwoven fabric is less than a predetermined value, the feed speed V is not changed from the initial value. If the deviation amount P is equal to or larger than the predetermined value, It is possible to simplify the control of the conveyance speed V by the conveyance speed (V) control device.

It is also possible to control the discharge amount and the voltage of the nozzle block 11 in addition to the control of the feed speed V so that when the air flow deviation amount P is less than a predetermined value, When the amount of deviation P is equal to or larger than the predetermined value, the discharge amount of the nozzle block 11 and the voltage intensity are controlled to be changed from the initial value so that the discharge amount of the nozzle block 11 and the voltage It is possible to simplify the control of the intensity of the light.

The main control device 7 includes a nozzle block 11, voltage generators 14a and 14b, a thickness measuring device 70, The elongated sheet conveying speed regulating device 30 and the air permeability measuring device 80 are controlled.

Here, the lobe device 100 may be provided at the rear end of the unit 10b positioned at the rear end of each of the units 10a and 10b of the electrospinning device 1 according to the present invention. The joining device 100 joins a support (not shown) on the long sheet 15 through each unit 10a, 10b.

At this time, the lapping apparatus 100 is provided below the nanofiber nonwoven fabric, and the support supplied through the lapping apparatus 100 is bonded to the lower surface of the nanofiber nonwoven fabric.

1, the laminate device 100 is provided on the lower surface of the nanofiber nonwoven fabric so that the support is bonded to the lower surface of the nanofiber nonwoven fabric, but the laminate device 100 100 may be provided on the top of the long sheet.

It is also possible that the lamination device 100 is provided on the upper and lower surfaces of the nanofiber nonwoven fabric so as to bond the base material to the upper and lower surfaces of the nanofiber nonwoven fabric.

A laminating device 90 for laminating the nanofiber web layer electrospun through each unit 10a and 10b of the electrospinning device 1 is provided at the rear end of the electrospinning device 1, And the post-processing of the nanofiber nonwoven fabric electrospun through the electrospinning device 1 is performed by the laminating device 90.

2. Method for manufacturing composite fiber comprising thermoplastic polyurethane substrate and nanofiber nonwoven fabric

Hereinafter, a method for producing the composite fiber including the thermoplastic polyurethane base material and the nanofiber nonwoven fabric of the present invention will be described using the electrospinning apparatus.

In the present invention, a thermoplastic polyurethane base is used as the long sheet 15.

First, the polyurethane is a polymer of a urethane bond formed by the reaction of a polyisocyanate and a polyalcohol. Polyurethane is excellent in elasticity, abrasion resistance, and processability, and is widely used in industrial, consumer products, and parts. Since the properties of polyurethane vary depending on the type of polyurethane, selection of a product suitable for the application is important.

The polyurethane is classified into two types, thermoplastic polyurethane and thermosetting polyurethane. The thermoplastic polyurethane has excellent characteristics such as strength, formability, chemical resistance, oil resistance and wear resistance. BACKGROUND ART [0002] Flexible nonwoven fabrics made of thermoplastic polyurethane (hereinafter referred to as "TPU") have been used for applications including clothing, sanitary materials, and sporting goods materials due to their high elasticity, low residual strain and excellent air permeability. The thermoplastic polyurethane nonwoven fabric produced by the so-called melt-blow spinning method has excellent stretchability, flexibility and air permeability, and has been conventionally used as a side band of paper diapers, a base fabric of first-aid bandages, And the like, which are relatively soft and stretchable, such as sports apparel, stretch cotton pads, and the like.

The process for producing the thermoplastic polyurethane is well known. That is, it is prepared by reacting a linear polyol containing a hydroxy end group such as a polyester polyol or a polyether polyol with a diisocyanate compound containing an isocyanate group at both terminals, and optionally, a chain extender, a monoamine compound Terminal stopping agents, and other additives.

Examples of the polyol include various diols comprising a linear homo or copolymer such as a polyester diol, a polyether diol, a polyester amide diol, a polyacryl diol, a polythioester diol, a polythioether diol, a polycarbonate diol, ≪ / RTI > may be used. More specific examples include polyalkylene ether glycols such as polyoxyethylene glycol, polyoxypropylene glycol, polytetramethylene ether glycol, copolymer polyether glycol composed of tetramethylene group and 3-methyl tetra ketylene group.

As the diisocyanate compound serving as a hard segment, an aromatic, aliphatic or alicyclic diisocyanate is used, for example, 4,4'-diphenyl ketadiisocyanate, 1,3- and 1,4-cyclohexylene diisocyanate, 1,6-hexamethylene diisocyanate, trimethylene diisocyanate, tetramethylene diisocyanate, isophorone diisocyanate, and the like, but are not limited thereto.

Examples of the chain extender include a diamine compound or a diol compound. Examples of the chain extender include a diamine compound such as methylene diamine, ethanol diamine, 1,2-propylene diamine and the like, and a diamine compound such as ethylene glycol, 1,3-propanediol, , Neopentyl glycol, and the like, but are not limited thereto.

Examples of the terminal terminating agent include monoamine compounds such as monoethanolamine, diethanolamine and diisopropylamine.

On the other hand, the number average molecular weight of the thermoplastic polyurethane is preferably 1,000 to 100,000.

In the present invention, such a thermoplastic polyurethane is used as a base material. The nonwoven fabric is produced by preparing a web (a state in which fibers are repeatedly laminated) and entangling the fibers physically and chemically together.

Typical nonwoven fabrication processes involve web formation and web bonding processes. The general process is used only for single-fiber nonwovens, and this process is not necessary because longwoven nonwovens use filaments by spinning. In the case of non-woven fabric, it is put in a compressed bale state, so that the nonwoven fabric must undergo the process of compressed fibers. The formation process of the web is a necessary process for forming the nonwoven fabric. The dry nonwoven fabric forms the web in the air, whereas the wet nonwoven fabric disperses the fibers to obtain the web. Therefore, in the dry nonwoven fabric, the arrangement of the fibers is mostly directional, but the wet nonwoven fabric has a random irregular arrangement of the fibers. However, the development of a random card machine for dry nonwovens also makes it possible to obtain a web having no directionality depending on its application.

As a method of forming the web, a spun bond method using long fibers produced by dissolving radiation from raw pellets, a dry method of forming a web by arranging short fibers in a predetermined direction in a card machine or the like, And a wet method in which the water is homogeneously dispersed and drained to form a web.

Methods for entangling the fibers include a thermal bond method in which a thermally soluble fiber is mixed with a web and a thermal roll is used, a chemical bond method in which a binder is bonded (adhered fat), a barb of a needle A meltblown method capable of forming webs randomly by impacting filaments with high-pressure air at the time of producing fibers, and capable of producing a web having a diameter of 0.5 to 30 microns, etc. .

Among them, the thermoplastic polyurethane base used in the present invention is preferably produced by the meltblown method, the spunbond method and the needle punch method among the above methods. The principle of the meltblown method is a melt spinning method using a thermoplastic resin, in which a high-temperature and high-pressure airflow is introduced into the outlet of the spinning nozzle to stretch and open the fibers, and then the fibers are accumulated on a collecting conveyor. The nonwoven fabric by this method has an advantage of being excellent in flexibility, impermeability and insulation. Generally, a thermoplastic polyurethane nonwoven fabric is produced by a meltblown spinning method. A general method of meltblown spinning will be described below. That is, the molten thermoplastic polymer is fed to nozzle holes arranged in a row, the molten polymer is continuously extruded from the nozzle holes, the hot gas is jetted at high speed from the slits arranged on both sides of the nozzle hole group, The polymer extruded from the nozzle holes is thinned and cooled to form continuous filaments and then the continuous filament group is accumulated on a moving conveyor net or the like to adhere the filaments to each other by the self-adhesiveness of the filaments themselves.

On the other hand, the spunbond method is a method in which a raw material is spun and self-bonded by heat to form a nonwoven fabric. It is a technology for forming a web by spun polypropylene or polyethylene terephthalate mainly by self-adherence by heat, and there is an advantage that the fabric design is easy.

In addition, in the case of the needle punching method, fibers are physically manufactured by combining webs using special needles, and it is possible to diversify the thickness of the product by the number of punching of needles and the density of needles.

The thermoplastic polyurethane nonwoven fabric produced by such a nonwoven fabric manufacturing method is preferably used as the base material used in the present invention. The thermoplastic polyurethane nonwoven fabric substrate has a structure in which the pores are small and uniformly dispersed and distributed in spite of the fact that the surface area is very low, very thin, soft and soft, and has air permeability as well as excellent elongation and expansion characteristics. It is also possible to attach a thinner, soft and soft composite material when combined with other members in that it can be composed of a thin nonwoven fabric. The thermoplastic polyurethane has a melting point of 80 to 200 ° C. Therefore, there is an advantage that the thermal adhesiveness is good and can be used for thermal bonding after the heat treatment. On the other hand, the basis weight of the base material is preferably 10 to 150 g / m < 2 >. If the basis weight is less than 10 g / m < 2 >, the physical properties of the base material are deteriorated. If the basis weight exceeds 150 g / m & .

The thermoplastic polyurethane nonwoven fabric can be hydrophobic or hydrophilic, can be introduced in color, and can be partially melted in a high-temperature laminating environment due to its thermoplastic characteristics, so that the thermoplastic polyurethane non- There is a possible advantage.

In the present invention, the kind of the polymer of the polymer solution used for spinning through each unit is not limited as long as it can be electrospun. However, the polymer may be polyimide (PI), polyacrylonitrile (PAN), polyethersulfone (PES) , Polyamide (PA), meta-aramid, polyvinylidene fluoride (PVDF) and polyurethane (PU). Among them, polyurethane (PU) , And is particularly preferable because of its strong adhesive force with thermoplastic polyurethane which is a substrate due to material similarity.

In order to produce the fiber of the present invention, first, the polymer spinning solution is supplied to the spinning solution main tank 8 connected to each unit 10a, 10b of the electrospinning device, and the polymer supplied to the spinning solution main tank 8 The spinning solution is continuously and quantitatively supplied into the plurality of nozzles 12 of the nozzle block 11 to which a high voltage is applied through a metering pump (not shown). The polymer spinning solution supplied from each of the nozzles 12 is electrospun on a thermoplastic polyurethane base material placed on a collector 13 with a high voltage applied thereto through a nozzle 12 to form a nanofiber web layer.

The basis weight of the nanofiber nonwoven fabric formed laminate is 1g / m ² at least 50 g / m ² or less is preferable and, 1g / m ² at least 20 g / m ² or less is particularly preferred. If it is less than 1 g / m ² or exceeds 50 g / m ² , the mechanical properties are undesirable.

On the other hand, the thermoplastic polyurethane base material in which the nanofiber nonwoven fabric is laminated in each unit 10a, 10b of the electrospinning device 1 includes a feed roller 3 operated by driving of a motor (not shown) 3 is transferred from the first unit 10a to the second unit 10b by the rotation of the auxiliary transfer device 16 driven by the rotation of the auxiliary transfer device 16 and the nano fiber nonwoven fabric is transferred onto the thermoplastic polyurethane substrate Continuously electroluminesced and laminated. Thereafter, the fiber can be manufactured through a process of heat fusion in the laminating apparatus 90.

3. Supports, thermoplastic polyurethane substrates, and nanofibers Web layer  METHOD OF MANUFACTURING INCLUDING FIBERS

According to one embodiment of the present invention, nanofiber nonwoven fabrics are successively laminated on the thermoplastic polyurethane base material in each unit 10a, 10b, and thereafter the laminate device 100 (100) located at the rear end of the electrospinning device 1 ), The support may be bonded to the other side of the thermoplastic polyurethane base, to which the nanofiber nonwoven fabric is not laminated, and thermally fused at the laminating apparatus 90 to produce the fiber. The support may be selected from the group consisting of a polyethylene terephthalate base, a cellulose base, a synthetic base, and a bicomponent base. At this time, the basis weight of the support is preferably 50 to 300 g / m ² .

4. High temperature radiation

According to an embodiment of the present invention, the polymer spinning solution can be electrospun through a nozzle at a high temperature of 45 to 120 DEG C by using the temperature regulating device 60. [ In general, the existing inventions have a diluting agent and a concentration adjusting device to maintain the concentration of the polymer spinning solution at a constant level. MEK (methyl ether ketone), THF (tetrahydrofuran), and alcohol are used as the diluent. The concentration of the polymer spinning solution recovered through the overflow system 200 in addition to the polymer spinning solution that is electrospun through the nozzle block 11 and accumulated in the collector 13 is higher than that of the polymer initially supplied from the main storage tank The concentration of the spinning solution is higher than that of the spinning solution. In order to keep the concentration of the polymer spinning solution at the level of the conventional electrospinning, a diluent is added. In addition, MEK or THF used as a diluent has low boiling point (b.p) (about 60 ° C) and is more easily scattered than the case of using DMAc alone as a solvent during electrospinning, so nanofiber formation is easy.

However, in the present invention, instead of keeping the concentration constant, the high-concentration polymer spinning solution to be reused is reused after overflow, and the viscosity of the polymer spinning solution is controlled constantly using the temperature control device 60, And it is easy to form nanofibers of the polymer spinning solution because it has excellent acidity under high temperature conditions for controlling high viscosity without using a diluent.

The viscosity refers to the ratio of the skew stress and the skewness rate of solute and solvent in the flowing liquid. In general, it is expressed in terms of the point dryness per cutting area, and the unit is dynscm-2gcm-1s-1 or poise (P). The viscosity decreases in inverse proportion to the temperature rise. If the viscosity of the solution is higher than the viscosity of the solvent, the flow of the liquid is distorted depending on the solute, and the flow rate of the liquid is lowered by the amount.

The viscosity of the solution is measured at various solution concentrations and extrapolated to a concentration of 0, and the relationship between the intrinsic viscosity (?) And the molecular weight M of the substance can be expressed as (?) = KMa. In this case, K, a is an integer depending on the type of solute or solvent and the temperature. Therefore, the viscosity value is affected by the temperature, and the degree of the change depends on the type of fluid. Therefore, when talking about viscosity, the values of temperature and viscosity should be specified.

When fabricating the nanofiber with the electrospinning device 1, the fiber diameter and radioactivity of the nanofiber produced, such as the type of polymer and solvent used, the concentration of the polymer solution, the temperature and humidity of the spinning room, And the like. That is, the physical properties of the polymer emitted from electrospinning are important. It has been considered that it is usually necessary to maintain the viscosity of the polymer at or below a predetermined viscosity at the time of electrospinning. This is because the higher the viscosity, the more the nano-sized fibers are not radiated smoothly through the nozzle 12. The higher the viscosity, the more unsuitable for fiberization through electrospinning.

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

As the temperature control device 60, both a heating device that can maintain the viscosity of the polymeric spinning solution having a high viscosity, which is reused through overflow, and a cooling device that can maintain the viscosity of the polymeric spinning solution having a relatively low viscosity, Any one of them may be provided.

In the temperature in the electrospinning region, the temperature of the region where the electrospinning occurs (hereinafter, referred to as the 'radiating region') changes the surface tension of the spinning solution by changing the viscosity of the spinning solution, . ≪ / RTI >

That is, when the temperature of the radiation region is relatively high, the nanofiber having a relatively small fiber diameter is produced when the viscosity of the solution is low, and the nanofiber having relatively large fiber diameter is produced when the viscosity of the solution is relatively high because the temperature is relatively low.

The concentration measuring device for measuring the concentration has a contact type and a non-contact type in direct contact with a solution, and a capillary type concentration measuring device and a disk (DISC) type concentration measuring device can be used as a contact type. A concentration measuring device using the infrared or a concentration measuring device using infrared can be used.

The heating device of the present invention may be an electric heater, a hot water circulating device, a hot air circulating device, or the like. In addition, devices capable of raising the temperature in the same range as the above devices can be borrowed.

As an example of the heating apparatus, the electro-thermal heater can be used in the form of a hot wire, and the coil-shaped hot wires 41 and 42 can be mounted inside the tube 40 of the nozzle block 11, (See Figs. 4 to 9).

It is also possible to have the configuration of the linear heat lines 41, 42 and the U-shaped pipe 43.

The heating apparatus includes a nozzle block 11 through which a polymer solution is radiated, a tank (main storage tank, intermediate tank or regeneration tank) and an overflow system 200 (in particular, a recovery tank to a recovery tank) (E.g., a transfer pipe to be transferred).

The cooling device of the present invention may be a cooling device including a chilling device, and the means for maintaining a constant viscosity of the polymer solution is usually applicable. The cooling device, like the heating device, may be provided in at least one of the nozzle block 11, the tank, and the overflow system 200, and is used to maintain a certain viscosity of the polymer solution.

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

The sensor is installed in a main storage tank (not shown), an intermediate tank 220, a regeneration tank 230, a nozzle block 11, an overflow system 200 or the like to measure the concentration of the flushing liquid in real time, The heating device and / or the cooling device is operated so that the viscosity is kept constant in the control device 60. [

According to an embodiment of the present invention, the concentration of the polymer spinning solution re-supplied through the overflow system 200 is 20 to 40%, which is 10-18% of the concentration of the polymer spinning solution used in conventional electrospinning Which is a high concentration solution.

The temperature of the polymer spinning solution according to the concentration of the polymer spinning solution is controlled at 45 to 120 ° C, not at room temperature, in order to make the viscosity of the polymer spinning solution re-supplied according to the present invention constant.

On the other hand, the viscosity of the polymer spinning solution of the present invention is preferably 1,000 to 5,000 cps, more preferably 1,000 to 3,000 cps. When the viscosity is 1,000 cps or less, the quality of the nanofibers to be electrospun is poor, and when the viscosity is 3,000 cps or more, the polymer spinning solution can not be easily discharged from the nozzle 12 during the electrospinning, thereby slowing the production speed.

In addition, since the viscosity of the polymer spinning solution is constant as the electrospinning progresses, the spinning easiness in electrospinning is excellent, and the concentration of the polymer spinning solution is increased, so that the amount of the solid content in the nanofiber integrated into the collector The productivity is increased.

In addition, the amount of the residual solvent of the nanofibers using electrospinning is lower than that of the conventional electrospinning, and thus it is possible to produce nanofibers of excellent quality.

The temperature control device 60 of the present invention measures the concentration of the intermediate tank 220 on an off-line basis and measures the concentration of the polymer solution 30 by controlling the temperature of the nozzle block 11 or the main storage tank It can be hand-operated to control the viscosity, and includes an automatic system that can control the temperature of the solution according to the concentration measurement through an automatic control system on-line.

5. Patterning

According to an embodiment of the present invention, the polymer spinning solution is electrospinned in a cross direction (CD direction) or machine direction (MD direction) to form a nanofiber web May be formed. Here Basis Weight or Grammage is defined as mass per unit area (g / m2).

The construction and working method of the electrospinning device for forming a nanofiber web having different basis weights according to an embodiment of the present invention will be described below. 16 is a layout diagram of a nozzle block installed in a unit of an electrospinning apparatus for forming a nanofiber web having different basis weights. The nozzles disposed in the unit may be applied to the front portion of the substrate, but are preferably applied to a specific portion of the substrate if necessary. In Fig. 16, the nozzles are divided into five groups of nine nozzles, one at the center and two at the bottom in the upper part. However, the arrangement of the nozzle and the nozzle block is not limited thereto, and it is obvious that those skilled in the art can appropriately design, change and arrange the nozzle in consideration of the number of the nozzles and the amount of the low melting point polymer to be radiated.

FIG. 17 is a plan view showing the electrospinning process according to the arrangement of the nozzle blocks shown in FIG. 16. The nozzle tubes 112a, 112b, 112c, and 112d having a rectangular parallelepiped shape and having a plurality of nozzles 112b, 112c, 112d, 112e, 112f, 112g, 112h, 112i, 112f, 112g, 112h, 112i are arranged in the nozzle block in the length and width direction of the substrate, Is connected to the spinning liquid main tank 8 and supplied with the polymer spinning solution filled in the spinning liquid main tank 8.

The nozzle tubes 112a, 112b, 112c, 112d, 112e, 112f, 112g, 112h and 112i are connected to the spinning liquid main tank 8 through a supply pipe 240, A plurality of nozzle tubes 112a, 112b, 112c, 112d, 112e, 112f, 112g, 112h, 112i and a spinning liquid main tank 8 are branched.

At this time, the supply piping 240, which is communicated to the nozzle tubes 112a, 112b, 112c, 112d, 112e, 112f, 112g, 112h and 112i in the spinning liquid main tank 8, And the supply amount adjusting means comprises valves 212, 213, 214, and 233.

The valves 212, 213, 214 and 233 are connected to the supply pipe 240 which is communicated to the nozzle tubes 112a, 112b, 112c, 112d, 112e, 112f, 112g, 112h and 112i in the spinning liquid main tank 8, 112b, 112c, 112d, 112e, 112f, 112g, 112h, 112i in the spinning liquid main tank 8 by the respective valves 212, 213, 214, 233, Is controlled by an on-off system in which the supply of the polymer solution is controlled and controlled.

That is, when the polymer spinning solution is supplied to the nozzle tubes 112a, 112b, 112c, 112d, 112e, 112f, 112g, 112h, 112i in the spinning liquid main tank 8 through the supply pipe 240, The opening and closing of the valves 212, 213, 214 and 233 provided in the supply pipe for supplying the main tank 8 and the nozzle tubes 112a, 112b, 112c, 112d, 112e, 112f, 112g, The nozzle tubes 112b, 112d, 112f, 112g, 112h, 112i, 112f, 112g, 112h, 112i at specific positions among the nozzle tubes 112a, 112b, 112c, 112d, 112e, 112b, 112c, 112d, 112e, 112e, 112c, 112d, 112e, 112e, 112e, 112e, 112e, 112e, 112e, 112e, 112f, 112g, 112h and 112i of the polymeric spinning solution is controlled and controlled.

The spray liquid main tank 8 and the nozzle tubes 112a, 112b, 112c, 112d, 112e, 112f, 112g, 112h, and 112i are connected to the supply pipe 240 112b, 112c, 112d, 112e, 112f, 112g, 112h, 112i in the spinning liquid main tank 8 are provided with valves 212, 213, 214, The nozzle tubes 112a, 112b, 112c, 112d, and 112d, which are arranged in the nozzle block 111 by opening specific valves 212, 213, 214, and 233 among the plurality of valves 212, 213, 214, 112b, 112d, 112f, 112g, 112h, 112i of the nozzle tubes 112a, 112b, 112e, 112f, 112g, 112h, 112i, 213, 214, and 233, such as blocking the supply of the polymer solution, to only the nozzle tubes 112a, 112c, and 112e at specific positions in the nozzle tube body arranged in the nozzle block 111, Room used by In the main tank 8 is supplied to the polymer spinning solution to be supplied to each nozzle tube (112a, 112b, 112c, 112d, 112e, 112f, 112g, 112h, 112i) is adjusted and controlled.

That is, the nozzles 111a provided in the supply pipe 240 and the nozzle pipes 112a, 112b, 112c, 112d, 112e, 112f, 112g, 112h and 112i are addressed, (111a).

The means for regulating the amount of radiation comprises valves 212, 213, 214 and 233.

By providing the valves 212, 213, 214 and 233 as the radiation amount adjusting means, it is possible to supply the respective nozzles 111a from the supply pipe 240 by opening and closing the valves 212, 213, 214 and 233 The valves 212, 213, 214 and 233 are controllably connected to a controller (not shown), and the valves 212, 213, 214, It is also possible that the opening and closing of the valves 212, 213, 214, and 233 are manually controlled according to the situation of the field and the operator.

In the present invention, if the amount of radiation of the polymer spinning solution which is supplied after being supplied to the nozzle 111a from the supply pipe 240 is easy to control and control, the radiation amount adjusting means is composed of the valves 212, 213, 214 and 233 The radiation amount adjusting means may be configured by various other structures and means, but is not limited thereto.

In the present invention, valves 212, 213, 214 and 233 are provided in the supply pipe 240 so that the nozzle tubes 112a, 112b, 112c, 112d, and 112d of the nozzle block 111 in the spinning liquid main tank 8, 112, 112f, 112g, 112h, 112i, and the valves 212, 213, 214, 233 are provided in the supply pipe 240 to control the flow rate of the polymer tubing liquid supplied to the nozzle tubes 112a, 112b, 112c, 112c, 112c, 112d, 112c, 112d, 112e, 112f, 112g, 112h, 112i and regulating and controlling the radiation amount of the polymer spinning solution which is electrospun through each nozzle 111a, The nanofiber web having different basis weights in the width direction of the base material 115 is formed by the polymer spinning solution electrospun in each of the nozzles 111a of the base materials 111a to 112d, 112e, 112f, 112g, 112h and 112i.

Fig. 18 is a plan view showing a state in which the nozzles in the spinning solution unit of the present invention are turned on and off in the CD direction, and Fig. 19 is a plan view showing a state in which the basis weight of the polymer in the spinning solution unit, As described above, the operation of the nozzles in the spinning solution unit can be electrically turned on and off to form nanofiber webs different in basis weight in the CD direction. FIG. 20 is a plan view showing a state in which the nozzle in the spinning solution unit of the present invention is turned on and off in the MD direction. As described above, the operation of the nozzle in the spinning solution unit is electrically turned on and off, A nanofiber web can be formed.

Example  One

Polyvinylidene fluoride (Pellethane 2363-80AE manufactured by Dow (USA) was used) and 87% of polyvinylidene fluoride were dissolved in dimethylacetamide (N, N-dimethylacetamide, DMAc) , The polyurethane spraying solution was injected into the spinning solution main tank of the first unit of the electrospinning device, and the polyvinylidene fluoride spinning solution was injected into the second unit. In the first unit of the electrospinning device, the polyurethane spraying solution was electrospun on a thermoplastic polyurethane base material (Bluecher Co., Ltd. IOH10UM4) having a basis weight of 30 g / m ² by applying an applied voltage of 20 kV to a basis weight of 5 g / m ² Were laminated to form a nonwoven fabric of polyurethane nanofibers. In the second unit, a polyvinylidene fluoride nanofiber nonwoven fabric having a basis weight of 5 g / m ² was laminated by applying the polyvinylidene fluoride spinning solution onto the polyurethane nanofiber nonwoven fabric by applying an applied voltage of 20 kV. At this time, the flow rate of the spinning solution was 0.1 mL / h, the temperature was 22 ° C, and the humidity was 20%.

Example 2

A composite fiber composed of a thermoplastic polyurethane base material and a polyurethane nanofiber was prepared in the same manner as in Example 1, except that the basis weight of the polyurethane nanofiber nonwoven fabric was changed to 3 g / m ² .

Example 3

A thermoplastic polyurethane base material and a polyurethane and polyvinylidene fluoride nanofiber were prepared in the same manner as in Example 1 except that a polyvinylidene fluoride spinning solution was used in the first unit and a polyurethane spinning solution was used in the second unit. To prepare a composite fiber.

Example 4

10 wt% of polyurethane (Pellethane 2363-80AE from DOW, USA) was dissolved in 90 wt% of NN-dimethylacetamide (DMAc) to prepare a spinning solution having a concentration of 10% and a viscosity of 1000 cps. Lt; / RTI > Thereafter, the spinning solution was transferred to the nozzle block, and the distance between the nozzle block and the collector was 20 cm, the applied voltage was 15 kV, the spinning liquid flow rate was 0.1 mL / h, and the temperature was 60 ° C. Electrons were spun on one side. Thereafter, the concentration of the spinning solution in the raw material tank was changed to 20% in the course of providing the raw material tank, which is one of the storage tanks, overflowed by the spinning process, and the viscosity was changed to 2000 cps. Thereafter, the temperature of the raw material tank was raised to 80 캜 to lower the viscosity to 1000 cps by the sensor of the temperature control device, and the polyurethane nanofibers were laminated by electrospinning on the meltblown thermoplastic polyurethane base material. Thereafter, a polyethylene terephthalate base material having a basis weight of 100 g / m < 2 > is laminated on the other surface of the thermoplastic polyurethane base material on which the polyurethane nanofibers are not laminated, and the base material is thermally fused to produce polyethylene terephthalate, thermoplastic polyurethane base, A composite fiber composed of nanofibers was prepared.

Example 5

An electrospinning unit 2 having a nozzle block including an on-off system designed to divide the nozzle block into two parts in the CD direction and to be connected to separate main tanks, respectively, in order to make the planar basis weight of the second nanofiber non- Was used in place of the polypropylene fiber.

Comparative Example 1

A composite fiber composed of a cellulose substrate and a polyurethane and polyvinylidene fluoride nanofiber was produced by the same manufacturing method except that a cellulose substrate was used instead of the thermoplastic polyurethane substrate as described in Example 1.

Test of adhesion between substrate and nanofiber nonwoven fabric layer

When 1 m ² of the composite fibers prepared in Examples and Comparative Examples were washed in a cycle of 1, 3, and 5 cycles with one wash, two rinse, and one dry cycle using a washing machine, the substrate and the nanofiber web layer We observed whether tearing of the liver occurred.

Example 1 Example 2 Example 3 Example 4 Example 5 Comparative Example 1 cycle O O O O O △ 3 cycles O O △ O O X 5 cycles O O △ O O X

(O: when no desorption occurred: when the desorption occurred at less than 50% of the total area, and when X: desorption occurred at more than 50% of the total area)

In the composite fibers according to Examples 1 to 5, the separation between the substrate and the nanofibers did not occur more easily than the comparative example even after 5 cycles of washing through a thermal fusion process without using a separate adhesive or hot melt layer.

1: electrospinning device, 3: feed roller,
5: take-up roller, 7: main control device,
8: spinning liquid main tank, 10a, 10b: unit,
11: nozzle block, 12: nozzle,
13: collector, 14, 14a, 14b: voltage generator,
15, 15a, 15b: long sheet, 16: auxiliary conveying device,
16a: auxiliary belt, 16b: auxiliary belt roller,
18: case, 19: insulating member,
30: Long sheet conveying speed adjusting device, 31: Buffer section,
33, 33 ': support roller, 35: regulating roller,
40: tube body, 41, 42: heat wire,
43: pipe, 60: temperature control device,
70: thickness measuring device, 80: air permeability measuring device,
90: laminating apparatus, 100: laminating apparatus,
111: nozzle block,
111a: nozzle, 112: nozzle tube,
112a, 112b, 112c, 112d, 112e, 112f, 112g, 112h, 112i:
115: substrate, 115a, 115b, 115c: nanofiber nonwoven fabric
200: overflow device, 211, 231: stirring device,
212, 213, 214, 233: valve, 216: second transfer pipe,
218: second conveyance control device, 220: intermediate tank,
222: second sensor, 230: regeneration tank,
232: first sensor, 240: supply pipe,
242: supply control valve, 250: circulating fluid recovery path,
251: first transfer pipe, 300: VOC recycling apparatus,
310: condenser, 311, 321, 331, 332: piping,
320: distillation device, 330: solvent storage device,
404: nozzle for supplying air, 405: nozzle plate,
407: first spinning solution storage plate, 408: second spinning solution storage plate,
410: overflow liquid temporary storage plate, 411: air storage plate,
412: overflow outlet, 413: air inlet,
414: nozzle support plate for supplying air, 415: overflow removing nozzle,
416: nozzle support plate for removing overflow, 500: multi-tubular nozzle,
501: inner tube, 502: outer tube,
503: the tip.

Claims (9)

Preparing a thermoplastic polyurethane base;
Moving the thermoplastic polyurethane base material to the electrospinning unit 1 of the electrospinning apparatus and electrospinning the polymer spinning solution on one side of the base material to form a first nanofiber nonwoven fabric layer;
Forming a second nanofiber nonwoven fabric layer on the first nanofiber nonwoven fabric layer by moving the laminate having the first nanofiber nonwoven fabric layer to the electrospinning unit 2; And
And thermally fusing a laminate in which two layers of the nanofiber nonwoven fabric layer are laminated on the base material,
Wherein the total basis weight of each of the nanofiber nonwoven fabric layers is 1 g / m ² or more and 50 g / m ² or less,
Wherein the first and second nanofiber nonwoven fabric layers are formed by electrospinning the polymer spinning solution with different basis weights in the transverse or longitudinal direction, thereby improving the adhesion between the substrate and the nanofiber nonwoven fabric.
The method according to claim 1,
Characterized in that a step of laminating at least one support selected from the group consisting of a polyethylene terephthalate base material, a cellulose base material and a bicomponent base material on the other surface of the thermoplastic polyurethane base material is added before the heat fusion step A method for manufacturing a composite fiber having improved adhesion between nanofiber nonwoven fabrics.
The method according to claim 1,
The polymer is selected from the group consisting of polyimide (PI), polyacrylonitrile (PAN), polyethersulfone (PES), polyamide (PA), polyvinylidene fluoride (PVDF), polyurethane Wherein the adhesion between the substrate and the nanofiber nonwoven fabric is improved.
The method according to claim 1,
Wherein the first nanofiber nonwoven fabric layer and the second nanofiber nonwoven fabric layer have different fiber diameters or different polymer types, and the adhesion between the substrate and the nanofiber nonwoven fabric is improved.
The method according to claim 1,
Wherein the first nanofiber nonwoven fabric layer is polyurethane (PU) and the second nanofiber nonwoven fabric layer is polyvinylidene fluoride (PVDF) or polyimide (PI). A method for producing a composite fiber.
The method according to claim 1,
Wherein the total basis weight of the nanofiber nonwoven fabric is 1 g / m ² or more and 20 g / m ² or less, wherein the adhesion between the substrate and the nanofiber nonwoven fabric is improved.
The method according to claim 1,
Wherein the electrospinning device is electrospinning the polymer spinning solution through a nozzle at a high temperature of 45 to 120 DEG C by using a temperature control device, wherein the adhesion between the substrate and the nanofiber nonwoven fabric is improved.
delete A composite fiber produced by the manufacturing method of claim 1.

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