KR101834415B1 - 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 a substrate and a nanofiber nonwoven fabric, comprising the steps of: preparing a first and a second thermoplastic polyurethane base; Moving the release paper to the electrospinning unit 1 of the electrospinning apparatus to electrospray the polymer spinning solution on one side of the substrate to form a first nanofiber nonwoven fabric layer; Moving the formed first nanofiber nonwoven fabric layer to the electrospun unit 2 to form a second nanofiber nonwoven fabric layer on the first nanofiber nonwoven fabric layer to produce a two-layered nanofiber nonwoven fabric layer; And thermally fusing a second thermoplastic polyurethane base material on the upper surface of the two-layered nanofiber nonwoven fabric layer by laminating two layers of the nanofiber nonwoven fabric layer on the first thermoplastic polyurethane base material, And a total basis weight of the fibrous nonwoven fabric is 1 g / m < 2 > to 50 g / m < 2 >, wherein the adhesion between the substrate and the nanofiber nonwoven fabric is improved.
According to the present invention, it is possible to provide a composite fiber in which nanofibers are strongly adhered to a base fiber and are not peeled off even after multiple washing, without the need for a separate adhesive or hot melt layer.

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. Recently, a study has been made on a method of making nanofibers into membranes and bonding them to different types of textiles. Korean Patent No. 10-0934117 discloses a conjugate fiber having improved adhesion between a nanofiber membrane and a different kind of fiber. However, the use of a separate polyurethane resin as an adhesive increases manufacturing cost and complicates the process.

Disclosure of the Invention The present invention has been made to solve the above problems and it is an object of the present invention to provide a thermoplastic polyurethane base material in which nanofibers are radiated, and the nanofibers are strongly adhered to the base fiber without additional adhesive or hot melt layer, A composite fiber in which nanofibers that do not have a laminate structure can be provided.

One embodiment of the present invention provides a method of manufacturing a nanofiber, comprising: preparing first and second thermoplastic polyurethane substrates as base fibers from which nanofibers are radiated; Moving the release paper to the electrospinning unit 1 of the electrospinning apparatus to electrospray the polymer spinning solution on one side of the substrate to form a first nanofiber nonwoven fabric layer; Moving the formed first nanofiber nonwoven fabric layer to the electrospun unit 2 to form a second nanofiber nonwoven fabric layer on the first nanofiber nonwoven fabric layer to produce a two-layered nanofiber nonwoven fabric layer; And thermally fusing a second thermoplastic polyurethane base material on the upper surface of the two-layered nanofiber nonwoven fabric layer by laminating two layers of the nanofiber nonwoven fabric layer on the first thermoplastic polyurethane base material, And a total basis weight of the fibrous 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 conjugate fiber having improved adhesion between a substrate and a nanofiber nonwoven fabric.

Wherein the first and second thermoplastic polyurethane-based nanofiber nonwoven fabrics are bonded to one surface of the other surface of the substrate, the polyethylene terephthalate substrate, the cellulose substrate, the synthetic substrate, and the binary substrate, A step of laminating the above supports may be added.

Here, the polymer is composed of polyimide (PI), polyacrylonitrile (PAN), PES (polyether sulfone), polyamide (PA), meta-aramid, polyvinylidene fluoride (PVDF) , And the like.

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 Can be provided.

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 is constituted by two or more electrospinning devices, wherein the bottom-up and top-down electrospinning devices are alternately arranged, and between the electrospinning devices, Device may be provided.

Also, the composite fiber produced according to the above-mentioned production method can be provided.

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 manufacturing a fiber having improved adhesion between the base material and the nanofiber nonwoven fabric, the electrospinning device is composed of two or more electrospinning devices, and the bottom-up and top- And a flip device for rotating the laminated body by 180 degrees is provided between each of the electrospinning devices, thereby providing a method for mass-producing the fibers in which the nanofibers are laminated.

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 apparatus for producing nanofibers according to the present invention,
FIG. 2 is a side view schematically showing a nanofiber manufacturing apparatus in which a bottom-up and top-down electrospun unit is alternately arranged according to the present invention
3 is a plan view schematically showing a nozzle block provided in each electrospinning device of the nanofiber manufacturing apparatus of the present invention,
4 is a front sectional view schematically showing a state in which a heating wire for temperature control is installed in a nozzle block installed in each electrospinning device of the nanofiber manufacturing apparatus of the present invention,
5 is a sectional view taken along the line AA in Fig. 4,
6 and 7 are cross-sectional views schematically showing a flip device used as an embodiment of a rotating device of a nanofiber manufacturing apparatus of the present invention,
8 is a side view schematically showing the arrangement of the apparatus for producing nanofibers of the present invention in the vertical direction,
9 is a bird's-eye view schematically showing the arrangement of the apparatus for producing nanofibers according to the present invention in a case where the apparatus is arranged in a U-
10 is a view illustrating a structure of a composite fiber in which a nanofiber nonwoven fabric is laminated on a thermoplastic polyurethane base fabricated according to an embodiment of the present invention,
11 is a view illustrating a structure of a composite fiber produced by laminating a nanofiber nonwoven fabric on a thermoplastic polyurethane base fabricated according to an embodiment of the present invention and supporting a support on the bottom of the thermoplastic polyurethane base fabric.

1. Description of an electrospinning device for making a nanofiber nonwoven fabric in the form of a membrane

end. Normal

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 10, 30 is sequentially arranged at a predetermined interval, Each of the units (10, 30) emits the same polymer spinning liquid individually or electrospun polymer spinning solution having different materials to produce a nanofiber nonwoven fabric.

The electrospinning apparatus used in an embodiment of the present invention may be configured to include a bottom-up electrospinning apparatus and a top-down electrospinning apparatus. It is also possible to arrange the bottom-up electrospinning device and the top-down electrospinning device at a predetermined interval, and place the bottom-up electrospinning device at the front end and the top-down electrospinning device at the rear end, or vice versa. A flip device may be provided between the bottom-up electrospinning device and the top-down electrospinning device.

As shown in Fig. 1, the case where the electrospinning device 1 according to the present invention is installed as two units is shown. The electrospinning device comprises an electrospinning unit 1 (10) and an electrospinning unit 2 (30), wherein the electrospinning unit 1 (10) and the electrospinning unit 2 (30) are arranged at regular intervals.

Here, the electrospinning unit 1 (10) and the electrospinning unit 2 (30) discharge the polymer spinning solution in the spinning solution main tanks 11 and 31, in which a polymer spinning solution (not shown) A nozzle block 13,33 in which a plurality of nozzles 15,35 are arranged and a nozzle block 15,35 positioned in the upper end of the nozzle 15,35 in the case of a bottom-up electrospinning device and the bottom of the nozzle 15,35 in the case of a top- (17, 37) spaced apart from the nozzles (15, 35) in order to accumulate the polymer spinning solution to be injected, and a voltage generating device (14) for generating a voltage in the collectors .

According to the structure as described above, the nanofiber manufacturing apparatus 1 according to the present invention is characterized in that the nanofiber manufacturing apparatus 1 according to the present invention comprises a spinning liquid 1 The polymer spinning solution supplied continuously and quantitatively in the plurality of nozzles 15 and 35 to which a high voltage is applied through the metering pump is supplied to the nozzles 15 and 35 through the nozzles 15 and 35, And is then radiated and focused on the collectors 17 and 37 to form nanofibers, and the formed nanofibers are embossed or needle punched into nonwoven fabrics.

On the other hand, the nozzle blocks 13 and 33 in which the nozzles 15 and 35 are disposed in the respective electrospinning devices are provided with a temperature control device 60 in each tube 112. That is, in order to adjust the temperature of the polymer spinning solution in the tubular body of the nozzle blocks 13 and 33 provided in the respective electrospinning devices 10 and 30 and supplied with the polymer spinning solution by the plurality of nozzles 15 and 35, A temperature control device is provided. Here, the flow of the polymer spinning solution in the nozzle blocks 13 and 33 is supplied from the spinning liquid main tanks 11 and 31 in which the polymer spinning solution is stored to each tube through a spinning solution flow pipe (not shown). The polymer spinning solution supplied to each tube is radiated and discharged through a plurality of nozzles 15 and 35, and is accumulated on the support 3 in the form of a nanofiber nonwoven fabric. At this time, the plurality of nozzles (15, 35), which are spaced apart from each other at a predetermined interval in the longitudinal direction, are mounted on the tubular body in a state of being electrically connected and electrically connected. Here, the temperature controller 60 is provided in the shape of a heat ray 113 on the inner circumference of the tube to control the temperature control of the polymer solution for supplying and flowing into the tubes. 3 to 5, a temperature regulating device 60 composed of a hot wire is formed on the periphery of the inside of the tubular body of the nozzle blocks 13 and 33 in a spiral manner on the inner circumference of the tubular body of the nozzle blocks 13 and 33 Thereby controlling the temperature of the polymer spinning solution supplied and introduced into the tubular body. In the present invention, it is common to spin at room temperature, but it is also possible to spin at a high temperature, preferably 45 to 120 ° C.

On the other hand, the electrospinning unit 1 (10) is disposed at the front end of the nanofiber manufacturing apparatus (1), the electrospinning unit 2 (30) is disposed at the rear end, and the polymer spinning solution is sprayed from each unit, A feed roller 5 for feeding the release paper 3 and a winding roller 9 for winding the release paper 3 on which nanofibers are laminated are provided at the end of the nanofiber manufacturing apparatus 1. [

On both sides of the collectors 17 and 37, conveying rollers 7 are provided and the nano-fibers are stacked on the respective collectors 17 and 37 via the conveying rollers 7, (3) is transported in the horizontal direction. The nanofibers produced by stacking the polymer spinning solution injected from the nozzles 15 of the bottom-up electrospinning device 10 on the support 3 of the collector 17 are injected into the collector of the top-down electrospinning device 30 (37), and conveying rollers (7) for repeatedly and continuously advancing the above process are provided at both ends of the respective collectors (17, 37).

I. Bottom-Up / Top-Down Shuffle

As shown in FIG. 2, the electrospinning unit 1 can be bottom-up and the unit 2 can be top-down. In the meantime, the present invention is characterized in that a rotating device 20 is provided between a bottom-up electrospinning device 10 'and a top-down electrospinning device 30'. The rotating device 20 is disposed between the electrospinning devices and rotates the supporting body 3 by 180 degrees so that the upper surface of the support body is rotated to the lower surface and the lower surface is rotated to the upper surface to be.

6 and 7 are cross-sectional views schematically showing the flip device 20-1 used as an embodiment of the rotating device. 6 is a cross-sectional view illustrating an initial operation of the flip device 20-1, and FIG. 7 is a cross-sectional view illustrating a process of the flip device 20-1.

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

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

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

The polymer spinning solution filled in the spinning solution main tank 11 of the bottom-up type electric device 10 is sprayed onto the support 3 of the collector 17 through the nozzle 15, The supporting body 3 on which the nanofibers are formed after the polymer spinning solution injected onto the support 3 of the collector 17 is integrated is rotated by the rotating device 20 by the bottom- The lower surface of the laminated support 3 is rotated 180 degrees to the upper surface. And then transferred onto the collector 37 of the top down electrospinning device 30 through the transport roller 7 and onto the support 3 on which the nanofibers transferred onto the collector 37 are laminated, The polymer spinning liquid filled in the spinning liquid main tank 31 of the spinning apparatus 30 is electrospun through the nozzle 35, and the above-mentioned process is continuously and repeatedly performed to produce the final product.

2. Method for producing a composite fiber comprising a thermoplastic polyurethane substrate and a nanofiber nonwoven fabric layer

Hereinafter, a method for producing a composite fiber having a structure in which a nanofiber nonwoven fabric is sandwiched between thermoplastic polyurethane substrates of the present invention using the electrospinning device will be described.

In the present invention, the release sheet 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 10, 30 or 30 'of the electrospinning device, and the spinning solution main tank 8 The supplied polymeric 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 release paper placed on a collector 13 with a high voltage applied thereto through a nozzle 12, and a nanofiber nonwoven fabric is laminated.

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 in which the first and second nanofiber nonwoven fabrics are laminated in each unit (10, 30 or 30 ') of the electrospinning device (1) Is transferred from the first unit 10 to the second unit 30 or 30 'by the rotation of the roller 3 and the auxiliary transfer device (not shown) driven by the rotation of the feed roller 3, The nanofiber nonwoven fabric is successively electrospun and laminated on the release paper. Thereafter, the nanofiber nonwoven fabric separated from the release paper is thermally fused with the first and second thermoplastic polyurethane base materials in a laminating apparatus (not shown) to produce a composite fiber having a structure in which the nanofiber nonwoven fabric is sandwiched between the thermoplastic polyurethane base materials . The laminating process is characterized in that it is possible to produce a conjugate fiber having improved adhesion between the substrate and the nanofiber nonwoven fabric without a separate adhesive or a step of laminating the hot-melt layer.

3. Method for producing fibers comprising a support, a thermoplastic polyurethane substrate, and a nanofiber nonwoven fabric

According to an embodiment of the present invention, the nanofiber nonwoven fabric is successively laminated on the release paper in each unit (0, 30 or 30 '), and then the nanofiber nonwoven fabric is separated from the release paper. Thereafter, the composite fiber can be manufactured through a process in which the first support, the first thermoplastic polyurethane base, the nanofiber nonwoven fabric, the second thermoplastic polyurethane base, and the second support are successively joined and heat-sealed in a laminating apparatus (not shown) . 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 .

Hereinafter, the effects of the present invention will be described in more detail with reference to concrete examples. These embodiments are only for the understanding of the present invention and do not limit the scope of the present invention.

Example 1

13% by weight of polyurethane (using Pellethane 2363-80AE from Dow (USA)) was dissolved in 87% by weight of NN-dimethylacetamide (DMAc) solvent to prepare a polymer spinning solution. The spent fluid of each unit was put into the main tank. The distance between the electrode and the collector on the release paper in each of the units in 40cm, 20kV applied voltage, the spinning liquid flow rate of 0.1mL / h, temperature 22 ℃, the conditions of humidity of 20% the basis weight by electrospinning the spinning liquid 5g / m ² of A polyurethane nanofiber nonwoven fabric was laminated. After the formed polyurethane nanofiber nonwoven fabric was separated from the release paper, a meltblown thermoplastic polyurethane base material (Bluecher Co. IOH10UM4) having a basis weight of 30 g / m ² was laminated on the lower surface of the nanofiber nonwoven fabric, To prepare a composite fiber having a structure in which polyurethane nanofibers are sandwiched between thermoplastic polyurethane substrates.

Example 2

The first unit is provided with a bottom-up electrospinning device and the second unit is provided with a downward-type electrospinning device. An electrospinning device equipped with a flip device is used therebetween, and a polygon having a basis weight of 3 g / The urethane nanofiber nonwoven fabric is continuously electrospun and laminated. After the formed polyurethane nanofiber nonwoven fabric was separated from the release paper, a meltblown thermoplastic polyurethane base material (Bluecher Co. IOH10UM4) having a basis weight of 30 g / m ² was laminated on the lower surface of the nanofiber nonwoven fabric, To prepare a composite fiber having a structure in which polyurethane nanofibers are sandwiched between thermoplastic polyurethane substrates.

Example 3

After separating the polyurethane nanofiber nonwoven fabric formed in Example 1 from the release paper, a meltblown thermoplastic polyurethane base material (Blueher Co., Ltd. IOH10UM4) having a basis weight of 30 g / m ² was laminated on the lower surface of the nanofiber nonwoven fabric, A polyethylene terephthalate base material having a basis weight of 100 g / m ² is laminated on the other side of the base material of the thermoplastic polyurethane on which the polyurethane nanofiber is not adhered, and the base material is subjected to a heat fusion process to form a first polyethylene terephthalate base material, a first thermoplastic polyurethane A conjugated fiber composed of a substrate, a polyurethane nanofiber, a second thermoplastic polyurethane base, and a second polyethylene terephthalate base was prepared.

Example  4

In Example 1, a polyurethane nanofiber nonwoven fabric was laminated on one surface of a meltblown thermoplastic polyurethane base material (first thermoplastic polyurethane base material), a thermoplastic polyurethane base material was laminated on the other surface of the nanofiber nonwoven fabric, 2 thermoplastic polyurethane base) A polyethylene terephthalate base having a basis weight of 100 g / m < 2 > is laminated on the other surface of the base material of each of the first and second thermoplastic polyurethanes not having the polyurethane nanofiber attached thereto, A composite fiber composed of a polyethylene terephthalate base material, a first thermoplastic polyurethane base material, a polyurethane nano fiber, a second thermoplastic polyurethane base material and a second polyethylene terephthalate base material was prepared.

Comparative Example 1

A composite fiber composed of a cellulose substrate and a polyurethane nanofiber was prepared by using the same manufacturing method as in Example 1 except that a cellulose base was used instead of the thermoplastic polyurethane base material.

Comparative Example 2

13% by weight of polyurethane (Pellethane 2363-80AE manufactured by Dow (USA)) was dissolved in 87% of dimethylacetamide (N, N-dimethylacetamide, DMAc) to prepare each spinning solution. The polyurethane spraying solution was introduced into the main tank. A polyurethane nanofiber nonwoven fabric having a basis weight of 10 g / m < ² > was laminated by applying the above-mentioned polyurethane spinning solution onto the release paper by applying an applied voltage of 20 kV.

Test of adhesion between substrate and nanofiber web 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 Comparative Example 1 1 cycle O O O O O 3 cycles O O O O △ 5 cycles 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)

The composite fibers according to Examples 1 to 3 did not desorb easily between the substrate and the nanofibers even after 5 cycles of washing through the heat fusion process without using a separate adhesive or hot melt layer.

Comparison of production time

The time taken until the nanofiber nonwoven fabric of Example 1 and Comparative Example 2 was formed on the release paper and wrapped around the winding roller was measured and compared.

Example 1 Comparative Example 2 Production time 90 minutes 182 minutes

As described above, by using both the bottom-up type and the bottom-up type simultaneously to manufacture the nanofibers, the quality of the nanofiber nonwoven fabric, which is an advantage of the bottom-up type, is increased.

1: a nanofiber manufacturing apparatus, 3: a support,
5: feed roller, 7: feed roller,
9: take-up roller, 10: electrospinning unit 1 (bottom-up type),
11: tank main tank, 13: nozzle block,
14: voltage generating device, 15: nozzle,
17: collector, 20: rotating device,
20-1: Flip device,
21, 21: left and right guide members,
22, 22: Left and right guide grooves,
30: electrospinning unit 2 (bottom-up) 30 ': electrospinning unit 2 (top-down),
31: Spray solution Main tank,
33: nozzle block, 35: nozzle
37: collector, 50: laminating device,
60: Temperature control device, 70: Air permeability measuring device,
112: tube, 113: heat line.

Claims (8)

Preparing first and second thermoplastic polyurethane substrates;
Transferring the release paper to the electrospinning unit 1 using the bottom-up electrospinning device of the electrospinning apparatus, and electrospinning the polymer spinning solution on one side of the release paper to form a first nanofiber nonwoven fabric layer;
The release paper on which the first nanofiber nonwoven fabric layer is laminated is rotated up and down by 180 degrees while passing through the flip device;
The formed first nanofiber nonwoven fabric layer is transferred to the unit 2 using the top-down electrospinning device of the electrospinning device to form a second nanofiber nonwoven fabric layer on the first nanofiber nonwoven fabric layer to form a two-layered nanofiber nonwoven fabric layer ;
The two-layered nanofiber nonwoven fabric layer is separated from the release paper and laminated on the first thermoplastic polyurethane base material,
Laminating a second thermoplastic polyurethane base on top of the two-layered nanofiber nonwoven fabric layer;
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 first and second thermoplastic polyurethane based non-woven fabrics; And
Thermally bonding the support, the thermoplastic polyurethane base and the two-layered nanofiber nonwoven fabric layer after laminating; Lt; / RTI >
Wherein the basis weight of the first and second nanofiber nonwoven fabrics is 1 g / m ² or more and 20 g / m ² or less,
Wherein the thermoplastic polyurethane base has a basis weight of 10 g / m ² or more and 150 g / m ² or less.
delete The method according to claim 1,
Wherein the polymer is at least one selected from the group consisting of polyimide (PI), polyacrylonitrile (PAN), PES, polyamide (PA), PVDF and polyurethane (PU) A method for manufacturing a composite fiber having improved adhesion between nanofiber nonwoven fabrics.
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 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.
delete delete A composite fiber produced by the production method according to any one of claims 1 to 5.

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