KR101771913B1

KR101771913B1 - Nano membrane including thermal stable polymer nano fiber and polyacrylonitrile nano fiber

Info

Publication number: KR101771913B1
Application number: KR1020150057430A
Authority: KR
Inventors: 박종철
Original assignee: (주)에프티이앤이
Priority date: 2015-04-23
Filing date: 2015-04-23
Publication date: 2017-08-28
Also published as: KR20160126422A

Abstract

BACKGROUND OF THE INVENTION 1. Field of the Invention [0001] The present invention relates to a nanomembrane including nanofibers, and more particularly, to a nanomembrane including a heat-resistant polymer nanofiber and a polyacrylonitrile nanofiber.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention [0001] The present invention relates to a nanomembrane including a thermostable polymer nanofiber and a polyacrylonitrile nanofiber,

BACKGROUND ART Conventionally, in order to prevent permeation of gas such as water vapor or oxygen in the field of foods, packaging materials, medicines, etc., a gas having a relatively simple structure in which an inorganic film such as a vapor deposition film of metal or metal oxide is formed on the surface of a resin substrate Barrier films have been used.

Recently, a gas barrier film preventing the permeation of water vapor and oxygen has been used in the field of electronic devices such as a liquid crystal display (LCD), a solar cell (PV), and an organic electroluminescence (EL) . That is, it is necessary to give such an electronic device a property of being flexible and light and hard to break, and a gas barrier film having the above properties is used.

Electronic devices based on nanofibers are still conceptual steps, but they have a wide surface area, a variety of surface treatments, the ease of compositing composites, It is necessary to make a fibrous structure to give flexibility. Therefore, the manufacture of transparent mat composed of nanofibers excellent in flexibility is likely to substitute many electronic devices market because of its ease of imparting electronic performance and various advantages. Examples of possible fiber-based electronic devices include textile solar cells, flexible transistors, flexible displays, external stimulus drug delivery, biosensors and gas sensors, light control functional textiles, functional apparel and functional products for the defense industry .

As a measure for obtaining a gas barrier film applicable to an electronic device, a method of forming an inorganic film thickened on a resin base can be mentioned. However, simply by thickening the inorganic film, defects such as cracks are liable to occur in the inorganic film, and sufficient gas barrier property can not be obtained. Therefore, a gas barrier film formed by using an organic film as an adhesive layer, specifically, a gas barrier film formed by alternately laminating a unit including an inorganic film and an organic film on a resin substrate in order to prevent a crack from occurring in the thickened inorganic film Film has been proposed.

Many efforts have been made to form networks with new types of fiber-like materials that are ideal for replacing existing materials in high-performance next-generation devices such as solar cells, touch screens, skin-like sensors, displays and smart windows However, it is not easy to produce a mat composed of transparent nanofiber.

SUMMARY OF THE INVENTION The present invention has been conceived in order to solve the above problems, and it is an object of the present invention to provide a method and an apparatus for separating at least two radiation sections and successively electromagnetically radiating different polymers in a nozzle block located in at least two radiation sections, A membrane can be manufactured and a number of divided radial spaces or a distance of a radial section can be varied to manufacture a nanomembrane suitable for desired product characteristics and a nanomembrane capable of reducing a total cost by simplifying a manufacturing process The purpose is to provide.

A first nanofiber layer is formed by electrospinning a heat-resistant polymer solution. And a second nanofiber layer laminated by electrospinning a polyacrylonitrile solution on the first nanofiber layer.

At this time, the nanomembrane may further include an adhesive layer on the first nanofiber layer, and the adhesive layer may be formed of at least one adhesive agent selected from the group consisting of a low melting point polyurethane, a hydrophobic polyurethane and a low melting point hydrophobic polyurethane Is formed by electrospinning.

Here, it is preferable that the adhesive solution is electrospun on the entire surface or a part of the first nanofiber layer.

Preferably, the adhesive solution electrospun to a part of the first nanofiber layer is electrospun in the longitudinal direction or the width direction of the first nanofiber layer.

The heat-resistant polymer solution and the polyacrylonitrile solution are electrospun through a temperature controller at a temperature of 50 to 100 ° C.

The viscosity of the heat-resistant polymer solution and the polyacrylonitrile solution through the temperature controller is preferably controlled to 1,000 to 3,000 cps.

The first nanofiber layer and the second nanofiber layer are different in basis weight along the longitudinal direction or the transverse direction.

The method of manufacturing a nanomembrane according to the present invention is characterized in that the nanomembrane is divided into at least two radiation sections, and the polymers different from each other are successively electrospun through the radiation sections to obtain a nanomembrane laminated in two or more layers, It is possible to simplify and simplify the manufacturing process of the semiconductor device, thereby reducing manufacturing cost and manufacturing time.

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 plan view schematically showing a nozzle block installed in each unit of the electrospinning apparatus according to the present invention,
5 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,
6 is a sectional view taken along the line A-A 'in Fig. 5,
7 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,
8 is a sectional view taken along the line B-B 'in Fig. 7,
Fig. 9 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, Fig.
10 is a sectional view taken along the line C-C 'in Fig. 9,
11 is a view schematically showing an auxiliary transfer device of an electrospinning device according to the present invention,
12 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,
FIG. 13 to FIG. 16 are side views schematically showing the operation of the long sheet conveying speed adjusting apparatus of the electrospinning apparatus according to the present invention,
17 is a side view schematically showing an electrospinning device for manufacturing a nanomembrane including an adhesive layer according to the present invention,
18 is a perspective view schematically showing a nozzle block installed in an adhesive (low-melting-point polymer) unit of an electrospinning apparatus according to the present invention,
19 is a plan view schematically showing a nozzle block provided in an adhesive (low melting point polymer) unit of an electrospinning device according to the present invention,
20 to 21 are plan views schematically showing an operation process in which an adhesive (low melting point polymer) and a polymer spinning solution are sequentially injected through a nozzle block installed in each unit of the electrospinning apparatus according to the present invention,
22 is a plan view schematically showing another embodiment according to a nozzle body arranged in a nozzle block of an electrospinning apparatus according to the present invention,
Fig. 23 is a front view of Fig. 22,
24 is a side view schematically showing another embodiment according to the nozzle body arranged in the nozzle block of the electrospinning apparatus according to the present invention,
25 and 26 show an operation process (in FIG. 25, a nozzle indicated by a dashed line is a closed nozzle) in which the polymer spinning solution is electrospun on the same plane of the base material through the nozzles of each nozzle tube of the electrospinning device according to the present invention , And the nozzle indicated by the broken line in Fig. 26 is located at the lower portion of the substrate)
27 is a plan view schematically showing another embodiment according to a nozzle body arranged in a nozzle block of the electrospinning apparatus according to the present invention,
28 is a perspective view schematically showing another embodiment according to a nozzle body arranged in a nozzle block of the electrospinning apparatus according to the present invention;
FIG. 29 and FIG. 30 are plan views schematically showing another embodiment according to an operation process of electropolishing the polymer spinning solution on the same plane of the base material through the nozzles of each nozzle tube of the electrospinning device according to the present invention. FIG.
31 is a schematic view showing a nanomembrane comprising a heat-resistant polymer nanofiber and a polyacrylonitrile nanofiber according to the present invention.

Hereinafter, the present invention will be described.

The present invention relates to a first nanofiber layer formed by electrospinning a hydrophilic polyurethane solution; And a second nanofiber layer laminated by electrospinning a hydrophobic polyurethane solution on the first nanofiber layer.

At this time, the nanomembrane is manufactured using an electrospinning device.

The heat-resistant polymer used in the present invention is preferably one kind of polymer selected from the group consisting of polyimide, meta-aramid, and polyethersulfone.

On the other hand, the polyimide which is one of the heat-resistant polymers used in the present invention can be prepared by a two step reaction.

The first step is a step of preparing polyamic acid. As shown in the following reaction formula 1, the polyamic acid is prepared by adding dianhydride to a reaction solution in which diamine is dissolved. In order to increase the degree of polymerization, Temperature, water content of the solvent, and purity of the monomer.

[Reaction Scheme 1]

As the solvent used in the first step, organic polar solvents such as dimethylacetamide (DMAc), dimethylformamide (DMF) and en-methyl-2-pyrrolidone (NMP) are mainly used. Examples of the anhydride include pyromellitic dianhydride (PMDA), benzophenonetetracarboxylic dianhydride (BTDA), 4,4'-oxydiphthalic anhydride (4,4'-oxydiphthalic anhydride) ODPA), biphenyltetracarboxylic dianhydride (BPDA), and bis (3,4'-dicarboxyphenyl) dimethylsilane dianhydride (SIDA). One can be used.

Examples of the diamine include 4,4'-oxydianiline (ODA), p-penylene diamine (p-PDA) and o-penylenediamine o-PDA) may be used.

Thereafter, as shown in the following Reaction Scheme 2, the following four methods are typical as a second step of dehydration and ring closure reaction for producing polyimide from the polyamic acid produced in the first step.

[Reaction Scheme 2]

First, in the re-impregnation method, a polyamic acid solution is added to an excess amount of a poor solvent to obtain a solid polyamic acid. As the re-precipitation solvent, water is mainly used, but toluene or ether can be used as a co-solvent .

The chemical imidization method is a method in which a imidization reaction is chemically performed using a dehydration catalyst such as acetic anhydride / pyridine, and is useful for producing a polyimide film.

The thermal imidization method is a method in which the polyamic acid solution is heated to 150 to 200 ° C to thermally imidize it. In the simplest process, the crystallization degree is high, and the amine exchange reaction occurs when the amine type solvent is used. have.

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

The specific gravity of the meta-aramid, which is one of the heat-resistant polymers used in the present invention, is preferably 1.3 to 1.4, and the weight average molecular weight is preferably 300,000 to 1,000,000. The most preferred weight average molecular weight is 3,000 to 500,000.

The meta-aramid comprises a meta-oriented synthetic aromatic polyamide. Meta-aramid polymers should have a fiber-forming molecular weight and may comprise polyamidic homopolymers, copolymers and mixtures thereof, which are predominantly aromatic, wherein at least 85% of the amide (-CONH-) bonds are directly attached to two aromatic rings Respectively. The ring may be unsubstituted or substituted. The polymer becomes a meta-aramid when the two rings or radicals are meta-oriented along the molecular chain with respect to each other. Preferably, the copolymer contains up to 10% other diamines substituted for the primary diamine used to form the polymer, or up to 10% other diacids substituted for the primary diacid chloride used to form the polymer It has a diacid chloride. Preferred meta-aramids are poly (meta-phenylene isophthalamide) (MPD-I) and copolymers thereof. One such meta-aramid fiber is < RTI ID = 0.0 > a < / RTI > children. Nomex < (R) > aramid fibers available from EI du Pont de Nemours and Company, but meta-aramid fibers are available from Teijin Ltd., Tokyo, Japan Tejinconex (registered trademark); New Star (TM) meta-aramid available from Yantai Spandex Co. Ltd, Shandong, China; And Chinfunex (registered trademark) Aramid 1313, available from Guangdong Charming Chemical Co., Ltd., Shinduo, Guangdong, China.

This meta-aramid is the first high heat-resistant aramid fiber that can be used at 350 ° C for a short time and at 210 ° C for continuous use. When exposed to temperatures above this temperature, it is carbonized without melting or burning like other fibers . Above all, unlike other products that are flame retarded or refractory treated, they do not emit toxic gases or harmful substances even when carbonized, and thus they have excellent properties as eco-friendly fibers.

In addition, the meta-aramid has a very strong molecular structure of the fiber itself, so it is not only strong in its original strength but also easily oriented in the fiber axis direction in the spinning stage to improve the crystallinity, There is an advantage to increase.

The polyethersulfone, which is one of the heat-resistant polymers used in the present invention, is an amber transparent, amorphous resin having the following repeating unit, and is generally produced by condensation polymerization of dichlorodiphenylsulfone.

[Reaction Scheme 3]

Polyethersulfone is a super heat resistant engineering plastic developed by ICI in the UK. It is a highly heat resistant polymer among thermoplastic plastics. Since the polyethersulfone is amorphous, the physical properties of the polyether sulfone are not lowered by temperature rise, and the temperature dependency of the flexural modulus is small, so that it hardly changes at -100 to 200 캜. The load-strain temperature is 200 to 220 占 폚, and the glass transition temperature is 225 占 폚. In addition, the creep resistance up to 180 占 폚 is the most excellent among the thermoplastic resins, and has the characteristic of being resistant to hot water and steam at 150 to 160 占 폚.

Due to such characteristics, polyethersulfone is used in optical disks, magnetic disks, electric and electronic fields, hydrothermal fields, automobile fields, and heat resistant paints.

Examples of the solvent usable with the polyethersulfone include acetone, tetrahydrofuran, methylene chloride, chloroform, dimethylformamide (DMF), dimethylacetamide (DMAc), N- N-methyl pyrrolidone (NMP), cyclohexane, water, or a mixture thereof, but the present invention is not limited thereto.

On the other hand, the polyacrylonitrile used in the present invention means a polymer of acrylonitrile (CH2 = CHCN).

[Reaction Scheme 4]

Here, the polyacrylonitrile resin is a copolymer made from a mixture of acrylonitrile and a monomer constituting the majority. Frequently used monomers include butadiene styrene vinylidene chloride or other vinyl compounds. The acrylic fiber contains at least 85% acrylonitrile, and the mode acrylic contains 35 to 85% acrylonitrile. When other monomers are included, the fiber has the property of increasing the affinity to the dye. More specifically, in the production of an acrylonitrile-based copolymer and spinning solution, in the case of producing an acrylonitrile-based copolymer, there is little contamination of nozzles in the course of manufacturing ultrafine fibers by electrospinning, Thereby increasing the solubility in the solvent and imparting better mechanical properties. In addition, polyacrylonitrile has a softening point of 300 ° C or more and is excellent in heat resistance.

The degree of polymerization of the polyacrylonitrile is preferably 1,000 to 1,000,000, and more preferably 2,000 to 1,000,000.

The polyacrylonitrile is preferably used within a range that satisfies the usage amount of the acrylonitrile monomer, the hydrophobic monomer and the hydrophilic monomer. When the polymer is polymerized, the weight% of the acrylonitrile monomer is too low to be electrospun when the weight% of the hydrophilic monomer and the weight% of the hydrophobic monomer are 3: 4 and the total monomer is less than 60, It is difficult to form a stable jet (JET) at the time of electrospinning as well as to cause contamination of the nozzle. If the ratio is more than 99, the spinning viscosity is too high to spin, and even if an additive capable of lowering the viscosity is added, the diameter of the microfine fibers becomes too large and the productivity of electrospray is too low to achieve the object of the present invention.

In addition, as much amount of comonomer is added to the acrylic polymer, the amount of the crosslinking agent must be increased so that the stability of electrospinning can be secured and deterioration of the mechanical properties of the nanofiber can be prevented.

The hydrophobic monomer may be an ethylene-based compound such as methacrylate, ethyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, vinyl acetate, vinyl pyrrolidone, vinylidene chloride or vinyl chloride, It is preferable to use at least one selected.

Wherein the hydrophilic monomer is selected from the group consisting of acrylic acid, allyl alcohol, methallyl alcohol, hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, butanediol monoacrylate, dimethylaminoethyl acrylate, butent ricarboxylic acid, vinyl It is preferable to use at least one selected from ethylene-based compounds such as sulfonic acid, allylsulfonic acid, methallylsulfonic acid, and para-styrenesulfonic acid and polyvalent acids or derivatives thereof.

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

Hereinafter, the electrospinning apparatus used in the present invention will be described with reference to Figs. 1 to 17. Fig.

FIG. 1 is a side view schematically showing an electrospinning apparatus according to the present invention, FIG. 2 is a side cross-sectional view schematically showing a nozzle of a nozzle block installed in each unit of the electrospinning apparatus according to the present invention, FIG. 4 is a cross-sectional view schematically showing a nozzle block provided in each unit of the electrospinning apparatus according to the present invention. FIG. 4 is a cross- Fig. 5 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, Fig. 6 is a sectional view taken on line A-A ' 7 is a schematic 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. 8 is a cross-sectional view taken along the line B-B 'in Fig. 7, and Fig. 9 is a schematic view 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 11 is a schematic view of an auxiliary transfer device of the electrospinning device according to the present invention, and FIG. 12 is a cross-sectional view of the electrospinning device according to the present invention. FIGS. 13 to 16 are side views schematically showing the operation of the long sheet conveying speed adjusting apparatus of the electrospinning apparatus according to the present invention.

As shown in the figure, an electrospinning device 1 according to the present invention comprises a bottom-up electrospinning device 1, at least one unit 10a or 10b is sequentially arranged at a predetermined interval, Each of the units 10a and 10b produces the nanomembrane by electrospinning the same polymer spinning solution individually or electrospinning the polymer spinning solution having different materials.

For this purpose, each of the units 10a and 10b is provided with a spinning liquid main tank 8 in which a polymer spinning solution is filled and a polymer spinning solution filled in the spinning solution main tank 8 in a predetermined amount A nozzle block 11 for discharging polymer flushing liquid filled in the spinning liquid main tank 8 and having 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 injected from the nozzle 13.

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, And the formed nanofiber is made of a nanomembrane.

Here, the unit 10a, which is located at the front end of each unit 10a, 10b of the electrospinning device 1, is provided in the unit 10a, and the nanofibers are laminated by spraying the polymer spinning solution. A feeding roller 3 for feeding the sheet 15 is provided and a long sheet 15 in which nanofibers are laminated is wound on the back of the unit 10b positioned at the rear end of each unit 10a and 10b Up rollers 5 are provided.

It is preferable that the elongate sheet 15 in which the polymer solution is laminated while passing through each of the units 10a and 10b is a release paper film and the polymer solution is irradiated on the collector 13 without the elongated sheet 15. [ .

At this time, the material of the polymer spinning solution to be radiated through each unit 10a, 10b of the electrospinning device 1 is not limited, but in the present invention, a polyethersulfone solution is used for the unit 10a, (10b) is characterized in that a hydrophobic polyurethane solution is 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.

Here, the nozzle block 11 includes a nozzle plate 405 in which multiple tubular nozzles 500 formed in a sheath-core type multi-tubular shape are arranged and a nozzle plate 405 disposed at a lower end of the nozzle plate 405 Two or more spinning solution storage plates 407 and 408 for supplying a polymer spinning solution (not shown) to the multi-tubular nozzle 500, an overflow removing nozzle 415 surrounding the multi-tubular nozzle 500, An overflow liquid temporary storage plate 410 connected to the overflow removing nozzle 415 and positioned directly above the nozzle plate 405 and an overflow liquid storage plate 410 positioned above the overflow liquid temporary storage plate 410, And an overflow removing nozzle support plate 416 for supporting the removal nozzle 415 by the overflow removing nozzle 415.

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.

In the embodiment of the electrospinning device 1 according to the present invention, the nozzle 12 is cylindrical, but as shown in FIG. 3, the nozzle 12 is formed as a wedge-shaped cylinder, And its tip portion 503 is formed in the shape of a fall tube having an angle of 5 to 30 degrees with respect to the axis.

Here, the tip portion 503 formed in the tubular shape is formed to be narrowed from the upper portion to the lower portion. However, the tip portion 503 may be formed in various other shapes as long as it is narrowed from the upper portion to the lower portion.

22 to 30, a nozzle body 112 according to an embodiment of the present invention will be described.

A nozzle block 111 of the electrospinning device 100 is provided with a plurality of nozzle tubes 112 arranged in the longitudinal direction thereof and a spinning solution main tank 120 for supplying a polymer solution for the nozzle tube 112, May be connected to each other.

The nozzle tubes 112a, 112b, 112c, 112d, 112e, 112f, 112g, 112h, and 112i, which are linearly formed on the upper surface of the nozzle block 111 and have a plurality of nozzles 111a linearly, A plurality of nozzle tubes 112a, 112b, 112c, 112d, 112e, 112f, 112g, 112h and 112i are arranged in the longitudinal direction of the substrate 115 in the longitudinal direction of the substrate 115, And the polymer spinning solution filled in the spinning solution main tank 120 is supplied.

Here, the nozzle tubes 112a, 112b, 112c, 112d, 112e, 112f, 112g, 112h, and 112i are connected to the spinning solution main tank 120 through a solution supply tube 121, A plurality of nozzle tubes 112a, 112b, 112c, 112d, 112e, 112f, 112g, 112h, 112i and a spinning liquid main tank 120 are branched.

At this time, a supply amount adjusting means (not shown) is connected to the solution supply pipe 121, which is communicated to the nozzle tubes 112a, 112b, 112c, 112d, 112e, 112f, 112g, 112h, 112i in the spinning liquid main tank 120, And the supply amount adjusting means is composed of a supply valve 122.

A supply valve 122 is provided in the solution supply pipe 121 which is communicated to each nozzle body 112a, 112b, 112c, 112d, 112e, 112f, 112g, 112h, 112i in the spinning liquid main tank 120 112b, 112c, 112d, 112e, 112f, 112g, 112h, 112i in the spinning liquid main tank 120 by the supply valves 122, And controlled on-off systems.

That is, when the polymer spinning solution is supplied to the nozzle tubes 112a, 112b, 112c, 112d, 112e, 112f, 112g, 112h, 112i from the spinning solution main tank 120 through the solution supply tube 121, By the opening and closing of the supply valve 122 provided in the solution supply pipe 121 for supplying the main tank 120 and the nozzle tubes 112a, 112b, 112c, 112d, 112e, 112f, 112g, 112h, The nozzle tubes 112b, 112d, 112f, 112g, 112h, 112i at specific positions among the nozzle tubes 112a, 112b, 112c, 112d, 112e, 112f, 112g, 112h, 112i arranged in the nozzle block 111 112b, 112c, 112d, 112e, 112f, 112g, 112h, 112i, 112f, 112g, 112h, 112i, 112f, 112h, 112h, 112h, The supply of the polymer solution is controlled and controlled.

For this purpose, the supply valve 122 is preferably controllably connected to a control unit (not shown). Preferably, the opening and closing of the supply valve 122 is automatically controlled by the control unit. However, It is also possible that the opening and closing of the supply valve 122 is manually controlled.

112b, 112c, 112d, 112e, 112f, 112g, 112h, 112i in the spinning liquid main tank 120. However, The supply amount adjusting means may be composed of various other structures and means, but the present invention is not limited thereto.

The solution supply pipe 121 is connected to the spinning solution main tank 120 and the nozzle tubes 112a, 112b, 112c, 112d, 112e, 112f, 112g, 112h and 112i, A supply valve 122 is provided at each of the nozzles 112a, 112b, 112c, 112d, 112e, 112f, 112g, 112h, 112i in the spinning liquid main tank 120 to supply a plurality of 112b, 112c, 112d, 112e, 112f, 112g, 112h, 112i arranged in the nozzle block 111 by opening the specific supply valve 122 of the supply valve 122, The nozzle tubular body 112a (112a, 112b, 112d, 112f, 112g, 112h, 112i) at the specific position among the nozzle tubular bodies provided in the nozzle block 111 by supplying the polymer solution, , 112c, and 112e of the spinning liquid main tank 120 are blocked by the opening and closing of the supply valve 122, The supply of the polymer spinning solution to be supplied to the (112a, 112b, 112c, 112d, 112e, 112f, 112g, 112h, 112i) is adjusted and controlled.

The polymer spinning solution supplied to the nozzle tubes 112a, 112b, 112c, 112d, 112e, 112f, 112g, 112h, 112i through the solution supply tube 121 in the spinning solution main tank 120 flows through the solution supply tube 121, 112b, 112c, 112d, 112e, 112f, 112g, 112h, 112i through a nozzle supply pipe 125 which is connected to the nozzles 121a.

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

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

The supply of the polymer solution to be supplied to each nozzle 111a from the nozzle supply pipe 125 is controlled individually by the nozzle valve 126 by the opening and closing of the nozzle valve 126, Preferably, the nozzle valve 126 is controllably connected to a control unit (not shown), and the opening and closing of the nozzle valve 126 is automatically controlled by the control unit. However, It is also possible that the opening and closing of the nozzle valve 126 are manually controlled.

In the embodiment of the present invention, if the amount of the spinning solution of the polymer spinning solution is easily controlled and controlled after being supplied to the nozzle 111a from the nozzle tube 112, The means for controlling the amount of radiation may be composed of various other structures and means, but is not limited thereto.

According to the structure described above, the solution supply pipe 121 and the nozzles 111a are connected to each other, and the nozzle valve 126 is provided in the nozzle supply pipe 125, Of the plurality of nozzle valves 126 when supplying the polymer spinning solution to the respective nozzles 111a through the respective nozzle tubes 112a, 112b, 112c, 112d, 112e, 112f, 112g, 112h, The polymer spinning solution is selectively discharged only from the nozzles 111a at specific positions among the nozzles 111a provided in the nozzle tubes 112a, 112b, 112c, 112d, 112e, 112f, 112g, 112h, Or a specific nozzle valve 126 is closed so that the nozzles 111a provided in the nozzle tubes 112a, 112b, 112c, 112d, 112e, 112f, 112g, 112h, The nozzle tubular body 112a, the tubular body 112a, the tubular body 112a, and the nozzle body 112b are separated from the spinning liquid main tank 120 by the nozzle valve 126, 112b, 112c, 112d, 112e, 112f, 112g, 112h, and 112i, the supply of the polymer spinning solution supplied to each nozzle 111a is individually controlled and controlled.

In an embodiment of the present invention, the solution supply pipe 121 is provided with a supply valve 122 so that the nozzle tubes 112a, 112b, 112c, 112d and 112e of the nozzle block 111 in the spinning liquid main tank 120 112b, 112c, 112d, 112f, 112g, 112h, and 112i, and a nozzle valve 126 is provided in the nozzle supply pipe 125 to adjust the supply amount of the polymer solution, 112b, 112c, 112d, 112e, 112f, 112c, 112d, 112e, 112f, 112f, 112g, 112h, 112i to regulate and control the radiation amount of the polymer spinning solution which is radiated through each nozzle 111a, 112a, 112b, 112g, 112h, and 112i, the nanofibers having different weights in the longitudinal direction of the base material 115 are laminated by the polymer spinning solution electrospunning from the respective nozzles 111a of the nozzle blocks 111, 111a are arranged, the respective nozzles 111a are directly controlled and controlled individually, The nanofibers having different basis weights may be laminated in the longitudinal direction of the base material 115 by controlling and controlling the amount of the spinning solution that is electrospun through the spinneret nozzle 111a, but the present invention is not limited thereto.

The MD direction used in the present invention means a machine direction, and means a longitudinal direction corresponding to the progress direction in the case of continuous production of fibers such as a film or a nonwoven fabric, and the CD direction means a perpendicular direction to the CD direction as a cross direction . MD is the machine direction / longitudinal direction, and CD is the width direction / transverse direction.

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".

A temperature regulating device 60 is provided in each tube 40 of the nozzle block 11 provided in each unit 10a and 10b of the electrospinning device 1 according to the present invention and the voltage generating devices 14a, 14b.

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, The temperature control device 60 is provided.

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 tubes 40, the temperature controller 60 is connected to the heating wires 41 and 42 or pipes 43 ).

In order to adjust the temperature of the plurality of tubes 40, a temperature controller 60 is provided.

5 to 6, a temperature regulating device 60 in the form of a heat line 41 is formed in a spiral shape on the periphery of the inner wall of the inner tube 40 of the nozzle block 11, And the temperature of the supplied and introduced polymer spinning solution is controlled.

In the embodiment of the present invention, the nozzle block 11 is spirally provided with a temperature adjusting device 60 in the shape of a heat ray 41 on the inner circumference of the tube 40. However, as shown in FIGS. 7 to 8, A plurality of temperature control devices 60 in the form of a heat line 42 may be radially provided on the inner circumference of the tube 40. As shown in Figures 9 to 10, It is also possible that the temperature regulating device 60 of the present invention is provided in the form of a "C"

In the meantime, instead of maintaining the concentration at a constant level, the present invention uses the polymer solution having a high concentration to be reused after the overflow, and adjusts the viscosity of the polymer solution to be constant by using the temperature regulating device 60, And it is easy to form nanofibers of the polymer solution because of its high acidity at 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 type of the polymer and solvent used, the concentration of the polymer solution, the temperature and humidity of the spinning room, It is known to affect radioactivity. That is, the physical properties of the polymer (polymer solution) 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 viscosity means that the nano-sized fibers are not smoothly radiated through the nozzle, and the higher the viscosity, the more unsuitable for fiberization through electrospinning.

The present invention is characterized in that it includes a temperature regulating device 60 for maintaining fiber viscosity suitable for electrospinning as described above.

The temperature regulating device 60 may include a heating device capable of keeping the viscosity of the polymer solution having a high viscosity reusable through overflow at a low level or a cooling device capable of maintaining a viscosity of the polymer solution having a relatively low viscosity at a high level .

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, . &Lt; / 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.

In particular, in the case of the polymer solution, the concentration of the polymer solution re-supplied through the overflow tends to increase. By measuring the concentration of the polymer solution in the intermediate tank 220 and adjusting the temperature using the temperature- The viscosity can be kept constant.

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 apparatus using a concentration measuring apparatus using infrared or the like 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 may be borrowed.

As an example of the heating device, the electro-thermal heater may be used in the form of a hot wire, and coil-shaped hot wires 62a and 62b may be mounted inside the tube 43 of the nozzle block 110, (See Figs. 5 to 10).

It is also possible to have the configuration of the linear heat lines 62a and 62b and the U-shaped pipe 63.

The heating device includes a nozzle block 110 through which the polymer solution is radiated, a tank (main storage tank, intermediate tank or regeneration tank) and an overflow system 200 (in particular, a tank And a transfer pipe).

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 may be provided in at least one of the nozzle block 110, the tank, and the overflow system 200 in the same manner as the heating device, and is used to maintain a certain viscosity of the polymer solution.

In addition, the temperature controller 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 on the main storage tank 210, the intermediate tank 220, the regeneration tank 230, the nozzle block 110 or the overflow system 200 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 heating device 60.

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

Further, in order to make the viscosity of the polymer solution re-supplied according to the present invention constant, the temperature of the polymer solution according to the concentration of the polymer solution is controlled at 45 to 120 ° C, not at room temperature, To < RTI ID = 0.0 > 100 C. < / RTI >

Meanwhile, the viscosity of the polymer solution of the present invention is preferably 1,000 to 5,000 cps, more preferably 1,000 to 3,000 cps. If the viscosity is 1,000 cps or less, the quality of the nanofibers to be electrospun is poor, and if the viscosity is 3,000 cps or more, the polymer solution can not be easily discharged from the nozzle 42 during the electrospinning, resulting in a slow production rate.

In the present invention, since the viscosity of the polymer solution is constant as the electrospinning progresses, the ease of spinning during electrospinning is excellent, and the concentration of the polymer solution is increased. As a result, the amount of solids in the nanofibers accumulated in the collector increases, There is an increasing effect.

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 controls the viscosity of the polymer solution through the temperature control of the nozzle block 110 or the main storage tank 210 by measuring the concentration of the intermediate tank 220 off- And an automatic system that can adjust the temperature of the solution according to the concentration measurement through an automatic control system on-line.

11, an auxiliary conveying device (not shown) for adjusting the conveying speed of the long sheet 15 to be 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 which can be driven by a motor. However, as shown in FIG. 12, 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 nanofibers discharged from the unit 10a located at the front end of the electrospinning device 1 is measured to be thinner than the deviation amount by the above-described structure, the feeding 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 nanofibers per unit area to increase the thickness.

When the thickness of the nanofibers 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 make the thickness thinner by reducing the discharge amount of the voltage generating device 11 and by controlling the intensity of the voltage of the voltage generating devices 14a and 14b to reduce the discharge amount of the nanofibers per unit area to reduce the amount of lamination, A nanomembrane having a thickness can be produced.

Here, the thickness measuring device 9 is disposed so as to face upward and downward with the elongated sheet 15 inserted and supplied therebetween. The thickness measuring device 9 measures the distance to the top or bottom of the elongate 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 together with the long sheet 15 on which the nanomembranes are laminated, and the propagation time of the longitudinal wave and the transverse wave is measured Then, from a predetermined equation using propagation time of the measured longitudinal waves and transverse waves, propagation velocity of longitudinal waves and transverse waves at the reference temperature of the elongate sheet 15 in which the nanomembranes are stacked, and temperature constants of longitudinal waves and transverse wave propagation velocities And a thickness measuring device using an ultrasonic longitudinal wave and a transverse wave to calculate the thickness of the object.

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 precise thickness regardless of the type of temperature distribution inside the nanomembrane.

Meanwhile, the thickness of the nanomembrane of the long sheet 15 to be transported after the polymer spinning solution is sprayed and laminated on the electrospinning device 1 according to the present invention is measured to determine the feeding speed of the long sheet 15 and the feed speed of the nozzle block 11 The elongated sheet conveying speed regulating device 30 for regulating the conveying speed of the long sheet 15 is further provided on the electrospinning device 1. The thickness measuring device 70 controls the conveying speed 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 in the respective units 10a and 10b so that when the elongated sheet 15 in which nanomembranes are laminated by the spinning solution injected by the nozzles 12 is conveyed, And is provided at a line and a rear end of a buffer zone 31 formed between the units 10a and 10b, respectively.

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 nanomembrane manufactured through the electrospinning device 1 at the rear of the unit 10d located at the rearmost end of each unit 10a, 10b of the electrospinning device 1 Device 80 is provided.

As described above, the conveying speed of the long sheet 15 and the nozzle block 11 are controlled based on the measured degree of air permeability of the nano-membrane 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 nanomembranes 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 amount of discharge of the block 11 is reduced and the intensity of the voltage of the voltage generating devices 14a and 14b is adjusted to reduce the discharge amount of the nanofibers per unit area to reduce the amount of lamination,

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

Here, when the air permeability deviation P of the nanomembrane is less than a predetermined value, the feed velocity V is not changed from the initial value, and when the deviation amount P is equal to or larger than the predetermined value, It is possible to control the feed speed V from the initial value so that the control of the feed speed V by the feed speed V control device can be simplified.

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.

A laminating apparatus 90 for laminating the nanomembranes electrospun through each unit 10a and 10b of the electrospinning apparatus 1 includes a unit 10b located at the rear end of each unit 10a and 10b And performs a post-process of the nanomembrane electrospun through the electrospinning device 1 by the laminating device 90. [

On the other hand, the present invention can include an adhesive layer on the nano fiber layer.

Hereinafter, an electrospinning apparatus for producing a nanomembrane including an adhesive layer will be described with reference to FIGS. 17 to 21. FIG.

FIG. 17 is a side view schematically showing an electrospinning device for producing a nanomembrane including an adhesive layer, and FIG. 18 schematically shows a nozzle block installed in an adhesive (low melting point polymer) unit of an electrospinning device according to the present invention. 19 is a plan view schematically showing a nozzle block provided in an adhesive (low-melting-point polymer) unit of an electrospinning apparatus according to the present invention, and Figs. 20 to 21 are plan views (Low-melting-point polymer) and a polymer spinning solution are sequentially injected through a nozzle block installed in the nozzle block.

As shown in the figure, the electrospinning device 1 according to the present invention is composed of a bottom-up electrospinning device, in which at least one unit 10a, 10b, 10c, 10d is sequentially arranged at a predetermined interval, The polymeric spinning solution or the solution of the same material in the upper direction is individually electrospun through the respective units 10a, 10b, 10c and 10d, or the polymer spinning solution of different materials is electrospun to prepare the nanomembrane.

In one embodiment of the present invention, the electrospinning device 1 is a bottom-up electrospinning device, but it may also be a top-down electrospinning device (not shown).

In the embodiment of the present invention, four units 10a, 10b, 10c and 10d of the electrospinning device 1 are provided, but the number of the units 10a, 10b, 10c and 10d is two Or more, but is not limited thereto.

Each of the units 10a, 10b, 10c and 10d of the electrospinning device 1 has a solution main tank 8 in which an adhesive agent (low melting point polymer) or a polymer solution is filled, (Not shown) for supplying the adhesive (low-melting-point polymer) or the polymer spinning solution filled in the tank main body 8 in a fixed amount and an adhesive (low-melting-point polymer) or a polymer spinning solution A nozzle block 11 in which a plurality of nozzles 12 in a pin shape are arranged and a nozzle 12 for accumulating an adhesive (low melting point polymer) or a polymer spinning solution injected from the nozzle 12, And a voltage generator 14a, 14b, 14c, 14d for generating a voltage in the collector 13. The voltage generator 14a,

According to the structure as described above, the electrospinning device 1 according to the present invention is characterized in that the adhesive (low melting point polymer) or the polymer spinning solution filled in each solution main tank 8 is continuously supplied to the nozzle block 11 through the metering pump And the adhesive agent (low-melting-point polymer) or the polymer spinning solution supplied to the nozzle block 11 is injected and focused on the collector 13 having a high voltage through the plurality of nozzles 12, Nanofibers and an adhesive (low melting point polymer) are laminated on the collector 13 to form a nanomembrane.

To this end, each unit 10a, 10b, 10c, 10d of the electrospinning device 1 is composed of spinning solution units 10a, 10c and an adhesive (low melting point polymer) 10b, 10d, In the nozzle block 11a in the spinning solution units 10a and 10c and the nozzle block 11b in the adhesive (low melting point polymer) unit 10b and 10d located at the rear end thereof, (10a and 10c) and an adhesive (low melting point polymer) unit 10b and 10d are alternately provided in the electrospinning device 1 so that the collector 13 is filled with a spinning solution and an adhesive (Low melting point polymer) are alternately injected.

The nozzle blocks 11a in the spinning solution units 10a and 10c of the nozzle blocks 11 provided in the units 10a to 10d are supplied to the solution main tank 8 filled with the spinning solution And the nozzle block 11b in the adhesive (low melting point polymer) unit 10b, 10d is connected to the solution main tank 8 filled with the adhesive (low melting point polymer).

In an embodiment of the present invention, each nozzle block 11 installed in each of the units 10a, 10b, 10c and 10d is individually connected to a corresponding number of the solution main tanks 8 to form an adhesive (low melting point polymer 10b, 10c, and 10d are connected to one solution main tank 8 to supply the polymer solution for the polymer solution. (Low-melting-point polymer) units 10a and 10c are also connected to one solution main tank 8 so as to be supplied with an adhesive (low-melting-point polymer).

Here, the nozzles 12 are arranged in a partial form in a specific region of the nozzle block 11a provided in the adhesive (low melting point polymer) unit 10b, 10d among the units 10a, 10b, 10c, A nozzle 12 installed in a specific region of the nozzle block 11a is connected to a solution main tank 8 filled with an adhesive (low melting point polymer) to receive an adhesive (low melting point polymer) The adhesive (low-melting-point polymer) received is sprayed onto the first nanofiber layer.

(Low-melting-point polymer) in a specific region and a specific region of the first nanofiber layer in a region and a partial form in the nozzle 12 arranged in a partial form in a specific region of the nozzle block 11a by the above- .

The nozzles 12 are partially arranged in a specific region of the nozzle block 11a in the embodiment of the present invention, but the adhesive (low melting point polymer) units 10b and 10d are disposed in the spinning solution units 10a, A plurality of nozzles 12 are arranged in the longitudinal direction of the nozzle block 11a in the same manner as the nozzle blocks 10a to 10c, (Not shown), and the respective nozzles 12 are branched into a plurality of supply pipes (not shown), and the supply pipes are individually opened and closed by valves (not shown), respectively, (Low-melting-point polymer) is injected only in the nozzle 12 provided in a partial form in a specific region by adjusting each of the above-mentioned valves to form an adhesive (low-melting-point polymer) in a specific region and a specific region of the first nano- to be formed so as to inject It is possible.

At this time, each of the nozzle tubes 40 arranged in the nozzle block 11a is connected to a solution main tank 8 filled with an adhesive (low melting point polymer) through a supply pipe and a valve, The plurality of nozzles 12 provided in the nozzles 40 are connected to the nozzle tube 40 and are respectively connected to the supply pipes branched to a plurality of nozzles and controlled by the respective valves, As shown in FIG.

When the adhesive (low melting point polymer) units 10b and 10d are formed in the same structure as the spinning solution units 10a and 10c, the nozzle tube 40 and the nozzle tube 40 of the nozzle block 11a By controlling the nozzles 12 individually, it is possible to control and control the injection position of the adhesive (low melting point polymer) on the first nanofiber layer and the shape and shape of the injection area of the adhesive (low melting point polymer) (Low melting point polymer) and the spray order of the polymer spinning solution can be variously controlled and controlled.

As described above, an adhesive (low melting point polymer) is first sprayed onto a specific region and a specific region on the first nanofiber layer during electrospinning of the polymer spinning solution on the first nanofiber layer to form a first nanofiber layer and a first nanofiber layer (Low melting point polymer) is injected only to a specific region and a specific region of the first nano fiber layer, and the adhesive (low melting point polymer) is injected into the first nanofiber layer by electrospinning The interference can be minimized and the performance and quality of the nanomembrane manufactured thereby can be improved.

A plurality of nozzles 12 are arranged in a partial shape in a specific region of each edge and a central portion of the nozzle block 11a in the embodiment of the present invention. However, the nozzles 12 arranged in the nozzle block 11a The shape, the position, and the position of the substrate.

Here, the valves are individually provided in the supply pipes of the plurality of nozzles 12 arranged in a partial form in a specific region of the nozzle block 11a, and the nozzles 12 ) May be separately controlled so as to spray the adhesive (low-melting-point polymer) in the specific region and the partial form on the substrate 15 while the nozzle forms another shape and shape.

Here, the unit 10a, which is located at the foremost end among the units 10a, 10b, 10c and 10d of the electrospinning device 1, is fed into the unit 10a, A feeding roller 3 for feeding the base material 15 in which the nanofibers are alternately injected by the electrospinning of the use liquid is provided and the unit 10d located at the rear end of each unit 10a, 10b, 10c, (Low-melting-point polymer) and a winding roller 5 for winding a substrate 15 on which nanofibers are laminated.

The substrate 15 to be fed and fed through the feeding roller 3 is fed into each of the units 10a, 10b, 10c and 10d of the electrospinning device 1 to the winding roller 5 side And an auxiliary transfer device (16) for adjusting the transfer speed of the substrate (15).

The main control unit is provided in the electrospinning apparatus 1 and includes a nozzle block 11 installed in each unit 10a, 10b, 10c and 10d, an auxiliary conveying unit 16 And the voltage generating devices 14a, 14b, 14c, and 14d and controls the thickness measuring device 70, the substrate conveying speed adjusting device 30, and the air permeability measuring device 80, which will be described later.

A laminating device 90 for laminating the nanofibers electrospun on the base material 15 through the respective units 10a, 10b, 10c and 10d of the electrospinning device 1 is installed in each of the units 10a, 10b, 10c, and 10d, and performs a post-process of the nanomembrane electrospun through the electrospinning device 1 by the laminating device 90. As shown in FIG.

As described above, the base material 15, in which the polymer spinning solution is electrospun and the nanofibers are laminated while passing through the units 10a, 10b, 10c and 10d of the electrospinning device 1, is preferably a release film , And it is more preferable to spin the polymer spinning solution on the collector (13) without the substrate (15).

At this time, the polymer spinning solution radiated through each unit 10a, 10b, 10c, 10d of the electrospinning device 1 is the same as described above. The polymer used as the adhesive is not particularly limited, but is preferably at least one selected from the group consisting of a low melting point polyurethane, a hydrophobic polyurethane and a low melting point hydrophobic polyurethane which are low melting point polymers.

The low melting point polyvinylidene fluoride (PVDF) used in the present invention has a melting point of 80 to 160 ° C.

There are a variety of ways to control the melting point of PVDF, generally using a method of manipulating the synthesis of PVDF copolymers and a method of controlling the PVDF weight average molecular weight.

As one of the methods for producing low melting point PVDF, it is desirable to control the content of comonomer to control the synthesis of the copolymer. In the present invention, it is particularly preferable to use a polyvinylidene fluoride (PVDF) -based copolymer having a comonomer content of 5 to 50% by weight as the polyvinylidene fluoride (PVDF) -based polymer. The comonomer may be at least one selected from the group consisting of tetrafluoroethylene (TFE), trifluoroethylene, hexafluoroisobutylene, perfluorobutylethylene, perfluoro (ethylene terephthalate), and the like, in addition to hexafluoropropylene (HFP) or chlorotrifluoroethylene (PPVE), perfluoroethyl vinyl ether (PEVE), perfluoromethyl vinyl ether (PMVE), perfluoro-2,2-dimethyl-1,3-dioxole (PDD), and perfluoro Methylene-4-methyl-1,3-dioxolane (PMD), etc. Among them, hexafluoropropylene (HFP) or chlorotrifluoroethylene (CTFE) , But the present invention is not limited thereto.

In the present invention, the weight average molecular weight of the polyvinylidene fluoride (PVDF) polymer having a melting point of 80 to 160 ° C is adjusted to 3,000 to 30,000 by controlling the weight average molecular weight of the polymer. . If the weight average molecular weight is more than 30,000, the melting point exceeds 160 ° C. If the weight average molecular weight is less than 3,000, the melting point becomes less than 80 ° C.

The low melting point polyester is preferably terephthalic acid, isophthalic acid, or a mixture thereof. It is also possible to add ethylene glycol as a diol component to further lower the melting point.

The low-melting polyurethane uses a mixture of a polyurethane having a degree of polymerization of 80-100 ° C and a high-degree of polyurethane having a softening temperature of 140 ° C or higher.

It is needless to say that the low melting point hydrophobic polyurethane, hydrophobic polyurethane and low melting point polyurethane described above may be used singly or in combination of two or more.

The polymer spinning solution supplied through the nozzles 12 in the units 10a and 10c positioned at the front end of each of the units 10a, 10b, 10c and 10d may be prepared by dissolving the polymer, which is a synthetic resin material capable of electrospinning, , And the type of the solvent is not limited as long as it can dissolve the polymer and is the same as that described above.

Here, an overflow device 200 is provided in the electrospinning device 1. That is, each of the solution main tanks 8, the second transfer pipe 216, the second transfer control device 218, and the intermediate tank (not shown) are connected to the respective units 10a, 10b, 10c and 10d of the electrospinning device 1 220 and a regeneration tank 230 are respectively provided in the overflow device 200.

The overflow device 200 is provided in each unit 10a, 10b, 10c and 10d of the electrospinning device 1 in the embodiment of the present invention. However, each of the units 10a, 10b, 10c and 10d It is also possible that the overflow device 200 is provided in any one of the units 10a to 10d and the remaining units 10b, 10c and 10d are integrally connected to the overflow device 200, An overflow device 200 is provided in an adhesive (low melting point polymer) unit 10b or 10d for spraying an adhesive (low melting point polymer) among the units 10a, 10b, 10c and 10d, It is also possible that the overflow device 200 is provided in each of the spinning solution units 10a and 10c.

An overflow device 200 is provided in any one unit 10b in which an adhesive (low melting point polymer) is injected among the units 10a, 10b, 10c and 10d of the electrospinning device 1, The other unit 10d is integrally connected to the flow device 200 or the polymeric spinning solution in each of the units 10a, 10b, 10c, and 10d is electrospun and the nanofibers are laminated It is also possible that the overflow device 200 is provided in the overflow device 10a and the remaining unit 10c is integrally connected to the overflow device 200. [

The solution main tank 8 provided in the adhesive (low melting point polymer) unit 10b, 10d among the units 10a, 10b, 10c, and 10d of the units has the adhesive (low melting point polymer) And the solution main tank 8 provided in the spinning solution units 10a and 10c stores the polymer spinning solution to be a raw material of the nanofibers. A separate stirring device 211 for preventing the separation and solidification of the adhesive (low-melting-point polymer) and the polymer spinning solution is provided in the solution main tank 8.

The second transfer pipe 216 is configured to include a pipe (unillustrated) connected to the solution main tank 8 or the regeneration tank 230 and valves 212, 213 and 214, (Low-melting-point polymer) or the polymer spinning solution is transferred from the solution main tank 8 or the regeneration tank 230 to the intermediate tank 220 in which the solution (low-melting-point polymer) or the polymer spinning solution is filled.

The second conveyance control unit 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.

Here, the valve 212 controls the transfer of the adhesive (low melting point polymer) or the polymer spinning solution from the solution main tank 8 filled with the adhesive (low melting point polymer) or the polymer spinning solution to the intermediate tank 220, The valve 213 controls the transfer of the adhesive (low-melting-point polymer) or the polymer spinning liquid from the regeneration tank 230 to the intermediate tank 220. The valve 214 is connected to the solution main tank 8 and the regeneration tank (Low-melting-point polymer) or the polymer spinning solution flowing into the intermediate tank 220 from the upper tank 230.

(Low melting point polymer) measured through the second sensor 222 provided in the intermediate tank 230, which will be described later, under the control of the valves 212, 213, and 214, The height is controlled.

The intermediate tank 220 separately stores an adhesive (low-melting-point polymer) or a polymer solution used in the solution tank 8 or the regeneration tank 230 filled with an adhesive (low-melting-point polymer) or a polymer solution, The nozzle block 11a provided in the adhesive (low melting point polymer) units 10a and 10c of the nozzle block 11 and the nozzle block 11b provided in the spinning solution units 10a and 10c And a second sensor 222 for supplying the adhesive solution (low-melting-point polymer) and the liquid level of the polymer solution.

Here, the second sensor 222 preferably comprises a sensor capable of measuring the liquid level of an adhesive (low-melting-point polymer) such as an optical sensor or an infrared sensor, or a polymer solution, but the present invention is not limited thereto.

A supply pipe 240 and a supply control valve 242 for supplying an adhesive (low-melting-point polymer) or polymer solution for the nozzle block 11 are provided in the lower part of the intermediate tank 220, The control valve 242 controls the supply operation of the adhesive (low melting point polymer) or the polymer spinning solution through the supply pipe 240.

The regeneration tank 230 stores an adhesive (low-melting-point polymer) or a polymer solution for use in an overflow and separately stores an adhesive (low-melting-point polymer) or an agitation device for preventing separation and coagulation of the polymer solution 231).

Here, the first sensor 232 preferably comprises a sensor capable of measuring the liquid surface height of an adhesive (low-melting-point polymer) such as an optical sensor or an infrared sensor or a polymer solution, but the present invention is not limited thereto.

On the other hand, the adhesive (low-melting-point polymer) or the polymer spinning solution overflowed in the nozzle block 11 is separately recovered through the solution recovery path 250 provided in the lower part of the nozzle block 11, The path 250 recovers the polymer spinning solution in the regeneration tank 230 through the first transfer pipe 251.

The first transfer pipe 251 includes a pipe (not shown) connected to the regeneration tank 230 and a pump (not shown). The pump is powered by an adhesive (low melting point polymer) The polymer spinning solution is transferred from the solution recovery path 250 to the regeneration tank 230.

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

When the number of the regeneration tanks 230 is two, the number of the valves 233 located above the regeneration tank 230 corresponds to the number of the regeneration tanks 230. Accordingly, the first transfer control device (not shown) (Low-melting-point polymer) or the polymer spinning solution into a plurality of regeneration tanks (not shown) by controlling at least two valves 233 located at the upper part according to the height of the liquid level of the first sensor 232 provided in the regeneration tank 230 230 to the regeneration tank 230, respectively.

The electrospinning device 1 includes an auxiliary conveying device 16, a moving speed regulating device 30, a temperature regulating device 60, a thickness measuring device 70, an air permeability measuring device 80, a VOC recycling device 300, and the like. The auxiliary transfer device, the moving speed adjusting device, the temperature adjusting device, the thickness measuring device, the air permeability measuring device, and the VOC recycling device are the same as described above. The case 18 constituting each unit of the electrospinning apparatus 1 is also the same as described above.

Hereinafter, the present invention will be described concretely with reference to Examples. However, the following Examples and Experimental Examples are merely illustrative of one form of the present invention, and the scope of the present invention is not limited by the following Examples and Experimental Examples .

Example 1

A spinning solution prepared by dissolving polyamic acid (PAA) having a viscosity of 100,000 cps and a solid content of 20% by weight in dimethylacetamide (DMAc) was charged into the spinning liquid main tank of the first unit, A spinning solution having a concentration of 15% by weight prepared by dissolving polyacrylonitrile (Hanil Synthetic Fiber) having an average molecular weight of 157,000 in dimethylacetamide (N, N-dimethylacetamide, DMAc) was added to the spinning liquid main tank of the second unit Respectively.

In the first unit of the electrospinning device, a polyamic acid spinning solution was electrospun on the collector under the conditions of a distance of 40 cm between the electrode and the collector, an applied voltage of 20 kV and a temperature of 70 ° C to obtain a polyamic acid nanofiber having a basis weight of 4 g / . In the second unit, a polyacrylonitrile solution was electrospinned under the conditions of a distance of 40 cm between the electrode and the collector, an applied voltage of 20 kV, and a temperature of 70 ° C to form polyacrylonitrile nanofibers having a basis weight of 4 g / m 2. Thereafter, the polyamic acid nanofiber was imidized with polyimide nanofiber by heat treatment at 200 ° C to prepare a nanomembrane.

Comparative Example 1

A spinning solution prepared by dissolving polyacrylonitrile (Hanil Synthetic Fiber) having a weight average molecular weight of 157,000 in dimethylacetamide (N, N-Dimethylacetamide, DMAc) was added to the spinning liquid main tank of the first unit. In the first unit of the electrospinning device, the polyacrylonitrile spinning solution was electrospun on the polyethylene terephthalate substrate under the conditions of a distance of 40 cm between the electrodes and the collector, an applied voltage of 20 kV, and a temperature of 22 ° C, and the basis weight was 4 g / To form a polyacrylonitrile nanofiber.

Experimental Example

The physical properties of the nanomembrane prepared in Example 1 and Comparative Example 1 were measured by the following methods, and the results are shown in Table 1 below.

(1) Measurement of water pressure: Water pressure was measured by the method of ISO 0811 standard.

(2) Measurement of air permeability: Air permeability was measured by the method of JIS L 1096 standard.

Example 1 Comparative Example 1 Water pressure (mmH2O) 4,500 3,500 Air permeability (cm 3 / sec / cm 2) 0.5 0.6

As can be seen from Table 1, the nanomembranes prepared by the examples of the present invention have improved water pressure and air permeability of at least 50% as compared with the comparative examples.

While the present invention has been particularly shown and described with reference to specific embodiments thereof, it will be understood by those skilled in the art that various changes and modifications may be made without departing from the spirit and scope of the invention as defined in the appended claims. Anyone with it will know easily.

1, 100: Electrospinning device 3: Feed roller
5: take-up roller 7: main control device
8: Fluid tank main tank
10a, 10b, 10c, 10d, 110, 110 '
11, 11a, 11b, 111: nozzle block 12, 111a: nozzle
112, 112a, 112b, 112c, 112d, 112e, 112f, 112g, 112h, 112i:
13: collector
14, 14a, 14b, 14c, 14d and 114:
15, 15a, 15b, 115: long sheet 16: auxiliary conveying device
16a: auxiliary belt 16b: auxiliary belt roller
18: Case 19: Insulation member
30: Long sheet conveying speed adjusting device 31: Buffer section
33, 33 ': support roller 35: regulating roller
40: Tubular body 41, 42: Heat line
43: pipe 60: thermostat
70: Thickness measuring device 80: Air permeability measuring device
90: laminating device 200: overflow device
211, 231: stirring device 212, 213, 214, 233: valve
216: second transfer pipe 218: second transfer control device
220: intermediate tank 222: second sensor
230: regeneration tank 232: first sensor
240: Supply piping 242: Supply control valve
250: spinning liquid recovery path 251: first transfer piping
300: VOC recycling device 310: condensing device
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 solution temporary storage plate
411: air storage plate 412: overflow outlet
413: Air inlet 414: Nozzle support plate for air supply
415: Nozzle for Overflow Removal
416: nozzle overflow removing nozzle support plate
500: multi-tubular nozzle 501: inner tube
502: outer tube 503:
115a, 115b, 115c: nanofibers
116a: conveying belt 116b: conveying roller
120: spinning fluid main tank 120a: primary spinning fluid main tank
120b: Second spinning solution main tank 120c: Third spinning solution main tank
121: solution supply pipe 121a: first supply pipe
121b: second supply pipe 121c: third supply pipe
122: supply valve 125: nozzle supply pipe
126: Nozzle valve

Claims

A first nanofiber layer formed by electrospinning a heat resistant polymer solution; And
And a second nanofiber layer laminated by electrospinning a polyacrylonitrile solution on the first nanofiber layer,
Wherein the first nanofiber layer and the second nanofiber layer are different in basis weight along the longitudinal direction or the transverse direction.

The method according to claim 1,
Wherein the heat-resistant polymer is one selected from the group consisting of polyimide, meta-aramid, and polyethersulfone.

delete

The method according to claim 1,
Wherein the heat-resistant polymer solution and the polyacrylonitrile solution are electrospun through a temperature controller at a temperature of 50 to 100 ° C.

The method of claim 6,
Wherein the viscosity of the heat-resistant polymer solution and the polyacrylonitrile solution is adjusted to 1,000 to 3,000 cps through the temperature controller.

delete