KR101771923B1 - Nanofiber filter including polyether sulfone nanofiber and hydrophobic polymer nanofiber with epoxy-amine adhension layer and its manufacturing method - Google Patents

Abstract

The present invention relates to a filter including a nanofiber and a method of manufacturing the same. The filter includes a polyether sulfone nanofiber and a hydrophobic polymer nanofiber layer on the substrate, and a solution of an epoxy resin and a curing agent between the substrate and the nanofiber layer and the nanofiber layer And is characterized in that the adhesive layer is formed by electrospinning, and there is an advantage that a continuous process can be performed, the process efficiency and mass production can be performed, and there is an advantage that desorption is not generated well.

Description

[0001] The present invention relates to a nanofiber filter including a polyether sulfone nanofiber having an epoxy-hardener adhesive layer and a hydrophobic polymer nanofiber, and a method for producing the nanofiber filter including a polyether sulfone nanofiber and a hydrophobic polymer nanofiber,

The present invention relates to a filter including a nanofiber and a method of manufacturing the same. The filter includes a polyether sulfone nanofiber and a hydrophobic polymer nanofiber layer on a substrate. The nanofiber layer and the nanofiber layer are coated with an epoxy resin- To form an adhesive layer, and a method of manufacturing the same.

Generally, a gas turbine used in a thermal power plant sucks and compresses purified air from the outside, injects compressed air into the combustor together with the fuel, mixes the mixed air and fuel, It is a type of rotary internal combustion engine that obtains the combustion gas and then injects it into the vane of the turbine to obtain the rotational force. Because these gas turbines are made up of very precise parts, they are periodically serviced and use air filters for pretreatment to purify the air in the air entering the compressor.

 The air filter is capable of supplying purified air by preventing foreign substances such as dust and dust contained in the air from permeating into the filter filter material when the combustion air sucked into the gas turbine is taken in the air. However, particles having a large particle size accumulate on the surface of the filter media, forming not only a filter cake on the surface of the filter media, but also accumulating fine particles in the filter media, thereby blocking the pores of the filter media. As a result, when the particles are accumulated on the surface of the filter media, there is a problem of increasing the pressure loss of the filter and decreasing the service life.

 On the other hand, a porous membrane of polytetrafluoroethylene (hereinafter referred to as " PTFE ") has been proposed as an air filter medium (see, for example, Japanese Patent Application Laid-Open No. 5-202217). In the case of using a PTFE porous film, a thermoplastic material such as a spunbonded nonwoven fabric using long fibers of core / sheath structure is applied to both surfaces of the PTFE porous film in order to prevent scratches and pinholes from occurring because the film itself is thin It has also been proposed to laminate and protect it. (See Japanese Unexamined Patent Publication No. 6-218899)

However, in the conventional air filter, particles having a large particle size accumulate on the surface of the filter material, so that the filter cake is formed on the surface of the filter material, and fine particles are accumulated in the filter material, thereby blocking the pores of the filter material. As a result, when the particles are accumulated on the surface of the filter media, there is a problem of increasing the pressure loss of the filter and decreasing the service life.

In order to solve the above-mentioned problems, various methods of manufacturing nano-sized fibers and applying them to filters have been developed and used. When nanofibers are applied to a filter, the specific surface area is larger than that of a conventional filter material having a large diameter, and the flexibility of the surface functional group is also good. In addition, by having the processing size of nano gold, it is possible to efficiently filter fine dust particles.

However, in the conventional nanofiber filter, a laminating process for laminating the substrate and the nanofiber web is performed as a post-process. However, due to differences in materials and components of the substrate and the polymer solution, the polymer solution is electrospun There is a problem in that the nanofiber webs to be laminated are desorbed.

SUMMARY OF THE INVENTION The present invention has been conceived to solve the above-mentioned problems, and it is an object of the present invention to provide a method of manufacturing a semiconductor device, which comprises polyether sulfone nanofibers and a hydrophobic polymer nanofiber layer on a substrate, And an adhesive layer is formed on the surface of the nanofiber filter, and a method for manufacturing the nanofiber filter.

The hydrophobic polymer used in the present invention is one selected from the group consisting of polyvinylidene fluoride, low melting point polyester and hydrophobic polyurethane.

In order to achieve the above object, A first nanofiber layer formed by electrospinning a polyethersulfone solution; And a second nanofiber layer formed by electrospinning a hydrophobic polymer solution. The adhesion between the substrate and the first nanofiber layer and between the first nanofiber layer and the second nanofiber layer is formed by electrospinning an epoxy resin solution and a curing agent solution Wherein the nanofiber filter is bonded through an adhesive layer.

On the other hand, the curing agent is preferably one selected from the group consisting of an amine curing agent, an acid anhydride curing agent and an imidazole curing agent, but is not limited thereto.

Here, the hydrophobic polymer is preferably one selected from the group consisting of polyvinylidene fluoride, low-melting-point polyester and hydrophobic polyurethane.

The adhesive layer may include a first adhesive layer; A second adhesive layer; And a first adhesive layer, or a second adhesive layer; A first adhesive layer; And the second adhesive layer may be formed in this order.

Further, the epoxy resin solution and the curing agent solution are electrospun on the entire surface or a part of the substrate and the first nanofiber layer.

In order to solve the above problems, the epoxy resin solution and the curing agent solution may be electrospun to the substrate and the first or the first nanofiber layer, and may be electrospun at a temperature of 50 to 100 ° C. It is possible.

In addition, in the present invention, when the first nanofiber layer and the second nanofiber layer are electrospun, they may have different basis weights along the longitudinal direction or the transverse direction.

The nanofiber filter manufactured according to the present invention is easier to adhere between the substrate layer and the polymer electrospinning layer than the conventional filter and is not easily separated from the polymer filter and is sprayed only on a specific region and a part of the substrate, The use of the curing agent is reduced and at the same time the interference of the epoxy resin-curing agent to the nanofiber filter can be minimized to improve the performance and quality of the nanofiber or nanofiber filter.

Further, the filter manufactured by the method can reduce the pressure loss, increase the filtration efficiency, and extend the life of the filter.

1 is a side view schematically showing an electrospinning apparatus according to the present invention;
Fig. 2 is a side sectional view schematically showing a nozzle of a nozzle block installed in a unit of the electrospinning apparatus according to the present invention. Fig.
Fig. 3 is a side 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. Fig.
4 is a plan view schematically showing a nozzle block installed in a spinning solution unit of an electrospinning apparatus according to the present invention.
5 is a perspective view schematically showing a nozzle block installed in an epoxy resin-curing agent unit of an electrospinning apparatus according to the present invention.
6 to 7 are plan views schematically showing an operation process of electrospinning the polymer spinning solution through the nozzles of each nozzle tube of the electrospinning device according to the present invention
8 to 9 are plan views schematically showing still another embodiment of the operation process of electrospinning the polymer spinning solution through the nozzles of each nozzle tube of the electrospinning device according to the present invention
FIGS. 10 and 11 are plan views schematically showing an operation process of sequentially spraying the epoxy resin, the curing agent, and the polymer spinning solution through the arrangement of the nozzle blocks in the epoxy resin-
12 is a perspective view schematically showing still another embodiment of a nozzle block installed in an epoxy resin-curing agent unit of an electrospinning apparatus according to the present invention.
13 and 14 are plan views schematically showing an operation process of sequentially spraying the epoxy resin, the curing agent, and the polymer spinning solution through the arrangement of the nozzle blocks in the epoxy resin-
15 is a perspective view schematically showing another form of a nozzle block installed in an epoxy resin-curing agent unit of an electrospinning apparatus according to the present invention;
16 and 17 are plan views schematically showing an operation process of sequentially spraying the epoxy resin, the curing agent and the polymer spinning solution through the arrangement of the nozzle blocks in the epoxy resin-curing agent unit as shown in Fig.
18 is a perspective 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.
19 is a sectional view taken along the line A-A 'in Fig. 18
Fig. 20 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
21 is a sectional view taken along the line B-B 'in Fig. 20
22 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
23 is a sectional view taken along the line C-C 'in Fig. 22
24 is a view schematically showing an auxiliary feeding apparatus of the electrospinning apparatus according to the present invention
25 is a view schematically showing another embodiment of the auxiliary belt roller of the auxiliary transfer device of the electrospinning apparatus according to the present invention
FIGS. 26 to 29 are side views schematically showing the operation of the long sheet conveying speed adjusting apparatus of the electrospinning apparatus according to the present invention
30 is a front view showing a laminated structure of the nanofiber filter manufactured by the present invention

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

The present invention is not limited to the scope of the present invention, but is merely an example, and various modifications can be made without departing from the technical spirit of the present invention.

The present invention relates to a substrate; A first nanofiber layer formed by electrospinning a polyethersulfone solution; And a second nanofiber layer formed by electrospinning a hydrophobic polymer solution. The adhesion between the substrate and the first nanofiber layer and between the first nanofiber layer and the second nanofiber layer can be controlled by a first adhesive layer formed by electrospinning an epoxy resin solution ; And a second adhesive layer formed by electrospinning a curing agent solution. The present invention also provides a nanofiber filter comprising the same.

At this time, the epoxy resin is an intermediate of a thermosetting resin and forms a three-dimensional network structure insoluble / infusible by reaction with a curing agent to exhibit physical properties inherent to epoxy, and the epoxy resin is adhered It has an advantage of being excellent in properties, mechanical strength, heat resistance, chemical resistance, water resistance, electric insulation property, moldability and impregnation property, easy production of a composite material, and realizing various properties according to the selection of a curing agent.

Nonlimiting examples of such epoxy resins include bisphenol A type epoxy resins, bisphenol F type epoxy resins, and bisphenol S type epoxy resins.

The above-mentioned bisphenol A type epoxy resin is represented by the following general formula (1), and the most commonly used epoxy resin is produced by a direct method or indirect method.

[Chemical Formula 1]

The bisphenol F type epoxy resin is represented by the following general formula (2) and is produced by the reaction of bisphenol F with ECH. The bisphenol F type epoxy resin has a lower viscosity than the bisphenol A type epoxy resin and theoretically has a somewhat lower mechanical and physical properties. And the like.

(2)

The bisphenol S type epoxy resin is represented by the following general formula (3), and is generally used for rapidly curing an epoxy adhesive, and is used as a reactant in a polymer reaction.

(3)

On the other hand, the curing agent is preferably one selected from the group consisting of an amine curing agent, an acid anhydride curing agent and an imidazole curing agent, but is not limited thereto.

Non-limiting examples of the amine-based curing agent include aliphatic polyamines, modified aliphatic polyamines, aromatic amines, tertiary amines, and secondary amines.

Examples of the aliphatic polyamines include diethylene triamine (DETA), triethylene tetramine (TETA), diethylamino propyl amine (DEAPA), Menthane diamine (MDA), N-aminoethyl piperazine Isophorone diamine (IPDA), but is not limited thereto.

Examples of the modified aliphatic polyamines include, but are not limited to, Epoxy Polyamine Adduct, Ethylene or Propylene Oxide, Polyamine adduct, Cyanoethylated Polyamine, and Ketone blocked Polyamine (Ketimine).

Examples of the aromatic amine include Meta phenylene Diamine (MPD), 4.4 'Dimethyl aniline (DAM or DDM), Diamino Diphenyl Sulfone (DDS), and Aromatic amine adduct.

Examples of the acid anhydride-based curing agent include polyamide (PA), tetrahydrophthalic anhydride (THPA), methyl tetrahydrophthalic anhydride (MTHPA), hexahydrophthalic anhydride (HHPA), and MNA.

Nonlimiting examples of the imidazole-based curing agent include 2MZ and 2E4MZ.

In addition, the curing agent solution may further include a curing accelerator.

The curing accelerator used in the present invention is not particularly limited as long as it is a curing accelerator generally used for accelerating the curing of the epoxy compound. Examples thereof include tertiary amines, tertiary amine salts, imidazoles, Quaternary ammonium salts, quaternary phosphonium salts, organic metal salts, and boron compounds. The curing accelerator may be used alone or in combination of two or more.

Examples of tertiary amines include lauryldimethylamino, N, N-dimethylcyclohexylamine, N, N-dimethylbenzylamine, N, N-dimethylaniline, (N, N- dimethylaminomethyl) (N, N-dimethylaminomethyl) phenol, 1,8-diazabicyclo [5.4.0] undecene-7 (DBU), 1,5-diazabicyclo [4.3.0] 5 (DBN).

Examples of the tertiary amine salt include a carboxylate, a sulfonate, and an inorganic acid salt of the above-mentioned tertiary amine. Examples of the carboxylate include salts of carboxylic acids having 1 to 30 carbon atoms (especially 1 to 10 carbon atoms) such as octylate (particularly fatty acid salts). Examples of the sulfonic acid salt include p-toluenesulfonic acid salt, benzenesulfonic acid salt, methanesulfonic acid salt and ethanesulfonic acid salt. Representative examples of tertiary amine salts include salts of 1,8-diazabicyclo [5.4.0] undecene-7 (DBU) (for example, p-toluenesulfonic acid salt and octylic acid salt).

Examples of the metal-based curing accelerator include organic metal complexes or organic metal salts of metals such as cobalt, copper, zinc, iron, nickel, manganese and tin. Specific examples of the organometallic complexes include organic cobalt complexes such as cobalt (II) acetylacetonate and cobalt (III) acetylacetonate, organic copper complexes such as copper (II) acetylacetonate, zinc An organic iron complex such as an organic zinc complex and iron (III) acetylacetonate, an organic nickel complex such as nickel (II) acetylacetonate, and an organic manganese complex such as manganese (II) acetylacetonate. Examples of the organic metal salt include zinc octylate, tin octylate, zinc naphthenate, cobalt naphthenate, stannous stearate and zinc stearate. As the metal curing accelerator, cobalt (II) acetylacetonate, cobalt (III) acetylacetonate, zinc (II) acetylacetonate, zinc naphthenate and iron (III) acetylacetonate are preferable from the viewpoints of curability and solvent solubility And particularly, cobalt (II) acetylacetonate and zinc naphthenate are preferable. The metal-based curing accelerator may be used singly or in combination of two or more.

 The addition amount of the metal-based curing accelerator is preferably in the range of from 25 to 500 ppm, more preferably from 40 to 200 ppm, of the metal based on the metal-based curing accelerator when the non-volatile content in the resin composition is 100 mass% . If it is less than 25 ppm, it tends to make it difficult to form a conductor layer having a low roughness with good adhesion to the surface of the insulating layer. When it exceeds 500 ppm, the storage stability and insulating property of the resin composition tend to be lowered.

Examples of the quaternary ammonium salt include tetraethylammonium bromide and tetrabutylammonium bromide.

 As the quaternary phosphonium salt, for example, the following formula (1)

(Wherein R1, R2, R3 and R4 are the same or different and each represents a hydrocarbon group of 1 to 16 carbon atoms, and X represents an anion residue of a carboxylic acid or an organic sulfonic acid).

 Examples of the hydrocarbon group having 1 to 16 carbon atoms include a linear or branched hydrocarbon group such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, s-butyl, t-butyl, pentyl, A straight chain alkyl group; Vinyl, allyl, crotyl group, etc.

A straight chain or branched alkenyl group; Aryl groups such as phenyl, toluyl, xylyl, naphthyl, anthryl, phenanthryl groups; And aralkyl groups such as benzyl and phenethyl groups. Of these, a straight or branched alkyl group having 1 to 6 carbon atoms, particularly a butyl group, is preferred.

 Examples of the "carboxylic acid" in the "anion residue of a carboxylic acid or an organic sulfonic acid" include aliphatic alcohols having 1 to 20 carbon atoms such as octanoic acid, decanoic acid, lauric acid, myristic acid and palmitic acid Monocarboxylic acids; 1,2,4,5-cyclohexanetetracarboxylic acid, bicyclo [2.2.1] heptane-2,3-dicarboxylic acid, methylbicyclo [2.2.1] heptane-2,3-dicarboxylate Alicyclic carboxylic acids (monocyclic alicyclic mono- or polycarboxylic acids, crosslinked cyclic mono- or polycarboxylic acids), and the like. The alicyclic carboxylic acid may have a substituent such as a linear or branched alkyl group having 1 to 4 carbon atoms such as a methyl group, an alkoxy group having 1 to 4 carbon atoms such as a methoxy group, or a halogen atom such as a chlorine atom It is possible. As the carboxylic acid, an aliphatic monocarboxylic acid having a carbon number of 10 to 18 and an alicyclic polycarboxylic acid having a carbon number of 8 to 18 are preferable.

Examples of the "organic sulfonic acid" in the above "anionic residue of a carboxylic acid or an organic sulfonic acid" include methanesulfonic acid, ethanesulfonic acid, 1-propanesulfonic acid, 2-propanesulfonic acid, Aliphatic sulfonic acids such as pentanesulfonic acid, 1-hexanesulfonic acid, 1-octanesulfonic acid, 1-decanesulfonic acid and 1-dodecane sulfonic acid (for example, aliphatic sulfonic acids having 1 to 16 carbon atoms); Benzene sulfonic acid, 3- (linear or branched octadecyl) benzene sulfonic acid, 4- (straight or branched octyl) benzene sulfonic acid, 3- (linear or branched dodecyl Benzenesulfonic acid, 4-methoxybenzenesulfonic acid, 4-ethoxybenzenesulfonic acid, 4- (4-methoxybenzenesulfonic acid), 4- Chlorobenzene sulfonic acid, and the like.

Representative examples of quaternary phosphonium salts include tetrabutylphosphonium decanoate, tetrabutylphosphonium laurate, tetrabutylphosphonium myristate, tetrabutylphosphoniumpolate, tetrabutylphosphonium cation and bicyclo [2.2 .1] heptane-2,3-dicarboxylic acid and / or methylbicyclo [2.2.1] heptane-2,3-dicarboxylic acid, a salt of an anion of tetrabutylphosphonium cation with 1,2,4 , Salts of anions of 5-cyclohexanetetracarboxylic acid, salts of anions of tetrabutylphosphonium cation and methanesulfonic acid, salts of anions of tetrabutylphosphonium cation and benzenesulfonic acid, salts of tetrabutylphosphonium cation and p-toluenesulfonic acid Salts of anions of tetrabutylphosphonium cation and 4-chlorobenzenesulfonic acid, salts of anions of tetrabutylphosphonium cation and dodecylbenzenesulfonic acid, and the like.

Examples of the boron compound include boron trifluoride, triphenylborate, and the like.

 Examples of the imidazole-based curing accelerator include 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, 2-methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-methylimidazole, 2-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-ethyl-4-methyl Imidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazolium trimellitate, 1-cyanoethyl-2-phenylimidazolium trimellitate, 2,4-diamino-6- [2'-methylimidazolyl- (1 ')] - ethyl-s-triazine, 2,4- (1 ')] - ethyl-s-triazine, 2,4-diamino-6- [2'-ethyl-4'-methylimidazolyl- , 4-diamino-6- [2'-methylimidazolyl- (1 ')] -ethyl-s-triazine isocyanuric acid adduct, Methyl-2-phenyl-4-methyl-5-hydroxymethylimidazole, 2,3-dihydro-1H- Imidazole compounds such as pyrrolo [1,2-a] benzimidazole, 1-dodecyl-2-methyl-3-benzylimidazolium chloride, 2-methylimidazoline, And adducts of a thiol compound with an epoxy resin.

 Examples of amine curing accelerators include trialkylamines such as triethylamine and tributylamine; amines such as 4-dimethylaminopyridine, benzyldimethylamine, 2,4,6-tris (dimethylaminomethyl) phenol, 1,8-diazabicyclo (5,4,0) -undecene (hereinafter abbreviated as DBU), and the like.

1 is a side view schematically showing an electrospinning apparatus according to the present invention. As shown in the figure, the electrospinning apparatus 1 according to the present invention comprises a bottom-up electrospinning apparatus 1, wherein at least one epoxy resin-curing agent unit 10a, 10c and a spinning liquid unit 10b, The epoxy resin-curing agent units 10a and 10c and the spinning solution units 10b and 10d may be made of the same or different epoxy resin-curing agent or polymer solution, To produce a nanofilter.

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).

The epoxy resin-curing agent unit and the spinning solution unit are each comprised of a main tank 8 in which an epoxy resin-curing agent or a polymer solution is filled, an epoxy resin-curing agent or a polymer spinning solution filled in the main tank 8 (Not shown) for supplying a predetermined amount of the epoxy resin-curing agent or polymer solution for filling the main tank 8 with a nozzle block A collector 13 which is spaced apart from the nozzle 12 by a predetermined distance and a voltage generating device 14a and 14b which generates a voltage to the collector 13 in order to accumulate the polymer spinning solution injected from the nozzle 12 and the nozzle 11, , 14c and 14d. (14c and 14d are not shown)

The electrospinning device 1 according to the present invention as described above is characterized in that an epoxy resin-curing agent or a polymer spinning liquid filled in the main tank 8 is supplied to the nozzle block 11 through a plurality of nozzles The epoxy resin-curing agent or the polymer decolourizing liquid supplied and continuously supplied into the collector 12 is radiated and focused on the collector 13 with the high voltage applied thereto through the nozzle 12, The nanofibers are formed on the sheet 15, and the nanofibers to be formed are made of a filter or a nonwoven fabric.

Here, a supply for feeding the elongated sheet 15, which is supplied into the epoxy resin-curing agent unit and which is formed by laminating the nanofiber nonwoven fabric by spraying the polymer spinning solution, is provided in front of the epoxy resin-curing agent unit of the electrospinning device 1 And a winding roller 5 for winding a long sheet 15 on which a nanofiber nonwoven fabric is laminated is provided at the rear of the unit located at the rear end.

On the other hand, it is preferable that the elongated sheet 15, in which the polymer spinning solution is laminated while passing through the epoxy resin-curing agent unit and the spinning solution unit, is made of nonwoven fabric or fabric, but is not limited thereto.

The spinning solution supplied through the nozzle 12 in the spinning solution unit of the electrospinning device 1 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, N, N-dimethylacetamide (DMAc), phenol, formic acid, sulfuric acid, m-cresol, thiuoroacetone hydride / dichloromethane, water, N-methyl Methyl isobutyl ketone, methyl ethyl ketone, aliphatic hydroxyl group, m-butyl alcohol, isobutyl alcohol, isopropyl alcohol, methyl alcohol, ethanol, aliphatic compounds such as methylene chloride, Hexane, tetrachlorethylene, acetone, propylene glycol as the glycol group, diethylene glycol, ethylene glycol, halogen compounds such as trichlorethylene, dichloromethane, Cyclohexanone as cyclohexane and cyclohexane and esters such as n-butyl acetate, ethyl acetate, butyl cellosolve as aliphatic ether group, acetic acid 2-ethoxy ethanol, 2- Ethoxyethanol, amide and dimethylformamide, or a mixture of plural kinds of solvents may be used.

N, N-dimethylacetamide is preferably used.

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

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

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

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

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 distal end portion 503 is formed in the shape of a tubular trunk having an axis of 5 to 30 degrees.

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.

On the other hand, the electrospinning device 1 according to the present invention is provided with an overflow device 200. Although the epoxy resin-curing agent unit 10a of the electrospinning apparatus 1 and the overflow apparatus 200 are provided in the spinning solution unit 10b in the embodiment of the present invention, It is also possible that any one of the spinning solution units is provided with the overflow device 200 and the unit positioned at the rear end of the overflow device 200 is integrally connected.

According to the structure as described above, the main tank 8 stores a 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 main tank 8 or the regeneration tank 230 and valves 212, 213 and 214. The main tank 8 or the regeneration 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 main tank 8 to the intermediate tank 220 and the valve 213 controls the transfer of the spinning liquid from the regeneration tank 230 to the intermediate tank 220 do. The valve 214 controls the amount of the polymer spinning solution flowing into the intermediate tank 220 from the 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, in order to condense and liquefy VOC (Volatile Organic Compounds) generated during spinning of the polymer spinning solution through the nozzle 12 to the epoxy resin-curing agent unit and the spinning solution unit of the electrospinning device 1 A distillation unit 320 for distilling and liquefying the condensed VOC through the condenser 310 and the condenser 310 and a solvent storage unit 330 for storing the liquefied solvent through the distillation unit 320 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 the epoxy resin-curing agent unit 10a and the spinning liquid unit 10b is introduced into the condenser 310 and the VOC in the liquefied state generated in the condenser 310 And pipes 311 and 331 for storing in the solvent storage device 330 are connected and connected, respectively.

That is, pipes 311 and 331 for interconnecting the epoxy resin-curing agent unit, the spinning solution unit and the condensing unit 310, and the condensing unit 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 epoxy resin-curing agent unit 10a and the spinning solution unit 10b to condense and liquefy A distillation unit 320 for heating the condensed VOC through the condenser 310 to make it into a vaporized state and then cooling it to make it in a liquefied state and a solvent for storing the liquefied VOC through the distillation unit 320 And a storage device 330.

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

That is, the epoxy resin-curing agent unit, the spinning solution unit and the condenser 310, the condenser 310 and the distillation unit 320, and the solvent storage unit 330 for interconnecting the distillation unit 320 and the solvent storage unit 330 And the pipes 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.

It is preferable that the case 18 constituting the epoxy resin-curing agent unit and the spinning solution unit of the electrospinning apparatus 1 is made of a conductive material, but the case 18 may be made of an insulator, The conductor and the 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 generator can be monitored, the abnormality of the electrospinning device 1 can be detected early, Continuous operation is possible, the production of nanofibers with required performance is stable, and mass production of nanofibers is possible.

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

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

The distance between the inner surface of the case 18 formed of an insulator and the outer surface of the collector 13 is smaller than the thickness a of the case 18 and the distance between the inner surface of the case 18 and the outer surface of the collector 13 The distance "b" is made to satisfy "a + b = 80 mm". Therefore, when 40 kV is applied between the nozzle block 11 and the collector 13 to perform electrospinning, an insulation breakdown that may occur between the collector 13 and the case 18 and other members And the leakage current can be limited within a predetermined range.

On the other hand, a temperature regulating device 60 is provided in each tube 40 of the epoxy resin-curing agent unit of the electrospinning device 1 according to the present invention and the nozzle block 11 provided in the spinning solution unit, It is connected.

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

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

As described above, the present invention uses a polymer solution for electrospinning. Generally, the existing inventions have a diluting agent and concentration adjusting devices to keep the concentration of the polymer solution constant.

MEK (methyl ether ketone), THF (tetrahydrofuran), and alcohol are used as the diluent. The concentration of the polymer solution recovered through the overflow device 200 in addition to the polymer solution that is electrospun through the nozzle block 11 and accumulated in the collector is higher than the concentration of the polymer solution initially supplied from the main tank 8 In the conventional electrospinning, a diluent was added to keep the concentration of the polymer solution at a certain level. In addition, MEK or THF used as a diluent has low boiling point (b.p) (about 60 ° C) and is more easily scattered than the case of using DMAc alone as a solvent during electrospinning, so nanofiber formation is easy.

However, in the present invention, instead of maintaining the concentration constant, the polymer solution of high concentration to be reused is reused after overflow, and the viscosity of the polymer solution is adjusted by using the temperature regulating device 60 to improve the efficiency of electrospinning And it is easy to form nanofibers of the polymer solution because of high acidity at a high temperature condition for controlling a high viscosity without using a diluent. 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.

In the present invention, the temperature control of the polymer solution is performed in such a manner that the thermostat 60 in the form of a heat ray 41 is spirally wound around the inner periphery of the tube 40 of the nozzle block 11 And the temperature of the polymer solution is supplied to the tubular body 40 to control the temperature of the polymer solution.

In the embodiment of the present invention, a thermostat 60 in the form of a heat ray 41 is spirally provided on the inner periphery of the tubular body 40 of the nozzle block 11 as shown in FIGS. 16 to 17 It is also possible that a plurality of temperature regulating devices 60 in the form of a heat line 42 are radially provided on the inner circumference of the tube 40. As shown in FIGS. 18 to 19, It is also possible that the thermostat 60 in the form of a substantially "C"

Through the temperature controller 60, the present invention can perform electrospinning at 50 to 100 ° C, which is higher than normal room temperature, which is the electrospinning temperature.

20, an epoxy resin-curing agent unit of the electrospinning device 1 according to the present invention and an auxiliary conveying device (not shown) for controlling the conveying speed of the elongated sheet 15 fed into and supplied into the spinning solution unit 16 are provided.

The auxiliary conveying device 16 is provided with a conveying unit 15 for conveying 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 installed in the epoxy resin- An auxiliary belt 16a rotating in synchronism with the speed 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. 1, a thickness measuring device 70 is provided between each unit of the electrospinning device 1, and the thickness of the sheet is measured according to the thickness measured by the thickness measuring device 70 V) and the nozzle block 11 are controlled.

When the thickness of the nanofiber nonwoven fabric discharged from a unit located at the distal end portion of the electrospinning device 1 is measured to be thinner than the deviation amount by the above-described structure, the conveyance speed V of the next unit is delayed, The discharge amount of the nanofiber nonwoven fabric per unit area can be increased and the thickness can be increased by increasing the discharge amount of the nanofiber nonwoven fabric 11 and adjusting the voltage intensity of the voltage generating device.

When the thickness of the nanofiber nonwoven fabric discharged from the epoxy resin-curing agent unit 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 spinning liquid unit is increased, The amount of discharge of the nanofiber nonwoven fabric per unit area can be reduced to reduce the amount of lamination by controlling the intensity of the voltage generator voltage by decreasing the discharge amount of the nano fiber 11, A fibrous nonwoven fabric 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 to the long sheet 15 laminated with the nanofiber nonwoven fabric so that the propagation time of the longitudinal wave and the transverse wave, that is, the time during which the ultrasonic signals of the longitudinal wave and the transverse wave reciprocate on the longitudinal sheet 15 A predetermined calculation using the propagation time of longitudinal waves and transverse waves and the propagation speed of longitudinal waves and transverse waves at the reference temperature of the elongated sheet 15 in which the nanofiber nonwoven fabric is laminated and the temperature constants of longitudinal waves and transverse wave propagation velocities Is a thickness measuring apparatus using an ultrasonic longitudinal wave and a transverse wave to calculate the thickness of the object from the equation.

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

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

The elongate sheet conveying speed regulating device 30 includes a buffer section 31 formed between the epoxy resin-curing agent unit 10a and the spinning solution unit 10b of the electrospinning device 1, A pair of support rollers 33 and 33 'provided on the support rollers 31 and 31 for supporting the long sheets 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 moved in the direction of conveyance of the long sheet 15 in which the nanofiber nonwoven fabric is laminated by the spinning liquid sprayed by the nozzles 12 in the epoxy resin- For supporting the conveyance of the elongate sheet 15 and provided at a line and a rear end of a buffer zone 31 formed between the respective units.

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 conveying speed and the moving time of the long sheet for each unit are adjusted.

In order to achieve this, a sensing sensor (not shown) for sensing the conveying speed of the long sheet in each unit is provided, and the movement of the adjusting roller 35 according to the conveying speed of the long sheet in each unit sensed by the sensing sensor And a main control unit 7 for controlling the main control unit.

According to an embodiment of the present invention, the conveying speed of the long sheet is sensed in the epoxy resin-curing agent unit and the spinning solution unit, and the control unit controls the movement of the regulating roller 35 according to the conveying speed of the long sheet It is possible to detect the driving speed of the auxiliary belt provided on the outside of the collector 13 or the auxiliary belt roller or motor (not shown) for driving the auxiliary belt for conveying the long sheet, And the movement of the roller 35 may be controlled.

When the detection sensor detects that the conveying speed of the long sheet in the epoxy resin-curing agent unit located at the tip of each unit is faster than the conveying speed of the long sheet in the spinning liquid unit located at the succeeding stage, As shown in FIGS. 22 and 23, is provided between the pair of support rollers 33 and 33 'to prevent the elongated sheet conveyed in the epoxy resin-curing agent unit from being sagged, while a long sheet 15 Curing agent unit positioned at the tip end of the elongated sheet 15 to be transferred to the spinning solution unit located at the rear end in the epoxy resin- So that the elongated sheet which is excessively conveyed to the buffer zone 31 located between the epoxy resin-curing agent unit and the spinning solution unit is pulled to be positioned at the tip Corrects and controls so that the conveying speed of the long sheet in the unit is equal to the conveying speed of the long sheet in the unit positioned at the succeeding stage while preventing sagging and wrinkling of the long sheet.

On the other hand, when the sensing sensor detects that the conveying speed of the long sheet in the epoxy resin-curing agent unit is slower than the conveying speed of the long sheet in the spinning liquid unit, as shown in FIGS. 24 to 25, The adjustment roller 35, which is provided between the pair of support rollers 33 and 33 'to prevent the transported long sheet from being torn, is moved upward while the long sheet 15 is wound, Curing agent unit out of the elongate sheets 15 conveyed to the spinning liquid unit in the unit, the elongated sheet wound by the regulating roller 35 is transferred to the buffer zone 31 located between the respective units, So that the transfer speed of the long sheet in the epoxy resin-hardener unit and the transfer speed of the long sheet in the spinning liquid unit become equal to each other, The dead will be prevented.

By adjusting the conveying speed of the long sheet conveyed into the spinning solution unit by the above-described structure, the conveying speed of the long sheet in the spinning liquid unit becomes equal to the conveying speed of the long sheet in the epoxy resin- have.

On the other hand, the electrospinning device 1 according to the present invention is provided with the air permeability measuring device 80. That is, an air permeability measuring device 80 for measuring the air permeability of the nanofiber nonwoven fabric manufactured through the electrospinning device 1 is provided behind the unit located at the rear end of each unit of the electrospinning device 1.

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

When the air permeability of the nanofiber nonwoven fabric discharged through each unit of the electrospinning device 1 is measured largely, the feeding speed V of the spinning liquid unit is decreased or the ejection amount of the nozzle block 11 is increased , The voltage of the voltage generator is controlled to increase the discharge amount of the nanofibers per unit area, thereby reducing the air permeability.

When the air permeability of the nanofiber nonwoven fabric discharged through each unit of the electrospinning device 1 is measured to be small, the feeding speed V of the spinning liquid unit is increased or the discharging amount of the nozzle block 11 is decreased And the voltage of the voltage generator is controlled to reduce the discharge amount of the nanofibers per unit area to reduce the amount of lamination, thereby increasing the air permeability.

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

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

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

The main control unit 7 includes a nozzle block 11, a voltage generator, a thickness measuring unit 70 and a long sheet conveying speed control unit Thereby controlling the apparatus 30 and the air permeability measuring apparatus 80. [

4 is a plan view schematically showing a nozzle block installed in a spinning liquid unit of an electrospinning apparatus according to the present invention. As shown in the drawing, the nozzles 12 are arranged in a line along the nozzle tube 40, and the spinning solution can be electrospun from the nozzle 12 over the entire surface of the substrate.

5 is a perspective view schematically showing a nozzle block installed in an epoxy resin-curing agent unit of an electrospinning apparatus according to the present invention. The nozzles disposed in the epoxy resin-curing agent unit may be applied to the front side of the substrate, but it is preferable that the nozzles are applied to a specific portion of the substrate as required. In Fig. 5, the nozzles are divided into five groups of nine nozzles, one at the center and two at the bottom in the upper part. However, the arrangement of the nozzle and the nozzle block is not limited to this, and it is obvious to those skilled in the art that the nozzle can be appropriately designed and modified in consideration of the number of the nozzles and the amount of the epoxy resin-curing agent to be radiated.

FIGS. 6 to 9 are plan views schematically illustrating the operation of electrospinning a polymer spinning solution on the same plane of a substrate through nozzles of each nozzle tube of an electrospinning apparatus for manufacturing a nanofiber web according to the present invention. The nozzle tubes 112a, 112b, 112c, 112d, 112e, 112f, 112g, 112h, and 112i having a plurality of nozzles 111a linearly arranged on the upper surface thereof are connected to the substrate 115 on the nozzle block 111, 112b, 112c, 112d, 112e, 112f, 112g, 112h, 112i are connected to the spinning liquid main tank 8, The polymer spinning solution filled in the tank 8 is supplied.

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

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

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

That is, when the polymer spinning solution is supplied to the nozzle tubes 112a, 112b, 112c, 112d, 112e, 112f, 112g, 112h, 112i in the spinning liquid main tank 8 through the supply pipe 240, The valves 212, 213, 214 and 233 provided in the supply pipe 240 for supplying the main tank 8 and the nozzle tubes 112a, 112b, 112c, 112d, 112e, 112f, 112g, The nozzle tubes 112b, 112d, 112f, 112g, 112g, 112d, 112d, 112d, 112e, 112f, 112g, 112h, 112i are arranged in the nozzle block 111, 112b, 112c, and 112d in the spinning liquid main tank 8 by opening and closing the valves 212, 213, 214, and 233 such that the polymer solution is selectively supplied only to the nozzles 112a, 112b, , 112e, 112f, 112g, 112h, and 112i of the polymeric spinning solution is controlled and controlled.

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

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

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

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

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

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

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.

Basis Weight or Grammage is defined as the mass per unit area, that is, the preferred unit, grams per square meter (g / m 2). In recent years, for the purpose of making the air filter and the unit lighter and more compact, a type of the filter having a smaller depth is required, and if the filter material having the same filtration area is put in the unit, the filter material faces contact each other due to the thickness of the filter material, There has been a problem in that the pressure loss of the air filter unit remarkably increases. To solve this problem, there has been an attempt to reduce the thickness of the filter material for the air filter, that is, to reduce the basis weight. However, such an attempt has been made to reduce the basis weight of the filter, and it is possible to solve the pressure loss of the air filter unit sufficiently when the basis weight is reduced for a specific portion of the filter for each specific industrial field to which the filter is applied. The strength of the filter medium can be maintained.

FIGS. 10 and 11 are plan views schematically showing an operation sequence in which the epoxy resin-curing agent and the polymer solution are sequentially injected through the arrangement of the nozzle blocks in the epoxy resin-curing agent unit as shown in FIG. 5, Through the arrangement, an epoxy resin-curing agent is applied to a portion of the substrate (one in the middle at the top and two in the bottom at the top) and then the polymer spinning solution is radiated to the front side of the substrate.

12 and 15 show a state in which the nozzle block provided in the epoxy resin-curing agent unit of the electrospinning apparatus according to the present invention is arranged in another form. Fig. 12 is arranged to face the longitudinal direction of the substrate, and Fig. 15 shows the shape arranged to face the width direction of the substrate. The operation of sequentially spraying the epoxy resin-curing agent and the polymer solution for spraying according to the discharge vessel of the nozzle as shown in FIGS. 12 and 15 is shown in FIGS. 13, 14 and 16, 17, respectively.

In the present invention, a substrate selected from cellulose, a two-component system, and a polyterephthalate is used as the elongated sheet 15, and polyethersulfone and hydrophobic polymer are used as a polymer for spinning solution.

In this case, the hydrophobic polymer is preferably one selected from the group consisting of polyvinylidene fluoride, low melting point polyester and hydrophobic polyurethane, but is not limited thereto.

The cellulose base material used in the present invention is preferably composed of 100% cellulose, but cellulose having a total mass ratio of 70 to 90: 10 to 30 mass% of polyethylene terephthalate (PET) It is also possible to use a substrate having a cellulose base coated with a flame retardant coating.

The binary substrate may be selected from a sheath-core type, a side by side type, and a C-type type. In the sheath-core type two-component substrate, the sheath portion is a low-melting-point polyester and the core portion is a high-melting-point polyethylene terephthalate.

Hereinafter, a method of manufacturing the nanofiber filter of the present invention will be described using the electrospinning device.

An epoxy resin solution and a curing agent are melted in an appropriate solvent to prepare an epoxy resin solution and a curing agent solution and this is supplied to the main tank 8 connected to the epoxy resin-curing agent units 1a and 10c of the electrospinning apparatus, The epoxy resin solution and the curing agent solution supplied to the nozzle block 8 are continuously supplied in a constant amount into the plurality of nozzles 12 of the nozzle block 11 to which a high voltage is applied through a metering pump (not shown). Epoxy resin supplied from the respective nozzles (12) was added and the curing agent solution having a weight of about 0.1g / m ² as electrospinning and focusing on a substrate positioned on hanging a high voltage collector 13, which via the nozzle 12 Thereby forming an adhesive layer.

That is, the adhesive layer includes a second adhesive layer formed by electrospinning an epoxy resin solution on a substrate placed on the collector 13 to form a first adhesive layer and electrospinning a solution of a curing agent on the first adhesive layer .

On the other hand, in the adhesive layer, a first adhesive layer is formed by electrospinning an epoxy resin solution on a substrate placed on the collector 13, a second adhesive layer is formed by electrospinning a solution of a curing agent on the first adhesive layer, The second adhesive layer, and the first adhesive layer in this order by forming a first adhesive layer by electrospinning an epoxy resin solution on the first adhesive layer, the second adhesive layer, and the first adhesive layer.

The adhesive layer is formed by electrospinning a solution of a curing agent on a substrate placed on the collector 13 to form a second adhesive layer and electrospinning an epoxy resin solution on the second adhesive layer to form a first adhesive layer, The first adhesive layer, the second adhesive layer, and the third adhesive layer in the order of the first adhesive layer, the second adhesive layer, and the second adhesive layer by electrospinning the curing agent solution on the first adhesive layer.

At this time, the curing agent solution may include a curing accelerator and the like, but is not limited thereto.

Next, a polyethersulfone spinning solution in which polyethersulfone is dissolved in a solvent is supplied to the main tank 8 connected to the spinning solution unit 10b of the electrospinning apparatus, and the hydrophobic polymer spinning solution, in which the hydrophobic polymer is dissolved in a solvent, To the main tank 8 connected to the unit 10d. The polyethersulfone solution supplied to the main tank 8 connected to the spinning solution unit 10b is electrospun through a nozzle block 11 to which a high voltage is applied through a metering pump, Thereby forming a nanofiber layer.

The epoxy resin solution and the curing agent solution are discharged from the epoxy resin-curing agent unit 10c through the nozzle to form another adhesive layer on the first nanofiber layer, and the main tank 8 connected to the spinning solution unit 10d, Is sprayed through the nozzle block 11 to form a second nanofiber layer on the another adhesive layer.

On the other hand, the substrate is rotated in the direction of the arrow C by the rotation of the feed roller 3 driven by the motor (not shown) and the auxiliary feed device 16 driven by the rotation of the feed roller 3, And the first and second nano fiber layers are laminated while being electrospun on the substrate while repeating the above-mentioned process.

Thereafter, the adhesive layer, the first nanofiber layer, another adhesive layer, and the second nanofiber layer laminated on the substrate are thermally fused to produce the filter of the present invention.

At this time, the epoxy resin contained in the adhesive layer and the curing agent react and cure through thermal fusion to produce a filter which is easy to bond between the substrate layer and the polymeric electrospinning layer and which does not easily escape.

Example 1

The epoxy resin solution and the curing agent solution were prepared by dissolving the epoxy resin and the amine curing agent in a solvent of DMAc (N, N-dimethylaceticamide) in an amount of 15% by weight to prepare epoxy resin-amine curing agent units 10a and 10c And put into the main tank.

A spinning solution having a concentration of 15% by weight prepared by dissolving polyethersulfone in dimethylacetamide (N, N-dimethylacetamide, DMAc) was prepared and the hydrophobic polyurethane was dissolved in dimethylacetamide ) To prepare a spinning solution having a concentration of 15 wt%, and the spinning solution was introduced into the main tank connected to the spinning solution units 10b and 10d.

An adhesive layer including an epoxy resin layer and a curing agent layer having a basis weight of 0.1 g / m < 2 > and having a basis weight of 0.1 g / m < 2 > was formed on the cellulose base material by a distance of 40 cm between the electrodes and the collector in the epoxy resin- Subsequently, a first nanofiber layer (polyethersulfone) having a basis weight of 0.5 g / m 2 was laminated on the spinning solution unit 10b by electrospinning the distance between the electrodes and the collector at 40 cm, an applied voltage of 25 kV, and 70 ° C. Another adhesive layer (epoxy resin layer and curing agent layer) was formed on the first nanofiber layer under the same electrospinning condition through the epoxy resin-curing agent unit 10c. The adhesive solution was injected onto the adhesive layer from the spinning solution unit 10d through the electrode- And a second nanofiber layer (hydrophobic polyurethane) having a basis weight of 0.5 g / m < 2 > was laminated by electrospinning at a distance of 40 cm and an applied voltage of 20 kV at 70 deg.

Example 2

A spinning solution having a concentration of 15% by weight prepared by dissolving polyethersulfone in dimethylacetamide (N, N-Dimethylacetamide, DMAc) was prepared and polyvinylidene fluoride having a weight average molecular weight (Mw) of 50,000 was dissolved in dimethylacetate Except that a spinning solution having a concentration of 15 wt% prepared by dissolving the spinning solution in an amide (N, N-dimethylacetamide, DMAc) was prepared and the spinning solution was put into a main tank connected to spinning solution units 10b and 10d The procedure of Example 1 was repeated.

Example 3

A spinning solution having a concentration of 15% by weight prepared by dissolving polyethersulfone in dimethylacetamide (N, N-Dimethylacetamide, DMAc) was prepared and the low melting point polyester having a melting point of 80 to 120 ° C was dissolved in trifluoroacetic acid trifluoroacetic acid) was prepared in the same manner as in Example 1, except that a spinning solution having a concentration of 15% by weight was prepared, and the spinning solution was introduced into a main tank connected to spinning solution units 10b and 10d Respectively.

Comparative Example 1

The cellulose substrate used in Example 1 was used as a filter media.

Comparative Example 2

A polyether sulfone solution was electrospun on a cellulose substrate to form a laminate of polyether sulfone nanofiber nonwoven fabrics to prepare a filter.

- Filtration efficiency measurement

The DOP test method was used to measure the efficiency of the fabricated nanofiber filter. The DOP test method measures the dioctyl phthalate (DOP) efficiency with an automated filter analyzer (AFT) of TSI 3160 from TSI Incorporated and measures the permeability, filter efficiency and differential pressure of the filter media material .

The automation analyzer is a device that automatically measures the velocity of air, DOP filtration efficiency, air permeability (permeability), etc. by passing DOP through the filter sheet by making particles of desired size and is a very important device for high efficiency filter.

The DOP% efficiency is defined as

DOP% efficiency = (1 - (DOP concentration downstream / DOP concentration upstream)) 100

The filtration efficiencies of Examples 1 to 3 and Comparative Example 1 were measured by the above-mentioned methods and are shown in Table 1.

Example 1 Example 2 Example 3 Comparative Example 1 0.35 탆 DOP
Filtration efficiency (%) 84 86 88 68

As described above, the filter including the nanofiber layer manufactured through the embodiment of the present invention is superior in filtration efficiency as compared with the comparative example.

- pressure drop and filter life measurement

The pressure drop of the fabricated nanofiber nonwoven filter was measured with ASHRAE 52.1 according to the flow rate of 50 / / m ³ , and the filter life was measured accordingly. Data comparing Examples 1 to 3 and Comparative Example 1 are shown in Table 2.

Example 1 Example 2 Example 3 Comparative Example 1 Pressure drop (in.w.g) 4.2 4.0 3.8 8 Filter life
(month) 6.2 6.1 6.5 4

According to Table 2, it can be seen that the filter manufactured through the embodiment of the present invention has a lower pressure drop due to a lower pressure drop than the comparative example, and the filter has a longer life span, resulting in superior durability.

- whether or not the nano fiber nonwoven fabric is removed

As a result of measuring whether or not the fabricated nanofiber nonwoven fabric and the filter substrate were desorbed by the ASTM D 2724 method, the nanofiber nonwoven fabric was not desorbed in the filters manufactured in Examples 1 to 3, The filter had a tendency to desorb the nanofiber nonwoven fabric.

Thus, as in the present invention, a nanofiber filter in which a polyether sulfone solution and a hydrophobic polymer solution are electrospun nanofiber layer is electrophoretically sprayed with an epoxy resin solution and a curing agent solution, It can be seen that separation does not occur well.

- Viscosity adjustment result by temperature control device

Example 4

A flushing solution having a concentration of 15% by weight prepared by dissolving polyethersulfone in dimethylacetamide (N, N-Dimethylacetamide, DMAc) was provided in the main tank 8. Thereafter, the spinning solution was moved from the main tank 8 to the nozzle block, and then the distance between the nozzle block and the collector was 40 cm and the applied voltage was 25 kV. In the course of preparing the main storage tank, which is one of the storage tanks, the concentration of the spinning solution in the main tank was changed to 15%, and the viscosity was changed to 2000 cps. Thereafter, the temperature of the main tank was raised to 70 ° C to lower the viscosity to 1000 cps by the sensor of the temperature controller, and electrospun was obtained to obtain nanofibers.

Example 5

As the concentration of the spinning liquid in the main tank 8 was changed to 20% by the overflowed solid content and the viscosity increased, the temperature of the main tank 8 was adjusted to 65 ° C The electrospinning was carried out in the same manner as in Example 4.

Example 6

As the concentration of the spinning solution in the main tank 8 was changed to 25% by the overflowed solids, the temperature of the main storage tank was raised to 80 DEG C by a temperature controller to maintain the viscosity at 1000 cps as the viscosity increased. The electrospinning was carried out in the same manner as in Example 4.

Example 7

As the concentration of the spinning solution in the main tank 8 was changed to 30% by the overflowed solids, the temperature of the main storage tank was raised to 95 ° C by a temperature controller to maintain the viscosity at 1000 cps as the viscosity increased. The electrospinning was carried out in the same manner as in Example 4.

Comparative Example 3

A spinning solution having a concentration of 10% and a viscosity of 1000 cps, prepared by dissolving polyethersulfone in dimethylacetamide (N, N-dimethylacetamide, DMAc), was prepared and provided in the main storage tank. Then, the spinning solution was moved from the main storage tank to the nozzle block, and then the distance between the nozzle block and the collector was 40 cm and the applied voltage was 25 kV. In the course of the subsequent spinning process, the overflowed solidified material was returned to the main storage tank, and the concentration of the spinning solution in the main storage tank was changed to 20%. To maintain the concentration again at 10%, DMAc was added And THF, which is a diluent, was added thereto to conduct electrospinning.

The spinning speed of the nanofibers produced by Examples 4 to 7 and Comparative Example 3 and the spinning speed when the nanofiber production amount was 0.2 g / m ² were measured and the results are shown in Table 3.

Example 4 Example 5 Example 6 Example 7 Comparative Example 3 density 15% 20% 25% 30% 10% Viscosity calendar
(1,000 cps) calendar
(1,000 cps) calendar
(1,000 cps) calendar
(1,000 cps) calendar
(1,000 cps) Winding speed
(m / min) 20 25 30 35 10

According to Table 3, as the concentration of the embodiment is higher and the viscosity is constant as compared with the comparative example, as the amount of the solid material to be laminated on the actual collector increases during spinning, the winding speed becomes faster and the production amount increases. Thus, it is expected that the embodiment will be able to obtain more efficient spinning and increased throughput than the comparative example.

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

Claims (8)

A substrate;
A first nanofiber layer formed by electrospinning a polyethersulfone solution; And
And a second nanofiber layer formed by electrospinning a hydrophobic polymer solution,
Wherein the adhesion between the substrate and the first nanofiber layer, between the first nanofiber layer and the second nanofiber layer is performed by electrospinning an epoxy resin solution; And a second adhesive layer formed by electrospinning a curing agent solution,
Wherein the first nanofiber layer and the second nanofiber layer have different weights in the longitudinal direction or in the transverse direction. The method according to claim 1,
Wherein the curing agent is one selected from the group consisting of an amine curing agent, an acid anhydride curing agent and an imidazole curing agent. The method according to claim 1,
Wherein the hydrophobic polymer is one selected from the group consisting of polyvinylidene fluoride, low melting point polyester, and hydrophobic polyurethane. The method according to claim 1,
Wherein the adhesive layer comprises: a first adhesive layer; A second adhesive layer; And a first adhesive layer, or a second adhesive layer; A first adhesive layer; And the second adhesive layer are formed in this order. The method according to claim 1,
Wherein the epoxy resin solution and the curing agent solution are electrospun on the substrate and the first or a part of the first nanofiber layer. 6. The method according to any one of claims 1 to 5,
Wherein the first and second nanofiber layers are formed by electrospinning at a temperature of 50 to 100 ° C. delete The method according to claim 1,
Wherein the polymer solution for forming the first and second nanofiber layers is maintained at a viscosity of 1,000 cps to 3,000 cps through a temperature controller.

Images