KR101792851B1 - Nanofiber filter including cellulose substrate and epoxy resin-curing agent - Google Patents

Nanofiber filter including cellulose substrate and epoxy resin-curing agent Download PDF

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KR101792851B1
KR101792851B1 KR1020150165601A KR20150165601A KR101792851B1 KR 101792851 B1 KR101792851 B1 KR 101792851B1 KR 1020150165601 A KR1020150165601 A KR 1020150165601A KR 20150165601 A KR20150165601 A KR 20150165601A KR 101792851 B1 KR101792851 B1 KR 101792851B1
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nozzle
solution
unit
electrospinning
epoxy resin
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KR1020150165601A
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KR20170060873A (en
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박종철
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(주)에프티이앤이
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D39/00Filtering material for liquid or gaseous fluids
    • B01D39/14Other self-supporting filtering material ; Other filtering material
    • B01D39/16Other self-supporting filtering material ; Other filtering material of organic material, e.g. synthetic fibres
    • B01D39/1607Other self-supporting filtering material ; Other filtering material of organic material, e.g. synthetic fibres the material being fibrous
    • B01D39/1615Other self-supporting filtering material ; Other filtering material of organic material, e.g. synthetic fibres the material being fibrous of natural origin
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D46/00Filters or filtering processes specially modified for separating dispersed particles from gases or vapours
    • B01D46/54Particle separators, e.g. dust precipitators, using ultra-fine filter sheets or diaphragms
    • B01D46/546Particle separators, e.g. dust precipitators, using ultra-fine filter sheets or diaphragms using nano- or microfibres
    • DTEXTILES; PAPER
    • D01NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01DMECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00Formation of filaments, threads, or the like
    • D01D5/0007Electro-spinning
    • D01D5/0015Electro-spinning characterised by the initial state of the material
    • D01D5/0023Electro-spinning characterised by the initial state of the material the material being a polymer melt
    • DTEXTILES; PAPER
    • D01NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01DMECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00Formation of filaments, threads, or the like
    • D01D5/0007Electro-spinning
    • D01D5/0061Electro-spinning characterised by the electro-spinning apparatus
    • DTEXTILES; PAPER
    • D04BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04HMAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H1/00Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/40Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
    • D04H1/42Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
    • D04H1/4374Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece using different kinds of webs, e.g. by layering webs
    • DTEXTILES; PAPER
    • D04BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04HMAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H1/00Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/70Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres
    • D04H1/72Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged
    • D04H1/728Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged by electro-spinning
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06MTREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/37Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/55Epoxy resins
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F02COMBUSTION ENGINES; HOT-GAS OR COMBUSTION-PRODUCT ENGINE PLANTS
    • F02CGAS-TURBINE PLANTS; AIR INTAKES FOR JET-PROPULSION PLANTS; CONTROLLING FUEL SUPPLY IN AIR-BREATHING JET-PROPULSION PLANTS
    • F02C7/00Features, components parts, details or accessories, not provided for in, or of interest apart form groups F02C1/00 - F02C6/00; Air intakes for jet-propulsion plants
    • F02C7/04Air intakes for gas-turbine plants or jet-propulsion plants
    • F02C7/05Air intakes for gas-turbine plants or jet-propulsion plants having provisions for obviating the penetration of damaging objects or particles
    • F02C7/052Air intakes for gas-turbine plants or jet-propulsion plants having provisions for obviating the penetration of damaging objects or particles with dust-separation devices
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D2239/00Aspects relating to filtering material for liquid or gaseous fluids
    • B01D2239/02Types of fibres, filaments or particles, self-supporting or supported materials
    • B01D2239/025Types of fibres, filaments or particles, self-supporting or supported materials comprising nanofibres
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D2239/00Aspects relating to filtering material for liquid or gaseous fluids
    • B01D2239/06Filter cloth, e.g. knitted, woven non-woven; self-supported material
    • B01D2239/0604Arrangement of the fibres in the filtering material
    • B01D2239/0631Electro-spun
    • DTEXTILES; PAPER
    • D10INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10BINDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B2505/00Industrial
    • D10B2505/04Filters

Abstract

The present invention relates to a nanofiber filter including nanofibers, and more particularly, to a nanofiber filter including an epoxy resin nanofiber and a hardener nanofiber.

Description

[0001] The present invention relates to a nanofiber filter including a cellulose substrate and an epoxy resin-curing agent,

The present invention relates to a nanofiber filter comprising nanofibres, and more particularly to a nanofiber filter comprising a cellulose substrate and an epoxy resin-curing agent.

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.

Disclosure of the Invention The present invention has been conceived to solve the problems as described above, and it is an object of the present invention to provide a method of manufacturing a semiconductor device, which comprises a step of dividing a radiation section into at least two or more and continuously spraying an epoxy resin and a curing agent in a nozzle block, A fiber filter is manufactured and the number of the divided radiation spaces or the distance of the radiation section can be varied to manufacture a nanofiber filter suited to a desired product characteristic and a manufacturing process can be simplified, It is an object of the present invention to provide a fiber filter.

The present invention relates to a cellulosic substrate; A first nanofiber layer formed by electrospinning an epoxy resin solution on the cellulose substrate; And a second nanofiber layer laminated by electrospinning a curing agent solution on the first nanofiber layer.

The present invention also provides a nanofiber filter characterized in that the epoxy resin solution and the curing agent solution are electrospun through a temperature controller at a temperature of 50 to 100 ° C.

Here, the viscosity of the epoxy resin solution and the curing agent solution is controlled to 1,000 to 3,000 cps through the temperature controller.

In addition, the present invention provides a nanofiber filter 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 of manufacturing a nanofiber filter according to the present invention comprises a nanofiber filter which is divided into at least two radiation sections and is continuously electrospun epoxy resin and a curing agent through each radiation section to form a laminate of two or more layers, The manufacturing process of the nanofiber filter can be simplified and simplified, thereby reducing the 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 line A-A '
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 '
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 line C-C '
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 plan view schematically showing another embodiment according to the nozzle body arranged in the nozzle block of the electrospinning apparatus according to the present invention,
18 is a perspective view schematically showing another embodiment according to the nozzle body arranged in the nozzle block of the electrospinning apparatus according to the present invention,
19 is a side view schematically showing another embodiment according to a nozzle body arranged in a nozzle block of the electrospinning apparatus according to the present invention,
20 and 21 show an operation process (in FIG. 20, a nozzle in which a nozzle indicated by a broken line is closed in FIG. 20) is irradiated through a nozzle of each nozzle tube of the electrospinning apparatus according to the present invention, And the nozzle indicated by the broken line in Fig. 21 is located at the lower portion of the substrate), which is a plan view schematically showing another embodiment,
22 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,
23 is a perspective view schematically showing another embodiment according to the nozzle body arranged in the nozzle block of the electrospinning apparatus according to the present invention,
FIG. 24 and FIG. 25 are plan views schematically showing another embodiment according to an operation process of electrospinning the epoxy resin and the curing agent on the same plane of the substrate through the nozzles of each nozzle tube of the electrospinning apparatus according to the present invention,
26 is a schematic view showing a nanofiber filter comprising a cellulose base material, an epoxy resin nanofiber, and a hardener nanofiber according to the present invention.

Hereinafter, the present invention will be described.

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 gist of the present invention.

The present invention relates to a nanofiber layer comprising: a first nanofiber layer formed by electrospinning an epoxy resin on a cellulose substrate; And a second nanofiber layer laminated by electrospinning a curing agent on the first nanofiber layer.

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]

Figure 112015115146413-pat00001

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)

Figure 112015115146413-pat00002

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 used as a reactant in a polymer reaction.

(3)

Figure 112015115146413-pat00003

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)

Figure 112015115146413-pat00004

(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; Straight or branched alkenyl groups such as vinyl, allyl, and crotyl; 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, 1-butanesulfonic acid, Aliphatic sulfonic acids such as 1-hexanesulfonic acid, 1-octanesulfonic acid, 1-decanesulfonic acid and 1-dodecane sulfonic acid (for example, an aliphatic sulfonic acid 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.

Meanwhile, the nanofiber filter is manufactured using an electrospinning device.

Hereinafter, the electrospinning device used in the present invention will be described with reference to Figs. 1 to 16. 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- 6 is a cross-sectional view taken along the line A-A 'in Fig. 7, and Fig. 7 is a cross-sectional view taken along line A-A' in Fig. Sectional view schematically showing another embodiment in which an electric heater is installed in a nozzle block installed in each unit of the electrospinning device according to the invention 9 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, FIG. 10 is a cross-sectional view taken along the line C-C 'of FIG. 10, FIG. 11 is a view schematically showing an auxiliary transfer device of the electrospinning apparatus 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 unit 10a, 10b produces a nanofiber filter by electrospinning the same spinning liquid individually or electrospinning spinning fluids with different materials.

To this end, each of the units 10a and 10b is supplied with a spraying liquid main tank 8 in which an epoxy resin and a hardening agent are filled, a epoxy resin filled in the spraying liquid main tank 8 and a hardening agent in a predetermined amount A nozzle block 11 for discharging the epoxy resin filled in the spinning liquid main tank 8 and a curing agent, the nozzle block 11 having a plurality of nozzles 12 arranged in a pin shape, (14a, 14b) for generating a voltage in the collector (13) and a collector (13) spaced apart from the nozzle (12) by a predetermined distance in order to accumulate an epoxy resin and a curing agent injected from the nozzle (12) Lt; / RTI >

The electrospinning device 1 according to the present invention has a structure in which the epoxy resin filled in the spinning liquid main tank 8 and the curing agent are supplied to the plurality of nozzles 12 And the supplied epoxy resin and light shade are radiated and focused on the collector 13 with a high voltage applied thereto through the nozzle 12 to be transferred onto the long sheet 15 moved on the collector 13 And the formed nanofiber is made of a nanofiber filter.

In this case, in the front of the unit 10a positioned at the tip of each unit 10a, 10b of the electrospinning device 1, a long sheet (not shown) in which nanofibers are laminated by injection of an epoxy resin into the unit 10a, And a feed roller 3 for feeding the elongated sheet 15 to which the nano fibers are laminated is provided at the rear of the unit 10b positioned at the rear end of each unit 10a and 10b Up roller 5 is provided.

On the other hand, the elongated sheet 15 on which the epoxy resin and the curing agent are laminated while passing through the units 10a and 10b is preferably a cellulose base.

At this time, the materials of the epoxy resin and the curing agent which are radiated through the respective units 10a and 10b of the electrospinning device 1 are not limited. In the present invention, an epoxy resin is used for the unit 10a, 10b are characterized by using a curing agent.

The epoxy resin and the curing agent supplied through the nozzles 12 in the units 10a and 10b are solutions in a suitable solvent and are not particularly limited as long as they can dissolve the epoxy resin and the curing agent , Such as phenol, formic acid, sulfuric acid, m-cresol, thifluoroacetone hydride / dichloromethane, water, N-methylmorpholine N-oxide, chloroform, tetrahydrofuran and aliphatic ketone Butyl alcohol, isobutyl alcohol, isopropyl alcohol, methyl alcohol, ethanol, hexane, aliphatic compound, tetrachlorethylene, acetone, propylene glycol, diethylene glycol , Ethylene glycol, halogen compounds such as trichlorethylene, dichloromethane, aromatic compounds such as toluene, xylene, aliphatic cyclic compound groups Cyclohexanone, cyclohexane and ester groups such as n-butyl acetate, ethyl acetate, butyl cellosolve as aliphatic ether group, acetic acid 2-ethoxy ethanol, 2-ethoxy ethanol, amide dimethyl formamide, dimethylacetamide Etc., and a plurality of kinds of solvents may be mixed and 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 apparatus 1 according to the present invention is composed of a multi-tubular nozzle 500, And two or more inner and outer tubes 501 and 502 are coupled in a sheath-core shape so as to be capable of simultaneously radiating electricity.

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 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.

18 to 26, a nozzle body 112 according to an embodiment of the present invention will be described.

The nozzle block 111 of the electrospinning device 100 includes a plurality of nozzle tubes 112 arranged in the longitudinal direction thereof and a spray liquid main tank 120 for supplying an epoxy resin and a curing agent to the nozzle tubes 112 ) May be provided.

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, Epoxy resin filled in the spinning liquid main tank 120 and a curing agent are 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 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 in 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 epoxy resins and curing agents 112b, 112c, 112d, 112e, 112f, 112g, 112h, 112i of the nozzle tubes 112a, 112b, 112c, 112d, 112h, 112i arranged in the nozzle block 111 by opening the specific supply valve 122 among the supply valves 122 The nozzle tube body 112b, 112d, 112f, 112g, 112h, 112i is supplied with an epoxy resin and a curing agent, or the specific supply valve 122 is closed and arranged in the nozzle block 111, The supply of the epoxy resin and the curing agent is stopped only to the nozzles 112a, 112c and 112e, The supply of the epoxy resin and the curing agent supplied to each of the nozzle tubes 112a, 112b, 112c, 112d, 112e, 112f, 112g, 112h, and 112i is controlled and controlled.

The epoxy resin and the curing agent supplied to the respective nozzle tubes 112a, 112b, 112c, 112d, 112e, 112f, 112g, 112h, 112i through the solution supply pipe 121 in the spinning liquid main tank 120, 112b, 112c, 112d, 112e, 112f, 112g, 112h, 112i through a nozzle supply pipe 125 communicated to the supply pipe 121. The nozzles 111a,

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 epoxy resin and the curing agent supplied to the respective nozzles 111a from the nozzle supply pipe 125 by the opening and closing of the nozzle valve 126 by individually providing the nozzle valves 126 And the nozzle valve 126 is controllably connected to a control unit (not shown). Preferably, 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 an embodiment of the present invention, the spinning amount adjusting means is composed of the nozzle valve 126. However, if it is easy to control and control the amount of radiation of the epoxy resin and the curing agent that is radiated after being supplied to the nozzle 111a from the nozzle tube 112 The radiation amount adjusting means may be configured by 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 epoxy resin and the curing agent to the respective nozzles 111a through the respective nozzle tubes 112a, 112b, 112c, 112d, 112e, 112f, 112g, 112h, The nozzle 111a of the nozzles 111a provided in the nozzle tubes 112a, 112b, 112c, 112d, 112e, 112f, 112g, 112h and 112i is selectively opened with epoxy resin and curing agent The nozzles 111a at specific positions among the nozzles 111a provided in the nozzle tubes 112a, 112b, 112c, 112d, 112e, 112f, 112g, 112h, The nozzle valve 126 selectively closes the electrification of the epoxy resin and the curing agent in the spinning liquid main tank 120, Up nozzle tube feeding of the polymer spinning solution to be supplied to the nozzles (111a) through (112a, 112b, 112c, 112d, 112e, 112f, 112g, 112h, 112i) are individually adjustable 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, 112c, 112f, 112g, 112h, 112i, and a nozzle valve 126 is provided in the nozzle supply pipe 125 to adjust the supply amount of the epoxy resin and the curing agent supplied to the nozzle tubes 112a, 112b, 112c, 112d, 112e, 112e, 112e, 112f, 112g, 112h, 112i and controlling and controlling the radiation amounts of the epoxy resin and the curing agent electrified through each nozzle 111a, The nozzle block 111 is formed by stacking nanofibers different in basis weight in the longitudinal direction of the base material 115 by an epoxy resin and a curing agent electrified by the respective nozzles 111a of the nozzles 112a, 112f, 112g, 112h, and 112i. After the nozzles 111a are arranged in the respective nozzles 111a, And nanofibers having different weights in the longitudinal direction of the base material 115 may be formed by controlling and controlling the amount of radiation of the epoxy resin and the curing agent which are controlled through the respective nozzles 111a through the above- It is not.

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 also referred to as machine direction / longitudinal direction, and CD is referred to as 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 epoxy resin and the curing agent 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 spinning solution through the nozzles 12 to the units 10a and 10b of the electrospinning device 1 A distillation unit 320 for distilling and condensing the condensed VOC through the condenser 310 and a solvent storage unit 330 for storing the liquefied solvent through the distillation unit 320, A recycling apparatus 300 is provided.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

The 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 spinning solution supplied to and introduced into the tubes 40, the temperature controller 60 is connected to the heating wires 41 and 42 or the pipe 43 provided at the periphery of the tube 40, .

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, It is preferable to adjust the temperature of the supplied and incoming spinning liquid.

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"

Meanwhile, in the present invention, instead of maintaining the concentration constant, the high-concentration epoxy resin and the curing agent to be reused are used again after the overflow, and the viscosity of the epoxy resin and the curing agent is constantly controlled using the temperature controller 60, And it is easy to form nanofibers of the epoxy resin and the curing agent at a high temperature condition in order to control the high viscosity without using a diluent.

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

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

When fabricating the nanofiber with the electrospinning device 1, the fiber diameter and radioactivity of the nanofiber produced, such as the type of polymer and solvent used, the concentration of the polymer solution, the temperature and humidity of the spinning room, And the like. That is, the physical properties of the polymer emitted from electrospinning are important. It has been considered that it is usually necessary to maintain the viscosity of the polymer at or below a predetermined viscosity at the time of electrospinning. This is because the higher 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 control device 60 for maintaining and controlling the fiber viscosity suitable for electrospinning as described above.

The temperature regulating device 60 may be provided with a heating device capable of keeping the viscosity of the high viscosity solution reused through the overflow low and a cooling device capable of maintaining the viscosity of the 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, . ≪ / 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 solution re-supplied through the overflow tends to increase. By measuring the concentration of the solution in the intermediate tank 220 and adjusting the temperature using the temperature-viscosity graph corresponding to the concentration, It 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 can 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 chiller, and the means for maintaining a constant viscosity of the solution is generally 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 constant viscosity of the 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 solution re-supplied through the overflow system 200 of the present invention is 20 to 40%, which is a high concentration solution compared to 10 to 18% of the concentration of the spinning solution used in ordinary electrospinning.

Further, in order to make the viscosity of the solution to be supplied again according to the present invention constant, the temperature of the solution according to the concentration of the solution is controlled at 45 to 120 ° C, not at room temperature, more preferably 50 to 100 ° C Lt; / RTI >

On the other hand, the viscosity of the solution of the present invention is preferably 1,000 to 5,000 cps, more preferably 1,000 to 3,000 cps. When the viscosity is 1,000 cps or less, the quality of the nanofibers to be electrospun is poor, and when the viscosity is 3,000 cps or more, the solution is not easily discharged from the nozzle 42 during the electrospinning, and the production speed is slowed down.

In addition, since the viscosity of the solution is constant as the electrospinning progresses, the ease of spinning during electrospinning is excellent, and the concentration of the solution is increased, so that the productivity of the nanofibers integrated in the collector increases due to an increase in the amount of solids, .

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 controller 60 of the present invention measures the concentration of the intermediate tank 220 in an off-line manner and controls the viscosity of the solution through the temperature control of the nozzle block 110 or the main storage tank 210 Which can be manually operated, and which can automatically 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 nanofiber filter 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 to the long sheet 15 having the nanofiber filter laminated thereon, and the time for which the ultrasonic signals of the longitudinal wave and the transverse wave move back and forth on the elongate sheet 15, A predetermined calculation using the propagation time of the longitudinal waves and the transverse waves and the propagation speed of longitudinal waves and transverse waves at the reference temperature of the elongate sheet 15 in which the nanofiber filters are stacked 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 accurately even if there is any type of temperature distribution inside the nanofiber filter.

Meanwhile, the thickness of the nanofiber filter of the elongated sheet 15 to which the spinning liquid is sprayed and laminated to the electrospinning device 1 according to the present invention is measured to determine the conveying speed of the elongate sheet 15, 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 unit 10a and 10b, respectively, when the long sheet 15, in which the nanofiber filter is laminated by the spinning solution injected by the nozzles 12, For supporting the conveyance of the sheet 15 and provided at the line and the rear end of the buffer zone 31 formed between the units 10a and 10b.

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

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

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

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

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

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

On the other hand, the electrospinning device 1 according to the present invention is provided with the air permeability measuring device 80. That is, the air permeability for measuring the air permeability of the nanofiber filter 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 A measuring device 80 is provided.

As described above, the conveyance speed of the long sheet 15 and the nozzle block 11 are controlled based on the air permeability of the nanofiber filter measured through the air permeability measuring device 80.

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

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

As described above, it is possible to manufacture a nanofiber filter having 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 nanofiber filter .

If the degree of air permeability P of the nano-fiber filter is less than the predetermined value, the feed speed V is not changed from the initial value. If the deviation amount P is equal to or larger than the predetermined value, It is possible to simplify the control of the conveyance speed V by the conveyance speed (V) control device.

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

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

A laminating apparatus 90 for laminating the nanofiber filters electrified through the respective units 10a and 10b of the electrospinning apparatus 1 is connected to a unit located at the rear end of each of the units 10a and 10b 10b and performs a post-process of the nanofiber filter electrospun through the electrospinning device 1 by the laminating device 90. [

Hereinafter, an electrospinning apparatus for producing a nanofiber filter will be described with reference to Fig.

1 is a side view schematically showing an electrospinning device for producing a nanofiber filter.

As shown in the drawing, an electrospinning apparatus 1 according to the present invention is composed of a bottom-up electrospinning apparatus, in which at least one unit 10a or 10b is sequentially arranged at a predetermined interval, and each unit 10a , 10b) to prepare nanofiber filters by individually electrospinning a spinning solution or other material solution of the same material, or by electrospinning spinning solutions of different materials.

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 addition, although two units 10a and 10b of the electrospinning apparatus 1 are provided in the embodiment of the present invention, the number of the units 10a and 10b is preferably two or more, But not limited thereto.

Each of the units 10a and 10b of the electrospinning device 1 is provided with a solution main tank 8 in which a spinning liquid is filled and a spinning solution filled in each of the solution main tanks 8 A nozzle block 11 in which a plurality of nozzles 12 in the form of pins are arranged and a nozzle 12 for spraying a spraying liquid filled in each of the solution main tanks 8, 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 spinning solution injected from the nozzle 13.

According to the above-described structure, the electrospinning device 1 according to the present invention is characterized in that the spinning liquid to be filled in each of the solution main tanks 8 is continuously and constantly supplied to the nozzle block 11 through the metering pump, The spinning solution supplied to the collector 11 is injected and focused on the collector 13 having a high voltage through the plurality of nozzles 12 and the nanofibers are stacked on the collector 13, .

To this end, each unit 10a, 10b of the electrospinning device 1 is composed of spinning solution units 10a, 10b, and in the nozzle block 11 in the spinning solution unit 10a located at the tip end, In the nozzle block 11 in the spinning solution unit 10b positioned at the rear end thereof, the spinning solution units 10a and 10b, in which the hardening agent is electrospun, are provided respectively in the electrospinning device 1 and the collector 13, An epoxy resin and a curing agent are sprayed respectively.

The nozzle block 11 installed in each of the units 10a and 10b is connected to a solution main tank 8 filled with a spinning solution.

In an embodiment of the present invention, the nozzle blocks 11 installed in the respective units 10a and 10b are individually connected to a corresponding number of the solution main tanks 8 to supply the spinning solution , And each of the units 10a and 10b is connected to one solution main tank 8 to receive the spinning solution.

Here, the unit 10a, which is located at the foremost end of each unit 10a, 10b of the electrospinning device 1, is provided with a unit 10a for supplying the nanofibers through which the nanofibers are injected by the electrospinning of the spinning solution And a feed roller 3 for feeding the base material 15 for winding the substrate 15 on which the nanofibers are laminated is provided on the rear side of the unit 10b positioned at the rear end of each unit 10a, A roller 5 is provided.

The substrate 15 is fed into each of the units 10a and 10b of the electrospinning device 1 through the feed roller 3 and fed to the take-up roller 5, And an auxiliary conveying device 16 for controlling the conveying speed of the conveying belt.

The electrospinning apparatus 1 is provided with a main control unit 7 which includes a nozzle block 11 installed in each of the units 10a and 10b, an auxiliary transfer unit 16, The apparatuses 14a and 14b are controlled and connected to the thickness measuring device 70, the substrate conveyance speed regulating device 30, and the air permeability measuring device 80, which will be described later.

On the other hand, a laminating apparatus 90 for laminating the nanofibers electrospun on the substrate 15 through the units 10a and 10b of the electrospinning apparatus 1 is provided at the end of each of the units 10a and 10b And a post-process of the nanofiber filter, which is provided at the rear of the unit 10b located at the end of the unit 10b and electrospun through the electrospinning device 1 by the laminating device 90, is performed.

As described above, it is preferable that the base material 15 on which the spinning solution is electrospun and the nanofibers are laminated while passing through the units 10a and 10b of the electrospinning device 1 is preferably a cellulose base material.

At this time, the spinning solution radiated through each unit 10a, 10b of the electrospinning device 1 is the same as described above.

The spinning solution supplied through the nozzles 12 in each of the units 10a and 10b is a solution in which a polymer as a synthetic resin material capable of electrospinning is dissolved in an appropriate solvent and the type of solvent is a solution capable of dissolving 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 piping 216, the second transfer control device 218, the intermediate tank 220, and the regeneration tank 218 are connected to the respective units 10a, 10b of the electrospinning apparatus 1, And an overflow device 200 having a configuration including a tank 230 are 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, It is also possible that the overflow device 200 is provided in the overflow device 200 and the remaining unit 10b is integrally connected to the overflow device 200.

According to the structure as described above, the solution main tank 8 provided in each of the units 10a and 10b stores the polymer solution for the raw material of nanofibers. In the solution main tank 8, a separate stirring device 211 for preventing the separation and coagulation of the polymer spinning solution is provided therein.

The second transfer pipe 216 is configured to include a pipe (not shown) connected to the solution main tank 8 or the regeneration tank 230 and valves 212, 213 and 214, The polymer spinning solution is transferred from the solution main tank 8 or the regeneration tank 230 in which the usage solution is filled to the intermediate tank 220.

The second conveyance control unit 218 controls the conveyance operation of the second conveyance pipe 216 by controlling the valves 212 and 213 of the second conveyance pipe 216.

The valve 212 controls the transfer of the polymer solution to the intermediate tank 220 from the solution main tank 8 filled with the polymer solution and the valve 213 is connected to the intermediate tank 220, The valve 214 controls the amount of the polymer solution to be introduced into the intermediate tank 220 from the solution main tank 8 and the regeneration tank 230.

As described above, the liquid surface height of the polymer spinning solution measured through the second sensor 222 provided in the intermediate tank 230 to be described later is controlled by the control of the valves 212, 213, and 214.

The intermediate tank 220 separately stores the polymer solution used in the solution tank 8 or the recovery tank 230 in which the polymer solution is filled and the solution 10a, And a second sensor 222 for supplying the polymer solution to the nozzle block 12 and measuring the height of the liquid level of the supplied polymer solution.

Here, the second sensor 222 is preferably a sensor capable of measuring the liquid level of the polymer solution, such as an optical sensor or an infrared sensor, but is not limited thereto.

A supply pipe 240 and a supply control valve 242 for supplying the polymer solution with the nozzle block 11 are provided in the lower part of the intermediate tank 220. The supply control valve 242 supplies And controls the supply operation of the polymer spinning solution through the pipe 240.

The regeneration tank 230 is provided with a stirring device 231 for storing the polymer spinning solution recovered by the overflow separately and for preventing the separation and coagulation of the polymer spinning solution.

Here, the first sensor 232 is preferably a sensor capable of measuring the liquid level of the polymer solution, such as an optical sensor or an infrared sensor, but is not limited thereto.

Meanwhile, the polymer solution for overflowing in the nozzle block 11 is separately recovered through the solution recovery path 250 provided in the lower part of the nozzle block 11, and the solution recovery path 250 is divided into the first The polymer spinning solution in the regeneration tank 230 is recovered through the transfer pipe 251.

The first transfer pipe 251 includes a pipe (not shown) connected to the regeneration tank 230 and a pump (not shown), and the polymer spinning solution is circulated through the solution return 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) Controls the two or more valves 233 positioned at the upper part according to the height of the liquid level of the first sensor 232 provided in the regeneration tank 230 so that the polymer solution is supplied to the regeneration tank 230 of the plurality of regeneration tanks 230 ) To be transported individually.

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, a method for producing a nanofiber filter including the cellulose base material and the epoxy resin-curing agent nanofiber of the present invention will be described using the electrospinning device.

In the present invention, two units 10a and 10b are used in the electrospinning apparatus, and an epoxy resin and a curing agent are used as the polymer.

 First, an epoxy resin solution in which an epoxy resin is dissolved in an organic solvent is supplied to a spinning liquid main tank 8 connected to the first unit 10a of the electrospinning apparatus, and a solution of a hardener, which dissolves the hardening agent in an organic solvent, 2 unit 10b and the epoxy resin solution and the curing agent solution supplied to the spinning solution main tank 8 are supplied to the spinning solution main tank 8 through nozzles to which a high voltage is applied through a metering pump Is continuously supplied in a constant quantity in the plurality of nozzles 12 of the block 11. [ The epoxy resin solution and the curing agent solution supplied from the respective nozzles 12 are electrospun and converged on the collector 13 having a high voltage through the nozzle 12 to laminate the epoxy resin nanofiber and the curing agent nanofiber . In the units 10a and 10b of the electrospinning device 1, the epoxy resin nanofibers are fed by the rotation of the feed roller 3 and the feed roller 3, which are operated by driving a motor (not shown) Is transferred from the first unit 10a to the second unit 10b by the rotation of the driven auxiliary transfer device 16 and the epoxy resin nanofiber and the hardener nanofibers are transferred onto the collector 13 while repeating the above- Continuously electroluminesced and laminated.

Epoxy resin nanofibers are laminated in the first unit 10a by varying the spinning conditions for the respective units 10a and 10b of the electrospinning device in the process of electroluminescence of the solution on the collector 13 by lamination , And curing agent nanofibers are successively laminated in the second unit 10b.

The voltage generating device 14a provided in the first unit 10a of the electrospinning device 1 and supplying a voltage to the first unit 10a applies a low radiation voltage to the epoxy resin nano- And a voltage generator 14b provided in the second unit 10b to supply a voltage to the second unit 10b is provided with a high radiation voltage so that the curing agent nanofiber is formed on the epoxy resin nanofiber And laminated. At this time, the radiation voltage given by each of the voltage generating devices 14a and 14b is 1 kV or more, preferably 15 kV or more, and the voltage given by the voltage generating device 14a of the first unit 10a is higher than that of the second unit 10b Is lower than the voltage applied by the voltage generating device 14b of the first embodiment.

In the present invention, the voltage of the first unit 10a of the electrospinning device 1 is lowered to laminate the epoxy resin nanofibers on the collector 13, and the voltage of the second unit 10b is increased, A nanofiber filter is manufactured by stacking nanofibers. However, it is also possible that the epoxy resin nanofiber is radiated and laminated in the first unit 10a and the curing agent nanofiber is radiated in the second unit 10b by varying the intensity of the voltage.

 In addition, three or more layers of epoxy resin and curing agent nanofibers having different fiber diameters and having different numbers of units of the above-mentioned electrospinning device 1 are formed on the collector 13 It would also be possible to produce nanofiber filters.

In the first unit 10a as described above, the epoxy resin solution is electrospun on the collector 13 to form a first nanofiber layer, which is an epoxy resin nanofiber. In the second unit 10b, the epoxy resin nanofiber It is possible to fabricate the nanofiber filter of the present invention through a process of laminating a second nanofiber layer, which is a hardening agent nanofiber, and then thermally fusing it.

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  One

A spinning solution prepared by dissolving an epoxy resin in a solvent of DMAc (N, N-dimethylaceticamide) in an amount of 15% by weight was introduced into the spinning main tank of the first unit and the amine curing agent was added to a solvent of DMAc (N, N-dimethylaceticamide) 15% by weight. The spinning solution having a concentration of 15% by weight was added to the spinning solution main tank of the second unit.

 In the first unit of the electrospinning device, an epoxy resin spinning solution was electrospun on a cellulose substrate at a distance of 40 cm between the electrodes and the collector under the conditions of an applied voltage of 20 kV and a temperature of 70 ° C to obtain an epoxy resin nanofiber having a basis weight of 4 g / . In the second unit, an amine curing agent solution was electrospun at a distance of 40 cm between the electrode and the collector at an applied voltage of 20 kV and a temperature of 50 캜 to form an amine curing agent nanofiber having a basis weight of 4 g / m 2 on the epoxy resin nano fiber layer And then heat sealed to produce a nanofiber filter.

Comparative Example  One

A spinning solution prepared by dissolving polyethersulfone 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 polyethersulfone spinning solution was electrospun on the polyethylene terephthalate substrate under the conditions of the distance between the electrode and the collector of 40 cm, the applied voltage of 20 kV and the temperature of 22 ° C, Ether sulfone nanofibers were formed.

Experimental Example

The properties of the nanofiber filters prepared in Example 1 and Comparative Example 1 were measured by the following methods. 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 the above Table 1, the nanofiber filter manufactured by the embodiment of the present invention has improved water pressure and air permeability of at least 50% compared to 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, 100: electrospinning device, 3: feed roller,
5: take-up roller, 7: main control device,
8: Spray solution Main tank,
10a, 10b, 10c, 10d, 110, 110 ': unit,
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, 114: voltage generator,
15, 15a, 15b, 115: 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, 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: Air supply nozzle support plate,
415: nozzle for overflow removal,
416: nozzle support plate for removing overflow, 500: multi-tubular nozzle,
501: inner tube, 502: outer tube,
503: tip end, 115a, 115b, 115c: nanofiber,
116a: conveying belt, 116b: conveying roller,
120: spinning liquid main tank, 120a: first spinning liquid main tank,
120b: second spinning solution main tank, 121: solution supply pipe,
121a: first supply pipe, 121b: second supply pipe,
122: supply valve, 125: nozzle supply pipe,
126: Nozzle valve.

Claims (4)

A cellulose substrate;
A first nanofiber layer formed by electrospinning an epoxy resin solution on the cellulose substrate; And
And a second nanofiber layer laminated by electrospinning a curing agent solution on the first nanofiber layer,
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 epoxy resin solution and the curing agent solution are electrospun through a temperature controller at a temperature of 50 to 100 ° C.
3. The method of claim 2,
Wherein the viscosity of the epoxy resin solution and the curing agent solution is controlled to 1,000 to 3,000 cps through the temperature controller.
4. The method according to any one of claims 1 to 3,
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.
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Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2012516399A (en) * 2009-01-28 2012-07-19 ドナルドソン カンパニー,インコーポレイティド Fiber medium and method and apparatus for forming the same

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2012516399A (en) * 2009-01-28 2012-07-19 ドナルドソン カンパニー,インコーポレイティド Fiber medium and method and apparatus for forming the same

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