KR101792850B1 - Nano fiber filter including bicomponent substrate and epoxy resin and curing agent - Google Patents
Nano fiber filter including bicomponent substrate and epoxy resin and curing agent Download PDFInfo
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- KR101792850B1 KR101792850B1 KR1020150165594A KR20150165594A KR101792850B1 KR 101792850 B1 KR101792850 B1 KR 101792850B1 KR 1020150165594 A KR1020150165594 A KR 1020150165594A KR 20150165594 A KR20150165594 A KR 20150165594A KR 101792850 B1 KR101792850 B1 KR 101792850B1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D39/00—Filtering material for liquid or gaseous fluids
- B01D39/14—Other self-supporting filtering material ; Other filtering material
- B01D39/16—Other self-supporting filtering material ; Other filtering material of organic material, e.g. synthetic fibres
- B01D39/1607—Other self-supporting filtering material ; Other filtering material of organic material, e.g. synthetic fibres the material being fibrous
- B01D39/1623—Other self-supporting filtering material ; Other filtering material of organic material, e.g. synthetic fibres the material being fibrous of synthetic origin
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D46/00—Filters or filtering processes specially modified for separating dispersed particles from gases or vapours
- B01D46/54—Particle separators, e.g. dust precipitators, using ultra-fine filter sheets or diaphragms
- B01D46/546—Particle separators, e.g. dust precipitators, using ultra-fine filter sheets or diaphragms using nano- or microfibres
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/0007—Electro-spinning
- D01D5/0015—Electro-spinning characterised by the initial state of the material
- D01D5/0023—Electro-spinning characterised by the initial state of the material the material being a polymer melt
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/0007—Electro-spinning
- D01D5/0061—Electro-spinning characterised by the electro-spinning apparatus
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- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING 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
- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/70—Non-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
- D04H1/72—Non-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
- D04H1/728—Non-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
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/55—Epoxy resins
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F02—COMBUSTION ENGINES; HOT-GAS OR COMBUSTION-PRODUCT ENGINE PLANTS
- F02C—GAS-TURBINE PLANTS; AIR INTAKES FOR JET-PROPULSION PLANTS; CONTROLLING FUEL SUPPLY IN AIR-BREATHING JET-PROPULSION PLANTS
- F02C7/00—Features, 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
- F02C7/04—Air intakes for gas-turbine plants or jet-propulsion plants
- F02C7/05—Air intakes for gas-turbine plants or jet-propulsion plants having provisions for obviating the penetration of damaging objects or particles
- F02C7/052—Air intakes for gas-turbine plants or jet-propulsion plants having provisions for obviating the penetration of damaging objects or particles with dust-separation devices
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2239/00—Aspects relating to filtering material for liquid or gaseous fluids
- B01D2239/02—Types of fibres, filaments or particles, self-supporting or supported materials
- B01D2239/025—Types of fibres, filaments or particles, self-supporting or supported materials comprising nanofibres
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2239/00—Aspects relating to filtering material for liquid or gaseous fluids
- B01D2239/06—Filter cloth, e.g. knitted, woven non-woven; self-supported material
- B01D2239/0604—Arrangement of the fibres in the filtering material
- B01D2239/0631—Electro-spun
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2239/00—Aspects relating to filtering material for liquid or gaseous fluids
- B01D2239/10—Filtering material manufacturing
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- D—TEXTILES; PAPER
- D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B2505/00—Industrial
- D10B2505/04—Filters
Abstract
The present invention relates to a nanofiber filter including nanofibers, and more particularly, to a nanofiber filter including nanofibers formed by electrospinning a mixed solution containing an epoxy resin and a curing agent on a binary substrate .
Description
The present invention relates to a nanofiber filter including nanofibers, and more particularly, to a nanofiber filter including nanofibers formed by electrospinning a mixed solution containing an epoxy resin and a curing agent on a binary substrate .
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 in order to solve the above-mentioned problems, and it is an object of the present invention to provide a nanofiber filter by electrospinning a mixed solution containing an epoxy resin and a curing agent on a binary substrate, It is an object of the present invention to provide a nanofiber filter capable of manufacturing a nanofiber filter suitable for a desired product characteristic by varying the distance and reducing the overall cost by simplifying the manufacturing process.
The present invention relates to a two-component substrate; And a nanofiber layer formed by electrospinning a mixed solution containing an epoxy resin and a curing agent on the binary substrate.
At this time, the mixed solution containing the epoxy resin and the curing agent is electrospun through a temperature controller at a temperature of 50 to 100 ° C.
The viscosity of the mixed solution containing the epoxy resin and the curing agent is preferably controlled to 1,000 to 3,000 cps.
Further, the nanofiber layer is characterized in that its basis weight is different along the longitudinal direction or the transverse direction.
The method of manufacturing a nanofiber filter according to the present invention can simplify and simplify the manufacturing process of the nanofiber filter, thereby reducing manufacturing cost and manufacturing time.
In addition, the nanofiber filter according to the present invention includes an epoxy resin, which is a thermosetting resin, so that when a certain heat is applied, the nanofiber filter reacts with the curing agent to cause curing. Accordingly, the nanofiber filter can be used as a repair adhesive for a torn filter, a non-woven fabric, etc. after applying a certain amount of heat.
1 is a side view schematically showing an electrospinning apparatus according to the present invention,
2 is a side sectional view schematically showing a nozzle of a nozzle block installed in each unit of the electrospinning apparatus according to the present invention,
3 is a side cross-sectional view schematically showing another embodiment according to a nozzle of a nozzle block installed in each unit of the electrospinning apparatus according to the present invention,
4 is a plan view schematically showing a nozzle block installed in each unit of the electrospinning apparatus according to the present invention,
5 is a front sectional view schematically showing a state in which an electric heater is installed in a nozzle block installed in each unit of the electrospinning apparatus according to the present invention,
6 is a sectional view taken along the line A-A 'in Fig. 5,
7 is a front sectional view schematically showing another embodiment in which an electric heater is installed in a nozzle block installed in each unit of the electrospinning apparatus according to the present invention,
8 is a sectional view taken along the line B-B 'in Fig. 7,
Fig. 9 is a front sectional view schematically showing another embodiment of a state in which an electric heater is installed in a nozzle block installed in each unit of the electrospinning apparatus according to the present invention, Fig.
10 is a sectional view taken along the line C-C 'in Fig. 9,
11 is a view schematically showing an auxiliary transfer device of an electrospinning device according to the present invention,
12 is a view schematically showing another embodiment of the auxiliary belt roller of the auxiliary transfer device of the electrospinning apparatus according to the present invention,
FIG. 13 to FIG. 16 are side views schematically showing the operation of the long sheet conveying speed adjusting apparatus of the electrospinning apparatus according to the present invention,
17 is a side view schematically showing an electrospinning device for manufacturing a nanofiber filter including an adhesive layer according to the present invention,
18 is a perspective view schematically showing a nozzle block installed in an adhesive (epoxy resin-curing agent) unit of an electrospinning apparatus according to the present invention,
19 is a plan view schematically showing a nozzle block installed in an adhesive (epoxy resin-curing agent) unit of an electrospinning device according to the present invention,
20 to 21 are plan views schematically showing an operation process in which an adhesive (epoxy resin-curing agent) and a spinning solution are sequentially injected through a nozzle block installed in each unit of the electrospinning apparatus according to the present invention,
22 is a plan view schematically showing another embodiment according to a nozzle body arranged in a nozzle block of an electrospinning apparatus according to the present invention,
23 is a front view of Fig. 22
24 is a side view schematically showing another embodiment according to the nozzle body arranged in the nozzle block of the electrospinning apparatus according to the present invention,
25 and 26 show an operation process (in FIG. 25, a nozzle indicated by a dashed line is a closed nozzle) in which the polymer spinning solution is electrospun on the same plane of the base material through the nozzles of each nozzle tube of the electrospinning device according to the present invention , And the nozzle indicated by the broken line in Fig. 26 is located at the lower portion of the substrate)
27 is a plan view schematically showing another embodiment according to a nozzle body arranged in a nozzle block of the electrospinning apparatus according to the present invention,
28 is a perspective view schematically showing another embodiment according to a nozzle body arranged in a nozzle block of the electrospinning apparatus according to the present invention;
FIG. 29 and FIG. 30 are plan views schematically showing another embodiment according to an operation process of electropolishing the polymer spinning solution on the same plane of the base material through the nozzles of each nozzle tube of the electrospinning device according to the present invention. FIG.
31 is a schematic view showing a nanofiber filter including a nanofiber including a binary material, an epoxy resin and a curing agent of the present invention.
Hereinafter, the present invention will be described.
The present invention relates to a two-component substrate; And a nanofiber layer formed by electrospinning a mixed solution containing an epoxy resin and a curing agent on the binary substrate.
At this time, the epoxy resin is an intermediate of a thermosetting resin and forms a three-dimensional network structure insoluble / infusible by reaction with a curing agent to exhibit physical properties inherent to epoxy, and the epoxy resin is adhered It has an advantage of being excellent in properties, mechanical strength, heat resistance, chemical resistance, water resistance, electric insulation property, moldability and impregnation property, easy production of a composite material, and realizing various properties according to the selection of a curing agent.
Nonlimiting examples of such epoxy resins include bisphenol A type epoxy resins, bisphenol F type epoxy resins, and bisphenol S type epoxy resins.
The above-mentioned bisphenol A type epoxy resin is represented by the following general formula (1), and the most commonly used epoxy resin is produced by a direct method or indirect method.
[Chemical Formula 1]
The bisphenol F type epoxy resin is represented by the following general formula (2) and is produced by the reaction of bisphenol F with ECH. The bisphenol F type epoxy resin has a lower viscosity than the bisphenol A type epoxy resin and theoretically has a somewhat lower mechanical and physical properties. And the like.
(2)
The bisphenol S type epoxy resin is represented by the following general formula (3), and is generally used for rapidly curing an epoxy adhesive and used as a reactant in a polymer reaction.
(3)
On the other hand, the curing agent is preferably one selected from the group consisting of an amine curing agent, an acid anhydride curing agent and an imidazole curing agent, but is not limited thereto.
Non-limiting examples of the amine-based curing agent include aliphatic polyamines, modified aliphatic polyamines, aromatic amines, tertiary amines, and secondary amines.
Examples of the aliphatic polyamines include diethylene triamine (DETA), triethylene tetramine (TETA), diethylamino propyl amine (DEAPA), Menthane diamine (MDA), N-aminoethyl piperazine Isophorone diamine (IPDA), but is not limited thereto.
Examples of the modified aliphatic polyamines include, but are not limited to, Epoxy Polyamine Adduct, Ethylene or Propylene Oxide, Polyamine adduct, Cyanoethylated Polyamine, and Ketone blocked Polyamine (Ketimine).
Examples of the aromatic amine include Meta phenylene Diamine (MPD), 4.4 'Dimethyl aniline (DAM or DDM), Diamino Diphenyl Sulfone (DDS), and Aromatic amine adduct.
Examples of the acid anhydride-based curing agent include polyamide (PA), tetrahydrophthalic anhydride (THPA), methyl tetrahydrophthalic anhydride (MTHPA), hexahydrophthalic anhydride (HHPA), and MNA.
Nonlimiting examples of the imidazole-based curing agent include 2MZ and 2E4MZ.
In addition, the mixed solution may further include a curing accelerator.
The curing accelerator used in the present invention is not particularly limited as long as it is a curing accelerator generally used for accelerating the curing of the epoxy compound. Examples thereof include tertiary amines, tertiary amine salts, imidazoles, Quaternary ammonium salts, quaternary phosphonium salts, organic metal salts, and boron compounds. The curing accelerator may be used alone or in combination of two or more.
Examples of tertiary amines include lauryldimethylamino, N, N-dimethylcyclohexylamine, N, N-dimethylbenzylamine, N, N-dimethylaniline, (N, N- dimethylaminomethyl) (N, N-dimethylaminomethyl) phenol, 1,8-diazabicyclo [5.4.0] undecene-7 (DBU), 1,5-diazabicyclo [4.3.0] 5 (DBN).
Examples of the tertiary amine salt include a carboxylate, a sulfonate, and an inorganic acid salt of the above-mentioned tertiary amine. Examples of the carboxylate include salts of carboxylic acids having 1 to 30 carbon atoms (especially 1 to 10 carbon atoms) such as octylate (particularly fatty acid salts). Examples of the sulfonic acid salt include p-toluenesulfonic acid salt, benzenesulfonic acid salt, methanesulfonic acid salt and ethanesulfonic acid salt. Representative examples of tertiary amine salts include salts of 1,8-diazabicyclo [5.4.0] undecene-7 (DBU) (for example, p-toluenesulfonic acid salt and octylic acid salt).
Examples of the metal-based curing accelerator include organic metal complexes or organic metal salts of metals such as cobalt, copper, zinc, iron, nickel, manganese and tin. Specific examples of the organometallic complexes include organic cobalt complexes such as cobalt (II) acetylacetonate and cobalt (III) acetylacetonate, organic copper complexes such as copper (II) acetylacetonate, zinc An organic iron complex such as an organic zinc complex and iron (III) acetylacetonate, an organic nickel complex such as nickel (II) acetylacetonate, and an organic manganese complex such as manganese (II) acetylacetonate. Examples of the organic metal salt include zinc octylate, tin octylate, zinc naphthenate, cobalt naphthenate, stannous stearate and zinc stearate. As the metal curing accelerator, cobalt (II) acetylacetonate, cobalt (III) acetylacetonate, zinc (II) acetylacetonate, zinc naphthenate and iron (III) acetylacetonate are preferable from the viewpoints of curability and solvent solubility And particularly, cobalt (II) acetylacetonate and zinc naphthenate are preferable. The metal-based curing accelerator may be used singly or in combination of two or more.
The addition amount of the metal-based curing accelerator is preferably in the range of from 25 to 500 ppm, more preferably from 40 to 200 ppm, of the metal based on the metal-based curing accelerator when the non-volatile content in the resin composition is 100 mass% . If it is less than 25 ppm, it tends to make it difficult to form a conductor layer having a low roughness with good adhesion to the surface of the insulating layer. When it exceeds 500 ppm, the storage stability and insulating property of the resin composition tend to be lowered.
Examples of the quaternary ammonium salt include tetraethylammonium bromide and tetrabutylammonium bromide.
As the quaternary phosphonium salt, for example, the following formula (1)
(Wherein R1, R2, R3 and R4 are the same or different and each represents a hydrocarbon group of 1 to 16 carbon atoms, and X represents an anion residue of a carboxylic acid or an organic sulfonic acid).
Examples of the hydrocarbon group having 1 to 16 carbon atoms include a linear or branched hydrocarbon group such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, s-butyl, t-butyl, pentyl, A straight chain alkyl group; 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 apparatus used in the present invention will be described with reference to Figs. 1 to 17. Fig.
FIG. 1 is a side view schematically showing an electrospinning apparatus according to the present invention, FIG. 2 is a side cross-sectional view schematically showing a nozzle of a nozzle block installed in each unit of the electrospinning apparatus according to the present invention, FIG. 4 is a cross-sectional view schematically showing a nozzle block provided in each unit of the electrospinning apparatus according to the present invention. FIG. 4 is a cross- Fig. 5 is a front sectional view schematically showing a state in which an electric heater is installed in a nozzle block installed in each unit of the electrospinning apparatus according to the present invention, Fig. 6 is a sectional view taken on line A-A ' 7 is a schematic view schematically showing another embodiment in which an electric heater is installed in a nozzle block installed in each unit of the electrospinning apparatus according to the present invention. 8 is a cross-sectional view taken along the line B-B 'in Fig. 7, and Fig. 9 is a schematic view showing another embodiment of a state in which an electric heater is installed in a nozzle block installed in each unit of the electrospinning apparatus according to the
As shown in the figure, an
The case of using two units will be described by way of example, but in the present invention, a unit is used to manufacture a nanofiber filter.
For this purpose, each of the
The
Here, the
On the other hand, it is preferable that the
The two-component base material is characterized by being a sheath-core type, a side by side type, and a C-type type. In the sheath-core type two-component substrate, the sheath portion is a low-melting-point polyester and the core portion is a high-melting-point polyethylene terephthalate.
In this case, the material of the polymer spinning solution to be radiated through each
The spinning solution supplied through the
2, the
Here, the
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
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
Here, the
22 to 30, a
A
The
Here, the
At this time, a supply amount adjusting means (not shown) is connected to the
A supply valve 122 is provided in the
That is, when the polymer spinning solution is supplied to the
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
The
The polymer spinning solution supplied to the
That is, the
Here, the
The supply of the polymer solution to be supplied to each
In the embodiment of the present invention, if the amount of the spinning solution of the polymer spinning solution is easily controlled and controlled after being supplied to the
According to the structure described above, the
In an embodiment of the present invention, the
The MD direction used in the present invention means a machine direction, and means a longitudinal direction corresponding to the progress direction in the case of continuous production of fibers such as a film or a nonwoven fabric, and the CD direction means a perpendicular direction to the CD direction as a cross direction . MD is the machine direction / longitudinal direction, and CD is the width direction / transverse direction.
On the other hand, the
Although the overflow device 200 is provided in each
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
The second
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
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
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
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
When the number of the regeneration tanks 230 is two or more, a plurality of
Meanwhile, the VOC recycling apparatus 300 is provided in the
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
That is, pipes 311 and 331 for interconnecting the
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
Here, the distillation apparatus 320 is preferably a fractionation apparatus, but it is not limited thereto.
That is, the piping for interconnecting the
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
It is also possible to eliminate the insulating
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
It is also possible to optimize the insulation between the
In addition, the leakage current can be stopped within a predetermined range, the current supplied from the
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
The distance between the inner surface of the case 18 formed of an insulator and the outer surface of the
Therefore, when 40 kV is applied between the
A
4, the
Here, the flow of the spinning liquid in the
The polymer spinning solution supplied to each
A plurality of
In order to control the temperature control of the spinning solution supplied to and introduced into the
In order to adjust the temperature of the plurality of
5 to 6, a
In the embodiment of the present invention, the
In the meantime, instead of maintaining the concentration at a constant level, the present invention uses the polymer solution having a high concentration to be reused after the overflow, and adjusts the viscosity of the polymer solution to be constant by using the
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
The present invention is characterized by including a
The
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 polymer solution re-supplied through the overflow tends to increase. By measuring the concentration of the polymer solution in the intermediate tank 220 and adjusting the temperature using the temperature- The viscosity can be kept constant.
The concentration measuring device for measuring the concentration has a contact type and a non-contact type in direct contact with a solution, and a capillary type concentration measuring device and a disk (DISC) type concentration measuring device can be used as a contact type. A concentration measuring apparatus using a concentration measuring apparatus using infrared or the like can be used.
The heating device of the present invention may be an electric heater, a hot water circulating device, a hot air circulating device, or the like. In addition, devices capable of raising the temperature in the same range as the above devices may be borrowed.
As an example of the heating device, the electro-thermal heater may be used in the form of a hot wire, and coil-shaped hot wires 62a and 62b may be mounted inside the
It is also possible to have the configuration of the linear heat lines 62a and 62b and the U-shaped pipe 63.
The heating device includes a nozzle block 110 through which the polymer solution is radiated, a tank (main storage tank, intermediate tank or regeneration tank) and an overflow system 200 (in particular, a tank And a transfer pipe).
The cooling device of the present invention may be a cooling device including a chilling device, and the means for maintaining a constant viscosity of the polymer solution is usually applicable. The cooling device may be provided in at least one of the nozzle block 110, the tank, and the overflow system 200 in the same manner as the heating device, and is used to maintain a certain viscosity of the polymer solution.
In addition, the
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
The concentration of the polymer solution re-supplied through the overflow system 200 of the present invention is 20 to 40%, which is a high concentration solution compared to the concentration of the polymer solution used in conventional electrospinning of 10 to 18%.
Further, in order to make the viscosity of the polymer solution re-supplied according to the present invention constant, the temperature of the polymer solution according to the concentration of the polymer solution is controlled at 45 to 120 ° C, not at room temperature, To < RTI ID = 0.0 > 100 C. < / RTI >
Meanwhile, the viscosity of the polymer solution of the present invention is preferably 1,000 to 5,000 cps, more preferably 1,000 to 3,000 cps. If the viscosity is 1,000 cps or less, the quality of the nanofibers to be electrospun is poor, and if the viscosity is 3,000 cps or more, the polymer solution can not be easily discharged from the nozzle 42 during the electrospinning, resulting in a slow production rate.
In the present invention, since the viscosity of the polymer solution is constant as the electrospinning progresses, the ease of spinning during electrospinning is excellent, and the concentration of the polymer solution is increased. As a result, the amount of solids in the nanofibers accumulated in the collector increases, There is an increasing effect.
In addition, the amount of the residual solvent of the nanofibers using electrospinning is lower than that of the conventional electrospinning, and thus it is possible to produce nanofibers of excellent quality.
The
11, an auxiliary conveying device (not shown) for adjusting the conveying speed of the
The auxiliary conveying
The
In the embodiment of the present invention, five
Meanwhile, in the embodiment of the present invention, the
At this time, the
The auxiliary conveying
In addition, in the embodiment of the present invention, the
On the other hand, the thickness measuring device 70 is provided in the
When the thickness of the nanofibers discharged from the
When the thickness of the nanofibers discharged from the
Here, the thickness measuring device 9 is disposed so as to face upward and downward with the
Thus, the thickness of the
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
Meanwhile, the thickness of the nanofiber filter of the
The elongated sheet conveying speed regulator 30 includes a buffer zone 31 formed between each
At this time, the support rollers 33 and 33 'are provided in the
The
To this end, a sensing sensor (not shown) for sensing the feeding speed of the
In one embodiment of the present invention, the conveying speed of the
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
On the other hand, if the conveyance speed of the
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
On the other hand, the
As described above, the conveyance speed of the
When the air permeability of the nanofiber nonwoven fabric discharged through each of the
When the air permeability of the nanofiber filter discharged through the
As described above, it is possible to manufacture a nanofiber filter having uniform air permeability by controlling the feeding speed of each
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
The main control device 7 includes a
A laminating apparatus 90 for laminating the nanofiber filters electrified through the
Hereinafter, the two-component substrate of the present invention using the electrospinning device; And a process for producing a nanofiber filter comprising an epoxy resin-curing agent nanofiber.
In the present invention, the
First, a mixed solution obtained by dissolving an epoxy resin and a curing agent in a solvent is supplied to a spinning liquid main tank 8 connected to the
A nanofiber filter in which the number of units of the
In the same manner as above, a mixed solution containing an epoxy resin and a curing agent is electrospun on the
At this time, the epoxy resin contained in the adhesive layer and the curing agent react with each other through thermal fusion to cure, thereby making it possible to manufacture a filter which does not easily separate.
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 having a concentration of 15% by weight, which was prepared by dissolving an epoxy resin and an amine curing agent in dimethylacetamide (N, N-dimethylacetamide, DMAc), was introduced into the spinning liquid main tank of the first unit. In the first unit of the electrospinning device, a mixed solution containing an epoxy resin and an amine curing agent was electrospun on the binary substrate to a distance of 40 cm between the electrode and the collector under the condition of an applied voltage of 20 kV and a temperature of 70 ° C, / m < 2 & gt ;.
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. The first unit of the electrospinning device on a two-component base polyethersulfone spinning liquid 40㎝ to the distance between the electrode and the collector, the applied voltage to 20kV, the basis weight by electrospinning under the conditions of temperature 22 ℃ 4g / m 2 of poly 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.
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: Fluid tank main tank
10a, 10b, 10c, 10d, 110, 110:
11, 11a, 11b, 111:
112, 112a, 112b, 112c, 112d, 112e, 112f, 112g, 112h, 112i:
13: collector
14, 14a, 14b, 14c, 14d and 114:
15, 15a, 15b, 115: long sheet 16: auxiliary conveying device
16a:
18: Case 19: Insulation member
30: Long sheet conveying speed adjusting device 31: Buffer section
33, 33 ': support roller 35: regulating roller
40:
43: pipe 60: thermostat
70: Thickness measuring device 80: Air permeability measuring device
90: laminating device 200: overflow device
211, 231: stirring
216: second transfer pipe 218: second transfer control device
220: intermediate tank 222: second sensor
230: regeneration tank 232: first sensor
240: Supply piping 242: Supply control valve
250: spinning liquid recovery path 251: first transfer piping
300: VOC recycling device 310: condensing device
311, 321, 331, 332: piping 320: distillation device
330: Solvent storage device 404: Nozzle for supplying air
405: nozzle plate 407: first spinning solution storage plate
408: second spinning solution storage plate 410: overflow solution temporary storage plate
411: air storage plate 412: overflow outlet
413: Air inlet 414: Nozzle support plate for air supply
415: Nozzle for Overflow Removal
416: nozzle overflow removing nozzle support plate 500: multiple tubular nozzle
501: Inner tube 502: Outer tube
503:
116a: conveying belt 116b: conveying roller
120: spinning fluid
120b: Second spinning solution
121:
121b:
122: supply valve 125: nozzle supply pipe
126: Nozzle valve
Claims (4)
And a nanofiber layer formed by electrospinning a mixed solution containing an epoxy resin and a curing agent on the binary substrate,
Wherein the nanofiber layer has a different basis weight in a longitudinal direction or in a transverse direction.
Wherein the mixed solution containing the epoxy resin and the curing agent is electrospun through a temperature controller at a temperature of 50 to 100 ° C.
Wherein the viscosity of the mixed solution containing the epoxy resin and the curing agent is adjusted to 1,000 to 3,000 cps through the temperature controller.
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)
| 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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| Publication number | Priority date | Publication date | Assignee | Title |
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| 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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