KR101824495B1

KR101824495B1 - Mask including epoxy resin-curing agent nano fiber

Info

Publication number: KR101824495B1
Application number: KR1020150180067A
Authority: KR
Inventors: 박종철
Original assignee: (주)에프티이앤이
Priority date: 2015-12-16
Filing date: 2015-12-16
Publication date: 2018-02-02
Also published as: KR20170071888A

Abstract

BACKGROUND OF THE INVENTION 1. Field of the Invention [0001] The present invention relates to a mask including nanofibers, and more particularly, to a mask including an epoxy resin-curing agent nanofiber between substrates.

Description

Mask including epoxy resin-curing agent nano fiber Mask including epoxy resin-

Facial mask is a thing that shields nose and mouth to prevent inhalation and scattering of germs and dusts of sanitary hygiene. Facial masks have been used since the 1919 Spanish cold, when influenza was prevalent. Currently, facial masks are made of cotton, non-woven fabric, paper and the like.

Conventional facial masks prevent the cold air from being directly blown through the nasal cavity or oral cavity, so that it can prevent some of them from being caught in a cold. However, the size of the pores is much larger than that of microbes or bacteria having a size of 0.1 탆 to 1.0 탆 There is a limitation in blocking microbes such as bacteria and fine dusts.

On the other hand, a nanofiber refers to a microfiber having a diameter of only a few tens to a few hundred nanometers, and is produced by an electric field. That is, nanofibers generate electrical repulsive force inside the polymer material by applying a high voltage electric field to the polymer material, which is the raw material, and the nanofibers are manufactured and produced by breaking the molecules into a nano-sized yarn shape.

At this time, as the electric field becomes stronger, the polymer material as the raw material is finely torn, so that a nanofiber having a thinning of 10 to 1000 nm can be obtained.

In the conventional technology for spinning nanofibers, since it is limited to a small-scale working line focused on a laboratory, there is a demand for a technique of spinning nanofibers by dividing a spinning section and using a unit concept. Meanwhile, The spinning solution is electrospun on one side of the supplied substrate to form a nanomembrane to form a nanofiber. That is, the conventional electrospinning device comprises a bottom-up or top-down electrospinning device, and the spinning solution is electrospun on only the bottom surface or the top surface of the substrate supplied into the electrospinning device to form a nanomembrane by laminating the nanomembrane.

As described above, since the electrospinning device comprises the bottom-up electrospinning device or the top-down electrospinning device, the spinning solution is electrospun to the bottom surface or the top surface of the substrate supplied from the outside and transported in a predetermined direction, .

As shown in FIG. 1, the top-down electrospinning device of the bottom-up or top-down electrospinning device includes a spinning solution main tank 120 filled with a polymer spinning solution and a polymer spinning solution filled in the spinning solution main tank 120 A nozzle block 111 for discharging the polymer solution in the spinning liquid main tank and having a plurality of nozzles 111a arranged in a pin shape and a nozzle block 111a And a voltage generator 114 for generating a high voltage in the collector 113. The collector 113 is disposed at a predetermined distance from the nozzle 111a in order to collect the polymer spinning solution injected from the collector 113, Units 110 and 110 '.

In the method of manufacturing a nanomembrane through the electrospinning device 100, the polymer spinning solution filled in the spinning liquid main tank 120 is continuously and quantitatively supplied to the nozzle block 111 to which a high voltage is applied through the metering pump, The polymer spinning solution supplied to the nozzle block 111 is radiated and focused on the collector 113 to which a high voltage is applied on the base material 115 conveyed in the electrospinning device 100 through the nozzle 111a A nanomembrane is laminated.

At this time, in the electrospinning apparatus 100, the substrate 115 is conveyed by the conveyance belt 116a rotated between the conveyance rollers 116b.

When the nanomembrane prepared by electrospinning the polymer spinning solution through the electrospinning device as described above is applied to a filter material used in an industrial field, the basis weight of the entire nanomembrane used as the filter material must be constant and uniform, It is possible to produce and sell the products satisfactorily. According to the filter used in the gas turbine of the thermal power plant, depending on the direction of the air flow, the position of the air inflow portion, the direction of the air exhaust portion and the position of the exhaust portion, It is necessary that the basis weight of the nanomembrane constituting the filter membrane is not necessarily constant. On the other hand, in the filter section where air filtration is active, the basis weight of the nanomembrane must be controlled to improve the air filtering efficiency, Since the air flow rate is not so large, the basis weight of the nanomembrane is greatly adjusted There is a need for a design that is more durable than the air filtration side.

Disclosure of the Invention The present invention has been devised to solve the problems as described above, and it is an object of the present invention to provide a mask having an excellent blocking ability against micro foreign matter by including an epoxy resin-curing agent nanofiber between the substrates.

The present invention relates to a first substrate; A nanofiber layer formed by electrospinning a mixed solution containing an epoxy resin and a curing agent on the first base material; And a second substrate formed on the nano fiber layer.

Here, 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.

In addition, the mixed solution is electrospun through a temperature controller at a temperature of 50 to 100 ° C.

In addition, the viscosity of the mixed solution through the temperature controller is preferably adjusted 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 present invention provides a mask containing epoxy resin-curing agent nanofibers between the substrates to improve the durability and productivity of the mask production, and the nanofiber layer having fine pores can capture microorganisms such as bacteria and fine dusts It is possible to provide a mask having an excellent blocking ability against micro foreign matter.

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 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 front view of Fig. 17
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 are diagrams showing an operation process 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 apparatus according to the present invention (the nozzle indicated by the broken line in FIG. , And the nozzle indicated by the broken line in Fig. 21 is located at the lower portion of the substrate)
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 a nozzle body arranged in a nozzle block of the electrospinning apparatus according to the present invention,
FIG. 24 and FIG. 25 are plan views schematically showing still another embodiment according to an operation process of electrospinning the polymer spinning solution on the same plane of the base material through the nozzles of each nozzle tube of the electrospinning apparatus according to the present invention,
26 is a schematic view showing a mask including the epoxy resin-curing agent nanofiber of the present invention.

Hereinafter, the present invention will be described.

In this case, the mask is manufactured using an electrospinning apparatus.

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.

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, but are not limited to, 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 and includes, for example, 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-based 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) benzenesulfonic acid, 3- (linear or branched dodecyl) benzene sulfonic acid, p-toluene sulfonic acid, 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.

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

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

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

For this purpose, each of the units 10a and 10b is provided with a spinning liquid main tank 8 in which a polymer spinning solution is filled and a polymer spinning solution filled in the spinning solution main tank 8 in a predetermined amount A nozzle block 11 for discharging polymer flushing liquid filled in the spinning liquid main tank 8 and having a plurality of nozzles 12 arranged in a pin shape, And a voltage generator 14a, 14b for generating a voltage in the collector 13, the collector 13 being spaced apart from the nozzle 12 by a predetermined distance in order to accumulate the polymer spinning solution injected from the nozzle 13.

The electrospinning device 1 according to the present invention has a structure in which the polymeric spinning liquid filled in the spinning liquid main tank 8 is supplied to a plurality of nozzles 12 formed in the nozzle block 11 through the metering pump, And the supplied polymer spinning solution is radiated and focused on the collector 13 having a high voltage applied thereto through the nozzle 12 to form nanofibers on the long sheet 15 which is moved on the collector 13, And the formed nanofibers are made of a mask.

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

On the other hand, it is preferable that the elongated sheet 15, in which polymer solution is laminated while passing through each of the units 10a and 10b, is a substrate selected from a cellulose base material, a binary material base material, and a polyethylene terephthalate base material.

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

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

In this case, the material of the polymer spinning solution to be radiated through each unit 10a, 10b of the electrospinning device 1 is not limited, but in the present invention, a mixed solution containing an epoxy resin and a curing agent Is used.

The spinning solution supplied through the nozzles 12 in the units 10a and 10b is a solution in which a polymer as a synthetic resin material capable of electrospinning is dissolved in a suitable solvent, But are not limited to, for example, phenol, formic acid, sulfuric acid, m-cresol, thifluoroacetone hydride / dichloromethane, water, N-methylmorpholine N-oxide, chloroform, tetrahydrofuran And aliphatic ketone groups such as methyl isobutyl ketone, methyl ethyl ketone, aliphatic hydroxyl group m-butyl alcohol, isobutyl alcohol, isopropyl alcohol, methyl alcohol, ethanol, aliphatic compounds such as hexane, tetrachlorethylene, acetone, , Diethylene glycol, ethylene glycol, halogen compounds such as trichlorethylene, dichloromethane, aromatic compounds such as toluene, xylene, aliphatic Cyclohexanone and cyclohexane as ester group and n-butyl acetate, ethyl acetate, butyl cellosolve as aliphatic ether group, acetic acid 2-ethoxyethanol, 2-ethoxyethanol, amide dimethylformamide, Dimethylacetamide, and the like, or a mixture of plural kinds of solvents may be used. The spinning solution preferably contains an additive such as a conductivity improver.

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

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

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

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

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

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

17 to 25, a nozzle body 112 according to an embodiment of the present invention will be described.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

On the other hand, the electrospinning device 1 according to the present invention is provided with an overflow device 200. That is, each of the units 10a and 10b of the electrospinning device 1 is provided with a spinning liquid main tank 8, a second transfer pipe 216, a second transfer control device 218, an intermediate tank 220, And an overflow device 200 including a tank 230 are respectively provided.

Although the overflow device 200 is provided in each unit 10a and 10b of the electrospinning device 1 according to the embodiment of the present invention, any one of the units 10a and 10b, And the unit 10b located at the rear end of the overflow device 200 may be integrally connected to the overflow device 200. In this case,

According to the structure as described above, the spinning liquid main tank 8 stores spinning solution to be a raw material of the nanofibers. The spinning liquid main tank 8 is provided therein with an agitating device 211 for preventing separation or coagulation of the spinning solution.

The second transfer pipe 216 is composed of a pipe connected to the spinning liquid main tank 8 or the regeneration tank 230 and valves 212 213 and 214, The spinning liquid is transferred from the tank 230 to the intermediate tank 220.

The second conveyance control device 218 controls the conveyance operation of the second conveyance pipe 216 by controlling the valves 212, 213 and 214 of the second conveyance pipe 216. The valve 212 controls the transfer of the spinning liquid from the spinning liquid main tank 8 to the intermediate tank 220 and the valve 213 is used to transfer the spinning liquid from the regeneration tank 230 to the intermediate tank 220. [ . The valve 214 controls the amount of the polymer spinning solution flowing into the intermediate tank 220 from the spinning liquid main tank 8 and the regeneration tank 230.

The control method as described above is controlled according to the liquid surface height of the spinning liquid measured by the second sensor 222 provided in the intermediate tank 230 to be described later.

The intermediate tank 220 stores the spinning solution supplied from the spinning liquid main tank 8 or the regeneration tank 230 and supplies the spinning solution to the nozzle block 11 and adjusts the liquid surface height of the spinning solution And a second sensor 222 for measuring the temperature.

The second sensor 222 may be a sensor capable of measuring the liquid level height, and is preferably formed of, for example, an optical sensor or an infrared sensor.

A supply pipe 240 and a supply control valve 242 for supplying a spinning solution to the nozzle block 11 are provided in the lower part of the intermediate tank 220. The supply control valve 242 is connected to the supply pipe 240 And the like.

The regeneration tank 230 has an agitating device 231 therein for storing the recovered circulating fluid and preventing separation or coagulation of the circulating fluid, and a first sensor 231 for measuring the liquid level of the recovered circulating fluid, (Not shown).

The first sensor 232 may be a sensor capable of measuring the liquid level height, and is preferably formed of, for example, an optical sensor or an infrared sensor.

On the other hand, the spinning liquid overflowed in the nozzle block 11 is recovered through the spinning liquid recovery path 250 provided below the nozzle block 11. [ The spinning solution recovery path 250 recovers the spinning solution to the regeneration tank 230 through the first transfer pipe 251.

The first transfer pipe 251 is provided with a pipe and a pump connected to the regeneration tank 230 and the spinning liquid is transferred from the spinning liquid recovery path 250 to the regeneration tank 230 by the power of the pump .

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

When the number of the regeneration tanks 230 is two or more, a plurality of valves 233 located above the regeneration tank 230 are also provided, so that a first transfer control device (not shown) It is possible to control the two or more valves 233 located at the upper part in accordance with the height of the liquid level of the first sensor 232 to control whether the spinning liquid is to be transferred to one of the plurality of regeneration tanks 230 do.

Meanwhile, the VOC recycling apparatus 300 is provided in the electrospinning apparatus 1. That is, a condenser (not shown) for condensing and liquefying VOC (Volatile Organic Compounds) generated during spinning of the polymer spinning solution through the nozzles 12 to the units 10a and 10b of the electrospinning device 1, (320) for distilling and liquefying the condensed VOC through the condenser (310) and the condenser (310), and a solvent storage device (330) for storing the liquefied solvent through the distillation device A VOC recycling apparatus 300 is provided.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

4, the tubular body 40 of the nozzle block 11, which is provided in each of the units 10a and 10b and to which the polymer solution is supplied by the plurality of nozzles 12 provided on the unit, The temperature control device 60 is provided.

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

The polymer spinning solution supplied to each tube 40 is discharged and injected through a plurality of nozzles 12 and accumulated on the long sheet 15 in the form of nanofibers.

A plurality of nozzles 12 are mounted at predetermined intervals in the longitudinal direction on each of the tubes 40. The nozzles 12 and the tubes 40 are electrically connected to the tube 40 .

In order to control the temperature control of the polymer spinning solution supplied to and introduced into the tubes 40, the temperature controller 60 is connected to the heating wires 41 and 42 or pipes 43 ).

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

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

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

In the meantime, instead of maintaining the concentration at a constant level, the present invention uses the polymer solution having a high concentration to be reused after the overflow, and adjusts the viscosity of the polymer solution to be constant by using the temperature regulating device 60, And it is easy to form nanofibers of the polymer solution because of its high acidity at high temperature conditions for controlling high viscosity without using a diluent.

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

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

When fabricating the nanofiber with the electrospinning device 1, the type of the polymer and solvent used, the concentration of the polymer solution, the temperature and humidity of the spinning room, It is known to affect radioactivity. That is, the physical properties of the polymer (polymer solution) emitted from electrospinning are important. It has been considered that it is usually necessary to maintain the viscosity of the polymer at or below a predetermined viscosity at the time of electrospinning. This is because the higher viscosity means that the nano-sized fibers are not smoothly radiated through the nozzle, and the higher the viscosity, the more unsuitable for fiberization through electrospinning.

The present invention is characterized by including a temperature control device 60 for maintaining the fiber viscosity suitable for electrospinning as described above.

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

In the temperature in the electrospinning region, the temperature of the region where the electrospinning occurs (hereinafter, referred to as the 'radiating region') changes the surface tension of the spinning solution by changing the viscosity of the spinning solution, . &Lt; / RTI >

That is, when the temperature of the radiation region is relatively high, the nanofiber having a relatively small fiber diameter is produced when the viscosity of the solution is low, and the nanofiber having relatively large fiber diameter is produced when the viscosity of the solution is relatively high because the temperature is relatively low.

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

The concentration measuring device for measuring the concentration has a contact type and a non-contact type in direct contact with a solution, and a capillary type concentration measuring device and a disk (DISC) type concentration measuring device can be used as a contact type. A concentration measuring apparatus using a concentration measuring apparatus using infrared or the like can be used.

The heating device of the present invention may be an electric heater, a hot water circulating device, a hot air circulating device, or the like. In addition, devices capable of raising the temperature in the same range as the above devices may be borrowed.

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

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

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

The cooling device of the present invention may be a cooling device including a chilling device, and the means for maintaining a constant viscosity of the polymer solution is usually applicable. The cooling device may be provided in at least one of the nozzle block 110, the tank, and the overflow system 200 in the same manner as the heating device, and is used to maintain a certain viscosity of the polymer solution.

In addition, the temperature controller 60 of the present invention includes a sensor for measuring the concentration and a temperature control unit (not shown) for controlling the temperature accordingly.

The sensor is installed on the main storage tank 210, the intermediate tank 220, the regeneration tank 230, the nozzle block 110 or the overflow system 200 to measure the concentration of the flushing liquid in real time, The heating device and / or the cooling device is operated so that the viscosity is kept constant in the heating device 60.

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

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

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

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

In addition, the amount of the residual solvent of the nanofibers using electrospinning is lower than that of the conventional electrospinning, and thus it is possible to produce nanofibers of excellent quality.

The temperature control device 60 of the present invention controls the viscosity of the polymer solution through the temperature control of the nozzle block 110 or the main storage tank 210 by measuring the concentration of the intermediate tank 220 off- And an automatic system that can adjust the temperature of the solution according to the concentration measurement through an automatic control system on-line.

11, an auxiliary conveying device (not shown) for adjusting the conveying speed of the long sheet 15 to be drawn into and supplied into each unit 10a, 10b of the electrospinning device 1 according to the present invention 16 are provided.

The auxiliary conveying device 16 is provided for controlling the conveying speed of the long sheet 15 so as to facilitate detachment and conveyance of the long sheet 15 attached by the electrostatic attraction to the collector 13 provided in each unit 10a, An auxiliary belt 16a rotating synchronously and an auxiliary belt roller 16b supporting and rotating the auxiliary belt 16a.

The auxiliary belt 16a is rotated by the rotation of the auxiliary belt roller 16b by the above structure and the long sheet 15 is rotated by the rotation of the auxiliary belt 16a to the units 10a and 10b And one auxiliary belt roller 16b of the auxiliary belt roller 16b is rotatably connected to the motor for this purpose.

In the embodiment of the present invention, five auxiliary belt rollers 16b are provided on the auxiliary belt 16a, and one of the auxiliary belt rollers 16b is rotated by the operation of the motor to rotate the auxiliary belt 16a At the same time, the remaining auxiliary belt rollers 16b are rotated. However, the auxiliary belt 16a is provided with two or more auxiliary belt rollers 16b, and one of the auxiliary belt rollers 16b is rotated by the operation of the motor , So that the auxiliary belt 16a and the remaining auxiliary belt roller 16b are rotated.

Meanwhile, in the embodiment of the present invention, the auxiliary transfer device 16 is composed of the auxiliary belt roller 16b and the auxiliary belt 16a that can be driven by the 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 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 on which the nanofibers are laminated, and the time for the ultrasonic signals of the longitudinal wave and the transverse wave to reciprocate on the longitudinal sheet 15, Then, from a predetermined equation using propagation time of the measured longitudinal waves and transverse waves, propagation speed of longitudinal waves and transverse waves at the reference temperature of the elongated sheet 15 in which nanofibers are stacked, and temperature constants of longitudinal waves and transverse wave propagation velocities And a thickness measuring device using an ultrasonic longitudinal wave and a transverse wave to calculate the thickness of the object.

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

The thickness of the mask of the long sheet 15 to be transported after the polymer spinning solution is sprayed and laminated on the electrospinning device 1 according to the present invention is measured to determine the conveying speed of the long sheet 15 and the conveying speed of the nozzle block 11. [ The elongated sheet conveying speed regulating device 30 for regulating the conveying speed of the long sheet 15 is further provided on the electrospinning device 1. The thickness measuring device 70 controls the conveying speed of the long sheet 15,

The elongated sheet conveying speed regulator 30 includes a buffer zone 31 formed between each unit 10a and 10b of the electrospinning device 1 and a buffer zone 31 provided on the buffer zone 31, A pair of support rollers 33 and 33 'for supporting the support rollers 15 and an adjustment roller 35 provided between the pair of support rollers 33 and 33'.

At this time, the support rollers 33 and 33 'are provided in the longitudinal direction of the elongate sheet 15 when the elongate sheet 15, in which nanofibers are laminated by the spinning solution injected by the nozzles 12 in the respective units 10a and 10b, And is provided at a line and a rear end of a buffer zone 31 formed between the units 10a and 10b, respectively.

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

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

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

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

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

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

On the other hand, the electrospinning device 1 according to the present invention is provided with the air permeability measuring device 80. That is, an air permeability measuring device (not shown) for measuring the air permeability of the mask 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, (80).

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

When the air permeability of the mask or the mask discharged through the units 10a and 10b of the electrospinning device 1 is measured to be large, the conveyance speed V of the unit 10b positioned at the rear end is slowed down, The discharge amount of the 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 mask discharged through the units 10a and 10b of the electrospinning device 1 is measured to be small, the feeding speed V of the unit 10b positioned at the rear end is increased, The amount of the nanofibers per unit area is reduced to reduce the amount of lamination by decreasing the amount of discharge of the nanofibers 11 and adjusting the intensity of the voltage of the voltage generators 14a and 14b to thereby increase the air permeability.

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

Here, when the air permeability deviation P of the mask is less than the predetermined value, the feed speed V is not changed from the initial value, and when the deviation amount P is equal to or larger than the predetermined value, It is possible to 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.

On the other hand, in the lapping machine 100 located at the rear end of the electrospinning device 1 after the nanofibers are laminated through the units 10a and 10b of the electrospinning device 1, It is possible to manufacture the mask through the process of joining to one surface of the substrate on which the fibers are laminated and thermally fusing with the laminating apparatus 90. [

Hereinafter, a method of manufacturing a mask including the epoxy resin-curing agent nanofiber of the present invention using the electrospinning device will be described.

In the present invention, one unit 10a is used in the electrospinning apparatus, and a mixed solution containing an epoxy resin and a curing agent is used as the polymer.

First, a mixed solution obtained by dissolving the mixed solution in an organic solvent is supplied to a spinning liquid main tank 8 connected to the first unit 10a of the electrospinning device, and the mixed solution supplied to the spinning liquid main tank 8 Is supplied continuously and quantitatively to the plurality of nozzles 12 of the nozzle block 11 to which a high voltage is applied through a metering pump (not shown). The mixed solution supplied from each of the nozzles 12 is electrospun and converged on a collector 13 having a high voltage applied thereto through a nozzle 12 to form an epoxy resin-curing agent nanofiber. The nanofibers stacked in each unit 10a and 10b of the electrospinning device 1 are rotated by a feed roller 3 and a feed roller 3 driven by a motor Curing agent nanofibers are successively transferred onto the collector 13 while being transferred from the first unit 10a to the second unit 10b by rotation of the driving auxiliary transfer device 16 and repeating the above- Electrospinning and lamination.

In addition, two or more epoxy resin-curing agent nanofibers having different fiber diameters and having different numbers of units of the above-mentioned electrospinning device 1 and having different voltages for each unit are laminated on the collector 13 It is also possible to manufacture a mask.

In the first unit 10a, the epoxy resin-curing agent solution is electrospun on the collector 13 to form a laminate of the nanofiber layer of the epoxy resin-curing agent nanofiber, It is possible to manufacture a mask through a process in which another substrate is bonded to one surface of the substrate on which the epoxy resin-curing agent nanofibers are laminated and thermally fused in the laminating apparatus 90 .

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

Example 1

A spinning solution 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. The first unit of the electrospinning apparatus 40㎝ the distance between the spinning liquid and the collector electrode on the substrate, the voltage applied to the basis weight by electrospinning at 20kV, at a temperature of 70 ℃ 4g / m ² of an epoxy resin-curing agent nanofiber And another substrate was bonded to one surface of the epoxy resin-curing agent nanofiber to which the base material was not bonded and heat-sealed to prepare a mask.

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

1, 100: Electrospinning device 3: Feed roller
5: take-up roller 7: main control device
8: Fluid tank main tank
10a, 10b, 10c, 10d, 110, 110:
11, 11a, 11b, 111: nozzle block 12, 111a: nozzle
112, 112a, 112b, 112c, 112d, 112e, 112f, 112g, 112h, 112i:
13: collector
14, 14a, 14b, 14c, 14d and 114:
15, 15a, 15b, 115: long sheet 16: auxiliary conveying device
16a: auxiliary belt 16b: auxiliary belt roller
18: Case 19: Insulation member
30: Long sheet conveying speed adjusting device 31: Buffer section
33, 33 ': support roller 35: regulating roller
40: Tubular body 41, 42: Heat line
43: pipe 60: thermostat
70: Thickness measuring device 80: Air permeability measuring device
90: laminating device 200: overflow device
211, 231: stirring device 212, 213, 214, 233: valve
216: second transfer pipe 218: second transfer control device
220: intermediate tank 222: second sensor
230: regeneration tank 232: first sensor
240: Supply piping 242: Supply control valve
250: spinning liquid recovery path 251: first transfer piping
300: VOC recycling device 310: condensing device
311, 321, 331, 332: piping 320: distillation device
330: Solvent storage device 404: Nozzle for supplying air
405: nozzle plate 407: first spinning solution storage plate
408: second spinning solution storage plate 410: overflow solution temporary storage plate
411: air storage plate 412: overflow outlet
413: Air inlet 414: Nozzle support plate for air supply
415: Nozzle for Overflow Removal
416: nozzle overflow removing nozzle support plate 500: multiple tubular nozzle
501: Inner tube 502: Outer tube
503: tip portions 115a, 115b, 115c: nanofibers
116a: conveying belt 116b: conveying roller
120: spinning fluid main tank 120a: primary spinning fluid main tank
120b: Second spinning solution main tank 120c: Third spinning solution main tank
121: solution supply pipe 121a: first supply pipe
121b: second supply pipe 121c: third supply pipe
122: supply valve 125: nozzle supply pipe
126: Nozzle valve

Claims

A first substrate;
A nanofiber layer formed by electrospinning a mixed solution containing an epoxy resin and a curing agent on the first base material; And
And a second substrate formed on the nano fiber layer,
Wherein the nanofiber layer has a different basis weight along the longitudinal direction or the transverse direction.

The method according to claim 1,
Wherein the curing agent is one selected from the group consisting of an amine-based curing agent, an acid anhydride-based curing agent, and an imidazole-based curing agent.

The method according to claim 1,
Wherein the mixed solution is electrospun through a temperature controller at a temperature of 50 to 100 ° C.

The method of claim 3,
Wherein the viscosity of the mixed solution is adjusted to 1,000 to 3,000 cps through the temperature controller.

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