JP4915329B2 - Method and apparatus for producing nanofiber and polymer web - Google Patents

Description

  The present invention relates to a nanofiber and a polymer web manufacturing method and apparatus for manufacturing a polymer web in which a plurality of types of nanofibers having different physical properties are manufactured at once and mixed or laminated together. It is about.

  Conventionally, a charge-induced spinning method (electrospinning method) is known as a method for producing a nanofiber having a submicron-scale diameter made of a polymer material. In the conventional charge-induced spinning method, a polymer solution is supplied to a needle-like nozzle to which a high voltage is applied, whereby the polymer solution that flows out linearly from this needle-like nozzle is charged, and the polymer solution As the solvent evaporates, the distance between the charged charges decreases and the acting Coulomb force increases. When the Coulomb force exceeds the surface tension of the linear polymer solution, the linear polymer solution explodes. The phenomenon called electrostatic explosion is repeated as primary, secondary, and in some cases, tertiary, etc., so that nanofibers made of polymer with a submicron diameter are produced. is there.

  By depositing the nanofibers thus manufactured on an electrically grounded substrate, a three-dimensional thin film having a three-dimensional network can be obtained, and by forming it thicker, it has a submicron network. Highly porous polymeric webs can be produced. As a method for producing this polymer web, a high-voltage charged polymer solution is discharged from a plurality of nozzles arranged in parallel to produce nanofibers by charge-induced spinning, and the nanofibers are electrically grounded. A method of manufacturing by depositing on a moving sheet on a collected body is known (for example, see Patent Document 1).

  Further, it is known that high functionality can be provided by laminating and depositing fibers having different physical properties such as different fiber diameters to form a laminated web. For example, it is known that a laminated web obtained by laminating webs having different average fiber diameters can maintain a solid separation performance in a liquid or gas over a long period of time as compared with a single-layer web. It is also known that a gap formed in a nonwoven fabric composed of fibers having different fiber diameters is suitable when culturing the nonwoven fabric or the like. It is also known that a higher strength can be obtained with a non-woven fabric or yarn made of fibers having a uniform fiber diameter than those made of fibers having different fiber diameters.

  Then, as a method for producing a laminated web composed of nanofibers having different fiber diameters, fibers spun by an electrospinning method are directly deposited to form a first web, and then electrospinning is performed on the first web. A method of manufacturing a laminated web by directly depositing fibers having different fiber diameters from the first web spun by the method to form a second web is known (for example, see Patent Document 2).

  A configuration example of this type of laminated web manufacturing apparatus will be described with reference to FIG. 12. First and second spinning nozzles 62a and 62b are respectively provided in first and second spinning vessels 61a and 61b having one end openings. The polymer solution supply means 63a and 63b respectively supply polymer solutions having the same composition but different molecular weight or concentration to the spinning nozzles 62a and 62b, and high voltage generation means 64a, A high voltage generated at 64b is applied, the collector 65 is disposed in contact with the one end opening of the spinning containers 61a and 61b, and the first is placed on the carrier sheet 66 moving on the collector 65. The laminated web 68 is manufactured by sequentially depositing the nanofibers 67a generated by the spinning nozzle 62a and the nanofibers 67b generated by the second spinning nozzle 62b. Has been.

In the configuration of FIG. 12, it is necessary to prepare a plurality of polymer solutions by arranging a plurality of polymer solution supply means 63a and 63b. For this reason, there is a problem that the production efficiency is low. In Patent Document 2, the relative humidity in the first and second spinning containers 61a and 61b is changed by the first and second gas supply units, respectively. It is disclosed that a polymer solution having the same composition and concentration is supplied using different polymer solution supply means, and the viscosity of the polymer solution flowing out from the spinning nozzle is varied to generate nanofibers having different fiber diameters. ing.
US Pat. No. 6,713,011 JP-A-2005-213668

  By the way, the nanofibers 67a and 67b are respectively generated by the plurality of spinning nozzles 62a and 62b arranged in parallel as described above, and the generated nanofibers 67a and 67b are formed on the support sheet 66 moving on the collection body 65. In the method of manufacturing the laminated web 68 by sequentially depositing, since the nanofibers 67a and 67b generated at a high voltage applied to the spinning nozzles 62a and 62b are charged, an electric field between the collector 65 and the electric field is collected. While flowing toward the collecting body 65, the influence of the high voltage applied to the adjacent spinning nozzles 62a and 62b even if the spinning nozzles 62a and 62b are disposed in the respective spinning containers 61a and 61b. The nanofibers 67a and 67b generated by the spinning nozzles 62a and 62b are uniformly formed on the support sheet 66. Not laminated, there is a problem that it is impossible to manufacture a highly laminate web 68 quality.

  In order to solve such a problem, the present applicant, first, as shown in FIG. 13, the nanofiber generating unit 41 and the first and second nanofiber generating means 42a and 42b are separated by an appropriate distance. A drum-shaped collection body 43 that is configured to be arranged in parallel and can be driven to rotate at an appropriate distance from the nanofiber generation unit 41 is disposed, and nanofiber generation means on the outer peripheral surface of the collection body 43 42a and 42b are arranged in contact with or in close proximity to the portions facing each other, configured to move the collection body 43 and the support member 44 in synchronization, and between the nanofiber generator 41 and the collection body 43. In order to reliably isolate the electric field in the space between the nanofiber generating means 42a and 42b, an isolating means 45 adapted to apply an AC voltage from an AC power supply 47 to the partition plate 46 is provided. It has been proposed (see Japanese Patent Application No. 2007-171950).

  Each nanofiber generating means 42a, 42b is rotationally driven around an axis perpendicular to the collecting body 43 and the supporting member 44, and a cylindrical container 48 provided with a plurality of small holes 49 or nozzle members on the peripheral surface. The cylindrical electrode 48 is combined with the collector 43 in the axial direction in the axial direction of the cylindrical container 48 and the reflective electrode 50 arranged on one side opposite to the arrangement direction of the carrier sheet 44, and is radial from the cylindrical container 48 by centrifugal force and electrostatic explosion. The nanofibers 51 a and 51 b generated in the above are made to flow toward the collecting body 43 and the carrying sheet 44 by the reflective electrode 50. 52 is a rotation driving means for the cylindrical container 48, and 53 is a high voltage generating means for applying a high voltage to the cylindrical container 48. An electric field is formed in the space between the grounded collector 43. . By applying the nanofiber generating means 42a and 42b using a rotating container such as the cylindrical container 48 in this way, the polymer solution flows out from the small hole 49 or the nozzle member by centrifugal force and is stretched by centrifugal force. Even if a large number of small holes 49 and nozzle members are arranged in parallel, high-quality nanofibers are generated without receiving mutual interference of electric charges. Therefore, a large amount of nanofibers can be efficiently generated, and a high-quality laminated polymer web 54 is obtained. Productivity can be dramatically improved.

  However, even in the configuration as shown in FIG. 13, the nanofiber generating unit 41 is configured by arranging a plurality of nanofiber generating means 42 a and 42 b in parallel, and thus there is a problem that the configuration becomes large and complicated. There is also a problem that nanofibers having different physical properties cannot be produced in a uniformly mixed state.

  The present invention solves the above-described conventional problems, and can efficiently produce a plurality of types of nanofibers having different physical properties at a time with a simple apparatus configuration, and deposits them by mixing or laminating them. An object of the present invention is to provide a nanofiber and a polymer web production method and apparatus capable of producing a polymer web.

A method of manufacturing a nano fiber of the present invention, each of the plurality of rotating container which is integrally coupled to a plurality of small holes are formed and concentrically to the outer peripheral portion, of the composition together with dissolved polymer material in a solvent In the process of supplying different polymer solutions, rotating the rotating container and charging the polymer solution flowing out from the small hole with electric charge, the polymer solution flowing out from the small hole is subjected to electrostatic explosion due to centrifugal force and evaporation of the solvent. And a step of producing a nanofiber made of a polymer material by stretching. Here, the composition of the polymer solution is different when the polymer substance (chemical formula) itself is different, when the polymer substance is the same and its molecular weight is different, when the polymer substance and its molecular weight are the same and the solvent is different, This includes the case where the polymer substance and its molecular weight and solvent are the same but only the concentration is different.

  According to this configuration, polymer solutions having different compositions are supplied into a plurality of rotating containers, and the rotating containers are rotated at high speed around the axis by a single driving means, and the electric field is formed. As a result, polymer solutions having different compositions simultaneously flow out of the small holes by the action of centrifugal force, and are stretched explosively by the action of centrifugal force and electrostatic explosion. Multiple types of nanofibers with different physical properties (diameter, material, etc.) corresponding to each other (such as molecular weight and substance) can be generated at one time. It can be manufactured efficiently at one time.

  Further, the method for producing a polymer web of the present invention is a method in which the nanofibers produced by the above-described nanofiber production method are arranged at intervals with respect to the rotating container, and the charged charge of the polymer solution flowing out from the small holes. And depositing on a collector or a support member disposed thereon having a planar spread applied with a reverse polarity voltage or grounded.

  According to this configuration, a plurality of types of nanofibers having different physical properties generated as described above are deposited on a collection body having a planar spread or a support member disposed on the collection body. A polymer web composed of a plurality of types of nanofibers can be produced efficiently at once.

  In addition, a group of small holes having different diameters is arranged for each of different regions in the axial direction in one or a plurality of rotating containers, or polymer solutions having different compositions are supplied into the rotating containers, and the rotating containers are supplied to the rotating containers. When the collectors are arranged so as to face each other with a gap in the radial direction, and the generated nanofibers are sequentially deposited on the support member moving in the axial direction of the rotating container, the nanofibers having different physical properties are sequentially deposited. Since they are laminated and deposited, a laminated polymer web can be efficiently produced at once with a simple apparatus configuration.

  In addition, when a voltage having the same polarity as the charged charge of the polymer solution flowing out from the small hole is applied to the conductive reflective electrode disposed on the side opposite to the collecting body with respect to the rotating container, the shaft is rotated against the rotating container. Even if the collectors are arranged so as to face each other in the core direction or the radial direction, the nanofibers flowing in directions other than the direction facing the collectors can be reliably flowed toward the collectors. The polymer web or the laminated polymer web can be produced efficiently without waste.

  In addition, when a gas flow is formed from the side opposite to the collector side toward the collector side with respect to the rotating container, the nanofibers flowing in the radial direction from the rotating container are placed on the gas stream and reliably flow to the collector side. Can efficiently and efficiently produce polymer webs or laminated polymer webs, and can facilitate the evaporation of solvents in a gas stream, resulting in more effective electrostatic explosion. Thus, the production efficiency of nanofibers can be further improved.

Apparatus for producing a nano fiber of the present invention includes a rotating container unit in which a plurality of rotating containers and a plurality of small holes are formed in the outer periphery diameter of the small hole are different from each other are integrally coupled concentrically, each rotating container Rotation drive means for rotating the shaft around its axis, polymer solution supply means for supplying a polymer solution in which a polymer substance is dissolved in a solvent in each rotation container, and a space between the rotation container unit And a first high-voltage generating means for generating a potential difference between at least the vicinity of the small hole of each rotating container and the collector, and is as simple as the nanofiber manufacturing apparatus. It is possible to efficiently manufacture nanofibers having different physical properties at once with a simple apparatus configuration.

  Further, another nanofiber manufacturing apparatus of the present invention includes a rotating container unit in which a plurality of rotating containers having a plurality of small holes formed in the outer peripheral portion are concentrically integrated, and each rotating container around its axis. A rotation driving means for rotating the rotating container unit, a polymer solution supplying means for supplying polymer solutions having different compositions obtained by dissolving a polymer substance in a solvent in each rotating container, and a rotating container unit spaced apart from each other. And a first high-voltage generating means for generating a potential difference between at least the vicinity of the small hole of each rotating container and the collecting body. By the action, they are charged and discharged simultaneously from the small holes, and they are explosively stretched by the action of centrifugal force and electrostatic explosion, so that they correspond to each other corresponding to multiple compositions (concentration, molecular weight, substance, etc.) of the polymer solution. object Multiple types of nanofibers with different diameters, materials, etc. will be generated at the same time, and similarly, multiple types of nanofibers with different physical properties can be efficiently manufactured at once with a simple device configuration. .

  Also, the polymer web manufacturing apparatus of the present invention is the above-described one of the nanofiber manufacturing apparatuses, wherein the collecting body is made of a conductor spreading in a planar shape, and the support member on which the generated nanofibers are deposited is the collecting body. A plurality of types of nanofibers having different physical properties are deposited on a supporting member that moves on a collection body having a planar spread, thereby providing a plurality of types of nanofibers. A polymer web composed of fibers can be efficiently produced at once with a simple apparatus configuration.

  In addition, a group of small holes having different diameters is arranged for each of different regions in the axial direction of one or a plurality of rotating containers, and a collecting body is arranged so as to face the rotating containers at an interval in the radial direction. However, if the supporting member moving means moves the supporting member in the axial direction of the rotating container, nanofibers having different physical properties can be sequentially stacked and deposited on the supporting member because of the different diameters. A laminated polymer web can be efficiently produced at once with a simple apparatus configuration.

  Further, polymer solutions having different compositions are supplied into a plurality of rotating containers, a collecting body is disposed so as to face the rotating containers at a radial interval, and the supporting member moving means includes a supporting member. When moving in the axial direction of the rotating container, nanofibers with different physical properties can be sequentially stacked and deposited on the support member due to the different composition, and it is efficient at once with a simple device configuration. Laminated polymeric webs can be produced.

  In addition, a conductive reflective electrode is disposed on the opposite side of the rotating container from the collector, and a second high voltage is applied to the reflective electrode that has the same polarity as the charged charge of the polymer solution flowing out of the small hole. When the voltage generating means is provided, even if the collecting body is arranged at an interval so as to face the rotating container in the axial direction or the radial direction, the nano-flow that flows in a direction other than the direction facing the collecting body Since the fiber can be reliably flowed toward the collector by the reflective electrode, the polymer web or the laminated polymer web can be efficiently produced without waste.

  Further, when a gas flow generating means for generating a gas flow from the side opposite to the collector side to the collector side with respect to the rotating container is provided, the nanofibers flowing in the radial direction from the rotating container are put on the gas stream and placed on the collector side. Therefore, the polymer web or the laminated polymer web can be produced efficiently without waste, and the evaporation of the solvent can be promoted by the gas flow. The production efficiency of nanofibers can be further improved by more effectively producing them.

  According to the nanofiber and polymer web manufacturing method and apparatus of the present invention, a polymer solution is supplied to one or a plurality of rotating containers, and the rotating containers are rotated around the axis at high speed and an electric field is formed. Thus, polymer solutions from small holes with different diameters of the rotating container or polymer solutions with different compositions from the small holes of the rotating container flow out simultaneously by the action of centrifugal force and explode by the action of centrifugal force and electrostatic explosion. Can be produced efficiently at a time with a simple device configuration of a plurality of types of nanofibers having different physical properties corresponding to the diameter of a plurality of types of small holes or the composition of the polymer solution, Moreover, a desired polymer web can be manufactured by mixing or laminating these nanofibers and depositing them.

  Hereinafter, embodiments of the method and apparatus for producing nanofibers and polymer webs of the present invention will be described with reference to FIGS.

(First embodiment)
First, the manufacturing apparatus of the polymer web of the 1st Embodiment of this invention is demonstrated with reference to FIGS.

  1 to 3, reference numeral 1 denotes a rotating container made of a cylindrical container having a diameter of 20 to 500 mm, and a large number of small holes 2 having a diameter of about 0.02 to 2 mm are arranged on the outer periphery at intervals of several mm. In this embodiment, the small hole 2 is constituted by a nozzle hole of a short nozzle member provided integrally on the outer periphery of the rotating container 1 as shown in FIG. (The structure of the opening hole is illustrated in FIG. 2). In the present embodiment, the rotary container 1 is divided into two regions 3a and 3b in the axial direction, the small hole 2 in the region 3a is configured by a relatively large diameter small hole 2a, and the small hole 2 in the region 3b is relatively In particular, the small hole 2b has a small diameter, and the diameter of the small hole 2 varies depending on the regions 3a and 3b.

  The rotary container 1 is integrally provided with a hollow rotary shaft 4 at the axial center position thereof, and the hollow rotary shaft 4 protrudes from one end of the rotary container 1 so as to be on one side in the axial direction of the rotary container 1. A support frame 5 having an electrically insulating structure is rotatably supported via a bearing 6 and can be rotationally driven by a rotational drive means (not shown). The rotating speed of the rotating container 1 is applied to a speed range from several hundred rpm to over 10,000 rpm, and the rotating speed is adjusted by the diameter of the small hole 2 and the viscosity of the polymer solution 7.

  One end of the hollow rotating shaft 4 is connected to a solution supply pipe (not shown) constituting a polymer solution supply means for supplying a polymer solution 7 in which a polymer substance is dissolved in a solvent, or a solution supply pipe (see FIG. (Not shown) is inserted from one end. As shown in FIG. 2, an outflow opening 8 for supplying the internal polymer solution 7 evenly into the rotating container 1 is appropriately formed in a portion of the hollow rotating shaft 4 facing the space in the rotating container 1. Yes.

  Examples of the polymer substance constituting the polymer solution 7 include polypropylene, polyethylene, polystyrene, polyethylene oxide, polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, poly-m-phenylene terephthalate, poly-p-phenylene isophthalate, polyfluoride. Vinylidene fluoride, polyvinylidene fluoride-hexafluoropropylene copolymer, polyvinyl chloride, polyvinylidene chloride-acrylate copolymer, polyacrylonitrile, polyacrylonitrile-methacrylate copolymer, polycarbonate, polyarylate, polyester carbonate, nylon, aramid, Polycaprolactone, polylactic acid, polyglycolic acid, collagen, polyhydroxybutyric acid, polyvinyl acetate, polypeptide, etc. are suitable Examples thereof include biopolymers such as nucleic acids and proteins. At least one selected from these can be used, but is not particularly limited thereto.

  Examples of the solvent that can be used include methanol, ethanol, 1-propanol, 2-propanol, hexafluoroisopropanol, tetraethylene glycol, triethylene glycol, dibenzyl alcohol, 1,3-dioxolane, 1,4-dioxane, methyl ethyl ketone, Methyl isobutyl ketone, methyl n-hexyl ketone, methyl n-propyl ketone, diisopropyl ketone, diisobutyl ketone, acetone, hexafluoroacetone, phenol, formic acid, methyl formate, ethyl formate, propyl formate, methyl benzoate, ethyl benzoate , Propyl benzoate, methyl acetate, ethyl acetate, propyl acetate, dimethyl phthalate, diethyl phthalate, dipropyl phthalate, methyl chloride, ethyl chloride, methylene chloride, chloroform, o Chlorotoluene, p-chlorotoluene, carbon tetrachloride, 1,1-dichloroethane, 1,2-dichloroethane, trichloroethane, dichloropropane, dibromoethane, dibromopropane, methyl bromide, ethyl bromide, propyl bromide, acetic acid, benzene , Toluene, hexane, cyclohexane, cyclohexanone, cyclopentane, o-xylene, p-xylene, m-xylene, acetonitrile, tetrahydrofuran, N, N-dimethylformamide, pyridine, water, etc., and at least one selected from these Although used, it is not particularly limited to these.

  In addition, an inorganic solid material can be mixed in the polymer solution 7. Examples of the inorganic solid material include oxides, carbides, nitrides, borides, silicides, fluorides, sulfides, etc. From the viewpoint of heat resistance and workability, oxides are used. preferable. The oxides include Al2O3, SiO2, TiO2, Li2O, Na2O, MgO, CaO, SrO, BaO, B2O3, P2O5, SnO2, ZrO2, K2O, Cs2O, ZnO, Sb2O3, As2O3, CeO2, V2O3, Cr2O3, Cr2O3, Cr2O3 , CoO, NiO, Y 2 O 3, Lu 2 O 3, Yb 2 O 3, HfO 2, Nb 2 O 5 and the like can be exemplified, and at least one selected from these can be used, but is not particularly limited thereto.

  A high voltage is applied to the rotary container 1 from the first high voltage generating means 9 through the bearing 6 and the hollow rotary shaft 4. As the first high voltage generating means 9, one that generates a high voltage of 1 kV to 100 kV, preferably 5 kV to 100 kV is applied, and one having a switch 9a for switching on / off its output is preferably used. Applied. A flat plate-like collection body 10 made of a conductor is disposed opposite to the rotating container 1 in the radial direction and spaced apart by an appropriate distance. The collection body 10 is connected to the low voltage side of the first high voltage generation means 9 and is electrically grounded by the grounding means 11, and an electric field is formed in the space between the rotating container 1 and the collection body 10. It is comprised so that. The collector 10 may be connected to a high voltage generating means (not shown) having a polarity opposite to that of the first high voltage generating means 9 instead of grounding. Alternatively, a high voltage may be applied to the collection body 10 side to set the rotating container 1 side to the ground potential.

  A reflective electrode 12 is disposed across the entire width in the axial direction of the rotating container 1 so as to face the rotating container 1 in the radial direction on the opposite side of the collecting body 10. As shown in FIG. 2, the reflecting electrode 12 is configured as a parabolic reflecting surface so as to reflect the polymer solution 7 that has flowed radially from the rotating container 1 and the nanofibers 16 generated thereby toward the collector 10. It is arranged to do. A high voltage having the same polarity as the charged charges of the polymer solution 7 and the nanofibers 16 flowing out from the rotating container 1 generated by the second high voltage generating means (not shown) is applied to the reflective electrode 12. Is done. The second high voltage generating means (not shown) can share the first high voltage generating means 9. Further, the reflecting electrode 12 is not limited to the rectangular reflecting surface, and the nanofibers 16 that have flowed in the opposite direction from the collecting body 10 by centrifugal force from the small holes of the rotating container 1 are gathered on the collecting body 10 side. What is necessary is just to comprise.

  A carrying sheet 13 as a carrying member is disposed in contact with or close to the surface of the collecting body 10 facing the rotating container 1. In order to move the carrying sheet 13 in the axial direction of the rotating container 1, the carrying sheet supply means 14 is provided on the upper side of the collecting body 10 in the carrying sheet moving direction, and the carrying sheet collection means 15 is provided on the lower side. The carrying sheet supply means 14 and the carrying sheet collection means 15 constitute a carrying member moving means.

  In the above configuration, a high voltage is applied to the rotating container 1 by the first high voltage generating means 9 to generate an electric field between the rotating container 1 and the collecting body 10, and a high voltage is generated in the rotating container 1. When the molecular solution 7 is rotated by a rotation driving means (not shown) while the molecular solution 7 is supplied, the small holes 2 of the rotating container 1 are applied by centrifugal force while the polymer solution 7 in the rotating container 1 is charged. It flows out linearly from (2a, 2b) and is further stretched by the action of centrifugal force, and the distance between the charged charges is reduced as the solvent in the polymer solution 7 evaporates. When the Coulomb force increases and the Coulomb force exceeds the surface tension of the linear polymer solution 7, a phenomenon occurs in which the linear polymer solution 7 is stretched explosively, and this phenomenon is called electrostatic explosion. Is repeated as primary, secondary, and possibly tertiary etc. Nanofibers 16 (16a, 16b) made of polymeric material of the sub-micron diameter are generated.

  Here, since the diameters of the small holes 2a and 2b formed in the two regions 3a and 3b in the axial center direction of the rotating container 1 are different, they are generated by the polymer solution 7 flowing out from the small holes 2a and 2b, respectively. The diameters of the nanofibers 16a and 16b are different. Specifically, as shown in FIG. 4, when the diameter of the small hole 2 is 0.5 mm, the generated nanofiber 16 has an average fiber diameter of about 300 nm and the diameter of the small hole 2 is 1.0 mm. The diameter is about 400 nm on average, the diameter of the small hole 2 is 1.5 mm, the fiber diameter is about 560 nm on average, the diameter of the small hole 2 is about 2.0 mm, and the fiber diameter is about about 800 nm on average. By making it different, nanofibers 16 having different fiber diameters can be generated. At this time, the inner diameter of the rotating container 1 is 30 mm, the rotation speed is 3000 rpm, the polymer solution 7 is 10% of polyvinyl alcohol, and water is used as the remaining solvent.

  In this embodiment, the fiber diameter of the nanofiber 16a generated in the relatively large-diameter small hole 2a in the region 3a of the rotating container 1 is large, and the nanofiber generated in the relatively small-diameter small hole 2b in the region 3b. The fiber diameter of the fiber 16b is small. Thus, these nanofibers 16a and 16b flow toward the collection body 10 by the electric field between the rotating container 1 and the collection body 10 and the action of the reflective electrode 12, respectively, and as shown in FIG. The nanofibers 16a generated in the small holes 2a in the region 3a on the upper side in the moving direction of the first layer are first deposited on the support sheet 13 to form the polymer web 17a composed of the nanofibers 16a having a large fiber diameter. Then, the nanofibers 16b generated in the small holes 2b in the lower region 3b are deposited to form the polymer web 17b composed of the nanofibers 16b having a small fiber diameter. In this way, a laminated polymer web 18 in which polymer webs 17a and 17b having different physical properties are sequentially laminated on the support sheet 13 is manufactured.

  In the above description, the example in which the single rotating container 1 is divided into the plurality of regions 3a and 3b in the axial direction and the small holes 2 having different diameters are disposed, is shown. Instead of being divided into 3b, a rotating container unit in which a plurality of rotating containers are arranged concentrically in parallel and integrally joined together, and small holes 2 having different diameters are arranged in each rotating container may be used. good. In the above description, an example in which polymer webs 17a and 17b made of nanofibers 16a and 16b having different physical properties are laminated in two layers has been described. However, a laminated polymer web 18 having three or more layers may be manufactured. it can.

  The laminated polymer web 18 produced as described above is applied to filter materials and other various functional materials. For example, in the case of a mask that has been manufactured by stacking four types of materials and forming a single four-layer structure through molding and compression processes, four layers of nanofibers with the physical properties of each material are stacked. By using this laminated polymer web, the manufacturing process can be greatly reduced. In addition, even in a three-layer sportswear that uses a hydrophilic material as the inner layer, a heat insulating material as the intermediate layer, and a water repellent material as the outer layer, a laminated polymer web in which nanofibers with such physical properties are sequentially deposited The manufacturing process can be greatly reduced by using.

(Second Embodiment)
Next, the manufacturing apparatus of the polymeric web of the 2nd Embodiment of this invention is demonstrated with reference to FIGS. In the following description of the embodiment, the same components as those in the preceding embodiment are denoted by the same reference numerals, description thereof is omitted, and only differences will be mainly described.

  In the first embodiment, small holes 2a and 2b having different diameters are disposed in a plurality of regions 3a and 3b divided in the axial direction of the rotating container 1, and polymer webs 17a and 17b having different physical properties are sequentially stacked. Although the example which manufactures the laminated polymer web 18 made to show was shown, in this embodiment, as shown to FIG. 6 (a), (b), the large diameter small hole 2a and the small diameter are formed in the outer periphery of the rotation container 1. As shown in FIG. A plurality of small holes 2b are arranged in a row along the axial direction alternately in the circumferential direction. By applying such a rotating container 1 to the polymer web manufacturing apparatus shown in FIG. 1, a plurality of types of nanofibers 16a and 16b having different fiber diameters and different physical properties are uniformly mixed. Single layer polymeric webs can be produced.

  In the example of FIG. 6, the small diameter small holes 2a and the small diameter small holes 2b are arranged so as to be alternately located in the circumferential direction and at the same position with a predetermined interval in the axial direction. However, as shown in FIG. 7, the arrangement positions of the small holes 2a and 2b in the axial direction may be shifted from each other so as to be positioned in the middle of the counterpart side. Further, as shown in FIG. 8, the small-diameter small holes 2a and the small-diameter small holes 2b are alternately arranged in the circumferential direction, and the small holes 2a and 2b are arranged so as to be spirally arranged on the outer periphery of the rotating container 1, respectively. Also good. In this way, the large-diameter small hole 2a and the small-diameter small hole 2b can be arranged based on an arbitrary arrangement rule other than these.

(Third embodiment)
Next, the manufacturing apparatus of the polymer web of the 3rd Embodiment of this invention is demonstrated with reference to FIGS.

  In the first embodiment, the polymer solution 7 is supplied into the single rotating container 1, and the nanofibers 16a and 16b having different physical properties are generated from the small holes 2a and 2b having different diameters formed in the rotating container 1. In this embodiment, as shown in FIGS. 9 and 10, in the present embodiment, a plurality of rotating containers 21a and 21b are arranged concentrically in parallel, and the composition of the rotating containers 21a and 21b is set. Different polymer solutions 7a and 7b are supplied to generate nanofibers 16a and 16b having different physical properties.

  The plurality of rotating containers 21 a and 21 b are integrally coupled by a concentric hollow rotating shaft 4 to form a rotating container unit, and these rotating containers 21 a are passed through solution supply pipes 22 a and 22 b inserted through the hollow rotating shaft 4. , 21b are supplied with polymer solutions 7a and 7b having different compositions. The hollow rotary shaft 4 is rotatably supported by the support frame 5 via the bearing 6, and is driven by a drive motor 23 a, a drive pulley 23 b fixed to the output shaft thereof, and a follower fixed to the hollow rotary shaft 4. It is configured to be rotationally driven by a rotational drive means 23 comprising a pulley 23c, a belt 23d wound around a drive pulley 23b and a driven pulley 23c.

  Further, in the present embodiment, the collecting body 10 is disposed at an appropriate distance on the other side in the axial center direction of the rotating containers 21a and 21b, that is, on the side opposite to the support frame 5, and the rotating containers 21a and 21b. A fan 25 that forms a gas flow 24 toward the collection body 10 through the space around the rotary containers 21a and 21b is disposed on one side in the axial direction. It is preferable that the gas flow 24 is warm air because the solvent of the polymer solutions 7a and 7b can be evaporated more efficiently and the nanofibers 16a and 16b are efficiently generated.

  In the above configuration, polymer solutions 7a and 7b having different compositions are supplied into the respective rotating containers 21a and 21b, and the rotating containers 21a and 21b are rotated by the rotation driving means 23, whereby the rotating containers 21a and 21b are rotated. As described above, nanofibers 16a and 16b made of polymer substances having different physical properties are efficiently generated in the polymer solutions 7a and 7b flowing out from the substrate. The generated nanofibers 16a and 16b are respectively located on one side in the axial direction of the rotary containers 21a and 21b by the electric field between the rotary containers 21a and 21b and the collector 10 and the gas flow 24 formed by the fan 25. A polymer web is produced that flows while being uniformly mixed with each other toward the collection body 10, deposited on the collection body 10, and nanofibers 16 a and 16 b having different physical properties are uniformly mixed and deposited on the collection body 10. Is done.

  In the configuration shown in FIGS. 9 and 10, a gas flow 24 is generated as a means for promoting the flow of the generated nanofibers 16 a and 16 b toward the collector 10 on the other side in the axial direction of the rotating containers 21 a and 21 b. Although the fan 25 is provided, as shown in FIG. 11, the reflective electrode 26 is provided on the opposite side of the collector 10 in the axial direction of the rotating containers 21a and 21b instead of the fan 25 or in combination with the fan 25. A high voltage having the same polarity as the charged charges of the polymer solutions 7a and 7b flowing out from the small holes 2 of the rotating containers 21a and 21b is applied to the reflecting electrode 26 by the second high voltage generating means 27. In this case, the nanofibers 16a and 16b can be reliably made to flow toward the collector 10 by the reflective electrode 26, so that the polymer web can be efficiently produced without waste. Rukoto can.

  Note that the second high voltage generating means 27 may be shared by the first high voltage generating means 9. In FIG. 11, 28a and 28b are containers for containing the polymer solutions 7a and 7b, 29a and 29b are supply pumps, and these containers 28a and 28b, supply pumps 29a and 29b, and solution supply pipes 22a and 22b are connected to each other. Thus, polymer solution supply means 30a and 30b are configured.

  In the above description, an example in which the diameters of the small holes 2 formed on the outer circumferences of the rotary containers 21a and 21b are the same is shown. However, the small holes 2a having different diameters are formed in the rotary containers 21a and 21b as in the first embodiment. 2b is formed and combined with polymer solutions 7a and 7b having different compositions to produce a polymer web on which nanofibers 16a and 16b having different physical properties are different in both composition and fiber diameter. You can also.

Further, the nanofibers 16a and 16b generated in the rotating containers 21a and 21b are caused to flow to the other side in the axial direction of the rotating containers 21a and 21b, and the nanofibers 16a and 16b are uniformly mixed and deposited on the collecting body 10. In the example shown in FIG. 1, the collection body 10 is disposed so as to face the rotating containers 21a and 21b in the radial direction in the same manner as in the first embodiment, and the rotating container 21a is disposed on the collection body 10. The laminated polymer web 18 may be manufactured by sequentially laminating polymer webs 17a and 17b having different physical properties on the support sheet 13 that moves in the axial direction of 21b.
In each of the above embodiments, a configuration in which a high voltage is applied to the rotating container 1 or 21a, 21b by the first high voltage generating unit 9 and the collector 10 is grounded is illustrated. The high voltage generating means 3 may apply a positive or negative high voltage and the rotating container 1 or 21a, 21b may be grounded, or a high voltage having a reverse polarity may be applied.

  According to the method and apparatus for producing nanofibers and polymer webs of the present invention, a plurality of types of nanofibers having different physical properties corresponding to the diameters of the plurality of types of small holes or the composition of the polymer solution can be obtained with a simple apparatus configuration. It can be produced efficiently at a time, and a desired polymer web can be produced by mixing or laminating and depositing these nanofibers. It can utilize suitably for manufacture of the various functional web laminated | stacked combining the nanofiber of various physical properties.

The front view which shows the principal part schematic structure of the manufacturing apparatus of the polymer web of the 1st Embodiment of this invention. AA arrow sectional drawing of FIG. The front view of the rotation container of the embodiment. The graph which shows the relationship between the diameter of the small hole of a rotation container, and the fiber diameter of nanofiber. Sectional drawing of the laminated polymer web manufactured in the embodiment. The rotation container in the manufacturing apparatus of the polymeric web of the 2nd Embodiment of this invention is shown, (a) is a front view, (b) is BB arrow sectional drawing of (a). The front view which shows the other structural example of the rotation container in the embodiment. The front view which shows another structural example of the rotation container in the same embodiment. The perspective view which shows the principal part schematic structure of the manufacturing apparatus of the polymer web of the 3rd Embodiment of this invention. The perspective view which shows the production | generation state of the nanofiber in the embodiment. The longitudinal cross-sectional front view which shows the modification structural example of the manufacturing apparatus of the polymer web of the embodiment. The front view which shows schematic structure of the manufacturing apparatus of the laminated polymer web of a prior art example. The perspective view which shows the principal part structure of the manufacturing apparatus of the polymeric web prior to this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Rotating container 2, 2a, 2b Small hole 3a, 3b Area | region 7, 7a, 7b Polymer solution 9 1st high voltage generation means 10 Collecting body 12 Reflecting electrode 13 Supporting sheet (supporting member)
14 Supporting sheet supply means (supporting member moving means)
15 Supporting sheet winding means (supporting member moving means)
16, 16a, 16b Nanofiber 17, 17a, 17b Polymer web 18 Laminated polymer web 21a, 21b Rotating container 22a, 22b Solution supply pipe (polymer solution supply means)
23 Rotation drive means 24 Gas flow 25 Gas flow generation means 26 Reflective electrode 27 Second high voltage generation means 30a, 30b Polymer solution supply means

Claims (12)

  Supplying a polymer solution having a different composition in which a polymer substance is dissolved in a solvent, respectively, into a plurality of rotating containers in which a plurality of small holes are formed in the outer peripheral portion and are concentrically integrated; The polymer solution that rotates and flows out of the small hole is charged with electric charge, and the polymer solution that flows out of the small hole is stretched by electrostatic explosion caused by centrifugal force and evaporation of the solvent to generate nanofibers composed of the polymer substance. And a process for producing nanofibers. The nanofibers produced by the method for producing nanofibers according to claim 1 are arranged at an interval with respect to the rotating container, and a voltage having a polarity opposite to the charged charge of the polymer solution flowing out from the small holes is applied. Or depositing on a grounded surface-collecting body or a support member disposed thereon. A group of small holes having different diameters is arranged for each of different regions in the axial direction in one or a plurality of rotating containers, or polymer solutions having different compositions are supplied into the rotating containers, The collectors are arranged so as to face each other with a gap in the radial direction, and the produced nanofibers are sequentially deposited on a support member moving in the axial direction of the rotating container to produce a laminated polymer web. The method for producing a polymer web according to claim 2 . Relative rotating container, the collecting body to the reflective electrode of the conductive placed on the opposite side, the charge of the polymer solution discharged from the small holes according to claim 2 or, characterized in that a voltage of the same polarity 3. The method for producing a polymer web according to 3 . The method for producing a polymer web according to any one of claims 2 to 4 , wherein a gas flow is formed from the side opposite to the collector side toward the collector side with respect to the rotating container.   A rotating container unit in which a plurality of rotating containers having a plurality of small holes formed in the outer peripheral portion and the diameters of the small holes being different from each other are concentrically integrated, and rotation driving means for rotating each rotating container around its axis A polymer solution supply means for supplying a polymer solution in which a polymer substance is dissolved in a solvent in each rotating container, a collector disposed at an interval with respect to the rotating container unit, and each rotating container An apparatus for producing nanofiber, comprising: a first high voltage generating means for generating a potential difference at least between the vicinity of the small hole and the collector.   A rotating container unit in which a plurality of rotating containers each having a plurality of small holes formed on the outer periphery are concentrically integrated, a rotation driving means for rotating each rotating container around its axis, and a height in each rotating container Polymer solution supply means for supplying polymer solutions having different compositions in which molecular substances are dissolved in a solvent, a collection body disposed at a distance from the rotating container unit, and at least near the small holes of each rotating container An apparatus for producing nanofibers, comprising: a first high voltage generating means for generating a potential difference with a collector. 8. The nanofiber manufacturing apparatus according to claim 6 or 7 , further comprising a support member moving means for moving the support member for depositing the generated nanofiber along the collection body, the collector being made of a conductor spreading in a planar shape. A polymer web manufacturing apparatus characterized by the above. Disposing a group of small holes having different diameters for each of different regions in the axial direction in one or a plurality of rotating containers, and disposing a collection body so as to face the rotating containers at an interval in the radial direction; 9. The apparatus for producing a polymer web according to claim 8, wherein the supporting member moving means moves the supporting member in the axial direction of the rotating container. A plurality of polymer solutions having different compositions are supplied into a plurality of rotating containers, and a collecting body is disposed so as to face the rotating containers at an interval in the radial direction. The apparatus for producing a polymer web according to claim 8, wherein the apparatus moves in the axial direction. A second high-voltage generation in which a conductive reflective electrode is disposed on the opposite side of the collecting body with respect to the rotating container, and a voltage having the same polarity as the charged charge of the polymer solution flowing out from the small hole is applied to the reflective electrode. The apparatus for producing a polymer web according to any one of claims 8 to 10 , further comprising means. The polymer web according to any one of claims 8 to 11 , further comprising gas flow generating means for generating a gas flow from the side opposite to the collector side to the collector side with respect to the rotating container. Manufacturing equipment.