JP5135638B2 - Nanofiber compounding method and apparatus - Google Patents

Description

  The present invention relates to a nanofiber combination method and apparatus for producing nanofibers made of a polymer material and using them as yarns.

  Conventionally, a charge-induced spinning method (also referred to as an 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, and the charge is charged to the polymer solution that flows out linearly from the needle-like nozzle. As the solvent in the charged linear polymer solution evaporates, the distance between the charged charges is reduced, the Coulomb force acting between the charged charges is increased, and the Coulomb force is linear polymer solution. The phenomenon that the linear polymer solution is stretched explosively at the time of surpassing the surface tension of this, the phenomenon called this electrostatic explosion is repeated as primary, secondary, and in some cases tertiary, Nanofibers made of macromolecules of submicron diameter are produced.

  In the conventional charge induction spinning method, only one to several nanofibers are produced from the tip of one nozzle, and thus there is a problem that productivity does not increase. Therefore, as a method for producing a large amount of nanofibers, a method using a plurality of nozzles has been proposed (see, for example, Patent Document 1). In this Patent Document 1, a polymer solution stored in a barrel is supplied to a number of needle-shaped nozzles charged by a pump and discharged to create a large amount of nanofibers, which have a different polarity from the nozzles. A technique for producing a highly porous polymer web having a very high porosity in which nanofibers are laminated in a three-dimensional network structure is disclosed by collecting and transporting them with a charged collector. Increased from an experimental level to a practical level.

Conventionally, nanofibers produced by the charge-induced spinning method have been manufactured as webs, and have been used in various ways such as artificial leather, filters, diapers, sanitary napkins, adhesive spinning agents, wiping cloths, artificial blood vessels, and bone fixation devices. It is difficult to obtain mechanical properties of 10 MPa or more, and there is a limit to the use in a wide range of applications. When trying to improve the mechanical properties by making the nanofiber web manufactured in this way into continuous yarns, It was pointed out that there was a problem that a short fiber was cut by cutting to a certain length and a separate spinning process was required to produce spun yarn from this short fiber. A technique for continuously producing yarn using a fiber web has been proposed (see, for example, Patent Document 2). In this Patent Document 2, nanofibers are spun on a static surface of water or an organic solvent in a collector charged in a polarity opposite to that of the nozzle from the nozzles charged in a row and deposited in a web. The web to be deposited is pulled up by a rotating roller rotating at a constant linear velocity from a point 1 cm or more away from one end side viewed in the row direction of the nozzles to form a continuous yarn, which is pressed, stretched, dried and wound. A continuous yarn is obtained by taking off. In addition, continuous yarn can be twisted.
JP 2002-201559 A JP-T-2006-507428

  However, the technique described in Patent Document 2 is generated from each nozzle due to the spread of the deposition area while generating nanofibers directly from each nozzle and statically depositing them at a position corresponding to the nozzle on the collector. Nanofibers are entangled with each other to form a narrow web, and the nanofibers are pulled out from one end of the web, and the continuous nanofibers are pulled out to the other end of the web and focused on a continuous yarn. Therefore, while the deposition of nanofibers spun from each nozzle is static and almost equivalent, the deposition is close to the pulling side because the pulling action tends to concentrate in the deposition area close to the pulling side. There may be a difference in the extraction amount of the nanofiber between the deposition area and the distant deposition area. There is a problem that a non stable difficult to properly control the thickness and mechanical properties of continuous yarn by being drawn in a state that caused the difference in. Further, there is a problem that it is necessary to suppress the drawing speed to make the drawing action evenly extend to the deposition area far from the drawing side, and it is difficult to manufacture in large quantities.

  In order to solve such problems, a nanofiber spinning device 51 as shown in FIG. 8 has been considered. In FIG. 8, the nanofiber spinning device 51 includes nanofiber generating means 52, a collecting electrode 53, a core yarn supplying means 54, and a collecting means 55. The nanofiber generating means 52 is supported so as to be rotatable around a vertical axis and has a cylindrical container 56 in which a large number of small holes 57 are formed on the peripheral surface, and a polymer solution supply for supplying the polymer solution into the cylindrical container 56. Means (not shown), first high voltage generating means 58 for applying a high voltage to the cylindrical container 56, rotational drive means (not shown) for rotationally driving the cylindrical container 56 in the direction of arrow a, and cylindrical container A reflective electrode 59 disposed on the upper part of the cylindrical container 56 and a second high voltage generating means 60 for applying a high voltage of the same polarity as the cylindrical container 56 to the reflective electrode 59, and flows out from the small hole 57 of the cylindrical container 56. The polymer solution is stretched by centrifugal force and electrostatic explosion to generate nanofibers 61, and the generated nanofibers 61 are made to flow while swirling toward the lower side of the cylindrical container 56 by the reflective electrode 59. Has been.

  The collecting electrode 53 has a disk shape, is coaxially and rotatably disposed below the cylindrical container 56, and has a through hole 62 through which the nanofiber 61 converged at the center thereof passes. The third high voltage generating means 63 is configured to apply a high voltage having a polarity opposite to that of the cylindrical container 56 and the reflective electrode 59, and the collection electrode 53 is moved to the arrow by the rotation driving means (not shown). It is configured to be driven to rotate in the direction of arrow b opposite to the direction a. The core yarn supplying means 54 is disposed above the nanofiber generating means 52, and is configured to feed the core yarn 64 and supply it downward from directly above the axial center position of the cylindrical container 56. The collecting means 55 is a collecting electrode. The yarn 65 disposed below the wire 53 and twisted and converged is passed through the through-hole 62 of the collecting electrode 53 and collected.

  In the above configuration, when the cylindrical container 56 is rotationally driven at high speed while supplying the polymer solution into the cylindrical container 56 of the nanofiber generating means 52, centrifugal force is applied to the charged polymer solution in the cylindrical container 56. Acting, flowing out from each small hole 57 and being stretched by the action of centrifugal force to produce a thin polymer linear body, and further being explosively stretched by electrostatic explosion from primary to tertiary, etc. The nanofibers 61 that are efficiently manufactured and generated flow while turning around the axis of the cylindrical container 56 toward the lower side of the cylindrical container 56 at the reflective electrode 59. Further, the nanofiber 61 that has flowed downward while swirling is strongly sucked toward the collection electrode 53 disposed below, and the collection electrode 53 is in a direction opposite to the swirl flow direction of the nanofiber 61. , The nanofibers 61 that are swirling and flowing are more strongly twisted, converged and combined, and a high-strength yarn 65 is efficiently formed. The formed yarn 65 passes through the through hole 62 at the center of the collecting electrode 53 and is collected by the collecting means 55 (see Japanese Patent Application No. 2007-141907).

  However, in the configuration as shown in FIG. 8, the flat collecting electrode 53 having a large area is disposed so as to face the nanofiber generating means 52, so that it occurs between the nanofiber generating means 52 and the collecting electrode 53. The electric lines of force are formed so as to spread over the entire surface of the collecting electrode 53, and the position where the nanofibers 61 are wound around the core yarn 64 is not constant because the nanofibers 61 flow along the electric lines of force. It has been found that there is a problem that the thickness of the yarn 65 to be generated is not constant, and the thickness of the yarn 65 varies.

  Therefore, the generated nanofibers have a potential difference with respect to the charged nanofibers, have a through hole in the shaft core, and have a maximum outer diameter of 1/10 or less of the distance from the spinning head. Electric force that is twisted by swirling and concentrating while sucking in, collecting the twisted nanofibers through the through hole of the collecting electrode, and converging from the spinning head around the axial core of the collecting electrode A stable line is formed, and all the nanofibers that swirl and flow are caused to flow along the lines of electric force to be stably focused on the axial core of the collecting electrode, so that there is no variation in thickness. A method has been proposed in which stable yarns are combined with good productivity at low cost (see Japanese Patent Application No. 2007-234762).

  However, even in such a spinning method, even if the generated nanofibers flow toward the collecting electrode having a maximum outer diameter of 1/10 or less of the distance to the spinning head, Since the focusing point is not stable due to the continuous surface or line, the focusing state of the nanofibers becomes unstable and the entanglement of the core yarn varies and the homogeneous yarn is stabilized. As a result, it has been found that there is a problem that it cannot be produced with high productivity.

  SUMMARY OF THE INVENTION The present invention solves the above-mentioned conventional problems, and combines nanofibers capable of stably producing high-strength and homogeneous yarns composed of nanofibers produced by a charge-induced spinning method with high productivity. It is an object to provide a method and apparatus.

The nanofiber compounding method of the present invention includes a core yarn supplying step of supplying a core yarn to a predetermined core yarn moving path, and a raw material solution flowing out from at least one small hole arranged around the core yarn moving path. A nanofiber generation process in which a raw material solution is charged with electric charges and stretched by electrostatic explosion to generate nanofibers, and a nanofiber charged on a collecting electrode in which a plurality of convex portions are arranged around the core yarn movement path An electric field is formed so as to be directed, and the small hole and the collecting electrode are rotated relative to each other around the core yarn moving path, and the nanofiber is entangled with the core yarn, and the nanofiber is entangled with the core yarn. possess a recovery step of recovering the yarn, in the recovery process, the core yarn travel path which is formed in an axial core portion of the collecting electrode is to suction through the through-holes penetrating.

  The raw material solution includes various synthetic resin materials and high-molecular substances such as biopolymers such as nucleic acids and proteins (in the present invention, not only general high-molecular substances having a molecular weight of 10,000 or more, but a molecular weight of 1000 to A solution in which a quasi-polymer substance of 10,000 is also dissolved in a solvent is preferably applied. The polymer substance is not limited to a single substance, and may be a mixture of various polymer substances. Furthermore, it is also possible to mix an inorganic solid material into the raw material solution.

  According to the above configuration, the raw material solution is charged and flows out from the small hole around the supplied core yarn, and electrostatic explosion occurs to generate the nanofiber. The generated nanofiber is between the small hole and the collecting electrode. In addition to flowing toward the collection electrode by the electric field formed in the electrode, the converging points of the flowing nanofibers are concentrated on these projections due to the provision of multiple projections on the collection electrode, and small holes and collection Since the electrode and the electrode are relatively rotated around the core yarn movement path, the nanofibers stably focused toward the plurality of convex portions are entangled evenly around the entire circumference of the core yarn, and the core yarn is nano-wired. Since the yarns in which the fibers are evenly entangled can be combined, by collecting the yarns, a high-strength and homogeneous yarn composed of nanofibers can be stably produced with high productivity.

  In addition, if the small hole is rotated around the core yarn movement path in the nanofiber generation process and the collecting electrode is rotated in the opposite direction to the small hole in the synthesizing process, the nanofiber is tightly wound around the core thread and becomes more entangled. High core yarn can be combined.

  In the recovery step, when suction is performed through the through-hole through which the core yarn movement path formed in the shaft core portion of the collection electrode penetrates, the nanofibers are drawn toward the shaft core of the collection electrode also by the suction airflow passing through the through-hole. A higher-strength yarn in which nanofibers are more entangled with the core yarn can be combined, and can be recovered as it is through the through hole.

Further, the nanofiber combination device of the present invention includes a core yarn supplying means for supplying the core yarn to a predetermined core yarn movement path, and at least one small hole arranged around the core yarn movement path to allow the raw material solution to flow out. The nanofiber generating means for charging the flowing raw material solution with electric charge and stretching it by electrostatic explosion to generate nanofibers, and a voltage having a polarity opposite to the charged charge of the raw material solution is applied or grounded , relatively a collecting electrode in which a plurality of protrusions around the core yarn travel path of the opposing surfaces are arranged in the nanofiber generating means, the eyelet and collecting electrode of Nanofa Lee bar generating means around the core yarn travel path A rotating means for rotating; a collecting means for collecting a yarn in which nanofibers are entangled with a core thread; and a suction means for sucking through a through-hole through which the core yarn moving path formed in the shaft core portion of the collecting electrode passes. Preparation Those were.

  According to this configuration, the core yarn is supplied by the core yarn supplying means, and the raw material solution is charged and discharged from the small hole around the core yarn by the nanofiber generating means, thereby generating an electrostatic explosion and generating nanofibers. The generated nanofibers flow toward a collecting electrode to which a voltage having a polarity opposite to that of the charged electric charge is applied or are grounded, and flow due to a plurality of convex portions provided on the collecting electrode. The focusing points of the nanofibers are concentrated on these convex parts, and the small holes and the collecting electrode are rotated relative to each other around the core yarn movement path by the rotating means, so that they are stable toward the plural convex parts. The nanofibers that are gathered together are evenly entangled around the entire circumference of the core yarn, and the yarn in which the nanofibers are evenly entangled with the core yarn is combined. High strength and level The can be produced stably with good productivity such yarn.

  The rotating means preferably includes at least a small hole rotating means for rotating the small hole around the core yarn moving path or an electrode rotating means for rotating the collecting electrode around the core yarn moving path.

  In addition, the rotating means includes both the small hole rotating means and the electrode rotating means, and when both rotating means have opposite rotation directions, the collecting electrode and the small holes rotate in the opposite directions, so that the nanofibers are core yarns. Therefore, it is preferable that a core yarn having higher strength can be combined.

  In addition, when a suction means for sucking through the through hole through which the core yarn moving path formed in the axial core portion of the collecting electrode passes, a suction air flow is formed through the through hole by sucking through the through hole. Also suitable for the field where the nanofibers are drawn towards the axial center of the collecting electrode, and a higher-strength yarn in which the nanofibers are more strongly entangled with the core yarn can be combined and recovered through the through hole. is there.

  According to the nanofiber combination method and apparatus of the present invention, the nanofiber generated by electrostatic explosion of the raw material solution flowing out from the small hole around the core yarn flows toward the collection electrode, and is applied to the collection electrode. The convergence point of the nanofiber that flows due to the provision of multiple convex portions concentrates on these convex portions, and the small holes and the collection electrode rotate relatively around the core yarn movement path. , Nanofibers that are stably focused toward multiple protrusions are entangled evenly around the entire circumference of the core yarn, so that high-strength and homogeneous yarns composed of nanofibers can be stably produced Can be manufactured well.

  Hereinafter, embodiments of the nanofiber combination method and apparatus of the present invention will be described with reference to FIGS.

(First embodiment)
First, a first embodiment of the nanofiber spinning device of the present invention will be described with reference to FIGS.

  In FIG. 1, reference numeral 1 denotes a nanofiber spinning device, and an electric field is provided between a spinning head 3 that flows out the raw material solution of the nanofiber 2 linearly and a spinning head 3 that is disposed around the spinning head 3. A nanofiber generating means 5 comprising an electric field generating electrode 4 for generating A collecting electrode 6 for collecting the generated nanofibers 2; and a core yarn supplying means 9 for supplying the core yarn 8 to a predetermined core yarn moving path 7 passing through the shaft core of the spinning head 3 and the collecting electrode 6; A recovery means 10 is provided for recovering the yarn 11 produced by entwining the nanofiber 2 around the core yarn 8.

  As shown in FIGS. 1 and 2, the spinning head 3 is rotatably supported around a vertical axis, and a plurality of small holes 12 having a diameter of about 0.1 to 2 mm are formed at a pitch of several mm on the peripheral surface. A rotating container 13 comprising a cylindrical container is provided, and the rotating container 13 is rotationally driven by a small hole rotating means 14 in the direction of arrow a. As the small hole rotating means 14, a DC motor disposed through an output shaft composed of a hollow shaft is suitably applied, and the rotating container 13 is connected to the output shaft or the hollow rotating shaft 15 connected to the same shaft. Installed.

  The raw material solution is obtained by dissolving a polymer substance in a solvent. Examples of the polymer substance include polypropylene, polyethylene, polystyrene, polyethylene oxide, polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, poly-m-phenylene terephthalate, Poly-p-phenylene isophthalate, polyvinylidene fluoride, polyvinylidene fluoride-hexafluoropropylene copolymer, polyvinyl chloride, polyvinylidene chloride-acrylate copolymer, polyacrylonitrile, polyacrylonitrile-methacrylate copolymer, polycarbonate, poly Arylate, polyester carbonate, nylon, aramid, polycaprolactone, polylactic acid, polyglycolic acid, collagen, polyhydroxybutyric acid, polyvinegar Vinyl, can be exemplified a polypeptide or the like as preferable, at least one selected from these are used, but the invention 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. The mixing ratio of the solvent and the polymer material varies depending on the solvent and the polymer material, but the amount of the solvent is preferably about 60% to 98%.

  In addition to the polymer substance and the solvent, an inorganic solid material can be mixed into the raw material solution. 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. Thus, by mixing an inorganic solid material such as TiO2, the yarn 11 composed of functional nanofibers having deodorizing and antibacterial functions and various catalytic functions can be produced, which is useful for clothing and other textile products. is there.

  The electric field generating electrode 4 is arranged in a ring shape at a predetermined interval from the peripheral surface of the rotating container 13 constituting the spinning head 3, and a high potential difference is applied between the small hole 12 of the rotating container 13 and the electric field generating electrode 4. Has been. In the present embodiment, at least the peripheral surface of the rotating container 13 or the vicinity of the small hole 12 has conductivity and is set to the ground potential, and is generated by the first high voltage generating means 16 with respect to the electric field generating electrode 4. A high voltage of the negative electrode is applied. Thus, an electric field is generated between at least the vicinity of the small hole 12 of the rotating container 13 and the electric field generating electrode 4, and a positive charge is induced in the small hole 12, and the charge is charged to the raw material solution flowing out of the small hole 12. As the solvent in the solution evaporates, the first to third, or even higher order electrostatic explosions occur and the nanofibers 2 are generated. The first high voltage generator 16 may apply a positive or negative high voltage to the rotating container 13 to set the electric field generating electrode 4 to the ground potential, but the rotating container 13 connected to the small hole rotating means 14 may be used. Is preferably set to the ground potential because the insulation structure becomes simple.

  An air blowing means 17 serving as a deflection flow means for deflecting and flowing the generated nanofibers 2 toward the collection electrode 6 is disposed on the upper side of the small hole rotation means 14 opposite to the rotation container 13. It is comprised so that the gas flow 18 may be sent toward the space between the surrounding surface and the electric field production | generation electrode 4. FIG. As the deflection flow means, a reflective electrode to which a high voltage having the same polarity as the charging polarity of the nanofiber 2 is applied may be disposed instead of or in combination with the air blowing means 17.

  The core yarn supplying means 9 is disposed further above the air blowing means 17. The core yarn supply means 9 includes a core yarn supply reel 9a wound around the core yarn 8 so that the core yarn 8 can be fed out, and a guide roller 9b that guides the fed core yarn 8 to be supplied to the upper end of the core yarn movement path 7. ing. The core yarn 8 fed out from the core yarn supply means 9 passes through the core yarn movement path 7, the through hole 17 a formed at the axial core position of the blower means 17, the hollow output shaft and the hollow rotary shaft of the small hole rotating means 14. It moves toward the axial center position of the collecting electrode 6 through the 15 hollow portions and the through hole of the rotating container 13.

  The collection electrode 6 is disposed on the same axis as the rotation axis of the rotary container 13 at a position away from the rotary container 13 of the spinning head 3 by an appropriate distance in the axial direction. The distance between the rotating container 13 and the collecting electrode 6 is that the first to third or higher order electrostatic explosion occurs in the raw material solution flowing out from the small hole 12 of the rotating container 13 to generate the nanofiber 2. This is the required distance required for As shown in FIGS. 1 and 2, the collecting electrode 6 is configured by a hollow shaft body 19 having a through hole 20 in the shaft core portion, and has an annular enlarged head portion 21 at one end on the spinning head 3 side. A plurality of, in the illustrated example, a pair of hemispherical convex portions 22 are disposed on the surface of the enlarged head 21 facing the spinning head 3. The collecting electrode 6 has a hollow shaft 19 supported by a bearing 23 so as to be rotatable about its axis, and the other end of the collecting electrode 6 by an electrode rotating means 24, which is an arrow b opposite to the rotational direction a of the rotating container 13. It is configured to be rotationally driven in the direction. As the electrode rotating means 24, a DC motor in which the hollow shaft 19 constituting the collecting electrode 6 itself is an output shaft is preferably applied. The collecting electrode 6 only needs to have at least the convex portion 22 of the enlarged head portion 21 having conductivity, and the other portions do not necessarily have conductivity.

  At least the convex portion 22 of the collecting electrode 6 is negative (1 to 100 kV, preferably 10 to 100 kV (a negative voltage is applied in the illustrated example). This is so that the nanofiber 2 has a positive charge. The second high voltage that generates a high voltage is applied because the positive electrode is applied as the voltage applied to the collecting electrode 6 when it is charged so as to have a negative charge. Connected to the generating means 25, an electric field is generated between at least the vicinity of the small hole 12 of the rotating container 13 and the collecting electrode 6. The rotating container 13 is configured to generate an electric field between at least the small hole 12 of the rotating container 13 and the convex portion 22 of the collecting electrode 6, and the second high voltage generating means 25 serves as an electric field generating means between the small hole 12 and the convex portion 22. It is composed. As shown in FIG. 2, the electric lines of force 26 generated by this electric field are directed from the vicinity of the small hole 10 of the rotating container 11 toward the electric field generating electrode 4, and then toward the convex portion 22 of the enlarged head 21 of the collecting electrode 6. And are formed so as to converge on the pair of convex portions 22.

  The outer periphery of the electrode rotating means 24 is coupled to the cylinder 27, and the suction means 28 is disposed at the lower end of the cylinder 27. When the suction means 28 is operated, the collecting electrode is passed through the space in the cylinder 27. The gas flow is sucked through the six through holes 20.

  In the above configuration, the rotary container 13 is rotationally driven while supplying the raw material solution into the rotary container 13 of the spinning head 3. Then, the raw material solution in the rotating container 13 is charged with electric charges in each small hole 12, and the raw material solution is surely linear toward the electric field generating electrode 4 by the action of the electric field between the electric field generating electrode 4 and the action of centrifugal force. And is stretched by the action of centrifugal force. After that, the solvent in the raw material solution that flowed linearly evaporates, and the diameter of the linear body was reduced. As a result, the charged charge was concentrated, and the Coulomb force exceeded the surface tension of the raw material solution. At that time, a primary electrostatic explosion occurred and the film was stretched explosively, and then the solvent was further evaporated to cause a secondary electrostatic explosion to be stretched explosively. In some cases, a third electrostatic explosion occurred. By being drawn, nanofibers 2 made of a polymer material having a submicron diameter are efficiently produced.

  The nanofibers 2 that are being generated or generated are generated from the outer periphery of the rotating container 13 toward the collecting electrode 6 by the gas flow 18 blown by the blowing means 17, and the axis of the rotating container 13 by the rotation of the rotating container 13. It will flow while turning around. In addition, when the gas flow 18 is made into warm air, since evaporation of a solvent is accelerated | stimulated, the production | generation of the nanofiber 2 can be accelerated | stimulated and it is preferable. The nanofibers 2 flowing while swirling on the gas flow 18 are strongly sucked toward the collecting electrode 6 along the electric force lines 26. Here, since the electric lines of force 26 are focused on the pair of convex portions 22 provided on the collecting electrode 6 as described above, as shown in FIG. The collecting electrode 6 is rotating in the direction opposite to the swirl flow direction of the nanofiber 2 and when the suction means 28 is further operated, the collecting electrode 6 enters the through-hole 20 of the collecting electrode 6. A suction airflow flowing in the direction is formed, and the nanofibers 2 are also brought toward the axial center of the collecting electrode 6 by this suction airflow, so that the nanofibers 2 that are stably focused toward the plurality of convex portions 22 are formed. The core yarn 8 is surely entangled and focused at once, and the yarn 11 in which the nanofibers 2 are evenly entangled with the core yarn 8 is combined. Thus, all the nanofibers 2 are uniformly twisted to produce a uniform yarn 11 having no variation in thickness entangled with the core yarn 8, and the high-strength yarn 11 is stably formed with good productivity. Is done. The formed yarn 11 passes through the through hole 20 of the collecting electrode 6, the space in the cylindrical body 27, and the shaft core portion of the suction means 28 and is collected by the collecting means 10.

  In the above description, an example in which the pair of convex portions 22 are provided on the enlarged head 21 of the collecting electrode 6 is shown, but the present invention is not limited to this, and is shown in FIGS. 4 (a) and 4 (b). As described above, three, four, or more convex portions 22 may be arranged at equal intervals in the circumferential direction.

  In the illustrated examples of FIGS. 1 and 2, an example in which the rotating container 13 having the small holes 12 formed on the peripheral surface is applied is shown. However, a large number of short nozzles are provided on the peripheral surface of the rotating container 13 at appropriate pitch intervals. It is good also as a structure which has arrange | positioned a member and made the nozzle hole formed in the nozzle member function as the small hole 12. FIG.

  Further, in the present embodiment, an example in which the rotating container 13 of the spinning head 3 is rotated in the direction of arrow a and the collecting electrode 6 is rotated in the direction of arrow b opposite to the direction a is shown. 3 may rotate only the collecting electrode 6 side without rotating, or conversely, only the spinning head 3 side may rotate without rotating the collecting electrode 6. Further, in any direction in which the rotating container 13 and the collecting electrode 6 are rotated, the rotating container 13 and the collecting electrode 6 are relatively rotated by making the number of rotations different. Also good. The rotation direction of the rotating container 13 and the collecting electrode 6 is not limited to the present embodiment, and the same can be considered in the following examples.

(Second Embodiment)
Next, a second embodiment of the nanofiber spinning device of the present invention will be described with reference to FIG. In the following description of the embodiments, the same components as those of the preceding embodiments are denoted by the same reference numerals, description thereof is omitted, and only differences will be mainly described.

  In the present embodiment, the wind tunnel 30 made of an insulating material surrounding the space between the electric field generating electrode 4 and the collecting electrode 6 is disposed. The wind tunnel 30 includes a cylindrical portion 30a extending from the lower edge of the electric field generating electrode 4 to a height position below the enlarged head 21 of the collecting electrode 6 and an end plate 30b that closes the lower end opening thereof. A hollow shaft body 19 of the collecting electrode 6 passes through the shaft core portion in a rotatable manner.

  According to the configuration of the present embodiment, when the generated nanofiber 2 swirls on the gas flow 18, the swirl range is reliably regulated by the wind tunnel 30. The yarn 11 can be entangled with the yarn 8 and the yarn 11 can be manufactured more stably. In particular, in the present embodiment, since the suction means 28 sucks through the through hole 20 in the axial center portion of the collecting electrode 6 as described above, the generated nanofiber 2 rides on the gas flow 18. The swirling flow and the gas flow 18 are sucked by the axial core portion of the collecting electrode 6 to reduce the swirling radius, and the nanofibers 2 are twisted more strongly and entangled with the core yarn 8, which is higher. A strong yarn 11 can be produced.

  Further, in the above description of the first and second embodiments, the air blowing means 17 has been described as air blowing substantially parallel to the axial direction of the spinning head 3, but the air blowing means 17 is connected to the collecting electrode from the spinning head 3 side. It may be configured to blow a swirling gas flow that swirls and flows toward the 6 side. In that case, the generated nanofibers 2 are swirled toward the collecting electrode 6 side on the swirling gas flow. Since the swirling gas flow is sucked through the through-hole 20 in the axial center portion of the collecting electrode 6, the swirling radius of the swirling gas flow becomes smaller and the swirling gas flow becomes stronger. The high-strength yarn 11 can be manufactured by entwining the nanofiber 2 that has been swirled and entangled with the core yarn 8 more strongly. Further, when the wind tunnel 30 is provided as in the second embodiment and the swirling gas flow is blown by the blowing means 17 and sucked by the axial core portion of the collecting electrode 6, the spinning head 3 and the collecting electrode 6 are arranged. Either or both of them can produce the yarn 11 by entwining the nanofiber 2 with the core yarn 8 without rotating.

Further, the above first, the Nanofa Lee bar generating means 5 of the second embodiment, an example configuration in which arranging the field generating electrodes 4 to face the small holes 12 of the outer peripheral surface of the rotating container 13, eyelet Electrostatic explosion can be generated in the raw material solution flowing out from the small hole 12 by the electric field between the electrode 12 and the collecting electrode 6, and in this case, the electric field generating electrode 4 is not necessarily provided.

(Third embodiment)
Next, a third embodiment of the nanofiber spinning device of the present invention will be described with reference to FIG.

   In the above embodiment, the spinning head 3 is composed of the rotating container 13 having the small holes 12 formed on the outer peripheral surface, and the raw material solution stored in the rotating container 13 is caused to flow out and extend by the centrifugal force generated by the rotation of the rotating container 13. In this embodiment, as shown in FIG. 6, the spinning head 3 is provided with a plurality of nozzle members 32 on the lower surface of the rotating container 31, and the raw material solution is allowed to flow out through the nozzle holes. A small hole 33 is formed. The collecting electrode 6 has a configuration in which an enlarged head 21 having a rotating heart shape with a heart-shaped cross section is provided at the upper end of the hollow shaft body 19, and a plurality of protrusions 22 project from the upper end of the enlarged head 21. ing.

  In the configuration of the present embodiment, the nanofiber 2 generated by flowing out the raw material solution from the small hole 33 flows according to the lines of electric force directed to the nearest convex portion 22, and the rotating container 31 rotates in the direction a. Since the collecting electrode 6 rotates in the opposite b direction, the nanofibers 2 flowing toward the convex portion 22 move along the core yarn moving path 7 passing through the rotating body 31 and the axial core of the collecting electrode 6. The core yarn 8 is entangled with the core yarn 8 reliably and stably, and a uniform and high-strength yarn 11 is formed. Note that at least one of the rotating container 31 and the collecting electrode 6 may be rotated.

(Fourth embodiment)
Next, a fourth embodiment of the nanofiber spinning device of the present invention will be described with reference to FIG.

  The present embodiment exemplifies a specific configuration example having the same basic configuration as that of the third embodiment but having a different detailed configuration. In FIG. 7, a lower end portion of a rotating cylinder 34 having electrical insulation is integrally fixed to the upper wall of the rotating container 31, and an intermediate portion of the rotating cylinder 34 is provided with a bearing 36 by an upper support frame 35. The upper portion of the rotating cylinder 34 is connected to the small hole rotating means 14. The rotating container 31 or at least the nozzle member 32 has conductivity, and the nozzle member 32 is electrically grounded via a conductive member 34 a provided on the rotating cylinder 34 and a bearing 36. In addition, when it earth | grounds via the bearing 36, when it has resistance value in the meantime, you may comprise so that it may connect directly to the electrically-conductive member 34a via a brush.

  The inner cylindrical wall 37 that forms a through-opening at the center of the rotating container 31 has an upper portion opened over the entire circumference, and the raw material solution supply means is provided in the annular housing space between the outer peripheral wall of the rotating container 31 and the inner cylindrical wall 37. The raw material solution supplied at 38 is accommodated and flows out from the small hole 33 through the nozzle member 32. The raw material solution supply means 38 takes out the raw material solution in the storage container 39 with the supply pump 40, penetrates the rotary cylinder 34, and is inserted into the rotary container 31. The raw material solution is supplied from 41a into the annular housing space. In the illustrated example, the raw material solution is caused to flow out of the small hole 33 by the action of gravity acting on the raw material solution, the centrifugal force generated by the rotation of the rotating container 31, and the electric field between the small hole 33 and the collecting electrode 6. As a configuration in which the inside can be pressurized, the raw material solution may be pushed out by pressure and allowed to flow out.

  In the same manner as in the above-described embodiment, the collecting electrode 6 has an intermediate portion of the hollow shaft body 19 having an annular enlarged head 21 provided with a convex portion 22 at its upper end, and is rotatable by a lower support frame 42 via a bearing 23. The lower part of the hollow shaft 19 is supported and connected to the electrode rotating means 24. A high voltage generated by the second high voltage generating means 25 is applied to the convex portion 22 via the conductive member 19 a provided on the enlarged head 21 and the hollow shaft body 19 and the bearing 23. The core yarn supply means 9 is disposed on the upper support frame 35. The collecting means 10 is disposed on the lower support frame 42 and positions the yarn take-up reel 10a for winding and collecting the manufactured yarn 11 and the lower end of the core yarn moving path 7, and the manufactured yarn. 11 is constituted by a guide roller 10b for taking out 11 from the core yarn moving path 7 to the side.

  Also in the present embodiment, as in the third embodiment, the raw material solution supplied into the rotating container 31 by the raw material solution supply means 38 flows out from the small hole 33 and is generated by electrostatic explosion. Flows in accordance with the electric lines of force toward the nearest convex portion 22, and the rotating container 31 rotates in the a direction and the collecting electrode 6 rotates in the reverse b direction. The nanofiber 2 to be wound is surely and stably wound around the core yarn 8 moving along the core yarn moving path 7 passing through the axis of the rotating body 31 and the collecting electrode 6, and is a uniform and high strength yarn. 11 is formed and recovered by the recovery means 10. Note that at least one of the rotating container 31 and the collecting electrode 6 may be rotated.

  In the above embodiment, the spinning head 3 is grounded, and a high voltage is applied to the electric field generating electrode 4 and the collecting electrode 6 or the collecting electrode 6, and between the spinning head 3 and the electric field generating electrode 4 and the spinning head 3. Although an example in which an electric field is generated between the spinning head 3 and the spinning head 3 and the collecting electrode 6 is shown, a high voltage is applied to the spinning head 3 to generate the electric field generating electrode 4 and the collecting electrode. 6 may be grounded, or high voltages having opposite polarities or the same polarity may be applied to the spinning head 3, the electric field generating electrode 4 and the collecting electrode 6. In short, the spinning head 3, the electric field generating electrode 4 and the collecting electrode may be applied. 6 may be configured so that a high potential difference is applied between them and an electric field is generated between them.

  In the above embodiment, the connection may be made via a bearing. However, if the bearing has a resistance component, the connection is made directly to the rotating shaft via a brush or the like. Also good.

  In the embodiment, since the charged nanofibers are surely collected toward the nearest convex portion by arranging a plurality of convex portions around the through-hole 20 of the collecting electrode 6, the core is stably provided. Nanofibers are entangled around the yarn 8, the shape of the produced yarn 11 is stabilized, and the recovery rate of the produced nanofiber is greatly improved.

  According to the nanofiber combination method and apparatus of the present invention, the nanofiber generated by electrostatic explosion of the raw material solution flowing out from the small hole around the core yarn flows toward the collection electrode, and the collection electrode The converging points of the flowing nanofibers are concentrated on these convex portions, and the small holes and the collecting electrodes are relatively rotated around the core yarn moving path. Because nanofibers that are stably focused toward multiple convex parts are entangled evenly around the entire circumference of the core yarn, high-strength and homogeneous yarns composed of nanofibers can be produced stably. Since it can be manufactured with good performance, it can be suitably used for production of a high-strength yarn composed of nanofibers.

The partial cross section front view which shows the whole schematic structure of the nanofiber synthesizing | combining apparatus in the 1st Embodiment of this invention. Explanatory drawing which shows the generation | occurrence | production state of the electric line of force between the spinning head and collection electrode in the embodiment. The top view explaining the action state of the electric line of force with respect to the nanofiber in the embodiment. (A), (b) is a top view which shows the other example of arrangement | positioning of the convex part in a collection electrode. The perspective view which shows the whole schematic structure of the nanofiber spinning device in the 2nd Embodiment of this invention. The perspective view which shows the principal part structure of the nanofiber spinning device in the 3rd Embodiment of this invention. The longitudinal side view which shows the whole schematic structure of the nanofiber synthesizing | combining apparatus in the 4th Embodiment of this invention. BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a perspective view showing an overall schematic configuration of a nanofiber spinning device that precedes the present invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Nanofiber spinning device 2 Nanofiber 5 Nanofiber production | generation means 6 Collection electrode 7 Core yarn movement path 8 Core yarn 9 Core yarn supply means 10 Collection means 11 Yarn 12, 33 Small hole 14 Small hole rotation means 20 Through hole 21 Expansion head Portion 22 Projection 24 Electrode rotating means 25 Second high voltage generating means (electric field generating means)
28 Suction means

Claims (5)

A core yarn supplying step of supplying the core yarn to a predetermined core yarn moving path;
A nanofiber generating step of flowing out the raw material solution from at least one small hole arranged around the core yarn movement path, charging the discharged raw material solution with electric charge, and drawing the nanofiber by electrostatic explosion;
An electric field is formed so that the charged nanofibers are directed to the collecting electrode on which a plurality of convex portions are arranged around the core yarn moving path, and the small hole and the collecting electrode are relatively rotated around the core yarn moving path. , A process of tying nanofibers around the core yarn,
Possess a recovery step of recovering the yarn was entangled nanofiber core yarn,
In the collection step, the nanofiber spinning method is characterized in that suction is performed through a through-hole through which the core yarn moving path formed in the axial core portion of the collecting electrode passes .   2. The nanofiber spinning method according to claim 1, wherein, in the nanofiber generating step, the small hole is rotated around the core yarn moving path, and the collecting electrode is rotated in a direction opposite to the small hole in the stitching step. A core yarn supplying means for supplying the core yarn to a predetermined core yarn movement path;
Nanofiber generating means arranged at the periphery of the core yarn movement path and having at least one small hole through which the raw material solution flows out, and generating a nanofiber by charging the flowing out raw material solution and stretching it by electrostatic explosion When,
A collecting electrode in which a plurality of convex portions are arranged around the core yarn movement path on the surface opposite to the nanofiber generating means, applied with a voltage having a polarity opposite to the charged charge of the raw material solution or grounded,
A rotation means for relatively rotating the eyelet and collecting electrodes around the core yarn travel path of Nanofa Lee bar generating means,
A collecting means for collecting the yarn in which the nanofiber is entangled with the core yarn ;
A nanofiber spinning device comprising suction means for sucking through a through hole formed in an axial core portion of the collecting electrode and through which the core yarn moving path passes . 4. The nano of claim 3 , wherein the rotating means comprises at least a small hole rotating means for rotating the small hole around the core yarn moving path or an electrode rotating means for rotating the collecting electrode around the core yarn moving path. Fiber spinning device. 5. The nanofiber spinning device according to claim 4, wherein the rotating means includes both small hole rotating means and electrode rotating means, and both rotating means have opposite rotation directions.

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