JP4904083B2 - Apparatus for producing polymer compound fiber structure by electrospinning method - Google Patents

Description

  The present invention relates to an apparatus for producing a polymer compound fiber structure by an electrostatic spinning method, and more particularly to an apparatus capable of producing a polymer compound fiber structure having a uniform thickness. The present invention also relates to a method for producing a fiber structure using the apparatus, and a fiber structure having a uniform thickness obtained by the method.

  In recent years, "regenerative medicine technology" that uses artificially cultured cells and tissues to repair the functions of damaged organs, bones, nerves, blood vessels, etc. has made remarkable progress. In conjunction with this, the development of scaffolding materials (Scaffold), which are considered to be necessary elements for regenerative medicine, has been activated along with cells and cell growth factors. It is necessary to provide scaffold materials of various shapes depending on the tissue to be regenerated, and materials having various three-dimensional structures such as fibers, membranes, and porous bodies have been studied.

  For example, Patent Documents 1 and 2 disclose a method for producing a porous polymer body using a freeze-drying method in which a polymer compound-containing solution is frozen and then placed under a vacuum under reduced pressure to volatilize the contained solvent. These porous bodies have a structure with a large specific surface area, and can be used as cell tissue formation and differentiation induction, and as a carrier for sustained-release drugs. However, since lyophilization generally requires high vacuum, it is expensive. A vacuum drying device or a container for cooling and capturing the volatilized solvent is required. Moreover, since these apparatuses require continuous and advanced maintenance, it is impossible to avoid an increase in equipment cost and maintenance cost required for these apparatuses.

  Patent Document 3 can be exemplified as a method for producing a porous body of a polymer compound without using a freeze-drying method. According to this publication, a frozen product is prepared by freezing a polymer compound-containing solution, and an extraction solvent that is poor with respect to the polymer compound and good with respect to the solvent is added thereto, and the solvent is removed from the frozen product. Thus, a porous body can be obtained at a low production cost without using an expensive freeze-drying apparatus. However, according to this method, since the extraction solvent is added in addition to the solvent contained in the solution, the problem of the solvent remaining in the porous body is highly likely to become serious. It becomes necessary to use the method together. This not only increases the equipment cost but also increases the operating cost.

  In addition, as a method of producing the fiber, a “molten spinning method” in which a polymer compound in a molten state is spun from a nozzle and cooled and solidified in the air or in a certain gas to obtain a fiber, or a polymer The compound-containing solution is spun from a nozzle, and the solvent component is evaporated from the nozzle to obtain fibers. The dry spinning method is also used to solidify the fibrous polymer compound spun from the nozzle in a coagulation liquid. The “wet spinning method” to be obtained is generally known.

  In addition to the “dry method” and “wet method”, the “spunbond method” in which a nonwoven fabric is obtained through a drawing and opening process after melt spinning, and a high temperature and high pressure at the melt spinning nozzle port are also available. A “melt blow method” or the like in which a nonwoven fabric is obtained by blowing an air stream and stretching and opening a fibrous polymer compound is generally known.

  From the viewpoints of cell growth and biodegradability, and the flexibility of the resulting fiber structure, fibers having submicron or nanoscale diameters are preferred as the fibers constituting the regenerative medicine scaffold described above. Though considered, the diameter of the fiber obtained by utilizing the above-described fiber manufacturing technology and nonwoven fabric manufacturing technology, and the diameter of the fiber constituting the nonwoven fabric are the same as those of existing fibers (several to several tens of μm). It is difficult to produce fibers having a suitable diameter. In addition, facilities used for extruding a polymer compound under high pressure and cooling / solidifying a fibrous polymer compound are complicated and expensive, which hinders an increase in manufacturing cost and stable product supply.

  Therefore, as a new spinning technique, “electrospinning” exemplified in Patent Documents 4 and 5 attracts attention. In this method, a polymer compound-containing solution is charged positively or negatively, and is spun through a nozzle or needle to a fibrous polymer compound deposit part charged to the opposite polarity or grounded. It is a method to do. According to this method, a fiber having a diameter of several nm can be produced. In addition, fiber structures of various shapes can be obtained by using fibrous polymer compound deposits of various shapes. For example, a flat nonwoven fabric can be formed into a cylindrical or rectangular parallelepiped by using a flat deposit. A fiber structure having a three-dimensional structure can be obtained by using the deposited portion.

  Patent Documents 6 and 7 disclose examples in which a roll electrode is used for the deposition part. According to these publications, a spinning nozzle that discharges a polymer compound-containing solution that is a raw material of a fiber, a feeder that continuously supplies the polymer compound-containing solution to the nozzle, and a roll-shaped electrode that faces the spinning nozzle The fiber structure can be obtained on the electrode by applying a high voltage to the tip of the spinning nozzle. Furthermore, a nonwoven fabric is obtained by cutting the fiber structure on a roll, and a cylindrical fiber structure is obtained by extracting the nonwoven fabric in the width direction of the electrode.

  However, in these methods, since the roll electrode has a length in the rotation axis direction with respect to the spinning nozzle fixed at one point, the distance between the spinning nozzle and the electrode is the largest on the electrode. Since a large amount of fibrous polymer compound is deposited near the site, the thickness of the nonwoven fabric or fiber structure finally obtained on the electrode tends to be uneven. Further, due to the eccentric rotation of the rotating shaft often found in a rotating body such as the illustrated roll electrode, the thickness of the non-woven fabric or the fiber structure obtained on the electrode further increases non-uniformity.

  Furthermore, according to this method, the supply of the polymer compound-containing solution to the spinning nozzle is performed by the supply machine, but the amount of the polymer compound-containing solution consumed by the spinning nozzle is extremely small, and the supply of the supply machine Although it depends on the accuracy, it is very difficult to accurately match the balance between the amount of spinning and the amount of supply of the polymer compound-containing solution. Once this balance is broken, there is a high possibility of causing problems such as clogging of the spinning nozzle tip and dripping due to the polymer compound-containing solution, which worsens the uneven thickness of the nonwoven fabric and fiber structure described above. It becomes a factor to make.

  When the thickness of the nonwoven fabric or fiber structure obtained in this way is uneven, for example, when they are used as a filter substrate, the pressure loss amount is uneven, so there is a high possibility of causing filtration failure. When used as a scaffold for regenerative medicine as described above, it adversely affects cell growth and biodegradability.

Japanese Patent Laid-Open No. 2000-329761 JP 2002-146084 A JP 2005-046538 A US Pat. No. 6,106,913 US Pat. No. 6,110,590 JP 2004-256773 A JP 2004-256974 A

  An object of the present invention is to provide an apparatus for producing a polymer compound fiber structure by an electrospinning method, more specifically, an apparatus capable of producing a polymer compound fiber structure having a uniform thickness. is there. Moreover, this invention is providing the manufacturing method of the fiber structure using the said apparatus, and the fiber structure with the uniform thickness obtained by this method.

The inventors diligently studied to solve the above-described problems, and led to the following invention.
1. At least one spinning section (A) for spinning a polymer compound-containing solution to which a positive or negative high voltage is applied;
At least one rotating columnar or cylindrical electrode (B) to which a high voltage having a polarity opposite to that of (A) is applied or grounded;
It comprises a device (C) that swings the spinning section (A) at a constant speed parallel to the rotation axis of the electrode (B), and a rotation drive device (D) of the electrode (B).
A fiber structure that discharges a polymer compound-containing solution from the spinning section (A) toward the electrode (B) and deposits the fiber structure made of the polymer compound on the columnar or cylindrical electrode (B). Manufacturing equipment,
The rotating columnar or cylindrical electrode (B) is fixed at both ends and has a rotation speed in the range of 0.5 to 100 rpm, and the columnar or cylindrical electrode (B) The outer diameter D (mm) and the maximum deflection width W (mm) in the radial direction of the portion where the rotating shaft is most distorted during rotation satisfy the following formulas (1) to (3): Compound fiber structure manufacturing equipment.
W <5 / D (where 0 <D ≦ 10) (1)
W <D / 20 (where 10 <D ≦ 100) (2)
W <5 (where 100 <D) (3)
2. 2. The manufacturing apparatus according to 1 , wherein a portion where the rotation axis is most distorted is a center in a length direction of the rotating electrode (B) .
3. 3. The manufacturing apparatus according to 1 or 2, which has a charge removal process .
4). In the spinning section (A), the electric attractive force generated between the spinning section (A) and the columnar or cylindrical electrode (B) and / or the liquid containing the polymer compound-containing solution held in the spinning section (A) 4. The production apparatus according to any one of 1 to 3 , wherein the polymer compound-containing solution is supplied by pressure applied to the head .
5. Production of holding and / or enclosing the spinning section (A), the electrode (B), the apparatus (C) for swinging the spinning section (A) at a constant speed, and the rotation driving apparatus (D) of the electrode (B) 5. The manufacturing apparatus according to any one of 1 to 4, wherein the volume resistivity of the structure of the apparatus base is in the range of 10 ¹⁰ to 10 ²⁰ Ω · m .
6). Spin at least one spinning part (A) that spins a polymer compound-containing solution to which a positive or negative high voltage is applied. The polymer compound-containing solution is discharged toward one rotating columnar or cylindrical electrode (B), and a fiber structure made of the polymer compound is deposited on the columnar or cylindrical electrode (B). A method of manufacturing a fiber structure, which is characterized by extruding the fiber structure in parallel with an axis to obtain a cylindrical fiber structure, with respect to the rotation axis of the columnar or cylindrical electrode (B), The spinning section (A) has a function of swinging at a constant speed in parallel, the rotating columnar or cylindrical electrode (B) is fixed at both ends, and the rotational speed is 0.5 to 100 rpm. And the cylinder Alternatively, the outer diameter D (mm) of the cylindrical electrode (B) and the maximum deflection width W (mm) in the radial direction of the portion where the rotation axis is most distorted during rotation satisfy the following formulas (1) to (3). A method for producing a polymer compound fiber structure, comprising:
W <5 / D (where 0 <D ≦ 10) (1)
W <D / 20 (where 10 <D ≦ 100) (2)
W <5 (where 100 <D) (3)
7). The process according to 6 you, wherein the wall structure of the cylindrical fibrous structure is a bellows.
8). Performing static elimination treatment on the fiber of the polymer compound spun from the spinning part (A) and / or the fiber structure of the polymer compound on the columnar or cylindrical electrode (B). 8. The production method according to 6 or 7,
9. In the swinging range of the spinning portion (A), the standard deviation σ (μm) of the tube wall thickness at an arbitrary point of 50 or more of the cylindrical fiber structure is within a range of less than 15. that the polymer compound fiber structure obtained by the production method according to any one of 6-8.

  By using the above-described apparatus for producing a polymer compound fiber structure using an electrostatic spinning method, a polymer compound fiber structure having a uniform thickness can be obtained. The fiber structure obtained in this way can be used, for example, as a scaffold material that is considered as an element necessary for regenerative medicine, and since its thickness is uniform, it is very effective in terms of cell growth and biodegradability. Material.

The manufacturing apparatus in the present invention will be described in detail below.
The apparatus of the present invention comprises at least one spinning section (A) for spinning a polymer compound-containing solution to which a positive or negative high voltage is applied.
At least one rotating columnar or cylindrical electrode (B) to which a high voltage having a polarity opposite to that of (A) is applied or grounded;
It comprises a device (C) for swinging the spinning section (A) at a constant speed parallel to the rotation axis of the electrode (B), and a rotation drive device (D) for the electrode (B).

The spinning section (A) is a part related to spinning of a polymer compound-containing solution equipped with a spinning nozzle, and a high voltage applying electrode is inserted in the nozzle so that a high voltage can be applied.
The columnar or cylindrical electrode (B) is a metal round bar or pipe material for obtaining a fiber structure made of the polymer compound on the surface thereof. In addition, as an electrode for applying a voltage having a polarity opposite to the polarity applied to the spinning nozzle or grounding the polymer compound so that the polymer compound can be spun by the electric attractive force generated by applying a high voltage. Also has a role.

The apparatus (C) for swinging the spinning section (A) at a constant speed parallel to the rotation axis of the electrode (B) includes a spinning nozzle swing motor provided to swing the spinning section (A) horizontally. The spinning device (A) is fixed on the swinging motor.
The rotation drive device (D) for the electrode (B) is a rotary motor having a rotation shaft at its center, and the rotation shaft and the electrode (B) are connected by a coupling to rotate the rotation shaft. By this, it is an apparatus which rotates the said electrode (B) equivalent to the said rotating shaft.

  FIG. 1 is a schematic side view showing an apparatus for producing a polymer compound fiber structure according to an embodiment of the present invention, and FIG. 2 is a schematic plan view showing the apparatus. FIG. 3 is a schematic side view showing an example in which a static eliminator is disposed between the spinning section (A) and the columnar or cylindrical electrode (B) in the apparatus, and FIG. It is a schematic side view showing an example in which a static eliminator is disposed at a position opposite to the spinning section (A) across a cylindrical electrode (B). Hereinafter, the present invention will be described in detail with reference to these drawings, but the scope of the present invention is not limited thereby.

  The spinning section (A) for spinning the polymer compound-containing solution, that is, the spinning nozzle 1 shown in FIGS. 1 and 2 is attached to a spinning nozzle holder 2 and has a high voltage applying electrode 3 therein. ing. In order to horizontally swing the spinning nozzle 1, the holder 2 is fixed to a spinning nozzle swinging motor 4 having a slide rail 5 by a spinning nozzle holder support 6. All of these components are on the base plate 7 for the spinning nozzle section. For example, the motor 4 is applied to the base plate 7 and the base plate so as not to adversely affect the arrangement of the components due to vibration caused by driving of the motor 4. 7 is fixed to an arbitrary horizontal plane. A high voltage application wiring bundling portion 8 is provided at the end of the electrode 3, and the high voltage application wiring 9 bound here extends to the high voltage supply device 10. As the holder 2 swings, the bundling portion 8 swings in the same manner, so that the wiring 9 repeatedly expands and contracts with respect to the fixed high voltage supply device 10. Therefore, the wiring 9 is a coil-shaped wiring or a wiring having a length several times the distance between the binding unit 8 and the high voltage supply device 10.

  One end point of the columnar or cylindrical electrode (B), that is, the columnar or cylindrical electrode 14 shown in FIGS. 1 and 2, is a columnar or cylindrical electrode bearing 11 and the other end point is a columnar or cylindrical electrode. It is fixed by a cylindrical electrode holder 15. The bearing 11 is supported by a columnar or cylindrical electrode bearing support 12, and the holder 15 is directly connected to a columnar or cylindrical electrode rotary motor 16. All of these components are on the base plate 13 for the fiber structure recovery unit, and the arrangement of each component is not adversely affected by vibrations caused by driving the columnar or cylindrical electrode rotation motor 16, for example, the motor 16. Is fixed to the base plate 13 and the base plate 13 is fixed to an arbitrary horizontal plane. In the holder 15, a ground wiring 17 that contacts the electrode 14 is provided, and the wiring 17 extends to the ground electrode 18. Further, for the purpose of reducing the scattering amount of the fiber structure and preventing the scattered fiber structure from adhering to the apparatus components, the bearing support portion for the cylindrical or cylindrical electrode is used for the bearing support portion 12 and the motor 16. A protective cover 19 and a rotary motor protective cover 20 are provided.

  High precision is required for the mounting and positioning of the bearing support 12 and the motor 16 on the base plate 13, and the bearing 11, the electrode 14, and the like supported by or directly connected to these components. The centers of the rotation axes of the holder 15 and the motor 16 are usually aligned on a straight line within a range of ± 0.05 mm.

  However, when driving of the motor 16 is started, a centrifugal force acts in the radial direction of the rotating shaft depending on the diameter, length, weight, and the number of rotations at that time, and particularly in the vicinity of the center of the rotating shaft. Distortion occurs on the rotating shaft. When the motor 16 rotates, when the distortion of the runout width W (mm) occurs on the rotation shaft, the distance from the tip of the spinning nozzle 1 to the surface of the electrode 14 (referred to as the spinning distance) is W (maximum). mm) will change. Such a change in the spinning distance adversely affects the magnitude of the electric attractive force and, in turn, the spinning amount of the polymer compound-containing solution spun from the spinning nozzle 1, and is thus obtained on the surface of the electrode 14. The thickness of the non-woven fabric and fiber structure to be produced is very uneven.

  Various methods can be exemplified as a method for keeping the runout width W to a minimum, but the method is not particularly limited. For example, it is also a suitable technique to suppress the rotation speed of the motor 16 as much as possible.

  However, as described above, the fact that both ends of the rotating shaft are firmly fixed with high accuracy may be a factor that enlarges the eccentric rotation. Consideration should also be given to giving some freedom to the fixed points.

  For example, it is also preferable to use, as the bearing 11, a part obtained by simply processing a resin into a cylindrical shape without using a general-purpose rolling ball bearing. The electrode 14 is press-fitted into the cylindrical part, and this electrode is mounted on the bearing support 12 and the electrode 14 is rotated, whereby unnecessary force related to the distortion of the rotating shaft described above is applied to the cylindrical part. Since most parts absorb, the deflection width W of the electrode 14 becomes smaller.

  In addition, when the bearing support portion 12 is fixed to the base plate 13, a method of installing a spring below the bolt used for fixing is also suitable. When the bearing support portion 12 is fixed to the base plate 13, the bearing support portion 12 is not completely fixed by the bolt, but is fixed by the spring so that a certain holding force is applied to the bearing support portion 12. Unnecessary force related to the distortion of the rotating shaft generated when the electrode 14 is rotated is absorbed by the minute movement of the bearing support 12 that is not completely fixed, and the deflection width W of the electrode 14 is further increased. It will be small.

By applying the above-described method for suppressing the eccentric rotation of the rotation shaft, the spinning distance described above becomes substantially constant, and the thickness of the nonwoven fabric or the fiber structure obtained on the electrode 14 becomes uniform. The runout width W (mm) of the rotating shaft capable of achieving such a uniform thickness of the fiber structure is given by the following formulas (1) to (3), where the outer diameter of the electrode 14 is D (mm). It becomes a range.
W <5 / D (where 0 <D ≦ 10) (1)
W <D / 20 (where 10 <D ≦ 100) (2)
W <5 (where 100 <D) (3)

  In addition, as a method for making the thickness of the obtained nonwoven fabric or fiber structure uniform, a method of spinning while spinning the spinning nozzle 1 horizontally in the rotation axis direction is also preferable. Therefore, in the present invention, the spinning nozzle 1 is attached to the spinning nozzle holder 2, and the holder 2 is further attached to the slide rail 5 via the spinning nozzle holder support 6. The spinning nozzle swinging motor 4 has a function of swinging the slide rail 5 in the horizontal direction, and when the limit point at both ends of the slide rail 5 is reached, the feed direction of the slide rail 5 is reversed. Is programmed to do so.

  Although the spinning nozzle 1 can be horizontally swung in the direction of the rotation axis by the above-described method, the rocking mechanism is not limited to the above. For example, the slide rail 5 can be replaced with a long threaded shaft, and a horizontal reciprocating motion can be developed even with a rotating cam.

The spinning nozzle 1, the cross-sectional area 1～8000Mm ^2, preferably circular or square 1～400Mm ^2, the tube ends are open used. Note that the inner diameter of the tube is attenuated from the middle of the tube toward the end point so that the cross-sectional area of one end point is 0.005 to 80 mm ² , preferably 0.005 to ¹ mm ² . The polymer compound-containing solution is spun from the end side where the inner diameter is attenuated.

  When the polymer compound fiber structure is manufactured, the polymer compound-containing solution is put into the spinning nozzle 1 and is further attached to the spinning nozzle holder 2 having the high voltage applying electrode 3. A high voltage is applied to the solution via the electrode 3. When the electric attractive force generated in the electrostatic field becomes larger than the surface tension of the droplet of the solution formed at the tip of the spinning nozzle 1, the solution is spun from the tip of the spinning nozzle 1. The spinning amount at this time is a very small amount of several tens of μg to several g / min per spinning nozzle as exemplified by the spinning nozzle 1.

  In the present invention, in the spinning part (A), the electric attractive force generated between the spinning part (A) and the columnar or cylindrical electrode (B) and / or the polymer retained in the spinning part (A) The polymer compound-containing solution is preferably supplied by the pressure applied to the liquid head of the compound-containing solution. In the conventional spinning method, a method of feeding the solution by a pump or pneumatic pressure is used to replenish the solution consumed by the spinning nozzle. Also in the electrospinning method, a pump or the like that can feed a very small amount of the solution is often employed. However, in these methods, since the solution is forcibly fed, it is extremely difficult to form a droplet that can be held at the tip of the spinning nozzle 1. If droplet formation of the solution cannot be confirmed at the tip of the spinning nozzle 1 due to insufficient liquid feeding, the surface tension of the solution becomes excessive with respect to the electric attractive force generated in the electrostatic field, and thus the spinning nozzle 1 The solution is not spun. Further, when the liquid feeding becomes excessive, the liquid droplets are not held at the tip of the spinning nozzle 1 and liquid dripping occurs. In some cases, the liquid droplets reach the columnar or cylindrical electrode 14. This not only makes the thickness of the resulting polymer compound fiber structure nonuniform, but also adversely affects the surface properties.

  In addition, the above-described pumps often generate unique pulsations due to the mechanism of the liquid feeding operation. Although the amount of liquid fed per unit time changes due to pulsation, the effect on the amount of spinning is enormous when handling a very small amount of spinning.

  When manufacturing a large number of fiber structures of limited varieties, it is necessary to adopt a liquid feeding mechanism that takes these existing problems into account, but when dealing with small quantities and many varieties, large-scale equipment and investment amount It is preferable to adopt a simple and elaborate liquid feeding mechanism that does not require the above.

  Therefore, in the present invention, both end points of the spinning nozzle 1 are opened, and only the pressure applied to the liquid head of the polymer compound-containing solution held in the spinning nozzle 1 and / or the electric attractive force generated in the electrostatic field is used. Supply the solution. As the solution is consumed, the pressure applied to the head of the solution held in the spinning nozzle 1 slightly changes. However, in the case of a large change that impedes droplet formation and holding at the tip of the spinning nozzle 1 Absent. According to this method, an appropriate droplet can be held at the tip of the spinning nozzle 1, and the solution can be stably spun.

  In the present invention, the distance H between the lower end of the electrode (B) and the structure (E) such as the gantry for the structure (E) such as the gantry existing under the columnar or cylindrical electrode (B). It is preferable to provide an appropriate amount. The polymer compound spun from the spinning nozzle 1 is deposited on the rotating columnar or cylindrical electrode 14 to form a polymer compound fiber structure. However, when the area where the fiber structure is deposited is not sufficient for the spinning amount, that is, when the outer diameter D of the electrode 14 is small, the fiber structure that could not be deposited on the electrode 14 14 is deposited on a structure such as another manufacturing apparatus frame located below 14. If these deposits that have not been deposited on the electrode 14 remain on the structure such as the manufacturing apparatus stand as they are, it will not be a big problem, but the lower portion of the electrode 14 is located further below. When the distance H to the structure (E) such as the manufacturing apparatus base is not sufficiently secured, the rotating electrode 14 may be mechanically wound up regardless of the electric attractive force. This also causes the thickness of the resulting polymer compound fiber structure to be non-uniform, as described above.

  Therefore, in the present invention, the distance H from the lower end portion of the electrode 14 to a structure (E) such as a manufacturing apparatus mount positioned further below is set to 100 mm or more. A more preferable range is 200 mm ≦ H.

  Further, in the present invention, the spinning section (A), the columnar or cylindrical electrode (B), the apparatus (C) for swinging the spinning section (A) at a constant speed, and the rotation drive apparatus (D) for the electrode (B) It is preferable that the volume specific resistivity of a structure such as a manufacturing apparatus pedestal that holds and / or surrounds is within an appropriate range. As described above, the polymer compound fiber structure manufacturing apparatus according to the present invention is composed of a large number of parts. For example, in consideration of avoiding the risk of adversely affecting the human body such as electric shock, the spinning nozzle holder 2 is preferably a material that insulates between the spinning spinning nozzle 1 and the metal spinning nozzle swinging motor 4, and captures the polymer compound fiber structure on the columnar or cylindrical electrode 14. In consideration of improving the collection rate, the grounding portion other than the electrode should be lost as much as possible, and the base plate 13 for the fiber structure recovery part, the bearing support part 12 for the columnar or cylindrical electrode, etc. should be made of an insulating material. It is preferable to select. Further, due to structural problems, even when a conductor is used as a material, the columnar or cylindrical electrode bearing support and the protective covers 19 and 20 of the rotary motor as exemplified in the present invention are processed with an insulating material, It is preferable to install.

Therefore, in the present invention, a manufacturing apparatus stand that holds and / or surrounds the spinning portion (A), the columnar or cylindrical electrode (B), the device (C) that swings at a constant speed, and the rotation drive device (D). It is preferable that the volume resistivity of the structure such as 10 ¹⁰ to 10 ²⁰ Ω · m. 1 and 2, the structure such as the manufacturing apparatus frame to be subjected to the spinning nozzle holder 2, the spinning nozzle unit base plate 7, the fiber structure recovery unit base plate 13, and the columnar or cylindrical electrode bearing support unit The protective cover 19 and the columnar or cylindrical electrode rotary motor protective cover 20 can be exemplified, but are not limited thereto.

  Examples of the material having the volume resistivity described above include polyacetal, ultrahigh molecular weight polyethylene, polyether ether ketone, polycarbonate, polyethylene terephthalate, polyethylene naphthalate, polybutylene terephthalate, acrylic, Teflon (registered trademark), MC nylon ( Registered trademark) and the like, and at least one selected from these can be used, but is not limited thereto.

Next, a method for producing a cylindrical polymer compound fiber structure using the production apparatus described above will be described in detail below.
First, a polymer compound-containing solution is charged into the spinning nozzle 1, and the spinning nozzle 1 is fixed to the spinning nozzle holder 2.

  Examples of the polymer compound used in the present invention include polypropylene, polyethylene, polystyrene, polyethylene oxide, polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, poly-m-phenylene terephthalate, poly-p-phenylene isophthalate, polyfluoride. Vinylidene, polyvinylidene fluoride-hexafluoropropylene copolymer, polyvinyl chloride, polyvinylidene chloride-acrylate copolymer, polyacrylonitrile, polyacrylonitrile-methacrylate copolymer, polycarbonate, polyarylate, polyester carbonate, nylon, aramid, poly Examples include caprolactone, polylactic acid, polyglycolic acid, collagen, polyhydroxybutyric acid, polyvinyl acetate, and polypeptide Can, at least one selected from these are used, but the invention is not particularly limited thereto.

  Examples of the solvent used in the present invention include methanol, ethanol, 1-propanol, 2-propanol, tetraethylene glycol, triethylene glycol, methyl isobutyl ketone, methyl-n-hexyl ketone, methyl-n-propyl ketone, and diisopropyl. Ketone, diisobutyl ketone, acetone, phenol, 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, o-chlorotoluene, p-chlorotoluene, chloroform, carbon tetrachloride, 1,1-dichloroethane, 1,2-dichloroethane, dichloropropane, dibromoethane, dibro Examples include propane, methyl bromide, ethyl bromide, propyl bromide, benzene, toluene, hexane, cyclohexane, cyclopentane, o-xylene, p-xylene, m-xylene, water, etc., and at least one selected from these However, it is not particularly limited to these.

Next, driving of the columnar or cylindrical electrode rotary motor 16 provided with the columnar or cylindrical electrode 14 is started. Rotational speed of the range of the cylindrical or cylindrical electrode 14 is 0.5～100Rpm, is set so as to satisfy the above equation (1) to (3). Below the stated range, the rotation of the motor 16 becomes unstable, and above the stated range, it becomes difficult to satisfy the above formulas (1) to (3).

  Next, the swing speed of the spinning nozzle swinging motor 4 is set and the driving is started, and the applied voltage is set by the high voltage applying device 10 to start the application of the high voltage. A polymer compound is spun from the tip of the spinning nozzle 1 and a fiber structure of the polymer compound is deposited on the rotating electrode 14.

  After leaving for a certain period of time, all power sources are shut off and the electrode 14 is removed from the apparatus. Then, the deposited polymer compound fiber structure is extruded in a direction parallel to the rotation axis to obtain a cylindrical polymer compound fiber structure.

  In the above-described extrusion operation of the polymer compound fiber structure, extrusion is performed while applying an equal force to both end points in the rotation axis direction of the fiber structure deposited on the electrode 14 and all arbitrary points. In this case, the tube wall structure of the fiber structure becomes a structure close to a plane, but according to the present invention, one end point in the rotation axis direction of the fiber structure deposited on the electrode 14 is fixed, By extruding while applying a uniform force from one end point, a tube wall structure having a bellows shape can be manufactured.

  Further, in the process of manufacturing the above-described polymer compound fiber structure, continuous between the spinning nozzle 1 and the electrode 14, that is, as shown in FIG. 3, and / or on the electrode 14, that is, as shown in FIG. Alternatively, the fiber structure can be neutralized intermittently. By performing the static elimination treatment, a polymer compound fiber structure having a fiber diameter and a basis weight that cannot be achieved in a normal production process can be produced. For example, the fiber structure having a multilayer structure can be obtained by performing intermittent treatment.

  The thickness of the polymer compound fiber structure manufactured by the above-described method is actually uniform within the swing range of the spinning nozzle 1. According to the present invention, within the oscillation range of the spinning nozzle 1, the standard deviation σ (μm) of the tube wall thickness at an arbitrary point of 50 or more in the cylindrical polymer compound fiber structure is less than 15. It becomes.

  Hereinafter, the present invention will be described in detail with reference to examples, but the present invention is not limited thereto.

[Example 1]
Into a glass container (internal volume: 50 mL), 2 g of polyacrylonitrile was added, and 6 g of ethanol and 12 g of N, N-dimethylformamide were further added. After sealing the container, the mixture was shaken and stirred in a hot water bath at 70 ° C., and it was confirmed that polyacrylonitrile was uniformly dissolved in the aforementioned solvent. The container was opened, 5 mL of the solution prepared by the above-described method was sucked up with a glass pipette with a suction rubber stopper, and the spinning nozzle 1 (total length: 120 mm, spinning side end cross-sectional area: 0.2 mm) made of a glass tube. ² and the other end cross-sectional area: 20 mm ² ). The spinning nozzle 1 is attached to the spinning nozzle holder 2 of the apparatus illustrated in FIGS. 1 and 2, and a cylindrical electrode 14 made of SUS316 having a diameter of 8 mm is attached between the electrode bearing 11 and the electrode holder 15. The spinning nozzle swinging motor 4, the electrode rotating motor 16, and the spinning nozzle 1 so that the swinging speed of the spinning nozzle 1 is 10 mm / second, the rotational speed of the cylindrical electrode 14 is 60 rpm, and the applied voltage to the prepared solution is 10 kV; The output value of the high voltage supply device 10 was adjusted. The distance H between the cylindrical electrode 14 and the fiber structure recovery part base plate 13 is 200 mm, the holder 2 is made of Teflon (registered trademark) (volume resistivity: 10 ¹⁸ Ω · m), the base plate 7 and 13 are made of MC nylon (registered trademark) (volume specific resistivity: 10 ¹³ Ω · m), and the material of the electrode bearing support protective cover 19 and the electrode rotary motor protective cover 20 is acrylic (volume specific) Resistivity: 10 ¹⁵ Ω · m). All the motor drive power and the high voltage supply device 10 were turned on, and the production of the polymer compound fiber structure was started. It was confirmed that the prepared solution spun at the tip of the spinning nozzle 1 and that ultrafine fibers were deposited on the cylindrical electrode 14 to form a fiber structure. In addition, during the production of the fiber structure, the state of rotation of the cylindrical electrode 14 is photographed all the time with an ultra-high speed camera (shooting speed: 350,000 frames / second), and the maximum shake width W is obtained from the obtained still image. Identified. The manufacturing time was set to 3 minutes, and when 3 minutes passed from the start of manufacturing, all power supplies were shut off, and the cylindrical electrode 14 was removed from the apparatus. When one end point of the electrode 14 is fixed and the obtained fiber structure is extruded while applying a uniform force from the other end point, a cylindrical fiber structure having a bellows-like tube wall structure is obtained. It was. And in order to confirm the uniformity of the tube wall thickness of the said fiber structure, the said fiber structure is cut | disconnected in the center axis direction of a cylinder, the thickness of 50 arbitrary points is measured with a micro gauge, and these average value _tav And the standard deviation σ was calculated. Amplitude W of the mean value t _av, standard deviation sigma, and the representative value t ₁ ~t 10 of the tube wall thickness of 10 extracted from randomly measured values described above for _50, further rotation axis as shown in Table 1 Met.

[Example 2]
4 is used together with the static eliminator, and the diameter D of the cylindrical electrode 14 is 120 mm, the rotational speed is 10 rpm, and the cylindrical electrode 14 and the base plate 13 for the fiber structure recovery unit are used. The same operation as in Example 1 was performed except that the distance H was 150 mm and the manufacturing time was 5 minutes. The average value t _av of the tube wall thickness (measured value) at 50 arbitrary points of the obtained fiber structure, the standard deviation σ, and representative of 10 tube wall thicknesses randomly extracted from the above-mentioned 50 measured values. The values t _{1 to} t ₁₀ and the runout width W of the rotating shaft were as shown in Table 1.

[Example 3]
The same operation as in Example 2 was performed except that the diameter D of the cylindrical electrode 14 was 12 mm, the rotation speed was 20 rpm, and the production time was 3 minutes. The average value t _av of the tube wall thickness (measured value) at 50 arbitrary points of the obtained fiber structure, the standard deviation σ, and representative of 10 tube wall thicknesses randomly extracted from the above-mentioned 50 measured values. The values t _{1 to} t ₁₀ and the runout width W of the rotating shaft were as shown in Table 1.

[Example 4]
It implemented similarly to Example 1 except the diameter D of the cylindrical electrode 14 having been 3 mm. The average value t _av of the tube wall thickness (measured value) at 50 arbitrary points of the obtained fiber structure, the standard deviation σ, and representative of 10 tube wall thicknesses randomly extracted from the above-mentioned 50 measured values. The values t _{1 to} t ₁₀ and the runout width W of the rotating shaft were as shown in Table 1.

[Example 5]
The same procedure as in Example 2 was performed except that the distance H between the columnar electrode 14 and the base plate 13 for the fiber structure recovery part was 50 mm and the manufacturing time was 8 minutes. The average value t _av of the tube wall thickness (measured value) at 50 arbitrary points of the obtained fiber structure, the standard deviation σ, and representative of 10 tube wall thicknesses randomly extracted from the above-mentioned 50 measured values. The values t _{1 to} t ₁₀ and the runout width W of the rotating shaft were as shown in Table 1.

[Example 6]
The material of the cylindrical electrode bearing support part protection cover 19 and the rotary motor protection cover 20 for the electrode is changed to SUS304, and the distance H between the electrode 14 and the fiber structure recovery part base plate 13 is set to 200 mm. Performed as in Example 3. The average value t _av of the tube wall thickness (measured value) at 50 arbitrary points of the obtained fiber structure, the standard deviation σ, and representative of 10 tube wall thicknesses randomly extracted from the above-mentioned 50 measured values. The values t _{1 to} t ₁₀ and the runout width W of the rotating shaft were as shown in Table 1.

[Comparative Example 1]
The cylindrical electrode bearing 11 and the bearing support 12 are removed from the apparatus used in Example 1, and the apparatus is changed so that the cylindrical electrode 14 is supported only by the electrode holder 15. The same operation as in Example 4 was performed except that the rotation speed of 14 was set to 100 rpm. The average value t _av of the tube wall thickness (measured value) at 50 arbitrary points of the obtained fiber structure, the standard deviation σ, and representative of 10 tube wall thicknesses randomly extracted from the above-mentioned 50 measured values. The values t _{1 to} t ₁₀ and the runout width W of the rotating shaft were as shown in Table 1.

[Comparative Example 2]
The same operation as in Example 1 was performed except that the diameter D of the cylindrical electrode 14 was 5 mm and the rotation speed was 400 rpm. The average value t _av of the tube wall thickness (measured value) at 50 arbitrary points of the obtained fiber structure, the standard deviation σ, and representative of 10 tube wall thicknesses randomly extracted from the above-mentioned 50 measured values. The values t _{1 to} t ₁₀ and the runout width W of the rotating shaft were as shown in Table 1.

It is a side schematic diagram of an example of a manufacturing device in the present invention. It is a plane schematic diagram of an example of a manufacturing device in the present invention. In the manufacturing apparatus in this invention, it is a schematic side view of the example which has arrange | positioned the static elimination apparatus between the spinning part (A) and the columnar or cylindrical electrode (B). FIG. 5 is a schematic side view of an example in which a static eliminator is disposed at a position opposite to the spinning portion (A) across a columnar or cylindrical electrode (B) in the production apparatus according to the present invention.

Explanation of symbols

1. Spinning nozzle 2. 2. Spindle nozzle holder 3. High voltage application electrode 4. Spinning nozzle swing motor 5. Slide rail 6. Spindle nozzle holder support section 7. Base plate for spinning nozzle 8. High voltage application wiring bundling section 10. High voltage application wiring High voltage supply device 11. 11. Bearing for cylindrical or cylindrical electrode 12. Bearing support for columnar or cylindrical electrode Base plate for fiber structure recovery unit 14. Columnar or cylindrical electrode 15. Column or cylindrical electrode holder 16. 18. Rotary motor for columnar or cylindrical electrode Ground wiring 18. Ground electrode 19. Protective cover for bearing support for columnar or cylindrical electrode 20. 20. Protective cover for cylindrical or cylindrical electrode rotation motor Static eliminator

Claims (9)

At least one spinning section (A) for spinning a polymer compound-containing solution to which a positive or negative high voltage is applied;
At least one rotating columnar or cylindrical electrode (B) to which a high voltage having a polarity opposite to that of (A) is applied or grounded;
It comprises a device (C) that swings the spinning section (A) at a constant speed parallel to the rotation axis of the electrode (B), and a rotation drive device (D) of the electrode (B).
A fiber structure that discharges a polymer compound-containing solution from the spinning section (A) toward the electrode (B) and deposits the fiber structure made of the polymer compound on the columnar or cylindrical electrode (B). Manufacturing equipment,
The rotating columnar or cylindrical electrode (B) is fixed at both ends and has a rotation speed in the range of 0.5 to 100 rpm, and the columnar or cylindrical electrode (B) The outer diameter D (mm) and the maximum deflection width W (mm) in the radial direction of the portion where the rotating shaft is most distorted during rotation satisfy the following formulas (1) to (3): Compound fiber structure manufacturing equipment.
W <5 / D (where 0 <D ≦ 10) (1)
W <D / 20 (where 10 <D ≦ 100) (2)
W <5 (where 100 <D) (3) The manufacturing apparatus according to claim 1, wherein a portion where the rotation axis is most distorted is a center in a length direction of the rotating electrode (B). The manufacturing apparatus of Claim 1 or 2 which has a static elimination apparatus. In the spinning section (A), the electric attractive force generated between the spinning section (A) and the columnar or cylindrical electrode (B) and / or the liquid containing the polymer compound-containing solution held in the spinning section (A) the pressure on the head, the manufacturing apparatus according to any one of claims 1-3, characterized by supplying the polymer-containing solution. Production of holding and / or enclosing the spinning section (A), the electrode (B), the apparatus (C) for swinging the spinning section (A) at a constant speed, and the rotation driving apparatus (D) of the electrode (B) an apparatus according to any one of claims 1 to 4, the volume resistivity of the device rack stand of the structure, characterized in that in the range of ¹⁰ 10 ~10 ²⁰ Ω · m. Spin at least one spinning part (A) that spins a polymer compound-containing solution to which a positive or negative high voltage is applied. The polymer compound-containing solution is discharged toward one rotating columnar or cylindrical electrode (B), and a fiber structure made of the polymer compound is deposited on the columnar or cylindrical electrode (B). the method for producing the fiber structure parallel to the axis extruding the fiber structure, characterized in that to obtain a cylindrical fiber structure with respect to the axis of rotation of those circular columnar or cylindrical electrode (B) The spinning section (A) has a function of swinging at a constant speed in parallel. The rotating columnar or cylindrical electrode (B) is fixed at both ends and has a rotational speed of 0.5 to in the range of 100 rpm, further the cylinder Or the outer diameter D (mm) and the rotary shaft during the rotation in the radial direction of the most distorted portion maximum amplitude W of the cylindrical electrode (B) (mm) satisfies the following formula (1) to (3) A method for producing a polymer compound fiber structure, comprising:
W <5 / D (where 0 <D ≦ 10) (1)
W <D / 20 (where 10 <D ≦ 100) (2)
W <5 (where 100 <D) (3) The manufacturing method according to claim 6, wherein the tube wall structure of the cylindrical fiber structure is bellows-like. Performing static elimination treatment on the fiber of the polymer compound spun from the spinning part (A) and / or the fiber structure of the polymer compound on the columnar or cylindrical electrode (B). The manufacturing method according to claim 6 or 7, wherein the manufacturing method is characterized. In the swinging range of the spinning portion (A), the standard deviation σ (μm) of the tube wall thickness at an arbitrary point of 50 or more of the cylindrical fiber structure is within a range of less than 15. A polymer compound fiber structure obtained by the production method according to any one of claims 6 to 8.

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