JP2007303015A - Static spinning apparatus - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a static spinning apparatus capable of obtaining a uniform fibrous web, and to provide a static spinning apparatus capable of settling troubles in nozzle change. <P>SOLUTION: The static spinning apparatus has axes of adjacent nozzle holes, which are inclined to each other. The static spinning apparatus includes cleaning means having a liquid-pooling container having a cylindrical surrounding wall capable of rotating around the axis of the surrounding wall, nozzle holes disposed on the surrounding wall to form a circle, and cleaning nozzle holes reaching a standing region facing the outer periphery of the surrounding wall with the rotation of the liquid-pooling container, rotationally driving means for the liquid-pooling container, and shut-off means to temporally shut off conduction of the reaching nozzle. A static spinning method uses a spinning solution including an adhesive. Further, the static spinning method using the spinning solution including polyethylene terephthalate and hexafluoroisopropanol, and the static spinning method using the spinning solution including sericin and fibroin are also provided. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to an electrospinning apparatus and a laminated sheet using a fiber web obtained by electrospinning.

  Electrostatic spinning is spinning in which an electric field is applied to a spinning solution discharged from a nozzle hole of a nozzle to form a fiber. Electrospinning can obtain fibers with submicron or nano-order fiber diameters, and can be made into fibers even with resins that are difficult to melt-spin, so application fields that could not be realized using conventional fibers Expansion to is expected.

  For example, as shown in FIG. 12, the fiber web is manufactured by electrostatic spinning. The polymer solution, which is a raw material sent to the distribution rectifying block 202 by the metering pump 201, is sent to the base portion 204 and passed through the fine nozzle holes 208. Simultaneously with extrusion, an electric field is applied by a high-voltage power source 206 to form fibers, and the fibers are accumulated on an accumulating device 207 including a collecting conveyor. This fiber has a three-dimensional network structure, and is accumulated by the accumulating device 207 to become a fiber web. (For example, see Patent Document 1)

  In electrostatic spinning, the fibers formed by discharging from the nozzle are charged, and the fibers formed by discharging from a plurality of nozzle holes are repelled because they have the same charge. The fiber groups interfere with each other and the collecting surface, and a uniform web is not obtained.

  On the other hand, clogging of the nozzle holes with dirt, foreign matter, etc. is an obstacle to obtaining a uniform web. Although clogging with foreign substances can be prevented to some extent by strengthening the filtration of the solution, no effective countermeasure has been found against the occurrence of contamination due to long-time use of the nozzle holes. For this reason, it is necessary to periodically stop the operation and replace the nozzles at the same time, which leads to a decrease in the operation rate and an increase in work for stopping, nozzle replacement, and restart, which is a major factor in increasing costs. It becomes.

Furthermore, the fiber web produced by electrospinning is formed into a sheet and wound up. This electrospun fiber sheet is laminated through a base fabric and an adhesive and used as a laminate. There are many. As described above, the production of the laminate requires at least three steps of the lamination step, the application of the adhesive to the base fabric or the laminate, and the curing step of the adhesive (for example, see Patent Document 2). Simplification of the process is desired.
JP-A 63-145465 JP 2005-527358 A

  An object of the present invention is to provide an electrostatic spinning device capable of obtaining a uniform fiber web.

  An object of the present invention is to provide an electrostatic spinning device that can eliminate troubles associated with nozzle replacement.

  An object of the present invention is to provide an electrospinning method in which the step of obtaining a laminate is simplified.

  The gist of the present invention is an electrospinning apparatus for producing a fiber by applying an electric field to a spinning solution discharged from a nozzle hole of a nozzle, the apparatus comprising a plurality of nozzles and adjacent to each other. It is an electrostatic spinning device in which the axial center directions of the holes are inclined to each other.

Further, the gist of the present invention is to provide a liquid storage container for temporarily storing a spinning solution, and for spinning that is discharged from a plurality of nozzle holes respectively connected to a liquid storage part of the liquid storage container. An electrospinning apparatus for applying an electric field to a solution to form a fiber,
The liquid reservoir has a cylindrical peripheral wall, the hollow portion of the peripheral wall serves as the liquid reservoir, and is rotatable about the axis of the peripheral wall;
The nozzle hole is arranged around the peripheral wall in the peripheral wall,
Cleaning means for cleaning the nozzle hole that has reached a stationary region facing the outer periphery of the peripheral wall as the liquid reservoir is rotated;
Rotation driving means for rotating the liquid reservoir, and
It is an electrostatic spinning device provided with a blocking means for temporarily blocking conduction of the nozzle hole reaching the region.

Further, the gist of the present invention is that the spinning solution discharged from the nozzle hole connected to the liquid storage portion of the liquid storage container for temporarily storing the spinning solution is subjected to an electric field to generate a fiber. A nozzle structure of an electrospinning device,
A funnel portion having a funnel-like shape and a flange portion formed on the upper edge of the funnel portion, wherein the plurality of funnel portions are arranged in parallel with each other and connected via the flange portion. A resin nozzle member,
A pressing member in which a plurality of through holes corresponding to each funnel portion is formed,
An insertion hole for inserting each funnel part is formed at the bottom of the liquid reservoir,
The funnel portion is inserted into the insertion hole in a state where the tube tip of the funnel portion protrudes to the outside of the liquid storage container, and the flange portion is superimposed on the bottom portion,
In the state where the through hole is electrically connected to the corresponding funnel portion, the flange portion is detachably sandwiched between the pressing member and the bottom portion.

Furthermore, the gist of the present invention is that fiber is produced by applying an electric field to the spinning solution discharged from the nozzle hole connected to the liquid reservoir portion of the liquid reservoir for temporarily storing the spinning solution. A nozzle structure of an electrostatic spinning device,
A funnel portion having a funnel-like shape and a flange portion formed on the upper edge of the funnel portion, wherein the plurality of funnel portions are arranged in parallel with each other and connected via the flange portion. A resin nozzle member,
A holding member formed with an insertion hole for inserting each funnel part,
A through hole corresponding to each funnel portion is formed at the bottom of the liquid reservoir,
In a state where the tube tip of the funnel portion protrudes to the outside of the liquid storage container and the through hole is connected to the corresponding funnel portion, the nozzle member is superimposed on the outside of the bottom portion,
The flange portion has a nozzle structure in which the funnel portion is inserted into the insertion hole and is detachably sandwiched between the pressing member and the bottom portion.

  Further, the gist of the present invention is that the molded article is composed of the nozzle member used in the nozzle structure.

Further, the gist of the present invention is an electrospinning method for obtaining a fiber web by collecting an electric field by applying an electric field to a spinning solution discharged from a nozzle hole and collecting it on a base sheet.
In the electrospinning method, the solution contains an adhesive as a dissolving component.

Furthermore, the gist of the present invention resides in a composite sheet obtained by laminating the fiber web obtained by the electrospinning method and the base sheet.
Furthermore, the gist of the present invention is an electrospinning method in which an electric field is applied to a spinning solution discharged from a nozzle hole to form a fiber,
The solution is an electrospinning method comprising polyethylene terephthalate and a solvent of polyethylene terephthalate, wherein the solvent contains hexafluoroisopropanol.

  The solvent can further include chloroform.

  Further, the gist of the present invention is that the solution further contains an adhesive as a dissolved component, and is made into a fiber by applying an electric field to the solution discharged from the nozzle hole, and is accumulated on the base sheet. It is the said electrospinning method which obtains a fiber web.

  The adhesive may be a chloroprene adhesive.

  Furthermore, the gist of the present invention resides in a composite sheet obtained by laminating the fiber web obtained by the electrospinning method and the base sheet.

Furthermore, the gist of the present invention is an electrospinning method in which an electric field is applied to a spinning solution discharged from a nozzle hole to form a fiber,
It is an electrospinning method in which the solution is a solution of sericin.

Furthermore, the gist of the present invention is an electrospinning method in which an electric field is applied to a spinning solution discharged from a nozzle hole to form a fiber,
The solution is an electrospinning method in which the solution is a solution of sericin and fibroin.

  The gist of the present invention is that the web is made of fibers obtained by the electrospinning method.

  Further, the gist of the present invention resides in a web made of fibers obtained by the electrospinning method.

  According to the present invention, an electrostatic spinning device capable of obtaining a uniform fiber web is provided.

  ADVANTAGE OF THE INVENTION According to this invention, the electrostatic spinning apparatus which can eliminate the trouble accompanying nozzle replacement | exchange is provided.

  According to the present invention, an electrospinning method is provided in which the step of obtaining a laminate is simplified.

  The aspect of the electrostatic spinning device of the present invention will be described. In addition, in this specification, the same code | symbol written over each figure shows the same or similar member and thing. In the electrospinning apparatus of the present invention, a base part in which a plurality of nozzles are arranged in the longitudinal direction is used as shown in FIG. A nozzle hole is formed in the nozzle, and an electric field is applied to the polymer solution discharged from the nozzle hole by an electric field by a high-voltage power source, and the fiber web is manufactured by collecting the polymer solution on a collecting device including a collecting conveyor. .

  In normal electrostatic spinning, the nozzle holes are arranged downward and in parallel with each other, whereas in the electrostatic spinning device of the present invention, the axial directions of the nozzles of each nozzle are oblique to each other. is doing.

  On the other hand, in the embodiment shown in FIG. 1 according to the present invention, the axial directions of the nozzle holes 8 projected on the plane perpendicular to the longitudinal direction of the cap portion 4 are inclined with respect to the adjacent nozzles 9. ing. In the embodiment shown in FIG. 2, with respect to the adjacent nozzles 9, the axial directions of the nozzle holes projected on the plane orthogonal to the longitudinal direction of the cap portion 4 are oblique to each other, and on the plane orthogonal to this plane The axial directions of the nozzle holes projected on are inclined. That is, the nozzle holes of adjacent nozzles are twisted with respect to each other.

  The fiber group formed by fiberizing the solution discharged from the nozzle holes is charged, and the fiber groups discharged from the nozzle holes adjacent to each other repel each other by electrostatic force and interfere with each other. Sprayed in a wider area than the collecting area to be collected, the collected web becomes uneven. The arrangement of the nozzle 9 shown in FIG. 1 or FIG. 2 prevents the phenomenon that the web is disturbed due to the interference between the fiber groups, and allows the fibers to be collected within a predetermined collection area within the target collection area. Fiber web is obtained.

  FIG. 3 shows an electrostatic spinning device 2 according to another embodiment of the present invention. The electrostatic spinning device 2 includes a liquid storage container 20 having a cylindrical peripheral wall 24. The liquid storage container 20 is a container for temporarily storing a spinning solution, and a hollow part of the liquid storage container 20 is a liquid storage part 22. A plurality of nozzles 9 in which nozzles 9 that conduct to the liquid reservoir 22 are formed are provided on the peripheral wall 24.

  The liquid reservoir 20 includes one side wall 26 and another side wall 28. The joint flange 30 at the edge of the peripheral wall 24 and the one side wall 26 and the joint flange 32 at the outer edge of the other side wall 28 are fastened by bolts 34 so that both side openings of the peripheral wall 24 are one side wall 26 and the other side wall. 28 is sealed.

  A drive shaft 38 having a common axis with the axis of the peripheral wall 24 is provided at the center of the one side wall 26, and the drive shaft 38 is formed with a through hole 36 in the axial direction and is externally inserted. It is supported by a bearing 40. Further, the drive shaft 38 is rotationally driven around its own axis by a drive source 43 via a gear group 42.

  At the center of the other side wall 28, a drive shaft 39 having a common axis with the axis of the peripheral wall 24 is provided, and the drive shaft 39 is formed with a through hole 37 in the axial direction and is externally inserted. Supported by a bearing 41. With this configuration, the liquid storage container 20 is supported via the bearings 40 and 41 and is driven to rotate by the drive source 43 around its own axis. The bearings 40 and 41 are fixed to a base (not shown).

  A blocking member 44 is installed in the hollow portion of the liquid reservoir 20. The blocking member 44 includes a semi-cylindrical curved plate 46, and bowl-shaped side plates 48 and 49 disposed on both sides of the curved plate 46, and the curved edge of the curved side 46 is curved. The parts are joined together and joined. A fixing arm 50 is joined to the side plate 48.

  The maximum curvature of the curved outer surface 47 of the curved plate portion 46 is substantially the same as the maximum curvature of the inner wall surface of the peripheral wall 24. Further, the blocking member 44 is fixed via a fixing arm 50 at a position where the axial center direction of the original cylinder of the semi-cylindrical shape coincides with the axial center of the peripheral wall 24, and thereby the curved plate portion 46. The outer curved surface and the inner wall surface of the peripheral wall 24 are substantially in surface contact over the entire surface of the contact portion. One end of the fixing arm 50 is fixed to the blocking member 44, is inserted through the through hole 36, and the other end is fixed to a device base (not shown) outside the liquid reservoir 20.

  Further, the through hole 37 is connected to a feed path 54 of a liquid feed pipe 52 for sending the solution to the liquid reservoir 22 via a rotary joint 56.

  On the peripheral wall 24, a plurality of nozzles 9 are arranged around the peripheral wall 24 in a circumferential direction and a normal direction.

  On the other hand, the electrostatic spinning device 2 including the collection unit 3 including the conveyor 70 such as a slat conveyor having a conveyance surface curved so that the collection surface is parallel to the outer peripheral surface of the peripheral wall 24 in FIG. As shown in the layout diagram, the nozzle hole which has moved to the stationary region 58 facing the outer peripheral surface of the peripheral wall 24 with the rotation of the liquid reservoir 20 and reached the stationary region 58 is cleaned. A cleaning means 60 such as 62 is provided. When the nozzle 9 that has reached the stationary region 58 is being cleaned by the cleaning means 60, the entrance of the nozzle hole inside the liquid reservoir 20 of the nozzle 9 is blocked by the curved plate portion 46 (FIG. 3). The conduction of the nozzle 9 is temporarily cut off. That is, the curved plate portion 46 is fixed at a position where the outer surface 47 faces the stationary region 58 with the peripheral wall 24 therebetween. The stationary region 58 is a region having a stationary relationship with a base (not shown) to which the bearings 40 and 41 are fixed.

  With this configuration, the nozzle 9 that has reached the stationary region 58 is cleaned by the cleaning means 60, while reaching the other stationary region 59 on the opposite side of the stationary region 58 with the axis of the peripheral wall 24 in between. The solution is discharged from the nozzle 9 and electrostatic spinning is performed. In this way, since the solution is constantly discharged from the nozzles 9 that have sequentially reached the other stationary regions 59 and electrostatic spinning is performed, while the nozzles 9 that have sequentially reached the stationary region 58 are sequentially cleaned, Spinning is continued without stopping the discharge of the nozzle 9 and the nozzle 9 is cleaned. The rotation of the liquid reservoir 20 may be continuous, but may be intermittent.

  The cleaning means 60 is not particularly limited as long as it cleans the nozzle 9, but may be cleaned by ejecting air or liquid in addition to the rotating brush.

  On the other hand, in the present invention, it is possible to replace the nozzle used for the electrospinning and to make it disposable, thereby eliminating the need for nozzle replacement and eliminating the need for nozzle cleaning. In order to make the nozzle disposable, it is necessary to reduce the cost of the nozzle while maintaining the sealing performance of the solution and to simplify the nozzle mounting operation.

  A nozzle structure 100 shown in FIG. 5 can be suitably used to satisfy this requirement.

  The nozzle structure 100 shown in FIG. 5 is fiberized by applying an electric field to the spinning solution discharged from the nozzle hole 105 connected to the liquid storage portion 103 of the liquid storage container 101 for temporarily storing the spinning solution. The nozzle structure of the electrostatic spinning device includes a resin nozzle member 102 and a pressing member 120 that presses and fixes the nozzle member 102. As shown in FIG. 7, the nozzle member 102 includes a funnel portion 112 having a funnel-like shape and a flange portion 116 formed on the upper edge portion 115 of the funnel portion 112, and the plurality of funnel portions 112 are shafts. The cores are arranged in parallel to each other and are connected via a flange 116.

  An insertion hole 114 for inserting the funnel portion 112 is formed in the bottom portion 110 of the liquid reservoir 101 corresponding to each funnel portion 112. The holding member 120 is formed with a plurality of through holes 124 corresponding to the funnel portions 112.

The funnel portion 112 is inserted into the insertion hole 114 in a state where the pipe tip 126 of the funnel portion 112 protrudes to the outside of the liquid storage container 101, and the flange portion 116 of the nozzle member 102 is superimposed on the bottom portion 110.
In a state where the through hole 124 is electrically connected to the corresponding funnel portion 112, the flange portion 116 is detachably sandwiched between the pressing member 120 and the bottom portion 110. The holding member 120 and the bottom part 110 are fastened by fastening bolts 131 with the flange part 116 therebetween.

  Moreover, the nozzle structure 100a shown in FIG. 6 can be used suitably as another aspect which satisfy | fills the above-mentioned requirements.

  The nozzle structure 100a shown in FIG. 6 is also the nozzle structure of an electrostatic spinning apparatus that applies an electric field to the spinning solution discharged from the nozzle hole 105 that is electrically connected to the liquid reservoir 103a of the liquid reservoir 101a to produce a fiber. A resin nozzle member 102 and a pressing member 120a for pressing and fixing the nozzle member 102 are provided.

  A through hole 134 corresponding to each funnel 112 is formed in the bottom 110a of the liquid reservoir 101a. A plurality of insertion holes 136 into which the funnel portions 112 are inserted are formed in the holding member 120 a so as to correspond to the funnel portions 112.

  The funnel portion 112 is inserted into the insertion hole 136 with the tube end 126 of the funnel portion 112 protruding to the outside of the liquid storage container 101, the flange portion 116 is superimposed on the holding member 120a, and the through hole 134 is a corresponding funnel. The flange 116 is detachably sandwiched between the pressing member 120a and the bottom 110a in a state of being electrically connected to the portion 112. The pressing member 120a and the bottom portion 110a are fastened by fastening bolts 131 with the flange portion 116 therebetween.

  Fixing of the pressing member and the bottom of the liquid storage container in the nozzle structure 100 and the nozzle structure 100a is not limited to an embodiment using a fastening bolt, and a patch and lock mechanism may be used. Other removable fixing methods may be used.

  With the configuration of the nozzle structure 100 and the nozzle structure 100a, the nozzle is mounted simply by setting the nozzle member on the bottom 110 and fixing the flange 116 with the pressing member. Further, the nozzle can be removed simply by removing the pressing member and removing the nozzle member 102 from the bottom. Further, since the nozzle member 102 is integrally connected except for the nozzle hole 105, the sealing performance of the solution is good. Further, the nozzle member 102 has a thin plate shape for any part of the end face shape of the longitudinal section, and the volume occupied by the actual material is small as a whole, and it is lightweight and can be manufactured at a low material cost.

  In still another embodiment of the present invention, polyethylene terephthalate is electrospun. Polyethylene terephthalate has a higher melting point than polypropylene, and it is difficult to make ultrafine fibers by melt spinning such as melt blow, and since there is no appropriate solvent, electrostatic spinning is also difficult. It became possible to make uniform ultrafine fibers.

  In the present invention, phenol, nitrobenzene, O-cresol, hexafluoroisopropanol, or the like can be used as a solvent for polyethylene terephthalate. Of these, hexafluoroisopropanol (HFIP) is preferably used. A mixed solvent of HFIP and chloroform is preferably used. The mixing weight ratio of the mixed solvent is preferably about 1: 1.

The conditions for electrospinning with these solvents are as follows: Solution concentration: 1 to 20% by weight
Nozzle hole diameter: 10 to 2000 μm
Number of nozzles: 1 to 20 / cm ²
Nozzle spacing: 2-20mm
Discharge amount: 0.01 to 1 g / mim / nozzle applied voltage: 5 to 50 KV
Distance between nozzle and collection surface: 3-30cm
Preferably, the fiber diameter of the resulting fiber is 10 nanometers to 10 microns.

  In yet another embodiment of the invention, sericin is electrospun. Sericin is difficult to fiberize by ordinary solution spinning, and in particular, it is difficult to obtain fine fibers having a diameter of 10 μm or less, but in the present invention, sericin can be made into ultrafine fibers.

  In this case, water, formic acid, HFIP or the like is preferably used as the solvent.

The conditions for electrospinning sericin with these solvents are as follows: Solution concentration: 1 to 40% by weight
Nozzle hole diameter: 10 to 2000 μm
Number of nozzles: 1 to 20 / cm ²
Nozzle spacing: 2-20mm
Discharge amount: 0.01 to 1 g / mim / nozzle applied voltage: 5 to 50 KV
Distance between nozzle and collection surface: 3-30cm
It is preferable that a fiber having a fiber diameter of 5 nanometers to 2 microns is obtained.

The molecular weight of sericin used for electrospinning is 200 to 400,000.
In the present invention, a mixture of sericin and fibroin can be electrospun in the same manner as sericin electrospinning. For example, electrostatic spinning is performed using a solution in which sericin powder and fibroin powder are dissolved in a solvent such as water, formic acid, hexafluoroisopropanol, or the like. Electrospinning of the mixture is possible regardless of the mixing ratio of sericin and fibroin.

  An auxiliary third component for adjusting the properties of the solution and fibers may be added to the solution of sericin used for the electrospinning, or the solution of sericin and fibroin. Examples of the third component include a viscosity modifier, a colorant, an antioxidant, and a filler. In the present specification, the sericin solution means a solution containing sericin as a main component of the substance to be dissolved and optionally containing additives. The solution of sericin and fibroin means a solution containing sericin and fibroin as the main components of the substance to be dissolved and optionally containing additives.

  The fiber web of sericin or a mixture of sericin and fibroin thus obtained has excellent biocompatibility, and is suitably used as a medical substrate or a cosmetic substrate. Particularly, in a fiber web of a mixture of sericin and fibroin, a mixture of 40 to 90% by weight of sericin is most preferable as a medical base material because of its excellent strength and biocompatibility.

  The fiber web obtained by electrospinning is often laminated as a laminate by laminating a sheet-like material such as a knitted fabric, nonwoven fabric, paper, and film with an adhesive. In order to manufacture such a laminate, a step of manufacturing a fiber web by electrostatic spinning, a step of applying an adhesive to the sheet-like material, the sheet-like material to which the adhesive is applied, and the fiber web, And a step of curing the adhesive by heating or the like.

In yet another embodiment of the invention, the laminate can be obtained with very few steps.
That is, in this embodiment, a solution in which a polymer and an adhesive are dissolved in a solvent is used as a spinning solution. This solution may be obtained, for example, by mixing an adhesive with a polymer solution.

  Using such a mixed solution as a spinning solution, the fiber web is collected on the surface of the sheet by electrostatic spinning to form a superposition of the fiber web and the sheet, and the superposition is heated. By pressing and / or drying, the adhesive is cured, cooled and cured after melting, and a laminate is obtained.

  In the composite sheet, which is a laminate obtained in this way, the adhesive is distributed over the entire surface length of the constituent fibers of the fiber web, so that the adhesiveness between the fiber web and the sheet is good and the adhesive The amount of is small. Furthermore, since the constituent fibers are also bonded to each other at the contact point by this adhesive, the fiber web is uniformly bonded with a small amount of adhesive, resulting in a high strength, low frictional flaking and a flexible web state. It is done.

As the polymer used in the spinning solution in this embodiment and fiberized,
Polyvinylidene fluoride, polyvinylidene fluoride-hexafluoropropylene copolymer, polyacrylonitrile, polyacrylonitrile-methacrylate copolymer, polymethyl methacrylate, polyvinyl chloride, polyvinylidene chloride-acrylate copolymer, polyethylene, polypropylene, polybenz Imidazole, polyvinyl alcohol, cellulose, cellulose acetate butyrate, polypropylene oxide, polyethylene sulfide, SBS copolymer, nylon 6, nylon 66, nylon 11, nylon 12, nylon 610, nylon 612, and copolymers thereof, polyhydroxy Butyric acid, polyvinyl acetate, polyethylene oxide, collagen, polylactic acid, polyglycolic acid, polylactic acid-glycolic acid copolymer, polyarylate Polypropylene fumarate, polypeptide, protein, coal tar pitch, petroleum pitch, polybutylene succinate, polyethylene succinate, polystyrene, polycarbonate, polyhexamethylene carbonate, polyvinyl isocyanate, polybutyl isocyanate, polymethyl methacrylate, polyethyl methacrylate, poly Normal propyl methacrylate, polynormal butyl methacrylate, polymethyl acrylate, polyethyl acrylate, polybutyl acrylate, polyethylene terephthalate, polybutylene terephthalate, polytrimethylene terephthalate, polyethylene naphthalate, polymers of these polyester resins, polyparaphenylene terephthalate Lamid, polyparaphenylene terephthalamide-3 4'-oxydiphenylene terephthalamide copolymer, polymetaphenylene isophthalamide, cellulose diacetate, cellulose triacetate, methylcellulose, propylcellulose, benzylcellulose, fibroin, natural rubber, polyvinyl methyl ether, polyvinyl ethyl ether, polyvinyl normal Examples include propyl ether, polyvinyl isopropyl ether, polyvinyl normal butyl ether, polyvinyl isobutyl ether, polyvinyl tertiary butyl ether, polyvinylidene chloride, polyvinyl methyl ketone, polymethyl isopropenyl ketone, polycyclopentene oxide, and polystyrene sulfone. A mixture of two or more polymers selected from these polymers may be used.

  The solvent is not particularly limited as long as it dissolves these polymers and evaporates at the spinning stage to form a fiber. For example, water, ethanol, methanol, isopropanol, acetone, sulfolane acetone, propanol, Dichloromethane, formic acid, hexafluoroisopropanol, hexafluoroacetone, methyl ethyl ketone, chloroform, isopropanol, toluene, tetrahydrofuran, benzene, benzyl alcohol, 1,4-dioxane, carbon tetrachloride, cyclohexane, cyclohexanone, methylene chloride, phenol, pyridine, trichloroethane, Acetic acid, N, N-dimethylformamide, dimethyl sulfoxide, N, N-dimethylacetamide, 1-methyl-2-pyrrolidone, ethylene carbonate, propylene -Bonate, dimethyl carbonate, acetonitrile, N-methylmorpholine-N-oxide, butylene carbonate, 1,4-butyrolactone, diethyl carbonate, diethyl ether, 1,2-dimethoxyethane, 1,3-dimethyl-2-imidazolidinone, Examples include 1,3-dioxolane, ethyl methyl carbonate, methyl formate, 3-methyl oxazolidine-2-one, methyl propionate, and 2-methyl tetrahydrofuran. One solvent may be used alone, or a mixture of a plurality of solvents may be used.

  The adhesive may be an adhesive that can bond a fiber web made of a polymer (excluding the adhesive) constituting the spun fiber and a sheet-like material, and is soluble in a solvent for spinning. Although not particularly limited, examples thereof include an adhesive made of hot melt resin, an elastomeric adhesive, an acrylic adhesive, an epoxy adhesive, and a vinyl adhesive. Examples of elastomeric adhesives include polychloroprene rubber, styrene / butadiene rubber, butyl rubber, acrylonitrile / butadiene rubber, ethylene / propylene rubber, chlorosulfonated polyethylene rubber, and epichlorohydrin rubber. The adhesive is preferably blended in an amount of 0.5 to 10% by weight based on the polymer constituting the fiber (excluding the adhesive).

  In particular, in the electrostatic spinning of polyethylene terephthalate, by mixing a chloroprene-based adhesive with a spinning solution, a web having a uniform fiber diameter can be obtained together with an adhesive effect.

Example 1
Electrospinning was performed under the following conditions.
Polymer: Polyethylene terephthalate Solvent: HFIP
Solution concentration: 10% by weight
Nozzle hole diameter: 800 μm
Number of nozzles: 1
Discharge amount: 0.12 g / mim
Applied voltage: 10-30KV
Distance between nozzle and collection surface: 10cm
As shown in FIG. 8, a fiber web composed of uniform fibers having an average fiber diameter of 100 nm was obtained.

Example 2
A fiber web was obtained in the same manner as in Example 1 except that HFIP / chloroform = 1: 1 (weight ratio) was used as the solvent. Although the average fiber diameter was about 100 nm, as shown in the cross-sectional photograph of FIG. 9, resin beads having a diameter of about 10 times the fiber diameter were scattered in the web.

Example 3
A solution obtained by adding 3% by weight of a 30% by weight solution of chloroprene rubber as an adhesive (solvent: mixed solvent of normal hexane, cyclohexane, acetone, and isopropyl acetate) to the solution used in Example 2 as an adhesive was used as a spinning solution. Otherwise, electrospinning was carried out in the same manner as in Example 1, and a fiber web having a basis weight of 20 g / m ² was accumulated on the surface of the drawing paper placed on the collecting surface. As shown in FIG. 10, no resin beads were observed in the web, and a web composed of uniform fibers having an average fiber diameter slightly thicker than the fibers obtained in Example 1 was obtained. The peel strength between the fiber web and drawing paper was 0.01 N / 2 cm. Further, this fiber web was not peeled off even by five reciprocating frictions (test cloth: No. 3 cotton (JISL 0803)) using a friction tester of a dyeing fastness test (for JIS L 0849).

Example 4
50% by weight vinyl acetate solution as an adhesive solution (solvent: mixed solvent of ethanol and acetone)
Except that was used, electrospinning was carried out in the same manner as in Example 3, and the fiber web was accumulated on the surface of the drawing paper placed on the collecting surface. The peel strength between the fiber web and drawing paper was 0.10 N / 2 cm. In addition, this fiber web was hardly peeled by five reciprocating frictions (test cloth: No. 3 cotton (JISL 0803)) by a friction tester of a dyeing fastness test (for JIS L 0849). Resin beads having a diameter of about 10 times the fiber diameter were scattered and produced.

Example 5
A fiber web as shown in FIG. 11 was obtained in the same manner as in Example 2 except that HFIP / chloroform / isopropyl acetate = 1: 1: 0.04 (weight ratio) was used as the solvent. In this fiber web, resin beads having a diameter of about 10 times the fiber diameter were scattered and formed. Similar beads were produced when normal hexane, cyclohexane or acetone was used instead of isopropyl acetate as the third solvent. Therefore, it was found that the presence of chloroprene rubber spun the formation of beads and spun uniform fibers.

Example 6
Polyacrylonitrile was dissolved in N, N-dimethylformamide to prepare a solution having a solution concentration of 10% by weight. A spinning solution was prepared by adding 30% by weight of a chloroprene rubber solution (solvent: normal hexane) as an adhesive to this solution in an amount equivalent to 3% by weight of the adhesive.
Nozzle hole diameter: 500 μm
Number of nozzles: 1
Discharge amount: 0.03 g / mim
Applied voltage: 10-30KV
Distance between nozzle and collection surface: 10cm
Electrospinning was performed, and a fiber web having a weight per unit area of 20 g / m ² was accumulated on the surface of the drawing paper placed on the collecting surface. The peel strength between the fiber web and drawing paper was 0.01 N / 2 cm.

Example 7
The silk thread was subjected to a heat treatment at 120 ° C. in an aqueous 0.5 wt% sodium carbonate solution for hr to separate it into fibroin and sericin. Sericin dissolved in this aqueous solution was taken out by drying the aqueous solution to obtain sericin powder.
This sericin powder was dissolved in water at 90 ° C. to prepare a 10 wt% sericin aqueous solution, and electrostatic spinning was performed under the following conditions.
Nozzle hole diameter: 800 μm
Number of nozzles: 1
Discharge amount: 0.12 g / mim
Applied voltage: 10-30KV
Distance between nozzle and collection surface: 10cm
The obtained fiber had a diameter of 100 to 1000 μm, and a uniform fiber web was collected.

Example 8
The fibroin yarn after treatment in Example 7 was washed with water, dried and then dissolved in a 1: 1 weight ratio solution of calcium carbonate / water to obtain an aqueous fibroin solution. This solution was desalted by dialysis and dried to obtain fibroin powder.
The sericin powder obtained in Example 7 and this fibroin powder were mixed at a weight ratio of 1: 1 and dissolved in HFIP to obtain a 10 wt% solution.
Using this solution, electrospinning was performed under the same conditions as in Example 6. The obtained fiber had a diameter of 100 to 1000 μm, and a uniform fiber web was collected. The strength was higher than that of the fiber web obtained in Example 6.

  In addition, the present invention can be carried out in a mode in which various improvements, modifications, and changes are added based on the knowledge of those skilled in the art without departing from the spirit of the present invention.

An example of the aspect of the nozzle used for the electrostatic spinning apparatus of this invention is shown, Fig.1 (a) is a front schematic diagram, FIG.1 (b) is a side schematic diagram. The other example of the aspect of the nozzle used for the electrostatic spinning apparatus of this invention is shown, Fig.1 (a) is a front schematic diagram, FIG.1 (b) is a side schematic diagram. It is a front partial cross section end surface schematic diagram which shows an example of the other aspect of the electrostatic spinning apparatus of this invention. It is a cross-sectional schematic diagram of the AA direction of FIG. 3a. It is a side surface schematic diagram which shows the structure including the collection part of the electrostatic spinning apparatus of this invention. It is a cross-sectional schematic diagram which shows an example of the nozzle structure in the further another aspect of the electrostatic spinning apparatus of this invention. It is a cross-sectional schematic diagram which shows another example of the nozzle structure in the further another aspect of the electrostatic spinning apparatus of this invention. It is a perspective view which shows the aspect of the nozzle member used for the electrostatic spinning apparatus of this invention. It is a photograph which shows the fiber web obtained by this invention. It is a photograph which shows the other fiber web obtained by this invention. It is a photograph which shows the other fiber web obtained by this invention. It is a photograph which shows the still another fiber web obtained by this invention. It is a schematic diagram explaining the general aspect of an electrostatic spinning apparatus.

Explanation of symbols

2: Electrostatic spinning device 4: Base part 8: Nozzle hole 9: Nozzle 24: Peripheral wall 20: Liquid reservoir 22: Liquid reservoir 26: One side wall 28: Other side wall 38: Drive shaft 36: Through hole 44: Blocking member 46: curved plate 37: through hole 52: liquid feed pipe 56: rotary joint 58: stationary region 60: cleaning means 100, 100a: nozzle structure 101, 101a: liquid reservoir 102: nozzle member 103, 103a: liquid reservoir Part 105: Nozzle hole 110, 110a: Bottom part 112: Funnel part 114, 136: Insertion hole 115: Upper edge part 116: Gutter part 120, 120a: Holding member 124, 134: Through hole 126: Pipe tip 202: Distribution rectifying block 201: Metering pump 204: Base 208: Nozzle hole 206: High voltage power supply 207: Accumulator

Claims (16)

An electrospinning apparatus for producing a fiber by applying an electric field to a spinning solution discharged from a nozzle hole of a nozzle, comprising a plurality of nozzles, and the axial directions of the nozzle holes adjacent to each other are obliquely inclined to each other Electrostatic spinning device. There is provided a liquid storage container for temporarily storing a spinning solution, and an electric field is applied to the spinning solution discharged from a plurality of nozzle holes connected to the liquid storage part of the liquid storage container so as to be fiberized. An electrospinning device,
The liquid reservoir has a cylindrical peripheral wall, the hollow portion of the peripheral wall serves as the liquid reservoir, and is rotatable about the axis of the peripheral wall;
The nozzle hole is arranged around the peripheral wall in the peripheral wall,
Cleaning means for cleaning the nozzle hole that has reached a stationary region facing the outer periphery of the peripheral wall as the liquid reservoir is rotated;
Rotation driving means for rotating the liquid reservoir, and
An electrostatic spinning device comprising: a blocking means for temporarily blocking conduction of the nozzle hole reaching the region. A nozzle structure of an electrostatic spinning device that applies an electric field to a spinning solution discharged from a nozzle hole that is electrically connected to a liquid reservoir portion of a liquid reservoir that temporarily stores a spinning solution,
A funnel portion having a funnel-like shape and a flange portion formed on the upper edge of the funnel portion, wherein the plurality of funnel portions are arranged in parallel with each other and connected via the flange portion. A resin nozzle member,
A pressing member in which a plurality of through holes corresponding to each funnel portion is formed,
An insertion hole for inserting each funnel part is formed at the bottom of the liquid reservoir,
The funnel portion is inserted into the insertion hole in a state where the tube tip of the funnel portion protrudes to the outside of the liquid storage container, and the flange portion is superimposed on the bottom portion,
A nozzle structure in which the flange portion is detachably sandwiched between the pressing member and the bottom portion in a state where the through hole is electrically connected to the corresponding funnel portion. A nozzle structure of an electrostatic spinning device that applies an electric field to a spinning solution discharged from a nozzle hole that is electrically connected to a liquid reservoir portion of a liquid reservoir that temporarily stores a spinning solution,
A funnel portion having a funnel-like shape and a flange portion formed on the upper edge of the funnel portion, wherein the plurality of funnel portions are arranged in parallel with each other and connected via the flange portion. A resin nozzle member,
A holding member formed with an insertion hole for inserting each funnel part,
A through hole corresponding to each funnel portion is formed at the bottom of the liquid reservoir,
In a state where the tube tip of the funnel portion protrudes to the outside of the liquid storage container and the through hole is connected to the corresponding funnel portion, the nozzle member is superimposed on the outside of the bottom portion,
A nozzle structure in which the flange portion is detachably sandwiched between the pressing member and the bottom portion by inserting the funnel portion into the insertion hole. The molded article which consists of the said nozzle member used for the nozzle structure of Claim 3 or 4. An electrospinning method in which an electric field is applied to a spinning solution discharged from a nozzle hole to form a fiber, which is accumulated on a substrate sheet to obtain a fiber web,
An electrospinning method, wherein the solution contains an adhesive as a dissolving component.
A composite sheet obtained by laminating the fiber web obtained by the electrospinning method according to claim 6 and the base sheet. An electrospinning method in which an electric field is applied to a spinning solution discharged from a nozzle hole to form a fiber,
The electrospinning method, wherein the solution contains polyethylene terephthalate and a solvent of polyethylene terephthalate, and the solvent contains hexafluoroisopropanol. The electrospinning method according to claim 8, wherein the solvent further contains chloroform. 10. The solution according to claim 8 or 9, wherein the solution further contains an adhesive as a dissolving component, and is made into a fiber by applying an electric field to the solution discharged from the nozzle hole and collected on a base sheet. Electrospinning method. The electrospinning method according to claim 10, wherein the adhesive is a chloroprene adhesive. A composite sheet obtained by laminating the fiber web obtained by the electrospinning method according to claim 10 or 11 and the base sheet. An electrospinning method in which an electric field is applied to a spinning solution discharged from a nozzle hole to form a fiber,
An electrospinning method, wherein the solution is a solution of sericin. An electrospinning method in which an electric field is applied to a spinning solution discharged from a nozzle hole to form a fiber,
An electrospinning method, wherein the solution is a solution of sericin and fibroin. A web comprising fibers obtained by the electrospinning method according to claim 13. A web comprising fibers obtained by the electrospinning method according to claim 14.