WO2016035458A1 - Procédé et dispositif de production de nanofibre, et procédé de production de non-tissé - Google Patents

Procédé et dispositif de production de nanofibre, et procédé de production de non-tissé Download PDF

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Publication number
WO2016035458A1
WO2016035458A1 PCT/JP2015/070371 JP2015070371W WO2016035458A1 WO 2016035458 A1 WO2016035458 A1 WO 2016035458A1 JP 2015070371 W JP2015070371 W JP 2015070371W WO 2016035458 A1 WO2016035458 A1 WO 2016035458A1
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Prior art keywords
solution
nozzle
liquid
tip
nanofiber
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PCT/JP2015/070371
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English (en)
Japanese (ja)
Inventor
小倉　徹
片井　幸祐
新井　利直
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富士フイルム株式会社
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Publication of WO2016035458A1 publication Critical patent/WO2016035458A1/fr

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    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00—Formation of filaments, threads, or the like
    • D01D5/04—Dry spinning methods
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F2/00—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof
    • D01F2/24—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof from cellulose derivatives
    • D01F2/28—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof from cellulose derivatives from organic cellulose esters or ethers, e.g. cellulose acetate
    • D01F2/30—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof from cellulose derivatives from organic cellulose esters or ethers, e.g. cellulose acetate by the dry spinning process
    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
    • D04H1/42—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
    • D04H1/425—Cellulose series
    • D04H1/4258—Regenerated cellulose series
    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/70—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres
    • D04H1/72—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged
    • D04H1/728—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged by electro-spinning

Definitions

  • the present invention relates to a nanofiber manufacturing method and apparatus, and a nonwoven fabric manufacturing method.
  • fibers having a nano-order diameter of several nm or more and less than 1000 nm are used as materials for products such as biofilters, sensors, fuel cell electrode materials, precision filters, electronic paper, etc. Development of applications in various fields is actively conducted.
  • the electrospinning method is performed using an electrospinning device (electrospinning device) having a nozzle, a collector, and a power source (see Patent Document 1). A voltage is applied between the nozzle and the collector by the power source, and for example, the nozzle is negatively charged and the collector is positively charged.
  • a conical protrusion composed of the solution is formed at the opening at the tip of the nozzle (hereinafter referred to as the tip opening).
  • This conical protrusion is called a Taylor cone.
  • the applied voltage is gradually increased and the Coulomb force exceeds the surface tension of the solution, the solution extends from the tip of the Taylor cone and a spinning jet is formed.
  • the spinning jet moves to the collector by Coulomb force and is collected as nanofibers on the collector.
  • the solution When using a solvent that easily evaporates (for example, a highly volatile solvent) for the solution sent from the nozzle, the solution may solidify and clog at the opening of the tip. Moreover, when the solution solidified to some extent moves away from the opening of the tip, the solidified solution may fall on the collecting surface of the nanofibers collected on the collector. Thus, the clogging or solidification of the solution makes it impossible to reduce the quality of the product or to use it as a product. For this reason, in Patent Document 2, the cleaning means is used to remove the solidified solution by bringing the flexible member into contact with the tip opening, or to remove the solidified solution by sucking the tip opening.
  • a solvent that easily evaporates for example, a highly volatile solvent
  • an air spraying portion is provided at a position separated from the nozzle tip opening by a predetermined distance, and air is sprayed by the air spraying portion in the traveling direction of the spinning jet to promote the movement of the spinning jet to the collector. Increasing fiber production.
  • a Taylor cone is stably formed, and the spinning jet and the flying of the fiber are also stabilized.
  • a solution in which the solvent easily evaporates for example, a solution having a high solvent evaporation rate
  • a Taylor cone cannot be formed, and even if it is formed, the solvent on the surface of the solution extruded from the nozzle evaporates quickly. By doing so, a liquid ball may be generated.
  • the liquid ball has a substantially spherical shape instead of a substantially conical shape like a Taylor cone, and the surface is increased in viscosity by evaporation of the solvent to form a skin, and the inside remains as a solution having a high solvent concentration.
  • liquid balls When liquid balls are generated, it becomes difficult to blow out the solution from the surface even if there is sufficient charge, and even if the spinning jet is ejected, the flight is discontinuous and the nanofiber has a uniform thickness. It becomes difficult to form.
  • the liquid ball may drop due to the vibration of the apparatus, etc., and sticks to the nanofiber accumulated on the collector in the form of a non-woven fabric and becomes a defect.
  • the integrated nanofiber may become unusable as a product, or the quality as, for example, a nonwoven fabric may deteriorate.
  • An object of this invention is to provide the nanofiber manufacturing method and apparatus which can maintain a Taylor cone stably, and can manufacture a nanofiber stably, and a nonwoven fabric manufacturing method in view of the said problem.
  • a cellulosic polymer is dissolved in a solvent, a solution charged in a first polarity is taken out from the nozzle, and the same substance as the solvent component is included at the tip from which the solution of the nozzle comes out.
  • a liquid having a lower concentration of the cellulosic polymer than the solution is supplied at a flow rate in a volume within the range of 5% to 20% of the solution, and the periphery of the solution from the tip is covered with the liquid. It is characterized by attracting the solution from the nozzle and collecting it as nanofibers by means of a collector charged to a second polarity opposite to the polarity.
  • the liquid it is preferable to supply the liquid by discharging the liquid from between the nozzle and a liquid feeding pipe arranged concentrically with the nozzle with a gap around the nozzle. It is preferable that the tip from which the liquid in the liquid feeding tube protrudes protrudes from the tip of the nozzle.
  • the cellulose polymer is preferably at least one of cellulose triacetate, cellulose diacetate, cellulose propionate, cellulose butyrate, cellulose acetate propionate, nitrocellulose, ethylcellulose, and carboxymethylethylcellulose.
  • the nanofiber production apparatus of the present invention includes a nozzle for dispensing a solution in which a cellulosic polymer is dissolved in a solvent, and a liquid containing a substance that is the same as the solvent component at the tip of the nozzle solution and having a lower concentration of the cellulosic polymer than the solution.
  • the apparatus includes a collector that collects as a fiber, and a voltage application unit that charges the solution and the collector with opposite polarities by applying a voltage to the solution and the collector that come out of the nozzle.
  • a liquid feeding pipe that is arranged concentrically with the nozzle with a gap around the outer periphery of the nozzle and supplies the liquid from the outer periphery. It is preferable that the tip from which the liquid in the liquid feeding tube protrudes protrudes from the tip of the nozzle.
  • the cellulose polymer is preferably at least one of cellulose triacetate, cellulose diacetate, cellulose propionate, cellulose butyrate, cellulose acetate propionate, nitrocellulose, ethylcellulose, and carboxymethylethylcellulose.
  • the method for producing a nonwoven fabric of the present invention includes a solution in which a cellulosic polymer is dissolved in a solvent and is charged to a first polarity from a nozzle.
  • a liquid having a lower concentration of the cellulosic polymer than the solution is supplied at a flow rate in a volume within the range of 5% or more and 20% or less, and the periphery of the solution from the tip is covered with the liquid.
  • the moving collector charged to the second polarity opposite to the polarity attracts the solution from the nozzle and collects it as a nanofiber on the support placed on the collector, and supports the collected nanofiber. It is configured as a non-woven fabric by being accumulated on the body.
  • a nanofiber manufacturing apparatus 150 shown in FIG. 1 is for manufacturing a nanofiber 46 from a solution 25 in which a cellulose polymer is dissolved in a solvent.
  • the nanofiber manufacturing apparatus 150 includes a spinning chamber 151, a solution supply unit 12, a nozzle 13, a coating solution supply unit 154 as a supply unit that supplies the coating solution 161, an accumulation unit 15, and a power source 65.
  • the spinning chamber 151 contains, for example, the nozzle 13, the liquid feeding pipe 160 of the coating liquid supply unit 154, a part of the accumulating unit 15, and the like, and is configured to be hermetically sealed to prevent solvent gas from leaking to the outside. is doing.
  • the solvent gas is obtained by vaporizing the solvent of the solution 25.
  • the solvent may be a simple substance or a mixture composed of a plurality of compounds.
  • a nozzle 13 is disposed in the upper part of the spinning chamber 151.
  • the nozzle 13 is for discharging the solution 25 in a state of being charged to the first polarity by the power source 65 as will be described later.
  • the nozzle 13 is formed of a cylinder, and the solution 25 is discharged from an opening 13a (hereinafter referred to as a tip opening) 13a.
  • the nozzle 13 is made of stainless steel having an outer diameter of 0.65 mm and an inner diameter of 0.4 mm, for example, and is cut so that a tip opening edge portion 13b around the tip opening 13a is orthogonal to the cylinder center direction.
  • the front end opening edge 13b which is the cut surface, is polished flat.
  • the liquid supply pipe 160 of the coating liquid supply unit 154 is disposed outside the nozzle 13 so as to be concentric with the nozzle 13.
  • the liquid feeding pipe 160 is a circular pipe disposed with a gap through which a coating liquid 161 described later flows between the outer periphery of the nozzle 13 and has an inner diameter larger than the outer diameter of the nozzle 13.
  • the concentricity does not necessarily have to be strict and may be substantially concentric with a deviation within 5% with respect to the inner diameter of the nozzle 13.
  • the liquid feeding pipe 160 forms a liquid feeding slit 162 between the tip opening 13 a of the nozzle 13 and discharges the coating liquid 161 from the liquid feeding slit 162.
  • the coating liquid 161 is supplied to the tip of the nozzle 13, and the periphery of the solution 25 coming out from the tip opening 13 a is covered with the coating liquid 161.
  • the coating liquid 161 is a liquid for covering the periphery of the solution 25 that has come out of the tip opening 13a.
  • the liquid feeding pipe 160 is made of stainless steel having an outer diameter of 11 mm and an inner diameter of 10 mm, for example, and the nozzle 13 is held by a spacer (not shown) so that the cylindrical center of the nozzle 13 and the cylindrical core of the liquid feeding pipe 160 coincide. ing.
  • the material of the nozzle 13 and the liquid feeding tube 160 may be made of a conductive material such as an aluminum alloy, a copper alloy, or a titanium alloy instead of stainless steel.
  • the solution 25 may come out of the tip opening 13a in a state where a voltage is applied in contact with the metal member at any location and is charged to the first polarity. Therefore, the tip opening 13a does not necessarily need to be made of a conductive material as long as a voltage is applied at any location and the first opening is charged when leaving the tip opening 13a.
  • the processing accuracy of the tip 13c of the nozzle 13 is important for the generation of the Taylor cone 44 and the stabilization of the spinning jet 45 extending from the Taylor cone. Therefore, for example, it is preferable that the tip 13c is coated with a fluorine-based material or the like because the nozzle 13 is kept clean.
  • the tip 160a of the liquid feeding tube 160 protrudes with a protruding amount L1 of, for example, about 5 mm with respect to the tip opening 13a.
  • a protruding amount L1 of, for example, about 5 mm with respect to the tip opening 13a.
  • the protruding amount L1 is preferably changed in accordance with the inner diameters of the nozzle 13 and the liquid feeding pipe 160, and is preferably set to a protruding amount L1 that more reliably prevents the surface of the formed Taylor cone 44 from drying.
  • the above-described coating liquid 161 is a liquid for covering the periphery of the solution 25 exiting from the tip opening 13a and the Taylor cone 44 formed from this solution, and includes the same substance as the solvent component of the solution 25. That is, the coating liquid 161 and the solvent of the solution 25 contain common components. For example, when the solvent of the solution 25 is a mixture, the coating liquid 161 may include at least one component thereof.
  • the coating liquid 161 may contain a cellulose-based polymer, and in this embodiment, the cellulose-based triacetate (TAC) is included as in the solution 25 as the cellulose-based polymer.
  • the concentration of TAC in the coating liquid 161 is 3% by mass, which is lower than the cellulose polymer concentration C in the solution 25 described later.
  • the coating liquid 161 may not contain a cellulosic polymer. That is, the concentration of the cellulose polymer in the coating liquid 161 may be 0 (zero), and the coating liquid 161 only needs to have a lower concentration of the cellulose polymer than in the solution 25.
  • the coating liquid 161 contains a cellulosic polymer
  • the cellulosic polymer is preferably the same substance as the cellulosic polymer contained in the solution 25.
  • a pipe 32 of the solution supply unit 12 is connected to the base end of the nozzle 13.
  • the solution supply unit 12 is for supplying the aforementioned solution 25 to the nozzle 13 of the spinning chamber 151.
  • the solution supply unit 12 includes a storage container 30, a pump 31, and a pipe 32.
  • the storage container 30 stores the solution 25 as a constant temperature within a range of 5 ° C. or higher and 40 ° C. or lower. Thereby, the temperature of the solution 25 which comes out of the nozzle 13 is made into the range of 5 to 40 degreeC. When the temperature of the solution 25 coming out of the nozzle 13 is 5 ° C.
  • the atmosphere (usually air) in the spinning area from the tip opening 13a to the support 60 on the collector 50 is compared to the case of less than 5 ° C. Condensation of the contained moisture is more reliably suppressed, and the nanofiber 46 is more stably manufactured from the solution 25 that has exited from the tip opening 13a.
  • the temperature is 40 ° C. or lower, the evaporation of the solvent is suppressed as compared with the case where the temperature is higher than 40 ° C., and the formation of liquid balls in the tip opening 13a is more reliably suppressed.
  • the pump 31 sends the solution 25 from the storage container 30 to the nozzle 13 via the pipe 32.
  • the flow rate of the solution 25 delivered from the nozzle 13 can be adjusted.
  • the flow rate of the solution 25 is 4 cm 3 / hour, but the flow rate is not limited to this.
  • the concentration C of the cellulose polymer in the solution 25 is preferably in the range of 2% by mass to 15% by mass. Thereby, manufacture of the nanofiber 46 and the nonwoven fabric 120 under the supply of the coating liquid 161 is stably continued.
  • the concentration C is more preferably in the range of 2% by mass or more and 10% by mass or less, and further preferably in the range of 2% by mass or more and 5% by mass or less.
  • concentration C is a value calculated
  • the concentration C is 4% by mass.
  • a pipe 38 of the coating liquid supply unit 154 is connected to the proximal end of the liquid feeding pipe 160.
  • the coating liquid supply unit 154 includes the above-described liquid feeding pipe 160, the flow rate adjustment valve 36, and the pipe 38.
  • the flow rate adjusting valve 36 is disposed outside the spinning chamber 11, but may be disposed inside the spinning chamber 11.
  • the flow rate adjusting valve 36 adjusts the flow rate of the coating liquid 161 from the liquid feeding slit 162.
  • the coating liquid 161 is discharged from the liquid feeding slit 162 at a flow rate ratio in the range of 5% to 20% with respect to the solution 25 from the tip opening 13a.
  • This flow rate is in volume. That is, when the flow rate in the volume of the solution 25 from the tip opening 13a is set to 100, it means that the flow rate in the volume of the coating liquid 161 from the liquid feeding slit 162 is in the range of 5 to 20.
  • the flow rate ratio is 5% or more, the coating liquid 161 reliably covers the periphery of the solution 25 coming out of the tip opening 13a as compared with the case of less than 5%.
  • the concentration of the cellulosic polymer does not decrease excessively in the solution 25 exiting from the tip opening 13a as compared with the case where the flow rate ratio is greater than 20%.
  • the flow rate ratio is more preferably in the range of 5% to 15%, and still more preferably in the range of 5% to 10%.
  • the accumulation unit 15 is disposed below the nozzle 13.
  • the stacking unit 15 includes a collector 50, a collector rotating unit 51, a support body supply unit 52, and a support body winding unit 53.
  • the collector 50 is for collecting the solution 25 exiting from the nozzle 13 as a nanofiber 46, and in this embodiment, collects it on a support 60 described later.
  • the collector 50 is composed of a band-shaped metal (for example, stainless steel) endless belt.
  • the collector 50 is not limited to stainless steel, and may be formed of a material that is charged by applying a voltage from the power source 65.
  • the collector rotating unit 51 is composed of a pair of rollers 55 and 56, a motor 57, and the like. The collector 50 is stretched horizontally around a pair of rollers 55 and 56.
  • a motor 57 disposed outside the spinning chamber 151 is connected to the shaft of one roller 55, and rotates the roller 55 at a predetermined speed. This rotation causes the collector 50 to circulate between the pair of rollers 55 and 56.
  • the moving speed of the collector 50 is 10 cm / hour, but is not limited to this.
  • the support body 60 made of a strip-shaped aluminum sheet (aluminum sheet) is supplied to the collector 50 by the support body supply section 52.
  • the support body 60 in the present embodiment has a thickness of approximately 25 ⁇ m.
  • the support 60 is for obtaining the nonwoven fabric 120 by accumulating (depositing) the nanofibers 46.
  • the support body 60 on the collector 50 is wound up by the support body winding part 53.
  • the support body supply unit 52 has a delivery shaft 52a.
  • a support roll 54 is attached to the delivery shaft 52a.
  • the support roll 54 is configured by winding the support 60.
  • the support winding portion 53 has a winding shaft 58.
  • the winding shaft 58 is rotated by a motor (not shown), and the support body 60 on which the nonwoven fabric 120 is formed is wound around the core 61 to be set.
  • the nonwoven fabric 120 is formed by integrating the nanofibers 46.
  • the nanofiber manufacturing apparatus 150 has a function of manufacturing the nonwoven fabric 120 in addition to the function of manufacturing the nanofiber 46.
  • the moving speed of the collector 50 and the moving speed of the support 60 are preferably the same so that friction does not occur between them. The same speed need not be exact. Further, the support 60 may be placed on the collector 50 and moved by the movement of the collector 50.
  • the nanofibers 46 may be directly accumulated on the collector 50 to form the nonwoven fabric 120.
  • the nonwoven fabric 120 may stick and be difficult to peel off. Therefore, as in this embodiment, it is preferable to guide the support body 60 on which the nonwoven fabric 120 is difficult to stick to the collector 50 and to accumulate the nanofibers 46 on the support body 60.
  • the power source 65 is a voltage application unit that applies a voltage to the nozzle 13 and the collector 50 to charge the nozzle to the first polarity, and charges the collector 50 to the second polarity opposite to the first polarity. .
  • the nozzle 13 is charged to minus ( ⁇ ) and the collector 50 is charged to plus (+).
  • the polarity of the nozzle 13 and the collector 50 may be reversed.
  • the voltage applied to the nozzle 13 and the collector 50 is 35 kV.
  • the distance L2 between the tip opening 13a of the nozzle 13 and the collector 50 varies depending on the type of the cellulose polymer and the solvent, the mass ratio of the solvent in the solution 25, etc., but is preferably in the range of 30 mm to 300 mm. In the embodiment, it is 180 mm.
  • the distance L2 is 30 mm or more, the spun jet 45 formed by jetting is more reliably split by repulsion due to its own charge before reaching the collector 50, compared to a case where the distance L2 is shorter than 30 mm. Therefore, the thin nanofiber 46 can be obtained more reliably.
  • the solvent evaporates more reliably by splitting in this way, it is more reliably prevented that the non-woven fabric has the solvent remaining.
  • the voltage to apply can be restrained low compared with the case where distance L2 is 300 mm or less and it is too long exceeding 300 mm, abnormal discharge is suppressed.
  • the thickness of the obtained nanofiber 46 varies depending on the magnitude of the voltage applied to the nozzle 13 and the collector 50. From the viewpoint of forming a thin fiber, it is preferable that the voltage is as low as possible. However, if it is lowered too much, it may not be in the form of a fiber but may become a ball and adhere to the collector 50 in some cases. Conversely, when the voltage is increased, the fiber becomes thicker, and when it is increased too much, the insulation of the device may be broken. Therefore, the voltage applied to the nozzle 13 and the collector 50 is preferably in the range of 2 kV to 40 kV, particularly preferably in the range of 20 kV to 35 kV.
  • cellulose triacetate As the cellulose-based polymer, cellulose triacetate (TAC) is used in the present embodiment, but is not limited thereto. TAC, cellulose diacetate (DAC), cellulose propionate, cellulose butyrate, cellulose acetate propionate , Nitrocellulose, ethylcellulose, or carboxymethylethylcellulose may be used.
  • TAC cellulose triacetate
  • DAC cellulose diacetate
  • DAC cellulose propionate
  • cellulose butyrate cellulose acetate propionate
  • Nitrocellulose ethylcellulose, or carboxymethylethylcellulose
  • Solvents for dissolving the cellulose polymer include methanol, ethanol, isopropanol, butanol, benzyl alcohol, acetone, methyl ethyl ketone, cyclohexanone, methyl acetate, ethyl acetate, propyl acetate, butyl acetate, methyl formate, ethyl formate, hexane, cyclohexane, dichloromethane Chloroform, carbon tetrachloride, benzene, toluene, xylene, dimethylformamide, NMP, diethyl ether, dioxane, tetrahydrofuran, 1-methoxy-2-propanol and the like. These may be used alone or in combination depending on the type of cellulosic polymer. In the present embodiment, a mixture of dichloromethane and NMP is used as the solvent.
  • the solvent When the solvent is composed of a single component, that is, when it is composed of one component, the formation of a liquid ball becomes remarkable when the boiling point of the solvent is about 50 ° C. or less.
  • the solution since a substance having a low boiling point has a high evaporation rate, the solution tends to form a liquid ball when used as a solvent.
  • a voltage is applied from the power source 65 to the nozzle 13 and the collector 50 that circulates and moves.
  • the solution 25 is continuously supplied from the storage container 30 to the nozzle 13, and the support body 60 is continuously supplied onto the moving collector 50.
  • the collector 50 that is positively charged by the application of the voltage attracts the solution 25 that has been negatively charged from the tip opening 13a, and a spinning jet 45 is formed.
  • the negatively charged spinning jet 45 splits into a smaller diameter due to repulsion due to its own charge while heading toward the collector 50, and accumulates on the support 60 as nanofibers 46.
  • the integrated nanofiber 46 is sent to the support winding portion 53 together with the support 60 as the nonwoven fabric 120.
  • the nonwoven fabric 120 is wound around the core 61 in a state where it overlaps with the support body 60.
  • the support body 60 having the nonwoven fabric 120 is removed from the winding shaft 58 in a roll form, and then cut into a desired size, for example, into a sheet shape.
  • the nonwoven fabric 120 is peeled off from the support body 60 according to a use, and is used.
  • the coating liquid 161 comes out from the liquid feeding slit 162 and is continuously supplied around the solution 25 coming out from the tip opening 13a. Thereby, since the coating liquid 161 is covered around the solution 25 from the tip opening 13a, the surface of the solution 25 coming out from the tip opening 13a is difficult to dry. Since the coating liquid 161 from the liquid feeding slit 162 is within a range of 5% or more and 20% or less with respect to the solution 25 from the tip opening 13a, the coating liquid 161 is surrounded around the solution 25 that has come out of the tip opening 13a. Is surely covered. Thereby, the Taylor cone 44 is formed reliably, and the formed Taylor cone 44 is hard to dry and is stably maintained.
  • the solution 25 exiting from the tip opening 13a does not excessively reduce the concentration of the cellulosic polymer by the coating liquid 161. Therefore, the spinning jet 45 is formed without cutting the solution 25 extending from the Taylor cone 44, and the nanofiber 46 is manufactured. Further, since the Taylor cone 44 is stabilized for a long time as described above, the nonwoven fabric made of the nanofibers 46 is stably manufactured.
  • the coating liquid 161 contains the same substance as that used as the solvent component of the solution 25, there is almost no difference in the solubility of the cellulosic polymer between the inside and the outside of the solution 25 exiting from the tip opening 13a. . For this reason, restrictions on the formulation of the solution 25 and the manufacturing conditions of the nanofiber 46 are reduced, and the degree of freedom is increased.
  • the coating liquid 161 has a lower cellulosic polymer concentration than the solution 25. For this reason, drying of the surface of the solution 25 coming out from the tip opening 13a is suppressed to form the Taylor cone 44, and drying of the surface of the formed Taylor cone 44 is also suppressed.
  • the coating liquid 161 reliably covers the periphery of the solution 25 that has come out of the tip opening 13a. There is no excessive decrease in the concentration of the cellulosic polymer. For this reason, the Taylor cone 44 is stably maintained, and the nanofiber 46 and the nonwoven fabric 120 are stably manufactured.
  • the liquid feeding pipe 160 is arranged on the outer periphery of the nozzle 13 concentrically with the nozzle 13, the entire periphery of the solution 25 coming out from the tip opening 13 a is more reliably covered with the coating liquid 161. For this reason, the Taylor cone 44 is more reliably formed, and the formed Taylor cone 44 is stabilized for a long time. Therefore, the nonwoven fabric which consists of the nanofiber 46 is manufactured stably.
  • the liquid feeding pipe 160 is arranged so as to protrude from the tip opening 13a of the nozzle 13, the formed Taylor cone 44 is more reliably covered with the coating liquid 161 and stabilized for a long time. For this reason, the nonwoven fabric which consists of nanofiber 46 is manufactured stably.
  • the coating liquid 161 covers the solution 25 coming out of the tip opening 13a and the Taylor cone 44 formed from the solution 25, the evaporation of the solvent of the solution 25 can be kept low. Thereby, the surface of the Taylor cone 44 does not become hard, and generation
  • the nanofiber 46 can be used for the production of biofilters, sensors, fuel cell electrode materials, precision filters, electronic paper, and the like.
  • a heat pipe wick that is used at a relatively low temperature has a large amount of heat to be transferred, and may be used for an ecosystem that uses underground heat, for example.
  • it can be used as a beauty pack material with a good texture.
  • the collector 50 has a smooth surface, but the shape of the collector 50 is not limited.
  • a cylindrical rotating body may be used instead of the collector 50.
  • the cylindrical nonwoven fabric is formed from the nanofibers 46 on the surface of the rotating body, the cylindrical nonwoven fabric is extracted from the rotating body after manufacturing and cut into a desired size and shape to obtain a predetermined nonwoven fabric product. It can be.
  • a cylindrical rotating body is used, a non-woven fabric cannot be continuously produced, but a uniform non-woven fabric product is easy to make. For this reason, there is a possibility that application to cell culture scaffolds, medical uses, and the like becomes easy. Further, by increasing the number of rotations of the rotator, the degree of orientation of the nanofiber can be increased, and an anisotropic product can be obtained.
  • the tip 160a of the liquid feeding pipe 160 protrudes from the tip opening 13a of the nozzle 13 so that the Taylor cone 44 is covered with the liquid feeding pipe 160.
  • the nozzle and the liquid feeding pipe are used.
  • the positional relationship of the tip with 160 is not limited to this.
  • the tip 170 a of the liquid feeding tube 170 may be positioned in accordance with the tip 13 c of the nozzle 13.
  • the tip 13c of the nozzle 13 is not hidden in the tip 170b of the liquid feeding tube 170, so that the tip 13c can be easily cleaned.
  • the same constituent members are denoted by the same reference numerals, and redundant description is omitted.
  • a guide tube 175 is movably attached to the distal end portion 170b of the liquid feeding tube 170 of the second embodiment.
  • the coating liquid 161 from the liquid feeding slit 162 covers the Taylor cone 44 by the guide pipe 175 and the liquid feeding pipe 170 at the guide position (see FIG. 4) where the guide pipe 175 is lowered. Therefore, drying of the surface of the Taylor cone 44 is reliably suppressed.
  • the tip 13c of the nozzle 13 can be exposed by sliding the guide tube 175 upward from the guide position to the retracted position. For this reason, the tip opening 13a of the nozzle 13 can be reliably cleaned.
  • the guide tube 175 may be urged so as to protrude toward the tip by a spring (not shown) or the like, and may be positioned at a protruding position and a retracted position by a click mechanism (not shown).
  • the liquid feeding pipe 160 and the liquid feeding pipe 170 are circular pipes having a uniform inner diameter and outer diameter, but the inner diameter and the outer diameter are coating liquid 161 like the liquid feeding pipe 180 of the fourth embodiment shown in FIG. And the circular pipe which is changing in the flow direction of solution 25 may be sufficient.
  • the liquid feeding pipe 180 has a tapered tapered portion 180c having an inner diameter and an outer diameter that gradually decrease in the flow direction of the coating liquid 161 and the solution 25, and a tip portion 180b having a uniform inner diameter and outer diameter.
  • the distal end portion 180b of the liquid feeding pipe 180 protrudes from the distal end 13c of the nozzle 13.
  • the distal end section 180b may be flush with the distal end 13c as in the liquid feeding pipe 170 of the second embodiment. Good.
  • the flow path of the coating liquid 161 is divided into four in the circumferential direction of the nozzle 13.
  • the flow path of the coating liquid 161 may be divided into a plurality of parts in the circumferential direction of the nozzle 13.
  • the partition member 190 c that partitions the flow path also has a holding function for holding the nozzle 13.
  • the tip 190b of the liquid feeding tube 190 protrudes from the tip 13c of the nozzle 13.
  • the tip 190b may be flush with the tip 13c as in the liquid feeding tube 170 of the second embodiment. Good.
  • the liquid feeding pipe 195 of the sixth embodiment shown in FIG. 7 is a hexagonal pipe.
  • the liquid feeding pipe is not limited to a circular pipe and may be a polygonal pipe.
  • the tip 195b of the liquid feeding tube 195 has its tip 195a protruding from the tip 13c of the nozzle 13, but may be positioned flush with the tip 13c as in the liquid feeding tube 170 of the second embodiment.
  • nozzle 13 only one nozzle 13 is used, but a plurality of nozzles 13 may be used.
  • the plurality of nozzles 13 be provided apart from each other in a direction orthogonal to the moving direction of the support 60.
  • the nozzles 13 may be arranged in a matrix in the moving direction of the support 60 and in a direction orthogonal to the moving direction.
  • the nanofiber 46 was manufactured as the nonwoven fabric 120 by the nanofiber manufacturing apparatus 150.
  • the flow rate of the solution 25 was 4 cm 3 / hour, and the flow rate of the coating liquid 161 from the liquid feeding slit 162 was 0.5 cm 3 / hour, which was smaller than the flow rate of the solution 25.
  • the concentration C of TAC as the cellulose polymer in the solution 25 was 4 mass%, and the concentration of TAC as the cellulose polymer in the coating liquid 161 was 3 mass%.
  • the composition of the solution 25 and the composition of the coating liquid 161 are as described above. Further, the material and size of the liquid feeding pipe 160 used, the protruding amount L1, the material and moving speed of the collector 50 and the support 60, the value of the applied voltage, and the like are as described above.
  • the nanofibers 46 could be manufactured continuously, and a long nonwoven fabric 120 was obtained.
  • Example 1 The conditions were the same as in Example 1 except that the coating liquid 161 was not supplied from the liquid feeding pipe 160.
  • the Taylor cone 44 was formed at the start of production. However, the shape of the Taylor cone 44 collapsed and a liquid ball was formed in about 5 minutes from the start of the formation of the spinning jet. Was interrupted. Several seconds later, the side of the liquid ball was torn and the yarn spouted out, but the formation of the spinning jet 45 was immediately interrupted. Thereafter, the spinning jet 45 was not formed, and the nanofiber 46 could not be manufactured.
  • Example 2 The conditions were the same as in Example 1 except that the flow rate of the coating liquid 161 from the liquid feeding slit 162 was 2 cm 3 / hour.
  • the Taylor cone 44 was formed at the start of production, but the shape of the Taylor cone 44 was not stable, and the nanofiber 46 was produced only intermittently.
  • Comparative Example 3 The same conditions as in Example 1 were used except that the coating liquid 161 in Example 1 was replaced with a coating liquid having a TAC concentration of 8% by mass. In Comparative Example 3, a liquid ball was formed, and the formation of the spinning jet 45 was intermittent. Yarns spout from the lower part and side part of the liquid ball, and as production continues, the liquid ball grows downward in an irregular shape and falls on the support 60 on the collector 50 in about 10 minutes from the start of production. did.

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Mechanical Engineering (AREA)
  • Spinning Methods And Devices For Manufacturing Artificial Fibers (AREA)
  • Nonwoven Fabrics (AREA)
  • Artificial Filaments (AREA)

Abstract

La présente invention concerne un procédé de production de nanofibre qui consiste : à évacuer, depuis la pointe d'une buse (13), une solution (25) obtenue par dissolution d'un polymère cellulosique dans un solvant ; et à appliquer une tension entre la solution (25) et un collecteur (50) pour former un jet de solution de filage (45) vers le collecteur (50) et produire une nanofibre (46). Dans le procédé, un liquide de revêtement (161) fourni à travers un tuyau d'alimentation en liquide (160) est évacué à travers une fente d'alimentation en liquide, qui est l'espace entre la paroi du tuyau d'alimentation en liquide (160) et la buse (13), à un débit qui est 5 à 20 % de celui de la solution (25), en recouvrant ainsi avec ce dernier la périphérie de la solution (25) évacuée depuis l'orifice de pointe. Le liquide de revêtement (161) comprend un composant qui est le même que dans le solvant de la solution (25), et a une concentration de polymère cellulosique inférieure à celle de la solution (25).
PCT/JP2015/070371 2014-09-04 2015-07-16 Procédé et dispositif de production de nanofibre, et procédé de production de non-tissé WO2016035458A1 (fr)

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WO2017158879A1 (fr) * 2016-03-16 2017-09-21 株式会社 東芝 Tête à buses et appareil d'électrofilage
WO2018147068A1 (fr) * 2017-02-13 2018-08-16 富士フイルム株式会社 Feuille et procédé permettant de produire une feuille
CN111918993A (zh) * 2018-03-28 2020-11-10 富士胶片株式会社 无纺布、纤维形成方法及无纺布制造方法

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JP2009035854A (ja) * 2007-07-11 2009-02-19 Panasonic Corp 微細高分子材料製造方法、微細高分子材料製造装置
JP2010236133A (ja) * 2009-03-31 2010-10-21 National Institute Of Advanced Industrial Science & Technology 二重管ノズルを用いたエレクトロスピニング法によるナノファイバー製造装置及び製造方法

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WO2017158879A1 (fr) * 2016-03-16 2017-09-21 株式会社 東芝 Tête à buses et appareil d'électrofilage
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CN111918993A (zh) * 2018-03-28 2020-11-10 富士胶片株式会社 无纺布、纤维形成方法及无纺布制造方法
CN111918993B (zh) * 2018-03-28 2022-07-26 富士胶片株式会社 无纺布、纤维形成方法及无纺布制造方法

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