WO2016035473A1 - Procédé de fabrication de nanofibres - Google Patents

Procédé de fabrication de nanofibres Download PDF

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Publication number
WO2016035473A1
WO2016035473A1 PCT/JP2015/070902 JP2015070902W WO2016035473A1 WO 2016035473 A1 WO2016035473 A1 WO 2016035473A1 JP 2015070902 W JP2015070902 W JP 2015070902W WO 2016035473 A1 WO2016035473 A1 WO 2016035473A1
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Prior art keywords
solution
nozzle
solvent
temperature
collector
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PCT/JP2015/070902
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English (en)
Japanese (ja)
Inventor
片井　幸祐
新井　利直
小倉　徹
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富士フイルム株式会社
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Publication of WO2016035473A1 publication Critical patent/WO2016035473A1/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
    • 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.
  • 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.
  • Patent Document 1 and Patent Document 2 describe fibers having an average diameter of 0.5 ⁇ m and 0.4 ⁇ m from an aramid polymer solution. Is manufacturing. In these methods, the solvent of the aramid polymer solution has a saturated vapor pressure of 8000 Pa or less at the spinning temperature.
  • one of the methods for producing nanofibers is an electrospinning method (electrospinning method, electrostatic spinning method).
  • the electrospinning method is performed by using an electrospinning apparatus (electrospinning apparatus) having a nozzle, a collector, and a power source, and a voltage is applied between the nozzle and the collector by the power source.
  • the nozzle is positive and the collector is negative.
  • an electrostatic spinning method for producing nanofibers having a diameter of less than 0.5 ⁇ m by setting the surface tension, evaporation rate, viscosity, and the like of a polymer solution to a predetermined value has been proposed (for example, Patent Document 3). reference).
  • the nanofiber can be produced by an electroblowing method in which a polymer solution is released together with a gas.
  • a method for obtaining a high treatment rate by setting the vapor pressure at 25 ° C. to 6 kPa or more, that is, a method for improving the production amount per unit time has been proposed (for example, see Patent Document 4).
  • cellulose acylate which is a cellulosic material, has been widely used for optical applications such as a support for photographic films and display materials, and has recently attracted attention as a biomass material.
  • Patent Document 1 As a solvent for dissolving cellulose acylate, there are dichloromethane, acetone and the like, but dichloromethane and acetone have a very large saturated vapor pressure and larger than 8000 Pa. For example, the saturated vapor pressure at 25 ° C. is 53316 Pa for dichloromethane and 30797 Pa for acetone. Therefore, the methods of Patent Document 1 and Patent Document 2 cannot be applied when producing nanofibers from a cellulose acylate solution.
  • Patent Document 3 also describes that the dispersion of the fiber diameter obtained from dichloromethane is too high, and the method of Patent Document 3 is based on a solution of cellulose acylate dissolved in dichloromethane. Therefore, it is difficult to continuously manufacture nanofibers.
  • Patent Document 4 uses a solvent having a high vapor pressure, and dichloromethane and acetone are described as such a solvent.
  • dichloromethane and acetone are described as such a solvent.
  • the polymer evaporates at the tip of the nozzle that discharges the polymer solution because of the high evaporation rate of the solvent, making continuous production difficult. .
  • an object of the present invention is to provide a nanofiber manufacturing method for continuously manufacturing nanofibers from a cellulose acylate solution in which cellulose acylate is dissolved in a solvent.
  • cellulose acylate is dissolved in a solvent, a solution charged in the first polarity is discharged from the nozzle, and charged to a second polarity opposite to the first polarity.
  • the solution drawn from the nozzle is attracted to the collector and collected as nanofibers.
  • the saturated vapor pressure of the solvent is Ps
  • the unit of Ps is kPa
  • the concentration of cellulose acylate in the solution is C
  • the unit of C is g / 100 cm. 3
  • Ps and C satisfy Ps ⁇ C ⁇ 300.
  • the saturated vapor pressure of the solvent is preferably in the range of 10 kPa to 50 kPa. It is preferable that the temperature of a solution exists in the range of 5 to 40 degreeC.
  • the difference between the temperature of the solution and the ambient temperature is within the range of ⁇ 15 ° C. or more and 15 ° C. or less by adjusting the ambient temperature Ta around the outlet where the nozzle solution exits.
  • the viscosity of the solution is preferably in the range of 1 mPa ⁇ s to 10 Pa ⁇ s.
  • the cellulose acylate is preferably at least one of cellulose triacetate, cellulose diacetate, cellulose acetate butyrate, and cellulose acetate propionate.
  • nanofibers can be continuously produced from a cellulose acylate solution.
  • a nanofiber manufacturing apparatus 110 shown in FIG. 1 is for manufacturing a nanofiber 46 from a solution 25 in which cellulose acylate is dissolved in a solvent.
  • the nanofiber manufacturing apparatus 110 includes a spinning chamber 111, a solution supply unit 112, a nozzle 13, an accumulation unit 15, and a power source 65.
  • the spinning chamber 111 accommodates, for example, the nozzle 13 and a part of the accumulating unit 15 and is configured to be hermetically sealed to prevent the solvent gas from leaking to the outside.
  • 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 111.
  • 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 tip opening 13a is an outlet through which the solution 25 exits.
  • 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 material of the nozzle 13 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 into contact with the metal member at any location, be applied with a voltage, and exit from the tip opening 13a in a state of being charged to the first polarity. Therefore, the tip opening 13a does not necessarily need to be a conductive material as long as a voltage is applied at any location up to the tip opening 13a and the first opening is charged when exiting the tip opening 13a. .
  • the solution supply unit 112 is for supplying the solution 25 to the nozzle 13 of the spinning chamber 111.
  • the solution supply unit 112 includes a storage container 30, a first temperature controller 133, a pump 31, and a pipe 32.
  • the storage container 30 stores the solution 25.
  • the first temperature controller 133 adjusts the temperature of the stored solution 25 via the storage container 30.
  • 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 3 cm 3 / hour, but the flow rate is not limited to this.
  • the saturated vapor pressure Ps (unit: kPa) of the solvent and the concentration C (unit: g / 100 cm 3 ) of the cellulose acylate satisfy the following condition (1).
  • the solution 25 is sent to the nozzle 13 in a state where this condition (1) is satisfied, and is discharged from the tip opening 13a.
  • the pipe 32 and the nozzle 13 are provided with temperature controllers (not shown) so that they are guided from the storage container 30 to the tip opening 13a and exit from the tip opening 13a in a state where the condition (1) is satisfied.
  • the temperature of the solution 25 is guided to the nozzle 13 while being kept at the temperature in the storage container 30 by these temperature controllers, and is discharged from the tip opening 13a.
  • the saturated vapor pressure Ps (t) of the solvent at the temperature t is obtained by the following equation (2).
  • the number of components of the solvent is n (n is a natural number of 1 or more)
  • the saturated vapor pressure of a single component i (i is a natural number of 1 to n) at temperature t is Pi (t)
  • the component i Let Xi be the molar fraction in the solvent.
  • the saturated vapor pressure Ps (t) is defined by the following equation.
  • Ps in the above condition (1) is obtained as the temperature t in the equation (2) by the temperature of the solution 25 coming out of the nozzle 13.
  • the saturated vapor pressure Ps is preferably in the range of 10 kPa to 50 kPa.
  • the solvent evaporates more easily than when the saturated vapor pressure Ps is less than 10 kPa, so that the droplets of the solution 25 and solid particles are not generated.
  • it is hard to evaporate a solvent when it is 50 kPa or less compared with the case where it is larger than 50 kPa, solidification by drying of the solution 25 is suppressed.
  • the first temperature controller 133 adjusts the saturated vapor pressure Ps of the solvent in the solution 25 by adjusting the temperature of the solution 25.
  • the saturated vapor pressure Ps can be adjusted by changing the mixing ratio of the solvent of the solution 25 as a mixture composed of a plurality of compounds instead of or in addition to the adjustment of the temperature of the solution 25.
  • the temperature of the solution 25 coming out of the nozzle 13 is preferably in the range of 5 ° C. or more and 40 ° C. or less, and in this embodiment, it is 25 ° C. ⁇ 1 ° C. (in the range of 24 ° C. or more and 26 ° C. or less).
  • the temperature of the solution 25 is 5 ° C.
  • the solution 25 is less likely to be gelled at a low temperature than when it is less than 5 ° C., and the solution 25 is stably discharged from the nozzle 13.
  • the temperature of the solution 25 is 40 ° C. or lower, intense evaporation (flash) due to the solvent exceeding the boiling point is less likely to occur than when the temperature is higher than 40 ° C., and solidification due to drying of the solution 25 is suppressed.
  • the temperature of the solution 25 exiting from the nozzle 13 is more preferably in the range of 10 ° C. or more and 35 ° C. or less, and further preferably in the range of 15 ° C. or more and 30 ° C. or less.
  • the viscosity of the solution 25 exiting from the nozzle 13 is preferably in the range of 1 mPa ⁇ s to 10 Pa ⁇ s.
  • the viscosity of the solution 25 can be adjusted by the temperature and the components of the solution 25.
  • the temperature of the solution 25 may be adjusted by the first temperature controller 133.
  • Examples of a method for adjusting the viscosity according to the components of the solution 25 include a method for changing the concentration C of cellulose acylate and a method for changing the solvent.
  • the solvent for example, when the solvent is composed of a simple substance, the kind of the simple substance is changed, or other ingredients are added to change the mixture, and when the solvent is a mixture, the composition ratio of the ingredients is mixed. And changing at least one of them.
  • the viscosity of the solution 25 exiting from the nozzle 13 is more preferably in the range of 1 mPa ⁇ s to 5 Pa ⁇ s, and still more preferably in the range of 2 mPa ⁇ s to 2 Pa ⁇ s.
  • the nozzle 13 is preferably provided with a cover 134 that covers the tip opening 13a and a second temperature controller 135 for adjusting the temperature inside the cover 134 as in the present embodiment.
  • a cover 134 that covers the tip opening 13a and a second temperature controller 135 for adjusting the temperature inside the cover 134 as in the present embodiment.
  • an opening 134 a for allowing the solution 25 to pass toward the collector 50 is formed between the tip opening 13 a and the collector 50.
  • the second temperature controller 135 By adjusting the internal temperature by the second temperature controller 135, the ambient temperature Ta around the tip opening 13a (around the outlet where the solution comes out) is adjusted.
  • the periphery is a range that covers at least the Taylor cone 44, and is preferably within a range of, for example, 20 mm from the tip opening 13a.
  • Ts-Ta the difference between the temperature Ts of the solution 25 coming out of the tip opening 13a and the atmospheric temperature Ta, that is, Ts-Ta within a range of ⁇ 15 ° C. to 15 ° C.
  • Ts-Ta is in the range of ⁇ 15 ° C. or more and 15 ° C. or less, the evaporation of the solvent is moderate compared to the case where Ts-Ta is outside this range, so that solidification due to drying of the solution 25 is suppressed, and There are no occurrences of ball-like droplets of the solution 25 or solid particles.
  • Ts—Ta is more preferably within a range of ⁇ 10 ° C. to 10 ° C., and further preferably within a range of ⁇ 5 ° C. to 5 ° C.
  • the method of adjusting the ambient temperature Ta around the tip opening 13a is not limited to the method using the cover 134 and the second temperature controller 135 of the present embodiment.
  • a gas such as air with a constant temperature is sent to the spinning chamber 111, and the temperature of the entire interior of the spinning chamber 111 is adjusted by this feeding.
  • Ta may be adjusted.
  • the atmospheric temperature Ta is adjusted to 25 ° C.
  • the relative humidity of the atmosphere around the tip opening 13a is set to 30% RH.
  • the cellulose acylate concentration C in the solution 25 is preferably in the range of 0.1 g / 100 cm 3 or more and 20 g / 100 cm 3 or less. Thereby, the viscosity of the solution 25 becomes moderate, and the molecules of the cellulose acylate are appropriately entangled with each other.
  • the concentration C is more preferably 0.5 g / 100 cm 3 or more and 15 g / 100 cm 3 or less, and further preferably 1 g / 100 cm 3 or more and 10 g / 100 cm 3 or less.
  • 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 made of an endless belt made of a band-like metal, for example, stainless steel.
  • 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 111 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 110 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. Further, the support body 60 may be placed on the collector 50 and moved as the collector 50 moves.
  • 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 13 to the first polarity, and charges the collector 50 to the second polarity opposite to the first polarity. is there.
  • the nozzle 13 is charged positively (+) and the collector 50 is negatively charged ( ⁇ ).
  • the polarity of the nozzle 13 and the collector 50 may be reversed. By passing through the nozzle 13, the solution 25 is charged to the first polarity.
  • the voltage applied to the nozzle 13 and the collector 50 is 30 kV.
  • the distance L2 between the tip opening 13a of the nozzle 13 and the collector 50 varies depending on the type of cellulose acylate 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 150 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 finely in this way, it is possible to more reliably prevent the non-woven fabric from which the solvent remains.
  • 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.
  • the voltage is as low as possible from the viewpoint of forming the nanofiber 46 to be thin, if it is too low, it may not be in the form of a fiber but may be in the form of a ball and adhere to the collector 50.
  • the voltage applied to the nozzle 13 and the collector 50 is preferably 2 kV or more and 50 kV or less, and particularly preferably 20 kV or more and 40 kV or less.
  • cellulose triacetate As the cellulose acylate, cellulose triacetate (TAC) is used in the present embodiment, but is not limited thereto. Only one kind of acyl group may be used for cellulose acylate, or two or more kinds of acyl groups may be used. When two or more kinds of acyl groups are used, it is preferable that one of them is an acetyl group.
  • the ratio in which the hydroxyl group of cellulose is esterified with a carboxylic acid, that is, the substitution degree of the acyl group satisfies all of the following formulas (I) to (III).
  • a and B represent the substitution degree of the acyl group
  • A is the substitution degree of the acetyl group
  • B is the substitution degree of the acyl group having 3 to 22 carbon atoms. It is.
  • the cellulose acylate is preferably at least one of TAC, cellulose diacetate (DAC), cellulose acetate butyrate, and cellulose acetate propionate.
  • Solvents for dissolving cellulose acylate 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, N-methylpyrrolidone (NMP), diethyl ether, dioxane, tetrahydrofuran, 1-methoxy-2-propanol and the like.
  • NMP N-methylpyrrolidone
  • the mixing ratio (mass ratio) in the case of mixing and using is a polymer. , Saturated vapor pressure Ps, viscosity of the solution 25, and the like.
  • a mixture of dichloromethane and NMP a mixture of dichloromethane and cyclohexanone, a mixture of acetone and cyclohexanenone, or the like is used.
  • 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 which is negatively charged by the application of voltage, attracts the solution 25 that has been positively charged from the tip opening 13a, and a spinning jet 45 is formed.
  • the positively 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 solution 25 in the storage container 30 is such that the saturated vapor pressure Ps of the solvent and the concentration C of cellulose acylate satisfy the condition (1)
  • the solution 25 exiting from the tip opening 13a of the nozzle 13 is a solvent
  • the saturated vapor pressure Ps and the cellulose acylate concentration C satisfy the condition (1).
  • a component that easily evaporates for example, a component that easily evaporates at room temperature
  • the solution 25 coming out from the tip opening 13a is suppressed from solidifying by drying and forms a liquid ball or the like in the tip opening 13a.
  • a substantially conical Taylor cone 44 is formed and its shape is maintained.
  • the nanofiber 46 and the nonwoven fabric 120 are manufactured continuously for a long time. Further, the change in the diameter of the nanofiber 46 can be suppressed to a small value. Therefore, the nonwoven fabric 120 has a suppressed variation in diameter.
  • the saturated vapor pressure Ps of the solvent is stabilized.
  • the saturated vapor pressure Ps of the solvent and the concentration C of the cellulose acylate are reliably maintained in the state satisfying the condition (1), the formation of the Taylor cone 44 is maintained, and the nanofiber is continuously formed for a long time. 46 and the nonwoven fabric 120 are manufactured.
  • the solution 25 exiting from the tip opening 13a has a saturated vapor pressure Ps of 10 kPa or more and 50 kPa or less due to appropriate evaporation of the solvent even if a component that easily evaporates is used in the solvent.
  • Taylor cone 44 is formed more stably. For this reason, the nanofiber 46 which was continuous for a long time is obtained, and the nanofiber 46 and the nonwoven fabric 120 are manufactured more stably continuously for a long time. In addition, the diameter of the nanofiber 46 becomes more uniform.
  • the temperature of the solution 25 is adjusted within a range of 5 ° C. or more and 40 ° C. or less, thereby suppressing gelation and rapid evaporation of the solvent due to the low temperature of the solution 25, the Taylor cone 44 is more reliably stabilized. To do. For this reason, the nanofiber 46 and the nonwoven fabric 120 are manufactured more stably continuously for a long time.
  • the difference Ts ⁇ Ta between the temperature Ts of the solution 25 exiting from the tip opening 13a and the ambient temperature Ta is within a range of ⁇ 15 ° C. or more and 15 ° C. or less, the evaporation of the solvent is brought into an appropriate state, and the Taylor cone 44 is formed.
  • the nanofibers 46 and the nonwoven fabric 120 are more stably manufactured continuously for a long time.
  • the Taylor cone 44 is more stably formed, and the nanofibers 46 and the nonwoven fabric 120 are more stably manufactured continuously for a long time.
  • the above configuration is particularly effective when producing nanofibers having an average diameter of 1 ⁇ m or less.
  • 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 resulting non-woven fabric 120 is increased in area and manufacturing efficiency is increased.
  • a solvent recovery unit (not shown) in the spinning chamber 111.
  • the liquid for covering contains at least one component of the solvent of the solution 25.
  • This coating liquid may contain the same cellulose acylate as that contained in the solution 25.
  • the nonwoven fabric 120 may be used as a material for paper diapers, masks, oil filters, exhaust gas filters, air filters, osmosis membranes, reverse osmosis membranes, moisture permeable / waterproof sheets, water retention sheets, cell culture sheets, etc. .
  • the nanofiber 46 was manufactured as the nonwoven fabric 120 by the nanofiber manufacturing apparatus 110.
  • the component of a solvent and the compounding ratio of a component are shown in the "solvent composition" column of Table 1.
  • the temperature Ts of the solution 25, the ambient temperature Ta around the tip opening 13a, the relative humidity of the atmosphere, the value of the voltage applied by the power source 65, and the flow rate of the solution 25 to the nozzle 13 are as described above.
  • the nanofiber 46 can be continuously manufactured, and the case where the non-woven fabric 120 is obtained is “pass”. The case where the solution 25 is solidified at the tip opening 13a and the nanofiber 46 is not continuously manufactured is “not acceptable”. Evaluated as “pass”. The evaluation results are shown in Table 1.

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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)
  • Artificial Filaments (AREA)
  • Nonwoven Fabrics (AREA)

Abstract

L'invention concerne une solution obtenue par dissolution d'acylate de cellulose dans un solvant qui est émise à partir de l'ouverture d'extrémité avant d'une buse. Dans la solution émise à partir de l'ouverture d'extrémité avant, la pression de vapeur saturée Ps du solvant et la concentration de l'acylate de cellulose satisfont Ps × C ≤ 300. Une tension est communiquée à la buse et à un collecteur, et la solution et le collecteur sont ainsi chargés avec des polarités inversées. En utilisant le collecteur, la solution émise à partir de l'ouverture d'extrémité avant est tirée et s'accumule sous la forme d'une nanofibre.
PCT/JP2015/070902 2014-09-04 2015-07-23 Procédé de fabrication de nanofibres WO2016035473A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2014180422A JP2016053232A (ja) 2014-09-04 2014-09-04 ナノファイバ製造方法
JP2014-180422 2014-09-04

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WO2016035473A1 true WO2016035473A1 (fr) 2016-03-10

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Cited By (3)

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WO2017131035A1 (fr) * 2016-01-26 2017-08-03 富士フイルム株式会社 Nanofibre et tissu non tissé
WO2017155054A1 (fr) * 2016-03-11 2017-09-14 国立大学法人北海道大学 Fibres d'acétate de cellulose, composition d'acétate de cellulose, et procédés de fabrication de celles-ci
WO2019187827A1 (fr) * 2018-03-28 2019-10-03 富士フイルム株式会社 Non-tissé, procédé de formation de fibre, procédé de fabrication de non-tissé

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109072538B (zh) * 2016-06-30 2021-07-20 富士胶片株式会社 纤维复合体、多孔质结构体及无纺布
EP3549623B1 (fr) * 2016-11-29 2023-08-16 FUJIFILM Corporation Utilisation d'un milieu filtrant d'adsorption sélective de composant sanguin et filtre sanguin
JP6755203B2 (ja) * 2017-02-13 2020-09-16 富士フイルム株式会社 シート及びシート製造方法
JP7214742B2 (ja) * 2018-09-06 2023-01-30 富士フイルム株式会社 不織布

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH03220305A (ja) * 1989-11-21 1991-09-27 I C I Japan Kk 静電紡糸の製造方法
JP2012502197A (ja) * 2008-09-05 2012-01-26 イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニー 高処理のエレクトロブロー法

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH03220305A (ja) * 1989-11-21 1991-09-27 I C I Japan Kk 静電紡糸の製造方法
JP2012502197A (ja) * 2008-09-05 2012-01-26 イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニー 高処理のエレクトロブロー法

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
HAIQING LIU ET AL.: "Cellulose Membranes from Electrospinning of Cellulose Acetate", JOURNAL OF POLYMER SCIENCE : PART B: POLYMER PHYSICS, vol. 40, no. Issue 18, 15 September 2002 (2002-09-15), pages 2119 - 2129, ISSN: 1099-0488 *

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2017131035A1 (fr) * 2016-01-26 2017-08-03 富士フイルム株式会社 Nanofibre et tissu non tissé
WO2017155054A1 (fr) * 2016-03-11 2017-09-14 国立大学法人北海道大学 Fibres d'acétate de cellulose, composition d'acétate de cellulose, et procédés de fabrication de celles-ci
WO2019187827A1 (fr) * 2018-03-28 2019-10-03 富士フイルム株式会社 Non-tissé, procédé de formation de fibre, procédé de fabrication de non-tissé
JPWO2019187827A1 (ja) * 2018-03-28 2021-02-18 富士フイルム株式会社 不織布、ファイバ形成方法及び不織布製造方法

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