WO2021181489A1 - Procédé de fabrication de nanofibre à faible solubilité - Google Patents

Procédé de fabrication de nanofibre à faible solubilité Download PDF

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Publication number
WO2021181489A1
WO2021181489A1 PCT/JP2020/010129 JP2020010129W WO2021181489A1 WO 2021181489 A1 WO2021181489 A1 WO 2021181489A1 JP 2020010129 W JP2020010129 W JP 2020010129W WO 2021181489 A1 WO2021181489 A1 WO 2021181489A1
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Prior art keywords
nanofibers
solubility
cross
low
water
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PCT/JP2020/010129
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English (en)
Japanese (ja)
Inventor
圭 渡邊
道 大澤
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株式会社ナフィアス
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Priority to JP2021538840A priority Critical patent/JP6957075B1/ja
Priority to PCT/JP2020/010129 priority patent/WO2021181489A1/fr
Publication of WO2021181489A1 publication Critical patent/WO2021181489A1/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
    • D01D5/06—Wet 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
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/58—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products
    • D01F6/70—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products from polyurethanes

Definitions

  • the present invention relates to a method for producing low-solubility nanofibers.
  • nanofibers having a fiber diameter of nano-order have an extremely large specific surface area, they have properties that are significantly different from ordinary fibers (fibers having a fiber diameter of about 1 ⁇ m or more) that have been conventionally used. Therefore, nanofibers are expected as materials for products having various performances (high ion permeability, high liquid retention, high adsorption capacity, etc.) that cannot be realized by ordinary fibers.
  • the electrospinning method is widely known as a method for producing nanofibers.
  • a polymer which is a raw material of nanofibers is dissolved in a solvent to prepare a spinning solution, and the spinning solution is refined by electrostatic force to produce nanofibers.
  • organic solvents organic solvents
  • the cost issue is a major obstacle to the spread of nanofibers and cannot be underestimated.
  • it is conceivable to use a water-soluble polymer in order to avoid the use of an organic solvent but when the water-soluble polymer is used as the main constituent material of the nanofiber, a post-treatment (chemical) that reduces the solubility of the nanofiber is performed.
  • Equipment for carrying out treatment or heat treatment is required, and such equipment also causes an increase in cost.
  • Another problem is that the types of water-soluble polymers are limited.
  • the conventional method for producing nanofibers using a polymer dispersion has a problem that it is difficult to produce nanofibers that are difficult to dissolve in an organic solvent.
  • an organic solvent-based electrolyte is often used in a capacitor or a battery having a high nominal voltage (such as a lithium ion secondary battery).
  • Separators using nanofibers exhibit excellent properties in many respects, such as electrolyte retention, ion permeability, and strength per thickness.
  • the nanofibers are easily dissolved in the electrolytic solution, it goes without saying that the separator using the nanofibers cannot be used together with the electrolytic solution.
  • the solubility of nanofibers in an organic solvent is a factor directly related to the range of application of nanofibers.
  • polyurethane-based nanofibers are easily dissolved in organic solvents, which has been a bottleneck in expanding the range of applications.
  • the present invention has been made to solve the above problems, and an object of the present invention is to provide a method for producing low-solubility nanofibers capable of producing low-solubility nanofibers which are difficult to dissolve in an organic solvent from a polyurethane dispersion liquid. And.
  • the method for producing low-solubility nanofibers of the present invention is a spinning solution preparation step of adding a cross-linking agent to a mixed solution of a water-soluble polymer aqueous solution and a polyurethane dispersion to prepare a spinning solution, and an electrospinning method. It is characterized by including a spinning step of forming nanofibers from the spinning solution and a cross-linking step of converting the nanofibers into low-solubility nanofibers by cross-linking.
  • the water-soluble polymer aqueous solution contains at least one of polyethylene oxide, polyethylene glycol, water-soluble nylon, polyvinyl alcohol, polyvinylpyrrolidone, and polyacrylamide. Is preferable.
  • the nanofibers are pressed and conveyed using a heating roll set to a temperature in the range of 50 ° C. to 180 ° C. It is preferable to carry out the heat treatment while performing the heat treatment.
  • the weight of the non-volatile component in the polyurethane dispersion is within the range of 1 to 5 times the weight of the water-soluble polymer component in the water-soluble polymer aqueous solution. It is preferable to have.
  • the cross-linking agent is a water-soluble carbodiimide cross-linking agent
  • the weight of the cross-linking agent in the spinning solution is the non-volatile content contained in the polyurethane dispersion. It is preferably in the range of 1% to 30% of the weight of the above.
  • the polyurethane in the polyurethane dispersion is preferably a polycarbonate-based polyurethane.
  • the average particle size of the dispersoid in the polyurethane dispersion is preferably 1 ⁇ m or less.
  • low-solubility nanofibers that are difficult to dissolve in an organic solvent can be produced from a polyurethane dispersion.
  • SEM image of nanofibers before the cross-linking process SEM image of low solubility nanofibers after the cross-linking step. SEM image of low solubility nanofibers after immersion in distilled water. SEM image of low solubility nanofibers after immersion in DMF.
  • the method for producing low-solubility nanofibers includes a spinning solution preparation step, a spinning step, and a cross-linking step.
  • the term "low-solubility nanofibers” refers to both water and N, N-dimethylformamide (hereinafter referred to as DMF), and the fiber shape remains even when immersed at 60 ° C. for 24 hours. It refers to nanofibers.
  • DMF N, N-dimethylformamide
  • the spinning solution preparation step is a step of preparing a spinning solution by adding a cross-linking agent to a mixed solution of a water-soluble polymer aqueous solution and a polyurethane dispersion.
  • polyurethane dispersion refers to an aqueous solution in which fine-grained polyurethane is dispersed.
  • the dispersion is sometimes referred to as an emulsion, emulsion, suspension, suspension, dispersion, colloidal solution or the like.
  • the water-soluble polymer aqueous solution contains a so-called water-soluble polymer.
  • a water-soluble polymer is a polymer that can be made into a stable aqueous solution.
  • the water-soluble polymer aqueous solution is among polyethylene oxide, polyethylene glycol, water-soluble nylon, polyvinyl alcohol, polyvinylpyrrolidone and polyacrylamide. It is preferable to contain at least one.
  • the type of polyurethane in the polyurethane dispersion is not particularly limited. However, considering that the object of the present invention is to produce low-solubility nanofibers and that electric power equipment (condenser or battery) is assumed as the intended use of the low-solubility nanofibers, polyurethane dispersion is performed.
  • the polyurethane in the liquid is preferably a polycarbonate-based polyurethane that is relatively resistant to water, organic solvents, heat, etc. due to the structure derived from the polyol.
  • the polyurethane dispersion and the spinning solution may contain a plurality of types of polyurethane and polyurethane monomers and oligomers. Further, the polyurethane dispersion liquid and the spinning solution may contain a polymer other than polyurethane or a substance other than the polymer as long as the effects of the present invention are not impaired.
  • the average particle size of the dispersoid (nonvolatile content) in the polyurethane dispersion is not particularly limited, but it should be 1 ⁇ m or less in consideration of the stability of the dispersion (difficulty of precipitation of the dispersion) and the ease of forming nanofibers. It is preferably 0.1 ⁇ m or less, and more preferably 0.1 ⁇ m or less.
  • the average particle size of the dispersoid in the spinning solution is the same as that in the polyurethane dispersion.
  • the weight of the non-volatile component in the polyurethane dispersion is preferably in the range of 1 to 5 times the weight of the water-soluble polymer component in the water-soluble polymer aqueous solution.
  • the cross-linking agent in the embodiment is for cross-linking polyurethane in a cross-linking step described later. Therefore, as the cross-linking agent, it is preferable to use one that does not start the cross-linking reaction in the spinning solution (one that starts the cross-linking reaction by an external stimulus such as heat or electromagnetic waves).
  • the cross-linking agent in the embodiment is a water-soluble carbodiimide cross-linking agent.
  • the type of water-soluble carbodiimide cross-linking agent can be specifically determined according to the type of polyurethane used. If the amount of the cross-linking agent is small, the solubility in an organic solvent may not be sufficiently lowered.
  • the weight of the cross-linking agent in the spinning solution is preferably in the range of 1% to 30% of the weight of the non-volatile content in the polyurethane dispersion.
  • the spinning solution may contain substances other than those described above.
  • substances include substances that assist electrospinning (eg, conductive aids and surfactants), substances that stabilize the state of the spinning solution (eg, emulsifiers) and functional substances (eg, inorganic particles, catalysts, etc.). Pigments) can be exemplified.
  • the spinning process is a process of forming nanofibers from a spinning solution by an electric field spinning method.
  • the electric field spinning method a known method can be used, and thus the description thereof will be omitted.
  • the cross-linking step is a step of converting nanofibers into low-solubility nanofibers by cross-linking.
  • the polyurethane is reacted with the cross-linking agent by applying an external stimulus (energy) to promote the polymerization of the polyurethane.
  • an external stimulus energy
  • a cross-linking agent capable of initiating (progressing) cross-linking of polyurethane by heat can be used, and in the cross-linking step, cross-linking can be started by performing heat treatment.
  • a treatment other than the heat treatment for example, irradiation with ultraviolet rays or visible light may be performed in the cross-linking step.
  • the heat treatment temperature is too low, the cross-linking of polyurethane may be insufficient. On the other hand, if the heat treatment temperature is too high, the fiber structure may be damaged. From such a viewpoint, it is preferable to carry out the heat treatment at a temperature in the range of 50 ° C. to 180 ° C.
  • the heat treatment time time for exposing the nanofibers to a high temperature
  • the heat treatment time can be relatively short, for example, 10 seconds or less. It can be 3 seconds or less. However, from the viewpoint of heat transfer and the like, the heat treatment time is preferably 0.1 seconds or longer. Therefore, in the cross-linking step in the embodiment, a heating roll (a transport mechanism using a roller capable of heating and pressurizing the transported object) set to a temperature within the range of 50 ° C. to 180 ° C. is used. The heat treatment can be performed while pressing and transporting the nanofibers.
  • the heat treatment using the heating roll can be carried out by forming nanofibers in a strip shape (forming a strip-shaped nanofiber non-woven fabric) in the spinning process and using equipment such as a so-called calendar machine (calender roll).
  • low-solubility nanofibers By carrying out the above steps, low-solubility nanofibers can be produced.
  • the method for producing low-solubility nanofibers may include steps other than the above. In addition, operations and the like not mentioned in the above description may be performed.
  • low-solubility nanofibers that are difficult to dissolve in an organic solvent can be produced from a polyurethane dispersion.
  • the low-solubility nanofibers produced by the method for producing low-solubility nanofibers of the present invention can also have low solubility in water.
  • the spinning solution contains the above-mentioned water-soluble polymer aqueous solution (polyethylene oxide or the like), stable electrospinning is possible with a relatively easy-to-use spinning solution. It becomes.
  • the heat treatment when the heat treatment is performed at a temperature in the range of 50 ° C. to 180 ° C. in the crosslinking step, the polymerization of polyurethane is sufficiently promoted. And it is possible to reduce the damage to the fiber structure due to heat.
  • heat treatment is performed while pressing and transporting the nanofibers using a heating roll set to a temperature in the range of 50 ° C. to 180 ° C.
  • a heating roll set to a temperature in the range of 50 ° C. to 180 ° C.
  • the weight of the non-volatile component in the polyurethane dispersion is in the range of 1 to 5 times the weight of the water-soluble polymer component in the water-soluble polymer aqueous solution. It is possible to produce low-solubility nanofibers having sufficient strength and stability, and it is possible to stably carry out the electrospinning method.
  • the weight of the cross-linking agent in the spinning solution is in the range of 1% to 30% of the weight of the non-volatile content contained in the polyurethane dispersion. It is possible to sufficiently reduce the solubility of low-solubility nanofibers in an organic solvent, and it is possible to suppress an increase in cost and probability of occurrence of side reactions.
  • the low-solubility nanofibers are compared with the case where a polyurethane of a system other than the polycarbonate-based polyurethane is used. It is possible to further reduce the solubility of the nanofibers in organic solvents and water, and further increase the heat resistance of the low-solubility nanofibers.
  • the method for producing low-solubility nanofibers when the average particle size of the dispersoid in the polyurethane dispersion is 1 ⁇ m or less, electrospinning is performed by suppressing precipitation of the dispersoid in the spinning solution. It is possible to increase the stability of.
  • PEO polyethylene oxide
  • PEO polyethylene oxide
  • polyurethane dispersion a water-dispersed polycarbonate-based polyurethane dispersion (anionic, milky white, non-volatile content 30%, average particle size to 0.06 ⁇ m) was used.
  • carbodiimide cross-linking agent a water-soluble carbodiimide cross-linking agent was used.
  • a commercially available cooking sheet (a paper sheet whose surface is coated with a low-friction resin) was used as a base material for electrospinning nanofibers.
  • the DMF used was purchased through Fujifilm Wako Pure Chemical Industries, Ltd. Distilled water used was prepared before the experiment.
  • the nanofiber production system ES200 in-house product of Nafias Co., Ltd. was used.
  • the calendar machine a thermal calendar machine (non-commercial product) for testing a prototype was used.
  • the basic structure of the test thermal calendar machine is similar to that of the generally widely known one.
  • the test thermal calendar machine includes an upper metal roll (diameter 100 mm, width 300 mm) and a lower rubber roll (diameter 100 mm, width 300 mm).
  • An air cylinder is provided on the upper metal roll side of the test thermal calendar machine so that pressure can be applied to an object passing between the rolls.
  • the lower rubber roll is connected to an electric motor so that it can be rotated while adjusting the rotation speed.
  • SEM scanning electron microscope
  • Electromagnetic Spinning Step In the electrospinning step, a 5 ml syringe equipped with a metal nozzle having a length of 19 G needle tip of 15 mm was filled with a spinning solution, and a positive electrode was attached to the metal nozzle. Then, a ground wire was connected to the rotatable metal drum collector, a cooking sheet was wound around the rotating portion of the metal drum collector, and electric field spinning was performed using the cooking sheet as a base material. The electric field spinning was carried out under the conditions of an applied voltage of 8 kV, a TCD of 12 cm, a syringe extrusion speed of 0.002 mm / min, a nozzle traverse width of 150 mm, and a collector rotation speed of 50 rpm.
  • cross-linking step a heat treatment accompanied by pressurization was carried out while transporting under the conditions of 130 ° C. and 30 cm / min using a thermal calendaring machine for testing.
  • heat treatment was performed with the nanofibers placed on the base material, and then the nanofibers were peeled off from the base material.
  • the low-solubility nanofibers according to the examples were produced.
  • FIG. 1 is an SEM image of nanofibers before the cross-linking step.
  • FIG. 2 is an SEM image of low-solubility nanofibers after the cross-linking step.
  • the fiber diameter tended to be slightly thicker, but it was confirmed that the fiber structure was maintained even after the cross-linking process was carried out.
  • the number of bead-shaped structures present in the SEM image is different between FIGS. 1 and 2, but this is due to the difference in the position where the SEM image is acquired, and the form of the nanofiber non-woven fabric is formed by cross-linking (heat treatment). Does not indicate that has changed. Further, the bead-like structure does not necessarily inhibit the function of the low-solubility nanofibers, but is not essential as the structure of the low-solubility nanofibers.
  • Solubility of low-solubility nanofibers In the test for solubility, a test piece made of non-woven fabric-like low-solubility nanofibers is immersed in distilled water, an SEM image is acquired to confirm the morphology, and then the test piece is immersed in DMF. The SEM image was acquired again and the morphology was confirmed again. The temperature of the distilled water and DMF at the time of immersion was 60 ° C., and the immersion time was 24 hours. The SEM image was acquired after the test piece was dried.
  • FIG. 3 is an SEM image of low-solubility nanofibers after immersion in distilled water. As shown in FIG. 3, it was confirmed that the fiber structure did not change even when immersed in distilled water.
  • FIG. 4 is an SEM image of low-solubility nanofibers after immersion in DMF. As shown in FIG. 4, it was confirmed that there was no change in the fiber structure even when immersed in DMF.
  • the method for producing low-soluble nanofibers of the present invention can produce low-soluble nanofibers that are difficult to dissolve in water or an organic solvent from a polyurethane dispersion.
  • the low-solubility nanofibers in the present invention are produced from finely divided polyurethane in a dispersion liquid, and are not in spite of having a very large specific surface area (a very large area in contact with water or an organic solvent).
  • An epoch-making result was obtained that the solubility in DMF, which has high solubility among protic solvents, can be lowered.
  • the present invention has been described above based on the above embodiments and examples, the present invention is not limited to the above embodiments and examples. It is possible to carry out in various ways within the range that does not deviate from the purpose. That is, the specific contents of the steps described in the above embodiment are examples, and can be changed as long as the effects of the present invention are not impaired.
  • the low-solubility nanofibers according to the present invention can be suitably used in various applications such as battery separators, capacitor separators, and fluid filters.

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

Abstract

La présente invention concerne un procédé de fabrication d'une nanofibre à faible solubilité, le procédé étant caractérisé en ce qu'il comprend : une étape de préparation d'une solution de filage consistant à ajouter un agent de réticulation à un liquide mixte comprenant une solution aqueuse d'un polymère soluble dans l'eau et un liquide de dispersion de polyuréthane, et à préparer une solution de filage ; une étape de filage permettant de former la nanofibre à partir de la solution de filage au moyen d'un électrofilage ; et une étape de réticulation permettant de convertir la nanofibre en une nanofibre à faible solubilité au moyen d'une réticulation.　L'utilisation dudit procédé de fabrication d'une nanofibre à faible solubilité permet de fabriquer une nanofibre à faible solubilité ne se dissolvant pas facilement dans l'eau ni dans un solvant organique (par exemple, le N,N-diméthylformaldéhyde), à partir du liquide de dispersion de polyuréthane.
PCT/JP2020/010129 2020-03-09 2020-03-09 Procédé de fabrication de nanofibre à faible solubilité WO2021181489A1 (fr)

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JP2021538840A JP6957075B1 (ja) 2020-03-09 2020-03-09 低溶解性ナノファイバーの製造方法
PCT/JP2020/010129 WO2021181489A1 (fr) 2020-03-09 2020-03-09 Procédé de fabrication de nanofibre à faible solubilité

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114318603A (zh) * 2021-12-01 2022-04-12 东华大学 一种棉纤维/热塑性聚氨酯纳米纤维混纺纱线的制备方法

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2009526917A (ja) * 2006-02-13 2009-07-23 ドナルドソン カンパニー，インコーポレイティド ポリマーブレンド、ポリマー溶液組成物、ポリマーブレンドから紡糸されたファイバおよび濾過への応用
JP2010236138A (ja) * 2009-03-31 2010-10-21 Toray Ind Inc 防水透湿繊維積層体
US20190046361A1 (en) * 2016-03-29 2019-02-14 Kyungpook National University Industry-Academic Cooperation Foundation Hydrophilic polyurethane nanofiber and method for manufacturing same

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2009526917A (ja) * 2006-02-13 2009-07-23 ドナルドソン カンパニー，インコーポレイティド ポリマーブレンド、ポリマー溶液組成物、ポリマーブレンドから紡糸されたファイバおよび濾過への応用
JP2010236138A (ja) * 2009-03-31 2010-10-21 Toray Ind Inc 防水透湿繊維積層体
US20190046361A1 (en) * 2016-03-29 2019-02-14 Kyungpook National University Industry-Academic Cooperation Foundation Hydrophilic polyurethane nanofiber and method for manufacturing same

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
ARAE, TSUKASA ET AL.: "Effect of addition of cross-linker on Electrospinning of PU prepolymer / PVA aqueous solution", PROCEEDINGS OF THE ANNUAL MEETING OF THE SOCIETY OF FIBER SCIENCE AND TECHNOLOGY, vol. 65, no. 3, Ja pan, Retrieved from the Internet <URL:http://ckpmac7.yz.yamagata-u.ac.jp/conf/2010/20109/seni/arae-yoko.pdf> [retrieved on 20200527] *
PHAM, QUYNH P.: "Electrospinning of Polymeric Nanofibers for Tissue Engineering Applications: A Review", TISSUE ENGINEERING, vol. 12, no. 5, 2006, pages 1197 - 1211, XP055513969, DOI: 10.1089/ten.2006.12.1197 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114318603A (zh) * 2021-12-01 2022-04-12 东华大学 一种棉纤维/热塑性聚氨酯纳米纤维混纺纱线的制备方法
CN114318603B (zh) * 2021-12-01 2023-08-22 东华大学 一种棉纤维/热塑性聚氨酯纳米纤维混纺纱线的制备方法

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