JP6906212B2 - Spinning method, spinning equipment and fiber bundle - Google Patents

Description

The present invention relates to a spinning method for producing a fiber bundle from a fine fibrous substance by the action of an electric field, a spinning device used for the spinning method, the spinning method, and a fiber bundle manufactured by the spinning device.

Since the beginning of this century, research and development related to nanotechnology has been actively developed, and nano-sized materials with properties and functions not found in conventional materials have been created. In addition, the utilization of naturally derived resources is regarded as important from the viewpoint of defossil resources and resource recycling.

Nanocellulose, which is one of the nano-sized substances, is a plant-derived fine fibrous substance, which is an extremely short fiber having a width of 1 to 100 nm and a length of several μm, but is much lighter and stronger than steel. Is considered to be 5 times (3 GPa) that of steel. Due to the unique properties of nanocellulose due to being a nano-sized substance, it is expected to be used in a wide range of fields from industrial to medical, such as additives for resins, filters, and cosmetics, and some have already been used. ..

As a means for utilizing the excellent strength characteristics of fine fibrous substances such as nanocellulose, it can be molded into a thread or a sheet, but if it can be molded into a thread, it can be further formed into a rope or cloth. Since it can be processed, it has the advantage of expanding the range of utilization.

Generally, yarns are produced by melt spinning, dry spinning, and wet spinning, but yarns having high strength are produced by gel spinning or liquid crystal spinning using a liquid crystal polymer. These manufacturing methods are methods in which a melt or solution of a raw material is extruded from a spinneret to form a fibrous material and then hardened, and are used for producing a thin and strong yarn called a filament yarn.

In each of the above methods, the raw material is extruded from the spinneret by applying pressure to the melt or liquid, electrospinning by applying a high voltage, or electrospinning in liquid in a low dielectric constant liquid. There is.

Patent Document 1 discloses an invention of wet spinning in which an aqueous dispersion of nanocellulose is injected into an alcohol-based organic solvent, a gelled portion is stretched, and the gelled portion is formed into a monofilament in the liquid.

Non-Patent Document 1 discloses an invention of wet spinning in which nanocellulose is processed into monofilament by extruding a dispersion having a nanocellulose concentration of about 2% into an acetone coagulation bath at a constant pressure from a nozzle.

FIG. 15 is a diagram showing an outline of the invention of wet spinning disclosed in Patent Document 1 and Non-Patent Document 1 below. As shown in the figure, the tip of the nozzle 102 of the injector 101 is arranged in the container 100 containing the coagulating liquid. The injector 101 is filled with a dispersion liquid 103 in which a polymer or a fine fibrous substance is dispersed in a solvent. When the dispersion liquid 103 is pressurized by the injector 101 and pushed out from the nozzle 102 into the coagulation liquid 104 in the container 100, the dispersion medium in the dispersion liquid 103 diffuses into the coagulation liquid 104, but fine fibrous substances and the like do not diffuse. Therefore, a continuous filament yarn 105 (fiber) is formed in the coagulating liquid 104.

Patent Document 2 discloses an invention of an in-liquid electrospinning method performed in a low dielectric constant liquid.

FIG. 16 is a diagram showing an outline of the submerged electrospinning method disclosed in Patent Document 2. As shown in the figure, in the container 200 containing the low dielectric constant liquid 201, a first electrode (electrospray nozzle, ESN) 203 that also serves as a nozzle of the injector 202 and a second electrode 204 facing the first electrode (electrospray nozzle, ESN) 203. Are arranged at intervals, and the first electrode 203 and the second electrode 204 are connected to the power supply 205. The syringe 202 is filled with the polymer solution 206. When the polymer solution 206 is pressurized by the injector 202 and extruded into the low dielectric constant liquid 201 from the nozzle which is the first electrode 203, nanofibers 207 made of the polymer are generated, and high on the second electrode 204. Nonwoven fabric 208 made of molecular fibers is formed.

JP 2011-246823 Japanese Unexamined Patent Publication No. 2014-224337

Iwamoto, S .; Isogai, A .; Iwata, T. Biomacromolecules 2011, 12, 831-836.

According to the invention disclosed in the prior art document, it is possible to extrude a dispersion liquid of a fine fibrous substance such as nanocellulose into a coagulation liquid and process it into a filament yarn 105 (FIG. 15), and the liquid. It was also possible to produce a non-woven fabric 208 (FIG. 16) of polymer fibers by the medium electrospinning method. However, it was not possible to directly produce a fiber bundle by accumulating fine fibrous substances.

The present invention has been made to solve the problems in the prior art, and includes a spinning method for producing a fiber bundle in one step by directly accumulating fine fibrous substances in a liquid by a wet method. It is an object of the present invention to provide a spinning apparatus for carrying out a spinning method, and further, a fiber bundle produced by the method and the apparatus.

The spinning method according to claim 1 is
First step of producing a fiber bundle by diameter giving an electric field to fine fibrous materials in the liquid is greater than or equal to 100 times the diameter length at 1 to 500 nm, it is integrated by aligning the orientation of the fine fibrous material It is characterized by having.

The spinning method according to claim 2 is the spinning method according to claim 1.
It is characterized by having a second step of continuously stretching the fiber bundle produced in the first step to manufacture a yarn.

The spinning method according to claim 3 is the spinning method according to claim 2.
In the first step, the fine fibrous material is characterized to be supplied to the liquid in the micro-fibrous material as a droplet form of dispersion obtained by dispersing in a dispersion medium.

The spinning apparatus according to claim 4 is
Electrodes that generate an electric field in the liquid,
A supply means for supplying an electric field in the liquid with a fine fibrous substance having a diameter of 1 to 500 nm and a length of 100 times or more the diameter.
And expansion means to the fiber bundle a gel consisting of the fine fibrous material orientation aligned integrated Waals force was continuously drawn out from the liquid by an electric field,
It is characterized by having.

The fiber bundle according to claim 5 is
A structure in which a plurality of filamentous substances composed of fine fibrous substances having a diameter of 1 to 500 nm and a length of 100 times or more the diameter, which are aligned by an electric field in a liquid and accumulated by intermolecular force, are accumulated in a coil shape. It has a diameter of 50 μm to 1000 μm .

The fiber bundle according to claim 6 is the fiber bundle according to claim 5 .
It is characterized in that a functional substance is contained in a state of being interposed between fine fibrous substances.

According to the spinning method according to claim 1, in the first step of applying an electric field to a fine fibrous substance in a liquid, the orientation and accumulation density of the fine fibrous substance are precisely controlled in a certain direction. It is possible to produce a bulky fiber bundle having a structure in which a plurality of filamentous substances composed of fine fibrous substances that are oriented and accumulated by intermolecular force are accumulated in a coil shape and have useful characteristics.

According to the spinning method according to claim 2, the fiber bundle produced in the first step of claim 1 can be continuously stretched to produce a yarn having an arbitrary length.

According to the spinning method according to claim 3, in the first step of claim 2, a dispersion liquid obtained by dispersing fine fibrous substances in a dispersion medium is supplied into the liquid in the form of droplets. , The required amount of fine fibrous material can be stably supplied at the required rate. Then, the droplets of the dispersion liquid containing the fine fibrous substance supplied into the liquid are stretched while losing the dispersion medium, gather at the strong position of the electric field in the liquid, and are accumulated in the same direction of the fine fibrous substance. , Many gather to form a filamentous gel. When this gel is pulled up from the liquid and dried, a fiber bundle can be obtained, and when the gel is pulled up from the liquid and dried while continuously forming the gel, a yarn having a desired length can be obtained.

According to the spinning apparatus according to claim 4, when an electric field is applied to a fine fibrous substance supplied into a liquid by a supply means to accumulate the fine fibrous substance, the orientation and accumulation density of the fine fibrous substance are precisely controlled. As a result, it is possible to produce a filamentous gel composed of fine fibrous substances oriented in a certain direction and accumulated by intermolecular force, and further, while continuously producing this gel, it is pulled up from the liquid by an stretching means and dried. By doing so, it is possible to produce a bulky thread of an arbitrary length having a structure in which a plurality of filamentous substances having useful properties as a fine fibrous substance are accumulated in a coil shape.

The fiber bundle according to claim 5 has a bulky structure in which fine fibrous substances are oriented in a certain direction and accumulated by intermolecular force, and is in the form of a plurality of filaments composed of fine fibrous substances having useful properties. It has a structure in which objects are integrated in a coil shape. This fiber bundle has a diameter of 50 μm to 1000 μm, and the fine fibrous substance constituting the fiber bundle is also called nanofiber, which has a diameter of 1 to 500 nm and a length of 100 times or more the diameter, and is nanocellulose. In addition to plant-derived substances such as, substances derived from animals, minerals, and synthetic polymers are also included.

The fiber bundle according to claim 6 has a functional substance interposed between the fine fibrous substances constituting the fiber bundle, and has characteristics according to the type of the functional substance. Such a fiber bundle can be produced in a small number of steps with a reduced environmental load by mixing a functional substance such as a dye component or metal particles with a dispersion medium in which a fine fibrous substance is dispersed.

It is a schematic diagram which shows the spinning method and the spinning apparatus of 1st Embodiment. It is a schematic diagram which showed how the fine fibrous substance is accumulated between electrodes in the spinning method and the spinning apparatus of 1st Embodiment. It is a schematic diagram which shows the spinning apparatus and spinning method of 2nd Embodiment. It is a figure which shows the photograph of the fiber bundle produced in Example 2. The fraction (a) is a diffraction diagram of a two-dimensional XRD (X-ray diffraction) of the fiber bundle manufactured in Example 2, and the segment (b) is an azimuth profile diagram. FIG. 3A is a diffraction diagram of a two-dimensional XRD (X-ray diffraction) of a fiber bundle manufactured in the spinning apparatus of Example 2 without generating an electric field, and FIG. It is a figure which shows the photograph of the fiber bundle produced in Example 3. It is a figure which shows the photograph of the fiber bundle produced in Example 5. It is a figure which shows the enlarged photograph of the fiber bundle produced in Example 5. It is a figure which shows the photograph of the fiber bundle produced in Example 6. It is a figure which shows the enlarged photograph of the fiber bundle produced in Example 6. It is a figure which shows the elemental analysis result by EDS of the fiber bundle produced in Example 6. It is a figure which shows the photograph of the fiber bundle produced in Example 7. It is a figure which shows the enlarged photograph of the fiber bundle produced in Example 7. It is a schematic diagram which shows the outline of the wet spinning. It is a schematic diagram which shows the outline of the liquid electrospinning method.

Hereinafter, embodiments and examples of the present invention will be described with reference to FIGS. 1 to 14 while appropriately comparing with Comparative Examples.

<< First Embodiment >> (Fig. 1)
FIG. 1 is a schematic view showing a spinning device M1 of the first embodiment and a spinning method by the spinning device M1, and FIG. 2 is a diagram in which fine fibrous substances are accumulated between electrodes in the spinning device M1 of the first embodiment. It is a schematic diagram which showed the state of forming a fiber bundle.

First, the outline of the spinning apparatus M1 and the spinning method of the first embodiment will be described.
As shown in FIG. 1, the spinning device M1 includes a container 10 in which a low dielectric constant liquid 3 is housed. The first electrode 1 and the second electrode 2 are arranged at predetermined intervals in the container 10, and the first electrode 1 and the second electrode 2 are connected to the power supply 4 (DC power supply in the present embodiment). It is connected.

As shown in FIG. 1, in the low dielectric constant liquid 3 of the container 10, a dispersion liquid in which fine fibrous substances are dispersed in a dispersion medium exists in the form of a large number of fine droplets 5. As shown in FIG. 2, each of the fine droplets 5 of the dispersion liquid in the low dielectric constant liquid 3 contains an indefinite amount of fine fibrous material 11 (see FIG. 2). These fine droplets 5 are supplied from the liquid surface of the low dielectric constant liquid 3 into the liquid or directly into the liquid by a supply means (not shown). That is, in the embodiment shown in FIG. 1, the first electrode 1 has only a function as an electrode, and the dispersion liquid is an appropriate supply means such as a nozzle or a dispenser (not shown) for supplying the dispersion liquid. Then, it is supplied in the form of droplets 5 in the low dielectric constant liquid 3.

As the means for supplying the dispersion medium, for example, the injector 202 of the spinning apparatus used in the submerged electrospinning method described with reference to FIG. 16 can be used. That is, as the first electrode 1 in FIG. 1, the electrospray nozzle (electrospray nozzle 203 in FIG. 16) of the injector of the spinning apparatus used in the submerged electrospinning method is used, and the counter electrode (second in FIG. 1) is used. A potential difference may be given between the electrode 2) and the dispersion liquid may be fragmented into finely charged droplets 5 and electrostatically sprayed from the electrospray nozzle toward the above.

As shown in FIG. 1, when a potential difference is applied between the first electrode 1 and the second electrode 2 by the power supply 4, a broken line is shown in FIGS. 1 and 2 between the first electrode 1 and the second electrode 2. An electric field as represented by the indicated electric lines of force E is formed. The fine droplets 5 of the dispersion liquid between the first electrode 1 and the second electrode 2 are stretched by the action of an electric field while losing the dispersion medium in the low dielectric constant liquid 3, and change from a substantially spherical shape to a substantially rotating elliptical shape. A large number of fine fibrous materials that are deformed and gather on the line connecting the first electrode 1 and the second electrode 2 where the electric field is the strongest, as shown by the white arrow A, as shown in FIG. Is thought to form a gel 6 that accumulates in the form of filaments.

As shown schematically in an enlarged manner in FIG. 2, the gel 6 on a virtual line connecting the first electrode 1 and the second electrode 2 has a large number of fine fibrous substances 11 in a certain direction due to the action of an electric field. It is oriented in the direction of, and is integrated with each other by intermolecular force. If the gel 6 is pulled up from the low dielectric constant liquid 3 and dried by another suitable means without destroying the filamentous structure, it is bulky and has useful properties consisting of the accumulated fine fibrous material 11. Fiber bundles can be produced. Further, although a specific example will be described later, a spun yarn can be produced by pulling up the fiber bundle from the low dielectric constant liquid 3 and drying it while continuously producing and extending the fiber bundle (second embodiment). , See FIG. 3).

Next, the details of the spinning method using the spinning device M1 of the first embodiment will be described.
In the present embodiment, the liquid in the container 10 to which the dispersion liquid containing the fine fibrous substance 11 is supplied by spraying or the like is not limited to a specific substance as long as it can form an electric field. , A liquid having a low dielectric constant is preferable, and this is referred to as the above-mentioned "low dielectric constant liquid 3".

The low dielectric constant liquid 3 refers to a liquid having a relative permittivity of 25 or less, preferably 20 or less, more preferably 15 or less, still more preferably 10 or less, still more preferably 5 or less. Examples of such liquids include hydrocarbons such as n-hexane, pentane, and decane, ethanol (relative permittivity 24.55), 1-butanol (relative permittivity 17.51), and 1-pentanol (relative permittivity 13.51). 9) Alcohols such as 1-octanol (relative permittivity 10.3), benzyl chloride (relative permittivity 7.0), chloroform (relative permittivity 6.15), 1-chlorooctane (relative permittivity 5. 05), carbon tetrachloride (relative permittivity 2.238), halogenated hydrocarbons such as perfluorohexane, and the like, and among them, hydrocarbons and the like are particularly preferable.

Examples of the halogen contained in the halogenated hydrocarbon include chlorine, fluorine, bromine, iodine and the like. The low dielectric constant liquid 3 may be used alone or in combination of two or more. According to the present embodiment, since the low dielectric constant liquid 3 having a dielectric constant that is substantially non-energized is used, a potential difference is generated between the first electrode 1 and the second electrode 2 to create a potential difference between the electrodes. An electric field can be formed, and by supplying the dispersion liquid as charged droplets 5 in this electric field, the droplet 5, the fine fibrous substance 11, and the fine fibrous substance 11 are accumulated in a filamentous form in the gel 6. Can be accumulated by the action of an electric field to produce a fiber bundle.

The fine fibrous substance 11 in the present embodiment is a fibrous substance having a diameter of 1 to several hundred nm and a length of 100 times or more the diameter. The diameter of the fine fibrous substance 11 is preferably 2 to 500 nm, more preferably 2 to 100 nm, and even more preferably 2 to 10 nm. As raw materials for such fine fibrous substances 11, plants such as wood pulp and bamboo, clothing for cotton products, raw materials containing cellulose such as cardboard, chitin, chitosan, carboxymethyl cellulose (CMC), and nano-based silk. Fibers and the like are known and are not particularly limited in the present invention. As a method for producing the fine fibrous substance 11 using the raw material, a high-pressure homogenizer, a water jet method, and TEMPO (2,2,6,6-tetramethylpiperidine 1-oxyl (2,2,6,6-)) Abbreviation for tetramethylpiperidine 1-oxyl)) Oxidation methods, utilization methods of microorganisms, etc. are known, but are not particularly limited in the present invention. It is also possible to use the fine fibrous substance 11 that has been subjected to the hydrophobic modification treatment.

As the dispersion medium (solvent for dispersing the fine fibrous substance 11) in which the fine fibrous substance 11 is dispersed in the present embodiment, an alcohol-based organic solvent such as ethanol is preferable.

In the present embodiment, the concentration of the fine fibrous substance 11 in the dispersion medium is not particularly limited, but the solid content concentration is preferably 0.0001 to 3.0%, more preferably 0.01 to 2.5%, and 0. 1 to 2.5% is more preferable. Within the above concentration range, it is possible to collect the fine fibrous substances 11 in the electric field to generate a gel 6 as a fiber bundle even at a low concentration.

In the present embodiment, when an electrospray nozzle (ESN) is used as the first electrode 1, the electrospray nozzle may have a shape and structure capable of forming an electric field with the second electrode 2 which is a counter electrode. For example, the nozzle diameter is preferably 0.1 to 0.5 mm, and the width between the inner diameter and the outer diameter of the nozzle is preferably as small as possible. Further, if the material of the nozzle is conductive, the dispersion liquid can be sprayed as charged droplets 5, and if the material is not conductive, a material having conductivity is used in the nozzle. The material of the nozzle is not particularly limited because it can be sprayed in the same way by incorporating it. In addition, a plurality of nozzles can be installed.

In the present embodiment, a supply means such as a nozzle for supplying the dispersion liquid and a first electrode 1 for forming an electric field in the low dielectric constant liquid 3 are configured as separate bodies (in the case of the configuration shown in FIG. 1). The material of the first electrode 1 is not particularly limited as long as it can form an electric field. Further, the shape of the first electrode 1 is not particularly limited, but a needle shape is preferable because it is necessary to reduce the cross-sectional area and concentrate the electric field in order to form the first electrode 1 into a thread shape.

In the present embodiment, as shown in FIG. 1, the second electrode 2 has a columnar shape as an example, but an electric field effective between the rod-shaped first electrode 1 or the electrospray nozzle, and the first electrode 1 having another shape. The shape and material thereof are not particularly limited as long as they have conductivity so as to form a columnar shape, but if a specific example is shown, the shape may be a columnar shape, a ring shape, a plate shape, or the like. Examples include mesh shape and rod shape. Examples of the material include metals such as stainless steel, platinum, aluminum, and copper.

In the present embodiment, the distance between the first electrode 1 and the second electrode 2 (for example, the distance between the tip of the electrospray nozzle which is the first electrode 1 and the facing surface of the second electrode 2) is not particularly limited. For example, it can be appropriately set within a range of 1 cm or more, preferably 2 cm or more. Further, for example, the upper limit of the distance between the tip of the electrospray nozzle, which is the first electrode 1, and the facing surface of the second electrode 2 is not particularly limited, and a thread-like gel 6 having an appropriate length can be produced between the two electrodes. Just do it. When the gel 6 is pulled up from the low dielectric constant liquid 3 and dried, it becomes a fiber bundle.

In the present embodiment, the arrangement of the first electrode 1 and the second electrode 2 for forming the electric field in the container 10 is not particularly limited as long as it is in the low dielectric constant liquid 3 housed in the container 10.

In the present embodiment, the lower limit of the potential difference given between the electrospray nozzle as the first electrode 1 and the second electrode 2 (opposite electrode) is not particularly limited, and is, for example, 0.1 kV or more, preferably 2 kV or more. It can be set as appropriate within. The upper limit of the potential difference given between the electrospray nozzle as the first electrode 1 and the second electrode 2 (opposite electrode) is not particularly limited, and is appropriately set within, for example, 20 kV or less, preferably 15 kV or less. Can be done.

The method of giving a potential difference between the electrospray nozzle as the first electrode 1 and the second electrode 2 (opposite electrode) is not particularly limited. For example, as shown in FIG. 1, one power supply 4 may be connected to the first electrode 1 (electrospray nozzle) and the second electrode 2 (opposite electrode), and a voltage may be applied between the two electrodes. Further, after setting a reference potential between the first electrode 1 (electrospray nozzle) and the second electrode 2 (opposite electrode), two power sources are used, and the first electrode 1 (with respect to the reference potential) is used. A method of controlling the potential of the electrospray nozzle) and the potential of the second electrode 2 (opposite electrode) with respect to the reference potential with separate power sources may be used.

That is, in the first embodiment, a potential difference may be generated between the first electrode 1 (electrospray nozzle) and the second electrode 2 (opposite electrode). Therefore, for example, the first electrode 1 (electrospray nozzle) may have a positive potential, and the second electrode 2 (opposite electrode) may have a negative potential. Further, the first electrode 1 (electrospray nozzle) may have a negative potential, and the second electrode 2 (opposite electrode) may have a positive potential. Further, the potential of the first electrode 1 (electrospray nozzle) may be set to 0, and the potential of the second electrode 2 (opposite electrode) may be set to a negative potential. Further, the potential of the first electrode 1 (electrospray nozzle) may be set to 0, and the potential of the second electrode 2 (opposite electrode) may be set to +. Further, the potential of the first electrode 1 (electrospray nozzle) may be set to −, and the potential of the second electrode 2 (opposite electrode) may be set to 0. Furthermore, the potential of the first electrode 1 (electrospray nozzle) may be set to +, and the potential of the second electrode 2 (opposite electrode) may be set to 0.

In the present embodiment, the first electrode 1 is used as an electrospray nozzle, and as the second electrode 2, a nozzle for supplying a dispersion liquid or a functional substance (sixth and seventh embodiments) described later can be used. The functional substance can be supplied in a dispersed state in the dispersion liquid. As a functional substance that can be mixed with the dispersion liquid, when supplied from an electrospray nozzle as the first electrode 1, any material having a size equal to or smaller than the nozzle diameter can be sprayed. For example, methylene blue, pigments, and dyes can be used as the dye component, metal nanoparticles and photocatalysts of various metals can be used as the metal particles, and ceramic nanoparticles can also be used.

(Example 1)
Next, a specific example (Example 1) of the spinning method using the spinning device M1 of the first embodiment will be described.
N-hexane is used as the low dielectric constant liquid 3 in the conceptual diagram of the spinning method shown in FIG. As the dispersion liquid in which the fine fibrous substance 11 is dispersed, a 0.5% ethanol dispersion liquid of hydrophobic nanocellulose (CNF) is used. As the first electrode 1, an electrospray nozzle (ESN) that also serves as a means for supplying the dispersion liquid is used. As the second electrode 2 which is the counter electrode (CE) facing the electrospray nozzle (ESN), a rod-shaped stainless steel electrode having a diameter of 1.6 mm is used. The distance between the first electrode 1 and the second electrode 2 is 25 mm, a high voltage of + 7 kV or more is applied between the electrodes, and the dispersion liquid is n- from the first electrode 1 (electrospray nozzle, ESN) at 0.02 ml / min. Introduce into a high electric field in hexane. It was confirmed that filamentous gel 6, which was not visually confirmed immediately after the start, was formed along the electric field between the two electrodes 3 minutes after the start. It was also confirmed that the filamentous gel 6 became thicker with time. It was also confirmed that the filamentous gel 6 was taken out from the liquid of n-hexane and dried to obtain a fiber bundle, and a yarn having a desired length could be produced from the fiber bundle.

(Comparative Example 1)
Next, an example in which a dispersion liquid substantially similar to that in Example 1 is spun by an electrospinning method in air will be described as Comparative Example 1.
A 0.5% ethanol dispersion of hydrophobic nanocellulose (CNF) was electrostatically sprayed in air in the apparatus shown in FIG. 16 with the container 10 and the low dielectric constant liquid 3 removed. +3.5 kV was applied to the electrospray nozzle (ESN) and −0.5 kV was applied to the second electrode 2 which was the counter electrode, and the flow rate of the dispersion liquid by the electrospray nozzle was set to 0.01 ml / min. In the electrospray in gas, no fiber bundle was formed between the electrodes, and only a laminated sheet-like object was formed on the counter electrode.

<< Second Embodiment >> (FIGS. 3 to 6)
FIG. 3 is a schematic view showing the spinning apparatus M2 and the spinning method of the second embodiment, and FIG. 4 is a diagram showing a photograph of the fiber bundle manufactured in the embodiment of the second embodiment. Further, FIG. 5 is a diffraction diagram and an azimuth profile diagram of a two-dimensional XRD (X-ray diffraction) of the fiber bundle manufactured in the embodiment of the second embodiment, and FIG. 6 is a comparative example of fiber 2 It is a diffraction diagram and the same direction profile diagram of the dimension XRD (X-ray diffraction).

First, the spinning apparatus M2 of the second embodiment will be described with reference to FIG.
As shown in FIG. 3, the spinning apparatus M2 includes a container 10 in which the low dielectric constant liquid 3 is housed. A first electrode 1 and a second electrode 2 connected to a power source 4 (DC power source 4 in this embodiment) are arranged in the container 10. The configurations of the low dielectric constant liquid 3 and the power supply 4 are the same as those in the first embodiment.

As shown in FIG. 3, the first electrode 1 is an electrospray nozzle (ESN), the electrospray nozzle is attached to an injector 7 which is a supply means, and the fine fibrous substance 11 is dispersed in the injector 7. The liquid 8 is filled. The second electrode 2, which is the counter electrode, is an electrode having substantially the same shape as that of the first embodiment (FIG. 1). The electrospray nozzle, which is the first electrode 1, is attached to the lower side of one side surface of the container 10 through a wall portion, and is directed obliquely upward (diagonally upward to the right in the figure). The second electrode 2 is arranged above the other side surface of the container 10 in the vicinity of the wall portion facing the injection direction of the dispersion liquid 8 by the electrospray nozzle. The fine fibrous substance 11, the dispersion liquid 8 of the fine fibrous substance 11, and other configurations and materials of the first and second electrodes 1 and 2 are the same as those in the first embodiment.

As shown in FIG. 3, a winder 9 is provided on the outside of the container 10 and the low dielectric constant liquid 3 and above the second electrode 2. The winder 9 is a cylindrical device that winds and rotates one end of a thread-like gel 6 continuously manufactured between both electrodes 1 and 2, and winds the thread-like gel 6 from a low dielectric constant liquid 3. It is an extension means that pulls out and dries it into a fiber bundle 12 and winds it up as a continuous thread.

Next, specific examples (Examples 2 to 7) of the spinning method using the spinning device M2 of the second embodiment will be described.

(Example 2)
Hydrophobically modified cellulose nanofibers (CNF) are used as the fine fibrous substance 11. The cellulose nanofibers are dispersed in a solvent of alcohols having 1 to 5 carbon atoms. The dispersion liquid 8 is supplied into the low dielectric constant liquid 3 (n-hexane or the like) by an electrospray which is the first electrode 1.

As shown in FIG. 3, the droplet 5 of the dispersion liquid 8 containing the cellulose nanofibers sprayed into the low dielectric constant liquid 3 is charged and loses the dispersion medium, and interacts with the electric field to cause the lines of electric force E. It accumulates in the electric field while extending in the direction, and as a result, a filamentous gel 6 (gel-like fiber) in which cellulose nanofibers are gathered is formed. By drying the gel 6 in air, a fiber bundle 12 (filamentous fiber) is produced. In order to continuously spin the fiber bundle 12, a spinning device M2 equipped with a winder 9 as shown in FIG. 3 is used. The voltage is preferably 3.0 to 10.0 kV, more preferably 5.0 to 7.0 kV. The flow rate of the dispersion liquid 8 by the electrospray nozzle is preferably 0.005 to 0.100 ml / min, more preferably 0.010 to 0.050 l / min, and further preferably 0.010 to 0.020 ml / min. preferable.

In the spinning apparatus M2 of the second embodiment provided with the winder 9, a filamentous gel 6 is generated in the low dielectric constant liquid 3 under the same conditions as those of the first embodiment and the first embodiment, and the second electrode 2 of the gel 6 is generated. The side end is pulled out from the low dielectric constant liquid 3 and wound around the winder 9, and while the filamentous gel 6 is continuously produced in the low dielectric constant liquid 3, the winder 9 starts from the low dielectric constant liquid 3. By pulling up the gel 6 into the air and winding it up, a thread obtained by elongating the fiber bundle 12 obtained by drying the gel 6 was obtained.

As shown in FIG. 4, as a production example, a yarn having a length of 60 cm and a width of 100 μm was obtained.
FIG. 5A is a diffraction diagram of a two-dimensional XRD of this thread (or the fiber bundle 12 constituting the thread), and the result of measuring the produced thread in an arrangement extending from top to bottom on the paper surface of the figure. Is. The azimuth is measured clockwise on the paper surface with 0 ° directly below the paper surface when the black point in the center of FIG. 5A is the origin. The strong X-rays detected can be seen on the left and right of the black dot in the center (two locations around 90 degrees and 270 degrees in azimuth), but the direction of the crystals is the same in the measured threads. It shows that they are aligned in the direction, that is, there is a part where the crystals are oriented.

FIG. 5B is an orientation profile diagram of the two-dimensional XRD of this yarn. There are two strong X-ray intensities shown on the vertical axis at two locations on the horizontal axis, around 90 degrees and around 270 degrees, which are consistent with the results shown in FIG. 5 (a).

(Comparative Example 2)
Next, when the dispersion liquid 8 substantially the same as in Example 2 was extruded into hexane without applying a voltage, a white substance was generated at the bottom of the container 10 after 5 minutes, and this was recovered after 30 minutes. When it was dried and observed, it had a ribbon-like structure. The results of analyzing this substance by the two-dimensional XRD method in the same manner as in Example 2 are shown in FIGS. 6 (a) and 6 (b). As shown in FIG. 6A, no diffraction pattern indicating high orientation was obtained from this white substance. Further, in FIG. 6B, the intensity of X-rays is constant regardless of the azimuth angle, and it can be interpreted that the crystals of the substance are not oriented.

In both FIGS. 5 (a) and 6 (a), there are bright small dots above and below the central black dot, but this is not due to the measured thread, and the X-ray light source has a vertically long shape. It is due to the fact that

(Example 3)
FIG. 7 shows a photograph of the fiber bundle 12 manufactured in Example 3. As the dispersion liquid 8 in which the fine fibrous substance 11 is dispersed, a 0.5% ethanol dispersion liquid 8 of hydrophobic nanocellulose (CNF) is used. A high voltage of 3.6 kV or more is applied between the electrospray nozzle (ESN) and the second electrode 2 which is the counter electrode (CE) facing the electrospray nozzle (ESN), and the other parts are manufactured under the same conditions as in Example 1. As a result of the above, as shown in FIG. 7, a fiber bundle 12 having a width of about 500 μm, in which a plurality of filamentous substances were accumulated instead of one thread, was obtained.

(Example 4)
Same as Example 1 except that the 0.5% ethanol dispersion 8 of hydrophobic nanocellulose (CNF) was not supplied from the electrospray nozzle but was supplied between the first and second electrodes 2 by a separate supply means. Manufactured under the conditions. As a result, if the fine fibrous substance 11 such as hydrophobic nanocellulose (CNF) is present in the electric field, the hydrophobic nanocellulose (CNF) can be applied by applying an electric field without performing electrostatic spraying using an electrospray nozzle. ) Accumulated to form filamentous gel 6.

(Example 5)
FIG. 8 is a diagram showing a photograph of the fiber bundle 12 manufactured by Example 5, and FIG. 9 shows an enlarged photograph of the fiber bundle 12 of FIG. The concentration of the ethanol dispersion 8 of hydrophobic nanocellulose (CNF) is 2.5%, the applied voltage of the electrospray nozzle (ESN) is +2.5 kV, and the voltage of the second electrode 2 which is the counter electrode (CE) is set. The production was carried out in the same manner as in Example 1 except that the concentration was −0.5 kV and the transfer rate of the dispersion liquid 8 was 0.01 ml / min. As a result, as shown in FIGS. 8 and 9, it was discovered that a fiber bundle 12 having a structure in which a plurality of filaments are integrated in a coil shape can be obtained.

(Example 6)
10 is a photograph of the fiber bundle 12 manufactured by Example 6, FIG. 11 is an enlarged photograph of the fiber bundle 12 of FIG. 10, and FIG. 12 is an EDS (energy) of the fiber bundle 12 of Example 6. The result of elemental analysis by a dispersed X-ray spectroscope) is shown. Production was carried out in the same manner as in Example 1 except that the following conditions were adopted.
Dispersion liquid 8: The concentration of the ethanol dispersion liquid 8 of hydrophobic nanocellulose (CNF) is set to 1%, and the dispersion liquid 8 has a diameter of 0. 0.5% of 6 μm tungsten fine particles were mixed.
Liquid transfer rate: 0.01 ml / min
Applied voltage: The electrospray nozzle (ESN) is set to +5.0 kV, and the second electrode 2 which is the counter electrode (CE) is set to 0.0 kV.

Tungsten particles did not appear to be diffused in the low dielectric constant liquid 3, and the tungsten particles gathered in the fiber bundle 12, and as shown in FIGS. 10 and 11, the tungsten particles were interposed between the fine fibrous substances 11. A tungsten-CNF composite fiber bundle contained in the state was obtained.

Further, as a result of measuring this tungsten-CNF composite fiber bundle by an elemental analysis method using EDS, as shown in FIG. 12, in addition to carbon (C) and oxygen (O) which are constituent elements of CNF, tungsten (W) Was detected, and the result was obtained that the structure was such that tungsten and CNF were uniformly composited. The tungsten-CNF composite fiber bundle or the yarn produced from the fiber bundle 12 has excellent printing resistance and also has a radiation protection function. _{According to the composite fiber bundle to which TiO 2} fine particles are added as a functional substance, or the yarn produced from the fiber bundle 12, the effect of preventing stains can be obtained by the function of the photocatalyst. Further, according to the composite fiber bundle to which Ag fine particles are added as a functional substance, or the yarn produced from the fiber bundle 12, it can be used as an antistatic material because electric conductivity can be obtained, and also has bactericidal and deodorant effects. Since it is obtained, it is also useful as a material for clothing and the like.

(Example 7)
FIG. 13 is a photograph of the fiber bundle 12 manufactured by Example 7, and FIG. 14 is an enlarged photograph of the fiber bundle 12 of Example 7. Production was carried out in the same manner as in Example 1 except that the following conditions were adopted.
Dispersion liquid 8: The concentration of the ethanol dispersion liquid 8 of hydrophobic nanocellulose (CNF) is set to 1%, and a small amount of methylene blue is used as a functional substance that gives a specific function to the fiber bundle 12 or the thread, which is a product, to the dispersion liquid 8. Was mixed.
Liquid transfer rate: 0.01 ml / min
Applied voltage: The electrospray nozzle (ESN) is set to +5.0 kV, and the second electrode 2 which is the counter electrode (CE) is set to 0.0 kV.

No appearance of methylene blue diffusing into the low dielectric constant liquid 3 was observed, and methylene blue gathered in the fiber bundle 12 and was uniformly dispersed among the fine fibrous substances 11, as shown in FIGS. 13 and 14. A fiber bundle 12 made of hydrophobic nanocellulose (CNF) uniformly dyed with methylene blue was obtained.

In the above-described embodiments and examples, a DC power supply (power supply 4) is connected to the first electrode and the second electrode, and the electric field generated in the liquid is an electrostatic field. However, this power source is not necessarily limited to a DC power source, and may be an AC power source or other non-DC power source, and the electric field for accumulating the fine fibrous substance 11 does not necessarily have to be an electrostatic field. If the power source is a DC power source as in the embodiment and the electric field is an electrostatic field, the filamentous gel 6 composed of the fine droplets 5 and the fine fibrous substance 11 collected between the electrodes always receives a constant force due to the electric field. .. However, if the electric field is a non-electrostatic field such as an AC electric field, the electric field strength changes periodically or aperiodically, so that the force applied to the fine droplets 5 and the filamentous gel 6 collected between the electrodes accordingly. Changes, and in the case of an AC electric field, the moment when it becomes 0 occurs regularly. Therefore, under the same other conditions, the thickness of the produced gel is larger than that in the case of the electrostatic field, and the degree of orientation of the fine fibrous substance is lower. Therefore, whether the power supply to be connected to the first electrode and the second electrode is a DC power supply or a non-DC power supply, and if it is a non-DC power supply, an AC power supply or another non-DC power supply, and further. , The frequency, amplitude, waveform, etc., the thickness of the gel produced, and the degree of orientation of the fine fibrous material can be appropriately set.

1 ... First electrode (for example, an electrospray nozzle that also serves as a means for supplying a dispersion liquid)
2 ... 2nd electrode 3 ... Low dielectric constant liquid 5 ... Droplets of dispersion liquid 6 ... Filamentous gel 7 ... Injector as supply means 8 ... Dispersion liquid containing fine fibrous material 9 ... Winder as extension means 10 ... Container 11 ... Fine fibrous material 12 ... Fiber bundle M1, M2 ... Spinning device E ... Electric lines of force

Claims (6)

First step of producing a fiber bundle by diameter giving an electric field to fine fibrous materials in the liquid is greater than or equal to 100 times the diameter length at 1 to 500 nm, it is integrated by aligning the orientation of the fine fibrous material A spinning method characterized by having. The spinning method according to claim 1, further comprising a second step of continuously stretching the fiber bundle produced in the first step to produce a yarn. In the first step, the fine fibrous material is spun according to claim 2, characterized in that it is supplied to the liquid in the micro-fibrous material as a droplet form of dispersion obtained by dispersing in a dispersion medium Method. Electrodes that generate an electric field in the liquid,
A supply means for supplying an electric field in the liquid with a fine fibrous substance having a diameter of 1 to 500 nm and a length of 100 times or more the diameter.
And expansion means to the fiber bundle a gel consisting of the fine fibrous material orientation aligned integrated Waals force was continuously drawn out from the liquid by an electric field,
A spinning device characterized by being equipped with. A structure in which a plurality of filamentous substances composed of fine fibrous substances having a diameter of 1 to 500 nm and a length of 100 times or more the diameter, which are aligned by an electric field in a liquid and accumulated by an intermolecular force, are accumulated in a coil shape. A fiber bundle having a diameter of 50 μm to 1000 μm. The fiber bundle according to claim 5, wherein the functional substance is contained in a state of being interposed between the fine fibrous substances.

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