JP5645110B2 - Composite nanofiber - Google Patents

Description

  The present invention relates to composite nanofibers. In the present invention, “nanofiber” refers to a fiber made of a polymer material and having an average diameter of about 1000 nm or less. “Composite nanofiber” refers to a nanofiber containing components other than a polymer material.

  Conventionally, nanofibers composed only of polymer materials, nonwoven fabrics composed of the nanofibers, yarns composed of the nanofibers, and methods for producing these are known (for example, see Patent Document 1). The “nanofiber” described in Patent Document 1 is a nanofiber made of only a polymer material. The “nonwoven fabric made of nanofibers” described in Patent Document 1 is made of the above-described nanofibers. In addition, the “thread made of nanofiber” described in Patent Document 1 is obtained by twisting the above-described nanofiber into a thread. FIG. 12 is a diagram showing a manufacturing apparatus for manufacturing nanofibers, non-woven fabrics made of nanofibers, and yarns made of nanofibers described in Patent Document 1. As shown in FIG. 12, the “nanofiber” and “nonwoven fabric made of nanofiber” described in Patent Document 1 applied a high voltage between a nozzle and a collector in an electrospinning apparatus (shown on the left side of FIG. 12). In this state, it can be produced by an electrospinning method (also referred to as an electrospinning method) in which a liquid made of a polymer material solution is discharged from a nozzle toward a collector. In addition, as shown in FIG. 12, the “yarn made of nanofibers” described in Patent Document 1 is a twisted yarn produced by electrospinning a “nonwoven fabric made of nanofibers” in a twisting device (shown on the right side of FIG. 12). Can be manufactured.

Special Table 2007-518891

  Meanwhile, in the technical field of fibers, there is always a demand for fibers having higher mechanical strength (for example, tensile strength) than conventional fibers and a method for producing such fibers. This is the same in the technical field of nanofibers, and nanofibers having higher mechanical strength than conventional nanofibers and methods for producing such nanofibers are required. The same applies to the technical field of “nonwoven fabric composed of nanofibers”, and “nonwoven fabric composed of nanofibers” having higher mechanical strength than conventional “nonwoven fabric composed of nanofibers” and “ There is a need for a method for producing a “nonwoven fabric comprising nanofibers” that can produce a “nonwoven fabric”. Furthermore, the same applies to the technical field of “threads made of nanofibers”, and “threads made of nanofibers” having higher mechanical strength than conventional “threads made of nanofibers” and such “nanofibers” There is a need for a process for producing “nanofiber yarns” that can produce “yarn yarns”.

  Then, this invention is made | formed in view of an above-described subject, and it aims at providing the nanofiber which has mechanical strength higher than the conventional nanofiber. It is another object of the present invention to provide a “nonwoven fabric made of nanofibers” comprising the nanofibers as described above and having higher mechanical strength than the conventional “nonwoven fabric made of nanofibers”. Another object of the present invention is to provide a “thread made of nanofibers” having higher mechanical strength than the conventional “thread made of nanofibers”. Furthermore, the manufacturing method of “nanofiber” capable of producing “nanofiber” having higher mechanical strength than conventional “nanofiber”, and higher mechanical strength than conventional “nonwoven fabric made of nanofiber” A method for producing “nonwoven fabric made of nanofibers” capable of producing “nonwoven fabric made of nanofibers” and “yarn made of nanofibers” having higher mechanical strength than conventional “thread made of nanofibers” can be produced. It aims at providing the manufacturing method of "the thread | yarn which consists of nanofibers".

  The inventors of the present invention have made extensive studies in order to solve the above problems, and as a result, POSS is chemically reacted with the cage silsesquioxane (POSS) in the polymer material constituting the nanofiber. Dispersed multi-walled carbon nanotubes (POSS-modified MWCNT), nanofibers having higher mechanical strength than conventional nanofibers, higher mechanical strength than conventional “nonwoven fabric made of nanofibers” It has been found that a “nonwoven fabric made of nanofibers” and a “thread made of nanofibers” having higher mechanical strength than the conventional “thread made of nanofibers” can be obtained, and the present invention has been completed. In addition, since the nanofibers as described above include components other than the polymer material (multi-walled carbon nanotubes chemically modified with a cage silsesquioxane), they are referred to as composite nanofibers.

[1] The “composite nanofiber” of the present invention is a multi-walled carbon nanotube (hereinafter referred to as MWCNT) in which POSS is chemically modified by reacting with a cage silsesquioxane (hereinafter referred to as POSS). The POSS-modified MWCNT is dispersed inside a nanofiber made of a polymer material.

  The composite nanofiber of the present invention is a composite nanofiber having mechanical strength higher than that of the conventional nanofiber because the POSS-modified MWCNT originally obtained from the high-strength MWCNT is dispersed inside the nanofiber. It becomes. In addition, since the composite nanofiber of the present invention is formed by dispersing POSS-modified MWCNT, which is a MWCNT chemically modified by POSS, inside the nanofiber, compared to the case of normal MWCNT, The dispersibility at is extremely high. Therefore, the composite nanofiber of the present invention can uniformly disperse the POSS-modified MWCNT in the nanofiber as compared with the composite nanofiber in which the normal MWCNT is dispersed inside the nanofiber. In addition, it becomes possible to disperse the POSS-modified MWCNT in a large amount in the nanofiber. Therefore, from this viewpoint, the composite nanofiber of the present invention is a composite nanofiber having higher mechanical strength than the composite nanofiber in which normal MWCNTs are dispersed inside the nanofiber.

  Further, as described above, the composite nanofiber of the present invention can uniformly disperse the POSS-modified MWCNT in the nanofiber as compared with the composite nanofiber in which the normal MWCNT is dispersed inside the nanofiber. It becomes possible. Therefore, from this viewpoint, the composite nanofiber of the present invention is a composite nanofiber having higher quality (homogeneity) than a composite nanofiber in which normal MWCNTs are dispersed inside the nanofiber.

  In addition, as described above, the composite nanofiber of the present invention can disperse POSS-modified MWCNT in a large amount in the nanofiber as compared to the composite nanofiber in which normal MWCNT is dispersed inside the nanofiber. It becomes possible. Therefore, from this viewpoint, the composite nanofiber of the present invention is a composite nanofiber having higher electrical conductivity and higher thermal conductivity than the composite nanofiber in which normal MWCNTs are dispersed inside the nanofiber. In the composite nanofiber of the present invention, POSS does not completely cover MWCNT due to steric hindrance peculiar to POSS. Therefore, MWCNT in which a normal organic group is chemically modified by graft polymerization or the like is made of nanofiber. Compared to the composite nanofiber dispersed inside, a larger proportion of the surface of the MWCNT can be exposed. Therefore, from this point of view, the composite nanofiber of the present invention has higher conductivity and higher conductivity than the composite nanofiber in which MWCNT in which a normal organic group is chemically modified by graft polymerization or the like is dispersed inside the nanofiber. It becomes a composite nanofiber having high thermal conductivity.

  Furthermore, according to the composite nanofiber of the present invention, as described above, the POSS-modified MWCNT is dispersed in a large amount in the nanofiber as compared with the composite nanofiber in which the normal MWCNT is dispersed inside the nanofiber. It becomes possible to do. For this reason, when the concentration of the POSS-modified MWCNT with respect to the POSS-modified MWCNT dispersion liquid is in the range of up to about 1% by weight, the electric conductivity of the POSS-modified MWCNT dispersion liquid can be increased, and electrospinning can be performed more smoothly. Is possible. Therefore, from this point of view, it has a finer fiber diameter and higher waterproofness, supple characteristics, large specific surface area, and higher substance carrying capacity than the composite nanofiber in which normal MWCNT is dispersed inside the nanofiber. Thus, it is possible to constitute a composite nanofiber having a high catalyst supporting ability. This is supported by the examples described later.

  The name “POSS” is an abbreviation of “Polyhedral Oligometric Silsesquioxanes” which represents “cage-like (polygonal) silsesquioxane” in English.

[2] In the composite nanofiber of the present invention, the POSS is preferably composed of POSS represented by the following formula (1).
(In the formula (1), “R” represents an alkyl group, and “R ′” represents a functional group having a reactive group at the terminal.)

  In the composite nanofiber of this invention, said POSS can be used suitably.

  In addition, as "R" in Formula (1), various alkyl groups, such as a linear thing, what has a branch, and what has a cyclic structure, can be used. In addition, as “R ′” in the formula (1), various functional groups such as linear, branched, cyclic structures and the like can be used. The same applies to [7] described later.

[3] The nonwoven fabric comprising the composite nanofiber of the present invention is characterized by comprising the composite nanofiber of the present invention.

  Since the nonwoven fabric composed of the composite nanofiber of the present invention is composed of the composite nanofiber of the present invention, it has high mechanical strength, high quality (homogeneity), high conductivity, high thermal conductivity, high waterproofness, and flexibility. It becomes a “nonwoven fabric composed of composite nanofibers” having excellent characteristics, a large specific surface area, a high substance supporting ability, a high catalyst supporting ability and the like.

[4] The yarn comprising the composite nanofiber of the present invention is characterized by comprising the composite nanofiber of the present invention.

  Since the yarn composed of the composite nanofiber of the present invention is composed of the composite nanofiber of the present invention, it has high mechanical strength, high quality (homogeneity), high conductivity, high thermal conductivity, high waterproofness, and flexibility. It becomes a “thread made of composite nanofiber” having excellent characteristics, a large specific surface area, a high substance supporting ability, a high catalyst supporting ability and the like.

[5] The composite nanofiber manufacturing method of the present invention includes a POSS-modified MWCNT preparation step of preparing POSS-modified MWCNT, which is a MWCNT in which POSS is chemically modified by reacting with POSS, and a polymer material solution or a molten polymer A POSS-modified MWCNT dispersion liquid producing step for producing a POSS-modified MWCNT dispersion liquid by dispersing the POSS-modified MWCNT in a liquid made of a material, and “POSS-modified MWCNT made of a polymer material from the POSS-modified MWCNT dispersion liquid” And a composite nanofiber manufacturing step of manufacturing a “composite nanofiber dispersed in the nanofiber” in this order.

  According to the method for producing a composite nanofiber of the present invention, as can be seen from the examples described later, the above-described features (high mechanical strength, high quality (homogeneity), high conductivity, high thermal conductivity, high waterproofness). Composite nanofibers of the present invention having high properties, supple characteristics, large specific surface area, high substance carrying ability, high catalyst carrying ability, etc.).

  In the present specification, the “polymer material solution” refers to a polymer material, which is a nanofiber material, dissolved in a solvent. The “molten polymer material” refers to a material obtained by melting a polymer material by heating. Among these, as the “liquid” used in the POSS-modified MWCNT dispersion liquid production step, it is more preferable to use a “polymer material solution” that easily reduces the viscosity.

[6] In the method for producing a composite nanofiber of the present invention, in the composite nanofiber manufacturing step, the POSS-modified MWCNT dispersion liquid is transferred from the nozzle to the collector in a state where a high voltage is applied between the nozzle and the collector. It is preferable to comprise an electrospinning step of producing “a composite nanofiber in which POSS-modified MWCNT are dispersed inside a nanofiber made of a polymer material”.

  By adopting such a method, as will be understood from the examples described later, the above-described features (high mechanical strength, high quality (homogeneity), high conductivity, high thermal conductivity, high waterproofness, suppleness, and so on) The composite nanofiber of the present invention having characteristics, a large specific surface area, a high substance supporting ability, a high catalyst supporting ability, etc.) can be produced.

[7] In the method for producing a composite nanofiber of the present invention, the POSS is preferably composed of POSS represented by the following formula (1).
(In the formula (1), “R” represents an alkyl group, and “R ′” represents a functional group having a reactive group at the terminal.)

  In the method for producing a composite nanofiber of the present invention, the above POSS can be suitably used.

[8] In the method for producing a composite nanofiber of the present invention, the reactive group includes an isocyanate group, and the POSS-modified MWCNT preparation step is performed on the outer surface of the MWCNT by performing acid treatment on the MWCNT. An acid treatment step for generating a reactive functional group; a POSS-modified MWCNT manufacturing step for manufacturing the POSS-modified MWCNT by reacting the reactive functional group in the MWCNT with the isocyanate group in the POSS; Are preferably included in this order.

  By setting it as such a method, the composite nanofiber of this invention can be manufactured using POSS which has the functional group which has an isocyanate group at the terminal.

[9] In the method for producing a composite nanofiber of the present invention, the reactive group comprises an amino group, and the POSS-modified MWCNT preparation step is performed on the outer surface of the MWCNT by subjecting the MWCNT to an acid treatment. An acid treatment step for generating a reactive functional group; and a halogenation step for generating a halogenated functional group by halogenating all or part of the reactive functional group in the MWCNT with a halogenating agent; It is preferable to include a POSS-modified MWCNT production process for producing the POSS-modified MWCNT by reacting the halogenated functional group in the MWCNT with the amino group in the POSS in this order.

  By setting it as such a method, the composite nanofiber of this invention can be manufactured using POSS which has the functional group which has an amino group at the terminal.

Note that chlorine can be preferably used as the halogen. In this case, it is preferable to use thionyl chloride (SOCl ₂ ) as the halogenating agent.

  In the method for producing a composite nanofiber according to [8] or [9] above, the reactive functional group is, for example, a carboxyl group (—COOH) or a hydroxy group (—OH).

  In the method for producing a composite nanofiber according to the above [8] or [9], it is preferable to use a catalyst for promoting the reaction in the POSS-modified MWCNT production process.

  In the method for producing a composite nanofiber of the present invention, the reactive group is a hydroxyl group, a carboxyl group, an epoxy group, a halogenated alkyl group, an imide group, a nitrile group, or an olefin group in addition to the isocyanate group or amino group described above. Other reactive groups can be used.

[10] The method for producing a nonwoven fabric composed of the composite nanofiber of the present invention includes a step of producing a composite nanofiber by the method for producing a composite nanofiber of the present invention.

  According to the method for producing a nonwoven fabric composed of composite nanofibers of the present invention, the above-mentioned features (high mechanical strength, high quality (homogeneity), high conductivity, high thermal conductivity, thin fiber diameter, high waterproofness, suppleness are provided. The composite nanofibers of the present invention having high characteristics, large specific surface area, high substance supporting ability, high catalyst supporting ability, etc.). Manufactures “nonwoven fabric made of composite nanofibers” with quality (homogeneity), high conductivity, high thermal conductivity, high waterproofness, supple characteristics, large specific surface area, high substance loading ability, high catalyst loading ability, etc. It becomes possible.

[8] A method for producing a yarn comprising the composite nanofiber of the present invention comprises a step of producing a composite nanofiber by the method of producing a composite nanofiber of the present invention, and a composite nanofiber obtained by twisting the composite nanofiber in a twisting device. And a twist yarn process for producing a yarn made of fibers in this order.

  According to the method for producing a yarn composed of the composite nanofiber of the present invention, the above-described features (high mechanical strength, high quality (homogeneity), high conductivity, high thermal conductivity, thin fiber diameter, high waterproofness, suppleness are provided. The composite nanofibers of the present invention having high characteristics, large specific surface area, high substance supporting ability, high catalyst supporting ability, etc.). Manufactures “yarns made of composite nanofibers” that have quality (homogeneity), high electrical conductivity, high thermal conductivity, high waterproofness, supple properties, large specific surface area, high substance loading capacity, high catalyst loading capacity, etc. It becomes possible.

  As described above, the “composite nanofiber”, “nonwoven fabric composed of composite nanofiber” and “thread composed of composite nanofiber” of the present invention have high mechanical strength, high quality (homogeneity), high conductivity, high It has excellent properties such as thermal conductivity, high waterproofness, supple characteristics, large specific surface area, high substance loading capacity, and high catalyst loading capacity, so various electronic and mechanical materials fields such as clothing (semiconductor materials, OLED materials) , LED materials, nano chemical sensor materials, MEMS materials, FED materials, battery materials such as catalyst supports for fuel cells, electromagnetic shielding materials, bimetal thermocouple materials, etc.), medical materials (biosensor carriers, biomedical materials, It can be widely used in fields such as medical MEMS, medical microrobots, and regenerative medical materials.

  The “composite nanofiber”, “nonwoven fabric composed of composite nanofiber” and “thread composed of composite nanofiber” of the present invention have high mechanical strength, high quality (homogeneity), and high conductivity as described above. Have excellent characteristics such as high thermal conductivity, high waterproofness, supple characteristics, large specific surface area, high substance loading ability, and high catalyst loading capacity, but at least one of these excellent characteristics (for example, Those having a high catalyst supporting ability are included in the present invention.

3 is a flowchart illustrating a method for manufacturing a composite nanofiber according to Embodiment 1. FIG. 3 is a schematic diagram for explaining an electrospinning process in the first embodiment. It is a schematic diagram shown in order to demonstrate the twisting process in Embodiment 3. It is a schematic diagram shown in order to demonstrate the electrospinning process in an Example. It is a graph which shows the result of the analysis by the Fourier-transform infrared spectroscopy (FT-IR) in an Example. It is an image by the high-resolution transmission electron microscope in an Example. It is a graph which shows the result of the thermogravimetric analysis in an Example. It is a graph which shows the result of the analysis by the Raman spectroscopy in an Example. It is a graph which shows the result of the wide angle X-ray diffraction in an Example. It is an image by the scanning electron microscope (SEM) in an Example. It is a graph shown in order to demonstrate the fiber diameter of the composite nanofiber in an Example. It is a figure which shows the manufacturing apparatus of the nanofiber in a prior art, and the thread | yarn consisting of a nanofiber.

  Hereinafter, the nanofiber of the present invention, the nonwoven fabric made of nanofiber, the yarn made of nanofiber, and the production method thereof will be described in more detail based on embodiments.

[Embodiment 1]
FIG. 1 is a flowchart showing a method of manufacturing a composite nanofiber according to Embodiment 1.
FIG. 2 is a schematic diagram for explaining the electrospinning process in the first embodiment.

  In the first embodiment, a method for producing a composite nanofiber and a composite nanofiber will be described.

1. Raw materials, catalysts and solvents Polymer materials used as raw materials include polylactic acid (PLA), polypropylene (PP), polyvinyl acetate (PVAc), polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyethylene naphthalate (PEN) , Polyamide (PA), polyurethane (PUR), polyvinyl alcohol (PVA), polyacrylonitrile (PAN), polyetherimide (PEI), polycaprolactone (PCL), polylactic glycolic acid (PLGA), silk, cellulose, chitosan, etc. Can be used. What is necessary is just to select an optimal thing according to a use etc.

  Various MWCNTs can be used as the MWCNT used as a raw material. As the MWCNT, a commercially available product or a synthesized product may be used.

As POSS, POSS represented by the following formula (1) is used.
(In the formula (1), R represents an alkyl group, and R ′ represents a functional group having a reactive group at the terminal.)
In Embodiment 1, the reactive group consists of an isocyanate group.
The POSS that can be used in the present invention is not limited to the above POSS, and various POSSs can be used.

2. Instruments, devices, etc. General-purpose instruments, devices, etc. can be used for the instruments, devices, etc.

3. Manufacturing method of composite nanofiber The manufacturing method of the composite nanofiber according to the first embodiment includes a POSS-modified MWCNT preparation step, a POSS-modified MWCNT dispersion liquid preparation step, and a composite nanofiber preparation step, as shown in FIG. Include in order. Hereinafter, each process will be described in this order.

3-1. POSS-modified MWCNT preparation step The POSS-modified MWCNT preparation step is a step of preparing POSS-modified MWCNT which is MWCNT in which POSS is chemically modified by reacting with POSS. The POSS-modified MWCNT preparation step in Embodiment 1 includes an acid treatment step and a POSS-modified MWCNT manufacturing step in this order.

(A) Acid treatment step The acid treatment step is a step of generating a reactive functional group on the outer surface of the MWCNT by subjecting the MWCNT to an acid treatment. By the acid treatment step, impurities contained in the MWCNT (mainly metal catalyst residue used during production) can be removed. As the acid used for the acid treatment, for example, a mixed acid of sulfuric acid and nitric acid (sulfuric acid: nitric acid = 3: 1, v / v) can be used. Moreover, you may use a heating and an ultrasonic treatment together as needed. In MWCNT after acid treatment, neutralization and drying can be performed by a conventional method.

(A) POSS-modified MWCNT production process The POSS-modified MWCNT production process is a process for producing POSS-modified MWCNT by reacting a reactive functional group in MWCNT with an isocyanate group in POSS.
In the reaction between the reactive functional group and the isocyanate group, a catalyst may be used as necessary. As the catalyst, for example, organic metals (such as organotin compounds) can be used. Moreover, you may perform a heating and ultrasonication as needed.

  The POSS-modified MWCNT preparation step is to prepare a POSS-modified MWCNT that has already been manufactured, such as purchasing a commercial product of “POSS-modified MWCNT, which is MWCNT chemically modified by reacting with POSS”. It is good.

3-2. POSS-modified MWCNT dispersion liquid preparation step The POSS-modified MWCNT dispersion liquid preparation step is a step of preparing a POSS-modified MWCNT dispersion liquid by dispersing POSS-modified MWCNT in a liquid made of a polymer material solution.
The solvent used in the polymer material solution can be appropriately selected according to the type of polymer used. For example, dichloromethane, dimethylformamide, dimethyl sulfoxide, methyl ethyl ketone, chloroform, acetone, water, formic acid, acetic acid, cyclohexane, THF and the like can be used. A plurality of types of solvents may be mixed and used.
Note that a liquid made of a molten polymer material can be used instead of a liquid made of a polymer material solution.

3-3. Composite nanofiber manufacturing process The composite nanofiber manufacturing process is a process of manufacturing “a composite nanofiber in which POSS-modified MWCNT is dispersed inside nanofibers made of a polymer material” from a POSS-modified MWCNT dispersion liquid. In the composite nanofiber manufacturing process, a high voltage (5 kV to 50 kV) is applied between the nozzle and the collector, and the POSS-modified MWCNT dispersion liquid is discharged from the nozzle toward the collector. It consists of an electrospinning process for producing “composite nanofibers dispersed inside nanofibers made of materials”.

Specifically, the electrospinning process can be performed using an electrospinning apparatus 100 as shown in FIG. As shown in FIG. 2, after filling the raw material tank 102 with the POSS-modified MWCNT dispersion liquid 10, the valve 104 is opened so that the solution can be supplied to the nozzle 106, and the nozzle 106 and the flat collector are formed using the high-voltage power source 110. The composite nanofibers 12 can be manufactured by applying a high voltage between them.
In addition, the electrospinning process in the present invention is not limited to that performed using the electrospinning apparatus as described above. For example, as a collector, not a flat plate collector but a rotating drum collector or the like can be used. Moreover, it can also carry out, moving base materials, such as a nonwoven fabric, between a collector and a nozzle.

Embodiment 1 in which POSS-modified MWCNTs, which are MWCNTs chemically modified by POSS by reaction with POSS, are dispersed inside nanofibers made of a polymer material by the above-described composite nanofiber manufacturing method. The composite nanofiber which concerns on can be manufactured. In the composite nanofiber according to Embodiment 1, POSS is made of POSS represented by the following formula (1).

(In the formula (1), R represents an alkyl group, and R ′ represents a functional group having a reactive group at the terminal.)
In Embodiment 1, the reactive group consists of an isocyanate group.

  Next, effects of the composite nanofiber and the method for manufacturing the composite nanofiber according to Embodiment 1 will be described.

  The composite nanofiber according to Embodiment 1 is a composite having POSS-modified MWCNT originally obtained from a high-strength MWCNT dispersed inside the nanofiber, and thus has a higher mechanical strength than the conventional nanofiber. It becomes nanofiber.

  Moreover, since the composite nanofiber according to Embodiment 1 is formed by dispersing POSS-modified MWCNT, which is a MWCNT chemically modified with POSS, inside the nanofiber, compared to the case of normal MWCNT. Dispersibility in the polymer is extremely high. Therefore, the composite nanofiber of the present invention can uniformly disperse the POSS-modified MWCNT in the nanofiber as compared with the composite nanofiber in which the normal MWCNT is dispersed inside the nanofiber. In addition, it becomes possible to disperse the POSS-modified MWCNT in a large amount in the nanofiber. Therefore, from this viewpoint, the composite nanofiber according to Embodiment 1 is a composite nanofiber having higher mechanical strength than the composite nanofiber in which normal MWCNTs are dispersed inside the nanofiber.

  In addition, the composite nanofiber according to Embodiment 1 is a composite nanofiber having higher quality (homogeneity) than a composite nanofiber in which normal MWCNTs are dispersed inside the nanofiber.

  In addition, the composite nanofiber according to Embodiment 1 is a composite nanofiber having higher electrical conductivity and higher thermal conductivity than the composite nanofiber in which normal MWCNTs are dispersed inside the nanofiber.

  In addition, since the composite nanofiber according to Embodiment 1 does not completely cover the MWCNT due to the steric hindrance peculiar to POSS, the MWCNT in which a normal organic group is chemically modified by graft polymerization or the like is nano. Compared to the composite nanofiber dispersed inside the fiber, a larger proportion of the surface of the MWCNT can be exposed. Therefore, from this point of view, the composite nanofiber according to Embodiment 1 is higher in conductivity than the composite nanofiber in which MWCNT in which a normal organic group is chemically modified by graft polymerization or the like is dispersed inside the nanofiber. Composite nanofibers having high thermal conductivity.

  In addition, according to the composite nanofiber according to Embodiment 1, it is possible to increase the electrical conductivity of the POSS-modified MWCNT dispersion liquid in the range where the concentration of the POSS-modified MWCNT to the POSS-modified MWCNT dispersion liquid is up to about 1% by weight. Thus, electrospinning can be performed more smoothly. Therefore, from this point of view, it has a finer fiber diameter and higher waterproofness, supple characteristics, large specific surface area, and higher substance carrying capacity than the composite nanofiber in which normal MWCNT is dispersed inside the nanofiber. Thus, it is possible to constitute a composite nanofiber having a high catalyst supporting ability.

  In addition, according to the method for producing a composite nanofiber according to Embodiment 1, the above-described features (high mechanical strength, high quality (homogeneity), high conductivity, high thermal conductivity, high waterproofness, supple characteristics, A composite nanofiber according to Embodiment 1 having a large specific surface area, a high substance supporting ability, a high catalyst supporting ability, etc.) can be produced.

  In addition, according to the method for producing a composite nanofiber according to Embodiment 1, the reactive group includes an isocyanate group, and the POSS-modified MWCNT preparation step includes an acid treatment step and a POSS-modified MWCNT production step in this order. Therefore, the composite nanofiber according to Embodiment 1 can be manufactured using POSS having a functional group having an isocyanate group at the terminal.

[Embodiment 2]
In Embodiment 2, the manufacturing method of the nonwoven fabric which consists of composite nanofiber, and the nonwoven fabric which consists of composite nanofiber are demonstrated.

The manufacturing method of the nonwoven fabric which consists of composite nanofiber which concerns on Embodiment 2 includes the process of manufacturing composite nanofiber with the manufacturing method of composite nanofiber which concerns on Embodiment 1. FIG. Since this step has already been described in the first embodiment, the details are omitted.
In the method for manufacturing a nonwoven fabric composed of composite nanofibers according to Embodiment 2, for example, the composite nanofiber according to Embodiment 1 may be manufactured simultaneously with the electrospinning apparatus, and the nonwoven fabric composed of composite nanofibers may be manufactured once. You may manufacture the nonwoven fabric which consists of composite nanofibers by compressing separately the composite nanofiber which concerns on Embodiment 1 collect | recovered.
By the method as described above, the “nonwoven fabric composed of composite nanofibers” composed of the composite nanofibers according to Embodiment 1 can be produced.

  Since the nonwoven fabric composed of the composite nanofibers according to Embodiment 2 is composed of the composite nanofibers according to Embodiment 1, high mechanical strength, high quality (homogeneity), high conductivity, high thermal conductivity, and high It becomes a “nonwoven fabric composed of composite nanofibers” having waterproofness, supple characteristics, a large specific surface area, a high substance supporting ability, and a high catalyst supporting ability.

  According to the method for producing a nonwoven fabric composed of composite nanofibers according to Embodiment 2, the above-described characteristics (high mechanical strength, high quality (homogeneity), high conductivity, high thermal conductivity, thin fiber diameter, high waterproofness) High-mechanical machinery because the composite nanofiber according to Embodiment 1 is used to produce a nonwoven fabric composed of composite nanofibers, which has supple characteristics, large specific surface area, high substance supportability, high catalyst supportability, etc.) "Non-woven fabric made of composite nanofibers with high strength (homogeneity), high electrical conductivity, high thermal conductivity, high waterproofness, supple characteristics, large specific surface area, high substance supportability, high catalyst supportability, etc. Can be manufactured.

[Embodiment 3]
FIG. 3 is a schematic diagram for explaining the twisting process in the third embodiment.

  In Embodiment 3, a method for producing a yarn made of composite nanofiber and a yarn made of composite nanofiber will be described.

  The manufacturing method of the thread | yarn consisting of the composite nanofiber which concerns on Embodiment 3 includes the process of manufacturing a composite nanofiber with the manufacturing method of the composite nanofiber which concerns on Embodiment 1, and the twisted thread process in this order. Hereinafter, each process will be described in this order.

1. The process of manufacturing a composite nanofiber by the manufacturing method of the composite nanofiber which concerns on Embodiment 1 By the method similar to the manufacturing method of the composite nanofiber which concerns on Embodiment 1, a composite nanofiber is manufactured. Since this step has already been described in the first embodiment, the details are omitted.

2. Twisted yarn process The twisted yarn process is a process for producing a “yarn made of composite nanofibers” by twisting composite nanofibers in a twisted yarn device.
In the twisting process according to the third embodiment, specifically, the composite nanofiber manufactured in the composite nanofiber manufacturing process is a strip-shaped non-woven fabric (nonwoven fabric made of composite nanofiber) 20, and as shown in FIG. The non-woven fabric 20 is passed through the twisting device 200 to obtain a “yarn made of composite nanofiber” 22. In FIG. 3, reference numeral 202 denotes a main twisting device that first uses the nonwoven fabric 20 as a twisted yarn, and reference numerals 204 and 206 denote yarn feeding devices that feed the yarn while further twisting the twisted yarn. At this time, the nonwoven fabric 20 may be twisted while the nonwoven fabric 20 is stretched by making the yarn feed speed of the yarn feed device 206 faster than the yarn feed speed of the yarn feed device 204.

  In addition to the above-described twisted yarn device, various twisted yarn devices can be used as the twisted yarn device used in the twisted yarn process, and can be appropriately selected depending on the type of the target “yarn made of composite nanofiber”.

  By the method for producing a yarn made of composite nanofiber as described above, a yarn made of the composite nanofiber according to Embodiment 3 can be produced.

  Next, the effect of the method for producing the yarn comprising the composite nanofiber and the yarn comprising the composite nanofiber according to Embodiment 3 will be described.

  Since the yarn composed of the composite nanofiber according to Embodiment 3 is composed of the composite nanofiber according to Embodiment 1, high mechanical strength, high quality (homogeneity), high conductivity, high thermal conductivity, and high It becomes a “thread composed of composite nanofibers” having waterproofness, supple characteristics, a large specific surface area, a high substance supporting ability, a high catalyst supporting ability, and the like.

  According to the method for producing a yarn composed of the composite nanofiber according to Embodiment 3, the above-described characteristics (high mechanical strength, high quality (homogeneity), high conductivity, high thermal conductivity, thin fiber diameter, high waterproofness) , Having a supple characteristic, a large specific surface area, a high substance supporting ability, a high catalyst supporting ability, etc.), the composite nanofiber according to Embodiment 1 is used to manufacture a yarn composed of the composite nanofiber, and thus a high machine “Yarn made of composite nanofibers that has high mechanical strength, high quality (homogeneity), high electrical conductivity, high thermal conductivity, high waterproofness, supple characteristics, large specific surface area, high substance supportability, high catalyst supportability, etc. Can be manufactured.

  Hereinafter, although the Example demonstrates the composite nanofiber of this invention and the manufacturing method of composite nanofiber in more detail, this invention is not restrict | limited at all to this.

[Example]
FIG. 4 is a schematic diagram for explaining the electrospinning process in the example.
FIG. 5 is a graph showing the results of analysis by Fourier transform infrared spectroscopy (FT-IR) in the examples. In FIG. 5, (a) shows the result for MWCNT before acid treatment, (b) shows the result for MWCNT after acid treatment, and (c) shows the result for POSS-modified MWCNT. It is. In FIG. 5, the vertical axis represents the infrared transmittance, and the horizontal axis represents the wave number.
FIG. 6 is an image obtained by a high-resolution transmission electron microscope in the example. 6 (a) is an image of MWCNT before acid treatment, FIG. 6 (b) is an image of MWCNT after acid treatment, and FIG. 6 (c) and FIG. 6 (d) are images of POSS-modified MWCNT. is there. 6C and 6D have different magnifications, and FIG. 6D shows an image enlarged at a higher magnification.

FIG. 7 is a graph showing the results of thermogravimetric analysis in the examples. In FIG. 7, (a) shows the result of MWCNT before acid treatment, (b) shows the result of MWCNT after acid treatment, and (c) shows the result of POSS-modified MWCNT. It is. In FIG. 7, the vertical axis represents relative weight (weight when the weight at 50 ° C. is 100%), and the horizontal axis represents temperature.
FIG. 8 is a graph showing the results of analysis by Raman spectroscopy in the examples. In FIG. 8, (a) shows the results for the nanofibers (PLA nanofibers) made only of PLA, and (b) shows the MWCNTs after acid treatment dispersed inside the nanofibers made of PLA. It is the result in the result in the composite nanofiber (acid-treated MWCNT composite nanofiber), and (c) shows the result in the composite nanofiber. In FIG. 8, the vertical axis represents the Raman scattering intensity, and the horizontal axis represents the wave number.

  FIG. 9 is a graph showing the results of wide-angle X-ray diffraction in the example. In FIG. 9, (a) shows the results for PLA nanofibers, (b) shows the results for acid-treated MWCNT composite nanofibers, and (c) shows POSS-modified MWCNTs with a value of 0.00. (D) shows the result for the composite nanofiber containing 0.3 wt% of POSS-modified MWCNT, and (e) shows the result for 0.5 wt% of POSS-modified MWCNT. It is a result in the composite nanofiber containing.

FIG. 10 is an image obtained by a scanning electron microscope (SEM) in the example. 10A is an image of PLA nanofibers, FIG. 10B is an image of composite nanofibers containing 0.1 wt% of POSS-modified MWCNT, and FIG. 10C is 0.3 wt. Of POSS-modified MWCNT. 10 (d) is an image of a composite nanofiber containing 0.5 wt% of POSS-modified MWCNT.
FIG. 11 is a graph shown to explain the fiber diameter of the composite nanofiber in the example. In FIG. 11, the vertical axis indicates the fiber diameter of nanofibers (composite nanofibers, acid-treated MWCNT composite nanofibers, and PLA nanofibers), and the horizontal axis indicates the amount of POSS-modified MWCNT or MWCNT after acid treatment. . Square marks (■) represent composite nanofibers, triangle marks (▲) represent acid-treated MWCNT composite nanofibers, and circle marks (●) represent PLA nanofibers.

1. Raw material, catalyst and solvent As polymer material, polylactic acid (hereinafter referred to as PLA) was used, and PLA used was RESOMER (registered trademark of Boehringer Ingelheim) L210S manufactured by Boehringer Ingelheim.
Also, as MWCNT, MWCNT obtained from Endo Group of Department of Electrical and Electronic Engineering, Shinshu University (purity is 95%, diameter is 20 nm to 70 nm, aspect ratio (numerical value of MWCNT length divided by MWCNT diameter) is 100 or more. Used).
As POSS, Isocyanatopropyldimethylsilylcyclohexyl-polyhedral oligomeric silsesquioxane (see the following formula (2), purchased from Tomen Plastics) was used. In addition, as shown in Formula (2), the POSS has a functional group having an isocyanate group at the terminal portion.

Further, dibutyltin dilaurate (hereinafter referred to as DBTDL, purchased from Aldrich) as a catalyst for reacting a reactive functional group (hydroxy group or carboxyl group) in MWCNT with an isocyanate group in POSS is used. The one with a purity of 95% was used.
Tetrahydrofuran (hereinafter referred to as THF) as a solvent used when the reactive functional group (hydroxy group or carboxyl group) in MWCNT and the isocyanate group in POSS are reacted is preliminarily formed by calcium hydride. The dried and distilled product was used.
As the solvent for preparing the polymer material solution, the purchased dichloromethane (hereinafter referred to as MC) and dimethylformamide (hereinafter referred to as DMF) were used as they were.

2. Instrument, apparatus, and analysis method Unless otherwise stated in the specification, each process was performed using a general-purpose laboratory instrument and an experimental apparatus.
As a high-voltage power source in the electrospinning process, CPS-60 K022V1 manufactured by Chumpa EMT was used.
Analysis by Raman spectroscopy was performed using a Kalab Optical Systems Hollab 5000 and an argon laser with a wavelength of 532 nm.
Analysis by Fourier transform infrared spectroscopy (FT-IR) was performed using THERMO NICOLET AVATAR 370 manufactured by Thermo Fisher Scientific. Spectrum range ^{600cm -1 ~4000cm -1,} resolution was measured at ^{4 cm -1.}
For observation with a scanning electron microscope (also referred to as SEM), VE-8800 manufactured by Keyence Corporation was used.

Analysis by wide-angle X-ray diffraction (also referred to as WAXD) was performed using Rotaflex RTP300 manufactured by Rigaku Corporation. The temperature was room temperature, and analysis was performed at 50 kV and 200 mA. As X-rays, CuKα rays filtered with nickel were used, and analysis was performed in the range of 5 ° <2θ <50 °.
Thermogravimetric analysis was performed using Rigaku's Thermo Plus 2 TG-8120. The analysis was performed in the range of 50 ° C. to 800 ° C. while purging nitrogen at a rate of 20 mL / min. The heating was performed at a rate of 20 ° C./min.
As a high-resolution transmission electron microscope (also referred to as HRTEM), JEM-2010FEF manufactured by JEOL Ltd. was used. The high-resolution transmission electron microscope was equipped with an omega filter, a multi-scan camera from Gatan and an energy dispersive X-ray analyzer from Oxford Instruments for analysis. The acceleration voltage was 200 kV.

3. Production method of composite nanofiber 3-1. POSS-modified MWCNT preparation step The POSS-modified MWCNT preparation step includes (a) an acid treatment step and (b) a POSS-modified MWCNT manufacturing step in this order. Hereinafter, each process is demonstrated in order.

(A) Acid treatment step First, 0.25 g of MWCNT was mixed with sonication in a mixed acid of 75 ml of sulfuric acid and 25 ml of nitric acid (that is, sulfuric acid: nitric acid = 3: 1, v / v) at 55 ° C. for 9 hours. Over a period of time. After the reaction, MWCNT were washed with distilled water until pH became neutral (washed 4 times) and dried under reduced pressure. The weight of MWCNT after acid treatment was 0.173%, and the yield was 69.2%.

(A) POSS-modified MWCNT production process First, 0.075 g of MWCNT after the acid treatment process was dispersed in 50 ml of THF by ultrasonic treatment (10 minutes) and introduced into a three-necked flask. Thereafter, a mixture consisting of 0.225 g POSS, 2 drops of DBTDL and 1 ml of THF was slowly dropped into the three-necked flask using a syringe. The reaction product was reacted at 80 ° C. for 5 hours, and further reacted at 90 ° C. for 1 hour. Thereafter, excess THF was added and further washed with THF several times to remove DBTDL and unreacted POSS. The residue was dried under reduced pressure to obtain POSS-modified MWCNT as shown in Formula (3). In addition, Formula (3) is a schematic diagram and does not indicate the structure itself confirmed by analysis.

  The produced POSS-modified MWCNT was stored by immersing it in a storage solution composed of MC: DMF = 7: 3 (w / w) MC / DMF mixed solvent. The preservation solution is the same as the MC / DMF mixed solvent described later.

3-2. POSS-modified MWCNT dispersion liquid preparation process First, a predetermined amount of PLA was dissolved in a MC / DMF mixed solvent (MC: DMF = 7: 3, w / w) to prepare a liquid made of a polymer material solution. Thereafter, a predetermined amount of the POSS-modified MWCNT was introduced together with the storage solution to disperse the POSS-modified MWCNT, thereby producing a POSS-modified MWCNT dispersion liquid.
The weight of PLA was determined to be 3 wt% based on the weight of the final POSS-modified MWCNT dispersion liquid.
For the POSS-modified MWCNT, the weight is determined so that it becomes 0.1 wt%, 0.3 wt%, or 0.5 wt% with respect to the weight of the final POSS-modified MWCNT dispersion liquid. Was made.

Specifically, a POSS-modified MWCNT dispersion liquid containing 0.1 wt% POSS-modified MWCNT is 0.15 g PLA, 4.5 g MC / DMF mixed solvent, 0.005 g POSS-modified MWCNT, and 0.5 g of storage. It was produced using the liquid.
The POSS-modified MWCNT dispersion liquid containing 0.3 wt% POSS-modified MWCNT uses 0.15 g PLA, 3.5 g MC / DMF mixed solvent, 0.015 g POSS-modified MWCNT, and 1.5 g storage solution. Made.
The POSS-modified MWCNT dispersion liquid containing 0.5 wt% POSS-modified MWCNT uses 0.15 g PLA, 2.5 g MC / DMF mixed solvent, 0.025 g POSS-modified MWCNT, and 2.5 g storage solution. Made.

3-3. Electrospinning process The electrospinning process was performed using an electrospinning apparatus 300 as shown in FIG. First, the POSS-modified MWCNT dispersion liquid 30 was filled in the plastic syringe 302 connected to the nozzle 306 so that the liquid 30 could be supplied to the nozzle 306. The copper wire 312 connected to the positive electrode side of the high voltage power source 310 was inserted into the POSS-modified MWCNT dispersion liquid 30 and the collector 308 made of metal was connected to the negative electrode side of the high voltage power source 310. The distance L between the nozzle 306 and the collector 308 is set to 15 cm, the angle of the plastic syringe 302 is tilted by 10 ° from the horizontal, a voltage of 12 kV is applied, and the electric field generated between the nozzle 306 and the collector 308 is combined. Nanofibers 32 were deposited on the collector 308 to produce composite nanofibers.

4). Analysis of POSS-modified MWCNT and composite nanofibers 4-1. Analysis of POSS-modified MWCNT The POSS-modified MWCNT prepared in “3-1. POSS-modified MWCNT preparation step” was analyzed by Fourier transform infrared spectroscopy (FT-IR). As shown in FIG. 5C, weak carbonyl (—C═O) and amine (—NH) absorption bands were detected at 1700 cm ⁻¹ and 1570 cm ⁻¹ , respectively. Further, at 1570 cm ⁻¹ , a wide and weak absorption band was also detected in which the absorption band of the N—H bond bending vibration in the amide bond and the absorption band of the C—N bond stretching vibration were combined. From the above results, it was confirmed that POSS modified MWCNT by urethane bond.

Further, the same POSS-modified MWCNT as described above was analyzed with a high-resolution transmission electron microscope (HRTEM).
The surface of MWCNT before acid treatment was relatively smooth and free from deposits, as shown in FIG. As shown in FIG. 6B, the surface of the MWCNT after the acid treatment was rough, but no deposits were observed. On the other hand, on the surface of the POSS-modified MWCNT, as shown in FIG. 6C and FIG.

Furthermore, the POSS-modified MWCNT similar to the above was analyzed by thermogravimetric analysis.
As shown in FIG. 7, the MWCNT after the acid treatment decomposed faster than the MWCNT before the acid treatment because of the presence of carboxyl groups and the like on the outer surface. The POSS-modified MWCNT produced a weight loss of approximately 14 wt% at 800 ° C. This is thought to be due to the decomposition of the alkyl group on POSS.

4-2. Analysis of composite nanofiber In the analysis of the composite nanofiber, for comparison, “composite nanofiber in which MWCNT after acid treatment is dispersed inside nanofiber made of PLA” (acid-treated MWCNT composite nanofiber) And “PLA nanofibers composed only of PLA” (PLA nanofibers) were also analyzed.

  The acid-treated MWCNT composite nanofiber is obtained by converting the acid-treated MWCNT obtained in “(a) Acid treatment step” of “3-1. POSS-modified MWCNT preparation step” in “3. Production method of composite nanofiber” above. Manufactured. Specifically, 0.15 g of PLA, 4.875 g of MC / DMF mixed solvent, 0.005 g of acid-treated MWCNT, and 0.125 g of storage solution contain 0.125% of MWCNT after acid treatment. An acid-treated MWCNT dispersion liquid was prepared, and then the same process as the “3-3. Electrospinning process” was applied to the liquid to produce an acid-treated MWCNT composite nanofiber.

  PLA nanofibers were produced by electrospinning without using POSS-modified MWCNTs. Specifically, a polymer material solution is prepared using 0.15 g of PLA and 5 g of MC / DMF mixed solvent, and then the same process as the above “3-3. Electrospinning process” is applied to the solution. As a result, PLA nanofibers were produced.

Analysis by Raman spectroscopy was performed on the composite nanofibers, acid-treated MWCNT composite nanofibers and PLA nanofibers manufactured in “3. Manufacturing method of composite nanofibers”.
As shown in FIG.8 (c), from the said composite nanofiber, the peak (1700cm < ^-1 > (graphite G band) and 1570cm < ^-1 > (graphite D band)) derived from POSS modification MWCNT and the peak derived from PLA (FIG. 8). (Refer to (a)).
Thereby, it was confirmed that the POSS-modified MWCNT was dispersed inside the nanofiber made of the polymer material.

  Analysis by wide-angle X-ray diffraction (WAXD) was performed on the same composite nanofiber, acid-treated MWCNT composite nanofiber, and PLA nanofiber.

  As shown in FIG. 9, as the amount of POSS-modified MWCNT increased, the characteristic peak of PLA (particularly around 2θ = 16 °) changed. This is considered to be because the POSS-modified MWCNT disturbs the crystal structure of PLA. Further, in the acid-treated MWCNT composite nanofiber, a peak characteristic of graphite (around 2θ = 26 °) was strongly detected. It was confirmed that the composite nanofiber can exist as a crystal in PLA when the concentration is 0.3 wt% or more (see 2θ = around 7 ° to 8 °, dotted circle).

Further, the same composite nanofiber, MWCNT composite nanofiber, and PLA nanofiber as those described above were analyzed by a scanning electron microscope (SEM).
As shown in FIG. 10, it was confirmed that any of the composite nanofibers produced in the examples had the same appearance as the PLA nanofibers. This indicates that the uniformity of the composite nanofiber is high.
Moreover, the fiber diameter of the composite nanofiber, the MWCNT composite nanofiber, and the PLA nanofiber was measured from an image obtained by an operation electron microscope. As a result, as shown in FIG. 11, it was confirmed that the fiber diameter of the composite nanofiber gradually decreased as the content of the POSS-modified MWCNT contained in the composite nanofiber increased. This is considered due to the conductivity of the POSS-modified MWCNT.

  As described above, as described in the examples, the “composite nanofiber” of the present invention “POSS-modified MWCNT, which is a MWCNT chemically modified by reacting with POSS, is a nanofiber made of a polymer material. It was revealed that the “composite nanofibers dispersed inside” “is actually manufactured” and “shows the above properties”.

  As mentioned above, although this invention was demonstrated based on said embodiment and Example, this invention is not limited to said embodiment and Example. The present invention can be carried out in various modes without departing from the spirit thereof, and for example, the following modifications are possible.

(1) In each of the above embodiments and examples, POSS having a functional group having an isocyanate group at the terminal is used as POSS, but the present invention is not limited to this. For example, POSS having a functional group having an amino group at the terminal or other functional groups can also be used. In this case, in the case of using POSS having a functional group having an amino group at the terminal, an acid treatment step for generating a reactive functional group on the outer surface of the MWCNT by subjecting the MWCNT to an acid treatment, and a halogenating agent To generate a halogenated functional group by halogenating all or part of the reactive functional groups in MWCNT, and reacting the halogenated functional group in MWCNT with the amino group in POSS By doing so, the POSS-modified MWCNT manufacturing process for manufacturing the POSS-modified MWCNT is performed in this order. By setting it as such a method, POSS modification MWCNT can be manufactured using POSS which has a functional group which has an amino group at the terminal.

DESCRIPTION OF SYMBOLS 10,30 ... POSS modified MWCNT dispersion liquid, 12,32 ... Composite nanofiber, 20 ... Nonwoven fabric, 22 ... Yarn made of composite nanofiber, 100, 300 ... Electrospinning apparatus, 102 ... Raw material tank, 104 ... Valve, 106, 306 ... Nozzle, 108, 308 ... Collector, 110, 310 ... High voltage power source, 200 ... Twist yarn device, 202 ... Main twist yarn device, 204, 206 ... Thread feeder, 302 ... Plastic syringe, 312 ... Copper wire

Claims (4)

A POSS-modified MWCNT preparation step of preparing a POSS-modified MWCNT that is a MWCNT in which POSS is chemically modified by reacting with POSS;
A POSS-modified MWCNT dispersion liquid producing step for producing a POSS-modified MWCNT dispersion liquid by dispersing the POSS-modified MWCNT in a liquid comprising a polymer material solution or a molten polymer material;
A composite nanofiber production process comprising, in this order, a composite nanofiber production step of producing “a composite nanofiber in which POSS-modified MWCNT is dispersed inside a nanofiber made of a polymer material” from the POSS-modified MWCNT dispersion liquid Because
The POSS consists of POSS represented by the following formula (1):
(In the formula (1), R represents an alkyl group, and R ′ represents a functional group having an isocyanate group at the terminal.)
The POSS-modified MWCNT preparation step includes
An acid treatment step of generating a reactive functional group on the outer surface of the MWCNT by subjecting the MWCNT to an acid treatment;
A composite nanofiber comprising a POSS-modified MWCNT production process for producing the POSS-modified MWCNT by reacting the reactive functional group in the MWCNT with the isocyanate group in the POSS in this order. Manufacturing method. The composite nanofiber manufacturing process includes:
In a state where a high voltage is applied between the nozzle and the collector, the POSS-modified MWCNT dispersion liquid is discharged from the nozzle toward the collector, and “POSS-modified MWCNT is dispersed inside the nanofiber made of the polymer material. The method for producing a composite nanofiber according to claim 1 , comprising an electrospinning process for producing a composite nanofiber ”. The manufacturing method of the nonwoven fabric consisting of composite nanofiber characterized by including the process of manufacturing composite nanofiber by the manufacturing method of composite nanofiber of Claim 1 or 2 . A step of producing a composite nanofiber by the method of producing a composite nanofiber according to claim 1 or 2 ,
A method for producing a yarn comprising composite nanofibers, comprising a twisting step of producing the yarn comprising composite nanofibers by twisting the composite nanofibers in a twisting device in this order.