KR101164010B1 - Method for manufacturing thread-shaped carbon nano structure - Google Patents

Abstract

PURPOSE: A method for manufacturing a carbon nanostructure of thread shape is provided to enhance conductivity and create a new structure. CONSTITUTION: A method for manufacturing a carbon nanostructure of thread shape comprises: a step of mixing fibers and dispersion solution of a carbon nanostructure to prepare a mixture dispersion solution; a step of preparing a carbon nanostructure-containing sheet of a band type; a step of preparing a carbon nanostructure-containing yarn; and a step of heating the carbon nanostructure-containing yarn. The fiber is a cellulose fiber.

Description

Method for manufacturing thread-shaped carbon nano structure

The present invention relates to a method for producing a real carbon nanostructure.

Recently, in the field of nanotechnology, research on carbon nanostructures having excellent conductivity, tensile strength characteristics, flexibility, thermal conductivity, heat resistance, and the like has been conducted. This carbon nanostructure is typically known as carbon nanotubes.

In addition, since the carbon nanostructure has the excellent properties as described above, it is applied to form a paper or sheet-like article containing the carbon nanostructure, and a conductive material, an electromagnetic shielding material, an electromagnetic wave absorbing material, a microwave absorption heating material, an electrode, The use of an ultrafine filter, a planar heating material, a catalyst carrier material, a fuel cell material, a secondary battery material, an electric vehicle, and the like has been studied.

Conventionally, as a method for producing a sheet-like article containing such a carbon nanostructure (hereinafter referred to as a carbon nanostructure-containing sheet), a wet papermaking method using a wire cloth or an impregnation method using a dispersion of a carbon nanostructure is known. It is proposed (for example, refer patent document 1). In the wet papermaking method, a dispersion of carbon nanostructures and fibers is mixed to produce a mixed dispersion, and then the mixed dispersion is wet-laid using a metal net to obtain a carbon nanostructure-containing sheet. In addition, the impregnation method impregnates the fiber mixture containing no carbon nanostructures with the dispersion liquid of the carbon nanostructures to obtain a carbon nanostructure-containing sheet.

According to the conventional method for producing a carbon nanostructure-containing sheet by wet papermaking or impregnation, it is possible to produce a carbon nanostructure-containing sheet adhered to a fiber surface in a state where the carbon nanostructures are dispersed relatively uniformly.

International Publication No. 2009/054415

However, since the carbon nanostructure-containing sheet produced by the conventional method for producing a carbon nanostructure-containing sheet contains most of the fibers other than the carbon nanostructure, it is difficult to increase the conductivity. In addition, the conventional carbon nanostructure-containing sheet has a problem that it is difficult to use in a high temperature environment.

In addition, there is always a demand in the industry for materials having a structure and properties different from those of conventional materials, which can be suitably used in various applications, and for producing such materials. In particular, the carbon nanostructure having the excellent properties as described above is expected to be applied to various fields in the future, it is not a conventional sheet-like article, high conductivity, and can produce a solid carbon nanostructure that can be used under high temperature environment. If you can, your chances of being able to live up to that expectation will increase dramatically.

Therefore, the present invention has a structure which does not exist conventionally, is high in conductivity, can be used in a high temperature environment, and it is possible to manufacture a solid carbon nanostructure having characteristics different from those of a conventional carbon nanostructure-containing sheet. An object of the present invention is to provide a method for producing a solid carbon nanostructure.

The present inventors have made intensive efforts to achieve the above object, and employs a method of carbonizing or removing fibers by heating carbon nanostructure-containing yarns produced using a mixed dispersion of carbon nanostructure dispersions and fibers. It was found that the carbon nanostructure having high conductivity and having a structure of a real carbon nanostructure which can be used in a high temperature environment or a structure which does not exist conventionally and having a characteristic different from that of a sheet containing a conventional carbon nanostructure can be manufactured. The present invention has been completed.

[1] The method for producing a real carbon nanostructure of the present invention comprises a first step of producing a mixed dispersion by mixing at least a dispersion of a carbon nanostructure and a fiber, and a band-shaped carbon nanostructure-containing fiber using the mixed dispersion. A second step of producing a sheet; a third step of producing a carbon nanostructure-containing yarn by twisting the band-shaped carbon nanostructure-containing fiber sheet; and heating the carbon nanostructure-containing yarn to obtain the fiber. And a fourth step of producing a carbon-shaped carbon nanostructure mainly composed of the carbon nanostructure by carbonization or removal, in this order.

For this reason, according to the manufacturing method of the real carbon nanostructure of this invention, the carbon nanostructure is carbonized or removed by carbonizing or removing the fiber in the carbon nanostructure containing yarn manufactured using the mixed dispersion liquid which mixed the dispersion liquid and the fiber of a carbon nanostructure at least. Since the actual carbon nanostructure is mainly composed of a carbon nanostructure, a yarn which has a structure which does not exist conventionally, has high conductivity, can be used under high temperature environment, or has a different characteristic from that of a conventional carbon nanostructure-containing sheet. It is possible to manufacture shaped carbon nanostructures.

In addition, according to the method for producing a real carbon nanostructure of the present invention, since the real carbon nanostructure is manufactured based on a carbon nanostructure-containing yarn produced using at least a carbon nanostructure-containing mixed dispersion in which the dispersion and the fibers of the carbon nanostructure are mixed. The carbon nanostructure is less likely to exist in the aggregated state, and it becomes possible to manufacture a real carbon nanostructure utilizing the characteristics such as conductivity of the carbon nanostructure.

In addition, according to the method for producing a real carbon nanostructure of the present invention, the carbon nanostructure-containing yarn as an intermediate is produced by twisting a band-shaped carbon nanostructure-containing sheet so that the strength of the actual carbon nanostructure to be manufactured. It becomes possible to increase.

In addition, in the manufacturing method of the real carbon nanostructure of this invention, a "carbon nanostructure" means the structure of a nanometer order comprised almost carbon atoms, and the graphene sheet which is a graphite-structured sheet, and one graphene sheet Single-walled carbon nanotubes that have become tubular, Multi-layered carbon nanotubes that have two or more graphene sheets layered in a tubular shape, Carbon nanocoils whose nanofibers have a diameter of less than 1000 nm in diameter, Carbon nanofibers, carbon nanohorns, carbon nanocapsules and the like can be exemplified preferably (hereinafter, the term "CNT" is used generically including these carbon nanostructures).

In addition, in the manufacturing method of the real carbon nanostructure of this invention, a "real carbon nanostructure" means the real thing comprised mainly by the carbon nanostructure.

In addition, in the manufacturing method of the real carbon nanostructure of this invention, the "carbon nano structure containing sheet" and the "carbon nano structure containing yarn" are a sheet-like object in which fiber is mainly comprised and the carbon nano structure is disperse | distributed. Or real shape.

[2] In the method for producing a real carbon nanostructure according to the present invention, it is preferable to pass the band-shaped carbon nanostructure-containing sheet in a twisted yarn device to draw the carbon nanostructure-containing yarn.

By such a method, it becomes possible to perform a 3rd process efficiently, and it becomes possible to manufacture a real carbon nano structure with high production efficiency.

[3] In the method for producing a real carbon nanostructure of the present invention, it is preferable that the fibers are cellulose fibers and the mixed dispersion is an aqueous mixed dispersion.

In this way, carbon nano structure-containing yarn having a structure in which the carbon nano structure is uniformly attached to the fiber surface can be produced as an intermediate, and a solid carbon nano structure in which the carbon nano structure is uniformly dispersed is produced. It can manufacture. It is because cellulose fiber has hydrophilic groups, such as a carboxyl group and a hydroxyl group, and is disperse | distributing to water well.

[4] In the method for producing a real carbon nanostructure of the present invention, the carbon nanostructure-containing sheet is continuously produced by spraying the mixed dispersion onto a mesh member, and the carbon nanostructure-containing sheet is cut to form the strip-shaped sheet. It is preferable to produce a carbon nanostructure-containing sheet.

By using such a method, the carbon nanostructure-containing sheet can be produced on the mesh member while passing a part of the solvent in the mixed dispersion liquid, so that the carbon nanostructure-containing sheet having a low solvent content can be produced, and the subsequent drying. It is possible to shorten the time and the like.

[5] In the method for producing a real carbon nanostructure of the present invention, the carbon nanostructure-containing sheet is continuously produced by coating the mixed dispersion on a substrate, and the carbon nanostructure-containing sheet is cut to cut the band-shaped carbon. It is preferable to produce a nanostructure-containing sheet.

By such a method, it becomes possible to manufacture a real carbon nano structure efficiently, without wasting a mixed dispersion liquid. In addition, since the carbon nanostructure-containing sheet is produced by coating on the substrate, it is possible to facilitate the management of the thickness of the carbon nanostructure-containing sheet to be produced.

[6] In the method for producing a real carbon nanostructure of the present invention, it is preferable to prepare a mixed dispersion by mixing at least the dispersion of the carbon nanostructure, the fiber and the thickener in the first step.

By such a method, it becomes easy to manufacture the carbon nanostructure fiber sheet as an intermediate body, and it becomes possible to manufacture a real carbon nanostructure with high production efficiency.

As the thickener, water-soluble polymers such as carboxymethyl cellulose, sodium alginate, methyl cellulose, hydroxymethyl cellulose, casein, sodium polyacrylate, styrene-maleic anhydride copolymer, inorganic polymers such as silicate, and the like can be used alone or in combination.

[7] In the method for producing a real carbon nanostructure of the present invention, it is preferable to prepare a mixed dispersion by mixing at least the dispersion of the carbon nanostructure and the dispersion of the fiber in the first step.

By such a method, it becomes possible to produce a mixed dispersion liquid having a good dispersion of the carbon nanostructure and the fiber and less likely to exist in the aggregated state of the carbon nanostructure.

The present invention has a structure which does not exist conventionally, has high conductivity, can be used in a high temperature environment, or can form a real carbon nano structure having a characteristic different from that of a conventional carbon nano structure-containing sheet. It provides a method for producing a carbon nano structure.

BRIEF DESCRIPTION OF THE DRAWINGS It is a figure shown for demonstrating the manufacturing method of the real shape CNT which concerns on Embodiment 1. FIG.
FIG. 2 is a diagram for explaining a second step of the method for producing a solid CNT according to the first embodiment.
FIG. 3 is a diagram for explaining a second step of the method for producing a solid CNT according to the first embodiment. FIG.
FIG. 4 is a diagram for explaining a third step of the method for producing a solid CNT according to the first embodiment.
FIG. 5 is a diagram for explaining a fourth step of the method for producing a solid CNT according to the first embodiment.
FIG. 6 is a diagram for explaining another example of the fiber deposit production process of the method for producing a yarn-like CNT according to the first embodiment.
FIG. 7 is a view for explaining a second step of the method for producing a solid CNT according to the second embodiment. FIG.
FIG. 8 is a diagram for explaining a second step of the method for producing a solid CNT according to the third embodiment.
FIG. 9 is a diagram for explaining a second step of the method for producing a solid CNT according to the third embodiment. FIG.
FIG. 10 is a diagram for explaining a method for manufacturing a solid CNT according to Modification Example 1. FIG.
FIG. 11 is a view for explaining a method for manufacturing a solid CNT according to the second modification. FIG.

EMBODIMENT OF THE INVENTION Hereinafter, the manufacturing method of the real carbon nanostructure of this invention is demonstrated based on embodiment shown in drawing.

 [Embodiment 1]

BRIEF DESCRIPTION OF THE DRAWINGS It is a figure shown for demonstrating the manufacturing method of the real shape CNT which concerns on Embodiment 1. FIG.

2 and 3 are diagrams for explaining a second step of the method for producing a solid CNT according to the first embodiment. FIG. 3A is a diagram illustrating a fiber deposit manufacturing process, FIG. 3B is a diagram illustrating a drying process, and FIG. 3C is a diagram illustrating a cutting process.

FIG. 4 is a diagram for explaining a third step of the method for producing a solid CNT according to the first embodiment.

FIG. 5 is a diagram for explaining a fourth step of the method for producing a solid CNT according to the first embodiment.

FIG. 6 is a diagram for explaining another example of the fiber deposit production process of the method for producing a yarn-like CNT according to the first embodiment.

As shown in FIGS. 1-5, the manufacturing method of the real CNT which concerns on Embodiment 1 is a 1st process (mixed dispersion preparation process) which mixes at least a CNT dispersion liquid and a fiber, and produces the mixed dispersion liquid 1A, CNT-containing yarn by twisting the second step (belt-shaped CNT-containing sheet preparing step) of producing the band-shaped CNT-containing sheet 7 using the mixed dispersion liquid 1A and the band-shaped CNT-containing sheet 7. (3) a fourth step (manufacture of twisted yarn) and a fourth step of producing a yarn-shaped CNT (10) mainly composed of CNTs by heating the CNT-containing yarn (9) to carbonize or remove the fibers ( Heating step) in this order. Hereinafter, the manufacturing method of the real CNT which concerns on Embodiment 1 according to a manufacturing process is demonstrated in detail.

In addition, in the following description, "a sheet-like fiber deposit" means the sheet-like thing of the state in which the carbon nanostructure and the fiber were deposited at least, and it means the state before drying.

(1) 1st process (mixed dispersion preparation process)

 The first step is a mixed dispersion preparation process for producing these mixed dispersions 1A by mixing the CNT dispersions and fibers produced such that the CNTs are dispersed and present. In this step, for example, as shown in FIG. 1, CNT dispersion liquid, fibers, and the like are introduced into the tank 21, and these are mixed by the mixing device 23 to produce a mixed dispersion liquid 1A.

The manufacturing method of a CNT dispersion liquid is not specifically limited, The method illustrated by International Publication No. 2009/054415, International Publication No. 2008/069150, etc. can be employ | adopted suitably. For example, a method of dispersing by ultrasonication using a surfactant to help disperse CNTs, a method of dispersing by ultrasonication using an organic solvent, or a repulsive force between molecules having the same polarity A method of dispersing, a method of adhering and dispersing a magnetic substance to CNT, a method of modifying and dispersing the surface of the CNT, or the like may be performed alone or in combination to prepare a CNT dispersion in which CNTs are uniformly dispersed without being aggregated.

The CNT used is not specifically limited. As an example of CNT, graphene sheet, single layer carbon nanotube, multilayer carbon nanotube, carbon nanocoil, carbon nanofiber, carbon nanohorn, carbon nanocapsule, etc. can be used individually or in combination. The CNT production method may be any method such as a CVD method or an arc discharge method.

The fiber mixed with the CNT dispersion is a material that is the main agent of the CNT-containing yarn 9 as an intermediate, and in Embodiment 1, cellulose fibers are used. As the cellulose fibers, for example, microfibrils fibers, biocellulose fibers, etc. obtained by treating wood pulp fibers, non-wood pulp fibers, and cellulose fibers may be used alone or in combination as appropriate.

The fibers are not mixed directly with the CNT dispersion liquid, but are prepared in advance with a fiber dispersion liquid (hereinafter referred to as a "fiber dispersion liquid") and then mixed with the CNT dispersion liquid. By producing the mixed dispersion 1A in this manner, the agglomeration of the fibers can be prevented.

As a CNT dispersion liquid, the CNT dispersion liquid containing surfactant is used, and as a fiber dispersion liquid, the fiber dispersion liquid containing a CNT fixation liquid is used. Surfactants (anionic surfactants) and fixers (cationic fixers) have opposite polarities. Then, the CNT fixer is adsorbed onto the fibers before the CNT dispersion and the fiber dispersion are mixed.

In addition to the mixed dispersion 1A, additives such as inorganic or organic adhesives, enhancers and thickeners can be appropriately mixed. It is preferable to determine the material to be mixed, the kind thereof, the mixing ratio and the like according to the use of the actual CNT 11 to be produced. Since the manufacturing method of the real CNT which concerns on Embodiment 1 includes the fiber deposit manufacturing process which injects the mixed dispersion liquid 1A into the mesh member 33, it is a viscosity so that the mixed dispersion liquid 1A may be sprayed by a spraying apparatus. It is important to adjust the density.

The mixed dispersion 1A may be either an organic dispersion or an aqueous dispersion, but is preferably an aqueous dispersion obtained by dispersing at least a CNT dispersion or cellulose fiber in a solvent such as a mixed solvent of water, water, and alcohol. If it is an aqueous dispersion liquid, CNT and cellulose fiber in the mixed dispersion liquid 1A will be easy to disperse | distribute uniformly.

In addition, the mixing apparatus 23 used for preparation of 1 A of mixed dispersion liquids is not specifically limited, A well-known optimal mixer can be selected from a well-known mixer.

(2) 2nd process (belt-shaped CNT containing sheet manufacturing process)

The 2nd process is a strip | belt-shaped CNT containing sheet manufacturing process which produces the strip | belt-shaped CNT containing sheet | seat 7 using 1 A of mixed dispersion liquids. Specifically, the fiber dispersion production process of spraying the mixed dispersion 1A onto the mesh member 33 to continuously produce the sheet-like fiber deposit 3A, and drying the sheet-like fiber deposit 3A to dry the CNT-containing sheet ( A drying step of 5A) and a cutting step of cutting the CNT-containing sheet 5A to produce the CNT-containing sheet 7 are performed in this order.

A fiber deposit manufacturing process is performed as follows. That is, as shown in FIG. 2, the endless belt-shaped mesh member 33 is rotated by the feed rollers 29 and 31 to one direction. In this state, as shown to FIG. 2 and FIG. 3 (a), 1 A of mixed dispersion liquid in the tank 21 is pumped toward the injection nozzle 27 by the pump 25, and it mixes When the pressure of the dispersion 1A exceeds the opening valve pressure of the injection nozzle 27, or is mixed from the injection nozzle 27 toward the mesh member 33 sent by the opening valve operation of the injection nozzle 27. The dispersion 1A is injected. The injection nozzle 27 itself may be provided with the pressurizing mechanism, and in this case, the injection operation of the mixed dispersion liquid 1A is controlled by the operation of the pressurizing mechanism of the injection nozzle 27.

In the example shown in FIG. 3A, the mixed dispersion 1A fed by the pump 25 is distributed in two systems, and the mixed dispersion 1A is injected from the two spray nozzles 27. Thereby, 3 A of sheet-like fiber deposits are produced on the mesh-like member 33, and the mesh-like member 33 which produced the sheet-like fiber deposits 3A on the upper surface is sent to a drying process sequentially.

In the manufacturing method of the real CNT which concerns on Embodiment 1, since the mixed dispersion liquid 1A is sprayed on the mesh member 33, a part of the solvent in the mixed dispersion liquid 1A is sprayed, and until it dries, a part of the solvent will be net-shaped member ( Fall through 33). The solvent dropped through the mesh member 33 is recovered in the solvent receiver 35.

Although the material itself which comprises the mesh member 33 is not specifically limited, The mesh member 33 is comprised by the conveying rollers 29 and 31 so that rotation is possible in one direction.

The number of injection nozzles 27 is not specifically limited, The mixed dispersion liquid 1A can be injected from one or several injection nozzles 27. Alternatively, as shown in FIG. 6, the mixed dispersion liquid 1A may be injected by the injection nozzles 27 ′ having the plurality of discharge ports arranged in the direction orthogonal to the moving direction of the mesh member 33.

The thickness of 3 A of sheet-like fiber deposits just after injection is 1 micrometer-1000 micrometers, for example. Since the mixed dispersion liquid 1A with a relatively large amount of solvent is used to enable the injection by the injection nozzle 17, the sheet-like fiber deposit 3A immediately after the injection (the sheet-like fiber deposit 3A in Fig. 3A). The thickness of S is slightly thicker than the thickness of CA-containing sheet 5A to be prepared.

In the fiber deposit production process, it is preferable to adjust the injection flow rate of the mixed dispersion liquid 1A and the conveyance speed of the mesh member 33 according to the thickness of the fiber deposit 3A to be produced.

Subsequently, the drying process of drying 3 A of sheet-like fiber deposits and producing 5 C of CNT containing sheets is performed as follows. That is, the sheet | seat on the mesh member 33 is made to pass through the mesh member 33 sent sequentially, as shown to FIG. 2 and FIG. 3 (b) in the drying apparatus comprised with the heaters 37a and 37b. The shape fiber deposit 3A is dried. Thereby, 5A of CNT containing sheets can be manufactured continuously.

The drying apparatus to be used is not particularly limited. For example, a heating wire, a warm air generator, an infrared heater, etc. can be used suitably.

The CNT-containing sheet may be dehydrated by passing the CNT-containing sheet 5A between a pair of rollers (not shown) between the fiber deposit production step and the drying step.

Drying conditions, such as temperature and time, can select an optimal value suitably according to the raw material of 1 A of mixed dispersion liquids, and the structure of a drying apparatus. The thickness of 5 C of CNT containing sheets produced is 10 micrometers-1000 micrometers, for example.

Subsequently, the cutting process of cutting the CNT-containing sheet 5A to produce the band-shaped CNT-containing sheet 7 is performed as follows. That is, as shown in FIG.2 and FIG.3 (c), the CNT containing sheet | seat 5A sent by the cutting device 39 can be cut | disconnected in width about 1 mm-100 mm, for example, and can be twisted yarn. The CNT-containing sheet 7 is produced. The cut CNT-containing sheet 7 is wound by the winding roller 41.

(3) Third process (twist yarn process)

The 3rd process is the twisted yarn process which produces the CNT containing yarn 9 by making the strip | belt-shaped CNT containing sheet 7 into twisted yarns. Specifically, the band-shaped CNT-containing sheet 7 is passed through the twist yarn 43 to produce the CNT-containing yarn 9 from the band-shaped CNT-containing sheet 7.

The third step is carried out as follows. That is, as shown in FIG. 4, the CNT containing yarn 9 can be manufactured by making the strip | belt-shaped CNT containing sheet 7 produced by the 2nd process into twist yarns using the main twist yarn 45. FIG. . At this time, by firmly twisting the CNT-containing yarn 9 to the left side of FIG. 4 using the yarn transfer apparatuses 47 and 49 to transfer the yarn, the firmly twisted CNT-containing yarn 9 is continuously manufactured. can do.

When the yarn is conveyed using the yarn feeders 47 and 49, if the yarn feed speed V1 of the yarn feed device 49 is faster than the yarn feed speed V2 of the yarn feed device 47, the CNT is included. Stretching similar 9 can also be performed.

The diameter of the CNT containing yarn 9 produced at the 3rd process is 1 micrometer-1000 micrometers, for example.

(4) 4th process (heating process)

The fourth step is a heating step of producing a yarn-shaped CNT 11 mainly composed of CNTs by heating the CNT-containing yarn 9 to carbonize or remove the fibers.

The fourth step is carried out as follows. That is, as shown in FIG. 5, the CNT containing yarn 9 is thrown in from the feeding roller 51 which wound the CNT containing yarn 9 produced by the 3rd process, and the said CNT containing yarn 9 is heated by the heating apparatus ( 55) to heat the CNT-containing yarn (9). Thereby, the fiber in the CNT containing yarn 9 is carbonized or removed, and the real CNT 11 can be manufactured continuously. The manufactured thread-shaped CNTs 11 are wound by the winding rollers 53.

The heating apparatus 55 to be used is not specifically limited. Although the combustion furnace is used as the heating apparatus 55 in the manufacturing method of the real CNT which concerns on Embodiment 1, the heating apparatus comprised using the heating wire, the heating apparatus using infrared rays, etc. can be used suitably.

In addition, heating conditions, such as temperature and time, can select an optimal value suitably according to the kind of cellulose fiber, the structure of the heating apparatus 55, and the characteristic of the actual CNT 11 to manufacture. In particular, the heating temperature and the heating time differ depending on whether some or all of the fibers are left in a carbonized state or the cellulose fibers are completely incinerated and removed. Complete removal of cellulose fibers requires heating to a temperature and time at which the fibers can be surely lost.

When cellulose fiber is removed completely, it is possible to set it as the real CNT 11 which is lightweight and can exhibit the characteristic of CNT further. On the other hand, when some or all of the fibers are carbonized and left, the yarn density is high and a relatively high strength solid CNT 11 can be obtained.

The diameter of the real CNT 11 produced after heat processing is 0.1 micrometer-100 micrometers, for example.

Through the above steps, the actual CNTs 11 can be manufactured.

According to the method for producing a yarn-like CNT according to the first embodiment, the yarn-like CNTs are carbonized or removed by heating the CNT-containing yarn 9 produced using the mixed dispersion liquid 1A in which at least the CNT dispersion and the fibers are mixed. Since (11) is manufactured, it becomes possible to manufacture a solid CNT having a structure which does not exist conventionally, has high conductivity, can be used in a high temperature environment, or has properties different from those of a conventional carbon nanostructure-containing sheet. .

Moreover, according to the manufacturing method of the real CNT which concerns on Embodiment 1, the real CNT 11 was made based on the CNT containing yarn 9 produced using the mixed dispersion 1A which mixed the CNT dispersion liquid and the fiber at least. Since it manufactures, there exists little possibility that CNT exists in the aggregated state, and it becomes possible to manufacture the real CNT which utilized the characteristics, such as electroconductivity of CNT.

Moreover, according to the manufacturing method of the real CNT which concerns on Embodiment 1, since the CNT containing yarn 9 as an intermediate is produced by twisting the strip | belt-shaped CNT containing sheet 7, the CNT containing yarn 9 is heated. It is possible to increase the strength of the actual CNT produced.

Moreover, according to the manufacturing method of the real CNT which concerns on Embodiment 1, since the CNT containing sheet 5A as an intermediate is continuously manufactured with the said mixed dispersion 1A, real CNT can be manufactured with high production efficiency, It is possible to mass-produce real CNTs according to industrialization.

Moreover, according to the manufacturing method of the real CNT which concerns on Embodiment 1, the mixed dispersion liquid 1A is sprayed on the mesh member 33, the CNT containing sheet 5A is produced continuously, and the CNT containing sheet 5A is carried out. After passing the strip-shaped CNT-containing sheet 7 through the twisted yarn device 43 to continuously produce the CNT-containing yarn 9, the CNT-containing yarn 9 was heated to form a real CNT 11. Since it is possible to manufacture, it is possible to build a production line to enable the mass production of real CNTs according to industrialization.

In addition, according to the manufacturing method of the real CNT which concerns on Embodiment 1, the sheet-like fiber deposit 3A is produced by spraying the mixed dispersion liquid 1A to the mesh member 33, and the sheet-like fiber deposit with low solvent content is produced. It becomes possible to manufacture, and it becomes possible to shorten the subsequent drying time.

Further, according to the method for producing a solid CNT according to the first embodiment, the fiber is a cellulose fiber, and since the mixed dispersion 1A is a mixed dispersion of an aqueous system, the CNT-containing yarn having a structure in which the CNTs are uniformly adhered to the fiber surface. It is possible to produce, and as a result, it becomes possible to manufacture a solid CNT in which CNTs are uniformly dispersed.

Moreover, according to the manufacturing method of the real CNT which concerns on Embodiment 1, since surfactant is contained in a CNT dispersion liquid, CNT disperse | distributes well in a CNT dispersion liquid.

In addition, according to the method for producing a yarn-like CNT according to the first embodiment, the CNT fixer is adsorbed onto the fiber before the CNT dispersion and the fiber dispersion are mixed, so that the CNT can be fixed to the surface of the fiber well.

Moreover, according to the manufacturing method of the real CNT which concerns on Embodiment 1, since a fixing liquid and surfactant have opposite polarity, CNTs are settled better by the surface of a fiber.

In addition, according to the method for producing a solid CNT according to the first embodiment, the mixed dispersion 1A is prepared by mixing at least the CNT dispersion and the fiber dispersion, so that the CNTs and the fibers are dispersed well and the CNTs may be present in the aggregated state. It becomes possible to produce 1 A of mixed dispersions with less.

[Embodiment 2]

FIG. 7 is a view for explaining a second step of the method for producing a solid CNT according to the second embodiment. FIG. In addition, unless otherwise indicated in the following drawings, the same code | symbol as FIG. 2 shows the same component, and these components can be comprised similarly according to the content demonstrated in Embodiment 1. As shown in FIG.

Although the manufacturing method of the real CNT which concerns on Embodiment 2 is basically the same process as the case of the manufacturing method of the real CNT which concerns on Embodiment 1 as shown in FIG. 7, the content of a 1st process is implemented. It differs from the case of the manufacturing method of the real CNT which concerns on the form 1.

That is, in the manufacturing method of the real CNT which concerns on Embodiment 2, these mixed dispersion liquid 1B is produced by mixing at least a CNT dispersion liquid, a fiber, and a thickener.

As the CNT dispersion and the fiber, those used in the method for producing the solid CNTs of Embodiment 1 can be suitably used. The fiber may mix what was previously set as the dispersion liquid of fiber. In addition, the mixed dispersion 1B is preferably an aqueous dispersion.

The thickener can be used as a retention enhancer or strength enhancer, and serves as an adhesive in the mixed dispersion, and it is easy to maintain the sheet-like fibrous deposits produced on the mesh member in a sheet form. To be mixed. As the thickener, water-soluble polymers such as carboxymethyl cellulose, sodium alginate, methyl cellulose, hydroxymethyl cellulose, casein, sodium polyacrylate, styrene-maleic anhydride copolymer, inorganic polymers such as silicate, and the like can be used alone or in combination. . Among these, as water-soluble polymers, cationic water-soluble polymers such as cationic starch of natural water-soluble polymer, polyethyleneimine of synthetic water-soluble polymer, cationic polyvinyl alcohol, cationic acrylamide-based polymer and anionic acrylamide-based polymer Anionic water-soluble polymers, such as these, can be used. As the water-soluble polymer, a water-soluble nonionic polymer, a water-soluble amphoteric polymer, or the like can also be used.

The 2nd process (a strip | belt-shaped CNT containing sheet manufacturing process), the 3rd process (twist yarn process), and a 4th process (heating process) are performed similarly to each process of the manufacturing method of the real CNT which concerns on Embodiment 1. Through the above process, real CNT can be manufactured continuously.

According to the manufacturing method of the real CNT which concerns on Embodiment 2, the effect similar to the effect obtained by the manufacturing method of the real CNT which concerns on Embodiment 1 can be acquired.

Moreover, according to the manufacturing method of the real CNT which concerns on Embodiment 2, since the thickener which functions as an adhesive agent is contained in the mixed dispersion liquid (1 microsecond), when it sprayed on the mesh member 33, the sheet-like fiber deposit 3B It is easy to maintain the sheet shape. Therefore, it becomes easy to manufacture sheet-like fiber deposit 3B, and it becomes possible to manufacture real CNT with high production efficiency. Moreover, the effect which becomes easy to manage the thickness of the CNT containing sheet | seat 5B to produce is also acquired.

[Embodiment 3]

8 and 9 are diagrams for explaining a second step of the method for producing a solid CNT according to the third embodiment. FIG. 9A is a diagram illustrating a fiber deposit manufacturing process, FIG. 9B is a diagram illustrating a drying process, and FIG. 9C is a diagram illustrating a cutting process.

Although the manufacturing method of the real CNT which concerns on Embodiment 3 contains the process similar to the case of the manufacturing method of the real CNT which concerns on Embodiment 2, the content of a 2nd process (a strip | belt-shaped CNT containing sheet production process) It differs from the case of the manufacturing method of the real CNT which concerns on Embodiment 2.

That is, in the manufacturing method of the real CNT which concerns on Embodiment 3, the sheet-like fiber deposit 3C is coated by coating the mixed dispersion liquid 1C on the base material 59, as shown to FIG. 8 and FIG. 9 (a). Has been produced continuously. Hereinafter, the manufacturing method of the real CNT which concerns on Embodiment 3 is demonstrated according to a manufacturing process.

(1) 1st process (mixed dispersion preparation process)

The first step is a mixed dispersion preparation step of producing these mixed dispersions 1C by mixing the CNT dispersions prepared so that the CNTs are dispersed and the fibers and the thickener. For example, as shown in FIG. 8, CNT dispersion liquid, fiber, water-soluble polymer, etc. are thrown into the tank 21, these are mixed by the mixing apparatus 23, and the mixed dispersion liquid 1C is produced.

Since a 1st process can be basically implemented similarly to the mixed dispersion liquid preparation process of the manufacturing method of the real CNT which concerns on Embodiment 2, detailed description is abbreviate | omitted. However, in the manufacturing method of the actual CNT which concerns on Embodiment 3, since the mixed dispersion liquid 1C is coated on the base material 59, the structure of the coating machine 57 used and the CNT containing sheet 5C to manufacture are produced It is important to adjust viscosity, density, etc. according to the thickness etc.).

In addition, in order to make it easy to hold | maintain the sheet-like fiber deposit 3C produced on the base material 59 in a sheet form, in the mixed dispersion liquid 1C similarly to the case of the manufacturing method of the real CNT which concerns on Embodiment 2, It is important to mix the thickener.

(2) 2nd process (belt-shaped CNT containing sheet manufacturing process)

The 2nd process is a strip | belt-shaped CNT containing sheet | seat preparation process which produces the strip | belt-shaped CNT containing sheet | seat 7 using the mixed dispersion liquid 1C. Specifically, the fiber dispersion production process of coating the mixed dispersion 1C on the substrate 59 to continuously produce the sheet-like fiber deposit 3C, and drying the sheet-like fiber deposit 3C to dry the CNT-containing sheet 5C. And a cutting step of cutting the CNT-containing sheet 5C to produce a strip-shaped CNT-containing sheet in this order.

First, a fiber deposit manufacturing process is performed as follows. That is, as shown in FIG. 8, the base material 59 is rotated in one direction by the feed rollers 29 and 31. FIG. In this state, as shown to FIG. 8 and FIG. 9 (a), the mixed dispersion liquid 1C is supplied to the coating machine 57 by the pump 25, and the base material 59 by the coating machine 57 is carried out. The mixed dispersion (1C) is coated on the C), and the sheet-like fiber deposit 3C is continuously produced. In the example shown to FIG. 8 and FIG. 9A, although the example which uses a roll coater as a coating machine 57 is shown, the coating machine 57 is not limited to a roll coater.

The base material 59 is comprised so that the mixed dispersion liquid 1C or its solvent may not pass, for example unlike the mesh member 33 used by the manufacturing method of the real CNT of Embodiment 1. In addition, the material itself which comprises the base material 59 is not specifically limited. The substrate 59 may be made of a material that does not permeate the solvent, such as a resin film, or may be made of a material that permeates the solvent, such as paper or nonwoven fabric.

The thickness of 3 C of sheet-like fiber deposits is 10 micrometers-1000 micrometers, for example. In the case of the method for producing the sheet-like fiber deposit 3C by coating, a mixed dispersion 1C having a high viscosity or high concentration can be used. There is a tendency to become somewhat thinner than the thickness of).

In the fiber deposit production process, it is preferable to adjust the viscosity of the mixed dispersion liquid 1C and the conveyance speed of the base material 59 in accordance with the thickness of the sheet-like fiber deposit 3C to be produced.

The drying step and the cutting step can be carried out in the same procedure as in the case of the method for producing the real CNTs according to the first embodiment. Thereby, a strip | belt-shaped CNT containing sheet can be produced.

(3) Third process (twist yarn process)

The 3rd process is a process of manufacturing a CNT containing yarn by making into the twisted yarn the strip | belt-shaped CNT containing sheet produced by the 2nd process. The 3rd process can be performed in the same procedure as the case of the manufacturing method of the real CNT which concerns on Embodiment 1. That is, the CNT-containing yarn in which the yarn is twisted firmly can be produced by passing the band-shaped CNT-containing sheet through the twist yarn 43.

(4) fourth process

The fourth step is a step of producing a solid CNT by heating the CNT-containing yarn produced in the third step to carbonize or remove the fibers in the CNT-containing yarn. The fourth step can be carried out in the same order as in the case of the method for producing a solid CNT according to the first embodiment. That is, real CNT can be manufactured by passing a CNT containing yarn through the heating apparatus 55. FIG.

Through the above steps, CNT-containing yarns can be continuously produced.

As explained above, although the content of the 2nd process (a strip | belt-shaped CNT containing sheet production process) differs from the case of the manufacturing method of the real CNT which concerns on Embodiment 2, the manufacturing method of the real CNT which concerns on Embodiment 3 is at least Since the CNT-containing yarn manufactured by using the mixed dispersion (1C) mixed with the CNT dispersion and the fiber is heated to carbonize or remove the fiber, a real CNT is produced, thus having a structure that does not exist in the past, high conductivity, and high temperature environment. It is possible to use it under the following, or it becomes possible to manufacture the solid CNT which has a characteristic different from the conventional carbon nanostructure containing sheet | seat.

In addition, according to the method for producing a real CNT according to the third embodiment, since a real CNT is produced based on a CNT-containing yarn produced using at least a CNT dispersion and a mixed dispersion (1C) in which fibers are mixed, the second embodiment is in accordance with the second embodiment. As in the case of the manufacturing method of the real CNTs according to the related art, there is little possibility that the CNTs are present in the aggregated state, and it is possible to produce the real CNTs utilizing the properties such as conductivity of the CNTs.

Moreover, according to the manufacturing method of the real CNT which concerns on Embodiment 3, since the CNT containing yarn as an intermediate body is produced by twisting a strip | belt-shaped CNT containing sheet, it is the same as the case of the manufacturing method of real CNT which concerns on Embodiment 2 Similarly, it becomes possible to raise the intensity | strength of the real CNT produced by heating a CNT containing yarn.

Moreover, according to the manufacturing method of the real CNT of Embodiment 3, since the sheet-like fiber deposit 3C is produced continuously with the said mixed dispersion 1C, it is the case of the manufacturing method of the real CNT of Embodiment 2, and Similarly, it is possible to produce real CNTs with high production efficiency, and mass production of real CNTs becomes possible due to industrialization.

Moreover, according to the manufacturing method of the real CNT which concerns on Embodiment 3, the strip | belt-shaped CNT containing sheet which produced the CNT containing sheet 5C continuously with the mixed dispersion liquid 1C, and cut | disconnected the CNT containing sheet 5C was carried out. Since the CNT-containing yarn 9 is continuously produced by passing the (7) through the twisting yarn device, the CNT-containing yarn 9 is heated to produce a real-shaped CNT 11, and thus the actual shape according to Embodiment 1 As in the case of the manufacturing method of CNT, a production line can be built and a real dispersion CNT can be manufactured with a high dispersion of mixed dispersion liquid.

In addition, according to the manufacturing method of the strip | belt-shaped CNT which concerns on Embodiment 3, since the thickener is contained in the mixed dispersion liquid, when the mixed dispersion liquid 1C is coated on the base material 59, the sheet-like fiber deposit 3C is sheet-shaped. It becomes possible to keep. Therefore, it becomes easy to manufacture 3 C of sheet-like fiber deposits, and it becomes possible to manufacture real CNT with high production efficiency. Moreover, the effect which becomes easy to manage the thickness of 5 C of CNT containing sheets to manufacture is also acquired.

Moreover, according to the manufacturing method of the actual CNT which concerns on Embodiment 3, it becomes possible to use effectively, without wasting 1C of mixed dispersion liquids, and to make it easy to manage the thickness of the CNT containing sheet 5C to produce. The effect which becomes possible is also acquired.

As mentioned above, although the manufacturing method of the real CNT of this invention was demonstrated based on the said embodiment, this invention is not limited to this, It is possible to implement in the range which does not deviate from the summary, for example, the following modifications It is also possible.

(1) The dimension, shape, arrangement, and material of each element shown in the above embodiments are exemplifications, and the present invention is not limited thereto. Determination can be made arbitrarily within the range which does not deviate from the meaning of this invention.

(2) Although the said mesh member 33 or the base material 59 itself is made to rotate in one direction in the said Embodiment 1-Embodiment 3, this invention is not limited to this. FIG. 10 is a view schematically showing a manufacturing method of a solid CNT according to Modification Example 1. FIG. As illustrated in FIG. 10, a substrate 63 having a rectangular shape is mounted on a belt conveyor 61 rotated in one direction by a transfer roller, and the substrate 63 is conveyed, and the substrate being conveyed ( The mixed dispersion liquid 1D may be sprayed onto 63 to form a rectangular sheet-like fiber deposit 3D to continuously produce the rectangular CNT-containing sheet 5D. In this case, after that, the rectangular CNT-containing sheet 5D is cut to produce a band-shaped CNT-containing sheet 7, and the band-shaped CNT-containing sheet 7 is twisted to produce a CNT-containing yarn. The CNT-containing yarn thus obtained can be heated to produce a solid CNT.

(3) In the first embodiment to the third embodiment, the strip-shaped CNT-containing sheet 7 is recovered in a state of being separated from the mesh member 33 or the substrate 59 as the substrate, but the present invention is limited thereto. It doesn't work. FIG. 11 is a view schematically showing a manufacturing method of a solid CNT according to Modification Example 2. FIG. As shown in FIG. 11, the CNT-containing sheet 5E may be recovered together with the substrate 69. In this case, the CNT-containing sheet 5E is then separated from the substrate 69, and then the CNT-containing sheet 5E is cut to produce a strip-shaped CNT-containing sheet 7, and the strip-shaped CNT-containing sheet 7 is obtained. CNT-containing yarn can be produced by using twisted yarn, and the obtained CNT-containing yarn can be heated to produce real CNT.

(4) In the first to third embodiments, the fiber deposit preparation step and the drying step of the second step are performed on a series of lines, but the fiber deposit preparation step and the drying step may be divided into separate lines and carried out. . In this case, when the rectangular base material 63 shown in FIG. 10 is used, it becomes possible to make the fiber deposit manufacturing process easy to move with a drying process, and also to form a large sheet at once using a large drying apparatus. It becomes possible to dry fiber deposits.

(5) In the above Embodiments 1 to 3, sheet-like fiber deposits 3A, 3B, and 3C are produced on the mesh member 33 or the base material 59 which are sequentially sent, and the CNT-containing sheets 5A and 5B. , 5C) are produced continuously, but the present invention is not limited to such a method. For example, a solid CNT may be produced by learning a whale papermaking method using at least a mixed dispersion mixture of a CNT dispersion and a fiber, and then papermaking using a iron net to produce a CNT-containing sheet.

1A, 1B, 1C, 1D, 1E, 1F: Mixed Dispersion
3A, 3B, 3C, 3D, 3E: sheet-like fiber deposits
5A, 5B, 5C, 5D, 5E: CNT-containing sheet
7: Band-shaped CNT-containing sheet
9: CNT-containing yarn
11: Real CNT
21: tank
23: mixing device
25: pump
27, 27 ': spray nozzle
29, 31: feed roller
33: mesh member
35: solvent receiving part
37a, 37b: heater
39: cutting device
41, 53, 67: winding roller
43: twister device
45: main twister device
47, 49: twisted yarn feed device
51, 65: feeding roller
55: heating device
57: coating machine (roll coater)
59, 63, 69: description
61: belt conveyor

Claims (7)

A first step of producing a mixed dispersion by mixing at least a dispersion of carbon nanostructures and fibers,
A second step of producing a band-shaped carbon nanostructure-containing sheet using the mixed dispersion;
A third step of producing a carbon nanostructure-containing yarn by twisting the band-shaped carbon nanostructure-containing fiber sheet, and
A fourth step of fabricating a real carbon nanostructure mainly composed of the carbon nanostructure by carbonizing or removing the fibers by heating the carbon nanostructure-containing yarn, and in this order;
The fiber is a cellulose fiber, the mixed dispersion is a water-based carbon nanostructure manufacturing method, characterized in that the mixed dispersion. The method of claim 1,
In the third step, the band-shaped carbon nanostructure-containing sheet is passed through a twisting yarn device and stretched to produce the carbon nanostructure-containing yarn. delete The method of claim 1,
The carbon nanostructure-containing sheet is continuously produced by spraying the mixed dispersion onto the mesh member, and the carbon nanostructure-containing sheet is cut to produce the strip-shaped carbon nanostructure-containing sheet, thereby producing a carbon-like structure. Method of making nanostructures. The method according to claim 1 or 2,
The carbon nanostructure-containing sheet, which is formed by coating the mixed dispersion on a substrate, is continuously produced, and the carbon nanostructure-containing sheet is cut to produce the strip-shaped carbon nanostructure-containing sheet. Method for producing a carbon nano structure. The method of claim 1,
In the first step, at least a dispersion of the carbon nanostructure, the fiber and the thickener are mixed to produce a mixed dispersion liquid, characterized in that for producing a carbon nanostructure. The method of claim 1,
In the first step, at least a dispersion of carbon nanostructures and a dispersion of fibers are mixed to produce a mixed dispersion.

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