KR20170067437A - Carbon nanotube fiber composite and the producing method thereof - Google Patents

Carbon nanotube fiber composite and the producing method thereof Download PDF

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KR20170067437A
KR20170067437A KR1020150174115A KR20150174115A KR20170067437A KR 20170067437 A KR20170067437 A KR 20170067437A KR 1020150174115 A KR1020150174115 A KR 1020150174115A KR 20150174115 A KR20150174115 A KR 20150174115A KR 20170067437 A KR20170067437 A KR 20170067437A
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carbon nanotube
polyaniline
coating layer
fibers
fiber composite
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KR102006719B1 (en
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남현
오유진
이영호
공명진
송동수
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주식회사 엘지화학
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    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
    • D01F9/08—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material
    • D01F9/12—Carbon filaments; Apparatus specially adapted for the manufacture thereof
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06B—TREATING TEXTILE MATERIALS USING LIQUIDS, GASES OR VAPOURS
    • D06B1/00—Applying liquids, gases or vapours onto textile materials to effect treatment, e.g. washing, dyeing, bleaching, sizing or impregnating
    • D06B1/02—Applying liquids, gases or vapours onto textile materials to effect treatment, e.g. washing, dyeing, bleaching, sizing or impregnating by spraying or projecting
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06B—TREATING TEXTILE MATERIALS USING LIQUIDS, GASES OR VAPOURS
    • D06B15/00—Removing liquids, gases or vapours from textile materials in association with treatment of the materials by liquids, gases or vapours
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06B—TREATING TEXTILE MATERIALS USING LIQUIDS, GASES OR VAPOURS
    • D06B3/00—Passing of textile materials through liquids, gases or vapours to effect treatment, e.g. washing, dyeing, bleaching, sizing, impregnating
    • D06B3/04—Passing of textile materials through liquids, gases or vapours to effect treatment, e.g. washing, dyeing, bleaching, sizing, impregnating of yarns, threads or filaments
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06C—FINISHING, DRESSING, TENTERING OR STRETCHING TEXTILE FABRICS
    • D06C7/00—Heating or cooling textile fabrics
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    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/244—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing sulfur or phosphorus
    • D06M13/248—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing sulfur or phosphorus with compounds containing sulfur
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
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    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
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    • D06M17/00—Producing multi-layer textile fabrics
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
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    • D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
    • D06M2101/40—Fibres of carbon
    • D—TEXTILES; PAPER
    • D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B2401/00—Physical properties
    • D10B2401/06—Load-responsive characteristics
    • D10B2401/063—Load-responsive characteristics high strength

Abstract

The present invention relates to a carbon nanotube fiber composite material and a method of manufacturing the carbon nanotube fiber composite material. More particularly, the present invention relates to a carbon nanotube fiber composite material which is obtained by forming a coating layer on carbon nanotube fibers to produce high density carbon nanotube fibers without using strong acids and oxidizing agents, To a carbon nanotube fiber composite material capable of realizing high density and high strength of carbon nanotube fibers by forming crosslinking between carbon nanotube fibers from a bonding thiol crosslinking agent and a method for producing the same.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a carbon nanotube fiber composite material,

The present invention relates to a carbon nanotube fiber composite material capable of realizing high density and high strength of a fiber by including a coating layer formed on the surface of the carbon nanotube fiber and a crosslinking agent for forming a crosslinking between the fibers by bonding thereto.

Carbon nanotubes are fine molecules with a diameter of 1 nm, which are formed by long carbon chains connected by hexagonal rings. Specifically, a honeycomb-like carbon plane in which three carbon atoms are combined is a cylindrical carbon crystal having a tube shape of 0.5 to 10 nm in diameter, which has high tensile strength and electrical conductivity and is attracting attention as a next-generation high-tech material.

Carbon nanotubes can be utilized as various types of materials. In particular, when carbon nanotubes are agglomerated and processed into a fiber form, it is possible to manufacture nanofibers which are excellent in electrical conductivity and thermal conductivity, such as super strong fibers that can not be broken, highly durable fibers that can withstand heat and friction, It is thought to be endless. Currently, carbon nanotube fibers are used in high-precision industrial fields such as semiconductors and displays in the form of antistatic fibers and low-hardness, high-capacity fibers, and their productivity is remarkably increased.

These carbon nanotube fibers undergo further processing before they are commercialized so as to have appropriate strength and physical properties. In particular, when direct spinning (direct spinning), which is one of common manufacturing methods in the production of carbon nanotube fibers, is used, a large amount of carbon nanotube fibers can be produced as compared with other methods, It is generally difficult to produce fibers of the above-mentioned type.

One of the methods that have been used conventionally is to chemically introduce a functional group onto the surface of carbon nanotube fibers using a strong acid, Chemical bonding. However, the above method can improve the strength of the carbon nanotube fibers. However, due to the use of a strong acid or an oxidizing agent, defects are formed on the fiber surface during the treatment, . Further, the reaction time is long and a high temperature condition is required for reflux of strong acid, etc., and there is a disadvantage that after the reaction, there is a problem of disposal of used strong acid.

Therefore, there has been a need for an improved method of manufacturing a carbon nanotube fiber capable of imparting excellent strength to carbon nanotube fibers without using a strong acid and an oxidizing agent.

A method for post-treatment of carbon nanotube fibers to improve mechanical strength (Korean Patent No. 10-1415255)

The inventors of the present invention conducted various studies in order to solve the above-mentioned conventional problems. As a result, it has been found that by coating the polyaniline layer on the surface of the carbon nanotube fibers and treating the thiol crosslinking agent bonded thereto, The carbon nanotube fiber composite material of the present invention was produced and it was confirmed that carbon nanotube fiber of high density and high strength can be produced without using strong acid and oxidizer.

Accordingly, an object of the present invention is to provide a carbon nanotube fiber composite material which is stable and has high density and high strength.

It is still another object of the present invention to provide a method for producing a carbon nanotube fiber composite material in which process efficiency and convenience are improved without using a strong acid and an oxidizing agent.

According to an aspect of the present invention,

A plurality of carbon nanotube fibers; And

A polyaniline coating layer formed on the fibrous phase; / RTI >

Wherein the plurality of carbon nanotube fibers form a crosslinking between fibers with a thiol-based crosslinking agent that binds on the polyaniline coating layer.

Further, according to the present invention,

(a) forming a polyaniline coating layer on a surface of a plurality of carbon nanotube fibers;

(b) coating a thiol based crosslinking agent solution on the coating layer; And

(c) performing a crosslinking reaction

And a method of producing the carbon nanotube fiber composite material.

Through the above-mentioned object, the carbon nanotube fiber composite material of the present invention is integrated at a high density and is stable and has high strength.

Further, according to the method for producing a carbon nanotube fiber composite material of the present invention, it is possible to modify the carbon nanotube fiber without causing a defect in the surface of the carbon nanotube fiber without using a strong acid and an oxidizing agent, Conditions are not required, the reaction time is significantly reduced, and the difficulty of the strong acid treatment used is not followed, thereby improving the efficiency and convenience of the entire process.

1 is a longitudinal sectional view of a carbon nanotube fiber composite material of the present invention.
FIG. 2 is a photograph of a bundle surface of a carbon nanotube fiber having no coating layer and no crosslinking by a scanning electron microscope. FIG.
3 is a scanning electron microscope (SEM) photograph of the bundle surface of the carbon nanotube fiber having the coating layer and the crosslinking according to the present invention.
4 is an image of IR data analysis result of the carbon nanotube fiber composite according to the present invention.

In the present invention, a carbon nanotube fiber composite material excellent in strength and a manufacturing method capable of manufacturing the carbon nanotube fiber composite material without using a strong acid and an oxidizing agent are proposed. Specifically, in the carbon nanotube fiber composite material of the present invention, a polymer layer is formed on the surface of individual strands of the bundled carbon nanotube fibers and is crosslinked from a thiol crosslinking agent bonded on each of the polymer layers. From this, the fiber bundle composed of the carbon nanotube fibers crosslinked with each other realizes high density and high strength.

As used herein, the term 'carbon nanotube fiber composite material' means a fiber unit composed of two or more carbon nanotube fiber strands capable of forming a bridge. Since the carbon nanotube fiber is used by bundling several strands of fibers in a commercial application, the 'carbon nanotube fiber composite material' itself becomes a single bundle-type fiber or a constituent part thereof .

The term "thiol crosslinking agent" refers to a crosslinking agent having two or more, preferably two to six, thiol groups (SH-) for crosslinking in a molecular structure and having a double bond (N = pH) Quot; means a substance capable of reacting with carbon nanotube fibers to form a bridge between carbon nanotube fibers.

Hereinafter, the contents of the present invention will be described in more detail. It is to be understood, however, that the scope of the present invention is not limited thereto and that the present invention covers all of the equivalent scope of the following description.

<Carbon nanotube fiber composite material>

The carbon nanotube fiber composite material of the present invention will be described in detail with reference to FIG.

FIG. 1 is a longitudinal cross-sectional view showing the structure of a carbon nanotube fiber composite material according to the present invention. The thiol based compound is represented by, for example, an alkane dithiol (n = 1 to 10) It is not.

1, a carbon nanotube fiber composite material 100 according to the present invention includes a carbon nanotube fiber 100, a polyaniline coating layer 20 formed on the fiber surface, and a thiol crosslinker (not shown) bonded on the polyaniline coating layer 20 30), and the thiol-based crosslinking agent bonded to the polyaniline coating layer forms a crosslinking between the carbon nanotube fibers.

The constitution of the carbon nanotube fiber composite material 100 of the present invention will be described in more detail as follows.

The carbon nanotube fibers 10 are not particularly limited in the present invention and may have various diameters and lengths depending on the use thereof. For example, the diameter may be 1 to 100 μm, and the specific diameter and length may be controlled by the apparatus used in the fabrication process of the fiber.

The polyaniline constituting the polyaniline coating layer 10 has a structure in which the quinoid diamine (-N = Ph = N- (a)) and the benzenoid diamine (benzenoid diamine, -NH-Ph-NH-, (b)). The constituent ratio varies depending on the oxidation state.

Figure pat00001

The term "emeraldine" refers to the fully oxidized polyaniline as pernigraniline, the fully-reduced polyaniline as leucoemeraldine, and the half-oxidized polyaniline as half-oxidized , Fenigraniline, x = 0, y = 1, luco emeraldine, and x = y = 0.5 in the following formula (1) (Macromolecules, 1994, 27, 518-525) . That is, fenigranalin corresponds to a structure having only quinoid diamine, luco emeraldine has benzenoid diamine only, and emeraldine has quinid diamine and benzenoid diamine in half.

The polyaniline constituting the polyaniline coating layer 10 of the present invention should have a structure containing a quinoid diamine (-N = Ph = N-) in order to react with the crosslinking agent to form a bond, for example, Polyaniline, or a mixture thereof may be used. The larger the degree of oxidation, the more quinoid diamine sites are included, which can provide a lot of crosslinking sites.

The thickness of the polyaniline coating layer 10 is preferably 0.1 to 0.2 times the diameter of the carbon nanotube fiber. When the thickness is less than the above range, the amount of polyaniline to be coated is too small to provide a base material for crosslinking formation. When the thickness exceeds the above range, the coating layer becomes excessively thick, thereby causing a problem such as reduction of physical properties of the carbon nanotube fiber It is because.

As the thiol crosslinking agent 30, an alkanedithiol (n = 1 to 10) is shown as an example in FIG. 1, but in a structure capable of being positioned between the carbon nanotube fibers 10, And it is not necessarily limited to dithiol. Specifically, a thiol compound containing 2 to 6 thiol groups (-SH) in a molecular structure is possible. When having at least two or more thiol groups, it can bond to both carbon nanotube fibers 10 to form a crosslink , And when the number of thiol groups in the molecular structure is excessively increased to 6 or more, the size of the molecule itself becomes so large that it is difficult to locate between the carbon nanotube fibers 10.

As the thiol crosslinking agent (30) of the present invention, dithiol, tithiol, tetrasiol or the like can be preferably used, and more preferably 1,2-ethanedithiol, 1,1- 1,2-propanedithiol, 1,3-propanedithiol, 2,2-propanedithiol, 2,5-hexanedithiol, 1,6-hexanedithiol, 2,9- 1,3-propanetriol, decanedithiol, decanedithiol, 1,2,3-propanetrythiol, 1,8-octanedithiol, 1,4-dithiophenol, and combinations thereof .

The polyaniline coating layer 20 described above and the thiol crosslinking agent 30 bonded thereto form a crosslinking bond between the carbon nanotube fibers 10.

Specifically, the crosslinking is formed by reacting a thiol group in the structure of the thiol-based crosslinker with respect to the quinoid moiety in the polyaniline molecular structure.

As an example of the crosslinked structure of the carbon nanotube fibers 100 of the present invention, a polyaniline coating layer crosslinked with 1,3-propanedisthiol is shown in the following formula (2) (indicating a crosslinking site) .

Figure pat00002

The carbon nanotube fiber composite material 100 according to the present invention, which forms the crosslinking on the polyaniline coating layer of different carbon nanotube fibers as shown in Formula 2, is structurally characterized by effectively reducing the slip between the fiber strands in the fiber bundle, Thereby making it possible to achieve a higher density. Accordingly, when the distance between the individual fiber strands is narrowed, the mutual attractive force, for example, the pi-pie bonding force existing between the carbon nanotube fibers is increased, and the bonding force provided by the crosslinking itself is added to improve the strength of the entire fiber bundle.

&Lt; Production method of carbon nanotube fiber composite material >

On the other hand, in the carbon nanotube composite material described above,

(a) forming a polyaniline coating layer on a surface of a plurality of carbon nanotube fibers;

(b) coating a thiol based crosslinking agent solution on the coating layer; And

(c) performing a crosslinking reaction

Can be produced through a method for producing a carbon nanotube fiber composite material.

At this time, among carbon nanotube fibers of the step (a) of the present invention, those prepared through direct spinning (direct spinning) are most preferably used. Direct spinning is one of the dry manufacturing methods of carbon nanotube fibers. It is a method of producing carbon nanotubes in a furnace by injecting a liquid carbon source and a catalyst together with a carrier gas into an upper injection port by vertically erected high temperature heating. And carbon nanotube aggregates, which have been brought down to the lower end of the heating furnace together with carrier gas, can be obtained by wind-up in or out of a heating furnace.

Hereinafter, the above production method will be described in more detail.

In the step (a), polyaniline is uniformly coated on the surfaces of the plurality of carbon nanotube fibers 10 to form a polyaniline coating layer 20. [ Specifically, the polyaniline coating layer 20 may be formed by providing a coating solution containing polyaniline on the surface of the carbon nanotube fibers 10, followed by heat treatment.

As the solvent for dissolving the polyaniline, N-methyl-2-pyrrolidone (NMP), dimethyl sulfoxide (DMSO), N, N-dimethylformamide N, N-dimethylformamide, DMF), and N, N-dimethylacetamide (DMAC).

As a method of coating the polyaniline solution, a spraying or an immersion process is possible, but preferably an immersion process can be carried out. The impregnation time in accordance with the immersion process may be changed depending on specific process conditions, and therefore, it is not limited to any specific range, but is preferably 30 minutes to 12 hours. Below this time range, a sufficient impregnation effect is hard to appear, and if the above range is exceeded, the difference in impregnation effect is not large and it is uneconomical. When considering both the efficiency of the process and the rate of impregnation, it is usually most preferable to impregnate it to about 2 hours or less.

After sufficiently impregnating the carbon nanotube fibers 10 with respect to the polyaniline solution, the carbon nanotube fibers 10 are taken out to remove excess solvent and heated so that the polyaniline is uniformly penetrated into the bundles of the plurality of carbon nanotube fibers bundled together So that it is firmly attached to its surface. During the heating process, the excess solvent may be further removed. In this case, a vacuum oven or the like may be used as needed.

The heating temperature in this step is preferably 50 to 150 占 폚. If the temperature is lower than the above-mentioned range, the uniform impregnation effect of the polyaniline on the carbon nanotube fibers is not sufficiently exhibited, and if it exceeds the above range, pyrolysis of the polyaniline, vaporization or other side reaction may occur. Most preferably, the heating temperature can be about 100 캜 or less.

The heating time may vary depending on the specific process conditions, so that it is not particularly limited. However, if the heating time is too short, the penetration of polyaniline into the carbon nanotube fiber bundle and the uniform adsorption on the surface can be reduced, In this case, the meaningless process can be continued and uneconomical. Therefore, it is preferably heated for about 30 minutes to 12 hours, and more preferably for about 1 hour for the sufficient effect of the present invention and efficient process execution.

Next, (b) is a step of coating a solution of a thiol crosslinking agent (30) on the polyaniline coating layer (20) coated on the carbon nanotube fibers (10). It should be noted that the crosslinking agent coating in the step (b) is a meaning distinct from the polyaniline coating in the step (a) described above in a concrete sense. That is, the coating in this step has a meaning as a material treatment for forming a bridge between carbon nanotube fibers, not for forming an independent coating layer on each carbon nanotube fiber.

As a method of providing the coating solution, a spraying or an immersion process is possible, but preferably an immersion process can be performed.

In the immersion step, the impregnation time may vary depending on the specific process conditions, and therefore, the impregnation time is not limited to any specific range, but is preferably 30 minutes to 12 hours. Below this time range, a sufficient impregnation effect is hard to appear, and if the above range is exceeded, the difference in impregnation effect is not large and it is uneconomical. Considering both the efficiency of the process and the rate of impregnation, it is most preferable to impregnate it to about 2 hours or less.

The total content of the thiol crosslinking agent is in the range of 1: 0.1 to 1: 1 by weight with the carbon nanotube fibers.

If the content of the crosslinking agent is less than the above range, the crosslinking effect is reduced. If the amount is more than the above range, side reactions may occur and the physical properties of the carbon nanotube fibers may be deteriorated.

Next, the step (c) is a step of forming a crosslinking between the carbon nanotube fibers through the reaction of the polyaniline and the thiol crosslinking agent.

The crosslinking reaction may be performed by heat treatment at 150 to 250 ° C or by irradiating ultraviolet rays. The crosslinking method may vary depending on the kind of the specific crosslinking material.

If the crosslinking agent coating solution is coated by impregnating the carbon nanotube fibers 10 in the step (b), the carbon nanotube fibers 10 are removed from the coating solution to remove excess solvent and then heated It is also possible to further remove excess solvent during the heating process. At this time, if necessary, a vacuum oven or the like may be used.

The heating temperature for the heat treatment in this step is preferably 150 to 250 ° C. If the temperature is lower than the above range, the crosslinking reaction is not sufficiently exhibited, and if it exceeds the above range, pyrolysis, vaporization, side reaction or the like of the polyaniline and / or thiol crosslinking agent may occur. Most preferably, this step can be carried out at a temperature of around 200 ° C.

The heating time may vary depending on the specific process conditions, and is not limited to any specific range. If the heating time is too short, the crosslinking reaction efficiency may deteriorate. If the heating time is excessively long, It can be heated to preferably about 30 minutes to 12 hours, more preferably about 2 hours, in order to exhibit a sufficient effect of the invention and to perform an efficient process.

The method of manufacturing the carbon nanotube fiber composite material 100 of the present invention described above is characterized by using no strong acid and no oxidizing agent. Accordingly, defects are formed on the surface of the carbon nanotube fibers during the manufacturing process, other excellent physical properties of the carbon nanotube fibers are not deteriorated, and low temperature conditions and short process times can be secured compared with the conventional methods, .

The carbon nanotube fiber composite material thus manufactured has high density and high strength and can be applied to various fields of clothing, semiconductor, display, sensor, etc. in the form of super strong fiber, high durable fiber, conductive fiber and the like.

Hereinafter, preparation examples, examples and experimental examples are presented to facilitate understanding of the present invention. It is to be understood, however, that the scope of the present invention is not limited thereto.

< Manufacturing example > - direct Spinning  Fabrication of Carbon Nanotube Fibers Used

A spinning solution in which 96.0% by weight of acetone and 4.0% by weight of thiophene were mixed and hydrogen as a carrier gas were prepared. The spinning solution was sublimated at 80 ml / hr, carrier gas at 2 L / min, catalytic precursor ferrocene at 80 ° C, and fed to a vertical cylindrical reactor heated to a temperature of 1,200 ° C at a rate of 0.015 L / Lt; / RTI &gt; Thereafter, the carbon nanotube fibers discharged to the discharge port at the lower end of the reactor were wound by a winding means composed of a bobbin and recovered.

 < Example > - Introduction of coating layer and crosslinking reaction

1. Impregnation with polyaniline

0.50 g of polyaniline (emeraldine state, molecular weight: 15,000) was stirred for 1 hour in 20.0 g of N-methyl-2-pyrrolidone. The polyaniline solution dissolved in NMP became dark green and the carbon nanotube fibers produced in the manufacturing process of the above example were impregnated into this solution for 2 hours. In this process, the polyaniline solution penetrated into the carbon nanotube fibers to be impregnated. After sufficient impregnation, the carbon nanotube fibers were taken out from the solution to remove excess polyaniline solution and then heated at 100 ° C for 1 hour.

2. Thiol crosslinking agent impregnation and crosslinking reaction

The polyaniline-impregnated carbon nanotube fibers were impregnated with 1,3-propanedithiol for 2 hours, heated at 200 ° C for 2 hours and heated to effect crosslinking reaction.

< Experimental Example  1> - Observation of surface of carbon bundle fiber bundle

The surface of the carbon nanotube fiber bundle prepared according to the above Preparation Example and Example 1 was compared and observed using a scanning electron microscope (20 um).

The results of observation of the bundle surface of the carbon nanotube fibers produced according to the above Preparation Example are shown in FIG. 2, and the results of observation of the bundle surface of the carbon nanotube fiber composite material prepared according to the above Examples are shown in FIG.

As a result of the above observation, as shown in FIG. 2, the bundles formed by the carbon nanotube fibers having no coating layer and no crosslinking are large and distinct in the fiber strands in the bundle, whereas, as shown in FIG. 3, It was confirmed that the bundle composed of the carbon nanotube fiber composite materials having the coating layer and the crosslinked structure was formed at a high density without any gap between the fibers in the bundle.

< Experimental Example  2> - Analysis of IR data on carbon nanotube fiber composites

In the Experimental Example 2, the carbon nanotube fiber composite according to the present invention was subjected to IR analysis to confirm the final structure. The IR data is shown in FIG.

Referring to the IR data of FIG. 4, it can be confirmed that a polyaniline coating layer and a thiol crosslinking agent for crosslinking the same are present on the carbon nanotube fiber composite material of the present invention.

< Experimental Example 3> - Carbon  Measurement of fracture strength of nanotube fiber composites

In Experimental Example 3, in order to measure the fracture strength of the carbon nanotube fiber composite material according to the present invention, an Favimum + Fiber Tester of Textechno was used. The gripping distance of the specimen was set at 20 mm and gripped at a rate of 2 mm / min in the tensile direction The fracture strength was measured until the fracture occurred.

The measurement results of the breaking strength are shown in Table 1 below.

Sample Processing method Breaking Strength ( cN ) Example Crosslinking 3.15 Manufacturing example Pristine 2.17

Referring to Table 1, it can be seen that the breaking strength of the coating layer of the present invention and the carbon nanotube fiber composite material according to the present invention improved about 1.5 times as compared with the case of the production example having no coating layer.

100: Carbon nanotube fiber composite material
10: Carbon nanotube fiber
20: polyaniline coating layer
30: thiol-based crosslinking agent

Claims (11)

A plurality of carbon nanotube fibers; And
A polyaniline coating layer formed on the fibrous phase; / RTI &gt;
Wherein the plurality of carbon nanotube fibers form cross-linking fibers from a thiol based cross-linking agent that binds on the polyaniline coating layer.
The method according to claim 1,
Wherein the diameter of the carbon nanotube fibers is 1 to 100 mu m.
The method according to claim 1,
Wherein the polyaniline coating layer comprises emeraldine or polyaniline in a pernigranaline state.
The method according to claim 1,
Wherein the polyaniline coating layer has a thickness of 0.1 to 0.2 times the diameter of the carbon nanotube fiber.
The method according to claim 1,
Wherein the thiol crosslinking agent comprises 2 to 6 thiol groups (SH-) in the molecular structure.
The method according to claim 1,
The thiol-based crosslinking agent is selected from the group consisting of 1,2-ethanedisthiol, 1,1-propanedisthiol, 1,2-propanedisthiol, 1,3-propanedisthiol, 2,5-hexanedithiol, 1,6-hexanedithiol, 2,9-decanedithiol, 1,2,3-propanetriethiol, 1,8-octanedithiol, 1,4- Dithiophenol, and combinations thereof. The carbon nanotube fiber composite material according to claim 1,
(a) forming a polyaniline coating layer on a surface of a plurality of carbon nanotube fibers;
(b) coating a thiol based crosslinking agent solution on the coating layer; And
(c) performing a crosslinking reaction
A method for producing a carbon nanotube fiber composite material according to claim 1.
8. The method of claim 7,
Wherein the forming of the polyaniline coating layer is performed by coating carbon nanotube fibers with a polyaniline coating solution and then heat treating the carbon nanotube fiber composite.
9. The method according to claim 7 or 8,
Wherein the coating is performed by spraying or dipping. &Lt; RTI ID = 0.0 &gt; 21. &lt; / RTI &gt;
9. The method of claim 8,
Wherein the heat treatment is performed at 50 to 150 ° C.
8. The method of claim 7,
Wherein the cross-linking reaction is performed by heat treatment at 150 to 250 ° C or irradiation of ultraviolet rays.
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