KR101984720B1 - Carbon nanotube fiber composite and the producing method thereof - Google Patents

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 for forming a coating layer on carbon nanotube fibers to produce high density carbon nanotube fibers without using strong acids and oxidizing agents, Carbon nanotube fiber composite material which can realize high density and high strength of carbon nanotube fiber by forming cross-linking between carbon nanotube fibers and fibers from alcohol-based, thiol-based, or mixed cross-linking agent will be.

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 and 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 a carbon nanotube fiber 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)

DISCLOSURE OF THE INVENTION The inventors of the present invention have conducted various researches to solve the above-mentioned problems of the related art. As a result, the inventors of the present invention have found that when an alcohol-based, thiol- It was confirmed that carbon nanotube fiber composite material capable of forming crosslinking between carbon nanotube fibers was prepared by treating mixed crosslinking agent and that it was possible to manufacture carbon nanotube fiber of high density and high strength without using strong acid and oxidizer, Completed.

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 (meth) acrylic acid-based polymer coating layer formed on the fibrous phase; / RTI >

The plurality of carbon nanotube fibers provide a carbon nanotube fiber composite material that forms cross-linkage between fibers and fibers from alcohol-based, thiol-based, or mixed cross-linking agents that bind on the (meth) acrylic acid-based polymer coating layer.

Further, according to the present invention,

(a) forming a (meth) acrylic acid-based polymer coating layer on a surface of a plurality of carbon nanotube fibers;

(b) coating the coating layer with an alcoholic, thiol, or mixed crosslinking agent solution thereof; 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, And the reaction time is also remarkably reduced, so that the troublesomeness of the strong acid treatment used is not followed and the efficiency and convenience of the entire process are improved.

1 is a longitudinal cross-sectional view (X = O or S) of the 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.

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, the carbon nanotube fiber composite material of the present invention is characterized in that a polymer layer is formed on the surface of individual strands of carbon nanotube fibers packed in a bundle, and an alcohol, thiol, or a mixture thereof To form cross-linking between fibers and fibers from the cross-linking agent. The fiber bundle composed of the crosslinked carbon nanotube fibers as described above 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 "alcohol-based crosslinking agent" or "thiol crosslinking agent" refers to a crosslinking agent having two or more hydroxyl groups (hydroxyl group, OH-) or thiol group (SH-) Refers to a material having 2 to 6 carbon atoms capable of reacting with a carboxyl group (-COOH) in poly (meth) acrylic acid to form crosslinks in the fibers and between fibers of the 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. In the compounds represented by a crosslinking agent, X represents O or S. FIG. 1, the crosslinking agent is shown in the form of an alkane diol or an alkane thiol (n = 1 to 10) in order to facilitate understanding, but the present invention is not limited thereto.

1, the carbon nanotube fiber composite material 100 of the present invention includes carbon nanotube fibers 10, a (meth) acrylic acid polymer coating layer 20 formed on the fiber surface, and a (meth) acrylic acid polymer coating layer And / or thiol-based crosslinking agent (30) bonded to the (meth) acrylic acid-based polymer coating layer, wherein the alcohol-based and / or thiol- .

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 (meth) acrylic acid-based polymer coating layer 20 is composed of one kind selected from the group consisting of polyacrylic acid, methacrylic acid / acrylic acid copolymer, and combinations thereof. These polymers all have a carboxyl group (-COOH) and can react with the functional groups of the crosslinking agent to form an ester bond and / or a thiosether bond for crosslinking.

The thickness of the (meth) acrylic acid polymer layer 20 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 the (meth) acrylic acid-based polymer to be coated is too small to provide a base material for crosslinking formation. When the thickness is above the range, the coating layer is too thick to reduce the physical properties of the carbon nanotube fiber And the like.

As the cross-linking agent (30), a cross-linking agent comprising an alcohol-based cross-linking agent, a thiol-based cross-linking agent, or a mixture thereof is used.

When the alcohol-based crosslinking agent has at least two hydroxyl groups, it can form a bridge between the carbon nanotube fibers 10. However, when the hydroxyl group in the molecular structure is excessively large, the size of the molecule itself becomes large, (OH-) in the molecular structure, because it becomes difficult to locate between the hydroxyl groups (10). The alcohol-based crosslinking agent of the present invention is represented by an alkanediol (preferably an alkylene glycol, n = 1 to 10) in FIG. 1, but if it has a structure capable of being positioned between the carbon nanotube fibers 10, The kind of the crosslinking agent is not necessarily limited to a compound or a diol having an alkane as its parent. However, in this case, if the molecular structure is excessively large, the carbon nanotube fibers 10 are located between the carbon nanotube fibers 10 and it is difficult to form the crosslinking. Therefore, the carbon nanotube fibers can be limited to materials having 1 to 10 carbon atoms. Specifically, the alcohol-based crosslinking agent usable in the present invention is preferably an alkane diol having 1 to 10 carbon atoms (preferably an alkylene glycol), a dialkylene glycol, a trialkylene glycol, a diphenol, and a combination thereof Can be used. More preferably, one selected from the group consisting of ethylene glycol, propylene glycol, butylene glycol, pentylene glycol, hexylene glycol, diethylene glycol, dipropylene glycol, triethylene glycol, diphenol and combinations thereof is used .

When the thiol crosslinking agent has at least two or more thiol groups, it can bond to both carbon nanotube fibers 10 to form crosslinking. However, when the thiol group in the molecular structure is excessively large, the size of the molecule itself becomes large, It is preferable to include 2 to 6 thiol groups (SH &lt; - &gt;) in the molecular structure because they are difficult to locate between nanotube fibers 10. The thiol crosslinking agent of the present invention is represented by an alkane dithiol (n = 1 to 10) in FIG. 1, but it should be limited only to a compound containing an alkane as a parent in the structure capable of being positioned between the carbon nanotube fibers It is not. However, when the molecular structure is excessively large, the carbon nanotube fibers 10 are located between the carbon nanotube fibers 10 and it is difficult to form the crosslinking. Therefore, the carbon nanotube fibers 10 can be limited to a material having 1 to 10 carbon atoms in the molecular structure. Specifically, as the thiol type crosslinking agent usable in the present invention, one selected from the group consisting of alkanedithiol, alkanetricol, dithiophenol and combinations thereof having 1 to 10 carbon atoms can be used. More preferably 1,2-ethanedithiol, 1,1-propanedithiol, 1,2-propanedithiol, 1,3-propanedithiol, 2,2- , 5-hexanedithiol, 1,6-hexanedithiol, 2,9-decanedithiol, 1,8-octanedithiol, 1,2,3-propanetrythiol, 1,4- Dithiophenol, and a combination of these may be used.

The (meth) acrylic acid-based polymer coating layer 20 and the alcohol-based, thiol-based, or mixed crosslinking agent 30 bonded thereto form a cross-link in the carbon nanotube fibers 10 and between the fibers.

Specifically, the crosslinking corresponds to an ester bond and / or a thioester bond. When the hydroxyl group (OH-) of the alcohol-based crosslinking agent reacts with the carboxyl group (COOH-) of the (meth) acrylic acid-based polymer, the ester bond or the thiol group (SH-) of the thiol- . Therefore, when the cross-linking agents are used in combination, an ester bond and a thioester bond may coexist in the carbon nanotube fiber composite material.

For the sake of clarity, as an example of the crosslinked structure, a structure in which crosslinking in a fiber (coating layer) is formed with a diethylene glycol on a polymethacrylic acid coating layer is shown in the following Chemical Formula 1, The cross-linked structure of the liver (coating layer) is shown in the following formula (2) (indicating cross-linking site).

The carbon nanotube fiber composite material 100 according to the present invention, which forms cross-linkages between fibers and fibers as shown in the above-described Formulas (1) and (2), can effectively reduce the slip between the fiber strands in the bundle due to its structural characteristics, . When the distance between the individual fibers is narrowed, the mutual attractive force between the fibers, such as the pi-pie bonding force existing between the carbon nanotube fibers, increases, and the bonding force provided from the crosslinking itself is added to improve the strength of the entire fiber bundle do.

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

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

(a) forming a (meth) acrylic acid-based polymer coating layer on a surface of a plurality of carbon nanotube fibers;

(b) coating the coating layer with an alcoholic, thiol, or mixed crosslinking agent solution thereof; And

(c) performing a crosslinking reaction; and

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), the (meth) acrylic acid polymer is uniformly coated on the surface of the carbon nanotube fibers 10 to form the (meth) acrylic acid polymer layer 20. Specifically, the (meth) acrylic acid-based polymer layer 20 is formed by providing a coating solution containing a monomer and an initiator or a coating solution containing poly (meth) acrylic acid on the surface of the carbon nanotube fibers 10 Followed by heat treatment.

The monomer may be acrylic acid, methacrylic acid, or a mixture thereof. Since the added monomer is polymerized in the form of a polymer, such as poly (meth) acrylic acid, and then acts as a substrate for the crosslinking reaction, It is used with initiators for polymerization.

The initiator may be a thermoinitiator and / or a photoinitiator depending on the polymerization method. Preferably, the initiator is selected from the group consisting of potassium persulfate (KPS), benzoyl peroxide (BPO), benzoin Benzoin methyl ether (BME), 2,2-dimethoxy-2-phenylacetophenone, and combinations thereof. Species can be used.

The above-mentioned monomer or polymer may be formed into a coating solution in the form of a diluted solution or the like in a conventional organic solvent.

As a method of providing the coating solution of this step, a spraying or an immersion process is all possible, but preferably an immersion process can be performed. The impregnation time in accordance with the immersion process may vary depending on the specific process conditions, and is not necessarily limited to any specific range, but may be 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.

After sufficiently impregnating the carbon nanotube fibers with the coating solution, the polymer nanofibers are removed from the coating solution to remove excess solvent and then heated to form a (meth) acrylic acid polymer coating layer. In the case of using a monomer and a thermal initiator, the monomer is polymerized in the form of poly (meth) acrylic acid during the heating process, and the polymer is evenly penetrated to the inner surface of the bundle of the carbon nanotube fiber composite material. If a photoinitiator is used instead of, or in addition to, a thermal initiator as an initiator, it may further include irradiating ultraviolet (UV) light for polymer polymerization. During the heating process, additional residual solvent may be further removed, and a vacuum oven or the like may be used as needed.

The heating is preferably performed at a temperature ranging from 150 to 250 ° C. Below the above-mentioned temperature range, it is difficult to obtain a uniform coating effect of the poly (meth) acrylic acid on the carbon nanotube fibers and a polymerization reaction in the case of containing the monomers. When the ratio exceeds the above range, thermal decomposition or vaporization of poly (meth) Side reactions may occur. Most preferably, this step can be carried out at a temperature of around 200 ° C.

The heating time may vary depending on specific process conditions, and is not particularly limited. When the heating time is too short, poly (meth) acrylic acid penetrates into the bundles of carbon nanotube fibers and is hardly uniformly coated. The polymerization rate thereof may also be lowered, and if the heating time is too long, a meaningless process may be continued and be uneconomical. Therefore, in order to sufficiently express the effect of the present invention and to perform an efficient process, it may be heated to preferably 30 to 12 hours, more preferably about 1 hour.

Next, the step (b) is a step of coating an alcohol-based, thiol-based or mixed crosslinking agent (30) solution on the (meth) acrylic acid-based polymer coating layer 20 coated on the carbon nanotube fibers 10 . However, the crosslinking agent coating in the step (b) is a meaning distinct from the poly (meth) acrylic acid coating in the above-mentioned step (a) in a concrete sense. That is, the coating in this step has a meaning as a material treatment for forming a bridge, not for forming an independent coating layer on each carbon nanotube fiber.

The coating can be carried out both by a spraying or an immersion process, but preferably by an immersion process.

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 crosslinking agent impregnated is in the range of 0.1: 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 crosslinks in the carbon nanotube fibers and between the fibers through the reaction of the poly (meth) acrylic acid with the crosslinking agent.

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

Particularly, in the case of heat treatment, if the impregnation coating method is used in the step (b), it is preferable to take out the carbon nanotube fibers 10 from the coating solution to remove excess solvent and then heat the coating solution. You can also remove more. At this time, a vacuum oven or the like may be used as needed.

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 cross-linking reaction is not sufficiently exhibited, and if exceeded, problems such as pyrolysis, vaporization, and side reaction of the (meth) acrylic acid polymer and the crosslinking agent may occur. Most preferably at a temperature of about 200 &lt; 0 &gt; C or less.

The heating time may vary depending on the specific process conditions and is not limited to a specific range. However, if the heating time is too short, the crosslinking reaction efficiency may be deteriorated. If the heating time is excessively long, In order to exhibit a sufficient effect of the present invention and to perform an efficient process, it may be heated to preferably 30 minutes to 12 hours, more preferably about 1 hour.

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 of polymethacrylic acid

The carbon nanotube fibers produced in the manufacturing process of the above production example were sufficiently impregnated in a polymethacrylic acid solution (25% aqueous solution) for 2 hours, and then taken out to remove excess polymethacrylic acid solution, followed by heating at 100 ° C for 1 hour Thereby forming a polymethacrylic acid coating layer.

2. Impregnation and cross-linking reaction of diethylene glycol

The carbon nanotube fibers impregnated with the polymethacrylic acid were impregnated in a diethylene glycol solution for 2 hours and then taken out to remove an excess amount of a diethylene glycol solution and then heated at 200 ° C for 1 hour to perform a crosslinking reaction Carbon nanotube fiber composite material.

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

In Experimental Example 1, surfaces of carbon nanotube fiber bundles prepared according to the above Preparation Examples and Examples were compared and observed using a scanning electron microscope.

Observation results of the surface of the bundle of the carbon nanotube fiber prepared according to the above Preparation Example are shown in FIG. 2, and the observation of the surface of the bundle of the carbon nanotube fiber composite of the present invention (with coating layer and crosslinking) The results are shown in Fig.

As a result of the observation, as shown in FIG. 2, the bundles of the coating layer and the fibers having no cross-linking were large and distinct in the fiber strands in the bundle, while the coating layer and the cross- It was confirmed that the bundle made of the fiber composite material having the bond had a high density without any gap between the fibers in the bundle.

< Experimental Example  2>

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 the carbon nanotube fiber composite material of the present invention has a polymethacrylic acid coating layer and a diethylene glycol crosslinked by ester bonding thereof.

< Experimental Example  3>

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 4.28 Manufacturing example Pristine 2.27

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 twice as much as that of the production example having no coating layer.

100: Carbon nanotube fiber composite material
10: Carbon nanotube fiber
20: (meth) acrylic acid-based polymer coating layer
30: Alcohol-based or thiol-based cross-linking agent

Claims (14)

A plurality of carbon nanotube fibers; And
(Meth) acrylic acid-based (meth) acrylic acid copolymer formed by one kind selected from the group consisting of polymethacrylic acid, polyacrylic acid, methacrylic acid / acrylic acid copolymer, A polymer coating layer; / RTI &gt;
Wherein the plurality of carbon nanotube fibers are selected from the group consisting of alkane dithiol having 1 to 10 carbon atoms, propanetriethol, dithiophenol, and combinations thereof, which are bonded on the (meth) acrylic acid polymer coating layer. A carbon nanotube fiber composite material which forms a cross-link between fibers and fibers by a thiol-based cross-linking agent of the species.
The method according to claim 1,
Wherein the diameter of the carbon nanotube fibers is 1 to 100 mu m.
delete The method according to claim 1,
Wherein the thickness of the (meth) acrylic acid polymer coating layer is 0.1 to 0.2 times the diameter of the carbon nanotube fiber.
delete delete delete delete (a) forming on a surface of a plurality of carbon nanotube fibers a (meth) acrylic acid-based polymer coating layer formed of one selected from the group consisting of polymethacrylic acid, polyacrylic acid, methacrylic acid / acrylic acid copolymer, ;
(b) coating one or more thiol-based crosslinking agent solutions selected from the group consisting of alkanedithiol, propanetriethol, dithiophenol and combinations thereof having 1 to 10 carbon atoms on the coating layer; And
(c) performing a crosslinking reaction
A method for producing a carbon nanotube fiber composite material.
10. The method of claim 9,
The (meth) acrylic acid-based polymer coating layer includes a coating solution containing a monomer and an initiator, or one selected from the group consisting of polymethacrylic acid, polyacrylic acid, methacrylic acid / acrylic acid copolymer, and combinations thereof Wherein the coating solution is coated on the surface of the carbon nanotube fiber and then heat-treated to form the coating solution.
11. The method of claim 10,
Wherein the monomer is one selected from the group consisting of acrylic acid, methacrylic acid, and combinations thereof.
11. The method of claim 10,
Wherein the heat treatment is performed at a temperature of 50 to 150 占 폚.
11. The method according to claim 9 or 10,
Wherein the coating is carried out by spraying or dipping. &Lt; RTI ID = 0.0 &gt; 21. &lt; / RTI &gt;
10. The method of claim 9,
Wherein the cross-linking reaction is performed by heat treatment at 150 to 250 ° C or irradiation of ultraviolet rays.

Images