KR101420084B1 - The preparing method of conductive long fiber and the conductive long fiber thereby - Google Patents

Abstract

The present invention relates to a method for manufacturing conductive long fiber and conductive long fiber manufactured thereby. More particularly, the present invention provides a method for manufacturing long fiber, comprising the steps of: manufacturing conductive long fiber by electrospinning a spinning solution including poly(amide-co-imide) and Poly(trimellitic anhydride chloride-co-4,4′-methylenedianiline), which are mixed in a weight ratio of 4.5:5.5 to 5.5:4.5 (step 1); and coating the surface of the long fiber with conductive particles by immersing the long fiber, which has been manufactured in the step 1, sequentially in aqueous solution of polyethyleneglycol (PEG), solution of conductive metal precursors and washing liquid (step 2), wherein step 2 is conducted continuously as the long fiber is moved to a recovery part for recovering long fiber. The method for manufacturing conductive long fiber according to the present invention does not require many devices or much time compared with existing surface treatment by alkali solution for electroless plating or a method using a precious metal catalyst. In addition, the present invention can be applied easily to industrial scenes as a single process for continuously coating can be developed, thus reducing electroless plating time and increasing productivity greatly.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention [0001] The present invention relates to a method for producing a conductive long fiber,

The present invention relates to a process for the production of conductive filaments and to the conductive filaments prepared thereby.

Human beings have steadily developed the textile industry since acquiring the fibers from the natural materials of the first time. Past fibers have been used for limited purposes such as clothing production, but with the development of the chemical industry in the 1940s, artificial synthetic fibers such as nylon have become possible to be used.

Since the 1960s, it has become possible to mass-produce high-strength carbon fibers. The development of these fibers has become the basis for the manufacture of fibers having nano diameters which are required in various fields of industry in recent years. Currently, nanofibers and carbon nanofibers are positioned as advanced technologies in high value-added industries such as composite materials, filters, biomaterials, cosmetics, and military.

In general, nanofibers are microfine fibers having a fiber diameter of 1 to 1,000 nm. Nanofibers can provide various physical and chemical properties that can not be obtained with micron-sized fibers. The nanofiber web has a porous As a separator type material, it can be very usefully used in various fields such as various filters, wound dressing, scaffolds, biochemical inorganic protective clothing, battery membranes for secondary batteries, and nanocomposites.

Meanwhile, since Formhals developed a device for the production of polymer fibers using electrostatic force in 1934, many researchers have applied a variety of electrospinning methods using various polymers to various electrospinning devices to increase the radioactivity and productivity of electrospinning. Are being actively developed and applied.

In recent years, flash fiber spinning, electrospinning, and meltblown spinning have been widely used in the manufacture of nanofibers. However, since flash spinning is highly productive and can be mass-produced, it is dangerous because it requires high pressure. There is a limit. In the case of the electrostatic spinning method, it is effective to narrow the fiber diameter, but the solvent used to dissolve the polymer is unstable, which limits the mass production and lowers the productivity. Meltblown spinning has a higher yield than flash spinning and electrostatic spinning, but has limitations in miniaturizing fiber diameter to the nanometer level.

In order to solve these problems, Korean Patent No. 10-2004-0040692 and Korean Patent No. 2003-0077384 propose a manufacturing method of microfibers in which productivity and yield are improved by compromising melt blown spinning and electrostatic spinning.

However, such conventional electrospinning techniques are intended to increase the productivity, mainly regarding the modification and improvement of the electrospinning device. These techniques have limitations in advancing the radiation efficiency and productivity of electrospinning because they are aimed only at improving the radiation method and the radiation condition by excluding the modification of the polymer material. Therefore, it is expected that if the raw material of polymer is improved and it is applied to commercial production through electrospinning to improve the productivity and increase the radiation efficiency, it will bring about a great synergy effect with improvement of the spinning device. Is known to affect the efficiency of electrospinning.

On the other hand, synthetic fibers such as polyamide fibers and polyethylene terephthalate fibers generally have a problem that static electricity is generated and are liable to be charged. To solve such a problem, techniques for imparting conductivity to fibers have been studied. Conductive fibers are widely used because they can be used in textile products such as carpets to provide antistatic properties. In order to produce highly conductive fibers, Japanese Patent Publication No. 57-25647 discloses that conductive layers are exposed on the surface of fibers A conductive fiber or a metal fiber produced by coating a conductive material on a surface of a fiber or a fiber has been disclosed.

In order to improve the electrical properties of the polymer fibers, many researches using conductive materials such as carbon black, carbon fiber, steel fiber, silver, nickel, copper, and platinum have been conducted In recent years, studies have been made to improve the efficiency of solar cells and super capacitors by using polymer fibers as electrode materials. In addition, there is a continuing need for research for manufacturing nano-sized conductive filament fibers applicable to various fields as described above.

Among the methods for improving electrical properties, the electroless plating method used for coating metal nanoparticles such as silver, nickel, copper, and platinum uses a dip coating method in which a mixed solution of a metal precursor and a reducing agent is used to dope. However, the dip coating method is a method of coating metal nanoparticles by direct reduction of metal nanoparticles by using a mixed solution of a metal precursor and a reducing agent. As a result, the solution used can not be used again, There is a drawback that it is complicated.

Accordingly, the inventors of the present invention have been studying a method of producing conductive filament fibers, and have found that when filamentous fibers are produced using polyamideimide and polytrimellitic anhydride chloride-4,4'-methylenedianiline, By moving long fibers through the recovery section, the conductive long fibers can be manufactured through a continuous process in which polyethylene glycol aqueous solution, conductive metal precursor aqueous solution, reducing solution and washing solution are successively carried, and the time is greatly shortened to facilitate mass production In addition, the present inventors have found that recycling of solutions can solve economic problems and environmental problems, and the present invention has been completed.

It is an object of the present invention to provide a method for producing a conductive filament and a conductive filament prepared by the method.

In order to achieve the above object,

(Poly (amide-co-imide)) and poly (trimellitic anhydride chloride-co-imide) mixed in a weight ratio of 4.5: 5.5 to 5.5: 4.5 and polytrimellitic anhydride-4,4'- 4,4'-methylenedianiline)) to prepare a long fiber (step 1); And

(Step 2) coating the conductive particles on the surface of the long fibers by sequentially carrying the long fibers prepared in step 1 on a polyethylene glycol (PEG) aqueous solution, a conductive metal precursor solution, a reducing solution and a washing solution And the step (2) is carried out continuously by moving the long fibers to the collecting part for collecting the long fibers.

In addition, the present invention provides a conductive long fiber produced by the above-mentioned production method.

Further, the present invention provides an electrode comprising the above conductive long fibers.

The method of producing conductive filament according to the present invention is a convenient method that does not require much equipment or time in comparison with the surface treatment using an alkaline solution or the use of a noble metal catalyst for the conventional electroless plating and a polyethylene glycol (PEG, polyethyleneglcol) Is hydrophilic, non-toxic, has affinity with biological species and chemical species, and can be used as an antibacterial agent, a biosensor, an electrode of a battery, and the like. In addition, the production method of the present invention can dramatically increase the productivity by shortening the electroless plating time by preparing long fibers by a single process which can continuously coat metal particles, There is an effect that can be made.

FIG. 1 is a schematic view illustrating a method for producing conductive filament fibers according to the present invention; FIG.
FIG. 2 is a schematic view illustrating a process of coating metal nanoparticles on a long fiber surface in a manufacturing method according to the present invention; FIG.
3 is an SEM image of the conductive filament prepared in Examples 1 to 5 according to the present invention;
4 (a) is an energy dispersive X-ray spectrum of the conductive filament prepared in Example 2 according to the present invention; (b) is an X-ray diffraction (XRD) graph;
5 is a graph showing the results of X-ray photoelectron spectroscopy (XPS) analysis of long fibers prepared in Examples 1 to 5 according to the present invention;
6 is a graph showing the results of X-ray photoelectron spectroscopy (XPS) analysis of long fibers prepared in Example 2, Comparative Example 1 and Comparative Example 2 according to the present invention;
FIG. 7 is a graph showing the results of analysis of FT-IR and fourier transform infrared spectroscopy of long fibers and polyethylene glycol prepared in Example 2, Comparative Example 1 and Comparative Example 2 according to the present invention;
FIG. 8 is a graph showing the results of analysis of FT-IR (fourier transform infrared spectroscopy) of long fibers prepared in Examples 1 to 4 and 5 according to the present invention;
9 is an image observed under an atomic force microscope of Example 2, Comparative Example 1 and Comparative Example 2 according to the present invention;
10 is a graph showing tensile strengths of long fibers prepared in Example 2, Comparative Example 1 and Comparative Example 4 according to the present invention.

The present invention

(Poly (amide-co-imide)) and poly (trimellitic anhydride chloride-co-imide) mixed in a weight ratio of 4.5: 5.5 to 5.5: 4.5 and polytrimellitic anhydride-4,4'- 4,4'-methylenedianiline)) to prepare a long fiber (step 1); And

(Step 2) coating the conductive particles on the surface of the long fibers by sequentially carrying the long fibers prepared in step 1 on an aqueous solution of polyethylene glycol (PEG), a conductive metal precursor solution, a reducing solution and a washing solution; And the step (2) is carried out continuously by moving the long fibers to the collecting part for collecting the long fibers.

Hereinafter, the present invention will be described in detail by steps.

In the method for producing a conductive long fiber according to the present invention, the step 1 is a step of mixing poly (amide-co-imide) mixed in a weight ratio of 4.5: 5.5 to 5.5: 4.5 and poly (trimellitic anhydride) A step of electrospinning a spinning solution containing 4,4'-methylenedianiline (poly (trimellitic anhydride chloride-co-4,4'-methylenedianiline)) to prepare long fibers.

The spinning solution of step 1 is prepared by dissolving polyamideimide and polytrimellitic anhydride chloride-4,4'-methylenedianiline in a weight ratio of 4.5: 5.5 to 5.5: 4.5 in a solvent. When the polyamideimide and polytrimellitic anhydride chloride-4,4'-methylenedianiline are mixed at a weight ratio exceeding the range described above, it is possible to prepare a spinning solution having a viscosity suitable for preparing long fibers through electrospinning A bead may be formed in the produced fiber or a problem that the diameter of the fiber is not uniform may occur.

The polytrimellitic anhydride chloride-4,4'-methylenedianiline is used as a lubricant and is used for producing long fibers according to the amount of the polytrimellitic anhydride-4,4'-methylenedianiline added The viscosity of the resulting mixture can be adjusted appropriately, and thus the long fibers can be electrospun with a homogeneous diameter.

The solvent of step 1 is preferably a solution obtained by mixing dimethylsulfoxide (DMSO) and tetrahydrofuran (THF) in a weight ratio of 7: 3 to 2: 8, more preferably 6 : 4. The tetrahydrofuran is a solvent having a five-membered ring structure. When it is used, the attraction due to the van der Waals force between the molecules can be improved. Therefore, the tetrahydrofuran can be appropriately added in the range of 30 to 80 wt% . At this time, when it exceeds 45% by weight, continuous long fibers may not be produced during electrospinning, and therefore it is most preferable to mix it at 40% by weight.

In step 1, it is preferable that the polyamideimide and polytrimellitic anhydride chloride-4,4'-methylenedianiline are dissolved in the solvent in an amount of 25 to 35% by weight. When polyamideimide and polytrimellitic anhydride chloride-4,4'-methylenedianiline are dissolved in a solvent in an amount of less than 25% by weight, the molecular weight of the spinning solution becomes low and it is difficult to produce long fibers through electrospinning , There is a problem that a large amount of beads exist in the formed fiber form. Further, when polyamideimide and polytrimellitic anhydride chloride-4,4'-methylenedianiline are dissolved in a solvent in an amount exceeding 35% by weight, electrospinning is difficult to perform due to entanglement of polymer chains.

The spinning solution in the step 1 can be adjusted to have a viscosity suitable for electrospinning so that long fibers can be produced by electrospinning. At this time, the applied voltage may be appropriately adjusted according to the composition of the prepared spinning solution, and the electrospinning of step 1 is preferably performed by applying a voltage of 8 to 15 kV.

If electrospinning is carried out under an applied voltage of less than 8 kV, there is a problem that the thickness of the fibers is increased and microfibers other than nanofibers are produced. Further, when the electrospinning is carried out under an applied voltage exceeding 15 kV, there is a problem in that economic loss is caused as unnecessary energy is consumed in terms of energy efficiency, and since the performance of electrospinning is very unstable, There is a difficult problem.

In the method for producing conductive long fibers according to the present invention, step 2 is a step of sequentially carrying the long fibers prepared in step 1 in an aqueous solution of polyethylene glycol (PEG), a conductive metal precursor solution, a reducing solution and a washing solution Thereby coating conductive particles on the surface of the long fibers,

The step 2 is a step of successively carrying the long fibers produced in step 1 onto the polyethylene glycol aqueous solution, the conductive metal precursor solution, the reducing solution and the washing solution by moving the long fibers with the recovery part for recovering the long fibers, To produce a conductive filament.

In the coating of metal nanoparticles, a commonly used dip coating method can be obtained by direct reduction of metal nanoparticles using a mixed solution of a metal precursor and a reducing agent. However, such a dip coating method has disadvantages in that the solution used can not be used again, and the time for immersion is prolonged, so that the production time is increased and complicated.

On the other hand, in the production method of the present invention, long fibers are produced by using polyamideimide and polytrimellitic anhydride chloride-4,4'-methylenedianiline, and then the long fibers are moved to a recovery unit for recovering long fibers Therefore, it is possible to shorten the production time of the conductive filament through the continuous process of successively carrying the polyethylene glycol aqueous solution, the conductive metal precursor solution, the reducing solution and the washing solution sequentially, and to solve the economical and environmental problems by recycling the solutions And is easy to apply to real industry.

Meanwhile, the concentration of the aqueous solution of polyethylene glycol (PEG) in step 2 is preferably an aqueous solution of polyethylene glycol having a concentration of 0.5 to 4 mol. When the concentration of the aqueous solution of polyethylene glycol is less than 0.5 mol, the surface of the long fiber is not sufficiently activated and the metal nanoparticles can not be uniformly formed on the surface of the long fiber. When the concentration exceeds 4 mol, There is a problem in that the metal nanoparticles can not be uniformly formed because the call is excessively supplied and polyethylene glycol pieces are precipitated.

At this time, the aqueous solution of polyethylene glycol in step 2 has a strong NH at the surface of the long fiber. O, OH ... O bonding and weak CH ... N and CH ... O bond to form a functional group. Metal ions may be bonded to the functional groups, and a crown-shaped metal complex compound having a crown ether structure may be bonded to the two functional groups (see FIG. 2).

The metal precursor of step 2 is a metal precursor such as a silver (Ag) precursor, a copper precursor, a nickel precursor, a platinum precursor and a palladium precursor. The metal precursors may be used alone or in combination of two or more. In this case, the metal precursor is a metal salt in which metal cations and anions are combined, and examples of the anions include organic acids such as NO ₃ ^- , S ₂ ^- , SO ₄ ^{2 -} , CO ₃ ^{2 -} , HSO ₄ ^- , HCO ₃ ^- And anions such as halide ions may be combined, but the metal precursor is not limited thereto.

The metal precursor solution of step 2 may be prepared by mixing a metal precursor and a solvent. The solvent to be mixed with the metal precursor solution is not particularly limited, but water, ethanol, methanol, dimethylformamide, chloroform and the like can be used. More preferably, water can be used.

On the other hand, the reducing solution in step 2 includes at least one selected from the group consisting of boron hydride of an alkali metal, borohydride of an alkaline earth metal, an organic compound containing an aldehyde group, formic acid, and acetic acid Can be used. For example, the alkali metal may be Na or K, the alkaline earth metal may be Ca or Mg, and the organic compounds containing the aldehyde group may include formaldehyde (HCHO), pentane such as xylose, hexane such as glucose, etc. . Preferably, sodium borohydride can be used. Sodium borohydride has strong reducibility and has the ability to reduce various metal ions.

In addition, the washing solution of step 2 may use water and C ₁ to C ₃ alcohol. For example, the C ₁ to C ₃ alcohol may be ethanol, isopropyl alcohol or the like.

Thus, conductive filaments are produced through a single process which is carried out continuously through an aqueous solution of polyethylene glycol (PEG, polyethyleneglcol), a metal precursor solution, a reducing solution and a washing solution by moving long fibers with a recovery section for recovering long fibers. can do.

The production of the conductive filament through the continuous process shortens the time remarkably, thereby facilitating mass production and solving the economical and environmental problems by recycling the solutions, thereby facilitating application to practical industries.

The present invention

A conductive filament produced by the above production method is provided.

The conductive filament fibers according to the present invention can be produced by making polyamideimide and polytrimellitic anhydride chloride-4,4'-methylenedianiline as raw materials as long fibers, and then plating the produced long fibers with metal do. At this time, the raw material polyamideimide and polytrimellitic anhydride chloride-4,4'-methylenedianiline are mixed in a weight ratio of 4.5: 5.5 to 5.5: 4.5, and as the weight ratio is mixed, a viscosity suitable for electrospinning Can be prepared.

In the conductive filament according to the present invention, the surface of the electrospun fiber is activated by an aqueous solution of polyethylene glycol (PEG, polyethyleneglcol) having a concentration of 0.5 to 4 mol, and the metal nanoparticles are uniformly electroless- And when the concentration of polyethylene glycol is 1 to 2 molar, the most homogeneous conductive filament can be produced.

In addition, the electroless plating process is continuously carried out through an aqueous solution of polyethylene glycol (PEG), a metal precursor solution, a reducing solution and a washing solution by moving the long fibers with the recovery part for recovering the long fibers, Can be manufactured.

The production of the conductive filament through the continuous process shortens the time remarkably, thereby facilitating mass production and solving the economical and environmental problems by recycling the solutions, thereby facilitating application to practical industries.

The present invention

An electrode comprising the above conductive long fibers is provided.

The conductive filament can exhibit excellent conductivity as the metal nanoparticles are plated on the surface of the fiber, and thus can be used as an electrode material.

Accordingly, the present invention provides the electrode including the conductive filament, and the electrode according to the present invention can improve the contact area of the electrode and can flow a large amount of current, thereby improving the efficiency. At this time, the electrode may be an electrode of electrolytic plating or electroless plating, and may be suitably used in various fields requiring conductive fibers in addition to the above-mentioned fields.

The present invention provides an electronic device selected from the group consisting of a solar cell, a supercapacitor, and a display device, including the electrode.

Hereinafter, the present invention will be described in more detail with reference to the following examples and experimental examples.

However, the following examples and experimental examples are illustrative of the present invention, and the content of the present invention is not limited by the following examples and experimental examples.

Example 1 Production of Conductive Long Fiber 1

Step 1: Poly (amide-co-imide) and poly (trimellitic anhydride chloride-co-4,4'-methylenedianiline) polytrimellitic anhydride chloride (DMSO) and tetrahydrofuran (THF) in a weight ratio of 6: 4 in a proportion of 30% by weight to prepare a spinning solution. .

The spinning solution was electrospun to prepare fibers. (MN-20G-13, Iwashita Engineering, JAPAN) and a syringe pump (KD Scientific-100, USA) having an inner diameter of 0.60 mm, an outer diameter of 0.90 mm and a length of 13 mm, And the spinning solution was spun through a needle with a voltage of 8 to 15 kV at a flow rate of 100 to 150 ml / min.

The distance between the tip of the electrospun needle and the collector collecting the radiated long fibers was fixed at 10 cm, and the first wet recovery was performed. Secondary recovery was carried out at a speed of 1000 to 1500 rpm by winding from a collector used for primary wet recovery using an alumina cylindrical drum collector. The recovered long fibers were dried in a vacuum chamber at a temperature of 190 캜 for 1 hour to evaporate the solvent. The electrospun filaments were then cyclized by heating in a furnace at a temperature of 240 DEG C for 1 hour.

Step 2: Polyethylene glycol (PEG) having a molecular weight of 8000 was dissolved in distilled water to prepare a 0.5 molar aqueous solution of polyethylene glycol.

Next, silver nitrate (AgNO ₃ ) was rapidly vigorously magnetic stirred until the distilled water solution became transparent to prepare a 0.1 molar silver nitrate silver solution and prepared in the second vessel.

Further, sodium borohydride (NaBH ₄ ) was dissolved in distilled water to prepare a reducing solution having a concentration of 0.5 mol, and the solution was prepared in a third container.

After the first to third vessels are arranged in order, the long fibers are moved by the recovering unit for recovering the long fibers, so that the polyethylene glycol (PEG) aqueous solution, the metal precursor solution, the reducing solution and the washing solution are continuously immersed To prepare conductive filament fibers.

Example 2: Production of conductive long fibers 2

Conductive long fiber was prepared in the same manner as in Example 1, except that the concentration of the aqueous solution of polyethylene glycol in the first container was 1 molar in Step 2 of Example 1.

≪ Example 3 > Production of Conductive Long Fiber 3

Conductive long fibers were prepared in the same manner as in Example 1 except that the concentration of polyethylene glycol aqueous solution in the first container was 2 molar in Step 2 of Example 1.

Example 4 Production of conductive filament 4

Conductive long fibers were prepared in the same manner as in Example 1, except that the concentration of the aqueous solution of polyethylene glycol in the first container was 4 molar in Step 2 of Example 1.

Example 5 Production of Conductive Long Fiber 5

Conductive long fibers were prepared in the same manner as in Example 1 except for the first container in Step 2 of Example 1 above.

≪ Comparative Example 1 &

Conductive long fibers were prepared in the same manner as in Example 1, except that only Step 1 of Example 1 was carried out.

≪ Comparative Example 2 &

Conductive long fibers were prepared in the same manner as in Example 2, except that only the first container was subjected to the step 2 of Example 2, and the second container and the third container were not used.

≪ Comparative Example 3 &

In step 1 of Example 1, the nanofibers were recovered without first wet recovery to prepare nanofibrous long fiber.

<Experimental Example 1> Scanning electron microscopic observation

In order to confirm the microstructure of the conductive long fibers according to the present invention, the conductive long fibers prepared in Examples 1 to 5 were observed using a scanning electron microscope (SEM, Philips, XL-30S FEG Scanned Electron Microscope) This is shown in Fig.

As shown in Fig. 3, the long fibers prepared in Examples 1 to 5 are long fibers composed of straightly straight strands, and according to an enlarged scanning electron microscope image on the right side, silver nanoparticles As shown in Fig.

It was confirmed that the metal nanoparticles were plated on the entire surface of the long fibers in the long fibers of Examples 1 to 4 in which the surface was activated with polyethylene glycol (PEG). In particular, the polyethylene glycol concentration When the concentration is 1 to 2 mol, it can be confirmed that silver nanoparticles are most uniformly plated. In addition, when the concentration of polyethylene glycol was 4 moles, it was confirmed that an excessively supplied polyethylene glycol fraction was precipitated. On the other hand, in the case of Example 5 in which a metal is plated without activating the surface, it can be confirmed that only a part of the surface is plated with silver nanoparticles.

Therefore, by activating the surface of the poly (ethylene glycol) long fiber and introducing silver ions through the silver nitrate solution, the silver nanoparticles are plated on the long fibers by the reduction of the silver ions through the reducing solution, It can be seen that the particles are homogeneously plated to produce long fibers having excellent conductivity.

<Experimental Example 2> Observation of surface of conductive filament

In order to observe the surface of the long fiber according to the present invention, the long fiber prepared in Example 2 was examined using an energy dispersive X-ray spectrum (EDS) a). Further, X-ray diffraction analysis (XRD) was carried out and the results are shown in Fig. 4 (b).

According to FIG. 4 (a), the EDS analysis shows that the surface of the PAI / PTACM long fibers has 90% or more of net silver. 4 (b), XRD analysis shows that peaks are generated at 38.2 °, 44.3 ° and 64.5 °, which is the face centered cubic of (111), (200) and (220) Indicating that silver exists and that no other impurities are present.

Therefore, it was confirmed that PAI / PTACM long fiber coated with pure silver containing no impurities was produced.

Experimental Example 3 X-ray photoelectron spectroscopy 1

In order to confirm the binding energy of silver nanoparticles according to the polyethylene glycol concentration according to the present invention, the conductive filament produced by Examples 1 to 5 was analyzed by X-ray photoelectron spectroscopy (XPS) ), Which is shown in Fig.

According to FIG. 5, it can be confirmed that the long fibers and the silver nanoparticles are bonded at different strengths in the conductive filament produced through Examples 1 to 5. This indicates that the concentration of polyethylene glycol aqueous solution plays an important role in activating the surface of the long fiber with polyethylene glycol. In addition, it can be seen that the concentration of the polyethylene glycol aqueous solution is the highest in Example 1, which is 1 molar concentration. Thus, when the concentration of the polyethylene glycol aqueous solution is 1 molar, As shown in FIG.

Experimental Example 4 X-ray photoelectron spectroscopy 2

X-ray photoelectron spectroscopy (XPS) was used to analyze the intensity of binding energy according to Example 2, Comparative Example 1 and Comparative Example 2. The results are shown in FIG. 6 Respectively.

According to Fig. 6 (a), peaks of C 1s, N 1s and O 1s can be confirmed. According to Fig. 6 (b), when the surface of long fibers is activated in aqueous polyethylene glycol solution as in Comparative Example 2, A single peak is observed around eV and the presence of Na 1s can be confirmed. Furthermore, the 1s O: N peak height ratio increases from 24 to 40, indicating that the surface of the poly (ethylene glycol) long fiber is activated and the ratio of the oxygen element is increased. Referring to Figure 6 (c), it is possible to confirm that a strong Ag 3p _3/2 and Ag 3p _1/2 peak is present, it can be seen that the nanoparticle is a polyethylene glycol and a strong interaction through which .

Experimental Example 5 Infrared Spectroscopic Analysis 1

In order to confirm the existence of the functional groups of Example 2, Comparative Example 1 and Comparative Example 2 according to the present invention, the analysis was performed by using infrared spectroscopy (FT-IR, fourier transform infrared spectroscopy) . The results of infrared spectroscopic analysis of polyethylene glycol (PEG) are shown in FIG.

According to Fig. 7, polyethylene glycol (PEG) has a molecular weight of 3221 cm ^-1 (ν _OH ), 2880 cm ^-1 (ν _{CH 2} ) alkyl group, 1109 cm ^-1 (ν _CO ) dialkyl ether, 959 cm ^-1 _{隆 CH ( oop )} ) and 841 cm ^-1 _{( 隆 CC ( oop )} ) bonds.

Referring to Figure 7 (a), PAI / PTACM is 3019 cm ^-1 (ν _CH) aryl ^{group, 1776, 1711 cm - 1 (} ν C = O) _{^{imide, 1690 cm -1 (ν C =}} O) amide I , 1597 cm ^-1 (ν _NH) amide _{^{II, 1495 cm -1 (ν C}} = C aromatic), 1367 cm ^-1 (imide _{^{stretch), 1219 cm -1 (ν CN}} ), 1086 cm -1 (ν CO ) Diaryl ether, 829 cm ^-1 (δ _{NH ( oop )} ) and 722, 605 cm ^-1 (δ _{CH ( oop )} ) and (δ _{CC (oop)} ) bonds.

According to Fig. 7 (b), when the PAI / PTACM filament surface is activated with polyethylene glycol, a peak of 2880 cm ^-1 (v _CH ) due to the -CH ₂ group appears.

At the same time, it can be seen that the (ν _CO ) dialkyl ether, δ _{CH ( oop )} and (δ _{CC (oop)} ) bonds of the polyethylene glycol are properly mixed. The polyethylene glycol of the article (ν _CO) cm 1104 is coupled to move as much as 5 cm ^{-1 -} it can be seen that changing to ^1, wherein the (ν _OH) bonds disappear or be substantially reduced. In addition, (ν _{C = O)} can be confirmed that the imide and amide (I) and (ν _NH) amide II binding strength is significantly reduced, the imide bond stretch at 1367 cm ^-1 1342 cm ^{- 1} and move to , and (ν _CN ) bonds move from 1219 to 1237 cm ^-1 .

This clearly shows that polyethylene glycol is bound to PAI / PTACM long fibers.

Experimental Example 6 Infrared Spectroscopic Analysis 2

In order to confirm the change with the concentration of the aqueous polyethylene glycol solution of Examples 1 to 5 according to the present invention, analysis was performed using infrared spectroscopy (FT-IR, fourier transform infrared spectroscopy) Respectively.

According to FIG. 8, as the concentration of polyethylene glycol increases, the transmittance at 2880 cm ^-1 (ν _CH ) gradually decreases. From this, it can be seen that the intensity of the bond of -CH ₂ group increases .

&Lt; Experimental Example 7 >

In order to confirm the microstructure of Example 2, Comparative Example 1 and Comparative Example 2 according to the present invention, they were observed using an atomic force microscope, and the results are shown in FIG.

According to FIG. 9, it can be confirmed that surface roughness of the surface increases as the long fiber is treated with polyethylene glycol and the silver is plated. As a result, it was confirmed that polyethylene glycol appeared on the surface of the long fiber in Comparative Example 2, and nanoparticles were formed in Example 2.

According to Fig. 9 (d), it can be seen that the size of the silver nanoparticles varies from about 20 nm to over 30 nm, and that the silver nanoparticles are densely coated on the surface of the nanofiber have.

<Experimental Example 8> Tensile strength analysis

In order to analyze the mechanical strengths of Example 2, Comparative Example 1 and Comparative Example 3 according to the present invention, KSL 2515 was analyzed using an universal testing machine (UTM, UTM) Respectively. At this time, the gauge length of the specimen was 30.0 mm, the cross ^- sectional velocity was 10.0 mm min ^{- 1} , and the tensile pressure was applied parallel to the axial direction.

As shown in FIG. 10, it can be seen that the aligned long fibers increase to tensile strength of 141.26 MPa, so that the tensile strength remarkably increases as compared with the long fibers of the nanoweb type. The silver-plated conductive filament shows a tensile strength of 122.4 MPa.

Thus, the silver plated conductive filament produced by the continuous process has a sufficient tensile strength similar to the tensile strength of the filament, so that it can be applied not only to the electrode but also to the field using the conductive fiber.

Claims (10)

(Poly (amide-co-imide)) and poly (trimellitic anhydride chloride-co-imide) mixed in a weight ratio of 4.5: 5.5 to 5.5: 4.5 and polytrimellitic anhydride-4,4'- 4,4'-methylenedianiline)) to prepare a long fiber (step 1); And
(Step 2) coating the conductive particles on the surface of the long fibers by sequentially carrying the long fibers prepared in step 1 on a polyethyleneglycol aqueous solution, a conductive metal precursor solution, a reducing solution and a washing solution, Wherein the step (2) is performed continuously by moving the long fibers with the recovery unit for recovering the long fibers.
The method according to claim 1,
Wherein the solvent of step 1 is a solution prepared by mixing dimethylsulfoxide (DMSO) and tetrahydrofuran (THF) in a weight ratio of 7: 3 to 2: 8.
The method according to claim 1,
Wherein the concentration of the aqueous solution of polyethylene glycol in step 2 is 0.5 to 4.0 molar.
The method according to claim 1,
Wherein the conductive metal precursor of step 2 is at least one selected from the group consisting of Ag precursor, Cu precursor, Ni precursor, Pt precursor and Pd precursor A method for producing conductive long fibers.
The method according to claim 1,
The reducing solution of step 2 includes at least one selected from the group consisting of boron hydride of an alkali metal, boron hydride of an alkaline earth metal, an organic compound containing an aldehyde group, formic acid, and acetic acid Wherein the conductive long fiber is formed by a method comprising the steps of:
The method according to claim 1,
Wherein the washing liquid of step 2 is at least one selected from the group consisting of water and C ₁ to C ₃ alcohols.
A conductive filament produced by the method of claim 1.
An electrode comprising the conductive long fiber of claim 7.
An electronic device comprising the electrode of claim 8.
10. The method of claim 9,
Wherein the electronic device is selected from the group consisting of a solar cell, a supercapacitor, and a display device.

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