KR101740849B1

KR101740849B1 - Platinum-decorated carbon nanoparticle embedded polyaniline/camphorsulfonic acid hybrid paste for flexible wideband dipole tag-antenna application

Info

Publication number: KR101740849B1
Application number: KR1020160006222A
Authority: KR
Inventors: 장정식; 조경희
Original assignee: 서울대학교산학협력단
Priority date: 2016-01-19
Filing date: 2016-01-19
Publication date: 2017-06-08

Abstract

The present invention relates to a process for preparing polypyrrole nanoparticles having a carboxyl functional group of uniform size, introducing platinum tetrachloride and sodium borohydride as a reducing agent, preparing carbon nanoparticles having platinum attached thereto by a chemical reduction method and a carbonization process, The polyaniline / camphorsulfonic acid, which is a conductive polymer, was synthesized by the interfacial polymerization method on the platinum-attached carbon nanoparticles to prepare a hybrid ink for screen printing. Using screen printing, a polyaniline / camphor Sulfonated hybrid micropatterns to provide performance as a broadband dipole antenna.
According to the present invention, a platinum-coated polyaniline / camphorsulfonic acid hybrid paste having uniform resistance characteristics was prepared, and a platinum-coated hybrid paste having a desired shape, size and uniform thickness was produced using a fine mesh of screen printing. The present invention provides a technique for easily forming a polyaniline / camphorsulfonic acid hybrid micropattern containing carbon particles on a flexible substrate, and has provided advantageous in mass production at a low cost by using relatively simple platinum-attached carbon nanoparticles. In addition, the polyaniline / camphorsulfonic acid hybrid micropattern containing platinum-coated carbon particles produced by the above technique was able to maintain high flexibility characteristics owing to excellent mechanical properties during folding or bending, and was also used as an electrode for a dipole tag antenna , It has antenna characteristics with high transmission power efficiency.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polyaniline / camphorsulfonic acid hybrid paste containing carbon nanoparticles with platinum, and a flexible broadband dipole tag antenna using the same,

The present invention can easily produce platinum-attached carbon nanoparticles using a dispersion polymerization method, a reducing agent, an ultrasonication method, and a carbonization method, and can produce polyaniline by interfacial polymerization To prepare a polyaniline containing platinum-bearing carbon nanoparticles, followed by doping with a basic solvent, and further doping with a secondary dopant camphorsulfonic acid (CSA) to prepare a platinum-coated carbon nanoparticle having high electrical conductivity A polyaniline / camphorsulfonic acid hybrid paste containing carbon nanoparticles with platinum on a flexible substrate was prepared by screen printing to prepare a polyaniline / camphorsulfonic acid hybrid micropattern containing a broadband dipole tag antenna tag antenna.

As interest in materials constituting flexible device systems such as portable electronic devices, roll-up displays, electronic paper, wearable devices, and mobile phones has increased, studies have been made to manufacture flexible, lightweight and easily adjustable materials . Among them, there is a method of coating a flexible substrate with carbon nanotubes (carbon nanotubes, carbon nanofibers) or conductive polymers (polyaniline, polypyrrole, polyphedoc) which are structurally flexible and have high electrical conductivity. However, it is difficult to control the final shape because the material is coated mainly by spin coating or multiple transfer processes. Therefore, conductive polymers (polyaniline / camphorsulfonic acid, polyaniline / polystyrenesulfonate, and pedol / polystyrenesulfonate), which can be prepared by a solution process, have been actively studied to replace coating methods.

The conductive polymer produced by the solution process is advantageous in that it can be formed into various shapes because the synthesis is simple, the electric conductivity is high, and the kind of the substrate is not affected. Among them, polyaniline / camphorsulfonic acid has high electrical conductivity and excellent workability in an organic solvent. In particular, polyaniline / camphorsulfonic acid exhibits a high electrical conductivity of 10 ² -10 ³ times higher than that of nanostructured polyaniline in powder form, because the polyaniline and camphorsulfonic acid are chemically bonded in an organic solvent, and the polymer chain is expanded in the coil structure It is because it changes.

In the latest research, a method of adding a carbonaceous material has been studied in order to improve the electrical conductivity of a conductive polymer produced by a solution process. When the carbon-based material is added, a pi-pi bond is formed between the quinoid ring of the polyaniline chain and the basal surface of the carbon-based material. At this time, the polyaniline coil structure expands due to the abundant black- . Among the carbon-based materials to be added, carbon nanoparticles are advantageous in that they are inexpensive and can be mass-produced. However, it is difficult to produce uniform and small-diameter particles, to be.

Therefore, it is possible to form a pattern of desired shape by synthesis technique and screen printing technique that can easily produce a solution process conductive polymer hybrid paste which is excellent in mechanical and electrical properties by adding uniform size carbon nanoparticles and can be applied to various substrates Therefore, development of a micropattern manufacturing technology applicable to a flexible electronic device system is strongly required for industrial application of various technologies.

DISCLOSURE OF THE INVENTION An object of the present invention is to provide a method for preparing a polyaniline / camphorsulfonic acid solution containing carbon nanoparticles with platinum attached thereto by a chemical reduction method and an interfacial polymerization method, Which can be applied to a broadband dipole antenna by printing a platinum-coated polyaniline / camphorsulfonic acid film containing carbon nanoparticles in a desired pattern on a flexible substrate by using a conductive ink as a conductive ink and controlling the screen printer. To provide a method of manufacturing a material.

The technical problem of the present invention is to provide a wideband dipole antenna electrode and a radio frequency identification tag antenna electrode application by using a polyaniline / camphorsulfonic acid pattern containing platinum-attached carbon nanoparticles produced by screen printing .

The inventors of the present invention have conducted various experiments and in-depth studies, and have found that by using a completely different method than the known methods, that is, by using the chemical reduction method and the interfacial polymerization method, the platinum- A conductive ink for screen printing was prepared and applied using a nanoparticle-containing polyaniline / camphorsulfonic acid hybrid, and a polyaniline / camphorsulfonic acid hybrid micropattern containing a platinum-attached carbon nanoparticle having a desired shape and size was formed on a flexible substrate Respectively. Also, it has been confirmed that the polyaniline / camphorsulfonic acid hybrid micropattern containing platinum-attached carbon nanoparticles prepared above can be applied to a wide band dipole tag antenna having excellent performance, leading to the present invention.

The present invention relates to a process for preparing polypyrrole nanoparticles having a carboxyl functional group of uniform size, introducing platinum tetrachloride and sodium borohydride as a reducing agent, preparing carbon nanoparticles having platinum attached thereto by a chemical reduction method and a carbonization process, The polyaniline / camphorsulfonic acid, which is a conductive polymer, was synthesized by the interfacial polymerization method on the platinum-attached carbon nanoparticles to prepare a hybrid ink for screen printing. Using screen printing, a polyaniline / camphor Sulfonated hybrid micropatterns to provide performance as a broadband dipole antenna.

The platinum-attached carbon nanoparticle-containing polyaniline / camphorsulfonic acid hybrid micropattern according to the screen printing according to the present invention and the application method thereof as a broadband dipole tag antenna electrode,

Introducing a platinum tetrachloride aqueous solution into an aqueous solution of a carboxylated polypyrrole nanoparticle into which (A) a functional group is introduced, preparing a carboxylated polypyrrole nanoparticle having platinum attached thereto by using a reducing agent and an ultrasonic treatment;

(B) subjecting the platinum-attached carboxylated polypyrrole nanoparticles to carbonization to produce platinum-attached carbon nanoparticles;

(C) dispersing the platinum-attached carbon nanoparticles in an aqueous acid solution, introducing an aniline monomer and ammonium persulfate as an oxidant to produce a platinum-bonded polyaniline composite having a platinum attached thereto by interfacial polymerization;

(D) introducing the platinum-attached polyaniline composite containing carbon nanoparticles into a basic solution to prepare a polyaniline composite containing carbon nanoparticles doped with platinum;

(E) introducing a secondary dopant camphorsulfonic acid into the polyaniline composite containing the doped platinum-attached carbon nanoparticles, and dispersing the camphorsulfonic acid in an organic cosolvent to prepare a polyaniline / camphorsulfonic acid hybrid paste containing platinum-attached carbon nanoparticles ;

(F) forming a polyaniline / camphorsulfonic acid hybrid micropattern containing carbon nanoparticles having platinum on a flexible substrate using the polyaniline / camphorsulfonic acid hybrid paste containing the platinum-attached carbon nanoparticles and screen printing; And

(G) applying the polyaniline / camphorsulfonic acid hybrid micropattern containing the platinum-attached carbon nanoparticles to an antenna analyzer to apply it as a broadband dipole tag antenna.

Unless otherwise specified herein, numerical ranges such as time, temperature, content, size and the like refer to ranges within which the manufacturing method of the present invention can be optimized.

The production method of polyaniline / camphorsulfonic acid hybrid paste containing platinum-attached carbon nanoparticles according to the present invention and production of platinum-attached carbon nanoparticle-containing polyaniline / camphorsulfonic acid hybrid micropatterns by screen printing are entirely new As a method, not only the loss of the conventional spin coating and transfer process method was minimized, but also a platinum-attached polyaniline / camphorsulfonic acid hybrid with a desired shape, size and uniform thickness using a screen mesh fine mesh The present invention provides a technique for easily forming a micropattern on a flexible substrate and provides an advantage of mass production of platinum-attached carbon nanoparticles having a uniform size at a low cost. The polyaniline / camphorsulfonic acid hybrid micropattern containing the platinum-attached carbon nanoparticles prepared by the above technique can have uniform electrical conductivity characteristics, and can exhibit high electrical conductivity when bending and folding due to external force. Not only the flexibility property can be maintained but also the polyaniline / camphorsulfonic acid hybrid micropattern containing the prepared platinum-attached carbon nanoparticles is used as an electrode for a dipole tag antenna, I could confirm. It is believed that the polyaniline / camphorsulfonic acid hybrid micropattern-based dipole tag antenna with platinum-attached carbon nanoparticles prepared as described above can be applied and implemented in a signal reception device such as an airport metal detector and a human body sensor network that recognize objects.

1 is a transmission electron microscope photograph of the carboxylated polypyrrole nanoparticles to which the functional group prepared in Example 1 of the present invention is introduced;
2 is a transmission electron micrograph of the platinum-attached carboxylated polypyrrole nanoparticles prepared in Example 1 of the present invention;
3 is a transmission electron micrograph of platinum-attached carbon nanoparticles prepared in Example 1 of the present invention;
4 is a scanning electron microscope (SEM) image of a platinum-bonded polyaniline / camphorsulfonic acid hybrid composite containing carbon nanoparticles prepared in Example 1 of the present invention;
5 is a view showing a micropattern based on the platinum-attached polyaniline / camphorsulfonic acid hybrid composite containing carbon nanoparticles prepared in Example 1 of the present invention;
6 is a graph showing the surface electrical conductivity distribution of the platinum-attached polyaniline / camphorsulfonic acid hybrid thin film containing carbon nanoparticles prepared in Example 1 of the present invention;
FIG. 7 is a graph showing surface resistance characteristics of a platinum-attached polyaniline / camphorsulfonic acid hybrid composite-containing micropattern containing carbon nanoparticles according to the folding angle and the number of times of bending in Example 1 of the present invention;
8 is a graph showing the performance of a platinum-attached polyaniline / camphorsulfonic acid hybrid composite-based micropatterned broadband dipole tag antenna fabricated in Example 1 of the present invention.

In the case of the carboxylated polypyrrole nanoparticles to which the functional group used in step (A) is introduced, a method for mass-producing conductive polypyrrole nanoparticles using dispersion polymerization (Reference Patent: KR 2007-0072017 A) was used. In order to introduce a functional group, pyrrole-3-carboxylic acid, which is a pyrrole monomer containing a carboxyl group, is mixed with 1 to 10 parts by weight of pyrrole relative to 100 parts by weight of pyrrole and used as a monomer to introduce a functional group To prepare carboxylated polypyrrole nanoparticles.

When the carboxylated polypyrrole nanoparticles to which the functional group is introduced are stirred and dispersed in distilled water, the amount of the nanoparticles is 0.001 to 20 parts by weight based on 100 parts by weight of distilled water. The stirring speed is in the range of 100 to 1000 rpm. The stirring temperature is in the range of 1 to 60 占 폚. The amount of the nanoparticles, the stirring speed, and the temperature conditions are not limited to these ranges and may be smaller or larger than the above ranges.

In order to prepare the platinum-attached polypyrrole nanoparticles in step (A), the ionized platinum particles should be evenly adhered to the surfaces of the carboxylated polypyrrole nanoparticles to which the functional groups have been introduced and reduced. For this, chemical reduction and ultrasonic treatment using a reducing agent should be performed. When platinum tetrachloride aqueous solution is introduced into the aqueous solution of the carboxylated polypyrrole nanoparticle into which the functional group is introduced, the concentration of platinum can be controlled by changing the concentration of the aqueous solution of tetrachloroplatinate to 0.1 to 50 millimoles (mM) with respect to 1 L of the nanoparticle aqueous solution. The concentration conditions are not limited to these ranges and may be smaller or larger than the above range.

In the preparation of the platinum-attached carboxylated polypyrrole nanoparticles, sodium borohydride (NaBH ₄ ) is preferably used as the reducing agent, but the present invention is not limited thereto. Examples of the reducing agent include sodium borohydride (NaBH ₄ ), lithium aluminum hydride (LiAlH ₄ ), hydrazine (N ₂ H ₄ ) and the like. Among them, sodium borohydride (NaBH ₄ ) is preferable. Sodium borohydride is a solid reducing agent that is easy to handle, low in cost, and a representative reducing agent used to reduce transition metal nanoparticles such as platinum.

The introduction amount of the reducing agent is preferably in the range of 0.0001 to 0.1 g, relative to 100 g of the aqueous solution of the carboxylated polypyrrole nanoparticle into which the functional group is introduced. If the amount of the reducing agent is less than 0.0001 g, platinum ions may be incompletely reduced. If the amount of the reducing agent is more than 0.1 g, the structure of the polypyrrole nanoparticles may be damaged due to excessive reducing agent. When using the reducing agent, the temperature is in the range of 1 ~ 80 ℃. The use time of the reducing agent is preferably from 30 minutes to 2 hours. The amount, temperature, and time conditions of the reducing agent are not limited to these ranges and may be smaller or larger than the above ranges.

For instrument probes used in ultrasonic treatment, use a probe having a diameter of 5 to 30 millimeters (mm). The ultrasonic treatment time is preferably 5 minutes to 6 hours. The ultrasonic treatment intensity is in the range of 1 ~ 30 W cm ^- ² . Ultrasonic frequencies are used in the range of 1 to 40 kHz. In ultrasonic treatment, the diameter, processing time, strength, and frequency of the probe are not limited to these ranges and may be smaller or larger than the above range.

The gas used to block oxygen in the carbonization process of carbonizing the carboxylated polypyrrole nanoparticles to which platinum is attached is not limited to nitrogen, argon, or neon when preparing the platinum-attached carbon nanoparticles, . The temperature of the carbonization process is preferably between 100 and 800 ° C. When the temperature of the carbonization process is 100 DEG C or less, incomplete carbonization occurs. When the temperature is 800 DEG C or more, the prepared carbon nanoparticles adhered to platinum are damaged. The carbonization time in the carbonization process is not particularly limited, and in the present invention, the carbonization time is preferably 1 to 5 hours.

When the platinum-attached carbon nanoparticles are dispersed in the aqueous acid solution in the step (C), it is preferable that the dispersion is carried out using ultrasonic treatment and the dispersing time is 12 to 36 hours. It is preferable that the addition amount of the acid aqueous solution is 500 parts by weight of 100 parts by weight of the platinum-attached carbon nanoparticles.

When the aniline monomer is introduced into the acid aqueous solution in which the platinum-attached carbon nanoparticles are dispersed, the introduction amount of the aniline monomer is such that the molar ratio of the acid and the aniline monomer in the acid aqueous solution is 100 to 800 molar ratio, If it is less than 100 mol, all of the monomers may not be formed as anilinium cation. If the molar ratio is more than 800, acid may be introduced excessively and efficiency may be deteriorated, resulting in cost problems in the manufacturing process have.

In the case of the acid used, the aniline monomer serves as an anilinium cation. The acid is not limited to hydrochloric acid, and all acids such as sulfuric acid, nitric acid and acetic acid are applicable.

When an aniline monomer is introduced into an acid aqueous solution and stirred, the stirring time is preferably 5 to 30 minutes. If the stirring time is less than 5 minutes, the aniline monomers may not be sufficiently formed as cations, and if the stirring time is more than 30 minutes, the process time becomes long, which is not preferable in terms of time and cost in the process. The stirring temperature is preferably at room temperature, but is not limited thereto and may be more or less than the above range.

When chloroform is added after introducing an aniline monomer, the amount of addition of chloroform is preferably 30 to 90 mL, and most organic solvents satisfying the condition that they are not mixed with water can be used, but chloroform is preferably used.

When an aqueous acid solution containing an oxidizing agent is mixed with an acid aqueous solution to which the chloroform is added to polymerize the aniline monomer with polyaniline, ammonium persulfate is preferably used as the oxidizing agent. The concentration of ammonium persulfate is preferably 3 to 5 M per liter of aqueous hydrochloric acid solution. Conductive polymers including polyaniline are known to have higher molecular weight and improved conductivity as the polymerization temperature is lowered. Conversely, when the polymerization temperature is lowered, the degree of polydispersity increases and the problem of difficulty in controlling the molecular weight occurs. The interface polymerization temperature of polyaniline is preferably -50 to -10 ° C. The polymerization time is usually a polymerization reaction time required for the complete polymerization of anilinium ions with a polymer, and is usually 12 to 36 hours, but is not limited to these ranges and may be smaller or larger than the above range .

In step (D), the hydrogen ion of the carbon nanoparticle-containing polyaniline complex to which platinum in the emeraldine salt state is adsorbed by the basic solution is dedoped and reduced to a brown emeraldine base state. The type of base used for dedoping is not particularly limited, but an aqueous ammonia solution is most preferred. The concentration of the basic solution is preferably 0.1 to 1.5 M per 1 L of water. If the concentration of the aqueous ammonia solution is less than 0.1 M, incomplete dedoping may occur. If the concentration of the aqueous ammonia solution is more than 1.5 M, There is an increase in cost and time.

The temperature and time for the dedoping is preferably 12 to 36 hours at room temperature, but is not limited to these ranges and may be less or more than the above range.

In step (E), a polyaniline composite containing a doped platinum-doped carbon nanoparticle is mixed with a secondary dopant camphorsulfonic acid and dispersed in an organic cosolvent using an ultrasonic mill to form a platinum-coated polyaniline / camphor Sulfonic acid hybrid paste can be obtained.

The amount of camphorsulfonic acid to be added is preferably from 25 to 125 moles per 100 moles of the polyaniline complex containing the dedoped platinum-attached carbon nanoparticles in order to obtain an appropriate viscosity when dissolved in an organic cosolvent, The electric conductivity is lowered, which is not preferable.

The secondary dopant used can be a high molecular weight organic acid such as camphorsulfonic acid (CSA), dodecylbenzenesulfonic acid (DBSA), and a strong hydrogen bonding action with the organic co- Possible camphorsulfonic acids are most preferred.

The organic co-solvent used is not particularly limited, but meta-cresol is most preferable for obtaining high conductivity. In the present invention, chloroform is used as a co-solvent for meta-cresol. When chloroform is used as a co-solvent for meta-cresol, the amount of chloroform is preferably 0 to 30 parts by weight relative to 100 parts by weight of meta-cresol. By dissolving the powder mixture in an organic cosolvent, the benzene ring of the polyaniline chain and the benzene ring of the meta-cresol form a hydrogen bond, thereby increasing the electrical conductivity and giving an appropriate viscosity to be used as a conductive ink for screen printing.

When dispersing the doped platinum-coated polyaniline composite containing camphorsulfonic acid into the organic cosolvent, the amount of the complex introduced is preferably 1 to 3 parts by weight, more preferably 3 to 3 parts by weight per 100 parts by weight of the organic cosolvent There may arise a problem that polyaniline gel is formed and the thin film can not be manufactured.

The solution in which the polyaniline / camphorsulfonic acid containing the dedoped platinum-attached carbon nanoparticles dissolved in the organic cosolvent is subjected to ultrasonic treatment to induce strong polarity and hydrogen bonding reaction between the polyaniline / camphorsulfonic acid molecule and the meta-cresol molecule, A polyaniline / camphorsulfonic acid hybrid paste containing platinum-attached carbon nanoparticles is prepared, and the ultrasonic treatment time is preferably 12 to 36 hours.

The screen printer used in step (F) is preferably a printer for an electronic device print pattern used in a Sun Mechanicix (SM-S550), but it is preferable to apply a fine mesh of a mask having openings having a predetermined pattern and a hydrophobic ink Since the printers capable of accurately printing polyaniline / camphorsulfonic acid hybrid paste containing carbon nanoparticles, which are controlled by a squeeze for supporting a membrane under the mask and a stage module supporting the membrane under the mask, can be used, Is not limited.

The flexible substrate used is not particularly limited and may be used as long as it is applicable to a printing apparatus. Among them, a polymer film such as a photo paper having good flexibility and good printing resolution, a polyethylene terephthalate film having excellent bending property and transparency, and a polyimide film are preferable.

The polyaniline / camphorsulfonic acid hybrid micropattern containing printed platinum-attached carbon nanoparticles can be freely adjusted in a desired shape and size over a large area by masking, and the thickness can also be controlled by the spacing of fine meshes, It is preferable to use a mask containing 250 to 300 fine meshes in an interval of 1 cm in order to control the fine thickness of the polyaniline / camphorsulfonic acid hybrid micropattern containing platinum-attached carbon nanoparticles. If the number of fine meshes is less than 250, the thickness of the printed micropattern becomes too thin. If the number of fine meshes is more than 300, the thickness may become too thick.

The squeeze speed of the screen printer is preferably at least 5,000 rpm, but is not limited thereto.

In the step (F), the polyaniline / camphorsulfonic acid hybrid micropattern containing platinum-attached carbon nanoparticles prepared in the step (F) is preferably a square or ring pattern of several tens to several hundreds of millimeters by fine meshes, The shape is not limited.

In order to measure the dipole tag antenna performance of the polyaniline / camphorsulfonic acid hybrid micropattern-containing dipole-tagged carbon nanoparticle-containing platinum-coated polyaniline / camphorsulfonic acid containing carbon nanoparticles with platinum attached to both ends of the thin film using a conductor metal A dipole tag antenna electrode connected to the hybrid thin film and capable of current flow is constituted. Copper tape and silver paste are preferably used for connection of the metal cable and the electrode.

In order to measure the performance of the polyaniline / camphorsulfonic acid hybrid micropattern-based dipole tag antenna containing the platinum-attached carbon nanoparticles, an antenna analyzer (E5071B ENA RF network analyzer, Agilent technologies) The VSWR, the return loss, the transmitted power efficiency, and the recognition distance of the dipole antenna are calculated through the following equation.

When the output terminal and the input terminal are connected between the polyaniline / camphorsulfonic acid hybrid thin film-based dipole tag antenna and the antenna analyzer port of the platinum-attached carbon nanoparticle, the reflection due to the impedance difference of two different connection terminals is reduced to maximize the power transmission It is preferable to set the impedance matching to 50 Ω. This is likely to reduce the possibility of oscillation and to maintain impedance to high frequencies.

It is preferable that the surface resistance value of the polyaniline / camphorsulfonic acid hybrid micropattern containing the platinum-attached carbon nanoparticles for the dipole tag antenna is 20 Ω / □ at the maximum.

[Example]

Hereinafter, specific examples of the present invention will be described with reference to examples, but the scope of the present invention is not limited thereto.

[Example 1]

10 mM of aqueous solution of platinum tetrachloride (PtCl ₄ ) and 0.001 g of sodium borohydride (NaBH ₄ ) were introduced into a solution in which 0.25 wt% of carboxylated polypyrrole nanoparticles having a functional group with a size of 60 nm had been dispersed in distilled water. After sonication, the mixture was rinsed with distilled water and dried to obtain platinum-adhered carboxylated polypyrrole nanoparticle powder. The carbonized polypyrrole nanoparticle powder was carbonized at 600 ° C in an argon atmosphere to obtain platinum-adhered carbon nanoparticles, 0.2 g of the resulting carbon nanoparticles was added to 100 g of a 2.5 M hydrochloric acid aqueous solution and subjected to ultrasonic treatment for 24 hours to disperse the nanoparticles in an aqueous hydrochloric acid solution and the aniline monomer was added thereto so that the molar ratio of [acid] / [aniline] And then 60 mL of chloroform was added to prevent freezing of the reaction solution. Phase separation was performed on the stirred solution. The temperature of the solution was lowered to -9 ° C., and 3.75 M ammonium persulfate solution was added as an oxidizing agent and stirred at -40 ° C for 24 hours. The product was rinsed with distilled water and dried to obtain a first doped platinum-coated polyaniline composite with carbon nanoparticles. M aqueous ammonia solution and stirred for 24 hours to obtain a polyaniline composite containing doped platinum-attached carbon nanoparticles. Then, 100 moles of camphorsulfonic acid was added to 100 moles of the polyaniline composite containing the doped platinum attached carbon nanoparticles The powder mixture was added with 2 wt% of m-cresol and chloroform (CHCl ₃ ) in an organic cosolvent mixed in a volume ratio of 7: 3, and the mixture was stirred for 3 hours and ultrasonicated for 24 hours to obtain platinum- After obtaining the nanoparticle-containing polyaniline / camphorsulfonic acid hybrid paste, 250 to 300 fine meshes Screen printing is performed on the photo paper using a scraper to produce a pattern for a wide band dipole tag antenna. A metal cable is connected to both ends of the fabricated pattern to make an electrode capable of flowing current, and the circuit is constructed by connecting it to an antenna analyzer. The mean frequency, bandwidth, voltage standing wave ratio (VSWR), return loss, and transmitted power efficiency of the dipole antenna are calculated through the antenna analyzer.

As a result of the analysis using the transmission electron microscope of the carboxylated polypyrrole nanoparticles into which the functional groups were introduced, it was confirmed that spherical nanoparticles of 65 nm in size having a uniform shape and size distribution were formed . (Fig. 1) Further, as a result of the analysis of the prepared platinum-attached carboxylated polypyrrole nanoparticles using a transmission electron microscope, it was confirmed that platinum particles having a size of 10 nm were uniformly dispersed on the surface of the carboxylated polypyrrole nanoparticles by ultrasonic treatment And it was confirmed that they were distributed. (FIG. 2) Also, it was confirmed that carbon nanoparticles were formed without collapse of the structure or deformation of platinum before and after the carbonization process, as a result of analyzing the prepared carbon nanoparticles with the platinum by using a transmission electron microscope. (Fig. 3)

The polyaniline / camphorsulfonic acid hybrid composite containing the platinum-attached carbon nanoparticles prepared above was analyzed by a scanning electron microscope, and it was found that the layered structure piled up in the horizontal direction could be confirmed, It was confirmed that the carbon nanoparticles were uniformly distributed. (Figure 4)

The platinum-coated polyaniline / camphorsulfonic acid hybrid paste containing the platinum-attached carbon nanoparticles was screen-printed on a flexible photo paper once to obtain platinum-coated polyaniline / camphorsulfonic acid hybrid thin films. As a result, 57 ㎛. As a result of the measurement of electrical conductivity, high electric conductivity of 792 S cm ^- ¹ was obtained. (Fig. 6)

[Example 2]

0.1 mM of aqueous solution of platinum tetrachloride (PtCl ₄ ) and 0.10 g of boron hydride were added to a solution in which 0.25 wt% of carboxylated polypyrrole nanoparticles having a functional group having a size of 60 nm was dispersed in distilled water by the same method as in Example 1 0.001 g of sodium (NaBH ₄ ) was introduced, ultrasonicated for 2 hours, washed with distilled water and dried to obtain a carboxylated polypyrrole nanoparticle powder having platinum attached thereto. The carbonized polypyrrole nanoparticle powder was carbonized at 600 ° C. in an argon atmosphere, 0.2 g of the platinum-attached carbon nanoparticles was added to 100 g of a 2.5 M hydrochloric acid aqueous solution and subjected to ultrasonic treatment for 24 hours to disperse the nanoparticles in an aqueous hydrochloric acid solution, and the aniline monomer was dissolved in [acid] / [aniline ] Was added, and the mixture was stirred for 1 hour. Then, 60 mL of chloroform was added to block the freezing of the reaction solution, and phase separation The solution was cooled to -9 ° C and 3.75 M ammonium persulfate solution was added as an oxidizing agent. The solution was stirred at -40 ° C for 24 hours. The product was washed with distilled water and dried to obtain a first- The carbon nanoparticle-containing polyaniline composite was dispersed in 1.2 M ammonia aqueous solution and stirred for 24 hours to obtain a polyaniline composite containing doped platinum-attached carbon nanoparticles. Then, a carbon nanoparticle-containing carbon nanoparticle- 2 mol% of a mixture of m-cresol and chloroform (CHCl ₃ ) in an organic solvent mixed at a ratio of 7: 3 by volume was added to 100 moles of the polyaniline complex containing 50 moles of camphorsulfonic acid and stirred for 3 hours. And ultrasonic treatment for 24 hours to obtain a platinum-coated polyaniline / camphorsulfonic acid hybrid paste containing carbon nanoparticles, A pattern for a wideband dipole tag antenna is manufactured by screen printing on a photo paper using a mask containing 250 to 300 fine meshes. A metal cable is connected to both ends of the fabricated pattern to make an electrode capable of flowing current, and the circuit is constructed by connecting it to an antenna analyzer. The mean frequency, bandwidth, voltage standing wave ratio (VSWR), return loss, and transmitted power efficiency of the dipole antenna are calculated through the antenna analyzer.

As a result of observing the prepared carboxylated polypyrrole nanoparticles having the platinum on a transmission electron microscope, it was confirmed that the size of the platinum particles was very small as several nm and the dispersion was uneven.

If the concentration of the aqueous solution of platinum tetrachloride is 0.1 mM or less, the amount of platinum introduced into the prepared carboxylated polypyrrole nanoparticles may be reduced.

[Example 3]

50 mM of aqueous solution of platinum tetrachloride (PtCl ₄ ) and 50 ml of boron hydride were added to a solution in which 0.25 wt% of carboxylated polypyrrole nanoparticles having a functional group having a size of 60 nm was dispersed in distilled water, 0.001 g of sodium (NaBH ₄ ) was introduced, ultrasonicated for 2 hours, washed with distilled water and dried to obtain a carboxylated polypyrrole nanoparticle powder having platinum attached thereto. The carbonized polypyrrole nanoparticle powder was carbonized at 600 ° C. in an argon atmosphere, 0.2 g of the platinum-attached carbon nanoparticles was added to 100 g of a 2.5 M hydrochloric acid aqueous solution and subjected to ultrasonic treatment for 24 hours to disperse the nanoparticles in an aqueous hydrochloric acid solution, and the aniline monomer was dissolved in [acid] / [aniline ] Was added, and the mixture was stirred for 1 hour. Then, 60 mL of chloroform was added to block the freezing of the reaction solution, and phase separation The solution was cooled to -9 ° C and 3.75 M ammonium persulfate solution was added as an oxidizing agent. The solution was stirred at -40 ° C for 24 hours. The product was washed with distilled water and dried to obtain a first- The carbon nanoparticle-containing polyaniline composite was dispersed in 1.2 M ammonia aqueous solution and stirred for 24 hours to obtain a polyaniline composite containing doped platinum-attached carbon nanoparticles. Then, a carbon nanoparticle-containing carbon nanoparticle- 2 mol% of a mixture of m-cresol and chloroform (CHCl ₃ ) in an organic solvent mixed at a ratio of 7: 3 by volume was added to 100 moles of the polyaniline complex containing 50 moles of camphorsulfonic acid and stirred for 3 hours. And ultrasonic treatment for 24 hours to obtain a platinum-coated polyaniline / camphorsulfonic acid hybrid paste containing carbon nanoparticles, By printing using a mask that contains the 250 to 300 of micro-mesh screen on Photo Paper it is produced in a pattern for a broadband dipole tag antenna. A metal cable is connected to both ends of the fabricated pattern to make an electrode capable of flowing current, and the circuit is constructed by connecting it to an antenna analyzer. The mean frequency, bandwidth, voltage standing wave ratio (VSWR), return loss, and transmitted power efficiency of the dipole antenna are calculated through the antenna analyzer.

As a result of observing the carboxylated polypyrrole nanoparticles with the platinum prepared by the transmission electron microscope, it was confirmed that the size of the platinum particles was as large as a few nanometers and the aggregation phenomenon occurred with each other.

If the concentration of the aqueous solution of platinum tetrachloride is 50 mM or more, the prepared platinum-adhered carboxylated polypyrrole nanoparticles may have too much platinum introduced therein, resulting in a problem of a bundle of platinum.

[Example 4]

10 mM of an aqueous solution of platinum tetrachloride (PtCl ₄ ) and 10 g of aluminum hydride (Al ₂ O ₃ ) were added to a solution in which 0.25 wt% of carboxylated polypyrrole nanoparticles having a functional group of 60 nm in size was dispersed in distilled water, 0.001 g of lithium (LiAlH ₄ ) was introduced and sonicated for 2 hours, washed with distilled water and dried to obtain a carboxylated polypyrrole nanoparticle powder having platinum attached thereto. Then, carbonization was carried out at 600 ° C. in an argon atmosphere, 0.2 g of the platinum-attached carbon nanoparticles was added to 100 g of a 2.5 M hydrochloric acid aqueous solution and subjected to ultrasonic treatment for 24 hours to disperse the nanoparticles in an aqueous hydrochloric acid solution, and the aniline monomer was dissolved in [acid] / [aniline ] Was added and the mixture was stirred for 1 hour. Then, 60 mL of chloroform was added to prevent the freezing of the reaction solution, phase separation was performed on the stirred solution After cooling, the solution was cooled to -9 ° C. and 3 M ammonium persulfate solution was added as an oxidizing agent. The solution was stirred at -40 ° C. for 24 hours. The product was washed with distilled water and dried to obtain a first- Carbon nanoparticle-containing polyaniline composite was dispersed in a 1.25 M aqueous ammonia solution and stirred for 24 hours to obtain a polyaniline composite containing doped platinum-attached carbon nanoparticles. Then, a doped platinum-coated carbon nanoparticle 2 mol% of a mixture of m-cresol and chloroform (CHCl ₃ ) in an organic solvent mixed at a ratio of 7: 3 by volume was added to 100 moles of the polyaniline complex containing 50 moles of camphorsulfonic acid and stirred for 3 hours. And ultrasonic treatment for 24 hours to obtain a platinum-coated polyaniline / camphorsulfonic acid hybrid paste containing carbon nanoparticles, A pattern for a wideband dipole tag antenna is manufactured by screen printing on a photo paper using a mask containing 250 to 300 fine meshes. A metal cable is connected to both ends of the fabricated pattern to make an electrode capable of flowing current, and the circuit is constructed by connecting it to an antenna analyzer. The mean frequency, bandwidth, voltage standing wave ratio (VSWR), return loss, and transmitted power efficiency of the dipole antenna are calculated through the antenna analyzer.

The prepared platinum-adhered carboxylated polypyrrole nanoparticles were observed with a transmission electron microscope. As a result, platinum particles having a size of about 9 nm were uniformly dispersed and introduced onto the surface of the carboxylated polypyrrole nanoparticles by ultrasonic treatment there was.

[Example 5]

10 mM of aqueous solution of platinum tetrachloride (PtCl ₄ ) and a solution of hydrazine (10 mM) were added to a solution in which 0.25 wt% of carboxylated polypyrrole nanoparticles having a functional group having a size of 60 nm was dispersed in distilled water by the same method as in Example 1 N ₂ H ₄ ) was introduced and ultrasonicated for 2 hours, washed with distilled water and dried to obtain a carboxylated polypyrrole nanoparticle powder having platinum attached thereto. The carbonized polypyrrole nanoparticle powder was carbonized at 600 ° C. in an argon atmosphere, 0.2 g of the platinum-attached carbon nanoparticles was added to 100 g of a 2.5 M hydrochloric acid aqueous solution and subjected to ultrasonic treatment for 24 hours to disperse the nanoparticles in an aqueous hydrochloric acid solution, and the aniline monomer was dissolved in [acid] / [aniline ] Was added and the mixture was stirred for 1 hour. Then, 60 mL of chloroform was added to prevent the freezing of the reaction solution, resulting in phase separation in the stirred solution The solution was cooled to -9 ° C and 3.75 M ammonium persulfate solution was added as an oxidizing agent. The solution was stirred at -40 ° C for 24 hours. The product was washed with distilled water and dried to obtain a first doped platinum- Containing polyaniline composite was dispersed in a 1.2 M ammonia aqueous solution and stirred for 24 hours to obtain a polyaniline composite containing doped platinum-attached carbon nanoparticles. Then, a doped platinum-coated polyaniline-containing carbon nanoparticle-containing polyaniline 2 wt% of a powder mixture having 50 moles of camphorsulfonic acid per 100 moles of the complex was added to the organic cosolvent mixed with 7: 3 by volume of m-cresol and chloroform (CHCl ₃ ), and the mixture was stirred for 3 hours and 24 For a period of time to obtain a platinum-coated polyaniline / camphorsulfonic acid hybrid paste containing carbon nanoparticles, Using that contain 250 to 300 of micro mesh mask by screen printing on photo paper to produce a pattern for a broadband dipole tag antenna. A metal cable is connected to both ends of the fabricated pattern to make an electrode capable of flowing current, and the circuit is constructed by connecting it to an antenna analyzer. The mean frequency, bandwidth, voltage standing wave ratio (VSWR), return loss, and transmitted power efficiency of the dipole antenna are calculated through the antenna analyzer.

The prepared platinum-adhered carboxylated polypyrrole nanoparticles were observed with a transmission electron microscope. As a result, it was confirmed that platinum particles of about 11 nm size were uniformly dispersed on the surface of the carboxylated polypyrrole nanoparticles by ultrasonic treatment there was.

[Example 6]

10 mM of aqueous solution of platinum tetrachloride (PtCl ₄ ) and 10 wt% of boron hydride were added to a solution in which 0.25 wt% of carboxylated polypyrrole nanoparticles having a functional group of 60 nm in size was dispersed in distilled water, 0.0001 g of sodium (NaBH ₄ ) was introduced, ultrasonicated for 2 hours, washed with distilled water and dried to obtain a carboxylated polypyrrole nanoparticle powder with platinum attached thereto. Then, carbonization was carried out at 600 ° C. in an argon atmosphere to remove platinum 0.2 g of the platinum-attached carbon nanoparticles was added to 100 g of a 2.5 M hydrochloric acid aqueous solution and subjected to ultrasonic treatment for 24 hours to disperse the nanoparticles in an aqueous hydrochloric acid solution, and the aniline monomer was dissolved in [acid] / [aniline ] Was added, and the mixture was stirred for 1 hour. Then, 60 mL of chloroform was added to block the freezing of the reaction solution, and phase separation The solution was cooled to -9 ° C and 3.75 M ammonium persulfate solution was added as an oxidizing agent. The solution was stirred at -40 ° C for 24 hours. The product was washed with distilled water and dried to obtain a first- The carbon nanoparticle-containing polyaniline composite was dispersed in 1.2 M ammonia aqueous solution and stirred for 24 hours to obtain a polyaniline composite containing doped platinum-attached carbon nanoparticles. Then, a carbon nanoparticle-containing carbon nanoparticle- 2 mol% of a mixture of m-cresol and chloroform (CHCl ₃ ) in an organic solvent mixed at a ratio of 7: 3 by volume was added to 100 moles of the polyaniline complex containing 50 moles of camphorsulfonic acid and stirred for 3 hours. And ultrasonic treatment for 24 hours to obtain a platinum-coated polyaniline / camphorsulfonic acid hybrid paste containing carbon nanoparticles, By printing using a mask that contains the 250 to 300 of micro-mesh screen on Photo Paper it is produced in a pattern for a broadband dipole tag antenna. A metal cable is connected to both ends of the fabricated pattern to make an electrode capable of flowing current, and the circuit is constructed by connecting it to an antenna analyzer. The mean frequency, bandwidth, voltage standing wave ratio (VSWR), return loss, and transmitted power efficiency of the dipole antenna are calculated through the antenna analyzer.

As a result of observing the prepared platinum-attached carboxylated polypyrrole nanoparticles with a high resolution transmission electron microscope, it was confirmed that the metal lattice of the platinum particles was not completely formed.

When the concentration of the sodium borohydride was 0.0001 g or less, platinum of the carboxylated polypyrrole nanoparticles having the platinum attached thereto could not be completely reduced, and it was confirmed that it was difficult to obtain dipole tag antenna characteristics.

[Example 7]

10 mM of aqueous solution of platinum tetrachloride (PtCl ₄ ) and 10 wt% of boron hydride were added to a solution in which 0.25 wt% of carboxylated polypyrrole nanoparticles having a functional group of 60 nm in size was dispersed in distilled water, 0.1 g of sodium (NaBH ₄ ) was introduced and ultrasonicated for 2 hours, washed with distilled water and dried to obtain a carboxylated polypyrrole nanoparticle powder having platinum attached thereto. Then, carbonization was carried out at 600 ° C. in an argon atmosphere, 0.2 g of the platinum-attached carbon nanoparticles was added to 100 g of a 2.5 M hydrochloric acid aqueous solution and subjected to ultrasonic treatment for 24 hours to disperse the nanoparticles in an aqueous hydrochloric acid solution, and the aniline monomer was dissolved in [acid] / [aniline ] Was added, and the mixture was stirred for 1 hour. Then, 60 mL of chloroform was added to prevent the freezing of the reaction solution and phase separation After the solution was cooled to -9 ° C, 3.75 M ammonium persulfate solution of hydrogen peroxide was added as an oxidizing agent and stirred at -40 ° C for 24 hours. The product was washed with distilled water and dried to obtain a first- Containing nanoparticle-containing polyaniline composite was dispersed in a 1.2 M aqueous ammonia solution and stirred for 24 hours to obtain a polyaniline composite containing doped platinum-attached carbon nanoparticles. Then, a carbon nanoparticle-containing doped platinum- 2 wt% of a powder mixture having 50 moles of camphorsulfonic acid per 100 moles of polyaniline complex was added to an organic cosolvent mixed with 7: 3 by volume of met-cresol and chloroform (CHCl ₃ ), followed by stirring for 3 hours, After sonication for 24 hours, a polyaniline / camphorsulfonic acid hybrid paste containing platinum-attached carbon nanoparticles was obtained, A pattern for a broadband dipole tag antenna is manufactured by screen printing on a photo paper using a mask containing 250 to 300 fine meshes. A metal cable is connected to both ends of the fabricated pattern to make an electrode capable of flowing current, and the circuit is constructed by connecting it to an antenna analyzer. The mean frequency, bandwidth, voltage standing wave ratio (VSWR), return loss, and transmitted power efficiency of the dipole antenna are calculated through the antenna analyzer.

As a result of observing the prepared carboxylated polypyrrole nanoparticles with the platinum on a transmission electron microscope, it was observed that the structure of the polypyrrole particles was damaged due to excessive reducing agent.

When the concentration of the sodium borohydride was 0.1 g or more, it was confirmed that the structure of the carboxylated polypyrrole nanoparticles having the platinum attached thereto was impaired and it was difficult to obtain dipole tag antenna characteristics.

[Example 8]

10 mM of aqueous solution of platinum tetrachloride (PtCl ₄ ) and 10 wt% of boron hydride were added to a solution in which 0.25 wt% of carboxylated polypyrrole nanoparticles having a functional group of 60 nm in size was dispersed in distilled water, 0.001 g of sodium (NaBH ₄ ) was introduced and ultrasonicated for 2 hours, washed with distilled water and dried to obtain a carboxylated polypyrrole nanoparticle powder having platinum attached thereto. Then, carbonization was carried out at 100 ° C. in an argon atmosphere, 0.2 g of the platinum-attached carbon nanoparticles was added to 100 g of a 2.5 M hydrochloric acid aqueous solution and subjected to ultrasonic treatment for 24 hours to disperse the nanoparticles in an aqueous hydrochloric acid solution, and the aniline monomer was dissolved in [acid] / [aniline ] Was added, and the mixture was stirred for 1 hour. Then, 60 mL of chloroform was added to block the freezing of the reaction solution, and phase separation The solution was cooled to -9 ° C and 3.75 M ammonium persulfate solution was added as an oxidizing agent. The solution was stirred at -40 ° C for 24 hours. The product was washed with distilled water and dried to obtain a first- The carbon nanoparticle-containing polyaniline composite was dispersed in 1.2 M ammonia aqueous solution and stirred for 24 hours to obtain a polyaniline composite containing doped platinum-attached carbon nanoparticles. Then, a carbon nanoparticle-containing carbon nanoparticle- 2 mol% of a mixture of m-cresol and chloroform (CHCl ₃ ) in an organic solvent mixed at a ratio of 7: 3 by volume was added to 100 moles of the polyaniline complex containing 50 moles of camphorsulfonic acid and stirred for 3 hours. And ultrasonic treatment for 24 hours to obtain a platinum-coated polyaniline / camphorsulfonic acid hybrid paste containing carbon nanoparticles, By printing using a mask that contains the 250 to 300 of micro-mesh screen on Photo Paper it is produced in a pattern for a broadband dipole tag antenna. A metal cable is connected to both ends of the fabricated pattern to make an electrode capable of flowing current, and the circuit is constructed by connecting it to an antenna analyzer. The mean frequency, bandwidth, voltage standing wave ratio (VSWR), return loss, and transmitted power efficiency of the dipole antenna are calculated through the antenna analyzer.

As a result of observing the prepared platinum-attached carbon nano-particles with a high-magnification transmission electron microscope, it was confirmed that the carbon lattice pattern due to carbonization was not completely formed.

When the temperature of the carbonization process is lower than 100 ° C. in the argon atmosphere, it can be confirmed that the prepared carbon nanoparticles are not fully carbonized, making it difficult to obtain dipole tag antenna characteristics.

[Example 9]

10 mM of aqueous solution of platinum tetrachloride (PtCl ₄ ) and 10 wt% of boron hydride were added to a solution in which 0.25 wt% of carboxylated polypyrrole nanoparticles having a functional group of 60 nm in size was dispersed in distilled water, 0.001 g of sodium (NaBH ₄ ) was introduced, ultrasonicated for 2 hours, washed with distilled water and dried to obtain a carboxylated polypyrrole nanoparticle powder with platinum attached thereto. Then, carbonization was carried out at 800 ° C. in an argon atmosphere, 0.2 g of the platinum-attached carbon nanoparticles was added to 100 g of a 2.5 M hydrochloric acid aqueous solution and subjected to ultrasonic treatment for 24 hours to disperse the nanoparticles in an aqueous hydrochloric acid solution, and the aniline monomer was dissolved in [acid] / [aniline ] Was added, and the mixture was stirred for 1 hour. Then, 60 mL of chloroform was added to block the freezing of the reaction solution, and phase separation The solution was cooled to -9 ° C and 3.75 M ammonium persulfate solution was added as an oxidizing agent. The solution was stirred at -40 ° C for 24 hours. The product was washed with distilled water and dried to obtain a first- The carbon nanoparticle-containing polyaniline composite was dispersed in 1.2 M ammonia aqueous solution and stirred for 24 hours to obtain a polyaniline composite containing doped platinum-attached carbon nanoparticles. Then, a carbon nanoparticle-containing carbon nanoparticle- 2 mol% of a mixture of m-cresol and chloroform (CHCl ₃ ) in an organic solvent mixed at a ratio of 7: 3 by volume was added to 100 moles of the polyaniline complex containing 50 moles of camphorsulfonic acid and stirred for 3 hours. And ultrasonic treatment for 24 hours to obtain a platinum-coated polyaniline / camphorsulfonic acid hybrid paste containing carbon nanoparticles, By printing using a mask that contains the 250 to 300 of micro-mesh screen on Photo Paper it is produced in a pattern for a broadband dipole tag antenna. A metal cable is connected to both ends of the fabricated pattern to make an electrode capable of flowing current, and the circuit is constructed by connecting it to an antenna analyzer. The mean frequency, bandwidth, voltage standing wave ratio (VSWR), return loss, and transmitted power efficiency of the dipole antenna are calculated through the antenna analyzer.

As a result of observation of the prepared platinum-attached carbon nanoparticles by a transmission electron microscope, the shape of the carbon nanoparticles was distorted and the size of the platinum particles was reduced to about 3 nm.

When the temperature of the carbonization process is higher than 800 ° C. in the argon atmosphere, it can be confirmed that the prepared carbon nanoparticles are damaged and the dipole tag antenna characteristics are difficult to obtain.

[Example 10]

10 mM of aqueous solution of platinum tetrachloride (PtCl ₄ ) and 10 wt% of boron hydride were added to a solution in which 0.25 wt% of carboxylated polypyrrole nanoparticles having a functional group of 60 nm in size was dispersed in distilled water, 0.001 g of sodium (NaBH ₄ ) was introduced, ultrasonicated for 2 hours, washed with distilled water and dried to obtain a carboxylated polypyrrole nanoparticle powder having platinum attached thereto. The carbonized polypyrrole nanoparticle powder was carbonized at 600 ° C. in an argon atmosphere, 0.2 g of the platinum-attached carbon nanoparticles was added to 100 g of a 2.5 M hydrochloric acid aqueous solution and subjected to ultrasonic treatment for 24 hours to disperse the nanoparticles in an aqueous hydrochloric acid solution, and the aniline monomer was dissolved in [acid] / [aniline ] Was added, and the mixture was stirred for 1 hour. Then, 60 mL of chloroform was added to block the freezing of the reaction solution, and phase separation The solution was cooled to -9 ° C and 3.75 M ammonium persulfate solution was added as an oxidizing agent. The solution was stirred at -40 ° C for 24 hours. The product was washed with distilled water and dried to obtain a first- The carbon nanoparticle-containing polyaniline composite was dispersed in 1.2 M ammonia aqueous solution and stirred for 24 hours to obtain a polyaniline composite containing doped platinum-attached carbon nanoparticles. Then, a carbon nanoparticle-containing carbon nanoparticle- 2 mol% of a mixture of m-cresol and chloroform (CHCl ₃ ) in an organic solvent mixed at a ratio of 7: 3 by volume was added to 100 moles of the polyaniline complex containing 50 moles of camphorsulfonic acid and stirred for 3 hours. And ultrasonic treatment for 24 hours to obtain a platinum-coated polyaniline / camphorsulfonic acid hybrid paste containing carbon nanoparticles, By printing using a mask that contains the 250 to 300 of micro-mesh screen on Photo Paper it is produced in a pattern for a broadband dipole tag antenna. A metal cable is connected to both ends of the fabricated pattern to make an electrode capable of flowing current, and the circuit is constructed by connecting it to an antenna analyzer. The mean frequency, bandwidth, voltage standing wave ratio (VSWR), return loss, and transmitted power efficiency of the dipole antenna are calculated through the antenna analyzer.

The ammonium persulfate was added as an oxidizing agent for the anilium cation. After 5 minutes, the reaction solution began to change to blue color. After 3 hours, the solution turned into a dark green color and the polymerization was completed. After repeated centrifugation, the supernatant was discarded and washed with distilled water to obtain a thick green polyaniline solution. When dried in a vacuum oven, powdery polyaniline was obtained. The prepared first-doped platinum-loaded polyaniline composite containing carbon nanoparticles was analyzed by scanning electron microscopy, and it was confirmed that a platinum-coated polyaniline composite having a size of about 250 to 300 nm was formed .

The prepared polyaniline composite was prepared as a thin film on a photo paper by screen printing, and its thickness and conductivity were measured. The thickness of the thin film was measured using an alpha-step apparatus, and it was confirmed that the thickness of the thin film was about 150 nm. Was measured by the 4-probe method to measure the accurate conductivity of the thin film, approximately 130 ~ 160 S cm ^- was achieved by the high conductivity of ^1.

[Example 11]

10 mM of aqueous solution of platinum tetrachloride (PtCl ₄ ) and 10 wt% of boron hydride were added to a solution in which 0.25 wt% of carboxylated polypyrrole nanoparticles having a functional group of 60 nm in size was dispersed in distilled water, 0.001 g of sodium (NaBH ₄ ) was introduced, ultrasonicated for 2 hours, washed with distilled water and dried to obtain a carboxylated polypyrrole nanoparticle powder having platinum attached thereto. The carbonized polypyrrole nanoparticle powder was carbonized at 600 ° C. in an argon atmosphere, 0.2 g of the platinum-attached carbon nanoparticles was added to 100 g of a 2.5 M hydrochloric acid aqueous solution and subjected to ultrasonic treatment for 24 hours to disperse the nanoparticles in an aqueous hydrochloric acid solution, and the aniline monomer was dissolved in [acid] / [aniline ] Was added, and the mixture was stirred for 1 hour. Then, 60 mL of chloroform was added to block the freezing of the reaction solution, and phase separation The solution was cooled to -9 ° C, and 3M ammonium persulfate solution was added as an oxidizing agent. The solution was stirred at -40 ° C for 24 hours. The product was washed with distilled water and dried to obtain a first- The carbon nanoparticle-containing polyaniline composite was dispersed in 1.2 M ammonia aqueous solution and stirred for 24 hours to obtain a polyaniline composite containing doped platinum-attached carbon nanoparticles. Then, a carbon nanoparticle-containing carbon nanoparticle- 2 mol% of a mixture of m-cresol and chloroform (CHCl ₃ ) in an organic solvent mixed at a ratio of 7: 3 by volume was added to 100 moles of the polyaniline complex containing 50 moles of camphorsulfonic acid and stirred for 3 hours. And ultrasonic treatment for 24 hours to obtain a polyaniline / camphorsulfonic acid hybrid paste containing platinum-attached carbon nanoparticles, A pattern for a broadband dipole tag antenna is manufactured by screen printing on a photo paper using a mask containing 250 to 300 fine meshes. A metal cable is connected to both ends of the fabricated pattern to make an electrode capable of flowing current, and the circuit is constructed by connecting it to an antenna analyzer. The mean frequency, bandwidth, voltage standing wave ratio (VSWR), return loss, and transmitted power efficiency of the dipole antenna are calculated through the antenna analyzer.

The prepared first order doped platinum-doped polyaniline composite containing carbon nanoparticles was prepared as a thin film on a photo paper by screen printing, and its thickness and conductivity were measured. The thickness of the thin film was measured using an alpha-step apparatus and confirmed to be about 170 nm thick. As a result of the measurement of the conductivity, a high conductivity of about 140 ~ 160 S cm ^- ¹ was obtained. If the concentration of the ammonium persulfate aqueous solution, which is an oxidizing agent to be added, is 3 M or less, all the monomers may not be able to be polymerized.

[Example 12]

10 mM of aqueous solution of platinum tetrachloride (PtCl ₄ ) and 10 wt% of boron hydride were added to a solution in which 0.25 wt% of carboxylated polypyrrole nanoparticles having a functional group of 60 nm in size was dispersed in distilled water, 0.001 g of sodium (NaBH ₄ ) was introduced, ultrasonicated for 2 hours, washed with distilled water and dried to obtain a carboxylated polypyrrole nanoparticle powder having platinum attached thereto. The carbonized polypyrrole nanoparticle powder was carbonized at 600 ° C. in an argon atmosphere, 0.2 g of the platinum-attached carbon nanoparticles was added to 100 g of a 2.5 M hydrochloric acid aqueous solution and subjected to ultrasonic treatment for 24 hours to disperse the nanoparticles in an aqueous hydrochloric acid solution, and the aniline monomer was dissolved in [acid] / [aniline ] Was added, and the mixture was stirred for 1 hour. Then, 60 mL of chloroform was added to block the freezing of the reaction solution, and phase separation The solution was cooled to -9 ° C, and an ammonium persulfate solution of hydrogen peroxide (5 M) was added as an oxidizing agent. The solution was stirred at -40 ° C for 24 hours. The product was washed with distilled water and dried to obtain a first- The carbon nanoparticle-containing polyaniline composite was dispersed in 1.2 M ammonia aqueous solution and stirred for 24 hours to obtain a polyaniline composite containing doped platinum-attached carbon nanoparticles. Then, a carbon nanoparticle-containing carbon nanoparticle- 2 mol% of a mixture of m-cresol and chloroform (CHCl ₃ ) in an organic solvent mixed at a ratio of 7: 3 by volume was added to 100 moles of the polyaniline complex containing 50 moles of camphorsulfonic acid and stirred for 3 hours. And ultrasonic treatment for 24 hours to obtain a polyaniline / camphorsulfonic acid hybrid paste containing platinum-attached carbon nanoparticles, A pattern for a broadband dipole tag antenna is manufactured by screen printing on a photo paper using a mask containing 250 to 300 fine meshes. A metal cable is connected to both ends of the fabricated pattern to make an electrode capable of flowing current, and the circuit is constructed by connecting it to an antenna analyzer. The mean frequency, bandwidth, voltage standing wave ratio (VSWR), return loss, and transmitted power efficiency of the dipole antenna are calculated through the antenna analyzer.

The prepared first order doped platinum-doped polyaniline composite containing carbon nanoparticles was prepared as a thin film on a photo paper by screen printing, and its thickness and conductivity were measured. The thickness of the thin film was measured using an alpha-step apparatus, and it was confirmed that the thickness was approximately 120 nm. The conductivity was measured to be about 120 ~ 130 S cm ^- ¹ . When the concentration of the aqueous ammonium persulfate solution, which is an oxidizing agent to be added, is 5 M or more, an oligomer having a low molecular weight can be produced.

[Example 13]

The first-order doped platinum-attached polyaniline composite powder containing carbon nanoparticles-containing polyaniline composite powder prepared by stirring at the polymerization temperature of -40 ° C for 24 hours was observed by a scanning electron microscope, and it was confirmed that a layered structure was formed .

[Example 14]

10 mM of aqueous solution of platinum tetrachloride (PtCl ₄ ) and 10 wt% of boron hydride were added to a solution in which 0.25 wt% of carboxylated polypyrrole nanoparticles having a functional group of 60 nm in size was dispersed in distilled water, 0.001 g of sodium (NaBH ₄ ) was introduced, ultrasonicated for 2 hours, washed with distilled water and dried to obtain a carboxylated polypyrrole nanoparticle powder having platinum attached thereto. The carbonized polypyrrole nanoparticle powder was carbonized at 600 ° C. in an argon atmosphere, 0.2 g of the platinum-attached carbon nanoparticles was added to 100 g of a 2.5 M hydrochloric acid aqueous solution and subjected to ultrasonic treatment for 24 hours to disperse the nanoparticles in an aqueous hydrochloric acid solution, and the aniline monomer was dissolved in [acid] / [aniline ] Was added, and the mixture was stirred for 1 hour. Then, 60 mL of chloroform was added to block the freezing of the reaction solution, and phase separation The solution was cooled to -9 ° C, and 3.75 M ammonium persulfate solution was added as an oxidizing agent. The solution was stirred at -20 ° C. for 24 hours. The product was washed with distilled water and dried to obtain a first- The carbon nanoparticle-containing polyaniline composite was dispersed in 1.2 M ammonia aqueous solution and stirred for 24 hours to obtain a polyaniline composite containing doped platinum-attached carbon nanoparticles. Then, a carbon nanoparticle-containing carbon nanoparticle- 2 mol% of a mixture of m-cresol and chloroform (CHCl ₃ ) in an organic solvent mixed at a ratio of 7: 3 by volume was added to 100 moles of the polyaniline complex containing 50 moles of camphorsulfonic acid and stirred for 3 hours. And ultrasonic treatment for 24 hours to obtain a platinum-coated polyaniline / camphorsulfonic acid hybrid paste containing carbon nanoparticles, By printing using a mask that contains the 250 to 300 of micro-mesh screen on Photo Paper it is produced in a pattern for a broadband dipole tag antenna. A metal cable is connected to both ends of the fabricated pattern to make an electrode capable of flowing current, and the circuit is constructed by connecting it to an antenna analyzer. The mean frequency, bandwidth, voltage standing wave ratio (VSWR), return loss, and transmitted power efficiency of the dipole antenna are calculated through the antenna analyzer.

And the mixture was stirred for 24 hours while maintaining the above-mentioned polymerization temperature at -20 占 폚 to prepare a first doped platinum-attached polyaniline composite with carbon nanoparticles. The resulting polyaniline composite powder was observed by a scanning electron microscope, and it was confirmed that a layered structure was formed. When the polymerization temperature is higher than -20 ° C, it is confirmed that the polymers are aggregated and the molecular weight and the conductivity are lowered.

[Example 15]

10 mM of aqueous solution of platinum tetrachloride (PtCl ₄ ) and 10 wt% of boron hydride were added to a solution in which 0.25 wt% of carboxylated polypyrrole nanoparticles having a functional group of 60 nm in size was dispersed in distilled water, 0.001 g of sodium (NaBH ₄ ) was introduced, ultrasonicated for 2 hours, washed with distilled water and dried to obtain a carboxylated polypyrrole nanoparticle powder having platinum attached thereto. The carbonized polypyrrole nanoparticle powder was carbonized at 600 ° C. in an argon atmosphere, 0.2 g of the platinum-attached carbon nanoparticles was added to 100 g of a 2.5 M hydrochloric acid aqueous solution and subjected to ultrasonic treatment for 24 hours to disperse the nanoparticles in an aqueous hydrochloric acid solution, and the aniline monomer was dissolved in [acid] / [aniline ] Was added, and the mixture was stirred for 1 hour. Then, 60 mL of chloroform was added to block the freezing of the reaction solution, and phase separation The solution was cooled to -9 ° C and 3.75 M ammonium persulfate solution was added as an oxidizing agent. The solution was stirred at -50 ° C for 24 hours. The product was washed with distilled water and dried to obtain a first- The carbon nanoparticle-containing polyaniline composite was dispersed in 1.2 M ammonia aqueous solution and stirred for 24 hours to obtain a polyaniline composite containing doped platinum-attached carbon nanoparticles. Then, a carbon nanoparticle-containing carbon nanoparticle- 2 mol% of a mixture of m-cresol and chloroform (CHCl ₃ ) in an organic solvent mixed at a ratio of 7: 3 by volume was added to 100 moles of the polyaniline complex containing 50 moles of camphorsulfonic acid and stirred for 3 hours. And ultrasonic treatment for 24 hours to obtain a platinum-coated polyaniline / camphorsulfonic acid hybrid paste containing carbon nanoparticles, By printing using a mask that contains the 250 to 300 of micro-mesh screen on Photo Paper it is produced in a pattern for a broadband dipole tag antenna. A metal cable is connected to both ends of the fabricated pattern to make an electrode capable of flowing current, and the circuit is constructed by connecting it to an antenna analyzer. The mean frequency, bandwidth, voltage standing wave ratio (VSWR), return loss, and transmitted power efficiency of the dipole antenna are calculated through the antenna analyzer.

And the mixture was stirred for 24 hours while maintaining the above-mentioned polymerization temperature at -50 占 폚 to prepare a first doped platinum-attached polyaniline composite with carbon nanoparticles. The resulting polyaniline composite powder was observed by a scanning electron microscope, and it was confirmed that a layered structure was formed. When the polymerization temperature is lower than -50 캜, the molecular weight of the polymer is increased and the polydispersity is increased, which makes it difficult to control the molecular weight.

[Example 16]

10 mM of aqueous solution of platinum tetrachloride (PtCl ₄ ) and 10 wt% of boron hydride were added to a solution in which 0.25 wt% of carboxylated polypyrrole nanoparticles having a functional group of 60 nm in size was dispersed in distilled water, 0.001 g of sodium (NaBH ₄ ) was introduced, ultrasonically treated for 30 minutes, washed with distilled water and dried to obtain a carboxylated polypyrrole nanoparticle powder having platinum attached thereto. Then, carbonization was carried out at 600 ° C. in an argon atmosphere, 0.2 g of the platinum-attached carbon nanoparticles was added to 100 g of a 2.5 M hydrochloric acid aqueous solution and subjected to ultrasonic treatment for 24 hours to disperse the nanoparticles in an aqueous hydrochloric acid solution, and the aniline monomer was dissolved in [acid] / [aniline ] Was added, and the mixture was stirred for 1 hour. Then, 60 mL of chloroform was added to prevent the freezing of the reaction solution and phase separation After the solution was cooled to -9 ° C, 3.75 M ammonium persulfate solution of hydrogen peroxide was added as an oxidizing agent and stirred at -40 ° C for 24 hours. The product was washed with distilled water and dried to obtain a first- Containing nanoparticle-containing polyaniline composite was dispersed in a 1.2 M aqueous ammonia solution and stirred for 24 hours to obtain a polyaniline composite containing doped platinum-attached carbon nanoparticles. Then, a carbon nanoparticle-containing doped platinum- 2 wt% of a powder mixture having 50 moles of camphorsulfonic acid per 100 moles of polyaniline complex was added to an organic cosolvent mixed with 7: 3 by volume of met-cresol and chloroform (CHCl ₃ ), followed by stirring for 3 hours, After sonication for 24 hours, a polyaniline / camphorsulfonic acid hybrid paste containing platinum-attached carbon nanoparticles was obtained, A pattern for a broadband dipole tag antenna is manufactured by screen printing on a photo paper using a mask containing 250 to 300 fine meshes. A metal cable is connected to both ends of the fabricated pattern to make an electrode capable of flowing current, and the circuit is constructed by connecting it to an antenna analyzer. The mean frequency, bandwidth, voltage standing wave ratio (VSWR), return loss, and transmitted power efficiency of the dipole antenna are calculated through the antenna analyzer.

The first-doped platinum-coated polyaniline composite containing carbon nanoparticles was dispersed in a 1.2 M aqueous ammonia solution and stirred for 24 hours to prepare a brown doped platinum-doped carbon nanoparticle in an emeraldine base state Containing polyaniline composite.

[Example 17]

10 mM of aqueous solution of platinum tetrachloride (PtCl ₄ ) and 10 wt% of boron hydride were added to a solution in which 0.25 wt% of carboxylated polypyrrole nanoparticles having a functional group of 60 nm in size was dispersed in distilled water, 0.001 g of sodium (NaBH ₄ ) was introduced, ultrasonicated for 2 hours, washed with distilled water and dried to obtain a carboxylated polypyrrole nanoparticle powder having platinum attached thereto. The carbonized polypyrrole nanoparticle powder was carbonized at 600 ° C. in an argon atmosphere, 0.2 g of the platinum-attached carbon nanoparticles was added to 100 g of a 2.5 M hydrochloric acid aqueous solution and subjected to ultrasonic treatment for 24 hours to disperse the nanoparticles in an aqueous hydrochloric acid solution, and the aniline monomer was dissolved in [acid] / [aniline ] Was added, and the mixture was stirred for 1 hour. Then, 60 mL of chloroform was added to block the freezing of the reaction solution, and phase separation The solution was cooled to -9 ° C and 3.75 M ammonium persulfate solution was added as an oxidizing agent. The solution was stirred at -40 ° C for 24 hours. The product was washed with distilled water and dried to obtain a first- Containing polyaniline composite was dispersed in 0.1 M ammonia aqueous solution and stirred for 24 hours to obtain a polyaniline composite containing doped platinum attached carbon nanoparticles. Then, a doped platinum-coated carbon nanoparticle- 2 mol% of a mixture of m-cresol and chloroform (CHCl ₃ ) in an organic solvent mixed at a ratio of 7: 3 by volume was added to 100 moles of the polyaniline complex containing 50 moles of camphorsulfonic acid and stirred for 3 hours. And ultrasonic treatment for 24 hours to obtain a platinum-coated polyaniline / camphorsulfonic acid hybrid paste containing carbon nanoparticles, By printing using a mask that contains the 250 to 300 of micro-mesh screen on Photo Paper it is produced in a pattern for a broadband dipole tag antenna. A metal cable is connected to both ends of the fabricated pattern to make an electrode capable of flowing current, and the circuit is constructed by connecting it to an antenna analyzer. The mean frequency, bandwidth, voltage standing wave ratio (VSWR), return loss, and transmitted power efficiency of the dipole antenna are calculated through the antenna analyzer.

The polyaniline composite containing the first doped platinum-coated carbon nanoparticles was dispersed in an aqueous 0.1M ammonia solution and stirred for 24 hours to prepare a polyaniline composite containing doped platinum-attached carbon nanoparticles. When the concentration of the aqueous ammonia solution is 0.1 M or less, all of the polyaniline may not be dedoped.

[Example 18]

10 mM of aqueous solution of platinum tetrachloride (PtCl ₄ ) and 10 wt% of boron hydride were added to a solution in which 0.25 wt% of carboxylated polypyrrole nanoparticles having a functional group of 60 nm in size was dispersed in distilled water, 0.001 g of sodium (NaBH ₄ ) was introduced, ultrasonicated for 2 hours, washed with distilled water and dried to obtain a carboxylated polypyrrole nanoparticle powder having platinum attached thereto. The carbonized polypyrrole nanoparticle powder was carbonized at 600 ° C. in an argon atmosphere, 0.2 g of the platinum-attached carbon nanoparticles was added to 100 g of a 2.5 M hydrochloric acid aqueous solution and subjected to ultrasonic treatment for 24 hours to disperse the nanoparticles in an aqueous hydrochloric acid solution, and the aniline monomer was dissolved in [acid] / [aniline ] Was added, and the mixture was stirred for 1 hour. Then, 60 mL of chloroform was added to block the freezing of the reaction solution, and phase separation The solution was cooled to -9 ° C and 3.75 M ammonium persulfate solution was added as an oxidizing agent. The solution was stirred at -40 ° C for 24 hours. The product was washed with distilled water and dried to obtain a first- The carbon nanoparticle-containing polyaniline composite was dispersed in a 1.5 M ammonia aqueous solution and stirred for 24 hours to obtain a polyaniline composite containing doped platinum-attached carbon nanoparticles. Then, a carbon nanoparticle-containing carbon nanoparticle- 2 mol% of a mixture of m-cresol and chloroform (CHCl ₃ ) in an organic solvent mixed at a ratio of 7: 3 by volume was added to 100 moles of the polyaniline complex containing 50 moles of camphorsulfonic acid and stirred for 3 hours. And ultrasonic treatment for 24 hours to obtain a platinum-coated polyaniline / camphorsulfonic acid hybrid paste containing carbon nanoparticles, By printing using a mask that contains the 250 to 300 of micro-mesh screen on Photo Paper it is produced in a pattern for a broadband dipole tag antenna. A metal cable is connected to both ends of the fabricated pattern to make an electrode capable of flowing current, and the circuit is constructed by connecting it to an antenna analyzer. The mean frequency, bandwidth, voltage standing wave ratio (VSWR), return loss, and transmitted power efficiency of the dipole antenna are calculated through the antenna analyzer.

The polyaniline composite containing the first-doped platinum-attached carbon nanoparticles was dispersed in a 1.5 M ammonia aqueous solution and stirred for 24 hours to prepare a polyaniline composite containing doped platinum-attached carbon nanoparticles. When the concentration of the aqueous ammonia solution is 1.5 M or more, the efficiency of the dedoping process becomes poor, which increases the cost and time of the process.

[Example 19]

10 mM of aqueous solution of platinum tetrachloride (PtCl ₄ ) and 0.001 g of sodium borohydride (NaBH ₄ ) were introduced into a solution in which 0.25 wt% of carboxylated polypyrrole nanoparticles having a functional group with a size of 60 nm had been dispersed in distilled water. After sonication, the mixture was rinsed with distilled water and dried to obtain platinum-adhered carboxylated polypyrrole nanoparticle powder. The carbonized polypyrrole nanoparticle powder was carbonized at 600 ° C in an argon atmosphere to obtain platinum-adhered carbon nanoparticles, 0.2 g of the resulting carbon nanoparticles was added to 100 g of a 2.5 M hydrochloric acid aqueous solution and subjected to ultrasonic treatment for 24 hours to disperse the nanoparticles in an aqueous hydrochloric acid solution and the aniline monomer was added thereto so that the molar ratio of [acid] / [aniline] And then 60 mL of chloroform was added to prevent freezing of the reaction solution. Phase separation was performed on the stirred solution. The solution was cooled to -9 ° C., and 3.75 M Of ammonium persulfate solution was added as an oxidizing agent and stirred at -40 ° C for 24 hours. The product was washed with distilled water and dried to obtain a first doped platinum-coated polyaniline composite particle containing carbon nanoparticles. Aqueous ammonia solution and stirred for 24 hours to obtain a polyaniline composite containing doped platinum-attached carbon nanoparticles. Then, 100 moles of camphorsulfonic acid was added to 100 moles of the polyaniline composite containing the doped platinum-attached platinum- 2 wt% of the mixture was added to the organic cosolvent mixed with m-cresol and chloroform (CHCl ₃ ) 7: 3 by volume, and the mixture was stirred for 3 hours and sonicated for 24 hours to prepare platinum- Containing polyaniline / camphorsulfonic acid hybrid paste was obtained, and then, in an interval of 1 cm, 250 to 300 fine mesh- Using the screen printing on photo paper to produce a pattern for a broadband dipole tag antenna. A metal cable is connected to both ends of the fabricated pattern to make an electrode capable of flowing current, and the circuit is constructed by connecting it to an antenna analyzer. The mean frequency, bandwidth, voltage standing wave ratio (VSWR), return loss, and transmitted power efficiency of the dipole antenna are calculated through the antenna analyzer.

A powder mixture having 50 moles of camphorsulfonic acid per 100 moles of the polyaniline composite containing the doped platinum-attached carbon nanoparticles was added to an organic cosolvent to obtain a polyaniline / camphorsulfonic acid hybrid paste containing platinum-attached carbon nanoparticles . The prepared hybrid paste was screen printed on a photo paper to prepare a thin film, and the thickness and the conductivity were measured. The conductivity was measured to be about 65 ㎛. As a result, high conductivity of about 750 ~ 850 S cm ^- ¹ was obtained.

[Example 20]

10 mM of aqueous solution of platinum tetrachloride (PtCl ₄ ) and 10 wt% of boron hydride were added to a solution in which 0.25 wt% of carboxylated polypyrrole nanoparticles having a functional group of 60 nm in size was dispersed in distilled water, 0.001 g of sodium (NaBH ₄ ) was introduced, ultrasonicated for 2 hours, washed with distilled water and dried to obtain a carboxylated polypyrrole nanoparticle powder having platinum attached thereto. The carbonized polypyrrole nanoparticle powder was carbonized at 600 ° C. in an argon atmosphere, 0.2 g of the platinum-attached carbon nanoparticles was added to 100 g of a 2.5 M hydrochloric acid aqueous solution and subjected to ultrasonic treatment for 24 hours to disperse the nanoparticles in an aqueous hydrochloric acid solution, and the aniline monomer was dissolved in [acid] / [aniline ] Was added, and the mixture was stirred for 1 hour. Then, 60 mL of chloroform was added to block the freezing of the reaction solution, and phase separation The solution was cooled to -9 ° C and 3.75 M ammonium persulfate solution was added as an oxidizing agent. The solution was stirred at -40 ° C for 24 hours. The product was washed with distilled water and dried to obtain a first- The carbon nanoparticle-containing polyaniline composite was dispersed in 1.2 M ammonia aqueous solution and stirred for 24 hours to obtain a polyaniline composite containing doped platinum-attached carbon nanoparticles. Then, a carbon nanoparticle-containing carbon nanoparticle- (M-cresol) and chloroform (CHCl ₃ ) in an amount of 2 wt% in an organic cosolvent mixed in a volume ratio of 7: 3 by volume was added to 100 moles of a polyaniline complex containing 25 moles of camphorsulfonic acid and stirred for 3 hours. And ultrasonic treatment for 24 hours to obtain a platinum-coated polyaniline / camphorsulfonic acid hybrid paste containing carbon nanoparticles, By printing using a mask that contains the 250 to 300 of micro-mesh screen on Photo Paper it is produced in a pattern for a broadband dipole tag antenna. A metal cable is connected to both ends of the fabricated pattern to make an electrode capable of flowing current, and the circuit is constructed by connecting it to an antenna analyzer. The mean frequency, bandwidth, voltage standing wave ratio (VSWR), return loss, and transmitted power efficiency of the dipole antenna are calculated through the antenna analyzer.

A powder mixture having 25 moles of camphorsulfonic acid per 100 moles of the polyaniline composite containing the doped platinum-attached carbon nanoparticles was added to an organic cosolvent to obtain a polyaniline / camphorsulfonic acid hybrid paste containing platinum-attached carbon nanoparticles . The prepared hybrid paste was screen printed on a photo paper to prepare a thin film, and the thickness and the conductivity were measured. The conductivity was measured to be approximately 780 ~ 850 S cm ^- ^{1 because} it was coated to a thickness of approximately 60 ㎛. When the addition amount of camphorsulfonic acid is 25 mol or less, there is a problem that the amount of the secondary dopant is small and the electrical conductivity can not be improved.

[Example 21]

10 mM of aqueous solution of platinum tetrachloride (PtCl ₄ ) and 10 wt% of boron hydride were added to a solution in which 0.25 wt% of carboxylated polypyrrole nanoparticles having a functional group of 60 nm in size was dispersed in distilled water, 0.001 g of sodium (NaBH ₄ ) was introduced, ultrasonicated for 2 hours, washed with distilled water and dried to obtain a carboxylated polypyrrole nanoparticle powder having platinum attached thereto. The carbonized polypyrrole nanoparticle powder was carbonized at 600 ° C. in an argon atmosphere, 0.2 g of the platinum-attached carbon nanoparticles was added to 100 g of a 2.5 M hydrochloric acid aqueous solution and subjected to ultrasonic treatment for 24 hours to disperse the nanoparticles in an aqueous hydrochloric acid solution, and the aniline monomer was dissolved in [acid] / [aniline ] Was added, and the mixture was stirred for 1 hour. Then, 60 mL of chloroform was added to block the freezing of the reaction solution, and phase separation The solution was cooled to -9 ° C and 3.75 M ammonium persulfate solution was added as an oxidizing agent. The solution was stirred at -40 ° C for 24 hours. The product was washed with distilled water, dried and dried to obtain a first- The dispersion was dispersed in a 1.2 M ammonia aqueous solution and stirred for 24 hours to obtain a polyaniline composite containing doped platinum-attached carbon nanoparticles. Then, a carbon nanotube-containing polyaniline composite containing carbon nanoparticles with a doped platinum- A powder mixture having 125 moles of camphorsulfonic acid per 100 moles of the particle-containing polyaniline composite was added to the organic cosolvent mixed with m-cresol and chloroform (CHCl ₃ ) in an amount of 7: 3 by volume, and the mixture was stirred for 3 hours After the mixture was stirred and ultrasonicated for 24 hours, a polyaniline / camphorsulfonic acid hybrid paste containing platinum-attached carbon nanoparticles was obtained, Using that contain 250 to 300 of micro mesh mask in case the screen printing on photo paper to produce a pattern for a broadband dipole tag antenna. A metal cable is connected to both ends of the fabricated pattern to make an electrode capable of flowing current, and the circuit is constructed by connecting it to an antenna analyzer. The mean frequency, bandwidth, voltage standing wave ratio (VSWR), return loss, and transmitted power efficiency of the dipole antenna are calculated through the antenna analyzer.

A powder mixture of 125 moles of camphorsulfonic acid per 100 moles of the polyaniline composite containing the doped platinum-attached carbon nanoparticles was added to an organic cosolvent to obtain a polyaniline / camphorsulfonic acid hybrid paste containing platinum-attached carbon nanoparticles . The prepared hybrid paste was screen printed on a photo paper to prepare a thin film, and the thickness and the conductivity were measured. The conductivity was measured to be about 60 ㎛ and the conductivity was about 720 ~ 750 S cm ^- ¹ . When the addition amount of camphorsulfonic acid is more than 125 molar ratio, the proportion of polyaniline is relatively decreased and the electrical conductivity is decreased.

[Example 22]

The polyaniline / camphorsulfonic acid hybrid paste containing platinum-attached carbon nanoparticles was prepared by adding a powder mixture of the polyaniline composite and camphorsulfonic acid to an organic cosolvent mixed in a volume ratio of 7: 3 of meta-cresol and chloroform And measured with a viscometer at 50 kPa s.

[Example 23]

10 mM of aqueous solution of platinum tetrachloride (PtCl ₄ ) and 10 wt% of boron hydride were added to a solution in which 0.25 wt% of carboxylated polypyrrole nanoparticles having a functional group of 60 nm in size was dispersed in distilled water, 0.001 g of sodium (NaBH ₄ ) was introduced, ultrasonicated for 2 hours, washed with distilled water and dried to obtain a carboxylated polypyrrole nanoparticle powder having platinum attached thereto. The carbonized polypyrrole nanoparticle powder was carbonized at 600 ° C. in an argon atmosphere, 0.2 g of the platinum-attached carbon nanoparticles was added to 100 g of a 2.5 M hydrochloric acid aqueous solution and subjected to ultrasonic treatment for 24 hours to disperse the nanoparticles in an aqueous hydrochloric acid solution, and the aniline monomer was dissolved in [acid] / [aniline ] Was added, and the mixture was stirred for 1 hour. Then, 60 mL of chloroform was added to block the freezing of the reaction solution, and phase separation The solution was cooled to -9 ° C and 3.75 M ammonium persulfate solution was added as an oxidizing agent. The solution was stirred at -40 ° C for 24 hours. The product was washed with distilled water and dried to obtain a first- The carbon nanoparticle-containing polyaniline composite was dispersed in 1.2 M ammonia aqueous solution and stirred for 24 hours to obtain a polyaniline composite containing doped platinum-attached carbon nanoparticles. Then, a carbon nanoparticle-containing carbon nanoparticle- (Meth) acrylate and chloroform (CHCl ₃ ) in an amount of 1 wt% in an organic cosolvent mixed in a volume ratio of 7: 3 by volume, and stirred for 3 hours. And ultrasonic treatment for 24 hours to obtain a platinum-coated polyaniline / camphorsulfonic acid hybrid paste containing carbon nanoparticles, By printing using a mask that contains the 250 to 300 of micro-mesh screen on Photo Paper it is produced in a pattern for a broadband dipole tag antenna. A metal cable is connected to both ends of the fabricated pattern to make an electrode capable of flowing current, and the circuit is constructed by connecting it to an antenna analyzer. The mean frequency, bandwidth, voltage standing wave ratio (VSWR), return loss, and transmitted power efficiency of the dipole antenna are calculated through the antenna analyzer.

The polyaniline / camphorsulfonic acid hybrid paste containing platinum-attached carbon nanoparticles was prepared by adding a powder mixture of the polyaniline composite and camphorsulfonic acid in an organic cosolvent mixed with a 7: 3 volume ratio of meta-cresol and chloroform And measured with a viscometer at 23 kPa s. If the addition ratio of the powder mixture to the organic cosolvent is less than 1 wt%, there may be a problem that the resolution is lowered when the micropattern is manufactured by screen printing due to the low viscosity.

[Example 24]

10 mM of aqueous solution of platinum tetrachloride (PtCl ₄ ) and 10 wt% of boron hydride were added to a solution in which 0.25 wt% of carboxylated polypyrrole nanoparticles having a functional group of 60 nm in size was dispersed in distilled water, 0.001 g of sodium (NaBH ₄ ) was introduced, ultrasonicated for 2 hours, washed with distilled water and dried to obtain a carboxylated polypyrrole nanoparticle powder having platinum attached thereto. The carbonized polypyrrole nanoparticle powder was carbonized at 600 ° C. in an argon atmosphere, 0.2 g of the platinum-attached carbon nanoparticles was added to 100 g of a 2.5 M hydrochloric acid aqueous solution and subjected to ultrasonic treatment for 24 hours to disperse the nanoparticles in an aqueous hydrochloric acid solution, and the aniline monomer was dissolved in [acid] / [aniline ] Was added, and the mixture was stirred for 1 hour. Then, 60 mL of chloroform was added to block the freezing of the reaction solution, and phase separation The solution was cooled to -9 ° C and 3.75 M ammonium persulfate solution was added as an oxidizing agent. The solution was stirred at -40 ° C for 24 hours. The product was washed with distilled water and dried to obtain a first- The carbon nanoparticle-containing polyaniline composite was dispersed in 1.2 M ammonia aqueous solution and stirred for 24 hours to obtain a polyaniline composite containing doped platinum-attached carbon nanoparticles. Then, a carbon nanoparticle-containing carbon nanoparticle- 3 mol% of a mixture of m-cresol and chloroform (CHCl ₃ ) in an organic solvent mixed at a ratio of 10: 0 by volume was added to 100 moles of the polyaniline complex containing 50 moles of camphorsulfonic acid and stirred for 3 hours. And ultrasonic treatment for 24 hours to obtain a platinum-coated polyaniline / camphorsulfonic acid hybrid paste containing carbon nanoparticles, A pattern for a wideband dipole tag antenna is manufactured by screen printing on a photo paper using a mask containing 250 to 300 fine meshes. A metal cable is connected to both ends of the fabricated pattern to make an electrode capable of flowing current, and the circuit is constructed by connecting it to an antenna analyzer. The mean frequency, bandwidth, voltage standing wave ratio (VSWR), return loss, and transmitted power efficiency of the dipole antenna are calculated through the antenna analyzer.

The polyaniline / camphorsulfonic acid hybrid paste containing platinum-attached carbon nanoparticles was prepared by adding a powder mixture of the polyaniline composite and camphorsulfonic acid to an organic cosolvent mixed with a 7: 3 volume ratio of meta-cresol and chloroform And measured by a viscometer at 75 kPa s. When the addition ratio of the powder mixture to the organic cosolvent is more than 3 wt%, it is confirmed that the polyaniline gel is formed at room temperature, and the thin film can not be manufactured by screen printing due to the high viscosity.

[Example 25]

The polyaniline / camphorsulfonic acid hybrid paste containing the platinum-attached carbon nanoparticles was screen-printed on a flexible photo paper using a mask containing 250 to 300 fine meshes in 1 cm increments, The polyaniline / camphorsulfonic acid hybrid micropattern containing the carbon nanoparticles was found to have a thickness of about 60 占 퐉 and the surface resistance was measured to be 5? / ?.

[Example 26]

10 mM of aqueous solution of platinum tetrachloride (PtCl ₄ ) and 10 wt% of boron hydride were added to a solution in which 0.25 wt% of carboxylated polypyrrole nanoparticles having a functional group of 60 nm in size was dispersed in distilled water, 0.001 g of sodium (NaBH ₄ ) was introduced, ultrasonicated for 2 hours, washed with distilled water and dried to obtain a carboxylated polypyrrole nanoparticle powder having platinum attached thereto. The carbonized polypyrrole nanoparticle powder was carbonized at 600 ° C. in an argon atmosphere, 0.2 g of the platinum-attached carbon nanoparticles was added to 100 g of a 2.5 M hydrochloric acid aqueous solution and subjected to ultrasonic treatment for 24 hours to disperse the nanoparticles in an aqueous hydrochloric acid solution, and the aniline monomer was dissolved in [acid] / [aniline ] Was added, and the mixture was stirred for 1 hour. Then, 60 mL of chloroform was added to block the freezing of the reaction solution, and phase separation The solution was cooled to -9 ° C and 3.75 M ammonium persulfate solution was added as an oxidizing agent. The solution was stirred at -40 ° C for 24 hours. The product was washed with distilled water and dried to obtain a first- The carbon nanoparticle-containing polyaniline composite was dispersed in 1.2 M ammonia aqueous solution and stirred for 24 hours to obtain a polyaniline composite containing doped platinum-attached carbon nanoparticles. Then, a carbon nanoparticle-containing carbon nanoparticle- 2 mol% of a mixture of m-cresol and chloroform (CHCl ₃ ) in an organic solvent mixed at a ratio of 7: 3 by volume was added to 100 moles of the polyaniline complex containing 50 moles of camphorsulfonic acid and stirred for 3 hours. And ultrasonic treatment for 24 hours to obtain a platinum-coated polyaniline / camphorsulfonic acid hybrid paste containing carbon nanoparticles, By using that contains the 250 to 300 mesh fine mask in the screen printing on a polyimide (PI) film to produce a pattern for a broadband dipole tag antenna. A metal cable is connected to both ends of the fabricated pattern to make an electrode capable of flowing current, and the circuit is constructed by connecting it to an antenna analyzer. The mean frequency, bandwidth, voltage standing wave ratio (VSWR), return loss, and transmitted power efficiency of the dipole antenna are calculated through the antenna analyzer.

The polyaniline / camphorsulfonic acid hybrid paste containing the platinum-attached carbon nanoparticles was screen-printed on a flexible photo paper using a mask containing 250 to 300 fine meshes in 1 cm increments, The polyaniline / camphorsulfonic acid hybrid micropattern containing the carbon nanoparticles was prepared and found to have a thickness of about 70 탆. The surface resistance was measured to be 8 Ω / □.

[Example 27]

10 mM of aqueous solution of platinum tetrachloride (PtCl ₄ ) and 10 wt% of boron hydride were added to a solution in which 0.25 wt% of carboxylated polypyrrole nanoparticles having a functional group of 60 nm in size was dispersed in distilled water, 0.001 g of sodium (NaBH ₄ ) was introduced, ultrasonicated for 2 hours, washed with distilled water and dried to obtain a carboxylated polypyrrole nanoparticle powder having platinum attached thereto. The carbonized polypyrrole nanoparticle powder was carbonized at 600 ° C. in an argon atmosphere, 0.2 g of the platinum-attached carbon nanoparticles was added to 100 g of a 2.5 M hydrochloric acid aqueous solution and subjected to ultrasonic treatment for 24 hours to disperse the nanoparticles in an aqueous hydrochloric acid solution, and the aniline monomer was dissolved in [acid] / [aniline ] Was added, and the mixture was stirred for 1 hour. Then, 60 mL of chloroform was added to block the freezing of the reaction solution, and phase separation The solution was cooled to -9 ° C and 3.75 M ammonium persulfate solution was added as an oxidizing agent. The solution was stirred at -40 ° C for 24 hours. The product was washed with distilled water and dried to obtain a first- The carbon nanoparticle-containing polyaniline composite was dispersed in 1.2 M ammonia aqueous solution and stirred for 24 hours to obtain a polyaniline composite containing doped platinum-attached carbon nanoparticles. Then, a carbon nanoparticle-containing carbon nanoparticle- 2 mol% of a mixture of m-cresol and chloroform (CHCl ₃ ) in an organic solvent mixed at a ratio of 7: 3 by volume was added to 100 moles of the polyaniline complex containing 50 moles of camphorsulfonic acid and stirred for 3 hours. And ultrasonic treatment for 24 hours to obtain a platinum-coated polyaniline / camphorsulfonic acid hybrid paste containing carbon nanoparticles, By screen printing on a polyethylene terephthalate (PET) film using a mask containing the 250 to 300 of the fine mesh are prepared in a pattern for a broadband dipole tag antenna. A metal cable is connected to both ends of the fabricated pattern to make an electrode capable of flowing current, and the circuit is constructed by connecting it to an antenna analyzer. The mean frequency, bandwidth, voltage standing wave ratio (VSWR), return loss, and transmitted power efficiency of the dipole antenna are calculated through the antenna analyzer.

The platinum-coated polyaniline / camphorsulfonic acid hybrid paste containing carbon nanoparticles was screen-printed on a flexible polyethylene terephthalate film with a mask containing 250 to 300 fine meshes in 1 cm increments to form platinum The polyaniline / camphorsulfonic acid hybrid micropattern containing the carbon nanoparticles thus adhered was found to have a thickness of about 72 탆, and the surface resistance was measured to be 8 Ω / □.

[Example 28]

The polyaniline / camphorsulfonic acid hybrid paste containing the platinum-attached carbon nanoparticles was screen-printed on a flexible photo paper one time by using a mask containing 250 fine meshes in 1 cm intervals to form platinum- The polyaniline / camphorsulfonic acid hybrid micropattern containing nanoparticles was found to have a thickness of about 70 μm. As a result of measuring the surface resistance, it was confirmed that the surface resistivity was uniformly in the range of 7 to 11 Ω / □ there was. It was confirmed that when a mask including 250 or less fine meshes in an interval of 1 cm is used, the thickness of the hybrid micropattern to be manufactured becomes as high as 70 탆 or more and can be easily delaminated by external force on a flexible film .

[Example 29]

The polyaniline / camphorsulfonic acid hybrid paste containing the platinum-attached carbon nanoparticles was screen-printed on a flexible photo paper with a mask containing 300 fine meshes in 1 cm increments to form a platinum-coated carbon The nanoparticle-containing polyaniline / camphorsulfonic acid hybrid micropatterns were prepared and found to have a thickness of about 50 탆. The surface resistance was measured to be 20 Ω / □. When a mask having 300 or more fine meshes in an interval of 1 cm is used, the thickness of the hybrid micropattern to be manufactured is increased to 50 탆 or more, and the surface resistance value is larger than 20 Ω / □, I could confirm.

[Example 30]

The surface resistance characteristics of the polyaniline / camphorsulfonic acid hybrid micropattern containing platinum-attached carbon nanoparticles prepared in Example 1 upon folding were observed. When compressive strain is applied to the polyaniline / camphorsulfonic acid hybrid micropattern containing platinum-attached carbon nanoparticles, when the surface resistance is flat due to structural packing during folding at -30 °, 5%, and it was confirmed that the folding to -180 ° caused an increase of 11%. On the contrary, when the tensile strain was applied, it was observed that the surface resistance value was continuously increased, and it was increased by 16% when folding up to 180 °. (Fig. 7)

[Example 31]

The surface resistance characteristics of the polyaniline / camphorsulfonic acid hybrid micropattern containing platinum-attached carbon nanoparticles prepared in Example 1 according to bending were observed. A total of 500 compressive stresses were repeatedly applied to the polyaniline / camphorsulfonic acid hybrid micropattern containing the platinum-attached carbon nanoparticles. As a result, the surface resistance value in the flat state after bending was 16 Ω / I was able to identify him. (Fig. 7)

The polyaniline / camphorsulfonic acid hybrid micropattern was repeatedly subjected to the same compressive stress 500 times repeatedly. As a result, the surface resistance value in a flat state after bending exhibited a high surface resistance characteristic of 38 Ω / □. As a result, it was confirmed that the mechanical properties were deteriorated.

[Example 34]

Dipole antenna characteristics of polyaniline / camphorsulfonic acid hybrid micropatterns containing platinum-attached carbon nanoparticles prepared in Example 1 were analyzed. The prepared platinum-attached polyaniline / camphorsulfonic acid hybrid micropattern-based dipole tag antenna electrode was connected to 0.5 mm metal cable of the antenna network analyzer port using silver paste at both ends. The resistance of a 0.5 mm metal cable for impedance matching is 50 Ω. Measure the impedance of the dipole tag antenna by measuring the impedance value of the input / output terminal through the network analyzer. As a result, it was confirmed that the antenna has high efficiency dipole tag antenna characteristics with a center frequency of 2.835 GHz, a bandwidth of 0.55 GHz, a standing wave ratio of 1.05, a reflection loss of 37.4, a power transmission efficiency of 99.6%, and a recognition distance of 0.45 m. (Fig. 8)

none.

Claims

Introducing a platinum tetrachloride aqueous solution into an aqueous solution of a carboxylated polypyrrole nanoparticle into which (A) a functional group is introduced, preparing a carboxylated polypyrrole nanoparticle having platinum attached thereto by using a reducing agent and an ultrasonic treatment;
(B) subjecting the platinum-attached carboxylated polypyrrole nanoparticles to carbonization to produce platinum-attached carbon nanoparticles;
(C) introducing an aniline monomer into the aqueous acid solution in which the platinum-attached carbon nanoparticles are dispersed, adding chloroform thereto, and mixing an aqueous acid solution containing ammonium persulfate, which is an oxidizing agent, Preparing a carbon nanoparticle-containing polyaniline composite;
(D) introducing the platinum-attached polyaniline composite containing carbon nanoparticles into a basic solution to prepare a polyaniline composite containing carbon nanoparticles doped with platinum;
(E) introducing a secondary dopant camphorsulfonic acid into the polyaniline composite containing the doped platinum-attached carbon nanoparticles, and dispersing the camphorsulfonic acid in an organic cosolvent to prepare a polyaniline / camphorsulfonic acid hybrid paste containing platinum-attached carbon nanoparticles ;
(F) The polyaniline / camphorsulfonic acid hybrid paste containing the platinum-attached carbon nanoparticles was screen-printed onto a flexible substrate to form a polyaniline / camphorsulfonic acid hybrid micropattern containing platinum-attached carbon nanoparticles using screen printing step; And
(G) a flexible broadband dipole using a polyaniline / camphorsulfonic acid hybrid paste containing platinum-attached carbon nanoparticles having high electrical conductivity, using the polyaniline / camphorsulfonic acid hybrid micropattern containing platinum-attached carbon nanoparticles as an antenna electrode Tag antenna manufacturing method

The electrochemical device according to claim 1, wherein a concentration of the introduced tetrachloroplatinum aqueous solution is 0.1 to 50 mM when the aqueous solution of the carboxylated polypyrrole nanoparticle into which the functional group is introduced is introduced into the aqueous solution of the carboxylated polypyrrole nanoparticle to which the functional group is introduced. For manufacturing a flexible broadband dipole tag antenna using the polyaniline / camphorsulfonic acid hybrid paste containing the carbon nanoparticles attached thereto

2. The method according to claim 1, wherein, when the aqueous solution of the carboxylated polypyrrole nanoparticle into which the functional group is introduced is treated with a reducing agent after introducing the aqueous solution of platinum tetrachloride, the reducing agent is selected from the group consisting of sodium borohydride (NaBH ₄ ) ₄ ) and hydrazine (N ₂ H ₄ ), wherein the polyaniline / camphorsulfonic acid hybrid paste containing platinum-attached carbon nanoparticles having high electrical conductivity is used.

The polymer electrolyte fuel cell according to claim 1, wherein when the aqueous solution of the carboxylated polypyrrole nanoparticle into which the functional group is introduced is treated with the reducing agent, the amount of the reducing agent introduced is from 0.0001 to 0.1 g. METHOD FOR MANUFACTURING FLEXIBLE WIDEBAND DIPOLT TAG ANTENNA USING PLANANED POLYANILINE / CAMPOSULFONIC ACID HYBRID PEAST INCLUDING CARBON NANOPARTICLES

The method for producing carbon nanoparticles according to claim 1, wherein, when the platinum-adhered carboxylated polypyrrole nanoparticles are subjected to a carbonization process to produce platinum-attached carbon nanoparticles, the temperature of the carbonization process is 100 to 800 ° C. Fabrication method of flexible broadband dipole tag antenna using polyaniline / camphorsulfonic acid hybrid paste containing platinum-attached carbon nanoparticles having electrical conductivity

The method according to claim 1, wherein, when an aniline monomer is introduced into the aqueous acid solution in which the platinum-attached carbon nanoparticles are dispersed, and chloroform is added thereto and an acid aqueous solution containing ammonium persulfate is mixed, A method for manufacturing a flexible broadband dipole tag antenna using a polyaniline / camphorsulfonic acid hybrid paste containing platinum-attached carbon nanoparticles having a high electrical conductivity, wherein the concentration of the aqueous acid solution is 3 to 5 M.

The method according to claim 1, wherein an aniline monolayer is introduced into the aqueous acid solution in which the platinum-adhered carbon nanoparticles are dispersed, chloroform is added thereto, and an aqueous acid solution containing an oxidizing agent and an antioxidant ammonium is mixed, Containing polyaniline / camphor sulfonic acid having a high electrical conductivity, which has a high electrical conductivity and is characterized in that the polymerization temperature of the interfacial polymerization method is in the range of -50 to -10 ° C when the polyaniline composite having the carbon nanoparticles attached thereto is produced. Manufacturing Method of Flexible Broadband Dipole Tag Antenna Using Hybrid Paste

The method of claim 1, wherein, when the platinum-attached polyaniline composite containing carbon nanoparticles is introduced into a basic solution, the concentration of the basic solution is 0.1 to 1.5 M, and the platinum-attached carbon having a high electrical conductivity Manufacturing Method of Flexible Broadband Dipole Tag Antenna Using Nanoparticle-Containing Polyaniline / Camposulfonic Acid Hybrid Paste

2. The method according to claim 1, wherein, when introducing camphorsulfonic acid as a secondary dopant into the doped platinum-attached polyaniline composite containing carbon nanoparticles, the addition amount of camphorsulfonic acid is 100 moles of carbon nanoparticles containing dedoped platinum A method for manufacturing a flexible broadband dipole tag antenna using polyaniline / camphorsulfonic acid hybrid paste containing platinum-attached carbon nanoparticles having a high electrical conductivity, wherein the polyaniline /

The method of claim 1, wherein when the camphorsulfonic acid as a secondary dopant is introduced into the polyaniline composite containing the doped platinum-attached carbon nanoparticles and dispersed in the organic cosolvent, the amount of the complex to be dispersed is set to 100 parts by weight 1 to 3 parts by weight of polyaniline / camphorsulfonic acid hybrid paste containing platinum-attached carbon nanoparticles having a high electrical conductivity.

The method according to claim 1, wherein when the platinum-attached polyaniline / camphorsulfonic acid hybrid paste containing carbon nanoparticles is screen-printed on a flexible substrate, the flexible substrate is selected from the group consisting of polyethylene terephthalate (PET), polyimide a method of manufacturing a flexible broadband dipole tag antenna using a polyaniline / camphorsulfonic acid hybrid paste containing platinum-attached carbon nanoparticles having high electrical conductivity, wherein the polyaniline / camphorsulfonic acid hybrid paste is one of photo paper

[3] The method of claim 1, wherein when platinum-coated polyaniline / camphorsulfonic acid hybrid paste containing carbon nanoparticles is screen-printed on a flexible substrate, the mesh used for screen printing has 250 to 300 fine meshes at intervals of 1 cm A method for manufacturing a flexible broadband dipole tag antenna using a polyaniline / camphorsulfonic acid hybrid paste containing platinum-attached carbon nanoparticles having high electrical conductivity