KR101890308B1 - Multi-layered conductive nano particles and preparation method of the same - Google Patents

Abstract

The present invention relates to a conductive nanoparticle having a multi-layered structure and a method of manufacturing the same. More particularly, the present invention relates to a multi-layered conductive nanoparticle including a core and a shell having one or more layers, Conductive nanoparticles having a multilayer structure in which at least one conductive polymer is coated, and a method for manufacturing the conductive nanoparticles.
The conductive nanoparticles of the present invention have a high conductivity and can remarkably shorten the process of manufacturing a core and a shell of one or more layers, which is advantageous in terms of time and cost, and also has advantages in luminescence, workability, dispersibility, elasticity and stretchability great.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention [0001] The present invention relates to a conductive nanoparticle,

The present invention relates to a conductive nanoparticle having a multi-layered structure and a method of manufacturing the same. More particularly, the present invention relates to a multi-layered conductive nanoparticle including a core and a shell having one or more layers, Conductive nanoparticles having a multilayer structure in which at least one conductive polymer is coated, and a method for manufacturing the conductive nanoparticles.

In general, nanoparticles have a medium size between molecular states and bulk states, and have new electromagnetic and optical properties different from bulk states. Particularly, the bulk particles are multidomain, and the nanoparticles are single domains. Due to the nature of these nanoparticles, they are being used for various purposes by designing molecules at the nanoscale. Among them, electroconductive polymer nanoparticles have electrical properties such as metal, but they are light and elastic polymer. Therefore, there are various uses such as conductive paint, coating for electromagnetic shielding, polymer additive, metal catalyst carrier, protein carrier and sensor material. Do. However, the conductive polymer is liable to be brittle, crystallized, and not well dispersed in an organic solution or an aqueous solution.

In order to solve such a problem, a method of producing a core-shell conductive polymer ball by coating a polypyrrole with a nano-sized polystyrene ball, a so-called 'latex ball', as a mold agent has been reported (Sun-Hee Cho et al. , Colloids and Surfaces A: Physicochem. Eng. Aspects 255 (2005) 79-83, Claire Mangeney et al., Langmuir 22 (2006) 10163-10169.). However, the above study necessarily requires a surfactant to coat polypyrrole having a hydrophilic group in the polystyrene having hydrophobic properties. At this time, the ratio between the core ball and the surfactant is one of the most important parameters and it is very difficult to determine the ratio.

Further, in order to coat polypyrrole and polyaniline on the polystyrene surface without using a surfactant, the surface of the polystyrene ball having hydrophobic properties is chemically modified by the introduction of a sulfonic acid group, and the conductive polymer, polypyrrole and polyaniline, (Yang Yang, et al., Materials Chemistry and Physics 92 (2005) 164-171). However, the above-mentioned study has a problem of using polystyrene as electromagnetic shielding paint having a size of 2 탆.

There is also known a technique relating to a process for producing nano-sized electroconductive polymer particles of emulsion polymerization (Korean Patent Registration No. 711,958 and Korean Patent Registration No. 0919272) which can be formed into a uniform size while retaining spherical shape without clumping together . However, the conductive polymer is vulnerable to impact and is broken.

In addition, two manufacturing methods have been developed in which the chemical oxidized polymer reaction is carried out in an organic solvent and an aqueous solution. When 3,4-alkylenedioxythiophene and an oxidizing agent are used in an organic solvent, poly (3,4-alkylenedioxythiophene), which is a conductive polymer, is obtained in powder form. On the other hand, in an aqueous solution, it can be obtained in the form of a colloidal conductive polymer aqueous solution using 3,4-alkylenedioxythiophene, an oxidizing agent, and a surfactant, and is commercially available from Bayer, Germany under the trade name of Baytron P Poly (3,4-alkylenedioxythiophene) is commercially available in the form of a dispersion in an aqueous solution and no accurate molecular weight distribution has been reported (Eur. Patent 440957, 1991., Eur. Patent 553671, 1993., US Patent 5,792,558, 1996). At this time, since the oxidant used is excess in ion form, unnecessary ions are removed and commercialized through an ion exchange resin.

A method for producing poly (3,4-ethylenedioxythiophene) from a monomer 2,5-dichloro-3,4-ethylenedioxythiophene as a starting material by using a nickel metal catalyst has also been reported Polymer, 2001, 42, 7229., Polymer, 2002, 43, 711.). The obtained polymer has no dopant and thus has no electric conductivity. Therefore, the polymer is doped again to impart conductivity to produce poly (3,4-ethylenedioxythiophene). This reaction is an application of an aryl-aryl condensation reaction in which a nickel catalyst proceeds while removing a halogen element. However, it is necessary to use expensive nickel catalysts such as bis (1,5-cyclooctadiene) -nickel (0), Ni (cod) 2 and 2,2'-bipyridyl and also to conduct the conductive polymer function It is not suitable for industrial use.

Korean Patent Application Nos. 10-2007-0009718 and 10-2008-0031828 disclose a core-shell type nanoparticle in which a core is prepared by polymerizing a vinyl-based, acrylic-based or styrene-based polymer and a shell is formed outside the core, But the conductivity is insufficient.

Disclosure of the Invention The present invention has been made to solve the above-mentioned problems, and it is an object of the present invention to provide a conductive nanoparticle having a large conductivity and including a core having excellent luminescence, workability, dispersibility, elasticity and stretchability, And to provide the above objects.

In addition, the present invention can dramatically shorten the process of manufacturing the core and the shell of one or more layers, which is advantageous in terms of time and economy, and it is possible to variously form the multi-layered functional polymer, And a conductive nanoparticle having a multilayer structure produced by the method.

The present invention also provides an electronic material, an optical material, a printing material, a film, a conductive paint, a coating agent for shielding electromagnetic wave, a polymer additive, a metal catalyst carrier, a protein carrier, and a sensor material, .

In order to achieve the above object,

In a conductive nanoparticle having a multi-layer structure including a core and at least one shell,

The present invention provides a conductive nanoparticle having multilayer structure in which at least one layer of a light emitting and conductive polymer acting as a shell acts on a conductive polymer particle serving as a core.

Also,

A) preparing a conductive polymer core; And

B) coating the conductive polymer core with a conductive polymer constituting one or more shell structures;

The present invention also provides a method for producing a conductive nanoparticle having a multi-layer structure.

The present invention also relates to an electronic material, an optical material, a printing material, a film, a conductive paint, a coating agent for electromagnetic shielding, a polymer additive, a metal catalyst carrier, a protein carrier, a sensor material, etc. .

According to the present invention, it is possible to provide a conductive nanoparticle having a large conductivity and a multilayer structure including a core having excellent luminescence, workability, dispersibility, elasticity and stretchability, and a shell having at least one layer, Layered structure in which the process for producing a shell having a layer or more can be remarkably shortened, which is advantageous in terms of time and economy, and which can stably form a multi-layered functional polymer and thus can stably form a conductive nanoparticle. Conductive nanoparticles of the present invention can be provided.

1 is a schematic view showing a conductive nanoparticle of a core-shell structure according to an embodiment of the present invention.
FIG. 2 is a schematic view showing conductive nanoparticles of a core-1, a, and 2-helix structure according to an embodiment of the present invention;
3 is a schematic view showing a conductive nanoparticle of a core-shell structure according to Example 1 of the present invention.
4 is a schematic view showing a conductive nanoparticle of a core-1-throne-2-shear structure according to Example 3 of the present invention.
5 is a TEM-image of the conductive nanoparticles of the core-shell structure according to Example 1 of the present invention.

Hereinafter, the present invention will be described in detail.

The conductive nanoparticle of the present invention has a multi-layered conductive nanoparticle including a core and at least one shell, wherein at least one layer of a light emitting and conductive polymer acting as a shell is coated on the conductive polymer particle serving as a core Conductive nanoparticles of a multilayer structure.

The multi-layered conductive nanoparticles of the present invention preferably have a particle size of 30-1000 nm, preferably 10-100 nm, and more preferably one or more shells of 10-100 nm.

Also, in the conductive nanoparticles of the multi-layer structure, the material constituting the core and the shell are all composed of conductive polymers. Specifically, the core may be polypyrrole, polyfuran or polythiophene, and the shell coated on the outside of the core may be composed of a material selected from the group consisting of polypyrrole, polyfuran and polythiophene. The shell may be formed of one layer as shown in FIG. 1, or may have two or more layers as shown in FIG. Preferably, the shell is composed of 1-3 layers.

Specific examples of the conductive nanoparticles of the multi-layer structure of the present invention include polypyrrole (core) -polythiophene (shell), polythiophene (core) -polyfuran (shell), polyfuran (core) -polypyrrole (shell) (Core) -Polyfuran (primary shell) -polythiophene (secondary shell), polythiophene (core) -polypyrrole (primary shell) -polythiophene (secondary shell) (Primary shell) - polythiophene (secondary shell). In particular, the core is preferably polypyrrole, and the shell is preferably composed of polythiophene at the outermost periphery. In this case, the conductivity is high, and the luminescent property, workability, dispersibility, elasticity and stretchability are excellent.

The conductive nanoparticles of the multi-layer structure are prepared by: A) preparing a conductive polymer core; And B) coating the conductive polymer core with a conductive polymer constituting one or more shell structures.

The step A) may be carried out by a known polymerization method, and preferably, a) a method in which a) thiophene, pyrrole or furan monomer is added to an aqueous solvent; A compound selected from the group consisting of HCl, HF, HBr, and HI; Stabilizers; And a first oxidizing agent to prepare an emulsion; And b) mixing and stirring the emulsion of step a) with a second oxidizing agent to prepare emulsion-state conductive particles.

In the present invention, the core may be represented by the following general formula (1).

[Chemical Formula 1]

Wherein R ₁ and R ₂ are each independently selected from the group consisting of hydrogen, halogen, hydroxy, C 1 -C 10 alkyl, alkoxy, carbonyl, Alkenylene, alkenyloxy, alkenyldioxy, alkynyloxy, alkynyldioxy of 8 membered alicyclic or aromatic ring structure, which may contain, besides hydrogen, carbon and oxygen atoms, nitrogen, sulfur , Phosphorus, selenium, silicon, and the like.

The thiophene, pyrrole, or furan monomer as the starting material is a starting material prepared from a polythiophene, a polypyrrole, and a polyfuran through a polymerization reaction, and any of thiophene, pyrrole, and furan, which are commonly used in the art, And may be represented by the following general formula (2), and is preferably thiophene, pyrrole, or furan which is substituted with alkyl ethoxy, carboxyl group, or at least one substituent selected therefrom.

(2)

In Formula 2, X, R ₁ and R ₂ are as defined above.

In addition, the compound selected from the group consisting of HCl, HF, HBr, and HI acts as a dopant while making the reaction solution acidic (pH 1-6), and particularly HCl is preferable. Due to the use of HC, etc., the conductive core produced by the present invention can produce a conductive polymer core in which electrical conductivity and processability are significantly improved compared to conventional polymers. The amount of the compound such as HCl is preferably 1 to 100 mole ratio of the monomer. If the molar ratio is less than 1, the reaction proceeds slowly and the yield is low and the electrical conductivity of the reaction product is low. When the molar ratio exceeds 100, the acid value of the product is high and it is difficult to neutralize and wash the product, Which is somewhat problematic for commercial use.

The solvent may be a mixture of one or more selected from the group consisting of C ₆ -C ₂₀ aliphatic and aromatic hydrocarbons, halogen-containing hydrocarbons, ketones, ethers, C ₂ -C ₂₀ alcohols, sulfoxides, amides, . More specifically, the C ₆ -C ₂₀ aliphatic and aromatic hydrocarbons include benzene, toluene, xylene, cumene, mesitylene, heptane, octane, Phenol and cresol. Examples of halogen-containing hydrocarbons include dichlorobenzene and chlorobenzene, which are carbon tetrachloride, chloroform, dichloromethane, dichloroethane, dibromoethane, trichloroethane, tribromoethane and halobenzene, , Ethanols such as diethyl ether, tetrahydrofuran (THF), dipropyl ether, dibutyl ether, methyl butyl ether and the like may be used. Diethylene glycol, ethylene glycol (EG) and the like. The C2-C20 alcohol and the sulfoxide series may be dimethylsulfoxide (DMSO), diphenyl ether, dioxane, diglyme, diethylene glycol, ), The amide series may include N, N-dimethylformamide (DMF), N-methylacetamide (NMAA), N, N-dimethylacetamide (DMA), N-methylpropionamide - Nmethylpyrrolidinone (NMP).

Preferably, the solvent is used in an amount of 1,000 to 3,000 parts by weight based on 100 parts by weight of the monomer, and water and C ₂ -C ₂₀ alcohols having a temperature range of 0 to 180 ° C, DMSO, DMF, NMP, ether, Polar solvents such as ethylene glycol and the like are suitable.

In addition, the stabilizer is mixed with the pyrrole and furan or derivatives thereof to impart stability to the particles. In order to achieve the object, any stabilizer commonly used in the art may be used. Examples of the stabilizer include poly (4-styrene sulfonic acid), poly (acrylic acid), poly (methacrylic acid), poly (maleic acid) , Poly (vinyl sulfonic acid), dodecyl trimethyl ammonium bromide, cetyl trimethlammonium bromide, didodecyl dimethyl ammonium bromide, didodecyl dimethyl ammonium bromide, bromide], Span 80, Tween 20, polyoxyethylene (20) sorbitanmonolaurate, perfluorooctanoic acid, cetylpyridinium chloride Cetylpyridinium chloride, benzalkonium chloride, and benzethonium chloride may be used alone or in combination of two or more. Polystyrene sulfonic acid is the most suitable stabilizer.

The amount of the stabilizer is preferably 0.01 to 2,000 parts by weight based on 100 parts by weight of the monomer. If the content is less than 0.01 part by weight, the concentration of the micelle may not be sufficient and it may not act as a stabilizer. Therefore, polymerization of the chain type nanoparticles can not be induced and aggregation of particles occurs. When the content exceeds 2,000 parts by weight, ) Is too large to form the chain-like nanoparticles.

In addition, the first oxidizing agent is for oxidizing the reduced second oxidizing agent to oxidize the second oxidizing agent when the second oxidizing agent is reduced by oxidizing the thiophene, pyrrole, or furan monomer. It is preferable to use an oxidizing agent having a relatively higher oxidizing power than the second oxidizing agent. Preferably, the oxidizing agent is at least one selected from the group consisting of peroxides [H ₂ O ₂ , (NH ₄ ) ₂ S ₂ O ₈ , O ₂ ] or oxygenates [HMnO ₄ , HNO ₃ , HClO ₄ ], halogens [F ₂ , Cl ₂ , Br ₂ ] or mixtures thereof.

The addition amount of the first oxidizing agent is preferably 0.01 to 10 mole ratio of the monomer. If the content of the first oxidizing agent is less than 0.01 mol, the reaction for reducing the second oxidizing agent does not occur sufficiently, and the degree of polymerization of the chain type nanoparticles is lowered. On the other hand, if the content of the first oxidizing agent is more than 10 mol% .

The second oxidizing agent is used for oxidizing monomers. Any oxidizing agent capable of achieving such a purpose may be used, but preferably a metal oxide such as FeCl ₃ , Fe (SO ₄ ) ₂ .6H ₂ O (II) complex or an iron (II) complex or a mixture thereof may be used. The amount of the iron (II) complex to be used is preferably 0.001 to 5 molar ratio relative to the monomer. In the present invention, when the amount of the second oxidizing agent is less than 0.001 mol, the polymerization reaction rate is very slow. If the amount of the second oxidizing agent is more than 5 mol, the polymerization reaction rate and electrical conductivity are increased but the physical properties of the conductive polymer are decreased.

In the present invention, the second oxidant can be directly incorporated into a mixture of starting materials for the polymerization reaction, for example, a mixture of a monomer, a compound such as HCl, a stabilizer, a first oxidizing agent and a solvent, (Deionized water, DI Water) and / or a mixture of the starting materials dissolved in an organic solvent.

In the present invention, the reaction temperature of the polymeric polymerization reaction is preferably 0-180 ° C, or the boiling point of the solvent used. It is stirred at a temperature of 0-180 ° C for 6-24 hours to conduct conductive water- Nanoparticles can be produced.

More preferably, the present invention relates to a process for the preparation of a composition comprising i) 0.01 to 2,000 parts by weight of a stabilizer relative to 100 parts by weight of a substituted or unsubstituted thiophene, pyrrole or furan monomer, and 0.01 to 10 mole ratio of said monomer, By weight of HCl having a temperature in the range of 0 to 180 DEG C of from 1,000 to 2,000 parts by weight of the emulsion of step 1), ii) adding the second oxidant to the emulsion of step i) in an amount of 0.001 To 5.0 molar ratio and stirring at 0 to 180 DEG C for 10 to 30 minutes, iii) the seed emulsion of step ii) is heated at a temperature of 0 to 180 DEG C for 6 to 24 hours Followed by stirring to prepare a conductive water dispersible nanoparticle including an emulsion oxidation polymerization step.

Further, it may further comprise drying step c) during the production of the core of step A). The drying in the step c) is a step of drying the conductive particles in an emulsion state and can be dried at room temperature -70 ° C.

The step B) of coating the conductive polymer constituting the shell structure of at least one layer with the conductive polymer core comprises forming a shell of at least one layer on the conductive polymer core prepared in the step A) , Preferably a) a conductive core in an aqueous solvent; Thiophene, pyrrole or furan monomers; A compound selected from the group consisting of HCl, HF, HBr, and HI; Stabilizers; And a first oxidizing agent to prepare an emulsion; And b) mixing and stirring the emulsion of step a) with a second oxidant to produce emulsion-state conductive particles. When a shell having two or more layers is to be formed, conductive nanoparticles having two or more layers can be prepared by using shell-formed particles instead of the conductive core used for forming the one-layer. Preferably, the shell is composed of 1-3 layers. The amount of the compound stabilizer, the first oxidizing agent, the second oxidizing agent, and the like selected from the group consisting of HCl, HF, HBr, and HI in the formation of the shell is determined based on the monomer of the shell to be polymerized, It can be used in accordance with the amount used in the production.

It may further comprise drying step c) of forming the shell of step B). The drying in the step c) is a step of drying the conductive particles in an emulsion state and can be dried at room temperature -70 ° C.

The present invention also provides an article comprising the conductive nanoparticles of the multi-layer structure, wherein the conductive nanoparticles of the multi-layer structure produced by the present invention have good processability and excellent conductivity, , Films, and the like, and can be applied to energy conversion and energy storage materials, antistatic materials, charge control materials, electrically conductive layer materials, pattern manufacturing materials, and printing ink materials. Further, the electronic material, the film, the toner and / or the ink as the printing material according to the present invention means the electronic material, toner and / or ink including the conductive nanoparticles of the multi-layer structure manufactured by the present invention. (Electronic material, toner, and / or ink) according to the present invention, and preferred electronic materials include a photovoltaic cell, a capacitor (used as an electrolyte), and a PCB printed circuit boards), and / or antistatic agents (which prevent the generation of static electricity from the surfaces of plastics, polymers, etc. through coatings).

Hereinafter, the present invention will be described in more detail with reference to the following examples. However, the scope of the present invention is not limited to the following examples.

[Example 1]

89 g of deionized water at 25 DEG C, 7.9 g of a 37 wt% hydrochloric acid aqueous solution and 6.9 g of an 18 wt% polystyrenesulfonic acid aqueous solution as a stabilizer, which were prepared by sequentially passing distilled water through a cation and anion exchange resin, To completely dissolve the stabilizer. Then, 0.5 g of the thiophene monomer was mixed and reacted at a temperature of 25 캜 for about 30 minutes to prepare an emulsion.

Next, in the closed reactor, 0.3 g of a 30% by weight aqueous hydrogen peroxide solution as the first oxidizing agent and 7 mg of ferric sulfate [Fe ₂ (SO ₄ ) ₃ ] as the initiator were added to the mixture in 5 g of deionized water To prepare a mixed solution containing a second oxidizing agent, and then the seed emulsion mixture was stirred at a temperature of 25 캜 for 12 hours to prepare emulsion polythiophene particles.

Then, the prepared emulsion polythiophene particles were dried at a temperature ranging from room temperature to 70 ° C to prepare polythiophene particles.

As a result, the conversion of the polythiophene emulsion was 99%, and the average particle size of the prepared polythiophene was 70 nm. The sheet resistance was measured by making a conductive film with a bar coating method (# 7 bar) 10 ^5.0 ohm / sq.

0.1 to 10 g of NMP, DMSO and ethylene glycol were dissolved in 10 g of the prepared polythiophene emulsion, and a conductive film was prepared by bar coating to obtain a sheet resistance value of 100 to 10 ^5.0 ohm / sq.

0.5 g of 3,4-ethylenedioxythiophene, which is a monomer for forming a shell, and 7.9 g of 37% by weight hydrochloric acid aqueous solution were mixed in the prepared polythiophene emulsion and reacted at 25 ° C for about 30 minutes to prepare an emulsion. The emulsion is a dispersion of polythiophene nanoparticles containing 3,4-ethylenedioxythiophene monomer.

Next, in the closed reactor, 0.3 g of a 30% by weight aqueous hydrogen peroxide solution as the first oxidizing agent and 7 mg of ferric sulfate [Fe ₂ (SO ₄ ) ₃ ] as the initiator were added to the mixture in 5 g of deionized water To prepare a mixed solution containing the second oxidizing agent, and then the seed emulsion mixture was stirred at a temperature of 25 캜 for 12 hours to polymerize the emulsion poly (3,4-ethylenedioxythiophene) shell. As a result, the conversion of poly (3,4-ethylenedioxythiophene) was 99%.

The conductive particles of the polythiophene / poly (3.4-ethylenedioxythiophene) core / shell structure in the prepared emulsion state are then dried at a temperature ranging from room temperature to 70 ° C to form polythiophene / poly (3,4-ethylenedioxythiophene ) Core / shell structure.

As a result, the polythiophene / poly (3,4-ethylenedioxythiophene) particle size was 80 nm on average and the shell thickness was 10 nm. The sheet resistance was measured using a bar coating method (# 7 bar) to obtain a conductive film of 10 ^5.0 ohm / sq.

0.1 to 10 g of NMP, DMSO and ethylene glycol were dissolved in 10 g of polythiophene / poly (3,4-ethylenedioxythiophene) emulsion, and a conductive film was prepared by a bar coating method. As a result, ^5.0 ohm / sq. ≪ / RTI >

[Example 2]

The procedure of Example 1 was repeated except that 69 g of a 18 wt% polystyrenesulfonic acid solution as a stabilizer was used. 7 mg of ferric sulfate, a second oxidizing agent, was added as an initiator to 5 g of deionized water to prepare a second oxidant Was mixed with the emulsion, and the mixture was reacted at a temperature of 25 캜 for about 30 minutes to prepare a seed emulsion.

The seed emulsion mixture was then stirred for 12 hours at a temperature of 25 DEG C in a closed reactor to prepare emulsion polypyrrole particles.

As a result, the conversion rate of the polypyrrole emulsion was 96%, and the average particle size of the polypyrrole particles was 50 nm. The sheet resistance was measured using a bar coating method (# 7 bar) to obtain a sheet resistance of 10 ^6.0 ohm / sq. < / RTI >

0.1 to 10 g of NMP, DMSO and ethylene glycol were dissolved in 10 g of the polypyrrole emulsion, and a conductive film was prepared by bar coating to obtain a sheet resistance value of 100 to 10 ^6.0 ohm / sq.

0.5 g of thiophene, which is a monomer for forming a shell, was mixed with the polypyrrole emulsion prepared above, and reacted at a temperature of 25 캜 for about 30 minutes to prepare an emulsion. The emulsion is a polypyrrole nanoparticle dispersion containing a thiophene monomer.

Next, in the closed reactor, 0.3 g of a 30% by weight aqueous hydrogen peroxide solution as the first oxidizing agent and 7 mg of ferric sulfate [Fe ₂ (SO ₄ ) ₃ ] as the initiator were added to the mixture in 5 g of deionized water To prepare a mixed solution containing a second oxidizing agent, and the seed emulsion mixture was stirred at a temperature of 25 캜 for 12 hours to polymerize the emulsion polythiophene shell. As a result, the conversion of polythiophene was 99%.

Then, the conductive particles of the polypyrrole / polythiophene (core / shell) structure in the emulsion state prepared above were dried at a temperature ranging from room temperature to 70 ° C to prepare conductive particles having a polypyrrole / polythiophene (core / shell) structure.

As a result, the average particle size of polypyrrole / polythiophene was 70 nm, and the sheet resistance was 10 ^5.0 ohm / sq. When the conductive film was formed by bar coating method (# 7 bar).

0.1 to 10 g of NMP, DMSO and ethylene glycol were dissolved in 10 g of the polypyrrole / polythiophene emulsion, and a conductive film was prepared by bar coating to obtain a sheet resistance value of 100 to 10 ^5.0 ohm / sq. The polypyrrole / polythiophene (core / shell) particles prepared above had luminescent properties in the red region.

[Example 3]

0.5 g of 3,4-ethylenedioxythiophene, which is a monomer for forming the outermost shell of the multi-layered structure, and 7.9 g of 37% by weight hydrochloric acid aqueous solution were mixed in the polypyrrole / polythiophene emulsion prepared in Example 2, For about 30 minutes to prepare an emulsion. The emulsion is a polypyrrole / polythiophene nano-particle dispersion containing 3,4-ethylenedioxythiophene monomer.

Next, in the closed reactor, 0.3 g of a 30% by weight aqueous hydrogen peroxide solution as the first oxidizing agent and 7 mg of ferric sulfate [Fe ₂ (SO ₄ ) ₃ ] as the initiator were added to the mixture in 5 g of deionized water To prepare a mixed solution containing the second oxidizing agent, and then the seed emulsion mixture was stirred at a temperature of 25 캜 for 12 hours to polymerize the emulsion poly (3,4-ethylenedioxythiophene) shell. As a result, the conversion of poly (3,4-ethylenedioxythiophene) was 99%.

The conductive particles of the polypyrrole / polythiophene / poly (3,4-ethylenedioxythiophene) multilayer structure prepared in the emulsion state are then dried in the range of room temperature to 70 ° C to form polypyrrole / polythiophene / poly (3,4- City Oppen) core / shell 1 / shell 2 structure.

As a result, the average particle size of the polypyrrole / polythiophene / poly (3,4-ethylenedioxythiophene) was 80 nm, and the shell thickness was 10 nm. The sheet resistance was measured using a bar coating method (# 7 bar) to obtain a conductive film of 10 ^5.0 ohm / sq.

Further, 0.1 to 10 g of NMP, DMSO and ethylene glycol was dissolved in 10 g of the polypyrrole / polythiophene / poly (3,4-ethylenedioxythiophene) emulsion, and the conductive film was prepared by a bar coating method. 10 ^5.0 ohm / sq.

As described above, those skilled in the art will understand that the present invention may be embodied in other specific forms without departing from the spirit or essential characteristics thereof. It is therefore to be understood that the embodiments described above are to be considered in all respects only as illustrative and not restrictive. The scope of the present invention should be construed as being included in the scope of the present invention without departing from the scope of the present invention as defined by the appended claims.

Claims (21)

In a conductive nanoparticle having a multi-layer structure including a core and at least one shell,
The conductive polymer particles serving as the core are coated with one or more layers of a light emitting and conductive polymer serving as a shell,
Wherein the core is formed of polypyrrole or polythiophene, and the outermost angle of the shell is formed of polythiophene or poly (3,4-ethylenedioxythiophene). The method according to claim 1,
Wherein the particles have a particle size of 10-1000 nm. The method according to claim 1,
Wherein the core is 10-100 nm in size. The method according to claim 1,
Wherein the shell is formed with 1-3 layers having a thickness of 10-100 nm on the outer surface of the core. delete delete A) preparing a conductive polymer core; And
B) coating the conductive polymer core with a conductive polymer constituting one or more shell structures;
Lt; / RTI >
Step A) comprises: a-1) adding a thiophene or pyrrole monomer to an aqueous solvent; A compound selected from the group consisting of HCl, HF, HBr, and HI; Stabilizers; And a first oxidizing agent to prepare an emulsion; And a-2) mixing and stirring the emulsion of step a-1) with a second oxidant to prepare emulsion-state conductive particles,
The step b) comprises: b-1) the conductive core prepared in step A) in an aqueous solvent; Thiophene or 3,4-ethylenedioxythiophene monomers; A compound selected from the group consisting of HCl, HF, HBr, and HI; Stabilizers; And a first oxidizing agent to prepare an emulsion; And b-2) mixing the emulsion of step b-1) with a second oxidizing agent and stirring to prepare emulsion-state conductive particles.
A method for producing conductive nanoparticles of a multilayer structure. delete 8. The method of claim 7,
Wherein the step (a-1) comprises using HCl. 8. The method of claim 7,
Wherein the compound selected from the group consisting of HCl, HF, HBr, and HI is introduced at a 1-100 mole ratio of the thiophene or pyrrole monomer in the step a-1) ≪ / RTI > 8. The method of claim 7,
Wherein the stabilizer is added in an amount of 0.01 to 2000 parts by weight based on 100 parts by weight of the thiophene or pyrrole monomer used in the step a-1). 8. The method of claim 7,
Wherein the first oxidizing agent is added at a mole ratio of 0.01 to 10 mol of the thiophene or pyrrole monomer in the step a-1). 8. The method of claim 7,
Wherein the second oxidizing agent is introduced at 0.001 to 5.0 mole ratio of the thiophene or pyrrole monomer in the step a-1). 8. The method of claim 7,
Wherein the first oxidizing agent is at least one selected from the group consisting of H ₂ O ₂ , (NH ₄ ) ₂ S ₂ O ₈ , HMnO ₄ , HNO ₃ , HClO ₄ , F ₂ , Cl ₂ and Br ₂ Wherein the conductive nanoparticles have an average particle size of less than 100 nm. 8. The method of claim 7,
Wherein the second oxidizing agent is at least one selected from the group consisting of FeCl ₃ , Fe (SO ₄ ) ₂ .6H ₂ O, and iron (II) complex. delete 8. The method of claim 7,
Wherein the step A) or the step b) further comprises a drying step. An electronic material comprising the conductive nanoparticles of the multilayer structure according to claim 1. An optical material comprising the conductive nanoparticles of the multilayer structure according to claim 1. A printing material comprising the conductive nanoparticles of the multilayer structure according to claim 1. A film comprising the conductive nanoparticles of the multilayer structure of claim 1.

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