WO2012169768A2

WO2012169768A2 - Multi-layered conductive nano particles and manufacturing method therefor

Info

Publication number: WO2012169768A2
Application number: PCT/KR2012/004437
Authority: WO
Inventors: 김중현; 김병욱; 이선종
Original assignee: 주식회사 한국엔티켐
Priority date: 2011-06-07
Filing date: 2012-06-05
Publication date: 2012-12-13
Also published as: WO2012169768A9; KR20120135691A; KR101890308B1; WO2012169768A3; CN103608284A; CN103608284B; TW201307189A

Abstract

The present invention relates to multi-layered, conductive nano particles and a manufacturing method therefor, and more specifically, to a multilayer structure, conductive nano particle comprising a core and more than one shell layer. The multi-layered, conductive nano particle is coated with more than one layer of light-emitting and conductive polymer which functions as a shell for the conductive polymer particle that, in turn, functions as a core, and the invention relates to a manufacturing method for the same. The multi-layered, conductive nano particles of the present invention demonstrate high electrical conductivity, the duration for the manufacturing process of the core and more than one shell layer is dramatically reduced, economic advantageous are demonstrated, and luminance, processability, dispersibility, elasticity and stretchability are all excellent.

Description

Conductive nanoparticles of multi-layer structure and method of manufacturing same

The present invention relates to a conductive nanoparticles having a multi-layer structure and a method for manufacturing the same, particularly in the conductive nano-particles having a multi-layer structure comprising a core and one or more layers, light emission and acting as a shell to the conductive polymer particles serving as a core and The present invention relates to a conductive nanoparticle having a multilayer structure coated with one or more conductive polymers and a method of manufacturing the same.

In general, nanoparticles are materials that fall between the molecular and bulk states, and have new electromagnetic and optical properties that differ from those of the bulk state. In particular, bulk particles are multidomain, while nanoparticles are single domain. Due to the characteristics of the nanoparticles, molecules have been designed at a nano size and used for various purposes. Among them, the electrically conductive polymer nanoparticles have the same electrical properties as metals but have the characteristics of light and elastic polymers, and thus have various uses such as conductive paints, electromagnetic wave shielding coatings, polymer additives, metal catalyst carriers, protein carriers, and sensor materials. Do. However, there is a problem that the conductive polymer is brittle, crystallized, and hardly dispersed in an organic solution or an aqueous solution.

In order to solve this problem, a method of preparing a core-shell conductive polymer ball by coating polypyrrole using a nano-sized polystyrene ball, a so-called 'latex ball' as a template 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 study requires a surfactant to coat polypyrrole with hydrophilic groups on polystyrene with hydrophobic properties. At this time, the ratio of the core ball and the surfactant is one of the very important parameters and it is very difficult to determine this.

In addition, in order to coat polypyrrole and polyaniline on the surface of polystyrene without using a surfactant, the surface of the hydrophobic polystyrene ball is chemically modified by the introduction of sulfonic acid groups, and the polypyrrole and polyaniline, which are conductive polymers, are coated to form a core-. Research into shell conducting balls is known (Yang Yang, et al., Materials Chemistry and Physics 92 (2005) 164-171.). However, the above research has a big problem in that the polystyrene has a size of 2 μm and is used as an electromagnetic shielding paint.

In addition, a technique for preparing nano-sized electrically conductive polymer particles of emulsion polymerization (Korean Patent Registration No. 711,958 and Korean Patent Registration No. 0919272) that can be formed in a uniform size without maintaining a spherical shape, is known. . However, the conductive polymer is weak to shock and remains a problem of breaking well.

In addition, two production methods have been developed in which the chemical oxidation polymer reaction is carried out in an organic solvent and an aqueous solution. When produced using 3,4-alkylenedioxythiophene and an oxidizing agent in an organic solvent, poly (3,4-alkylenedioxythiophene), which is a conductive polymer in powder form, is obtained. On the other hand, in the 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. Poly (3,4-alkylenedioxythiophene) is commercially available in the form of a dispersion in aqueous solution and no exact molecular weight distribution has been reported (Eur. Patent 440957, 1991., Eur. Patent 553671, 1993., US Patent 5,792,558, 1996). At this time, the oxidant used is left in excess in the form of ions, and removes and commercializes unnecessary ions through the ion exchange resin.

In addition, a method of preparing poly (3,4-ethylenedioxythiophene) from monomer 2,5-dichloro-3,4-ethylenedioxythiophene as a starting material using a nickel metal catalyst has also been reported ( Polymer, 2001, 42, 7229., Polymer, 2002, 43, 711.). In this case, the obtained polymer does not have a dopant (dopant), so there is no electrical conductivity, thereby giving a conductivity through the doping process to prepare poly (3,4-ethylenedioxythiophene). This reaction is an application of the aryl-aryl condensation reaction that proceeds while the nickel catalyst removes the halogen element. However, a mixed nickel catalyst of expensive bis (1,5-cyclooctadiene) -nickel (0), Ni (cod) 2, and 2,2'-bipyridyl must be used. It is not suitable for industrial use.

In addition, Korean Patent Application Nos. 10-2007-0009718 and 10-2008-0031828 disclose core-shell-type nanoparticles prepared by polymerizing vinyl, acrylic, or styrene polymers to form a core, and forming a shell around the core. It is disclosed that the technique for producing, but the situation is lacking conductivity.

The present invention has been made to solve the above-described problems, the conductive nanoparticles of a multi-layer structure comprising a core and one or more shells having high conductivity and excellent luminescence, processability, dispersibility, elasticity and elasticity, and a method of manufacturing the same. The purpose is to provide.

In addition, the present invention can significantly shorten the process for manufacturing the core and one or more layers of shells, which is advantageous in time and economically, and forms a variety of multi-functional polymers, thereby stably forming the conductive nano An object of the present invention is to provide a method for producing particles and conductive nanoparticles having a multilayer structure prepared by the method.

The present invention also provides an electronic material, an optical material, a printing material, a film, a conductive paint, an electromagnetic shielding coating agent, a polymer additive, a metal catalyst carrier, a protein carrier, a sensor material, and the like, which include the conductive nanoparticles. For the purpose of

The present invention to achieve the above object

In the conductive nanoparticles of a multilayer structure comprising a core and one or more layers of shells,

The present invention provides a conductive nanoparticle having a multilayer structure in which at least one layer of light emitting and conductive polymers serving as shells is coated on conductive polymer particles serving as cores.

In addition, the present invention

A) preparing a conductive polymer core; And

B) coating a conductive polymer constituting at least one layer of the shell structure on the conductive polymer core;

It provides a method for producing a conductive nanoparticles of a multi-layer structure comprising a.

In addition, the present invention is an electronic material, an optical material, a printing material, a film, a conductive paint, an electromagnetic shielding coating agent, a polymer additive, a metal catalyst carrier, a protein carrier, a sensor material, etc., comprising the conductive nanoparticles of the multilayer structure. To provide.

According to the present invention, it is possible to provide a conductive nanoparticle having a high conductivity and a multi-layered structure comprising a core and one or more layers of shells having excellent luminescence, processability, dispersibility, elasticity and elasticity, and a method of manufacturing the same. The method of manufacturing a shell having more than one layer can be drastically shortened, which is advantageous in terms of time and economics, and in the method of producing a multi-layered conductive nanoparticle and stably forming a multifunctional polymer, It is possible to provide a conductive nanoparticles of a multi-layer structure manufactured by.

1 is a schematic diagram showing conductive nanoparticles of a core-shell structure according to an embodiment of the present invention.

Figure 2 is a schematic diagram showing the conductive nanoparticles of the core-shell shell-secondary shell structure according to an embodiment of the present invention.

Figure 3 is a schematic diagram showing the conductive nanoparticles of the core-shell structure according to Example 1 of the present invention.

Figure 4 is a schematic diagram showing the conductive nanoparticles of the core-shell shell secondary shell structure according to Example 3 of the present invention.

5 is a TEM-image of conductive nanoparticles having a core-shell structure according to Example 1 of the present invention.

Hereinafter, the present invention will be described in detail.

Multi-layered conductive nanoparticles of the present invention is a multi-layered conductive nanoparticles comprising a core and at least one layer of shell, wherein the light emitting and conductive polymers acting as a shell is coated on the conductive polymer particles acting as a core Multi-layered conductive nanoparticles.

The multi-layered conductive nanoparticles of the present invention preferably have a particle size of 30-1000 nm, preferably at least one layer of 10-100 nm shell coated on a 10-100 nm core.

In addition, the conductive nanoparticles of the multi-layered structure are all composed of a conductive polymer material constituting the core and shell. Specifically, the core may be polypyrrole, polyfuran or polythiophene, and the shell coated on the outside of the core may be made of a material selected from the group consisting of polypyrrole, polyfuran and polythiophene. The shell may be composed of one layer as shown in FIG. 1, or may be composed of two or more layers as shown in FIG. 2. Preferably the shell consists of 1-3 layers.

Specific examples of the conductive nanoparticles having a multilayer structure of the present invention include polypyrrole (core) -polythiophene (shell), polythiophene (core) -polyfuran (shell), polyfuran (core) -polypyrrole (shell), polypyrrole (Core) -polyfuran (primary shell) -polythiophene (secondary shell), polythiophene (core) -polypyrrole (primary shell) -polythiophene (secondary shell), polypyrrole (core) -poly Thiophene (primary shell) -polythiophene (secondary shell) and the like can be configured in various ways, in particular, the core is preferably polypyrrole, the shell is preferably composed of polythiophene in the outermost. In this case, the conductivity is high, and the light emitting property, workability, dispersibility, elasticity and elasticity are excellent.

The conductive nanoparticles of the multi-layer structure is A) preparing a conductive polymer core; And B) coating a conductive polymer constituting at least one layer of the shell structure on the conductive polymer core.

Step A) may use a known polymerization method, preferably a) a thiophene, pyrrole or furan monomer in an aqueous solvent; Compounds selected from the group consisting of HCl, HF, HBr and HI; Stabilizer; And mixing the first oxidant to prepare an emulsion. And b) mixing the second oxidant into the emulsion of step a) and stirring to prepare conductive particles in an emulsion state.

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

[Formula 1]

In Formula 1, X represents sulfur, nitrogen, oxygen, phosphorus, silicon, or arsenic, and R ₁ and R ₂ are each independently hydrogen, halogen, hydroxy, C1-C10 alkyl, alkoxy, carbonyl, 3 to 8 may be alkylene, alkenylene, alkenyloxy, alkenyldioxy, alkynyloxy, alkynyldioxy in the membered alicyclic or aromatic ring structure, which may be nitrogen, sulfur in addition to hydrogen, carbon, oxygen atoms And atoms such as phosphorus, selenium, and silicon.

The starting material thiophene, pyrrole or furan monomer is a starting material prepared from polythiophene, polypyrrole and polyfuran through a polymerization reaction, and any thiophene, pyrrole and furan commonly used in the art may be used. For example, the thiophene, pyrrole or furan substituted with at least one or more substituents selected from alkyl ethoxy, carboxyl sulfone groups or these may be represented by the following Chemical Formula 2, for example.

[Formula 2]

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

In addition, the compound selected from the group consisting of HCl, HF, HBr and HI makes the reaction solution acid (pH 1-6) and at the same time acts as a dopant (dopant), especially HCl is preferred. The conductive core prepared according to the present invention due to the use of the HC | etc. can be produced a conductive polymer core significantly improved electrical conductivity and processability compared to the conventional polymer. The amount of the compound such as HCl is preferably used in 1 to 100 mole ratio (mole ratio) of the monomer. In the case where the molar ratio is less than 1, the progress of the reaction is delayed, the yield is low, and the electrical conductivity of the reaction product is low. When the molar ratio is more than 100, the acid value of the product is high, which makes it difficult to neutralize and wash the production cost. This increase is somewhat problematic for commercial use.

In addition, the solvent is a mixture of one or two 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, and water It can also be used. More specifically, C ₆ -C ₂₀ aliphatic and aromatic hydrocarbons include alkanes hexane, heptane, octane, nonane, decane, and alkylbenzenes benzene, toluene, xylene, cumene, mesitylene, Phenol, cresol, and the like, and halogen-containing hydrocarbons include carbon tetrachloride, chloroform, dichloromethane, dichloroethane, dibromoethane, trichloroethane, tribromoethane, and halobenzenes such as dichlorobenzene and chlorobenzene, and ketones include acetone. , Propanone, butanone, pentanone, hexanon, heptanone, octanon, acetophenone and the like, and ethers are diethyl ether, tetrahydro hulan (THF), dipropyl ether, dibutyl ether, methyl butyl ether , Diphenyl ether, dioxane, diglyme, diethylene glycol, ethylene glycol (EG), and C2-C20 alcohols and sulfoxides are dimethylsulfoxide (DMSO). ), Amide series include N, N-dimethylformamide (NMF), N-methylacetamide (NMAA), N, N-dimethylacetamide (DMA), N-methylpropionamide (NMPA) and N Methylpyrrolidinone (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, water having a temperature range of 0-180 ℃ and C ₂ -C ₂₀ alcohols, DMSO, DMF, NMP, ether, Polar solvents such as ethylene glycol and the like are suitable.

In addition, the stabilizer (Stabilizer) is mixed with the pyrrole and furan or derivatives thereof to impart the stability of the particles, any stabilizer (stabilizer) commonly used in the art to achieve this purpose may be used. As the stabilizer, poly (4-styrene sulfonic acid), poly (acrylic acid), poly (methacrylic acid) polymaleic acid, poly (maleic acid) Poly (vinyl sulfonic acid), dodecyl trimethyl ammonium bromide, cetyl trimethlammonium bromide, dododecyl dimethyl ammonium bromide bromide], Span 80, Tween 20, polyoxyethylene (20) sorbitanmonolaurate, Perfluorooctnoic acid, cetylpyridinium chlor Cetylpyridinium chloride, benzalkonium chloride and benzethonium chloride may be used alone or in combination of two or more thereof. As the most ideal stabilizer, polystyrene sulfonic acid is suitable.

The amount of the stabilizer used 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 parts by weight, the micelle formation concentration does not function as a stabilizer, so it is not possible to induce the polymerization of the chain-type nanoparticles, and the aggregation of the particles occurs. The amount of c) may be so excessive that formation of the chained nanoparticles may be difficult.

In addition, when the first oxidant is reduced by oxidizing the thiophene, pyrrole or furan monomer, the first oxidant is to oxidize the reduced second oxidant again so that the second oxidant has an oxidizing power. As long as it can be used, any one may be used, but an oxidizing agent having a relatively higher oxidizing power than the second oxidizing agent is preferable. Preferably, peroxides [H ₂ O ₂ , (NH ₄ ) ₂ S ₂ O ₈ , O ₂ ] or oxygen acids [HMnO ₄ , HNO ₃ , HClO ₄ ], halogens [F ₂ , Cl ₂ , Br ₂ ] or mixtures thereof.

The amount of the first oxidizing agent added is preferably 0.01 to 10 mole ratio of the monomer. If the content of the first oxidant is less than 0.01 molar ratio, the reaction for reducing the second oxidant may not occur well, and thus the degree of polymerization of the chain-type nanoparticles may be lowered. Can be.

In addition, the second oxidizing agent is for oxidizing the monomer, and any oxidizing agent capable of achieving this purpose may be used, but preferably, a metal oxide such as FeCl ₃ , Fe (SO ₄ ) ₂ ㆍ 6H ₂ O Iron (III) complexes, iron (II) complexes or mixtures thereof, and the like may be used, and the amount of use thereof may be 0.001 to 5 mole ratio with respect to the monomer. In the present invention, if the amount of the second oxidant is less than 0.001 mole ratio of the monomer, the polymerization rate is very slow. If the amount of the second oxidant is more than 5 mole ratio, the rate of polymerization and the electrical conductivity are increased, but the physical properties of the produced conductive polymer are decreased.

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

In addition, in the present invention, the reaction temperature of the polymer polymerization reaction is preferably 0-180 ° C., or the temperature at which the solvent is used, and is stirred for 6 to 24 hours at a temperature of 0 to 180 ° C. to conduct conductive water dispersibility through the emulsion oxidation polymerization step. Nanoparticles can be prepared.

More preferably, the present invention comprises 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 the first oxidizing agent of the monomer. Emulsion preparation step of mixing an acidic aqueous solution of pH 1 to 6 by adding HCl having a temperature range of 0 to 180 ℃ of 1,000 to 2,000 parts by weight of ii) the second oxidizing agent in the emulsion of step i) 0.001 A seed emulsion preparation step of mixing at a molar ratio of about 5.0 to 5.0 and then stirring at 0 to 180 ° C. for 10 to 30 minutes, iii) the seed emulsion of step ii) at a temperature of 0 to 180 ° C. for 6 to 24 hours. By stirring, the conductive water-dispersible nanoparticles may be prepared including an emulsion oxidation polymerization step.

In addition, the manufacturing of the core of step A) may further include a drying step of c). The drying of step c) is a step of drying the conductive particles in an emulsion state and may be dried at room temperature-70 ° C.

B) coating the conductive polymer constituting the shell structure of at least one layer on the conductive polymer core of the present invention is to form a shell with a conductive polymer to form at least one layer on the conductive polymer core prepared in step A) Known methods of forming can be used, preferably a) a conductive core in an aqueous solvent; Thiophene, pyrrole or furan monomers; Compounds selected from the group consisting of HCl, HF, HBr and HI; Stabilizer; And mixing the first oxidant to prepare an emulsion. And b) mixing the second oxidant into the emulsion of step a) and stirring to form conductive particles in an emulsion state, thereby forming a shell of one layer. In addition, in the case of forming a shell having two or more layers, when the shell is formed in place of the conductive core used in forming the first layer, conductive nanoparticles having a plurality of layers in two layers or steps may be manufactured. Preferably the shell consists of 1-3 layers. The amount of the compound stabilizer, the first oxidant, the second oxidant and the like selected from the group consisting of HCl, HF, HBr and HI in forming the shell is based on the monomers of the shell to be polymerized. It can be used according to the quantity used at the time of manufacture.

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

In another aspect, the present invention provides an article comprising the conductive nanoparticles of the multi-layered structure, the conductive nanoparticles of the multi-layered structure prepared by the present invention has good processability and excellent conductivity, so electronic materials, optical materials, printing materials It can be used in the film, energy conversion and energy storage material, antistatic material, charge control material, electrically conductive layer material, pattern manufacturing material, printing ink material and the like. In addition, the electronic material, the film, the toner and / or ink as the printing material according to the present invention mean an electronic material, toner and / or ink including the conductive nanoparticles of the multilayer structure manufactured by the present invention. Any product that is conventional in the art, including its configuration, will correspond to the electronic materials, toners and / or inks according to the present invention, and preferred electronic materials include photovoltaic cells, capacitors (used as an electrolyte) and PCBs ( printed circuit board) Substrate coating agent (conventional metal plating can minimize environmental pollution) and / or antistatic agent (to prevent static electricity generated on the surface of plastic, polymer, etc. through coating, etc.).

Hereinafter, preferred examples are provided to help understanding of the present invention, but the following examples are merely to illustrate the present invention, and the scope of the present invention is not limited to the following examples.

Example 1

89 g of deionized water at 25 ° C., 7.9 g of 37 wt% aqueous hydrochloric acid solution, and 6.9 g of 18 wt% polystyrene sulfonic acid solution as a stabilizer were mixed after distilled water was sequentially passed through a cation and an anion exchange resin, followed by stirring. Stabilizer was completely dissolved. Then, 0.5 g of thiophene as a monomer was mixed and reacted at a temperature of 25 ° C. for about 30 minutes to prepare an emulsion.

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

Then, the polythiophene particles in the emulsion state prepared above were dried in a range of room temperature to 70 ° C. to prepare polythiophene particles.

As a result, the conversion rate of the polythiophene emulsion was 99%, and the average polythiophene particle size was 70 nm, and the sheet resistance was measured by using a bar coating method (# 7 bar) to make a conductive film. 10 ^5.0 ohm / sq. Was obtained.

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

In the polythiophene emulsion prepared above, 0.5 g of 3,4-ethylenedioxythiophene, a monomer to form a shell, and 7.9 g of 37 wt% aqueous hydrochloric acid solution were mixed and reacted at a temperature of 25 ° C. for about 30 minutes to prepare an emulsion. The emulsion is a polythiophene nanoparticle dispersion containing 3,4-ethylenedioxythiophene monomers.

In a closed reactor, the mixture was then mixed with 0.3 g of an aqueous 30% by weight aqueous hydrogen peroxide solution as a first oxidant and 7 mg of ferric sulfate [Fe ₂ (SO ₄ ) ₃ ] as a second oxidant to 5 g of deionized water. After preparing a mixed solution containing a second oxidizing agent and the seed emulsion mixture was stirred for 12 hours at a temperature of 25 ℃ to polymerize the poly (3.4-ethylenedioxythiophene) shell in the emulsion state. As a result, the conversion of poly (3,4-ethylenedioxythiophene) was 99%.

Then, the prepared conductive particles of the polythiophene / poly (3.4-ethylenedioxythiophene) core / shell structure in the emulsion state were dried at a temperature ranging from room temperature to 70 ° C. to polythiophene / poly (3.4-ethylenedioxythiophene). ) Conductive particles having a core / shell structure were prepared.

As a result, the polythiophene / poly (3.4-ethylenedioxythiophene) particle size was 80 nm on average and the shell thickness was 10 nm. The conductive film was prepared by the bar coating method (Bar coating method, # 7 bar) and the sheet resistance was measured to obtain 10 ^5.0 ohm / sq.

In addition, as a result of dissolving 0.1-10 g of NMP, DMSO, and Ethylene glycol in 10 g of the polythiophene / poly (3.4-ethylenedioxythiophene) emulsion prepared, the conductive film was prepared by the bar coating method. ^5.0 ohm / sq. Was obtained.

Example 2

In the same manner as in Example 1, 69 g of a 18% by weight polystyrene sulfonic acid solution as a stabilizer was used, and 7 mg of ferric sulfate, a second oxidant, was mixed with 5 g of deionized water as an initiator. After preparing a mixed solution containing the mixture was mixed with the emulsion and reacted for about 30 minutes at a temperature of 25 ℃ to prepare a seed emulsion.

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

As a result, the conversion rate of the polypyrrole emulsion was 96%, and the average polypyrrole particle size was 50 nm, and the surface resistance was measured by using a bar coating method (# 7 bar) to measure the sheet resistance of 10 ^6.0 ohm / got sq.

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

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

In a closed reactor, the mixture was then mixed with 0.3 g of an aqueous 30% by weight aqueous hydrogen peroxide solution as a first oxidant and 7 mg of ferric sulfate [Fe ₂ (SO ₄ ) ₃ ] as a second oxidant to 5 g of deionized water. After preparing a mixed solution containing a second oxidant and the seed emulsion mixture was stirred for 12 hours at a temperature of 25 ℃ to polymerize the poly thiophene shell in the emulsion state. As a result, the polythiophene conversion was 99%.

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

As a result, the average particle size of polypyrrole / polythiophene was 70 nm, which was 10 ^5.0 ohm / sq. As a result of measuring a sheet resistance using a bar coating method (# 7 bar).

In addition, 0.1-10 g of NMP, DMSO, and Ethylene glycol were dissolved in 10 g of the polypyrrole / polythiophene emulsion prepared to prepare a conductive film by a bar coating method, thereby obtaining 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

The polypyrrole / polythiophene emulsion prepared in Example 2 was mixed with 0.5 g of 3,4-ethylenedioxythiophene, which is a monomer to form the outermost shell of the multilayer structure, and 7.9 g of 37% by weight aqueous hydrochloric acid solution at a temperature of 25 ° C. The reaction was prepared by reacting for about 30 minutes at. The emulsion is a polypyrrole / polythiophene nanoparticle dispersion containing 3,4-ethylenedioxythiophene monomers.

Then, the conductive particles of the polypyrrole / polythiophene / poly (3.4-ethylenedioxythiophene) multilayer structure prepared in the above emulsion state were dried at a temperature ranging from room temperature to 70 ° C. to polypyrrole / polythiophene / poly (3.4-ethylenedioxane. Citofene) conductive particles having a core / shell1 / shell2 structure were prepared.

As a result, the polypyrrole / polythiophene / poly (3.4-ethylenedioxythiophene) particle size was 80 nm on average and the shell thickness was 10 nm. This bar coating method (Bar coating method, # 7 bar ) as a result of making the sheet resistance of conductive films measuring 10 ^5.0 ohm / sq. Was obtained.

In addition, 0.1-10 g of NMP, DMSO, and Ethylene glycol was dissolved in 10 g of the polypyrrole / polythiophene / poly (3.4-ethylenedioxythiophene) emulsion prepared to prepare a conductive film by a bar coating method. 10 ^5.0 ohm / sq. Was obtained.

As described above, those skilled in the art will understand that the present invention can be implemented in other specific forms without changing the technical spirit or essential features. Therefore, the embodiments described above are to be understood as illustrative and not restrictive in all aspects. The scope of the present invention should be construed that all changes or modifications derived from the meaning and scope of the following claims and equivalent concepts rather than the detailed description are included in the scope of the present invention.

Claims

In the conductive nanoparticles of a multilayer structure comprising a core and one or more layers of shells,

Multi-layered conductive nanoparticles coated with one or more layers of light emitting and conductive polymers acting as shells on conductive polymer particles serving as cores.
The method of claim 1,

The particles are multi-layered conductive nanoparticles, characterized in that the particle size of 10-1000 nm.
The method of claim 1,

The core is a conductive nanoparticles of a multi-layered form, characterized in that the size of 10-100 nm.
The method of claim 1,

The shell has a multi-layered conductive nanoparticles, characterized in that 1-3 is formed in the outer layer of the core having a thickness of 10-100 nm.
The method of claim 1,

The core is a conductive nanoparticles of a multi-layered form, characterized in that formed of polypyrrole.
The method of claim 1,

Conductive nanoparticles of a multilayer structure characterized in that the outermost shell is formed of polythiophene.
A) preparing a conductive polymer core; And

B) coating a conductive polymer constituting at least one layer of the shell structure on the conductive polymer core;

Method for producing a conductive nanoparticles of a multi-layer structure comprising a.
The method of claim 7, wherein

Step A is a) thiophene, pyrrole or furan monomer in an aqueous solvent; Compounds selected from the group consisting of HCl, HF, HBr and HI; Stabilizer; And mixing the first oxidant to prepare an emulsion. And b) mixing and stirring a second oxidizing agent in the emulsion of step a) to prepare conductive particles in an emulsion state.
The method of claim 8,

Method for producing a conductive nanoparticles of a multi-layer structure, characterized in that using the HCl in step a).
The method of claim 8,

The compound selected from the group consisting of HCl, HF, HBr and HI in the step a) is a method for producing a conductive nanoparticles of a multi-layer structure, characterized in that the input of 1-100 mole ratio (mole ratio) of the monomer.
The method of claim 8,

The stabilizing agent in step a) is a method for producing a conductive nanoparticles of a multi-layer structure, characterized in that 0.01 to 2000 parts by weight based on 100 parts by weight of the monomer used.
The method of claim 8,

The first oxidizing agent in step a) is a method for producing a conductive nanoparticles having a multi-layer structure, characterized in that the input of 0.01 to 10 mole ratio (mole ratio) of the monomer.
The method of claim 8,

The second oxidizing agent in step b) is a method of producing a conductive nanoparticles of a multi-layer structure, characterized in that the input of 0.001 to 5.0 mole ratio (mole ratiod) of the monomer.
The method of claim 8,

The first oxidant is 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 Method for producing a conductive nanoparticles of a multi-layer structure.
The method of claim 8,

The second oxidizing agent is selected from the group consisting of FeCl 3 , Fe (SO 4 ) 2 .6H 2 O, and iron (II) complexes.
The method of claim 7, wherein

The step B) is a) a conductive core prepared in step A) in an aqueous solvent; Thiophene, pyrrole or furan monomers; Compounds selected from the group consisting of HCl, HF, HBr and HI; Stabilizer; And mixing the first oxidant to prepare an emulsion. And b) mixing and stirring a second oxidant in the emulsion of step a) to prepare conductive particles in an emulsion state.
The method of claim 7, wherein

Step A) or step B) is a method for producing a conductive nanoparticles of a multi-layer structure, characterized in that it further comprises a drying step.
An electronic material comprising the conductive nanoparticles of the multilayer structure of claim 1.
An optical material comprising the conductive nanoparticles of the multilayer structure of claim 1.
A printing material comprising the conductive nanoparticles of the multilayer structure of claim 1.
A film comprising the conductive nanoparticles of the multilayer structure of claim 1.