KR100375525B1 - Method for Manufacturing of Metallic Nanoparticles in Surfactant Solutions and Method to use the same - Google Patents
Method for Manufacturing of Metallic Nanoparticles in Surfactant Solutions and Method to use the same Download PDFInfo
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Abstract
본 발명은 미세금속입자 제조시 입자가 형성되는 용액에 계면활성제를 첨가하여 금속입자 핵의 표면에 흡착시킴으로써 입자의 성장을 막아 입자의 직경이 300㎚ 이하이고 크기분포가 균일한 미세금속입자를 제조하는 방법에 관한 것이다. 이와 아울러 제조된 금속입자의 산화를 방지하기 위하여 산화방지제를 함께 첨가함으로써 미세금속입자들이 금속산화물로 전환되는 것을 방지하는 기술에 관한 것이다.The present invention prevents the growth of particles by adding a surfactant to the surface of the metal particle nucleus by adding a surfactant to the solution in which the particles are formed during the production of the fine metal particles to produce a fine metal particles having a diameter of 300 nm or less and uniform size distribution It is about how to. In addition, the present invention relates to a technique for preventing the conversion of the fine metal particles to the metal oxide by adding an antioxidant together to prevent the oxidation of the produced metal particles.
본 발명에 따르면 다양한 미세 금속입자를 경제적이고 간단한 제조공정으로 대량생산할 수 있다.According to the present invention, various fine metal particles can be mass-produced in an economical and simple manufacturing process.
Description
본 발명은 계면활성제 수용액내에서의 미세금속입자의 제조방법 및 그 이용방법에 관한 것으로, 보다 상세하게는 미세금속입자의 제조시 계면활성제 수용액을 첨가하여 금속입자 핵의 표면에 계면활성제를 흡착시킴으로써 입자의 성장을 막아 미세하고 크기분포가 균일한 미세금속입자를 제조할 수 있는 계면활성제 수용액내에서의 미세금속입자의 제조방법 및 그 이용방법에 관한 것이다.The present invention relates to a method for preparing micrometal particles in an aqueous solution of a surfactant and a method of using the same, and more particularly, by adsorbing a surfactant on the surface of a metal particle nucleus by adding an aqueous surfactant solution during preparation of the micrometal particles. The present invention relates to a method for producing fine metal particles in an aqueous solution of a surfactant which can prevent the growth of particles and to produce fine metal particles having a uniform size distribution, and a method of using the same.
입자의 활용기술에서 입자의 크기가 미세단위(300㎚이하)로 작게 되면 입자의 물성 및 성능이 입자 크기가 ㎛ 이상인 경우와는 매우 다르게 된다. 이는 입자의 표면 대 질량의 비율이 증가됨으로써 단위 질량당 표면적이 증가되어 입자의 성능이 향상되고 입자의 융점이 감소되는 등 물성이 변화되며 입자의 색상까지 크기에 따라 변화되는 등 큰 입자의 경우와는 다른 성질을 나타낸다.When the particle size is reduced to fine units (300 nm or less) in the particle utilization technology, the physical properties and performance of the particle are very different from those when the particle size is larger than or equal to μm. This is due to the increase in the surface-to-mass ratio of the particles, which increases the surface area per unit mass, which improves the performance of the particles, reduces the melting point of the particles, and changes the physical properties of the particles. Has different properties.
또한, 입자의 활용기술에서 입자를 작게 하는 것만큼 형성되는 입자의 크기를 균일하게 하는 것도 매우 중요하다. 입자의 크기가 불균일하면 각각의 입자마다 성능 및 물성이 다르므로 첨단분야에의 응용에 제한을 받게 된다. 일례로 입자형태의 소재는 촉매, 센서, 정보기록 매체(자성체), 연마제(chemical mechanical polishing 포함), 항균 및 살균 입자, 의약용, 전자파 차단목적, 디스플레이 분야(형광체) 등 넓은 분야에 이용됨에 따라 입자의 크기를 작고 균일하게 제조하는 연구가 활발히 진행되고 있다.In addition, in the technology of particle utilization, it is also very important to make the size of the particles formed as small as the particles are made smaller. If the particle size is non-uniform, each particle has different performance and physical properties, thereby limiting its application to advanced fields. For example, the material in the form of particles is used in a wide range of fields such as catalysts, sensors, information recording media (magnetic materials), abrasives (including chemical mechanical polishing), antibacterial and sterilizing particles, pharmaceuticals, electromagnetic shielding purposes, and display fields (phosphors). Research into producing small and uniform particle sizes has been actively conducted.
이러한 미세 금속입자를 제조하는 방법에는 기계적으로 그라인딩(grinding) 하는 방법, 공침법, 분무법, 졸-겔법, 전기 분해법, 역상 마이크로에멀젼 이용법 등 다양한 종류가 있다. 그러나, 현재 가장 많이 이용되고 있는 금속 제조기술의 하나인 공침법으로 제조된 금속입자는 입자의 크기, 모양, 크기분포의 제어가 불가능하며, 그 밖의 전기분해법과 졸-겔법은 제조경비가 비싸고 대량생산이 어려운 문제점이 있으며, 역상 마이크로에멀젼법은 입자의 크기, 모양, 크기분포의 제어가 쉬우나 제조공정이 매우 복잡하여 실용화되지 못하고 있다.There are various kinds of methods for preparing such fine metal particles, such as mechanical grinding, coprecipitation, spraying, sol-gel, electrolysis, and reverse phase microemulsion. However, metal particles produced by coprecipitation, one of the most widely used metal fabrication techniques, cannot control particle size, shape, and size distribution. Other electrolysis and sol-gel methods are expensive to manufacture and bulky. Production is difficult, and the reversed phase microemulsion method is easy to control the size, shape, size distribution of the particles, but the manufacturing process is very complicated and has not been put to practical use.
이에 본 발명은 계면활성제를 이용하여 크기 분포가 균일한 미세 금속입자를 경제적이고 간단한 공정으로 대량 생산하는 방법을 제공하는데 그 목적이 있다.Therefore, an object of the present invention is to provide a method for mass production of fine metal particles having a uniform size distribution using an economical and simple process using a surfactant.
본 발명의 다른 목적은 상기 방법으로 제조된 미세 금속입자의 산화를 방지하여 입자의 성능을 장기간 지속시킬 수 있는 방법을 제공하는데 있다.Another object of the present invention is to provide a method for preventing the oxidation of the fine metal particles produced by the above method to sustain the performance of the particles for a long time.
본 발명의 또 다른 목적은 상기 방법으로 제조된 미세 금속입자들을 고분자 막이나 다른 매개체내에 분산시켜 사용함으로써 미세 금속입자의 활용범위를 넓히는데 있다.Still another object of the present invention is to widen the application range of the fine metal particles by dispersing the fine metal particles prepared by the above method in a polymer film or another medium.
도1은 본 발명에 따라 제조된 은입자의 크기 및 분포를 나타내는 전자현미경사진이다.1 is an electron micrograph showing the size and distribution of silver particles prepared according to the present invention.
상기 목적을 달성하기 위한 본 발명에 따른 계면활성제 수용액내에서의 미세 금속입자의 제조방법은 히드라진(hydrazine), 리튬알루미늄보로히드라이드 (LiAlBH4), 소디움보로히드라이드(NaBH4) 및 에틸렌옥사이드(ethyleneoxide)로 이루어진 그룹에서 선택된 하나 이상의 금속이온환원제와 계면활성제를 물에 용해시켜 용액Ⅰ을 제조하는 단계, 제조하고자 하는 금속입자의 이온을 낼 수 있는 수용성염을 물에 용해시켜 용액Ⅱ를 제조하는 단계 및 상기 용액Ⅰ을 교반하면서 상기 용액Ⅱ를 서서히 첨가하여 금속이온을 금속입자로 환원시키는 단계를 포함하는 것을 특징으로 한다.Method for producing fine metal particles in the aqueous solution of the surfactant according to the present invention for achieving the above object is hydrazine, lithium aluminum borohydride (LiAlBH 4 ), sodium borohydride (NaBH 4 ) and ethylene Dissolving at least one metal ion reducing agent and a surfactant selected from the group consisting of ethyleneoxide in water to prepare a solution I, dissolving a water-soluble salt capable of producing ions of the metal particles to be prepared in solution II Preparing and gradually adding the solution II while stirring the solution I to reduce metal ions to metal particles.
상기 방법으로 금(Au), 은(Ag), 구리(Cu), 철(Fe), 백금(Pt), 팔라듐(Pd) 또는 아연(Zn) 등의 미세 금속입자를 제조할 수 있다.By the above method, fine metal particles such as gold (Au), silver (Ag), copper (Cu), iron (Fe), platinum (Pt), palladium (Pd), or zinc (Zn) may be manufactured.
이하에서 본 발명을 보다 상세히 설명한다.본 발명에서는 금(Au), 은(Ag), 구리(Cu), 철(Fe), 백금(Pt), 팔라듐(Pd) 또는 아연(Zn) 등과 같은 금속입자를 계면활성제의 고체흡착 성질을 이용하여 수용액내에서 미세 크기(300㎚이하)로 경제적인 공정으로 제조하는 방법에 관한 것이다. 이때 계면활성제가 금속이온으로부터 환원에 의하여 금속입자를 형성할 때 입자의 크기와 크기분포를 조절하는 역할을 하게 된다. 계면활성제는 계면에 흡착하고자 하는 고유의 성질때문에 금속입자가 형성되는 용액내에서 금속입자 핵의 표면에 흡착하여 핵끼리의 융합을 막아주며 환원된 금속원자가 핵 표면으로의 결합을 지연 또는 막아주어 크기분포가 균일한 미세 금속입자가 제조되도록 하는 역할을 한다.상기 계면활성제 수용액내에서의 미세 금속입자의 제조방법은 수용성의 은염, 구리염, 금염, 철염, 팔라듐염, 아연염 중 제조하고자 하는 미세 금속 입자의 이온을 낼 수 있는 염을 수용액에 용해시킨다. 다른 수용액에는 히드라진 (hydrazine), 소디움보로히드라이드(NaBH4), 리튬알루미늄보로히드라이드 (LiAlBH4) , 옥소화합물 또는 기타 환원제중에서 단독 또는 2종 이상의 물질과 계면활성제를 수용액에 용해시킨 다음 여기에 상기 염이 포함된 용액을 저어주면서 서서히 첨가하면 계면활성제의 종류와 농도에 따라 크기 및 크기분포가 다른 미세입자가 제조된다. 여기서 첨가될 수 있는 계면활성제는 비이온성, 음이온성, 양이온성, 양쪽성의 탄화수소계, 실리콘계, 플로로카본계 등 모든 종류의 계면활성제가 사용될 수 있으며, 특히 비이온성 또는 음이온성 계면활성제를 사용하는 것이 좋다.또한, 본 발명에서는 상기 제조된 미세 금속입자들이 공기 또는 수분과 장시간 접촉시 산소와 반응하여 산화물로 전환되어 입자의 성능이 떨어지게 되는 것을 방지하기 위하여 미세 금속입자의 제조시에 항산화제를 첨가할 수 있다. 이때 사용되는 항산화제로 부틸히드록시톨루엔(butylhydroxytoluene) 또는 비타민 E 유도체가 바람직하게 사용될 수 있다.[실시예]본 발명에 따른 계면활성제 수용액내에서의 미세금속입자의 제조방법의 구체적인 일례로 미세은(Ag)입자의 제조방법을 설명하면 다음과 같다.1.25g의 폴리옥시에틸렌솔비탄모노라우레이트(Tween20)와 0.07g의 히드라진 (hydrazine)이 용해된 물 100g을 교반시키면서 0.04g의 AgNO3가 용해된 수용액 5g을 서서히 첨가하면 미세 은입자가 제조되며 수용액에 분산된 상태에서는 연노란색을 나타낸다.상기 방법으로 제조된 은입자는 도1의 전자현미경 사진에 나타낸 바와 같이 평균 입자크기가 20㎚로 미세하며 입자의 분포가 균일함을 알 수 있다.본 발명에 따라 제조된 미세 금속입자는 단독 또는 2종 이상을 혼합하여 폴리에스테르, 폴리에틸렌, 폴리프로필렌, 폴리우레탄, 폴리비닐클로라이드, 폴리아크릴레이트 또는 아크릴로니트릴-부타디엔-스티렌 등의 고분자 막에 분산시켜 필름을 제조할 수 있다. 또한, 상기 미세 금속입자의 단독 또는 2종 이상의 혼합물을 항균 및 살균, 의약품, 연마제(Chemical Mechanical Polishing 포함), 대전방지, 전자파 차단, 전기/전자 재료, 감광, 촉매등의 목적으로도 활용될 수 있다.Hereinafter, the present invention will be described in more detail. In the present invention, a metal such as gold (Au), silver (Ag), copper (Cu), iron (Fe), platinum (Pt), palladium (Pd), zinc (Zn), or the like may be used. It relates to a method for producing particles in an economical process at a fine size (300 nm or less) in an aqueous solution using the solid adsorption properties of the surfactant. In this case, when the surfactant forms metal particles by reduction from metal ions, the surfactant plays a role of controlling the size and size distribution of the particles. Surfactants are adsorbed on the surface of metal particle nuclei in the solution in which metal particles are formed due to the inherent nature of adsorption at the interface, preventing the fusion between nuclei, and reduced metal atoms delaying or preventing binding to the nucleus surface. The method of producing fine metal particles in the aqueous solution of the surfactant is a fine to be prepared in water-soluble silver salt, copper salt, gold salt, iron salt, palladium salt, zinc salt. A salt capable of producing ions of metal particles is dissolved in an aqueous solution. In another aqueous solution, a single or two or more substances and surfactants are dissolved in an aqueous solution of hydrazine, sodium borohydride (NaBH 4 ), lithium aluminum borohydride (LiAlBH 4 ), oxo compound or other reducing agent. When the solution containing the salt is slowly added while stirring, fine particles having different sizes and size distributions are prepared according to the type and concentration of the surfactant. The surfactant that can be added here can be used all kinds of surfactants, such as nonionic, anionic, cationic, amphoteric hydrocarbon, silicone, fluorocarbon, etc., in particular using nonionic or anionic surfactant In addition, in the present invention, in order to prevent the fine metal particles prepared above from reacting with oxygen or oxygen after prolonged contact with air or moisture, the fine metal particles are converted into oxides, thereby reducing the performance of the particles. Can be added. At this time, a butylhydroxytoluene or a vitamin E derivative may be preferably used as an antioxidant. [Example] Fine silver (Ag) is a specific example of a method for preparing micrometal particles in an aqueous solution of a surfactant according to the present invention. The method for preparing the particles is as follows: 1.25 g of polyoxyethylene sorbitan monolaurate (Tween20) and 0.07 g of hydrazine (100 g) of water in which 0.04 g of AgNO 3 is dissolved while stirring When 5 g of aqueous solution is slowly added, fine silver particles are prepared, and light yellow is obtained when dispersed in the aqueous solution. Silver particles prepared by the above method have a fine average particle size of 20 nm as shown in the electron micrograph of FIG. It can be seen that the distribution of particles is uniform. The fine metal particles produced according to the present invention may be polyester or polyethylene , Polypropylene, polyurethane, polyvinyl chloride, polyacrylate or acrylonitrile-butadiene-styrene and the like can be dispersed in a polymer film to prepare a film. In addition, the single or a mixture of two or more of the fine metal particles may be used for the purpose of antibacterial and sterilization, pharmaceuticals, abrasives (including chemical mechanical polishing), antistatic, electromagnetic shielding, electrical / electronic materials, photosensitization, catalysts, etc. have.
본 발명에 따르면 다양한 미세 금속입자를 경제적이고 간단한 제조공정으로 대량생산이 용이하고 형성되는 입자의 크기가 미세하며(300㎚이하) 크기분포가 균일하여 입자의 성능이 우수하고 입자의 크기가 적으므로 고분자 필름에 분산시 필름의 외형이 투명 또는 반투명 상태를 유지하고 금속입자의 산화방지를 위하여 항산화제와 함께 이용함으로써 미세금속입자의 성능을 장시간 유지할 수 있다.또한, 본 발명에 따라 제조된 미세 금속입자를 고분자 막이나 다른 매개체내에 분산시킴으로써 항균 및 살균 등의 의약용 뿐 아니라 전자파 차단과 감광 목적 등의 다양한 분야에 이용이 가능하여 미세 금속입자의 활용 범위를 넓히는 효과가 있다.According to the present invention, it is easy to mass-produce various fine metal particles in an economical and simple manufacturing process, and the size of the formed particles is fine (less than 300 nm) and the size distribution is uniform, so that the performance of the particles is excellent and the size of the particles is small. When dispersed in a polymer film, the appearance of the film may be maintained in a transparent or translucent state and used together with an antioxidant to prevent oxidation of the metal particles, thereby maintaining the performance of the fine metal particles for a long time. By dispersing the particles in a polymer film or other media, it can be used in various fields such as antimicrobial and sterilization, as well as electromagnetic shielding and photosensitive purposes, thereby expanding the application range of the fine metal particles.
이상에서 본 발명은 기재된 구체예에 대해서만 상세히 설명되었지만 본 발명의 범위내에서 다양한 변형 및 수정이 가능함은 당 업계에서 통상의 기술을 가진 자에게는 명백한 것이며, 이러한 변형 및 수정이 첨부된 특허청구범위에 속함은 당연한 것이다.Although the present invention has been described in detail only with respect to the embodiments described, it will be apparent to those skilled in the art that various modifications and variations are possible within the scope of the present invention, and such modifications and variations are included in the appended claims. Belonging is natural.
Claims (14)
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KR100477912B1 (en) * | 2002-02-20 | 2005-03-17 | (주)엔피텍 | A Method for Manufacturing of Colloidal Silver in Organic Solvents containing Ethanol |
CN101180372B (en) | 2005-05-25 | 2012-05-09 | Posco公司 | Ag-containing solution, antibacterial resin composition comprising the solution and antibacterial resin coated steel plate |
KR100795480B1 (en) * | 2006-04-14 | 2008-01-16 | 광주과학기술원 | Method for the Preparation of Gold Nanoparticles |
KR100763036B1 (en) * | 2006-10-23 | 2007-10-04 | (주)바이오니아 | A method for preparation of silver nano colloid controlling particle size |
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