KR102254960B1 - Synthetic method of multi-walled carbon nanotubes conductive dispersion liquid using milling process - Google Patents

Synthetic method of multi-walled carbon nanotubes conductive dispersion liquid using milling process Download PDF

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KR102254960B1
KR102254960B1 KR1020190051724A KR20190051724A KR102254960B1 KR 102254960 B1 KR102254960 B1 KR 102254960B1 KR 1020190051724 A KR1020190051724 A KR 1020190051724A KR 20190051724 A KR20190051724 A KR 20190051724A KR 102254960 B1 KR102254960 B1 KR 102254960B1
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박수영
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극동대학교 산학협력단
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    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
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    • B01J37/0045—Drying a slurry, e.g. spray drying
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Abstract

본 발명은 밀링공정을 이용한 다중벽 탄소나노튜브 전도성 분산액의 제조방법에 관한 것으로서, 상세하게는 기계적 밀링을 이용하여 분산성이 향상된 다중벽 탄소나노튜브 전도성 분산액의 제조방법에 관한 것이다. 이를 위하여 본 발명은, Iron(Ⅲ) Nitrate Nonahydrate(Fe(NO₃)₃9H₂O)과 Cobalt(Ⅱ) Nitrate Hexahydrate(Co(NO₃)₂6H₂O)를 혼합하여 교반한 제1용액과 Ammonium Carbonate((NH₄)₂CO₃)를 용해한 제2용액을 제조한 후, Aluminum Hydroxide(Al(OH)₃)를 용해한 제3용액에 혼합하여 교반한 후 여과 및 건조하여 금속촉매를 만드는 금속촉매제조단계; 상기 금속촉매를 CVD 합성장치에 넣고 탄소나노튜브를 합성하는 합성단계; 상기 탄소나노튜브를 밀링장치에 넣고 수계분산제, 소포제 및 용매를 첨가하여 밀링처리하여 탄소나노튜브용액을 만드는 밀링단계; 및 상기 탄소나노튜브용액에 분산제, 바인더, 보조용매제, 습윤제 및 용매를 분산시켜 전도성 분산액을 만드는 분산단계; 를 포함하는 것을 특징으로 하는 것이 바람직하다. The present invention relates to a method of manufacturing a multi-walled carbon nanotube conductive dispersion using a milling process, and more particularly, to a method of manufacturing a multi-walled carbon nanotube conductive dispersion with improved dispersibility using mechanical milling. To this end, the present invention is the first solution and Ammonium Carbonate ((NH₄)₂CO₃) mixed and stirred with Iron(III) Nitrate Nonahydrate (Fe(NO₃)₃9H₂O) and Cobalt(II) Nitrate Hexahydrate (Co(NO₃)₂6H₂O). After preparing a second solution in which Aluminum Hydroxide (Al(OH)₃) is dissolved, the mixture is stirred, filtered and dried to form a metal catalyst; A synthesis step of synthesizing carbon nanotubes by putting the metal catalyst in a CVD synthesizer; A milling step of putting the carbon nanotubes in a milling device and milling by adding an aqueous dispersant, an antifoaming agent, and a solvent to prepare a carbon nanotube solution; And a dispersion step of dispersing a dispersant, a binder, a co-solvent, a wetting agent, and a solvent in the carbon nanotube solution to prepare a conductive dispersion. It is preferably characterized in that it comprises a.

Description

밀링공정을 이용한 다중벽 탄소나노튜브 전도성 분산액의 제조방법 {Synthetic method of multi-walled carbon nanotubes conductive dispersion liquid using milling process}Synthetic method of multi-walled carbon nanotubes conductive dispersion liquid using milling process

본 발명은 밀링공정을 이용한 다중벽 탄소나노튜브 전도성 분산액의 제조방법에 관한 것으로서, 상세하게는 기계적 밀링을 이용하여 분산성을 향상시킨 다중벽 탄소나노튜브 전도성 분산액의 제조방법에 관한 것이다. The present invention relates to a method of manufacturing a multi-walled carbon nanotube conductive dispersion using a milling process, and more particularly, to a method of manufacturing a multi-walled carbon nanotube conductive dispersion with improved dispersibility using mechanical milling.

탄소나노튜브는 우수한 전기적, 기계적, 광학적인 특성으로 인하여 전자, 환경, 센서, 에너지, 디스플레이 등의 소재로 사용되는 등 폭넓고 다양한 분야에서 각광을 받고 있다. 탄소나노튜브는 직경이 수 nm인데 비하여 길이는 마이크로미터 단위로서 종횡비(길이/직경)가 큰 일차원적 형상과 더불어 튜브형태의 독특한 구조를 가지는 나노소재로, 그래파이트의 변형된 형태이며 튜브형태로 감겨져 있는 한 겹의 구조를 단일벽 탄소나노튜브라 하며, 여러 겹의 튜브 형태로 감겨져 있는 소재의 경우 다중벽 탄소나노튜브라 칭한다. Carbon nanotubes are in the spotlight in a wide variety of fields, such as being used as materials such as electronics, environment, sensors, energy, and displays due to their excellent electrical, mechanical, and optical properties. Carbon nanotubes are nanomaterials that have a one-dimensional shape with a large aspect ratio (length/diameter) in micrometers compared to several nm in diameter, and a unique structure in the form of a tube.It is a modified form of graphite and is wound in a tube shape. The single-walled structure is called a single-walled carbon nanotube, and in the case of a material wound in the form of a multi-layered tube, it is called a multi-walled carbon nanotube.

탄소나노튜브는 나노 크기의 입자로 점성이 높기 때문에 탄소나노튜브를 균일하게 분산시키기가 어려우므로 고유 특성을 제대로 이용할 수 없는 어려움을 가지고 있기 때문에, 낮은 분산성을 개선하기 위해서는 튜브 사이의 반 데르 발스 결합을 끊어주어 응집을 억제하여야 한다. Because carbon nanotubes are nano-sized particles and have high viscosity, it is difficult to uniformly disperse carbon nanotubes, so it is difficult to properly use their intrinsic properties.In order to improve low dispersibility, van der Waals between tubes is difficult. Agglomeration should be suppressed by breaking the bond.

또한 탄소나노튜브를 금속이나 고분자와 함께 복합체로 제조할 때 고체 표면에 액체가 퍼지는 정도인 젖음성이 좋지 않아 복합체를 제조하기 어려운 문제점을 가지고 있다. 따라서 탄소나노튜브를 이용하여 우수한 복합체를 만들기 위하여 표면개질의 개선방법이나 분산화방법 등의 복합체의 구조를 용도에 맞게 개량하는 많은 연구들이 진행되고 있다. In addition, when carbon nanotubes are manufactured as a composite with a metal or a polymer, there is a problem in that it is difficult to manufacture a composite due to poor wettability, which is the degree to which liquid spreads over a solid surface. Therefore, in order to make an excellent composite using carbon nanotubes, many studies are being conducted to improve the structure of the composite, such as a method for improving surface modification or a method for dispersing, to suit the purpose.

복합체를 제조하기 위한 방법 중의 하나로 기계적 교반 방법이 있으며, 이는 강한 전단력으로 탄소나노튜브의 표면을 물리적으로 기능화하기 때문에 분산성이 향상되는 장점이 있어 기계적 교반 방법에 대한 연구가 지속적으로 이루어지고 있으며 탄소나노튜브의 분산상태가 복합체 물성에 영향을 미친다고 보고되었다. 또한, 탄소나노튜브 분산의 상태에 따른 물성의 특징을 파악할 수 있는 방법을 개발하는 것은 탄소나노튜브의 응용에 있어 중요한 부분이기 때문에 탄소나노튜브를 효과적으로 분산하여 재료와 혼합하는 방법으로 밀링하는 방식에 대한 많은 연구가 진행되고 있다. One of the methods for manufacturing the composite is the mechanical stirring method, which physically functionalizes the surface of the carbon nanotubes with strong shearing force, and has the advantage of improving dispersibility.Therefore, studies on the mechanical stirring method are continuously being conducted. It has been reported that the dispersion state of the nanotubes affects the properties of the composite. In addition, developing a method that can grasp the properties of the physical properties according to the state of carbon nanotube dispersion is an important part of the application of carbon nanotubes. Therefore, the method of milling by effectively dispersing and mixing carbon nanotubes with materials There is a lot of research going on.

한편, 액제를 분말제 형태로 바꾸는 가장 일반적인 방법 중의 하나인 SD(Spray Drying, 분무건조)법은 콜로이드 상태의 유체를 미세한 액적(스프레이) 형태로 발생시키고, 높은 온도의 가스 매개체를 활용하여 건조시켜 구형의 분말입자를 얻는 공정이다. 일반적으로는 미세한 분말을 얻기 위해 이류체 노즐(two fluid nozzle)을 활용하게 되며, 이류체 노즐은 수십에서 수백 마이크론 크기의 액적들을 대량으로 발생시킬 수 있는 장점을 가지고 있다. Meanwhile, SD (Spray Drying) method, one of the most common methods of converting liquids into powder forms, generates colloidal fluids in the form of fine droplets (sprays) and dry them using a high temperature gas medium. This is the process of obtaining spherical powder particles. In general, a two fluid nozzle is used to obtain a fine powder, and the two fluid nozzle has the advantage of generating droplets of a size of tens to hundreds of microns in large quantities.

SD법으로 얻어지는 금속촉매분말들의 특성은 유체와 높은 온도의 가스 매개체를 분사시키는 이류체 노즐의 압력 및 분무용액의 특성에 크게 의존한다. 이러한 제조 조건을 변화시킴으로서 치밀한 입자, 속이 빈 입자, 기공이 많은 입자 등 다양한 특성을 가지는 금속촉매입자들의 제조가 가능하다. SD법으로 제조한 금속촉매 분말은 표면적이 넓어져 금속촉매의 앞뒤로 다중벽 탄소나노튜브 성장핵이 형성될 수 있기 때문에 높은 탄소나노튜브 합성수율을 얻게 되어 생산성이 향상될 수 있는 효과가 있다.The properties of the metal catalyst powders obtained by the SD method largely depend on the pressure of the air-fluid nozzle that injects the fluid and the high temperature gas medium and the properties of the spray solution. By changing these manufacturing conditions, it is possible to manufacture metal catalyst particles having various properties such as dense particles, hollow particles, and particles with many pores. Since the metal catalyst powder prepared by the SD method has a large surface area, and multi-walled carbon nanotube growth nuclei can be formed in front of and behind the metal catalyst, a high carbon nanotube synthesis yield can be obtained, thereby improving productivity.

또 다른 금속촉매제조 방법인 DP법(Deposition precipitation)은 금속촉매의 전구체염용액과 pH 조절제가 담지체 분산액 내에서 반응하여 침전체가 생성되고, 이들이 담지체 표면에 흡착 및 고화되는데 이는 기존의 공침법 및 함침법에 의해 제조된 금속촉매들과는 비교할 수 없는 금속촉매의 균일도와 탄소나노튜브의 합성 수율이 현저함을 보여 탄소나노튜브 제조용 금속촉매의 제조에 가장 적당한 방법이라 할 수 있다. In the DP method (Deposition precipitation), which is another method of manufacturing a metal catalyst, a precursor salt solution of a metal catalyst and a pH adjuster react in the carrier dispersion to form a precipitate, which is adsorbed and solidified on the surface of the support. The uniformity of the metal catalyst and the synthesis yield of carbon nanotubes are remarkable, which cannot be compared with the metal catalysts prepared by the immersion method and the impregnation method, so it can be said to be the most suitable method for the production of a metal catalyst for producing carbon nanotubes.

또한, 탄소나노튜브의 길이와 직경분포를 최소화 하기 위해서는 기계적 밀링 처리 공정 중 하나인 볼밀링 처리를 사용할 수 있다. 볼밀링 과정을 통해 탄소나노튜브의 bendng 결합과 나노튜브간의 접촉 증가가 탄소나노튜브의 전기적 성질을 변화시키게 되어 다중벽 탄소나노튜브의 저항도 증가시키며, 볼밀링 처리 시간이 길어질수록 탄소나노튜브의 길이가 지수함수적으로 감소한다. 이렇게 길이가 짧아진 탄소나노튜브는 우수한 분산력이 가지기 때문에 분산액을 제조하는데 적합하며, 때문에 볼밀링은 탄소나노튜브를 분산시키거나 타재료와 혼합하여 복합화 시킬 수 있는 효과적인 공정으로 여겨진다. 또한, 탄소나노튜브 소재의 보관과 사용상의 편리성이 더욱 증가되는 장점이 있어 이에 대한 많은 연구가 행해져 왔다.In addition, in order to minimize the distribution of the length and diameter of the carbon nanotubes, a ball milling treatment, which is one of the mechanical milling treatment processes, may be used. The increase in contact between the carbon nanotubes and the bendng bond of the carbon nanotubes through the ball milling process changes the electrical properties of the carbon nanotubes, thereby increasing the resistance of the multi-walled carbon nanotubes. The length decreases exponentially. Since carbon nanotubes with such a short length have excellent dispersing power, they are suitable for preparing dispersions. Therefore, ball milling is considered an effective process that can disperse carbon nanotubes or mix them with other materials to make them complex. In addition, since there is an advantage of further increasing the convenience of storage and use of carbon nanotube materials, many studies have been conducted on this.

이러한 밀링 방식에도 어트리터밀, 수평밀, 진동밀, 수평식밀 등의 다양한 밀링방식이 있으며 장치에 따라 상당히 다른 결과를 얻을 수 있으며, 탄소나노튜브의 습식 밀링처리 공정의 경우 수계 밀링처리 및 유기 밀링처리 등 첨가제의 공정과 작업공정조건 등 연구자마다의 조건이 다르기 때문에 다양하고 체계적인 연구가 필요한 실정이다. There are various milling methods such as attritor mill, horizontal mill, vibration mill, horizontal mill, etc. for these milling methods, and very different results can be obtained depending on the device. In the case of the wet milling process of carbon nanotubes, water-based milling treatment and organic milling Since the conditions of each researcher such as the process of additives such as treatment and working process conditions are different, various and systematic studies are required.

분산제는 일반적으로 분산작용이 요구되는 용도에 사용되는 계면활성제의 총칭이며, 고체와 액체의 성질에 현저한 변화를 주어 분산효과를 나타내는 것을 분산제라 부른다. 분산제는 분산매(dispersion medium)내에 고체 입자들을 젖게 하고, 분쇄를 도우며 입자들의 재응집을 방지하는 기능을 가진다. 분산의 안정화에 미치는 중요인자로서 분산제의 종류와 농도 등을 들 수 있으며, 분산제는 고체 입자 표면에 흡착되어 전하를 띄거나 입체 안정화 효과를 유발하여 고체 입자들 간의 충돌로 인한 응집을 막아주는 역할을 한다.Dispersant is a generic term for surfactants generally used in applications requiring a dispersing action, and those exhibiting a dispersing effect by giving a remarkable change in the properties of solids and liquids are called dispersants. The dispersant has the function of wetting the solid particles in the dispersion medium, aiding in grinding and preventing re-aggregation of the particles. Important factors affecting the stabilization of dispersion include the type and concentration of the dispersant, and the dispersant is adsorbed on the surface of the solid particles and has a charge or causes a steric stabilization effect to prevent agglomeration due to collisions between solid particles. do.

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상술한 문제점을 해결하기 위하여 창안된 본 발명에 의한 밀링공정을 이용한 다중벽 탄소나노튜브 전도성 분산액의 제조방법은, 탄소나노튜브를 다양한 응용분야에 적용할 수 있도록 탄소나노튜브에 대한 밀링공정을 통하여 탄소나노튜브 분산액을 제조함에 있어 가장 이상적인 분산 및 조합을 이룰 수 있는 조건을 찾아 제공하는 것을 목적으로 한다. In order to solve the above-described problem, the method of manufacturing a multi-walled carbon nanotube conductive dispersion using a milling process according to the present invention is made through a milling process for carbon nanotubes so that the carbon nanotubes can be applied to various applications. In preparing a carbon nanotube dispersion, the purpose is to find and provide conditions that can achieve the most ideal dispersion and combination.

본 발명의 또 다른 목적은, DP법이나 SD법으로 제조한 금속촉매를 사용하여 다중벽 탄소나노튜브를 합성한 후 일정시간 기계적인 밀링 처리를 가해 분산성이 향상된 다중벽 탄소나노튜브 전도성 분산액의 제조 방법을 제공하는 것을 목적으로 한다. Another object of the present invention is to synthesize a multi-walled carbon nanotube using a metal catalyst prepared by the DP method or the SD method, and then apply a mechanical milling treatment for a certain period of time to obtain a conductive dispersion of multi-walled carbon nanotubes with improved dispersibility. It is an object of the present invention to provide a manufacturing method.

본 발명의 또 다른 목적은, 다중벽 탄소나노튜브 전도성 분산액의 제조에 있어 다른 재료와의 혼합이 용이하고 젖음성이 증가한 분산액의 제조 방법을 제공하는 것을 목적으로 한다. Another object of the present invention is to provide a method for preparing a dispersion in which a multi-walled carbon nanotube conductive dispersion is easily mixed with other materials and has increased wettability.

본 발명이 이루고자 하는 기술적 과제는 이상에서 언급한 기술적 과제로 제한되지 않으며, 언급되지 않은 또 다른 기술적 과제들은 아래의 기재로부터 본 발명이 속하는 기술분야에서 통상의 지식을 가진 자에게 명확하게 이해될 수 있을 것이다. The technical problem to be achieved by the present invention is not limited to the technical problems mentioned above, and other technical problems that are not mentioned can be clearly understood by those of ordinary skill in the technical field to which the present invention belongs from the following description. There will be.

전술한 목적을 달성하기 위해 창안된 본 발명에 의한 밀링공정을 이용한 다중벽 탄소나노튜브 전도성 분산액의 제조방법은 Iron(Ⅲ) Nitrate Nonahydrate(Fe(NO₃)₃9H₂O)과 Cobalt(Ⅱ) Nitrate Hexahydrate(Co(NO₃)₂6H₂O)를 혼합하여 교반한 제1용액, Ammonium Carbonate((NH₄)₂CO₃)를 용해한 제2용액 및 Aluminum Hydroxide(Al(OH)₃)를 용해한 제3용액을 각각 제조한 후, 상기 제3용액에 상기 제1용액 및 상기 제2용액을 혼합하여 교반한 혼합용액을 만들고, 상기 혼합용액을 여과 및 건조하여 금속촉매를 만드는 금속촉매제조단계; 상기 금속촉매를 CVD 합성장치에 넣고 700~750℃의 온도로 탄소나노튜브를 합성하는 합성단계; 상기 탄소나노튜브를 밀링장치에 넣고 수계분산제, 소포제 및 용매를 첨가한 후 밀링처리하여 탄소나노튜브용액을 만드는 밀링단계; 및 상기 탄소나노튜브용액에 분산제, 바인더, 보조용매제, 습윤제 및 용매를 분산시켜 전도성 분산액을 만드는 분산단계; 를 포함하는 것을 특징으로 하는 것이 바람직하다. The manufacturing method of the multi-walled carbon nanotube conductive dispersion using the milling process according to the present invention invented to achieve the above object is Iron(III) Nitrate Nonahydrate(Fe(NO₃)₃9H₂O) and Cobalt(II) Nitrate Hexahydrate(Co (NO₃)₂6H₂O) was mixed and stirred, the second solution was dissolved in Ammonium Carbonate ((NH₄)₂CO₃), and the third solution was dissolved in Aluminum Hydroxide (Al(OH)₃). 3, a metal catalyst manufacturing step of mixing the first solution and the second solution to prepare a stirred mixed solution, and filtering and drying the mixed solution to produce a metal catalyst; A synthesis step of synthesizing carbon nanotubes at a temperature of 700 to 750°C by putting the metal catalyst in a CVD synthesizer; A milling step of adding the carbon nanotubes to a milling device, adding an aqueous dispersant, an antifoaming agent, and a solvent, followed by milling to prepare a carbon nanotube solution; And a dispersion step of dispersing a dispersant, a binder, a co-solvent, a wetting agent, and a solvent in the carbon nanotube solution to prepare a conductive dispersion. It is preferably characterized in that it comprises a.

또한, 상술한 특징에 더하여, 상기 제1용액은 용매 100중량부에 대하여 Iron(Ⅲ) Nitrate Nonahydrate (Fe(NO₃)₃9H₂O) 25.02중량부 및 Cobalt(Ⅱ) Nitrate Hexahydrate (Co(NO₃)₂6H₂O) 7.55중량부를 용해하며, 상기 제2용액은 용매 100중량부에 대하여 Ammonium Carbonate ((NH₄)₂CO₃) 100중량부를 용해하며, 상기 제3용액은 용매 100중량부에 대하여 Aluminum Hydroxide (Al(OH)₃) 50중량부를 용해하는 특징을 더 포함하는 것도 바람직하다. In addition to the above-described features, the first solution contains 25.02 parts by weight of Iron(III) Nitrate Nonahydrate (Fe(NO3)₃9H₂O) and 7.55 parts by weight of Cobalt(II) Nitrate Hexahydrate (Co(NO₃)₂6H₂O) based on 100 parts by weight of the solvent. Dissolves parts by weight, and the second solution dissolves 100 parts by weight of Ammonium Carbonate ((NH₄)₂CO₃) based on 100 parts by weight of the solvent, and the third solution is Aluminum Hydroxide (Al(OH)₃) based on 100 parts by weight of the solvent. It is also preferable to further include a feature of dissolving 50 parts by weight.

한편 본 발명에 의한 밀링공정을 이용한 다중벽 탄소나노튜브 전도성 분산액의 제조방법에서 상기 금속촉매제조방법은 상기 금속촉매제조단계는 Iron(Ⅲ) Nitrate Nonahydrate (Fe(NO₃)₃9H₂O), Cobalt(Ⅱ) Nitrate Hexahydrate (Co(NO₃)₂6H₂O)및 Aluminium nitrate nonahydrate (Al(NO₃)₃을 용매에 용해한 금속촉매전구체용액을 공기와 혼합시켜 이류체를 제조한 후, 상기 이류체를 반응로에 투입하여 분사 및 건조하는 것을 특징으로 하는 것도 가능하다. Meanwhile, in the manufacturing method of the multi-walled carbon nanotube conductive dispersion liquid using the milling process according to the present invention, the metal catalyst manufacturing step includes Iron(III) Nitrate Nonahydrate (Fe(NO3)₃9H₂O), Cobalt(II). A metal catalyst precursor solution in which nitrate hexahydrate (Co(NO₃)₂6H₂O) and aluminum nitrate nonahydrate (Al(NO₃)₃ are dissolved in a solvent is mixed with air to prepare a two-fluid, and then the two-fluid is injected into the reactor and sprayed. It is also possible to be characterized by drying.

이 경우, 상기 금속촉매전구체용액의 Iron(Ⅲ) Nitrate Nonahydrate (Fe(NO₃)₃9H₂O), Cobalt(Ⅱ) Nitrate Hexahydrate (Co(NO₃)₂6H₂O)및 Aluminium nitrate nonahydrate (Al(NO₃)₃)의 질량비는 1000: 250: 1200인 것을 포함도록 하고, 상기 반응로의 온도는 800℃이며 상기 이류체의 압력은 3.5kgf인 것을 특징으로 하는 것이 바람직하다. In this case, the mass ratio of Iron(III) Nitrate Nonahydrate (Fe(NO₃)₃9H₂O), Cobalt(II) Nitrate Hexahydrate (Co(NO₃)₂6H₂O) and Aluminum nitrate nonahydrate (Al(NO₃)₃) in the metal catalyst precursor solution is 1000: 250: 1200 is included, the temperature of the reaction furnace is 800 ℃, it is preferably characterized in that the pressure of the air flow is 3.5kgf.

본 발명에 의한 밀링공정을 이용한 다중벽 탄소나노튜브 전도성 분산액의 제조방법은 DP법이나 SD법으로 제조한 금속촉매를 사용하여 다중벽 탄소나노튜브를 합성한 후 일정시간 동안 기계적인 밀링 처리를 함으로써 분산성이 향상된 다중벽 탄소나노튜브 전도성 분산액을 얻을 수 있는 효과가 있다. The method for preparing a conductive dispersion of multi-walled carbon nanotubes using the milling process according to the present invention is to synthesize the multi-walled carbon nanotubes using a metal catalyst prepared by the DP method or the SD method, and then mechanically milling for a certain period of time. There is an effect of obtaining a multi-walled carbon nanotube conductive dispersion with improved dispersibility.

뿐만 아니라, 본 발명에 의한 기계적 밀링조건을 이용한 다중벽 탄소나노튜브 전도성 분산액의 제조 방법은 밀링공정을 진행함으로서 Bulk density가 증가되어 비산성을 향상시키기 때문에 다른 재료와의 혼합이 용이하고 젖음성이 증가한 다중벽 탄소나노튜브 전도성 분산액을 제조할 수 있는 효과가 있다. In addition, the manufacturing method of the conductive dispersion of multi-walled carbon nanotubes using the mechanical milling conditions according to the present invention increases the bulk density and improves the scattering property by performing the milling process, so that mixing with other materials is easy and the wettability is increased. There is an effect that can prepare a multi-walled carbon nanotube conductive dispersion.

또한, 본 발명에 의한 기계적 밀링조건을 이용한 다중벽 탄소나노튜브 전도성 분산액의 제조 방법은 밀링처리 공정을 거쳐 비산성이 향상되고 전기전도성이 증가하기 때문에 탄소나노튜브 소재의 사용상 편리성이 증가된 다중벽 탄소나노튜브 전도성 분산액의 제조 방법을 제조할 수 있는 효과가 있다.In addition, the method of manufacturing a multi-walled carbon nanotube conductive dispersion using mechanical milling conditions according to the present invention is a multi-walled carbon nanotube material with increased convenience in use because the scattering property is improved and electrical conductivity is increased through a milling process. There is an effect of manufacturing a method for preparing a conductive dispersion of wall carbon nanotubes.

이와 더불어 본 발명에 의한 다중벽 탄소나노튜브 전도성 분산액의 제조 방법은 SD법으로 제조한 금속촉매를 사용함으로 인해 금속촉매의 앞뒤로 다중벽 탄소나노튜브 성장핵이 형성될 수 있기 때문에 높은 합성수율을 얻게 되어 생산성이 향상될 수 있는 효과가 있다. In addition, the method for preparing a multi-walled carbon nanotube conductive dispersion according to the present invention obtains a high synthesis yield because multi-walled carbon nanotube growth nuclei can be formed in front of and behind the metal catalyst due to the use of the metal catalyst prepared by the SD method. There is an effect that can be improved productivity.

도 1은 본 발명에 의한 다중벽 탄소나노튜브 전도성 분산액 제조방법 중 DP법에 의한 촉매로 제조하는 공정의 흐름도이다.
도 2는 본 발명에 의한 다중벽 탄소나노튜브 전도성 분산액 제조방법 중 SD법에 의한 촉매로 제조하는 공정의 흐름도이다.
도 3는 본 발명의 실시예에서 제조된 분산액의 밀링단계에서 투입된 원료에 대한 함량과 용도를 나타낸 표이다.
도 4는 본 발명의 제조실시예에서 사용된 밀링처리장비의 사진이다.
도 5는 본 발명의 제조실시예 1을 통하여 합성된 다중벽 탄소나노튜브의 주사전자현미경(SEM)사진이다.
도 6은 본 발명의 제조실시예 2를 통하여 합성된 다중벽 탄소나노튜브의 주사전자현미경(SEM)사진이다.
도 7은 본 발명의 실시예 1에 의한 다중벽 탄소나노튜브의 특성을 분석한 표이다.
도 8은 본 발명의 실시예 2에 의한 다중벽 탄소나노튜브의 특성을 분석한 표이다.
도 9는 본 발명의 제조실시예 1 및 2에 의해 제조된 다중벽 탄소나노튜브의 응집체직경 그래프이다.
도 10은 본 발명의 제조실시예 1 및 2에 의해 제조된 다중벽 탄소나노튜브의 번들길이 그래프이다.
도 11은 본 발명의 제조실시예 1 및 2에 의해 제조된 다중벽 탄소나노튜브의 번들직경 그래프이다.
도 12는 본 발명의 제조실시예 1 및 2에 의해 제조된 다중벽 탄소나노튜브의 Bulk density 그래프이다.
도 13은 본 발명의 제조실시예 1 및 2에 의해 제조된 다중벽 탄소나노튜브의 paste점도 그래프이다.
도 14는 본 발명의 제조실시예 1 및 2에 의해 제조된 다중벽 탄소나노튜브의 1 pass 표면 저항 그래프이다.
도 15는 본 발명의 제조실시예 1 및 2에 의해 제조된 다중벽 탄소나노튜브의 2 pass 표면 저항 그래프이다.1 is a flow chart of a process for preparing a catalyst according to the DP method in a method for preparing a conductive dispersion of multi-walled carbon nanotubes according to the present invention.
2 is a flow chart of a process of preparing a catalyst according to the SD method in the method for preparing a conductive dispersion of multi-walled carbon nanotubes according to the present invention.
3 is a table showing the contents and uses of the raw materials introduced in the milling step of the dispersion prepared in the embodiment of the present invention.
Figure 4 is a photograph of the milling processing equipment used in the manufacturing embodiment of the present invention.
5 is a scanning electron microscope (SEM) photograph of a multi-walled carbon nanotube synthesized through Preparation Example 1 of the present invention.
6 is a scanning electron microscope (SEM) photograph of a multi-walled carbon nanotube synthesized through Preparation Example 2 of the present invention.
7 is a table analyzing the characteristics of a multi-walled carbon nanotube according to Example 1 of the present invention.
8 is a table analyzing the characteristics of a multi-walled carbon nanotube according to Example 2 of the present invention.
9 is a graph of an aggregate diameter of multi-walled carbon nanotubes prepared according to Preparation Examples 1 and 2 of the present invention.
10 is a graph of bundle lengths of multi-walled carbon nanotubes prepared according to Preparation Examples 1 and 2 of the present invention.
11 is a graph of bundle diameters of multi-walled carbon nanotubes prepared according to Preparation Examples 1 and 2 of the present invention.
12 is a graph of bulk density of multi-walled carbon nanotubes prepared according to Preparation Examples 1 and 2 of the present invention.
13 is a graph of paste viscosity of multi-walled carbon nanotubes prepared according to Preparation Examples 1 and 2 of the present invention.
14 is a 1 pass surface resistance graph of multi-walled carbon nanotubes prepared according to Preparation Examples 1 and 2 of the present invention.
15 is a 2 pass surface resistance graph of multi-walled carbon nanotubes prepared according to Preparation Examples 1 and 2 of the present invention.

이하에서 상술한 목적과 특징이 분명해지도록 본 발명을 상세하게 설명할 것이며, 이에 따라 본 발명이 속하는 기술 분야에서 통상의 지식을 가진 자가 본 발명의 기술적 사상을 용이하게 실시할 수 있을 것이다. 또한 본 발명을 설명함에 있어서 본 발명과 관련한 공지기술 중 이미 그 기술 분야에 익히 알려져 있는 것으로서, 그 공지기술에 대한 구체적인 설명이 본 발명의 요지를 불필요하게 흐릴 수 있다고 판단되는 경우에 그 상세한 설명을 생략하기로 한다. Hereinafter, the present invention will be described in detail so that the above-described objects and features become clear, and accordingly, a person of ordinary skill in the technical field to which the present invention pertains will be able to easily implement the technical idea of the present invention. In addition, in describing the present invention, when it is determined that a detailed description of the known technology may unnecessarily obscure the subject matter of the present invention, a detailed description thereof will be provided as it is already well known in the technical field among the known technologies related to the present invention. I will omit it.

아울러, 본 발명에서 사용되는 용어는 가능한 한 현재 널리 사용되는 일반적인 용어를 선택하였으나, 특정한 경우는 출원인이 임의로 선정한 용어도 있으며 이 경우는 해당되는 발명의 설명부분에서 상세히 그 의미를 기재하였으므로, 단순한 용어의 명칭이 아닌 용어가 가지는 의미로서 본 발명을 파악하여야 함을 밝혀두고자 한다. 실시 예들에 대한 설명에서 사용한 용어는 단지 특정한 실시 예를 설명하기 위해 사용된 것으로, 실시 예들을 한정하려는 의도가 아니다. 단수의 표현은 문맥상 명백하게 다르게 뜻하지 않는 한, 복수의 표현을 포함한다. In addition, the terms used in the present invention have selected general terms that are currently widely used as much as possible, but there are terms arbitrarily selected by the applicant in certain cases, and in this case, the meaning of the terms has been described in detail in the description of the corresponding invention. It should be noted that the present invention should be understood as the meaning of the term, not the name of. The terms used in the description of the embodiments are only used to describe specific embodiments, and are not intended to limit the embodiments. Singular expressions include plural expressions unless the context clearly indicates otherwise.

실시 예들은 여러 가지 형태로 변경을 가할 수 있고 다양한 부가적 실시 예들을 가질 수 있는데, 여기에서는 특정한 실시 예들이 도면에 표시되고 관련된 상세한 설명이 기재되어 있다. 그러나 이는 실시 예들을 특정한 형태에 한정하려는 것이 아니며, 실시 예들의 사상 및 기술 범위에 포함되는 모든 변경이나 균등물 내지 대체물을 포함하는 것으로 이해되어야 할 것이다. The embodiments may be changed in various forms and may have various additional embodiments, in which specific embodiments are indicated in the drawings and related detailed descriptions are described. However, this is not intended to limit the embodiments to a specific form, and it should be understood to include all changes, equivalents, or substitutes included in the spirit and scope of the embodiments.

다양한 실시 예들에 대한 설명 가운데 “제1”“제2”“첫째”또는“둘째”등의 표현들이 실시 예들의 다양한 구성요소들을 수식할 수 있지만, 해당 구성요소들을 한정하지 않는다. 예를 들어, 상기 표현들은 해당 구성요소들의 순서 및/또는 중요도 등을 한정하지 않는다. 상기 표현들은 한 구성요소를 다른 구성요소와 구분 짓기 위해 사용될 수 있다. In the description of various embodiments, expressions such as “first,” “second,” “first,” or “second” may modify various elements of the embodiments, but do not limit the corresponding elements. For example, the expressions do not limit the order and/or importance of corresponding elements. The above expressions may be used to distinguish one component from another component.

본 발명에 의한 밀링공정을 이용한 다중벽 탄소나노튜브 전도성 분산액의 제조방법은, 금속촉매를 제조하여 다중벽 탄소나노튜브(MWCNT)를 합성하고, 합성된 다중벽 탄소나노튜브를 밀링처리한 후 이를 분산하여 전도성분산액으로 제조하도록 하는 것이 바람직한데, 본 발명에서는 상기 다중벽 탄소나노튜브의 합성에 사용되는 금속촉매의 제조방법으로서, DP법(deposition precipitation)에 의하여 제조하는 방법과 SD(Spray Drying)법에 의하여 제조하는 방법을 동시에 제시하고 있으며, 두 방법 중 하나를 선택적으로 적용하는 것이 가능하다.The method for preparing a conductive dispersion of multi-walled carbon nanotubes using a milling process according to the present invention is to synthesize a multi-walled carbon nanotube (MWCNT) by preparing a metal catalyst, and milling the synthesized multi-walled carbon nanotubes. It is preferable to disperse and prepare a conductive dispersion. In the present invention, as a method of manufacturing a metal catalyst used for synthesis of the multi-walled carbon nanotubes, a method of manufacturing by DP (deposition precipitation) and SD (Spray Drying) The method of manufacturing by the method is presented at the same time, and it is possible to selectively apply one of the two methods.

금속촉매제조방법 중에 하나인 DP법에 의하여 제조된 금속촉매를 사용하는 경우, 탄소나노튜브를 합성할 때 합성 수율이 현저하게 좋아지기 때문에 탄소나노튜브의 대량생산에 효과적으로 적용될 수 있으며, 또 다른 방법인 SD법으로 만들어진 금속촉매는, 금속촉매의 앞뒤에 탄소나노튜브의 성장 핵이 형성될 수 있어 뛰어난 탄소나노튜브의 합성수율을 가지고 있고 이로 인해 생산성이 우수해지는 장점이 있기 때문에 고수율로 다중벽 탄소나노튜브를 합성할 수 있다는 효과가 있다. 또한, 다중벽 탄소나노튜브의 밀링처리를 통해 분산액을 제조하는 경우에는 전기전도성과 분산성이 향상되는 장점이 있기 때문에 산업현장에서 다양한 전자, 환경, 센서, 에너지, 디스플레이 소재로 활용될 수 있다.In the case of using a metal catalyst prepared by the DP method, which is one of the metal catalyst manufacturing methods, it can be effectively applied to mass production of carbon nanotubes because the synthesis yield is remarkably improved when synthesizing carbon nanotubes. The metal catalyst made by the phosphorus SD method has an excellent synthesis yield of carbon nanotubes because the growth nuclei of carbon nanotubes can be formed in front and rear of the metal catalyst. There is an effect that carbon nanotubes can be synthesized. In addition, in the case of manufacturing a dispersion through milling of multi-walled carbon nanotubes, it can be used as various electronic, environment, sensor, energy, and display materials in industrial sites because of the advantages of improving electrical conductivity and dispersibility.

이하에서는 본 발명에 의한 바람직한 실시예에 의한 다중벽 탄소나노튜브 전도성 분산액의 제조방법에 대하여 첨부된 도면을 참조하여 설명한다. 도 1은 본 발명에 의한 다중벽 탄소나노튜브 전도성 분산액이 제조되는 공정 중 DP법으로 금속촉매를 제조한 후 다중벽 탄소나노튜브 및 분산액을 만드는 공정에 대한 흐름도이다. 도 1에서 보는 바와 같이 본 발명에 의한 밀링공정을 이용한 다중벽 탄소나노튜브 전도성 분산액의 제조방법에서는 먼저 DP법에 의한 금속촉매제조단계(s110~s160)를 수행하도록 하는 것이 바람직하다.Hereinafter, a method of preparing a conductive dispersion of multi-walled carbon nanotubes according to a preferred embodiment of the present invention will be described with reference to the accompanying drawings. 1 is a flowchart illustrating a process of preparing a multi-walled carbon nanotube and a dispersion after preparing a metal catalyst by the DP method in the process of preparing a multi-walled carbon nanotube conductive dispersion according to the present invention. As shown in FIG. 1, in the method of manufacturing a multi-walled carbon nanotube conductive dispersion using a milling process according to the present invention, it is preferable to first perform the metal catalyst manufacturing steps (s110 to s160) by the DP method.

따라서 가장 먼저 Iron(Ⅲ) Nitrate Nonahydrate(Fe(NO₃)₃9H₂O)와 Cobalt(Ⅱ) Nitrate Hexahydrate(Co(NO₃)₂6H₂O)를 용매에 넣어 용해한 제1용액을 만드는 과정(s110 단계)을 수행하도록 하는 것이 바람직하다. 여기서 상기 제1용액을 만드는 데 사용되는 용매는 DI water로 하되, 상기 DI water 100중량부에 대하여 상기 Iron(Ⅲ) Nitrate Nonahydrate 25.02중량부와 Cobalt(Ⅱ) Nitrate Hexahydrate 7.55중량부를 순서대로 넣고 Magnetic Stirrer를 사용하여 20분간 용해하는데 완전한 수용액의 상태가 될 때까지 용해하는 것이 바람직하다. Therefore, first of all, it is necessary to perform the process of making the first solution (step s110) by putting Iron(III) Nitrate Nonahydrate (Fe(NO₃)₃9H₂O) and Cobalt(II) Nitrate Hexahydrate (Co(NO₃)₂6H₂O) in a solvent. desirable. Here, the solvent used to make the first solution is DI water, but with respect to 100 parts by weight of the DI water, 25.02 parts by weight of the Iron(III) Nitrate Nonahydrate and 7.55 parts by weight of Cobalt(II) Nitrate Hexahydrate are put in order and magnetic stirrer It is preferable to dissolve for 20 minutes by using to dissolve until a complete aqueous solution is obtained.

그 다음에는 Ammonium Carbonate((NH₄)₂CO₃)를 용매에 넣어 용해한 제2용액을 만드는 과정(s120 단계)을 수행하도록 하는 것이 바람직하다. 여기서 상기 제2용액을 만드는 데 사용되는 용매 또한 DI water로 하는 것이 바람직하며, 상기 DI water 100중량부에 대하여 상기 Ammonium Carbonate 100중량부를 넣고 약 2시간 동안 bath sonic을 사용하여 용해하며, 고형분이 완전히 용해되어 완전한 수용액 상태로 될 때까지 용해하도록 하는 것이 바람직하다. 그 다음에는 Aluminum Hydroxide(Al(OH)₃)를 용매에 넣어 용해한 제3용액을 만드는 과정(s130 단계)을 수행하도록 하는 것이 바람직하다. 상기 제3용액을 만드는 데 사용되는 용매 또한 DI water로 하는 것이 바람직하며, 상기 DI water 100중량부에 대하여 상기 Aluminum Hydroxide 50중량부를 넣고 완전히 섞일 때까지 Mechanical Stirrer로 교반하도록 하는 것이 바람직하다. 상기 제1용액, 상기 제2용액 및 상기 제3용액이 만들어진 후에는 상기 제3용액에 상기 제1용액 및 상기 제2용액을 혼합한 혼합용액을 만들어 주는 것이 바람직하다(s140 단계). 상기 혼합용액은 상기 제3용액을 Mechanical Stirrer로 교반하면서 Dropping Funnel을 사용하여 제조된 상기 제1용액 및 상기 제2용액을 가하도록 하는 것이 바람직하다. After that, it is preferable to perform a process (step s120) of making a second solution in which Ammonium Carbonate ((NH₄)₂CO₃) is dissolved in a solvent. Here, the solvent used to make the second solution is also preferably DI water, and 100 parts by weight of the Ammonium Carbonate is added to 100 parts by weight of the DI water and dissolved using a bath sonic for about 2 hours, and the solid content is completely It is preferable to dissolve until it dissolves and becomes a complete aqueous solution. After that, it is preferable to perform a process (step s130) of making a third solution in which Aluminum Hydroxide (Al(OH)₃) is dissolved in a solvent. The solvent used to make the third solution is also preferably DI water, and 50 parts by weight of the Aluminum Hydroxide is added to 100 parts by weight of the DI water, and the mixture is stirred with a mechanical stirrer until completely mixed. After the first solution, the second solution, and the third solution are prepared, it is preferable to prepare a mixed solution obtained by mixing the first solution and the second solution in the third solution (step S140). As for the mixed solution, it is preferable to add the first solution and the second solution prepared using a dropping funnel while stirring the third solution with a mechanical stirrer.

그 다음에는 상기 혼합용액을 여과하는 여과과정(s150 단계)을 거치도록 하는 것이 바람직한데, 상기 여과과정은 상기 혼합용액을 Filtering 장치를 이용하여 거르는 것으로서, Buchner Funnel에 여과지를 올리고, 상기 혼합용액을 두세 번에 걸쳐서 나누어 거르도록 하는 것이 바람직하다. 상기 여과과정(s150 단계)을 거친 뒤에는 건조과정(s160 단계)을 거치도록 하는 것이 바람직한데, 상기 건조과정(s160 단계)은 상기 여과지에 걸러진 Cake를 떨어내어 오븐에 넣은 뒤 150도의 온도로 16시간 이상 건조하도록 하는 것이 바람직하다. Next, it is preferable to undergo a filtration process (step s150) of filtering the mixed solution. In the filtration process, the mixed solution is filtered using a filtering device, and a filter paper is placed on the Buchner Funnel, and the mixed solution is added. It is advisable to filter it in two or three times. After passing through the filtration process (step s150), it is preferable to go through a drying process (step s160). In the drying process (step s160), after dropping the cake filtered on the filter paper and putting it in an oven, it is at a temperature of 150 degrees for 16 hours. It is desirable to dry it longer.

본 발명에 의한 밀링공정을 이용한 다중벽 탄소나노튜브 전도성 분산액의 제조방법에서 사용되는 금속촉매는 철(Fe)과 코발트(Co)을 이용하는 것이 바람직하다. 따라서 상술한 바와 같이 철의 전구체물질인 Iron(Ⅲ) Nitrate Nonahydrate와 코발트의 전구체물질인 Cobalt(Ⅱ) Nitrate Hexahydrate를 용해한 상기 제1용액을 제조하여 사용하는 것이다.It is preferable to use iron (Fe) and cobalt (Co) as the metal catalyst used in the method for preparing the multi-walled carbon nanotube conductive dispersion liquid using the milling process according to the present invention. Therefore, as described above, the first solution obtained by dissolving Iron(III) Nitrate Nonahydrate, which is a precursor material of iron, and Cobalt(II) Nitrate Hexahydrate, which is a precursor material of cobalt, is prepared and used.

한편 상술한 방법에 의하여 제조된 상기 제1용액은 pH조절제인 Ammonium Carbonate를 용해한 상기 제2용액과 혼합 시 금속산화물 또는 금속수산화물입자의 형태로 고화되며, Aluminum Hydroxide를 용해한 상기 제3용액에 섞일 때 상기 제3용액 상에 흡착되며, 금속산화물(또는 금속수산화물)과 상기 제3용액의 혼합물의 금속촉매 입자 형태로 상기 혼합용액 내에서 침전될 수 있다. 따라서 상기 제3용액에 상기 제1용액과 상기 제2용액을 가할 때 바람직한 양을 조절하여 금속촉매를 제조하여야 하며, 이는 전이 금속 전구체로부터 금속산화물 또는 금속수산화물의 침전을 형성하는 데 적정량의 pH조절제를 첨가하여야 금속 성분의 정량 침전을 유도하기 적합하기 때문이다. 따라서, 본 발명에서는 상기 제1용액, 상기 제2용액 및 상기 제3용액의 제조에 사용되는 Iron(Ⅲ) Nitrate Nonahydrate, Cobalt(Ⅱ) Nitrate Hexahydrate, Ammonium Carbonate 및 Aluminum Hydroxide 각각의 성분비(중량)를 250.2: 75.5: 2000: 1000으로 하는 것이 바람직하다.Meanwhile, the first solution prepared by the above method is solidified in the form of metal oxide or metal hydroxide particles when mixed with the second solution in which Ammonium Carbonate, a pH adjusting agent, is dissolved, and when mixed in the third solution in which Aluminum Hydroxide is dissolved. It is adsorbed on the third solution, and may be precipitated in the mixed solution in the form of metal catalyst particles of a mixture of a metal oxide (or metal hydroxide) and the third solution. Therefore, when the first solution and the second solution are added to the third solution, a metal catalyst must be prepared by adjusting a preferable amount, which is an appropriate amount of a pH adjusting agent to form a precipitate of a metal oxide or a metal hydroxide from a transition metal precursor. This is because it is suitable to induce quantitative precipitation of metal components only when is added. Therefore, in the present invention, the component ratio (weight) of each of Iron(III) Nitrate Nonahydrate, Cobalt(II) Nitrate Hexahydrate, Ammonium Carbonate, and Aluminum Hydroxide used to prepare the first solution, the second solution, and the third solution It is preferable to set it as 250.2: 75.5: 2000: 1000.

상기 금속촉매제조단계(s110~s160 단계)를 수행한 뒤에는, 상기 금속촉매를 CVD 합성장치에서 혼합가스를 투입하여 가열하는 탄소나노튜브를 합성하는 합성단계(s170 단계)를 거치도록 하는 것이 바람직하다. 상기 합성단계(s170 단계)에서는 합성온도를 750℃로 하여 약 30분 정도 진행하도록 하는 것이 바람직하다. 상기 합성단계(s170 단계)에서는, 연속공정이 가능한 화학기상증착법(Chemical Vapor Deposition)을 통해 다중벽 탄소나노튜브를 합성하도록 하는 것이 바람직하다. After performing the metal catalyst manufacturing step (steps s110 to s160), it is preferable to undergo a synthesis step (step s170) of synthesizing carbon nanotubes heated by injecting a mixed gas into the metal catalyst in a CVD synthesis device. . In the synthesis step (step s170), it is preferable to proceed for about 30 minutes at a synthesis temperature of 750°C. In the synthesis step (s170 step), it is preferable to synthesize the multi-walled carbon nanotubes through a chemical vapor deposition method capable of a continuous process.

그 다음에 합성된 다중벽 탄소나노튜브에 대하여 일정시간동안 밀링처리 공정을 거치도록 하여 탄소나노튜브용액을 제조하는 것이 바람직하다(s180). 이를 위하여는, 제조된 다중벽 탄소나노튜브를 원소재로 사용하여 수계분산제 및 소포제 등을 첨가하는 것이 바람직한데, 도 3에 도시된, 밀링과정의 투입원료에 대한 함량 및 용도(S1)에서 보는 바와 같이 탄소나노튜브 3.50%에 대하여 수계 분산제인 Solspers-46000 3.75%와 수계 소포제인 Dynol 604 4.04%를 첨가한 후, 나머지 88.71%를 DI water로 채워준 상태에서 밀링공정을 수행하도록 하는 것이 바람직하다. 도 4는 본 발명의 제조실시예에 사용된 밀링장비에 대한 사진이다.Then, it is preferable to prepare a carbon nanotube solution by subjecting the synthesized multi-walled carbon nanotubes to a milling process for a certain period of time (s180). To this end, it is preferable to use the prepared multi-walled carbon nanotubes as a raw material and add a water-based dispersant and an antifoaming agent, etc., as shown in Figure 3, as shown in the content and use of the input raw material in the milling process (S1). As described above, it is preferable to perform the milling process while filling the remaining 88.71% with DI water after adding 3.75% of the aqueous dispersant Solspers-46000 and 4.04% of the aqueous antifoaming agent to 3.50% of carbon nanotubes. Figure 4 is a photograph of the milling equipment used in the manufacturing embodiment of the present invention.

그 다음에는 상기 탄소나노튜브용액을 분산하여 분산액을 만들어주는 것이 바람직하다(s190). 이를 위하여 분산제, 바인더, 보조용매제, 습윤제 및 물을 첨가하여 탄소나노튜브를 분산시킴으로써 다중벽 탄소나노튜브의 전도성 분산액을 제조하는 것이 바람직한데, 도 3에 도시된, 분산과정의 투입원료에 대한 함량 및 용도(S2)에서 보는 바와 같이 다중벽 탄소나노튜브 분산액 24.66%에 대하여 분산제로서 Disponil 32 1.64%, 바인더로서 HU-580 6.14%, 슬립제로서 IE349 4.09%, 보조용매로 1-PrOH 1.90% 및 NMP 0.23%, 습윤제로 BYK-346 1.06%를 넣고 DI water 60.28%를 첨가하여 분산액을 제조하는 것이 바람직하나, 첨가한 분산제, 바인더, 슬립제, 보조용매, 습윤제 및 용매에 대하여 그 종류가 한정되는 것은 아니다. After that, it is preferable to make a dispersion by dispersing the carbon nanotube solution (s190). To this end, it is preferable to prepare a conductive dispersion of multi-walled carbon nanotubes by adding a dispersant, a binder, a co-solvent, a wetting agent, and water to disperse the carbon nanotubes. As shown in the content and use (S2), for 24.66% of the multi-walled carbon nanotube dispersion, Disponil 32 1.64% as a dispersant, HU-580 6.14% as a binder, IE349 4.09% as a slip agent, and 1-PrOH 1.90% as a co-solvent And 0.23% of NMP and 1.06% of BYK-346 as a wetting agent, and 60.28% of DI water is preferably added to prepare a dispersion, but the types of the added dispersant, binder, slip agent, co-solvent, wetting agent, and solvent are limited. It does not become.

도 2는 본 발명에 의한 다중벽 탄소나노튜브 전도성 분산액이 제조되는 공정 중 SD법에 의하여 금속촉매를 제조한 후 다중벽 탄소나노튜브 및 분산액을 제조하는 공정에 대한 흐름도이다. 여기에서도 먼저 도 2에서 보는 바와 같이 SD법에 의한 금속촉매제조단계(s210~s230 과정)를 수행하도록 하는데, 가장 먼저 Iron(Ⅲ) Nitrate Nonahydrate(Fe(NO₃)₃9H₂O), Cobalt(Ⅱ) Nitrate Hexahydrate(Co(NO₃)₂6H₂O) 및 Aluminium nitrate nonahydrate(Al(NO₃)₃)을 용매에 넣어 용해한 금속촉매전구체용액을 만드는 과정(s210 단계)을 수행하도록 하는 것이 바람직하다. 여기서 상기 금속촉매전구체용액을 만드는 데 사용되는 용매는 DI water로 하되, 상기 DI water 10kg(10L)에 대하여 상기 Iron(Ⅲ) Nitrate Nonahydrate, Cobalt(Ⅱ) Nitrate Hexahydrate 및 Al(NO₃)₃)의 질량이 각각 1000g, 250g 및 1200g이 되도록 하여 섞은 후, 완전히 섞일 때까지 Mechanical Stirrer로 교반하도록 하는 것이 바람직하다(s210 과정). 그 다음에는 상기 금속촉매전구체용액을 반응로에 공기와 함께 동시 투입하여 건조하는 것이 바람직하며(s220~s230 과정), 이때 금속촉매의 크기를 5~8μm로 일정하게 조정할 수 있도록 하기 위하여 반응로의 온도는 800℃로 항상 유지시키는 것이 바람직하다. 2 is a flowchart illustrating a process of manufacturing a multi-walled carbon nanotube and a dispersion after preparing a metal catalyst by the SD method in the process of preparing a multi-walled carbon nanotube conductive dispersion according to the present invention. Here, as shown in FIG. 2, the metal catalyst manufacturing step (s210 to s230 process) is first performed by the SD method. First, Iron(III) Nitrate Nonahydrate(Fe(NO₃)₃9H₂O), Cobalt(II) Nitrate Hexahydrate It is preferable to perform a process (step s210) of making a metal catalyst precursor solution in which (Co(NO₃)₂6H₂O) and aluminum nitrate nonahydrate (Al(NO₃)₃) are dissolved in a solvent. Here, the solvent used to make the metal catalyst precursor solution is DI water, and the mass of the Iron(III) Nitrate Nonahydrate, Cobalt(II) Nitrate Hexahydrate and Al(NO3)₃) with respect to 10kg (10L) of DI water It is preferable to mix with each of 1000g, 250g, and 1200g, and then stir with a mechanical stirrer until completely mixed (s210 process). Next, it is preferable to simultaneously put the metal catalyst precursor solution into the reaction furnace with air and dry it (s220 to s230 process), and at this time, in order to adjust the size of the metal catalyst to 5 to 8 μm. It is desirable to keep the temperature at 800°C all the time.

그 다음에는 상기 금속촉매를 CVD 합성장치에서 혼합가스를 투입하여 가열하는 탄소나노튜브를 합성하는 합성단계(s240 단계)를 거치도록 하는 것이 바람직하다. 상기 합성단계(s240 단계)에서는 합성온도를 750℃로 하여 약 30분 정도 진행하도록 하는 것이 바람직하다. 상기 합성단계(s240 단계)에서는, 연속공정이 가능한 화학기상증착법(Chemical Vapor Deposition)을 통해 다중벽 탄소나노튜브를 합성하도록 하는 것이 바람직하다. Next, it is preferable to undergo a synthesis step (step s240) of synthesizing carbon nanotubes heated by introducing a mixed gas to the metal catalyst in a CVD synthesis apparatus. In the synthesis step (step s240), it is preferable to set the synthesis temperature to 750° C. and proceed for about 30 minutes. In the synthesis step (step s240), it is preferable to synthesize the multi-walled carbon nanotubes through a chemical vapor deposition method capable of a continuous process.

또한, 여기서도 DP법을 통한 전도성 분산액의 제조방법과 마찬가지로 합성된 다중벽 탄소나노튜브에 대하여 일정시간동안 밀링처리 공정을 거치도록 하여 탄소나노튜브용액을 제조하는 것이 바람직하다(s250). 이를 위하여는, 제조된 다중벽 탄소나노튜브를 원소재로 사용하여 수계분산제 및 소포제 등을 첨가하는 것이 바람직한데, 도 3에 도시된, 밀링과정의 투입원료에 대한 함량 및 용도(S1)에서 보는 바와 같이 탄소나노튜브 3.50%에 대하여 수계 분산제인 Solspers-46000 3.75%와 수계 소포제인 Dynol 604 4.04%를 첨가한 후, 나머지 88.71%를 DI water로 채워준 상태에서 밀링공정을 수행하도록 하는 것이 바람직하다.In addition, it is preferable to prepare a carbon nanotube solution by subjecting the synthesized multi-walled carbon nanotubes to a milling process for a certain period of time, similar to the method for preparing a conductive dispersion through the DP method (s250). To this end, it is preferable to use the prepared multi-walled carbon nanotubes as a raw material and add a water-based dispersant and an antifoaming agent, etc., as shown in Figure 3, as shown in the content and use of the input raw material in the milling process (S1). As described above, it is preferable to perform the milling process while filling the remaining 88.71% with DI water after adding 3.75% of the aqueous dispersant Solspers-46000 and 4.04% of the aqueous antifoaming agent to 3.50% of carbon nanotubes.

이렇게 밀링처리된 탄소나노튜브용액를 분산하여 분산액을 만들어주는 것이 바람직하다(s260). 밀링처리는 3시간, 6시간 및 9시간으로 하였으며, 이를 위하여 분산제, 바인더, 보조용매제, 습윤제 및 용매로서 물을 첨가하여 다중벽 탄소나노튜브를 분산시킴으로써 다중벽 탄소나노튜브의 전도성 분산액을 제조하는 것이 바람직한데, 도 3에 도시된, 분산과정의 투입원료에 대한 함량 및 용도(S2)에서 보는 바와 같이 다중벽 탄소나노튜브 분산액 24.66%에 대하여 분산제로서 Disponil 32 1.64%, 바인더로서 HU-580 6.14%, 슬립제로서 IE349 4.09%, 보조용매로 1-PrOH 1.90% 및 NMP 0.23%, 습윤제로 BYK-346 1.06% 를 넣고 DI water 60.28%를 첨가하여 분산액을 제조하는 것이 바람직하다.It is preferable to disperse the milled carbon nanotube solution to make a dispersion (s260). The milling treatment was 3 hours, 6 hours, and 9 hours, and for this purpose, water was added as a dispersant, a binder, a co-solvent, a wetting agent, and a solvent to disperse the multi-walled carbon nanotubes to prepare a conductive dispersion of the multi-walled carbon nanotubes. It is preferable to do, as shown in Fig. 3, as shown in the content and use of the input raw material in the dispersion process (S2), for 24.66% of the multi-walled carbon nanotube dispersion, Disponil 32 1.64% as a dispersant and HU-580 as a binder. It is preferable to prepare a dispersion by adding 6.14%, IE349 4.09% as a slip agent, 1-PrOH 1.90% and NMP 0.23% as a co-solvent, and 1.06% BYK-346 as a wetting agent, and DI water 60.28%.

분산제를 첨가하여 탄소나노튜브 분산액을 제조하는 이유는 나노크기의 탄소나노튜브가 반데르발스 작용으로 인해 응집하려는 특성이 있어 분산제가 탄소나노튜브 번들에 침투되어 튜브와 튜브 사이의 상호작용을 약화시킴으로써 탄소나노튜브의 분산을 향상시키고 분산액의 점도를 제어하는 역할을 하기 때문으로, 분산제는 경계면의 장력을 완화시키는 계면활성제나 수계 분산제 등을 사용하는 것이 바람직하다,The reason for preparing a carbon nanotube dispersion by adding a dispersant is that nano-sized carbon nanotubes tend to agglomerate due to the Van der Waals action, so the dispersant penetrates the carbon nanotube bundle and weakens the interaction between the tube and the tube. Since it plays a role in improving the dispersion of carbon nanotubes and controlling the viscosity of the dispersion, the dispersant is preferably a surfactant or an aqueous dispersant that relieves the tension of the interface.

분산성으로 높이기 위해서 분산액에 더 첨가할 수 있는 첨가제의 종류로는 습윤제, 슬립제, 소포제, 바인더 등이 있으며, 습윤제는 고체 물질이 물에 젖기 쉬운 표면 에너지를 감소시키는 계면 활성제이며, 슬립제 또한 필름이나 시트가 잘 미끄러지도록 하기 위한 첨가제로서 마찰계수를 줄이는데 필요한 윤활작용을 해주고, 소포제는 계면활성제보다 더 강력한 흡착성질을 갖는 또 다른 계면활성 물질이며, 바인더(결합제)는 탄력성과 점착성을 높여 강도를 증가시키기 위해 첨가하는 물질이다. 본 발명에 의해 제조되는 분산액의 분산성을 증강시키는 목적으로 첨가한 첨가제는 앞서 서술한 특정 용액 외에 같은 효과를 가지는 용액은 무엇이든 사용 가능하여 본 발명에 의한 첨가한 분산제, 바인더, 슬립제, 소포제, 습윤제 및 용매에 대하여 상술한 물질로 특정되는 것은 아니다.Types of additives that can be further added to the dispersion to increase dispersibility include wetting agents, slip agents, antifoaming agents, and binders, and wetting agents are surfactants that reduce the surface energy that solid substances are likely to get wet with water. As an additive to make the film or sheet slip well, it provides the necessary lubrication action to reduce the coefficient of friction, and the antifoaming agent is another surface-active material that has stronger adsorption properties than the surfactant, and the binder (binder) increases elasticity and adhesiveness. It is a substance added to increase The additive added for the purpose of enhancing the dispersibility of the dispersion prepared by the present invention can be any solution having the same effect in addition to the above-described specific solution. Thus, the added dispersant, binder, slip agent, and antifoam agent according to the present invention can be used. , The wetting agent and the solvent are not specified as the above-described substances.

이하에서는 실시예, 실험예 및 제조실시예 등을 통하여 본 발명을 보다 상세하게 설명한다. 이하에서 설명되는 실시예 등은 본 발명의 이해를 돕기 위하여 예시적으로 나타낸 것이며, 본 발명은 여기서 설명되는 일 실시예와 다르게 다양하게 변형되어 실시될 수 있음이 이해되어야 할 것이다. 이와 같이 본 발명의 범주 및 기술사상 범위 내에서 다양한 변경 및 수정이 가능함은 본 기술분야에서 통상의 지식을 가진 자에게 있어서 명백한 것이며, 이러한 변형 및 수정이 첨부된 특허청구범위에 속하는 것도 당연한 것이다. Hereinafter, the present invention will be described in more detail through Examples, Experimental Examples, and Manufacturing Examples. It should be understood that the embodiments and the like described below are illustratively shown to aid understanding of the present invention, and the present invention may be variously modified and implemented differently from the exemplary embodiment described herein. As described above, it is obvious to those of ordinary skill in the art that various changes and modifications can be made within the scope of the present invention and the scope of the technical idea, and it is natural that such modifications and modifications fall within the appended claims.

[실시예 1] DP법으로 제조한 금속촉매로 다중벽 탄소나노튜브 합성[Example 1] Synthesis of multi-walled carbon nanotubes with metal catalyst prepared by DP method

DP법을 이용하여 금속촉매를 제조하였다. 원재료 중 Iron(Ⅲ) Nitrate Nonahydrate (이하 FeN)으로 대정사 제품이며, Cobalt(Ⅱ) Nitrate Hexahydrate (이하 CoN)의 제조사는 JUNSEI, Ammonium Carbonate (이하 NH₄)의 제조사는 삼전, Aluminum Hydroxide (이하 Al(OH)₃)은 KC사 제품을 이용하였다. A metal catalyst was prepared using the DP method. Among the raw materials, Iron(Ⅲ) Nitrate Nonahydrate (hereinafter referred to as FeN) is a Daejeongsa product, and the manufacturer of Cobalt(II) Nitrate Hexahydrate (hereinafter referred to as CoN) is JUNSEI, and the manufacturer of Ammonium Carbonate (hereinafter referred to as NH₄) is Samjeon, Aluminum Hydroxide (hereinafter, Al OH)₃) was manufactured by KC.

(1) 1L 의 DI water에 FeN 250.2g과 CoN 75.5g을 순서대로 넣고 Magnetic Stirrer를 사용하여 20분간 교반하여 완전한 수용액 상태로 만들어 제1용액을 제조하였다. 이때 Impeller의 회전속도는 350으로 설정하였다.(1) 250.2 g of FeN and 75.5 g of CoN were sequentially added to 1 L of DI water and stirred for 20 minutes using a magnetic stirrer to make a complete aqueous solution to prepare a first solution. At this time, the impeller's rotational speed was set to 350.

(2) Ammonium Carbonate(이하 NH₄) 2kg을 2L의 DI water에 넣고 용해하여 제2용액을 제조하였는데, 2시간 동안 bath Sonic을 사용하여 완전한 수용액 상태로 만들었다.(2) 2 kg of Ammonium Carbonate (hereinafter referred to as NH₄) was added to 2L of DI water and dissolved to prepare a second solution, which was made into a complete aqueous solution using bath Sonic for 2 hours.

(3) 대용량 비커에 2L의 DI water를 넣은 후 Al(OH)₃ 1kg을 넣어 혼합하고 Mechanical Stirrer를 사용하여 5분간 교반함으로써 제3용액을 제조하였다. 이 때 Impeller의 회전속도는 850으로 하였다. (3) After adding 2L of DI water to a large-capacity beaker, 1kg of Al(OH)₃ was added to mix, and a third solution was prepared by stirring for 5 minutes using a mechanical stirrer. At this time, the impeller's rotational speed was set to 850.

(4) 상기 제3용액을 Mechanical Stirrer로 교반하면서, Dropping Funnel을 사용하여 상기 제1용액과 상기 제2용액을 20분간 떨어뜨려 혼합용액을 제조하였다. (4) While stirring the third solution with a mechanical stirrer, the first solution and the second solution were dropped for 20 minutes using a dropping funnel to prepare a mixed solution.

(5) 이렇게 제작된 혼합용액을 진공 Filtering 장치를 사용하여 거르는 과정을 진행하였는데, 2set 의 Buchner Funnel에 필터지를 2장 올리고, 용액을 1/2씩 나누어 거르는 과정을 반복하였다. (5) The thus prepared mixed solution was filtered using a vacuum filtering device. Two filter papers were placed on 2 sets of Buchner Funnel, and the process was repeated by dividing the solution by half.

(6) 은박 호일에 걸러진 Cake를 떨어내어, Box형 Oven에서 온도를 150℃로 설정하고 16시간 동안 건조하여 금속촉매를 수득하였다. (6) The cake filtered on the silver foil was dropped, and the temperature was set to 150°C in a box-type oven and dried for 16 hours to obtain a metal catalyst.

(7) 상기 금속촉매를 CVD 합성 장치에 넣고 750도에서 30분간 합성하여 다중벽 탄소나노튜브를 수득한다. (7) The metal catalyst was put in a CVD synthesis apparatus and synthesized at 750° C. for 30 minutes to obtain a multi-walled carbon nanotube.

[실시예 2] SD법으로 제조한 금속촉매로 다중벽 탄소나노튜브 합성[Example 2] Synthesis of multi-walled carbon nanotubes with a metal catalyst prepared by the SD method

SD법을 이용하여 다중벽 탄소나노튜브를 합성하였다. 원재료 중 Iron(Ⅲ) Nitrate Nonahydrate(이하 FeN)으로 대정사 제품이며, Cobalt(Ⅱ) Nitrate Hexahydrate(Co(NO₃)₂6H₂O이하 CoN)의 제조사는 JUNSEI, Aluminium nitrate nonahydrate(이하 AlN)의 대정사의 제품을 사용하였다. Multi-walled carbon nanotubes were synthesized using the SD method. Among the raw materials, Iron(III) Nitrate Nonahydrate (hereinafter referred to as FeN), which is a product of Daejeongsa, and the manufacturer of Cobalt(II) Nitrate Hexahydrate (Co(NO₃)₂6H₂O or less CoN) is the product of Daejeongsa such as JUNSEI and Aluminum nitrate nonahydrate Was used.

(1) 10L의 DI water에 FeN 1,000g, CoN 250g 및 AIN 1200g을 넣고 Mechanical Stirrer를 사용하여 30분간 교반하여 용해시켜 금속촉매전구체용액을 만들었다. 완전히 수용액 상태가 된 것을 확인하여 고형분이 완전히 녹지 않으면 위의 용해 작업을 완전히 녹을 때까지 반복하여 진행하였다. (1) 1,000 g of FeN, 250 g of CoN and 1200 g of AIN were added to 10 L of DI water, stirred for 30 minutes using a mechanical stirrer, and dissolved to prepare a metal catalyst precursor solution. It was confirmed that the solution was completely in an aqueous solution state, and if the solid content was not completely dissolved, the above dissolution operation was repeated until completely dissolved.

(2) 이류체 노즐을 이용하여 상기 금속촉매전구체용액과 공기를 섞어 반응로에 분사하여 건조함으로써 금속촉매를 수득하였는데, 이 때 반응로의 온도는 800℃로 하였다. 반응로 내의 온도를 균일하게 유지할 수 있도록 온도를 상중하 3곳에서 측정하여 800℃의 온도를 계속하여 유지시켰다. 분사되는 금속촉매 크기를 5~8μm로 일정하게 유지할 수 있도록 이류체 노즐의 압력은 3.5kgf로 하여 분사하였다. (2) A metal catalyst was obtained by mixing the metal catalyst precursor solution and air using a two-fluid nozzle, spraying it into a reaction furnace, and drying it, and the temperature of the reaction furnace was 800°C. In order to keep the temperature in the reaction furnace uniform, the temperature was measured at three locations above and below, and the temperature of 800°C was continuously maintained. In order to keep the size of the sprayed metal catalyst constant at 5-8 μm, the pressure of the air-fluid nozzle was 3.5 kgf and sprayed.

(3) 상기 금속촉매를 CVD 합성 장치에 넣고 750℃에서 30분간 합성하여 다중벽 탄소나노튜브를 수득하였다.(3) The metal catalyst was put in a CVD synthesis apparatus and synthesized at 750° C. for 30 minutes to obtain a multi-walled carbon nanotube.

[제조실시예 1] 실시예 1에 의하여 제조된 다중벽 탄소나노튜브로 분산액 제조[Manufacturing Example 1] Preparation of dispersion from multi-walled carbon nanotubes prepared according to Example 1

실시예 1에서 제조된 다중벽 탄소나노튜브를 원소재로 사용하여 다중벽 탄소나노튜브의 전도성 분산액을 제조하였다.A conductive dispersion of multi-walled carbon nanotubes was prepared using the multi-walled carbon nanotubes prepared in Example 1 as a raw material.

(1) 다중벽 탄소나노튜브 3.50%에 대하여 수계 분산제인 Solspers-46000 3.75% 및 수계 소포제로서 Dynol 604 4.04%을 넣고 나머지 88.71%를 DI water로 혼합액을 만들었다. (1) To 3.50% of the multi-walled carbon nanotubes, 3.75% of Solspers-46000 as an aqueous dispersant and 4.04% of Dynol 604 as an aqueous antifoam were added, and the remaining 88.71% was mixed with DI water.

(2) 혼합액을 3등분하여 밀링장비에 넣고 각각 밀링처리 하여 탄소나노튜브용액을 만들었는데, 각각에 대한 밀링시간은 3시간, 6시간 및 9시간으로 달리하였다. (2) The mixed solution was divided into 3 parts, placed in a milling machine, and milled to make a carbon nanotube solution. The milling time for each was changed to 3 hours, 6 hours and 9 hours.

(3) 밀링처리된 3종류의 탄소나노튜브용액에 각각에 대하여 분산제, 바인더, 보조용매제, 습윤제 및 물을 첨가한 후 분산시켜 3종류의 전도성 분산액을 각각 제조하였다. 이 때 배합비율은, 탄소나노튜브용액 24.66%에 대하여 분산제로서 Disponil 32 1.64%, 바인더로서 HU-580 6.14%, 슬립제로서 IE349 4.09%, 보조용매로 1-PrOH 1.90%, NMP 0.23%, 습윤제로 BYK-346 1.06%을 넣고 DI water 60.28%가 첨가하였다. (3) A dispersant, a binder, a co-solvent, a wetting agent, and water were added to each of the three milled carbon nanotube solutions, and then dispersed to prepare three conductive dispersions. At this time, the blending ratio is 1.64% of Disponil 32 as a dispersant, 6.14% of HU-580 as a binder, 4.09% of IE349 as a slip agent, 1.90% of 1-PrOH, 0.23% of NMP, as a wetting agent with respect to 24.66% of the carbon nanotube solution. 1.06% of BYK-346 was added and 60.28% of DI water was added.

[제조실시예 2] 실시예 2에 의하여 제조된 다중벽 탄소나노튜브로 분산액 제조[Manufacturing Example 2] Preparation of dispersion from multi-walled carbon nanotubes prepared according to Example 2

실시예 2에 의하여 제조된 다중벽 탄소나노튜브에 대하여, 제조실시예 1에 사용한 방법과 동일한 방법으로, 밀링처리과정을 거쳐 3종류의 전도성 분산액을 각각 제조하였다.With respect to the multi-walled carbon nanotubes prepared in Example 2, in the same manner as in Preparation Example 1, three types of conductive dispersions were each prepared through a milling process.

제조된 다중벽 탄소나노튜브 분산액들 각각에 대하여 다양한 실험을 실시하였는데, 밀링처리공정에서 밀링시간에 따른 분산의 정도와 형상을 파악하여 최적의 밀링공정 시간을 찾을 수 있었으며, 합성된 다중벽 탄소나노튜브에 대하여 Bulk density, 응집체직경, 번들길이 및 번들직경 등의 형상과 특성의 차이를 분석하였다. 그리고 탄소나노튜브가 가지는 형상에 대항 외형적인 특성인 Bulk density, 번들길이, 번들직경 및 응집체직경을 파악하기 위하여 SEM사진을 분석하였다. 또한 밀링처리된 다중벽 탄소나노튜브를 고분자수지와 혼합하여 압출기 공정을 진행한 후 얻은 복합체 시트에 대하여 면 저항을 분석하였다. 이와 더불어 복합체 시트를 태워서 내부에서 탄소나노튜브가 분산된 형상을 관찰하여 분산성과의 상관관계를 파악하고 밀링처리에 따른 소재의 변화를 알아보았다. 이하에서는 각각의 실험예와 그 결과에 대하여 설명한다. Various experiments were conducted on each of the prepared multi-walled carbon nanotube dispersions, and the optimal milling process time was found by grasping the degree and shape of dispersion according to the milling time in the milling process. The differences in shape and properties such as bulk density, aggregate diameter, bundle length and bundle diameter were analyzed for the tube. In addition, SEM photographs were analyzed to determine bulk density, bundle length, bundle diameter, and aggregate diameter, which are external characteristics against the shape of carbon nanotubes. In addition, the sheet resistance was analyzed for the composite sheet obtained after the milled multi-walled carbon nanotubes were mixed with a polymer resin and subjected to an extruder process. In addition, by burning the composite sheet and observing the shape of the carbon nanotubes dispersed inside, the correlation between the dispersibility was identified, and the change of the material according to the milling treatment was investigated. Hereinafter, each experimental example and its results will be described.

[실험예 1] SEM 사진 관찰[Experimental Example 1] SEM photo observation

탄소나노튜브가 가지는 형상에 대한 외형적인 특성인 Bulk density, 번들길이, 번들직경 및 응집체직경을 파악하기 위하여 SEM사진을 분석하였다. 도 5는 DP법으로 제조된 금속촉매로 다중벽 탄소나노튜브를 합성한 것에 대한 사진이며, 도 6은 SD법으로 제조된 금속촉매로 다중벽 탄소나노튜브를 합성한 것에 대한 사진으로서, 각각에 대하여 밀링 전의 다중벽 탄소나노튜브의 외형과 3시간, 6시간 및 9시간 동안 밀링처리 한 후의 다중벽 탄소나노튜브 각각에 대하여 100배 및 1000배의 SEM 이미지로 응집체직경, 번들길이 및 번들직경을 관찰한 사진이다. SEM photographs were analyzed to determine bulk density, bundle length, bundle diameter, and aggregate diameter, which are the external characteristics of the shape of carbon nanotubes. FIG. 5 is a photograph of synthesizing multi-walled carbon nanotubes with a metal catalyst prepared by the DP method, and FIG. 6 is a photograph of synthesizing multi-walled carbon nanotubes with a metal catalyst prepared by the SD method. For each of the multi-walled carbon nanotubes before milling and the multi-walled carbon nanotubes after milling for 3 hours, 6 hours and 9 hours, the aggregate diameter, bundle length, and bundle diameter were determined by SEM images of 100 and 1000 times. This is the picture I observed.

관찰된 다중벽 탄소나노튜브의 형상을 볼 때 밀링처리 후 번들이 둥글게 뭉쳐있는 이미지를 보여주고 있는데, 이것은 밀링공정시 물리적인 힘에 의하여 응집체 및 번들이 분쇄되어 다중벽 탄소나노튜브가 짧아지게 되고, 건조 과정에서 분쇄된 다중벽 탄소나노튜브 등이 재 응집되는 성질을 가지고 있는 것에 기인한 것으로 판단되었다. When looking at the observed shape of the multi-walled carbon nanotubes, an image of the bundles being rounded after the milling process is shown.This is because the aggregates and bundles are crushed by physical force during the milling process, resulting in shortening of the multi-walled carbon nanotubes. In addition, it was determined that the multi-walled carbon nanotubes pulverized during the drying process were re-aggregated.

[실험예 2] Bulk density 측정[Experimental Example 2] Bulk density measurement

Bulk density는 다중벽 탄소나노튜브의 가장 중요한 특성 가운데 하나로다중벽 탄소나노튜브의 응용에 있어 적정 수준의 부피밀도가 필요하다. 따라서 Bulk density의 측정을 위해 메스실린더를 이용하여 다중벽 탄소나노튜브 무게를 측정하였고, 탭핑을 100회 진행한 후에 눈금을 확인하여 용량을 확인함으로써 Bulk density를 측정하였다. Bulk density is one of the most important properties of multi-walled carbon nanotubes, and an appropriate level of bulk density is required for applications of multi-walled carbon nanotubes. Therefore, to measure the bulk density, the weight of the multi-walled carbon nanotube was measured using a measuring cylinder, and after tapping was performed 100 times, the bulk density was measured by checking the scale by checking the capacity.

도 7에는 제조실시예 1을 통한 DP법을 적용하여 만든 다중벽 탄소나노튜브에 대한 밀링처리 전후의 Bulk density 측정결과와 오차범위가 도시되어 있으며, 도 8에는 제조실시예 2을 통한 SD법을 적용하여 만든 다중벽 탄소나노튜브에 대한 밀링처리 전후의 Bulk density 측정결과가 오차범위와 함께 도시되어 있다. 그리고 도 12에는 제조실시예 1에 의하여 제조된 다중벽 탄소나노튜브와 제조실시예 2에 의하여 제조된 다중벽 탄소나노튜브에 대한 Bulk density를 비교한 그래프이다. 도 7, 도 8 및 도 12에서 보듯이 Bulk Density는 밀링처리 시간이 늘어남에 따라 함께 증가함을 확인할 수 있었다. 7 shows the bulk density measurement results and error ranges before and after milling for the multi-walled carbon nanotubes made by applying the DP method according to Preparation Example 1, and FIG. 8 shows the SD method according to Preparation Example 2. Bulk density measurement results before and after milling for multi-walled carbon nanotubes made by applying are shown along with the error range. And Figure 12 is a graph comparing the bulk density of the multi-walled carbon nanotubes prepared according to Preparation Example 1 and the multi-walled carbon nanotubes prepared according to Preparation Example 2. As shown in FIGS. 7, 8, and 12, it was confirmed that the bulk density increased as the milling treatment time increased.

[실험예 3] 응집체직경, 번들직경 및 번들길이 측정[Experimental Example 3] Measurement of aggregate diameter, bundle diameter and bundle length

SEM(Scanning Electron Microscope)을 이용하여 밀링 전의 다중벽 탄소나노튜브의 외형과 밀링처리공정을 3시간, 6시간 및 9시간으로 나누어 진행 한 후에 100, 1000배의 이미지를 찍었다. 그리고 SEM이미지를 분석하여 응집체직경, 번들길이, 번들직경을 측정하였다. 도 7에는 제조실시예 1을 통한 DP법을 적용하여 만든 다중벽 탄소나노튜브에 대한 밀링처리 전후의 측정결과와 오차범위가 도시되어 있으며, 도 8에는 제조실시예 2를 통한 SD법을 적용하여 만든 다중벽 탄소나노튜브에 대한 밀링처리 전후의 측정결과가 오차범위와 함께 도시되어 있다,Using a SEM (Scanning Electron Microscope), the appearance of the multi-walled carbon nanotube before milling and the milling process were divided into 3 hours, 6 hours and 9 hours, and then 100, 1000 times images were taken. And the SEM image was analyzed to measure the aggregate diameter, bundle length, and bundle diameter. 7 shows the measurement results and error ranges before and after milling for the multi-walled carbon nanotubes made by applying the DP method according to Manufacturing Example 1, and FIG. 8 shows the SD method according to Manufacturing Example 2 The measurement results before and after milling for the multi-walled carbon nanotubes made are shown along with the error range.

도 7에서 보는 바와 같이 제조실시예 1에서 다중벽 탄소나노튜브의 응집체 직경은 밀링처리 전부터 밀링처리 후 6시간까지 약 32.2μm에서 23.3μm으로 감소하였으며 9시간의 밀링처리 시에는 응집체직경이 다시 26.1μm로 상승함을 알 수 있었다. 번들길이는 밀링처리 전부터 밀링처리 시간에 따라 각각 45.1μm, 55.5μm, 33.7μm 및 44.2μm으로 밀링처리 3시간에서 증가하였다가 밀링처리 6시간에서 감소하였고, 9시간 밀링처리 시 다시 증가하는 것을 확인할 수 있었다. 번들직경의 경우 밀링처리 전부터 밀링처리 시간에 따라 각각 6.2μm, 5.1μm, 3.5μm 및 4.8μm로서 밀링처리 후 6시간까지 감소하였다가 9시간 밀링처리 시 다시 증가하는 것을 확인할 수 있었다.As shown in Figure 7, the aggregate diameter of the multi-walled carbon nanotubes in Preparation Example 1 decreased from about 32.2 μm to 23.3 μm from before milling to 6 hours after milling, and after 9 hours of milling, the aggregate diameter was again 26.1. It can be seen that it rises to μm. Bundle length was 45.1μm, 55.5μm, 33.7μm, and 44.2μm, respectively, from before milling treatment to 45.1μm, 55.5μm, 33.7μm, and 44.2μm. Could. In the case of the bundle diameter, it was confirmed that it was 6.2 μm, 5.1 μm, 3.5 μm, and 4.8 μm, respectively, depending on the milling treatment time from before the milling treatment, which decreased up to 6 hours after the milling treatment, and then increased again after the 9 hours milling treatment.

그리고 도 8에서 보는 바와 같이 제조실시예 2에서 다중벽 탄소나노튜브의 응집체 직경은 밀링처리 전 48.0μm에서 밀링처리 3시간과 6시간에서 각각 40.4μm, 36.3μm으로 줄어들었으며 밀링처리 9시간에서는 36.6μm으로 6시간과 비교하였을 때 변화가 거의 없었다. 번들길이는 밀링처리 전 79.2μm에서 밀링처리 후 3시간과 6시간에서 각각 35.8μm과 27.3μm으로 줄어들었으며, 밀링처리 9시간 이후부터는 번들길이가 30.4μm로 다시 늘어나는 경향을 나타내고 있었다. 그리고 번들직경의 경우 밀링처리 전 8.8μm 에서 밀링처리 3시간과 6시간 후에는 각각 1.6μm과 1.1μm으로 작아졌으며, 이후 밀링처리 9시간 후에는 1.2μm으로 6시간과 비교하여 큰 변화를 보이지 않았다.And, as shown in FIG. 8, the aggregate diameter of the multi-walled carbon nanotubes in Preparation Example 2 was reduced from 48.0 μm before milling to 40.4 μm and 36.3 μm at 3 hours and 6 hours of milling treatment, respectively, and 36.6 at 9 hours of milling treatment. There was little change compared to 6 hours in μm. The bundle length decreased from 79.2 μm before milling to 35.8 μm and 27.3 μm at 3 hours and 6 hours after milling treatment, respectively, and after 9 hours of milling treatment, the bundle length showed a tendency to increase again to 30.4 μm. And the bundle diameter decreased from 8.8μm before milling to 1.6μm and 1.1μm after 3 hours and 6 hours of milling treatment, respectively, and 1.2μm after 9 hours of milling treatment, showing no significant change compared to 6 hours. .

측정결과를 볼 때 제조실시예 1과 제조실시예 2에서 얻은 다중벽 탄소나노튜브 중 6시간의 밀링처리 공정을 통해 얻어진 다중벽 탄소나노튜브의 응집체직경은 각각 23.3μm과 36.3μm이며 번들직경은 3.5μm와 1.1μm번들길이가 33.7μm과 27.3μm로서 다중벽 탄소나노튜브의 특성이 가장 우수한 것으로 파악되었다. 또한 이러한 외형적인 분석을 통하여, 분산에 영향을 미치는 외형적인 요소를 분석하였는데, 외형의 특성이 반데르발스 힘과 상관관계가 있음을 알 수 있었다. 즉 제조실시예1 과 2를 통해 합성된 다중벽 탄소나노튜브는 밀링처리를 통하여 물리적인 분쇄가 이루어진 후 건조 시 뭉치는 현상이 약해지는 것을 보였는데, 이는 반데르발스 힘에 의해 응집이 약하게 형성되는 것으로 판단되다. 따라서 다중벽 탄소나노튜브는 밀링처리 되었을 때 밀링처리 전보다 응집력은 더 낮고 분산력이 더 높아지는 것으로 판단되었다. Looking at the measurement results, the aggregate diameters of the multi-walled carbon nanotubes obtained through the 6-hour milling process among the multi-walled carbon nanotubes obtained in Preparation Example 1 and Preparation Example 2 were 23.3 μm and 36.3 μm, respectively, and the bundle diameter was The bundle lengths of 3.5 μm and 1.1 μm were 33.7 μm and 27.3 μm, and the characteristics of the multi-walled carbon nanotube were found to be the best. In addition, through this external analysis, the external factors that influence the variance were analyzed, and it was found that the characteristics of the appearance were correlated with the van der Waals force. That is, it was shown that the multi-walled carbon nanotubes synthesized through Preparation Examples 1 and 2 were physically pulverized through milling treatment and then agglomerated upon drying was weakened, which was weakly formed by the van der Waals force. Be judged to be. Therefore, when the multi-walled carbon nanotubes were milled, it was judged that the cohesive strength was lower and the dispersing power was higher than before the milling treatment.

[실험예 4] 점도특성[Experimental Example 4] Viscosity Characteristics

Brookfield사의 cone/paste viscometer를 이용하여 점도특성을 측정하였는데, 다중벽 탄소나노튜브에 대하여 밀링처리 전후를 비교하였으며, 3.7%의 함량으로 제조된 paste를 이용하여 측정하였다.The viscosity characteristics were measured using a Brookfield cone/paste viscometer, and the multi-walled carbon nanotubes were compared before and after milling, and measured using a paste prepared with a content of 3.7%.

점도특성 측정결과 또한 도 7 및 도 8에 도시되어 있는데, 도 7에서 보는 바와 같이 제조실시예 1에서 다중벽 탄소나노튜브의 점도특성을 살펴보면, 밀링처리 3시간 후 다중벽 탄소나노튜브가 7,656cP로 밀링처리 전인 7,084cP보다 높은 점도 값을 나타내었다. 이는 밀링처리가 되면서 다중벽 탄소나노튜브의 번들길이가 짧아지면서 비표면적이 증가하며 이로 인하여 증가된 비표면적에 용매가 더 많이 소요되기 때문에 점도가 증가하는 현상이 발생한다고 판단했다. 하지만 6시간 밀링처리 후에는 점도가 급격히 낮아져 3,559cP가 된 것을 확인할 수 있었으며 9시간 밀링처리 이후에는 4,520cP으로 점도가 다소 상승하는 것을 확인할 수 있었다. 이렇게 밀링처리 6시간에서 급격한 점도의 감소가 이루어지는 것은 3시간 밀링처리 후에 다중벽 탄소나노튜브의 길이가 물리적 힘에 의하여 더욱 짧아지면서 분산되어 균일한 분포가 형성되어 유동성이 향상되기 때문에 점도가 낮아지며, 결과적으로 점도가 낮아짐으로 인해 젖음성이 증가하는 결과를 가져올 것으로 판단되었다.The viscosity characteristic measurement results are also shown in Figs. 7 and 8. As shown in Fig. 7, looking at the viscosity characteristics of the multi-walled carbon nanotubes in Preparation Example 1, the multi-walled carbon nanotubes were 7,656 cP after 3 hours of milling treatment. It exhibited a higher viscosity value than 7,084cP before the furnace milling treatment. It was determined that as the milling treatment was performed, the bundle length of the multi-walled carbon nanotubes was shortened and the specific surface area increased. As a result, the viscosity increased because more solvent was required for the increased specific surface area. However, after 6 hours of milling treatment, the viscosity rapidly decreased to 3,559 cP, and after 9 hours of milling treatment, it was confirmed that the viscosity slightly increased to 4,520 cP. This rapid decrease in viscosity after 6 hours of milling treatment is that after 3 hours of milling treatment, the length of the multi-walled carbon nanotubes is further shortened by the physical force and dispersed to form a uniform distribution and thus the viscosity is lowered. As a result, it was judged that lowering the viscosity would lead to an increase in wettability.

그리고 도 8에서 보는 바와 같이 제조실시예 2에서 다중벽 탄소나노튜브의 점도특성을 살펴보면, 밀링처리 전의 12,250cP에서 밀링처리 3시간 공정 시에는 13,512cP로 다소 증가하였으며 밀링처리 6시간 후에는 5,640cP으로 급격히 낮아졌다. 그리고 9시간 밀링공정 후에는 7,825cP로 다시 증가하는 현상을 보여주고 있었다. 이러한 현상은 제조실시예 1로 제조된 다중벽 탄소나노튜브의 점도특성과 유사한 결과를 나타내고 있었다. 결과적으로 볼 때 밀링처리 시 물리적 힘에 의하여 다중벽 탄소나노튜브의 번들길이가 짧아지면서 비표면적이 증가하여 증가된 비표면적에 용매가 더 많이 소요되어 점성이 증가하는 것으로 판단되었다. And looking at the viscosity characteristics of the multi-walled carbon nanotubes in Preparation Example 2, as shown in FIG. 8, from 12,250 cP before the milling treatment to 13,512 cP at the time of 3 hours of milling treatment, and 5,640 cP after 6 hours of milling treatment. Fell sharply. And after 9 hours of milling process, it showed a phenomenon of increasing again to 7,825cP. This phenomenon showed a result similar to the viscosity characteristics of the multi-walled carbon nanotubes prepared in Preparation Example 1. As a result, it was judged that during the milling treatment, the bundle length of the multi-walled carbon nanotubes was shortened due to the physical force, and the specific surface area increased, so that more solvent was required for the increased specific surface area, resulting in an increase in viscosity.

[실험예 5] 면저항 특성[Experimental Example 5] Sheet resistance characteristics

제조실시예 1과 2에서 각각 제조된 각각의 다중벽 탄소나노튜브(MWCNT) 2wt%에 LDPE5321의 폴리에틸렌(Polyethylene, PE)을 twin 압출기에 투입시켜 각각의 펠렛을 생성하였다. Twin Extruder의 장비로 진행하였으며, 멜팅온도를 150℃에서 진행하였다. feeder와 Twin Extruder 자체 rpm은 각각 5와 200으로 설정하였으며 펠렛 형태를 핫프레스에서 sheet형태로 MWCNT/PE 복합체를 제작하여 면저항을 측정하였다. 핫프레스 공정은 펠렛 100g을 계량하여 180℃ 온도로 약 2분간 가열하고 2분간 냉각모드를 진행하여 sheet를 만들었다. 이렇게 만들어진 sheet는 4-probe 면저항 측정장비로 9곳의 상중하부의 3곳씩 면저항값을 측정하여 전기전도성을 분석하였다. MWCNT/PE 복합체 내의 전기전도성을 알아보기 위하여 압출평가를 밀링 전과 밀링처리 시간별로 3,6 및 9시간으로 진행하였으며, 압출평가는 1pass와 2pass로 나누어 진행하였다.Polyethylene (PE) of LDPE5321 was added to 2 wt% of each of the multi-walled carbon nanotubes (MWCNT) prepared in Preparation Examples 1 and 2, respectively, in a twin extruder to produce pellets. It was carried out with the equipment of Twin Extruder, and the melting temperature was carried out at 150℃. The feeder and twin extruder's own rpm were set to 5 and 200, respectively, and the sheet resistance was measured by making the MWCNT/PE composite in the form of a sheet in a hot press as a pellet form. In the hot press process, 100g of pellets were weighed, heated at 180°C for about 2 minutes, and cooled for 2 minutes to make a sheet. The sheet made in this way was subjected to a 4-probe sheet resistance measuring device to measure the sheet resistance value at each of the upper, middle, and lower parts of 9 locations to analyze the electrical conductivity. In order to find out the electrical conductivity in the MWCNT/PE composite, extrusion evaluation was performed for 3, 6 and 9 hours before milling and for each milling treatment time, and the extrusion evaluation was divided into 1 pass and 2 pass.

면저항 측정결과 또한 도 7 및 도 8에 도시되어 있는데, 도 7에 보는 바와 같이 제조실시예 1에 의해 제조된 MWCNT/PE 복합체로 압출평가를 진행 시 1pass의 경우는 밀링처리 전 4.33Ω/㎡에서 밀링처리 3시간 후는 3.62Ω/㎡, 밀링처리 6시간 후 3.08Ω/㎡로 점차 감소하였으며, 9시간 밀링처리 후에는 3.48Ω/㎡로 다시 상승하는 결과를 보였다. 다만 2pass의 경우 밀링처리 전 2.84Ω/㎡에서 3시간 밀링처리 후 2.96Ω/㎡과 6시간 밀링처리 후 2.55Ω/㎡로 1pass의 면저항의 변화 폭보다 적음을 알 수 있었다. 밀링 시간에 따른 면저항 특성이 변화하는 현상은 밀링처리를 통한 MWCNT의 물리적 분쇄를 통하여 소재의 길이가 짧아지고 복합체 내의 네트워크를 형성하기 적절한 수준으로 존재하기 때문으로 판단되었다. 따라서 6시간의 밀링처리 후 다중벽 탄소나노튜브 분산액을 제조하게 되면 면저항이 작기 때문에 분산력이 우수한 분산액을 제조할 수 있다. The sheet resistance measurement results are also shown in FIGS. 7 and 8. As shown in FIG. 7, when the extrusion evaluation is performed with the MWCNT/PE composite prepared according to Preparation Example 1, in the case of 1 pass, at 4.33 Ω/m 2 before milling. After 3 hours of milling treatment, it gradually decreased to 3.62Ω/㎡, and after 6 hours of milling treatment, it gradually decreased to 3.08Ω/㎡, and after 9 hours of milling treatment, it increased to 3.48Ω/㎡ again. However, in the case of 2pass, it was found that the change in sheet resistance of 1pass was less than the change in sheet resistance of 1pass, from 2.84Ω/㎡ before milling to 2.96Ω/㎡ after 3 hours milling treatment and 2.55Ω/㎡ after 6 hours milling treatment. The change in the sheet resistance characteristics according to the milling time was determined because the length of the material was shortened through physical pulverization of the MWCNT through the milling treatment and existed at an appropriate level to form a network in the composite. Therefore, if a multi-walled carbon nanotube dispersion is prepared after 6 hours of milling, a dispersion having excellent dispersing power can be prepared because the sheet resistance is small.

도 8에서 보는 바와 같이 제조실시예 2에 의한 밀링처리 전후의 다중벽 탄소나노튜브를 이용하여 압출평가 진행 시, 압출평가 1pass의 경우 밀링처리 전 4.81Ω/㎡ 보다 밀링처리 3시간 공정에서 6.13Ω/㎡으로 면저항값이 높아짐을 보였다. 하지만 6시간의 밀링공정 이후에는 4.11Ω/㎡로 낮아지는 결과값을 확인할 수 있었으며, 9시간 밀링처리 후에는 다시 5.49Ω/㎡로 높아짐을 알 수 있었다. 압출평가 2pass의 경우도 1pass 와 유사한 결과값을 보이고 있으며, 밀링처리 전의 2.65Ω/㎡에서 3시간 밀링처리 후 3.29Ω/㎡ 면저항값이 높아졌으나 6시간 밀링처리시 2.37Ω/㎡로 밀링처리 전 MWCNT/PE 복합체의 포면저항값이 낮아지는 것을 확인할 수 있었다. 하지만 밀링처리 9시간 이후부터는 다시 면저항값이 2.87Ω/㎡로 증가함을 보였다. 압출평가를 통하여 밀링처리 후 6시간 공정에서 MWCNT/PE 복합체의 면저항값이 가장 우수하게 관찰되어 밀링처리가 6시간이 가장 적절한 공정조건임을 확인할 수 있었다.As shown in Fig. 8, when extrusion evaluation is performed using multi-walled carbon nanotubes before and after milling according to Preparation Example 2, in the case of extrusion evaluation 1 pass, 6.13 Ω in a 3 hour milling process than 4.81 Ω/㎡ before milling. It was shown that the sheet resistance value increased to /㎡. However, after 6 hours of milling process, the result value decreased to 4.11 Ω/㎡, and after 9 hours of milling treatment, it was found that it increased to 5.49 Ω/㎡ again. Extrusion evaluation 2pass shows similar results to 1pass. After milling for 3 hours at 2.65Ω/㎡ before milling, the sheet resistance value of 3.29Ω/㎡ increases, but when milling for 6 hours, it is 2.37Ω/㎡ before milling. It was confirmed that the foam resistance value of the MWCNT/PE composite was lowered. However, after 9 hours of milling treatment, the sheet resistance value again increased to 2.87Ω/㎡. Through the extrusion evaluation, the sheet resistance value of the MWCNT/PE composite was best observed in the 6-hour process after the milling process, and it was confirmed that the 6-hour milling process was the most appropriate process condition.

도 9에서부터 도 15까지는 DP법과 SD법으로 제조된 다중벽 탄소나노튜브를 밀링처리하여 각각의 특성별로 비교하여 그래프로 나타내었다. 분석한 항목들은 분산 등에 영향을 미치는 인자들로서도 9는 응집체직경, 도 10은 번들길이, 도 11은 번들직경, 도 12는 Bulk density, 도 13은 점도, 도 14는 압출평가 1pass, 도 15는 압출평가(2pass)에 대해서 다중벽 탄소나노튜브의 특성을 비교하였다. 9 to 15 are shown in graphs by comparing each characteristic by milling the multi-walled carbon nanotubes manufactured by the DP method and the SD method. The analyzed items are factors affecting dispersion, etc.FIG. 9 is an aggregate diameter, FIG. 10 is a bundle length, FIG. 11 is a bundle diameter, FIG. 12 is a bulk density, FIG. 13 is a viscosity, and FIG. 14 is an extrusion evaluation 1pass, and FIG. 15 is For the extrusion evaluation (2pass), the properties of the multi-walled carbon nanotubes were compared.

도 9에서는 응집체직경을 다중벽 탄소나노튜브의 종류에 따라 비교하여 나타내었다. 도 9에서도 보듯이 응집체직경의 크기 차이는 있으나 두 소재의 특성이 비슷한 경향성을 보이고 있음을 알 수 있다. 도 10에서는 밀링처리 시간이 증가함에 따라 Bulk density도 같이 증감함을 나타내고 있으며, 도 11와 도 12에서는 번들길이와 번들직경으로 두 가지 모두 밀링처리 시간이 6시간 공정일 때 가장 짧은 길이를 나타내고 있으며 9시간 이후에 다시 증감함을 보이고 있다. 도 13의 점도특성의 경우도 두 소재의 특성값이 밀링처리 후 3시간 공정은 점도가 오히려 상승하였으며 6시간과 9시간의 공정처리에서는 점도가 낮아지는 것을 확인할 수 있었다. 또한 도 14와 도 15에 도시된 압출평가 결과는 다중벽 탄소나노튜브 소재별과 1pass, 2pass에 대해서 각각 비교하였을 때, 6시간 밀링처리를 진행했던 다중벽 탄소나노튜브의 복합체가 면저항이 낮아 가장 우수한 결과값을 보여주고 있다. In FIG. 9, the aggregate diameter was compared and shown according to the type of multi-walled carbon nanotubes. As shown in FIG. 9, although there is a difference in the size of the aggregate diameter, it can be seen that the characteristics of the two materials show similar trends. In Fig. 10, the bulk density increases and decreases as the milling processing time increases, and in Figs. 11 and 12, both the bundle length and the bundle diameter show the shortest length when the milling processing time is a 6-hour process. It shows an increase or decrease again after 9 hours. In the case of the viscosity characteristics of FIG. 13, it was confirmed that the viscosity of the two materials increased during the 3 hour process after the milling treatment, and the viscosity decreased during the 6 hours and 9 hours process treatment. In addition, the extrusion evaluation results shown in FIGS. 14 and 15 show that the composite of the multi-walled carbon nanotubes, which was milled for 6 hours, has the lowest sheet resistance when compared for each material of the multi-walled carbon nanotubes and for 1 pass and 2 passes, respectively. It shows excellent results.

실험의 결과들을 토대로 다중벽 탄소나노튜브의 외형적인 특성으로는 응집체직경, 번들직경, 번들길이가 작아질수록 소재의 응용이 필요한 고분자 복합체 및 paste에서 분산성이 증가함을 알 수 있었으며, Bulk density의 증가로 다중벽 탄소나노튜브의 비산성 또한 증가하게 되어 사용상의 불편이 개선되는 결과를 얻을 수 있었다. 이렇게 다중벽 탄소나노튜브를 6시간의 밀링처리를 거치게 되면 밀링처리 전의 소재보다 분산성과 젖음성이 높아지며 사용상의 편의성이 훨씬 더 좋아지기 때문에 이러한 장점을 가진 다중벽 탄소나노튜브 전도성 분산액을 제조할 수 있을 것이다. Based on the results of the experiment, as the external characteristics of the multi-walled carbon nanotubes, it was found that as the aggregate diameter, bundle diameter, and bundle length decrease, the dispersibility increases in polymer composites and pastes that require application of the material. With the increase of, the scattering property of the multi-walled carbon nanotubes also increased, resulting in improved inconvenience in use. If the multi-walled carbon nanotubes are milled for 6 hours, dispersibility and wettability are higher than that of the material before the milling treatment, and the convenience of use is much better.Therefore, a multi-walled carbon nanotube conductive dispersion solution with these advantages can be prepared. will be.

상술한 여러 가지 예로 본 발명을 설명하였으나, 본 발명은 반드시 이러한 예들에 국한되는 것이 아니고, 본 발명의 기술사상을 벗어나지 않는 범위 내에서 다양하게 변형 실시될 수 있다. 따라서 본 발명에 개시된 예들은 본 발명의 기술 사상을 한정하기 위한 것이 아니라 설명하기 위한 것이고, 이러한 예들에 의하여 본 발명의 기술 사상의 범위가 한정되는 것은 아니다. 본 발명의 보호 범위는 아래의 청구범위에 의하여 해석되어야 하며, 그와 동등한 범위 내에 있는 모든 기술사상은 본 발명의 권리범위에 포함되는 것으로 해석되어야 한다. Although the present invention has been described with various examples described above, the present invention is not necessarily limited to these examples, and various modifications may be made without departing from the spirit of the present invention. Therefore, the examples disclosed in the present invention are not intended to limit the technical idea of the present invention, but to explain the technical idea, and the scope of the technical idea of the present invention is not limited by these examples. The scope of protection of the present invention should be interpreted by the claims below, and all technical ideas within the scope equivalent thereto should be construed as being included in the scope of the present invention.

Claims (5)

삭제delete 삭제delete Iron(Ⅲ) Nitrate Nonahydrate(Fe(NO₃)₃9H₂O)과 Cobalt(Ⅱ) Nitrate Hexahydrate(Co(NO₃)₂6H₂O)를 혼합하여 교반한 제1용액, Ammonium Carbonate((NH₄)₂CO₃)를 용해한 제2용액 및 Aluminum Hydroxide(Al(OH)₃)를 용해한 제3용액을 각각 제조한 후, 상기 제3용액에 상기 제1용액 및 상기 제2용액을 혼합하여 교반한 혼합용액을 만들고, 상기 혼합용액을 여과 및 건조하여 금속촉매를 만드는 금속촉매제조단계;
상기 금속촉매를 CVD 합성장치에 넣고 700~750℃의 온도로 탄소나노튜브를 합성하는 합성단계;
상기 탄소나노튜브를 밀링장치에 넣고 수계분산제, 소포제 및 용매를 첨가한 후 밀링처리하여 탄소나노튜브용액을 만드는 밀링단계; 및
상기 탄소나노튜브용액에 분산제, 바인더, 보조용매제, 습윤제 및 용매를 분산시켜 전도성 분산액을 만드는 분산단계; 를 포함하되,
상기 금속촉매제조단계는 Iron(Ⅲ) Nitrate Nonahydrate(Fe(NO₃)₃9H₂O), Cobalt(Ⅱ) Nitrate Hexahydrate(Co(NO₃)₂6H₂O) 및 Aluminium nitrate nonahydrate(Al(NO₃)₃)을 용매에 용해한 금속촉매전구체용액을 공기와 혼합시켜 이류체를 제조한 후, 상기 이류체를 반응로에 분사 및 건조하여 금속촉매를 만드는 것을 특징으로 하는 다중벽 탄소나노튜브 전도성 분산액의 제조 방법 Iron(III) Nitrate Nonahydrate(Fe(NO₃)₃9H₂O) and Cobalt(II) Nitrate Hexahydrate(Co(NO₃)₂6H₂O) were mixed and stirred, the first solution, Ammonium Carbonate ((NH₄)₂CO₃) dissolved in the second solution, and After each preparing a third solution in which Aluminum Hydroxide (Al(OH)₃) is dissolved, the first solution and the second solution are mixed with the third solution to make a stirred mixed solution, and the mixed solution is filtered and A metal catalyst manufacturing step of drying to form a metal catalyst;
A synthesis step of synthesizing carbon nanotubes at a temperature of 700 to 750°C by putting the metal catalyst in a CVD synthesizer;
A milling step of putting the carbon nanotubes in a milling device, adding an aqueous dispersant, an antifoaming agent, and a solvent, followed by milling to prepare a carbon nanotube solution; And
A dispersing step of dispersing a dispersant, a binder, a co-solvent, a wetting agent, and a solvent in the carbon nanotube solution to prepare a conductive dispersion; Including,
The metal catalyst manufacturing step is a metal catalyst obtained by dissolving Iron(III) Nitrate Nonahydrate (Fe(NO₃)₃9H₂O), Cobalt(II) Nitrate Hexahydrate (Co(NO₃)₂6H₂O) and aluminum nitrate nonahydrate (Al(NO₃)₃) in a solvent. A method for producing a conductive dispersion of multi-walled carbon nanotubes, characterized in that a precursor solution is mixed with air to prepare a two-fluid, and then the air-fluid is sprayed and dried in a reaction furnace to form a metal catalyst. 제3항에 있어서,
상기 금속촉매전구체용액는 용매, Iron(Ⅲ) Nitrate Nonahydrate(Fe(NO₃)₃9H₂O), Cobalt(Ⅱ) Nitrate Hexahydrate(Co(NO₃)₂6H₂O) 및 Aluminium nitrate nonahydrate(Al(NO₃)₃) 각각의 질량비가 10000: 1000: 250: 1200인 것을 특징으로 하는 다중벽 탄소나노튜브 전도성 분산액의 제조 방법The method of claim 3,
The metal catalyst precursor solution has a mass ratio of each of the solvent, Iron(III) Nitrate Nonahydrate(Fe(NO3)₃9H₂O), Cobalt(II) Nitrate Hexahydrate (Co(NO₃)₂6H₂O) and Aluminum nitrate nonahydrate (Al(NO₃)₃). : 1000: 250: 1200, characterized in that the method for producing a multi-walled carbon nanotube conductive dispersion 제3항에 있어서,
상기 반응로의 온도는 800℃이며 상기 이류체의 분사압력은 3.5kgf인 것을 특징으로 하는 다중벽 탄소나노튜브 전도성 분산액의 제조 방법 The method of claim 3,
The temperature of the reaction furnace is 800°C and the injection pressure of the airflow body is 3.5kgf.
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