KR20020082243A - Electromagnetic radiation shielding composition and preparing method thereof - Google Patents
Electromagnetic radiation shielding composition and preparing method thereof Download PDFInfo
- Publication number
- KR20020082243A KR20020082243A KR1020010021107A KR20010021107A KR20020082243A KR 20020082243 A KR20020082243 A KR 20020082243A KR 1020010021107 A KR1020010021107 A KR 1020010021107A KR 20010021107 A KR20010021107 A KR 20010021107A KR 20020082243 A KR20020082243 A KR 20020082243A
- Authority
- KR
- South Korea
- Prior art keywords
- solution
- dopant
- resin composition
- polyaniline
- solvent
- Prior art date
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/08—Metals
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K9/00—Screening of apparatus or components against electric or magnetic fields
- H05K9/0073—Shielding materials
- H05K9/0075—Magnetic shielding materials
Abstract
Description
본 발명은 전자기파 차폐 특성을 갖는 고분자성 수지 조성물 및 그 제조방법에 관한 것으로, 보다 자세하게는 전도성을 갖는 고분자물질을 사용하여 가벼움, 유연성, 가공용이성 및 내부식성등의 고분자물질의 특성을 그대로 가지면서도 전자기파 차폐효과가 뛰어난 조성물 및 그 제조방법에 관한 것이다The present invention relates to a polymeric resin composition having electromagnetic wave shielding properties and a method of manufacturing the same, and more particularly, using a polymeric material having conductivity, while maintaining the properties of the polymeric material such as lightness, flexibility, processability, and corrosion resistance. It relates to a composition having excellent electromagnetic shielding effect and a method of manufacturing the same.
전기, 전자 및 정보통신 관련기기의 발달이 우리 생활을 보다 편리하고 윤택하게 하지만 한편으로는 제4의 공해 또는 무형의 환경오염물질로 불리우는 전자기파를 발생시켜 인간에 해를 끼치고 있다. 이러한 전자기파는 각종 기계의 오작동 원인이 되어 산업재해를 일으키기도 하고 인체에 직·간접적으로 작용하여 심각한 영향을 주기도 하는데, 이러한 예로 자동차 고전압 발생장치 및 시동시 점화장치의 스파크(spark)로 인해 생기는 전파 노이즈에 의한 내부제어장치 및 전자제품의 효율 저하 및 수명단축, 전자장비들 사이의 상호교란, 인체의 마이크로파에 대한 장기노출의 경우 야기되는 녹내장, 각종 암 발생, 생식능력의 저하 등을 유발한다. 따라서 현재 전세계적으로 전자기파에 대한 규제가 강화되고 있을뿐 아니라 이러한 전자기파로부터 보호하기 위해 전자기파 장해에 대한 측정 및 연구가 필요하고, 이에 따라 측정설비 및 우수한 차폐재료의 개발이 절대적으로 요구되어 오고 있으며, 이에 부응한 종래 전자기파의 차폐재료로는 전기 전도도 와 유전상수가 높아서 전자기파의 반사나 흡수계수가 높은 구리, 철, 알루미늄, 아연, 주석, 베릴륨 등의 금속과 페라이트, 유전체 등의 세라믹물질이 주로 이용되어 왔다.The development of electrical, electronic and telecommunication related equipment makes our lives more convenient and profitable, but on the other hand, it causes harm to humans by generating electromagnetic waves called fourth pollution or intangible environmental pollutants. These electromagnetic waves may cause malfunctions of various machines and cause industrial accidents, and may also have serious effects by directly or indirectly affecting the human body. For example, radio waves generated by sparks of high voltage generators and ignition devices at start-up It reduces the efficiency and lifespan of internal control devices and electronic products due to noise, disturbs the interaction between electronic equipments, glaucoma caused by long-term exposure to microwaves, various cancers, and decreases fertility. Therefore, not only are the regulations on electromagnetic waves strengthening around the world, but also measurement and research on electromagnetic interference are required to protect against such electromagnetic waves. Accordingly, the development of measuring equipment and excellent shielding materials is absolutely required. As a shielding material of the conventional electromagnetic wave, the electrical conductivity and the dielectric constant are high, and the metals such as copper, iron, aluminum, zinc, tin, and beryllium, which have high electrical conductivity and dielectric constant, and ceramic materials such as ferrite and dielectric are mainly used. Has been.
그러나 종래 금속이 경우 무겁고, 공기중에서 산화되며, 실제적인 형태로 가공하기가 용이하지 않고 값비싼 단점이 있으며, 세라믹의 경우도 고온에서 열처리해야 하고, 여러가지 형태로의 가공이 쉽지 않으며 깨지기 쉬운 단점이 있다.However, the conventional metal is heavy, oxidized in the air, not easy to be processed into a practical form and expensive disadvantages, ceramics also need to be heat treated at a high temperature, and processing in various forms is not easy and fragile have.
이러한 단점을 보완하기 위해 섬유강화 복합재료, 플라스틱 복합재료 등 전도성복합체의 사용이 개발되고 있는데, 예를 들어 대한민국 특허출원 제1991-25644호의 「전자파 차폐용 열경화성 수지조성물」, 대한민국특허출원 제1999-20817호의 「전자기파를 차폐하는 합성수지 제품의 제조방법」 및 대한민국 특허출원 제 1997-24215호의 「전자기파 흡수용 도포조성물, 이의 제조방법 및 이의 도포 방법」이 개시되어 있으나 이들은 단순히 금속과 수지를 기계적으로 층별로 도포하거나 물리적으로 블렌딩한 것에 지나지 않으며 비록 이들 재료들이 종래 금속재료에 비해 가벼우며, 가공용이성 및 내부식성 개선된 장점은 있으나 전자기파 차폐효과가 미약하다는 단점이 있어 실용화에는 문제점이 있다.In order to make up for these drawbacks, the use of conductive composites such as fiber-reinforced composites and plastic composites is being developed. For example, Korean Patent Application No. 1991-25644, "Thermosetting Thermosetting Resin Composition," Korean Patent Application No. 1999- 20817, "Method of Manufacturing Synthetic Resin Products for Shielding Electromagnetic Waves," and Korean Patent Application No. 1997-24215, "Compositions for Absorption of Electromagnetic Waves, Methods for Manufacturing the Same, and Methods for Applying Them." Although it is only applied or physically blended with these materials, although these materials are lighter than the conventional metal materials, and have the advantages of ease of processing and corrosion resistance, they are disadvantageous in that they have a weak electromagnetic shielding effect.
본 발명자등은 상술한 문제점을 해결하며, 우수한 전자기파 차폐 특성을 갖을뿐아니라 유연성, 가공용이성 및 내부식성등을 갖는 조성물에 대해 면밀히 검토한 결과, 종래의 전자기파 차폐용 물질과는 전혀 다른 새로운 물질인 전도성 고분자물질을 사용하여 합성조건 및 가공방법을 변화시킴으로써 이러한 과제를 해결할 수 있는 방법을 알아내었으며, 이를 필름으로 제조하여 시험한 결과 전자제품등에서 발생하는 유해 전자기파를 효과적으로 차폐시킴을 발견하여 본 발명을 완성하였다.The present inventors have solved the above-described problems, and as a result of closely examining compositions having not only excellent electromagnetic wave shielding properties but also flexibility, processability, and corrosion resistance, the present inventors have described a novel material that is completely different from the conventional electromagnetic wave shielding material. We found a way to solve this problem by changing the synthesis conditions and processing method using a conductive polymer material, and found that it effectively shields harmful electromagnetic waves generated in electronic products, etc. as a result of manufacturing the film and tested it Was completed.
이와같이 본 발명의 목적은 기존의 전자기파 차폐물질과 달리 전자기파 차폐특성이 우수할뿐만 아니라 유연성, 가공용이성 및 내부식성등이 뛰어난 새로운 형태의 수지 조성물을 제공하는데 있다.As described above, an object of the present invention is to provide a new type of resin composition having excellent electromagnetic wave shielding properties as well as excellent flexibility, processability, and corrosion resistance, unlike conventional electromagnetic wave shielding materials.
본 발명의 다른 목적은 전자기파를 효율적으로 차폐할 수 있는 상기 수지 조성물의 제조방법을 제공하는데 있다.Another object of the present invention is to provide a method for producing the resin composition that can effectively shield electromagnetic waves.
상기 목적을 달성하기 위한 본 발명의 전자기파 차폐 특성을 갖는 고분자 수지 조성물은 전도성 고분자물질 100중량부를 용매 50내지150 중량부에 용해한 후 금속성 첨가물을50 내지100중량부를 부가하거나 또는 도판트로 도핑하여 조성됨을 특징으로한다.The polymer resin composition having electromagnetic wave shielding properties of the present invention for achieving the above object is formed by dissolving 100 parts by weight of a conductive polymer material in 50 to 150 parts by weight of a solvent, and then adding 50 to 100 parts by weight of a metallic additive or doping with a dopant. To be characterized.
상기 전도성 고분자물질은 특히 폴리아닐린 또는 폴리피롤임을 특징으로 한다. 상기 용매로는 특히 DMSO, NMP, 크레솔, 클로로포름이 바람직하다. 또한 상기 금속성 첨가물질로는 페라이트(ferrite), 흑연(graphite), 은(Ag)이 바람직하며 도판트로는 HDBSA, NSA, HCSA등이 바람직하며, 특히 이들중 은 또는 HDBSA이 특히 바람직하다. 더욱이 본 발명은 상기 조성물의 제조방법과 이렇게 제조된 조성물로부터 각종 전자기파 차폐성 필름을 제조함을 특징으로한다.The conductive polymer is particularly characterized by being polyaniline or polypyrrole. Especially as said solvent, DMSO, NMP, cresol, and chloroform are preferable. In addition, as the metallic additive, ferrite, graphite, silver (Ag) are preferable, and as the dopant, HDBSA, NSA, HCSA, etc. are preferable, and among these, silver or HDBSA is particularly preferable. Furthermore, the present invention is characterized by producing a variety of electromagnetic shielding film from the method for producing the composition and the composition thus prepared.
상기와 같이 구성된 본 발명은 고분자성 수지를 주성분으로 하기 때문에 종래 금속 차폐재료에 비해 가벼울 뿐 아니라 유연성 및 가공용이성을 그대로 가지므로 여러 가지의 형태로 제조가 용이하며 차폐효율조절이 화학적 처리에 의해 가능하다.The present invention configured as described above is lighter than the conventional metal shielding material because it has a polymeric resin as a main component, and thus has flexibility and processing ease as it is, making it easy to manufacture in various forms and controlling the shielding efficiency by chemical treatment. Do.
이하, 본 발명을 실시예 및 비교예를 통하여 보다 자세하게 설명하지만 본 발명의 범위가 여기에 한정되지 않음은 명백하다.Hereinafter, although an Example and a comparative example demonstrate this invention in detail, it is clear that the scope of the present invention is not limited to this.
실시예 1Example 1
폴리아닐린(emeraldine base;이하 EB라 한다.)의 제조.Preparation of polyaniline (emeraldine base; hereinafter referred to as EB).
아닐린은 진공증류(vacuum distillation)하여 사용하였고, 산화제인 암모니움 퍼설페이트[(NH4)2S2O8: Aldrich사 제품]와 도판트(dopant)인 HCl은 구입하여 그대로 사용하였다.Aniline was used by vacuum distillation, and the ammonium persulfate ((NH 4 ) 2 S 2 O 8 : product of Aldrich) and the dopant HCl were used as they were.
먼저 20mL(0.22 mol)의 아닐린을 1 M HCl 300mL에 녹여 0℃로 냉각시켰다.별도로 11.5g(0.05mol)의 암모니움 퍼설페이트를 1 M HCl 200mL에 녹여 0℃로 냉각시켰다. 0℃가 된 후 산화제가 포함된 용액을 아닐린이 포함된 용액에 자석젓개로 저어주며 2분에 걸쳐 첨가하였다.First 20 mL (0.22 mol) of aniline was dissolved in 300 mL of 1 M HCl and cooled to 0 ° C. Separately 11.5 g (0.05 mol) of ammonium persulfate was dissolved in 200 mL of 1 M HCl and cooled to 0 ° C. After reaching 0 ° C., the solution containing the oxidant was added to the solution containing aniline over a 2 min.
5분 정도 지난 후 용액은 반응하여 짙은 녹색을 띄기 시작하였고 시간이 지남에 따라 구리 빛 광택을 용액 표면에 나타내었다. 반응물을 계속 자석젓개로 저어주며 온도를 0℃로 유지시키고 90분 동안 방치하였다.After about 5 minutes the solution reacted and began to develop a dark green color and over time the copper luster appeared on the surface of the solution. The reaction was stirred with a magnetic stir to maintain the temperature at 0 ° C. and left for 90 minutes.
90분이 지난 후 #1 핫만(Whatman)거름종이를 사용하여 뷔흐너 깔때기(Buchner funnel)내에서 여과하고 침전물은 1M HCl로 무색이 될 때까지 씻어준 후 10분 정도 흡인을 통하여 수분을 제거하였다.After 90 minutes, the filter was filtered in a Buchner funnel using # 1 Whatman filter paper, and the precipitate was washed until it was colorless with 1M HCl, and then water was removed by suction for about 10 minutes.
걸러진 조각(filter cake)을 다시 1 M HCl 10mL 속에서 혼탁액을 만든 후 500mL, 1M HCl 용액에 넣어 밀봉시키고 자석젓개로 저어주며 15시간 방치후 뷔흐너 깔때기로 여과하였다.The filtered cake (filter cake) was made again in 10 mL of 1 M HCl, the solution was put into 500 mL, 1 M HCl solution, sealed and stirred with a magnetic spoon, and filtered for 15 hours and then filtered using a Buchner funnel.
이때 1 M HCl 2L를 사용하여 여과액이 무색이 될 때까지 씻어주고 10분 정도 흡인을 통하여 탈수시켜 50% 양성자화된 폴리아닐린을 얻었다. 50% 양성자화된 조각을 다시 0.1 N NH4OH 500mL 용액내에서 15시간 동안 자석젓개로 저어주며 반응시켰다. 이때 1 N NH4OH 용액을 가하여 용액의 pH를 9로 유지하였다.At this time, the filtrate was washed with 1 M HCl 2L until it was colorless and dehydrated by suction for 10 minutes to obtain 50% protonated polyaniline. The 50% protonated flakes were reacted again with a magnetic paddle for 15 hours in 500 mL of 0.1 N NH 4 OH solution. At this time, 1 N NH 4 OH solution was added to maintain the pH of the solution at 9.
15시간이 지난 후 반응용액을 여과하고 0.1 N NH4OH로 씻어주었다. 걸러진 조각은 10-3torr의 진공 라인과 연결된 건조 튜브 내에서 48시간 동안 진공하에 건조하여 EB를 수득했다. 건조된 분말은 막자사발로 균일하게 갈은 후 실험에 사용하였다.After 15 hours, the reaction solution was filtered and washed with 0.1 N NH 4 OH. The filtered pieces were dried under vacuum for 48 hours in a drying tube connected with a vacuum line of 10 −3 torr to obtain EB. The dried powder was uniformly ground with a mortar and then used for the experiment.
실시예 2Example 2
폴리아닐린 프리 스탠딩 필름(free standing film)의 제조.Preparation of Polyaniline Free Standing Film.
실시예 1에서 수득한 폴리아닐린 분말을 시약스푼으로 서서히 30mL의 NMP 용액에 자석젓개로 저어주며 첨가하였다. 첨가후 약 10분간 자석젓개로 더 저어준 후 얻어진 용액을 유리솜이 채워진 주사기내에 넣고 압력을 가해 녹지 않은 부분을 제거하여 균일한 용액을 제조하였다.The polyaniline powder obtained in Example 1 was added to the 30 mL NMP solution by stirring with a magnetic spoon slowly with a reagent spoon. After the addition, the resultant was further stirred with a magnetic spoon for about 10 minutes, and the resulting solution was placed in a syringe filled with glass wool to apply a pressure to remove the undissolved portion, thereby preparing a uniform solution.
깨끗하게 닦고 건조시킨 수평이 조절된 유리기판위에 용액을 부은 후 60℃로 조절된 대류 오븐(convection oven)내에서 15시간 정도 건조시켜 폴리아닐린 프리 스탠딩 필름을 제조하였다.The solution was poured onto a glass substrate which had been cleaned and dried horizontally, and then dried in a convection oven controlled at 60 ° C. for about 15 hours to prepare a polyaniline free standing film.
실시예 3-5Example 3-5
캠포설폰 산(Camphorsulfonic acid;CSA)이 도핑된 폴리아닐린 프리 스탠딩 필름의 제조.Preparation of Polyaniline Free Standing Film Doped with Camphorsulfonic Acid (CSA).
폴리아닐린 분말 0.724g 과 CSA 0.927g을 막자사발내에서 10분 정도 고르게 교반하였다. 분말을 각 용매 즉,m-크레솔;실시예3, 포름산;실시예4, 크로로포름;실시예5로 서서히 첨가하여 녹인다.0.724 g of polyaniline powder and 0.927 g of CSA were stirred evenly in the mortar for about 10 minutes. The powder is gradually dissolved in each solvent, namely m -cresol; Example 3, formic acid; Example 4, chloroform; Example 5.
약 10여분간 자석젓개로 더 저어준 후 얻어진 용액을 유리솜이 채워진 주사기내에 넣고 압축시켜 녹지 않은 부분을 제거하여 균일한 용액을 제조하였다.After stirring for about 10 minutes with a magnetic stirrer, the resulting solution was placed in a syringe filled with glass wool and compressed to remove the undissolved portion to prepare a uniform solution.
깨끗하게 닦고 건조시킨 수평이 조절된 유리기판위에 이 용액을 부은 후 60℃로 조절된 오븐내에서 15시간 정도 건조시켜을 프리 스탠딩 필름을 제조하였다.The solution was poured onto a glass substrate having a clean, dried, horizontally controlled glass substrate, and then dried in an oven controlled at 60 ° C. for about 15 hours to prepare a free standing film.
실시예 6-8Example 6-8
도데실 벤젠술폰산(Dodecylbenzensulfonic acid;dBSA)이 도핑된 폴리아닐린 프리 스탠딩 필름의 제조.Preparation of polyaniline free standing film doped with dodecylbenzensulfonic acid (dBSA).
여러 가지 용매 즉,m-크레솔;실시예6, 포름산;실시예7, 크로로포름;실시예8내에 DBSA 0.980g을 녹인 용액에 폴리아닐린 분말 0.543g을 무게비율로 3wt.%가 되게 녹인후 약 10여분간 자석젓개로 더 저어주었다.0.543 g of polyaniline powder was dissolved in a solution of 0.980 g of DBSA in various solvents, namely m -cresol; Example 6, formic acid; Example 7, Chroform; Stir for about 10 minutes with a magnetic spoon.
얻어진 용액을 필터로 유리솜이 채워진 주시기내에 넣고 압축시켜 녹지 않는 부분을 제거하여 균일한 용액을 제조하였다. 깨끗하게 닦고 건조시킨 수평이 조절된 유리기판 위에 이 용액을 부은 후 60℃로 조절된 오븐에서 15시간 정도 건조시켜 프리 스탠딩 필름을 제조하였다.The obtained solution was placed in a glass filled with glass wool with a filter and compressed to remove the insoluble portion to prepare a uniform solution. The solution was poured onto a glass substrate, which was cleaned and dried horizontally, and then dried for 15 hours in an oven controlled at 60 ° C. to prepare a free standing film.
실시예 9-16Example 9-16
폴리피롤 프리 스탠딩 필름의 제조.Preparation of Polypyrrole Free Standing Film.
전도성 고분자물질로 폴리아닐린 대신 폴리피롤을 사용한 것과 도판트 및 용매를 다음과 같이 사용한 것 외에는 상기 각 실시예에 준해서 폴리피롤 프리 스탠딩 필름을 제조하였다.A polypyrrole free standing film was prepared according to each of the above examples except that polypyrrole was used instead of polyaniline as a conductive polymer material and a dopant and a solvent were used as follows.
실시예 9; 도판트:HDBSA 용매:m-크레솔Example 9; Dopant: HDBSA Solvent: m-cresol
실시예 10; 도판트:HDBSA 용매:크로로포름Example 10; Dopant: HDBSA solvent: Chloroform
실시예 11; 도판트:HDBSA 용매:DMSOExample 11; Dopant: HDBSA Solvent: DMSO
실시예 12; 도판트:HDBSA 용매:NMPExample 12; Dopant: HDBSA Solvent: NMP
실시예 13; 도판트:NSA 용매:m-크레솔Example 13; Dopant: NSA Solvent: m-cresol
실시예 14; 도판트:NSA 용매:크로로포름Example 14; Dopant: NSA solvent: chloroform
실시예 15; 도판트:NSA 용매:DMSOExample 15; Dopant: NSA Solvent: DMSO
실시예 16; 도판트:NSA 용매:NMPExample 16; Dopant: NSA Solvent: NMP
실시예 17Example 17
가공조건을 달리한 폴리아닐린 프리 스탠딩 필름의 제조.Preparation of polyaniline free standing film with different processing conditions.
0.22mol의 아닐린을 1 M HCl 300mL에 녹여 상온에 보관하였다. 별도로 0.11mol의 암모니움 퍼옥시디설페이트(ammonium peroxydisulfate)를 1 M HCl 200mL에 녹여 상온에 보관하였다.0.22 mol of aniline was dissolved in 300 mL of 1 M HCl and stored at room temperature. Separately, 0.11 mol of ammonium peroxydisulfate was dissolved in 200 mL of 1 M HCl and stored at room temperature.
상온에서 산화제가 포함된 용액을 아닐린이 포함된 용액에 자석젓개로 저어주며 2분에 걸쳐 서서히 첨가하였고, 반응물을 계속 자석젓개로 저어주면서 상온에서 90분 동안 방치하였다.At room temperature, the solution containing the oxidant was slowly added to the aniline-containing solution with a magnetic paddle over 2 minutes, and the reaction was left at room temperature for 90 minutes while stirring with a magnetic paddle.
90분이 지난 후 반응용액을 #1 핫만 거름종이를 사용하여 뷔흐너 깔때기내에서 여과하였으며 침전물은 1 M HCI로 무색이 될 때까지 씻어주었고 10분 정도 흡인상태에서 방치하였다.After 90 minutes, the reaction solution was filtered in a Buchner funnel using # 1 Hotman filter paper, and the precipitate was washed until it was colorless with 1 M HCI, and left for about 10 minutes with suction.
이 걸러진 조각을 다시 1M HCl 10mL속에서 혼탁액을 만들고 1M HCl 500mL용액에 넣어 밀봉시켜 자석젓개로 저어주면서 15시간 방치 후 뷔흐너 깔때기로 여과하였다. 이때 1M HCl 2L를 사용하여 여과액이 무색이 될 때까지 씻어주고 10분 정도 흡인하여 수분을 제거하여 50% 양성자화된 폴리아닐린을 얻었다.The filtered piece was again made into a turbid solution in 10 mL of 1 M HCl, sealed in a 500 mL solution of 1 M HCl, stirred for 15 hours while stirring with a magnetic spoon and filtered with a Buchner funnel. At this time, 1M HCl 2L was washed until the filtrate was colorless and aspirated for 10 minutes to remove the water to obtain a 50% protonated polyaniline.
이 50% 양성자화된 조각을 다시 500mL, 0.1 N NH4OH 용액내에서 15시간 자석젓개로 저어주었으며 이때 0.1 N NH4OH 용액을 가하여 반응용액을 pH 9로 유지하였다. 15시간이 지난 후 반응용액을 여과하였고 0.1 N NH4OH 씻어주었다.The 50% protonated fragment was again stirred with a magnetic paddle in 500 mL, 0.1 N NH 4 OH solution for 15 hours, and 0.1 N NH 4 OH solution was added to maintain the reaction solution at pH 9. After 15 hours, the reaction solution was filtered and washed with 0.1 N NH 4 OH.
걸러진 조각은 10-3torr의 진공라인과 연결된 건조 튜브내에서 48시간 동안 진공하에 건조하였다. 건조된 분말을 막자사발로 균일하게 갈은후 30mL의 NMP용액을 자석젓개로 저어주며 서서히 첨가하였다.The filtered pieces were dried under vacuum for 48 hours in a drying tube connected to a vacuum line of 10 −3 torr. The dried powder was uniformly ground with a mortar and pestle, and 30 mL of NMP solution was added slowly with a magnetic stir.
첨가후 약 10여분간 자석젓개로 더 저어준 후 얻어진 용액을 필터로 유리솜이 채워진 주사기내에 넣고 압축시켜 녹지 않은 부분을 제거함으로써 균일한 용액을 제조하였다. 깨끗하게 닦고 건조시킨 수평이 조절된 유리기판 위에 용액을 부은 후 100℃로 유지된 오븐에서 8시간 정도 건조시켜 프리 스탠딩 필름을 제조하고 1 M HCl로 24시간 도핑하여 전도성 폴리아닐린 프리 스탠딩 필름을 제조하였다.After stirring for about 10 minutes after the addition of a magnetic paddle, the resulting solution was put into a syringe filled with glass wool with a filter and compressed to remove undissolved parts to prepare a uniform solution. The solution was poured onto a glass substrate that had been cleaned and dried horizontally, and then dried for 8 hours in an oven maintained at 100 ° C. to prepare a free standing film, and then doped with 1 M HCl for 24 hours to prepare a conductive polyaniline free standing film.
실시예 18Example 18
유전체, 자성체가 첨가된 폴리아닐린의 프리 스탠딩 필름 제조.Preparation of free standing film of polyaniline with added dielectric and magnetic material.
실시예 1에서 수득한 폴리아닐린분말 2g을 NMP 용액에 자석젓개로 저어주며 시약스푼으로 서서히 첨가한 다음 자성체인 페라이트(Ni,Zn-Fe2O3)분말 1.5g을 첨가하여 잘 교반하였다. 깨끗하게 닦고 건조시킨 수평이 조절된 유리기판위에 이 용액을 부은 후 60℃로 조절된 오븐내에서 15시간 건조시켜 프리 스탠딩 필름을 제조하였다.2 g of the polyaniline powder obtained in Example 1 was stirred in a NMP solution with a magnetic spoon and slowly added with a reagent spoon. Then, 1.5 g of magnetic ferrite (Ni, Zn-Fe 2 O 3 ) powder was added thereto and stirred well. The solution was poured onto a glass substrate which had been cleaned and dried horizontally, and then dried in an oven controlled at 60 ° C. for 15 hours to prepare a free standing film.
실시예 19-23Example 19-23
무기물, 금속이 첨가된 폴리아닐린의 프리 스탠딩 필름 제조.Preparation of free standing film of polyaniline with addition of inorganic material and metal.
실시예 1에서 수득한 폴리아닐린분말을 2g씩 NMP 용액에 자석젓개로 저어주며 시약 스푼으로 서서히 첨가한 다음, 이들 용해액 각각에 카본블랙1g, 흑연(graphite)1g, 1.5g, 2g , 은(Ag)분말 1g을 각각 첨가하여 잘 교반한다.2 g of the polyaniline powder obtained in Example 1 was added to the NMP solution with a magnetic paddle and slowly added with a reagent spoon. Then, 1 g of carbon black, 1 g of graphite, 1.5 g, 2 g, and silver (Ag) were added to each of these solutions. ) Add 1 g of powder and stir well.
깨끗하게 닦고 건조시킨 수평이 조절된 유리기판위에 이 용액을 부은 후 60℃로 조절된 오븐내에서 15시간 정도 건조시켜 프리 스탠딩 필름을 제조하였다.The solution was poured onto a glass substrate with a clean, dried, horizontally controlled glass substrate, and then dried in an oven controlled at 60 ° C. for about 15 hours to prepare a free standing film.
시험예Test Example
전자기파 차폐효율 측정.Measurement of electromagnetic shielding efficiency.
본 발명의 실시예에 따라 제조된 각 필름의 전기 전도도와 전자기파의 차폐효율을 측정하였으며, 전자기파 차폐효율 측정은 미 국립 표준기술연구원 (NIST)에서 개발된 원역장 차폐효과 측정셀 (ASTM: D 4935-89 규격)로 플랜지형 동축전송선The electrical conductivity and shielding efficiency of electromagnetic waves of each film prepared according to the embodiment of the present invention were measured, and the electromagnetic shielding efficiency was measured by a far field shielding effect measuring cell (ASTM: D 4935) developed by the National Institute of Standards and Technology (NIST). Flange type coaxial transmission line
(flanged circular coaxial transmission-line)을 사용하였다. 사용된 필름의 모양은 디스크형이고, 10MHz~1GHz의 주파수 영역에서 차폐효율을 측정하였다.(flanged circular coaxial transmission-line) was used. The shape of the film used was disk-shaped, shielding efficiency was measured in the frequency range of 10MHz ~ 1GHz.
다음 표 1 및 2에 그 결과를 나타냈다 .The results are shown in Tables 1 and 2 below.
표 1Table 1
표 2TABLE 2
상기 구성에 따른 본 발명의 전자기파 차폐 특성을 갖는 고분자 수지 조성물은 주요 구성성분인 고분자의 유연성이 거의 그대로 유지됨으로 전자파가 누출되는 부분에의 박막 코팅(thin film coating), 섬유, 엘라스토머(elastomer), 접착제, 도료등의 형태로 가공하여 실제구조물에 적용시 임의적으로 가공이 용이하며, 부식이 되지 않으며, 가공조건의 조절에 따라 차폐효율의 조절이 가능한 유용한 발명이다.The polymer resin composition having the electromagnetic wave shielding property of the present invention according to the above configuration is a thin film coating (fiber, elastomer) on the part where the electromagnetic wave is leaked because the flexibility of the polymer which is a main component is almost maintained as it is It is a useful invention that can be easily processed when applied to the actual structure by processing in the form of adhesive, paint, etc., does not corrode, and can control the shielding efficiency according to the control of the processing conditions.
Claims (4)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020010021107A KR20020082243A (en) | 2001-04-19 | 2001-04-19 | Electromagnetic radiation shielding composition and preparing method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020010021107A KR20020082243A (en) | 2001-04-19 | 2001-04-19 | Electromagnetic radiation shielding composition and preparing method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| KR20020082243A true KR20020082243A (en) | 2002-10-31 |
Family
ID=27701764
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| KR1020010021107A KR20020082243A (en) | 2001-04-19 | 2001-04-19 | Electromagnetic radiation shielding composition and preparing method thereof |
Country Status (1)
| Country | Link |
|---|---|
| KR (1) | KR20020082243A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2006135182A1 (en) * | 2005-06-15 | 2006-12-21 | Chang Sung Corporation | Thin multi-layered electro-magnetic absorption film by controlling surface resistance |
| CN101280106B (en) * | 2008-05-30 | 2010-06-02 | 昆明理工大学 | Preparation of magnetic conductive polyaniline nanometer composite material |
| CN108251053A (en) * | 2018-03-09 | 2018-07-06 | 钢铁研究总院 | Graphene ferrite polymer ternary nano composite wave-suction material and preparation method thereof |
| CN108752905A (en) * | 2018-05-04 | 2018-11-06 | 南京恒新新材料有限公司 | A kind of composite wave-suction material and preparation method thereof based on silver-colored@polypyrroles core-shell nano fiber |
| CN112709012A (en) * | 2020-12-17 | 2021-04-27 | 安徽工程大学 | Preparation method of electromagnetic shielding composite fiber membrane |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR970051464A (en) * | 1995-12-20 | 1997-07-29 | 정몽원 | Electromagnetic shielding material |
| KR970058474A (en) * | 1995-12-20 | 1997-07-31 | 정몽원 | Electromagnetic shielding case |
| KR19980046471A (en) * | 1996-12-12 | 1998-09-15 | 오상수 | Electromagnetic shielding clothing |
| KR19980046470A (en) * | 1996-12-12 | 1998-09-15 | 오상수 | Electromagnetic shielding clothing |
| KR100193184B1 (en) * | 1996-12-12 | 1999-06-15 | 오상수 | Navigation system monitor case with electromagnetic shielding |
-
2001
- 2001-04-19 KR KR1020010021107A patent/KR20020082243A/en not_active Application Discontinuation
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR970051464A (en) * | 1995-12-20 | 1997-07-29 | 정몽원 | Electromagnetic shielding material |
| KR970058474A (en) * | 1995-12-20 | 1997-07-31 | 정몽원 | Electromagnetic shielding case |
| KR19980046471A (en) * | 1996-12-12 | 1998-09-15 | 오상수 | Electromagnetic shielding clothing |
| KR19980046470A (en) * | 1996-12-12 | 1998-09-15 | 오상수 | Electromagnetic shielding clothing |
| KR100193184B1 (en) * | 1996-12-12 | 1999-06-15 | 오상수 | Navigation system monitor case with electromagnetic shielding |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2006135182A1 (en) * | 2005-06-15 | 2006-12-21 | Chang Sung Corporation | Thin multi-layered electro-magnetic absorption film by controlling surface resistance |
| CN101280106B (en) * | 2008-05-30 | 2010-06-02 | 昆明理工大学 | Preparation of magnetic conductive polyaniline nanometer composite material |
| CN108251053A (en) * | 2018-03-09 | 2018-07-06 | 钢铁研究总院 | Graphene ferrite polymer ternary nano composite wave-suction material and preparation method thereof |
| CN108251053B (en) * | 2018-03-09 | 2021-03-30 | 钢铁研究总院 | Graphene ferrite polymer ternary nano composite wave-absorbing material and preparation method thereof |
| CN108752905A (en) * | 2018-05-04 | 2018-11-06 | 南京恒新新材料有限公司 | A kind of composite wave-suction material and preparation method thereof based on silver-colored@polypyrroles core-shell nano fiber |
| CN108752905B (en) * | 2018-05-04 | 2021-04-27 | 南京恒新新材料有限公司 | Preparation method of composite wave-absorbing material based on silver @ polypyrrole core-shell nanofibers |
| CN112709012A (en) * | 2020-12-17 | 2021-04-27 | 安徽工程大学 | Preparation method of electromagnetic shielding composite fiber membrane |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Yuping et al. | Investigation of electrical conductivity and electromagnetic shielding effectiveness of polyaniline composite | |
| Saini et al. | Electrostatic charge dissipation and electromagnetic interference shielding response of polyaniline based conducting fabrics | |
| Kumar et al. | Freestanding conducting polyaniline film for the control of electromagnetic radiations | |
| Akşit et al. | Electromagnetic and electrical properties of coated cotton fabric with barium ferrite doped polyaniline film | |
| US6380346B1 (en) | Heterogeneous reaction method for preparing functionalized polyanilines | |
| EP0921147B1 (en) | Transparent conducting polymers | |
| KR20020082243A (en) | Electromagnetic radiation shielding composition and preparing method thereof | |
| EP0673042A1 (en) | Soluble and processable doped electrically conductive polymer and polymer blend thereof | |
| US7273918B2 (en) | Thermally stable self-doped functionalized polyanilines | |
| Mohan et al. | Effective electromagnetic shield using conductive polyaniline films | |
| KR20050053040A (en) | Emi/emc shielding sheet and the method for making it | |
| JPH09183945A (en) | Conductive polyaniline doped with camphorsulfonic acid | |
| Ogura et al. | Thermal properties of poly (anthranilic acid)(PANA) and humidity‐sensitive composites derived from heat‐treated PANA and poly (vinyl alcohol) | |
| KR20010109813A (en) | Method of making absorbent material for electromagnetic waves using a soluble polyaniline salt | |
| KR200237938Y1 (en) | Electromagnetic wave absorbing cloth | |
| KR100374719B1 (en) | Method for Preparation of the Soluble Poly(3,4-ethylenedioxythiophene) Powder | |
| KR200237936Y1 (en) | Electromagnetic wave absorbing cloth | |
| KR100490882B1 (en) | Synthetic Method of Polyaniline and application for electroststic discharge and EMI Shielding | |
| KR100498577B1 (en) | EMI paint and the method for making it | |
| KR100548045B1 (en) | Conductive polymer film and method for preparing the same | |
| CN110218409B (en) | Preparation method of polyacrylonitrile electromagnetic shielding film | |
| KR100549992B1 (en) | Thiophen monomer, method for preparing the same, polythiophen derivative and copolymer using the thiophen monomer | |
| CN110219166B (en) | Preparation method of acrylic fiber blended electromagnetic shielding fabric | |
| KR100503893B1 (en) | An electroconductive polymer having a polyhedraloligomericsilsesquinoxane substituent and preparation method thereof | |
| Aizamddin et al. | Electrical conductivity and thermal stability of conductive polyaniline fabric-based polyacrylonitrile blends |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A201 | Request for examination | ||
| E902 | Notification of reason for refusal | ||
| E902 | Notification of reason for refusal | ||
| N231 | Notification of change of applicant | ||
| E601 | Decision to refuse application |