KR100854319B1 - Polymer solution, manufacturing method thereof and manufacturing method of transfarent conducting polymer film - Google Patents
Polymer solution, manufacturing method thereof and manufacturing method of transfarent conducting polymer film Download PDFInfo
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Abstract
Description
본 발명은 폴리머 용액과 그 제조방법 및 투명 전도성 폴리머 필름의 제조방법에 관한 것으로, 더욱 상세하게는 빛의 투과성이 우수하고 전도성이 우수한 투명 전도성 폴리머 필름을 형성할 수 있는 폴리머 용액과 그 제조방법 및 이를 이용한 투명 전도성 폴리머 필름을 제조하는 방법에 관한 것이다. The present invention relates to a polymer solution, a method for manufacturing the same, and a method for producing a transparent conductive polymer film, and more particularly, a polymer solution capable of forming a transparent conductive polymer film having excellent light transmittance and excellent conductivity, and a method for manufacturing the same; It relates to a method of manufacturing a transparent conductive polymer film using the same.
일반 도전성 폴리머 용액은 금속류, 탄소 파우더 및 옥사이드(oxide)를 사용하여 제조하며, 이와 같은 원료는 전기 전도도와 투과율에 영향을 주어 여러 가지 노력에도 불구하고 높은 전기 전도도와 투과율을 실현하는 것이 어려운 문제점이 있다. General conductive polymer solutions are prepared using metals, carbon powders and oxides, and these raw materials affect the electrical conductivity and transmittance, which makes it difficult to achieve high electrical conductivity and transmittance despite various efforts. have.
본 발명이 해결하고자 하는 과제는 금속류, 탄소 파우더 및 옥사이드(oxide)를 사용함이 없이도 투명하고 전도성이 우수한 투명 전도성 필름을 형성할 수 있는 폴리머 용액을 제공함에 있다. The problem to be solved by the present invention is to provide a polymer solution capable of forming a transparent conductive film having a transparent and excellent conductivity without using metals, carbon powder and oxide (oxide).
본 발명이 해결하고자 하는 다른 과제는 금속류, 탄소 파우더 및 옥사이드(oxide)를 사용함이 없이도 투명하고 전도성이 우수한 투명 전도성 필름을 형성할 수 있는 폴리머 용액의 제조방법을 제공함에 있다. Another object of the present invention is to provide a method for preparing a polymer solution capable of forming a transparent conductive film having excellent transparency and conductivity without using metals, carbon powders and oxides.
본 발명이 해결하고자 하는 또 다른 과제는 금속류, 탄소 파우더 및 옥사이드(oxide)를 사용함이 없이도 투명하고 전도성이 우수한 투명 전도성 필름을 제조하는 방법을 제공함에 있다. Another problem to be solved by the present invention is to provide a method for producing a transparent conductive film having excellent transparency and conductivity without using metals, carbon powder and oxide (oxide).
본 발명은, 코팅되어 투명하고 전도성을 갖는 투명 전도성 폴리머 필름을 형성하는 폴리머 용액에 있어서, 상기 투명 전도성 폴리머 필름의 전기 전도도를 조절하는 폴리비닐알콜과, 상기 폴리머 용액의 구조 강도를 조절하는 폴리비닐아세트아미드와, 내마찰성과 접착성을 조절하는 폴리아크릴아미드와, 산화-환원 반응에서 전자받게로 작용하는 질산과, 상기 투명 전도성 폴리머 필름의 투과율을 조절하는 메타크릴산메틸에스테르 및 폴리머 용액의 점성을 유지하는 노말 메틸 피롤리돈 용매를 적어도 포함하는 폴리머 용액을 제공한다. The present invention is a polymer solution coated to form a transparent conductive polymer film having a transparent, conductive, polyvinyl alcohol for controlling the electrical conductivity of the transparent conductive polymer film, polyvinyl for controlling the structural strength of the polymer solution Viscosity of acetamide, polyacrylamide for controlling friction and adhesion, nitric acid acting as electron acceptor in redox reaction, methacrylic acid methyl ester and polymer solution for controlling transmittance of the transparent conductive polymer film It provides a polymer solution containing at least a normal methyl pyrrolidone solvent to maintain.
상기 폴리머 용액은 폴리비닐알콜 11∼13.5중량%와, 폴리비닐아세트아미드 11∼13.5중량%와, 폴리아크릴아미드 11∼13.5중량%와 , 질산 11∼13.5중량%와, 메타크릴산메틸에스테르 5∼20중량%와, 노말 메틸 피롤리돈 용매 30∼50중량%를 포함한다. The polymer solution is 11 to 13.5% by weight of polyvinyl alcohol, 11 to 13.5% by weight of polyvinyl acetamide, 11 to 13.5% by weight of polyacrylamide, 11 to 13.5% by weight of nitric acid, and 5 to 5 methacrylic acid methyl ester. 20 weight% and the normal methyl pyrrolidone solvent 30-50 weight%.
상기 투명 전도성 폴리머 필름은 빛에 대하여 75∼98％의 투과율과, 0.1×10-2∼1×103Ω·cm의 비저항을 갖는다. The transparent conductive polymer film has a transmittance of 75 to 98% with respect to light and a specific resistance of 0.1 × 10 −2 to 1 × 10 3 Pa · cm.
또한, 본 발명은, 코팅되어 투명하고 전도성을 갖는 투명 전도성 폴리머 필름을 형성하는 폴리머 용액을 제조하는 방법에 있어서, 상기 투명 전도성 폴리머 필름의 전기 전도도를 조절하는 폴리비닐알콜을 얻는 단계와, 교반기에 상기 폴리비닐알콜과 상기 폴리머 용액의 구조 강도를 조절하는 폴리비닐아세트아미드를 배합하는 단계와, 상기 교반기에 내마찰성과 접착성을 조절하는 폴리아크릴아미드와 산화-환원 반응에서 전자받게로 작용하는 질산을 투입하여 혼합하는 단계와, 상기 교반기에 폴리머 용액의 점성을 유지하는 노말 메틸 피롤리돈 용매를 투입하여 교반하는 단계 및 상기 교반기에 상기 투명 전도성 폴리머 필름의 투과율을 조절하는 메타크릴산메틸에스테르를 투입하여 교반하는 단계를 포함하는 폴리머 용액의 제조방법을 제공한다. In addition, the present invention is a method for producing a polymer solution coated to form a transparent conductive polymer film having a transparent, conductive, comprising the steps of obtaining a polyvinyl alcohol to control the electrical conductivity of the transparent conductive polymer film, Blending the polyvinyl alcohol and polyvinylacetamide to control the structural strength of the polymer solution, the polyacrylamide to control friction and adhesion to the stirrer, and nitric acid acting as an electron acceptor in an oxidation-reduction reaction Adding and mixing, and adding and stirring a normal methyl pyrrolidone solvent that maintains the viscosity of the polymer solution in the stirrer, and methyl methacrylate to control the transmittance of the transparent conductive polymer film in the stirrer. Providing a method for producing a polymer solution comprising the step of adding and stirring .
상기 교반기에 상기 폴리비닐알콜은 11∼13.5중량%, 상기 폴리비닐아세트아미드는 11∼13.5중량%, 상기 폴리아크릴아미드는 11∼13.5중량%, 상기 질산은 11∼13.5중량%, 상기 메타크릴산메틸에스테르는 5∼20중량%, 상기 노말 메틸 피롤리돈 용매는 30∼50중량%를 투입하는 것이 바람직하다. 11-13.5 weight% of the polyvinyl alcohol, 11-13.5 weight% of the polyvinyl acetamide, 11-13.5 weight% of the polyacrylamide, 11-13.5 weight% of the nitric acid, and the methyl methacrylate. It is preferable to add 5-20 weight% of esters, and 30-50 weight% of the said normal methyl pyrrolidone solvents.
상기 폴리비닐알콜을 얻는 단계는, 교반기에 비닐아세테이트와 메탄올을 투입하고, 수산화나트륨 용액을 투입하여 교반하는 단계와, 상기 교반기에 침전된 침전물을 여과 및 건조하는 단계와, 여과 및 건조된 결과물과 증류수를 반응기에 투입하고, 반응기를 가열하는 단계와, 반응기의 온도를 냉각시킨 다음, 수산화나트륨 용액을 투입하여 교반하는 단계 및 수산화나트륨이 투입된 결과물에 황산을 투입하여 반응시키는 단계를 포함할 수 있다. The obtaining of the polyvinyl alcohol may include adding vinyl acetate and methanol to a stirrer, adding sodium hydroxide solution, stirring, filtering and drying the precipitate precipitated in the stirrer, and filtering and drying the resulting product. Distilled water may be added to the reactor, the reactor may be heated, the reactor may be cooled, the sodium hydroxide solution may be added and stirred, and sulfuric acid may be added to the resultant to which sodium hydroxide is added. .
또한, 본 발명은, 투명 전도성 폴리머 필름의 전기 전도도를 조절하는 폴리비닐알콜을 얻는 단계와, 교반기에 상기 폴리비닐알콜과 폴리머 용액의 구조 강도를 조절하는 폴리비닐아세트아미드를 배합하는 단계와, 상기 교반기에 내마찰성과 접착성을 조절하는 폴리아크릴아미드와 산화-환원 반응에서 전자받게로 작용하는 질산을 투입하여 혼합하는 단계와, 상기 교반기에 폴리머 용액의 점성을 유지하는 노말 메틸 피롤리돈 용매를 투입하여 교반하는 단계와, 상기 교반기에 상기 투명 전도성 폴리머 필름의 투과율을 조절하는 메타크릴산메틸에스테르를 투입하고 교반하여 폴리머 용액을 얻는 단계와, 상기 폴리머 용액이 코팅하려는 대상에 노즐로 분사하여 코팅하는 단계 및 코팅된 상기 폴리머 용액을 80℃ 내지 110℃의 온도에서 건조하는 단계를 포함하는 투명 전도성 폴리머 필름의 제조방법을 제공한다.In addition, the present invention, the step of obtaining a polyvinyl alcohol to control the electrical conductivity of the transparent conductive polymer film, the step of blending the polyvinyl alcohol and polyvinyl acetamide to control the structural strength of the polymer solution in the stirrer, and Adding a polyacrylamide to control abrasion resistance and adhesion with nitric acid acting as an electron acceptor in the oxidation-reduction reaction, and mixing a normal methyl pyrrolidone solvent to maintain viscosity of the polymer solution in the stirrer. Adding and stirring, injecting and stirring methyl methacrylate, which controls the transmittance of the transparent conductive polymer film, to the stirrer to obtain a polymer solution, and spraying a coating onto a target to which the polymer solution is to be coated by a nozzle. And drying the coated polymer solution at a temperature of 80 ° C. to 110 ° C. It provides a method for producing a transparent conductive polymer film comprising.
상기 교반기에 상기 폴리비닐알콜은 11∼13.5중량%, 상기 폴리비닐아세트아미드는 11∼13.5중량%, 상기 폴리아크릴아미드는 11∼13.5중량%, 상기 질산은 11∼13.5중량%, 상기 메타크릴산메틸에스테르는 5∼20중량%, 상기 노말 메틸 피롤리 돈 용매는 30∼50중량%를 투입하는 것이 바람직하다. 11-13.5 weight% of the polyvinyl alcohol, 11-13.5 weight% of the polyvinyl acetamide, 11-13.5 weight% of the polyacrylamide, 11-13.5 weight% of the nitric acid, and the methyl methacrylate. It is preferable to add 5-20 weight% of esters, and 30-50 weight% of the said normal methyl pyrrolidone solvent.
상기 폴리비닐알콜을 얻는 단계는, 교반기에 비닐아세테이트와 메탄올을 투입하고, 수산화나트륨 용액을 투입하여 교반하는 단계와, 상기 교반기에 침전된 침전물을 여과 및 건조하는 단계와, 여과 및 건조된 결과물과 증류수를 반응기에 투입하고, 반응기를 가열하는 단계와, 반응기의 온도를 냉각시킨 다음, 수산화나트륨 용액을 투입하여 교반하는 단계 및 수산화나트륨이 투입된 결과물에 황산을 투입하여 반응시키는 단계를 포함할 수 있다. The obtaining of the polyvinyl alcohol may include adding vinyl acetate and methanol to a stirrer, adding sodium hydroxide solution, stirring, filtering and drying the precipitate precipitated in the stirrer, and filtering and drying the resulting product. Distilled water may be added to the reactor, the reactor may be heated, the reactor may be cooled, the sodium hydroxide solution may be added and stirred, and sulfuric acid may be added to the resultant to which sodium hydroxide is added. .
본 발명에 의하면, 일반 도전성 폴리머 용액과는 달리 금속류와 탄소 파우더 및 일체의 옥사이드(oxide)를 사용하지 않고도 폴리머 용액을 얻을 수 있으며, 상기 폴리머 용액을 코팅하려는 대상물에 코팅하여 폴리머 필름을 형성하는 경우 우수한 전도성과 투명성을 갖다. According to the present invention, unlike a general conductive polymer solution, it is possible to obtain a polymer solution without using metals, carbon powders, and any oxides, and to form a polymer film by coating the polymer solution on an object to be coated. It has excellent conductivity and transparency.
이하, 첨부된 도면을 참조하여 본 발명에 따른 바람직한 실시예를 상세하게 설명하기로 한다. 그러나, 이하의 실시예는 이 기술분야에서 통상적인 지식을 가진 자에게 본 발명이 충분히 이해되도록 제공되는 것으로서 여러 가지 다른 형태로 변형될 수 있으며, 본 발명의 범위가 다음에 기술되는 실시예에 한정되는 것은 아니다. Hereinafter, exemplary embodiments of the present invention will be described in detail with reference to the accompanying drawings. However, the following embodiments are provided to those skilled in the art to fully understand the present invention, and may be modified in various forms, and the scope of the present invention is limited to the embodiments described below. It doesn't happen.
본 발명의 바람직한 실시예에 따른 폴리머 용액은, 폴리비닐알콜(PVA) 11∼13.5중량%, 폴리비닐아세트아미드(PNVA) 11∼13.5중량%, 폴리아크릴아미드(PAAM) 11∼13.5중량%, 질산(Nitric acid) 11∼13.5중량%, 노말 메틸 피롤리돈(Normal methyl pyrolidone; NMP) 용매(Solvent) 30∼50중량%, 메타크릴산메틸에스테르(CH2=C(CH3)CO2CH3; MMA) 5∼20중량%를 포함한다. Polymer solution according to a preferred embodiment of the present invention, polyvinyl alcohol (PVA) 11-13.5% by weight, polyvinyl acetamide (PNVA) 11-13.5% by weight, polyacrylamide (PAAM) 11-13.5% by weight, nitric acid (Nitric acid) 11-13.5 wt%, Normal methyl pyrolidone (NMP) Solvent 30-50 wt%, Methacrylic acid methyl ester (CH 2 = C (CH 3 ) CO 2 CH 3 MMA) 5 to 20% by weight.
비닐아세테이트(Vinylacetate)로부터 이멀젼(Emulsion) 중합을 통해 폴리비닐아세티이트(Polyvinylacetate)를 제조하고, 폴리비닐아세티이트(Polyvinylacetate)를 가수분해하여 얻어진 폴리비닐알콜(PVA)은 합성고분자 중에서 수용성이라는 특이한 성질을 갖고 있다. Polyvinylacetate is prepared by emulsion polymerization from vinylacetate, and polyvinyl alcohol (PVA) obtained by hydrolyzing polyvinylacetate is water-soluble in synthetic polymers. It has an unusual property.
폴리비닐알콜(PVA)의 비중은 0.3∼0.7이고, 열안정성 및 열가소성은 100∼140℃ 정도이다. 폴리비닐알콜(PVA)은 단시간의 가열로는 외관의 변화가 없으나 150℃ 전후에서 구조변화가 일어나기 시작해 그 이상에서는 서서히 착색되며, 300℃ 부근에서 분해된다. 또한, 폴리비닐알콜(PVA)은 온수(75℃ 이상)에서는 녹지만, 냉수에서는 팽윤만 되는 난용성이다. 폴리비닐알콜(PVA)은 산 또는 알카리 용액에는 팽윤되거나 또는 용해된다. 폴리비닐알콜(PVA)은 폴리머 용액 내에 항장력, 인장강도, 신장도, 내마모성의 안정성을 높이기 위해 사용된다. 상기 폴리비닐알콜(PVA)의 배합비가 11중량% 미만이면 폴리머 용액 내의 안전성이 떨어지고, 13.5중량%를 초과하면 폴리머 용액 내의 전기 전도도가 높게 나타나는 문제점이 있으므로, 그 배합비를 11∼13.5중량%로 하는 것이 바람직하며, 가장 바람직하게는 12.5 중량%로 한다. The specific gravity of polyvinyl alcohol (PVA) is 0.3 to 0.7, and thermal stability and thermoplasticity are about 100 to 140 ° C. Polyvinyl alcohol (PVA) has no change in appearance with a short heating time, but structural changes begin to occur around 150 ° C, and gradually become colored and decompose around 300 ° C. In addition, polyvinyl alcohol (PVA) is poorly soluble in hot water (75 ° C or higher), but swells only in cold water. Polyvinyl alcohol (PVA) is swollen or dissolved in acid or alkaline solutions. Polyvinyl alcohol (PVA) is used to increase the stability of tensile strength, tensile strength, elongation and wear resistance in the polymer solution. If the blending ratio of the polyvinyl alcohol (PVA) is less than 11% by weight, the safety in the polymer solution is lowered. If the blending ratio is more than 13.5%, the electrical conductivity in the polymer solution is high. Therefore, the blending ratio is 11 to 13.5% by weight. It is preferable that it is 12.5 weight% most preferably.
폴리비닐아세트아미드(PNVA)는 이온 농도가 높은 물이나 액체의 흡수 등 지금까지 흡수성 수지를 이용하는 것이 어려웠던 용도에 응용이 가능한 비이온계 흡수 수지이다. 폴리비닐아세트아미드(PNVA)는 페놀성의 수산기(OH기)를 갖는 물질이나 단백질 등의 성분에 높은 흡착능을 갖기 때문에 폴리머 용액 내의 구조 강도를 일정하게 유지한다. 상기 폴리비닐아세트아미드(PNVA)가 11중량% 미만이면 폴리머 용액 내의 구조 강도가 낮아지고, 13.5중량%를 초과하면 폴리머 용액 내의 합성된 높은 흡착능을 갖기 때문에 용액 내의 화합물들과 반응하여 쉽게 파괴될 우려가 있으므로, 그 배합비를 11∼13.5중량%로 하는 것이 바람직하고, 가장 바람직하게는 12.5중량%로 한다. Polyvinylacetamide (PNVA) is a nonionic absorption resin that can be applied to applications where it has been difficult to use water absorbent resins such as water or liquid absorption having high ion concentration. Polyvinylacetamide (PNVA) has a high adsorption capacity to a component such as a protein, a substance having a phenolic hydroxyl group (OH group), and thus maintains a constant structural strength in the polymer solution. When the polyvinyl acetamide (PNVA) is less than 11% by weight, the structural strength in the polymer solution is lowered, and when the polyvinylacetamide (PNVA) is more than 13.5%, it has a high adsorption capacity synthesized in the polymer solution, so that it may easily react with the compounds in the solution and be destroyed. Therefore, the blending ratio is preferably 11 to 13.5% by weight, most preferably 12.5% by weight.
폴리아크릴아미드(PAAM)는 아크릴아미드로부터 얻어지는 선상 중합체며, 폴리머 용액 내의 응집제로 사용된다. PH에 의한 점도 변화가 거의 없어 필름 제조 시 내마찰성을 강하고 우수하게 하는 것으로, 그 배합비가 11중량% 미만이면 폴리머 용액 내의 내마찰성이 좋지 않게 되고, 13.5중량%를 초과하면 필름 제조 시 폴리머 용액 내의 접착성이 떨어진다. 그 배합비를 11∼13.5중량%로 하는 것이 바람직하고, 더욱 바람직하게는 12.5중량%로 한다.Polyacrylamide (PAAM) is a linear polymer obtained from acrylamide and is used as a flocculant in a polymer solution. There is almost no viscosity change due to PH, which makes the friction resistance strong and excellent during film production. If the blending ratio is less than 11% by weight, the friction resistance in the polymer solution is not good. Poor adhesion. The blending ratio is preferably 11 to 13.5% by weight, more preferably 12.5% by weight.
질산(Nitric acid)은 폴리머 용액 내에 수소와 질산 이온으로 완전히 이온화되며, 산화-환원 반응에서 전자받게로 작용한다. 질산의 배합비가 11중량% 미만이 되면 폴리머 용액 내의 반응에서 전자받게로의 작용이 이루어지지 않고, 13.5중량%를 초과하면 폴리머 용액 내의 강한 산화제 작용으로 전기 전도성에 악영향을 주므 로, 그 배합비를 11∼13.5중량%로 하는 것이 바람직하고, 더욱 바람직하게는 12.5중량%로 한다. Nitric acid is completely ionized with hydrogen and nitrate ions in the polymer solution and acts as an electron acceptor in the redox reaction. When the compounding ratio of nitric acid is less than 11% by weight, the reaction in the polymer solution does not act as an electron acceptor. When the compounding ratio is more than 13.5% by weight, the strong oxidizing agent in the polymer solution adversely affects electrical conductivity. It is preferable to set it as -13.5 weight%, More preferably, you may be 12.5 weight%.
노말 메틸 피롤리돈(Normal methyl pyrolidone; NMP) 용매(Solvent)는 유기물에 대한 용해력이 뛰어나면서 독성이 낮아 친환경 반도체 세정제로 사용되는 기능성 화학물질로서, 폴리머 용액 내 화합물들의 점성을 유지하는 역할을 한다. 상기 NMP(Normal methyl pyrolidone) 용매(Solvent)의 배합비가 30중량% 미만이 되면 폴리머 용액 내의 점성이 강하여 분사 시 효율이 떨어지고, 50중량%를 초과하면 폴리머 용액 내의 점성이 떨어지게 되어 필름 제조 시 용이하지 않게 되므로, 그 배합비를 30∼50중량%로 하는 것이 바람직하고, 가장 바람직하게는 40중량%로 한다. Normal methyl pyrolidone (NMP) Solvent is a functional chemical used as an environmentally friendly semiconductor cleaner due to its high solubility in organics and low toxicity, and serves to maintain the viscosity of the compounds in the polymer solution. . When the compounding ratio of the NMP (Normal methyl pyrolidone) solvent (Solvent) is less than 30% by weight, the viscosity in the polymer solution is strong, so that the efficiency is reduced during spraying, and when it exceeds 50% by weight, the viscosity in the polymer solution is poor, and thus it is not easy to prepare the film. Since the blending ratio is preferably 30 to 50% by weight, most preferably 40% by weight.
메타크릴산메틸에스테르(CH2=C(CH3)CO2CH3; MMA)는 아크릴 수지(acrylic resin)의 하나로 아크릴산이나 메타아크릴산 등의 에스테르로부터 중합한 합성수지로서, 투명성이 좋은 플라스틱으로 빛 특히 자외선을 보통 유리보다 쉽게 통과시킨다. 메타크릴산메틸에스테르(MMA)는 유리 이상의 투명성이 있고, 유리 무게의 절반밖에 안되므로 가볍고 가공성이 뛰어나다. 메타크릴산메틸에스테르(MMA)는 폴리머 용액의 상기 폴리머릭(Polymeric) 화합물들과 직접 결합하며, 필름 제조 시 투과율 및 전기 전도성에 영향을 준다. 메타크릴산메틸에스테르(MMA)의 배합비가 5중량% 미만이 되면 폴리머 용액 내의 폴리머릭(Polymeric) 화합물들과 결합력이 약하게 되고, 20중량%를 초과하면 전기 전도성에 나뿐 영향을 주므로, 그 배합비를 5∼20중량%로 하는 것이 바람직하고, 가장 바람직하게는 10중량%로 한다. Methacrylic acid methyl ester (CH 2 = C (CH 3 ) CO 2 CH 3 ; MMA) is one of acrylic resins and is a synthetic resin polymerized from esters such as acrylic acid and methacrylic acid. Passes ultraviolet rays more easily than ordinary glass. Methacrylic acid methyl ester (MMA) has a transparency greater than glass and is light and excellent in processability because it is only half the glass weight. Methacrylic acid methyl ester (MMA) directly bonds with the above polymeric compounds in a polymer solution and affects the transmittance and electrical conductivity in film production. When the blending ratio of methyl methacrylate (MMA) is less than 5% by weight, the bonding strength with the polymeric compounds in the polymer solution becomes weak, and when the blending ratio exceeds 20% by weight, it only affects electrical conductivity. It is preferable to set it as 5 to 20 weight%, Most preferably, you may be 10 weight%.
상기와 같은 폴리머 용액을 이용한 투명 전도성 폴리머 필름은 1㎝×1㎝에 대하여 0.1×10-2∼1×103Ω·cm의 비저항, 바람직하게는 1×10-2 Ω·cm의 비저항을 갖게 되어 우수한 도전성과 투명성을 가지게 된다. 또한, 상기 투명 전도성 폴리머 필름은 빛에 대하여 75∼98％의 투과율를 갖는다. The transparent conductive polymer film using the polymer solution as described above has a specific resistance of 0.1 × 10 −2 to 1 × 10 3 Pa · cm, preferably 1 × 10 −2 Pa · cm with respect to 1 cm × 1 cm. It has excellent conductivity and transparency. In addition, the transparent conductive polymer film has a transmittance of 75 to 98% with respect to light.
상기 폴리머 용액을 이용하여 투명 전도성 폴리머 필름을 제조하는 방법에 대해 설명하면 다음과 같다. Referring to the method for producing a transparent conductive polymer film using the polymer solution as follows.
먼저 비닐아세테이트(Vinylacetate)로부터 이멀젼(Emulsion) 중합을 통해 폴리비닐아세티이트(Polyvinylacetate)를 제조하고, 또한 이를 가수분해하여 폴리비닐알콜(PVA)을 얻는다. 폴리비닐알콜(PVA)의 단량체인 비닐알콜은 불안정하여 존재하지 않기 때문에 폴리비닐알콜(PVA)은 비닐알코올로부터는 제조할 수 없고 폴리비닐아세테이트(PVAC)로부터 고분자 반응으로 제조한다. 실제로는 폴리비닐알콜(PVA)은 폴리비닐아세테이트(PVAC)를 메탄올 용액 중에서 알칼리 또는 산을 촉매로 하여 에스테르 교환 반응으로 제조하는 일반화 되어있는 방법을 사용할 수 있다.First, polyvinylacetate is prepared through emulsion polymerization from vinylacetate, and also hydrolyzed to obtain polyvinyl alcohol (PVA). Since vinyl alcohol, which is a monomer of polyvinyl alcohol (PVA), is unstable and does not exist, polyvinyl alcohol (PVA) cannot be produced from vinyl alcohol, but is produced by polymer reaction from polyvinyl acetate (PVAC). In practice, polyvinyl alcohol (PVA) may be a generalized method of preparing polyvinylacetate (PVAC) by transesterification reaction with alkali or acid as catalyst in methanol solution.
이멀젼 중합은 일반적인 방법을 사용할 수 있는데, 예컨대 비닐아세테이트(Vinylacetate) 단량체(Monomer)에 용매, 유화제(Surfactant) 및 반응개시제를 가하여 교반하면서 작은 입자(micelles) 혹은 작은 입자체(aggregates)를 형성시킨 후, 가온 중합한다. 이멀젼(Emulsion) 중합은 반응 시간, 교반 속도, 수소이온농도 등이 중합 조건이 될 수 있으며, 이를 적절하게 조절하여 중합 반응을 유도한다. 유화제(Surfactant)는 중합반응(Polymerization) 진행 동안에 단량체(monomer), 중 합체(polymer)의 표면에 포화되어 분산매중에 분산 용해되도록 하는 역할을 한다. 유화제(Surfactant)로는 폴리옥시에틸렌(polyoxyethylene)과 같은 비이온계면활성제(nonionic surfactant) 또는 알킬 황산염(Alkyl Sulfate)과 같은 음이온계면활성제(anionic surfactant)가 사용될 수 있다. 반응개시제로는 포타슘 퍼설페이트(Potassium Persulfate), 암모늄 퍼설페이트(Ammonium Persulfate) 등이 사용될 수 있다. 용매로는 메탄올(Methyl Alcohol)이 사용될 수 있다. 비닐아세테이트(Vinylacetate)로부터 이멀젼(Emulsion) 중합을 통해 폴리비닐아세티이트(Polyvinylacetate)를 얻을 수 있고, 폴리비닐아세티이트(Polyvinylacetate)를 가수분해함으로서 폴리비닐알콜(PVA)을 얻을 수 있다. Emulsion polymerization can be carried out using a general method, for example, by adding a solvent, emulsion and reaction initiator to the vinylacetate monomer (Monomer) to form small particles (microelles) or small aggregates (aggregates) while stirring After that, warm polymerization is carried out. In the emulsion polymerization, the reaction time, stirring speed, hydrogen ion concentration, and the like may be polymerization conditions, and appropriately controlled to induce a polymerization reaction. Emulsifiers (Surfactant) is saturated to the surface of the monomer (polymer), the polymer (polymer) during the polymerization process (Polymerization) and serves to disperse and dissolve in the dispersion medium. As an emulsifier, a nonionic surfactant such as polyoxyethylene or anionic surfactant such as alkyl sulfate may be used. Potassium persulfate, ammonium persulfate, and the like may be used as the reaction initiator. Methanol may be used as the solvent. Polyvinylacetate can be obtained through emulsion polymerization from vinylacetate, and polyvinyl alcohol (PVA) can be obtained by hydrolyzing polyvinylacetate.
이하 본 발명의 바람직한 실시예에 따라 폴리비닐알콜(PVA)를 얻는 방법을 더욱 구체적으로 설명한다. Hereinafter, a method of obtaining polyvinyl alcohol (PVA) according to a preferred embodiment of the present invention will be described in more detail.
하기 표 1은 비닐아세테이트로부터 이멀젼(Emulsion) 중합을 통해 폴리비닐아세티이트(Polyvinylacetate)를 제조하고, 폴리비닐아세티이트(Polyvinylacetate)를 가수분해하여 얻어지는 폴리비닐알콜(PVA)에 사용되는 물질들의 특징을 나타낸 것이다. Table 1 is a polyvinyl acetate (Polyvinylacetate) prepared by the emulsion (Emulsion) polymerization from vinyl acetate, and the material used for polyvinyl alcohol (PVA) obtained by hydrolyzing polyvinylacetate (Polyvinylacetate) It is characterized by their characteristics.
도 1은 비닐아세테이트로부터 이멀젼(Emulsion) 중합을 통해 폴리비닐아세티이트(Polyvinylacetate)를 제조하고, 폴리비닐아세티이트(Polyvinylacetate)를 가수분해하여 폴리비닐알콜(PVA)을 얻는 과정을 설명하기 위하여 도시한 도면이다. FIG. 1 illustrates a process of preparing polyvinylacetate through emulsion polymerization from vinyl acetate, and obtaining polyvinyl alcohol (PVA) by hydrolyzing polyvinylacetate. It is shown for the purpose of illustration.
표 1 및 도 1을 참조하면, 교반기에 비닐아세테이트(Vinylacetate) 2.0g과 메탄올(CH3OH) 100㎖을 투입하고, 40％ 수산화나트륨(NaOH) 용액 2㎖를 투입하여 교반한다. 이때, 교반기의 회전속도는 600∼1500 rpm 정도로 한다. Referring to Table 1 and FIG. 1, 2.0 g of vinyl acetate and 100 ml of methanol (CH 3 OH) were added to a stirrer, and 2 ml of 40% sodium hydroxide (NaOH) solution was added and stirred. At this time, the rotation speed of the stirrer is about 600 to 1500 rpm.
교반기를 20분∼1시간 정도 교반한 다음, 20∼30분 정도 방치하게 되면 교반기에 백색 침전물이 생기게 된다. 이 백색 침전물을 여과기를 이용하여 여과한 다음, 열풍 건조 등의 방법을 이용하여 건조하게 되면 폴리비닐아세테이트(Polyvinylacetate)를 얻을 수 있다. After stirring the stirrer for 20 minutes to 1 hour, and then left for 20 to 30 minutes, a white precipitate is formed in the stirrer. The white precipitate is filtered using a filter, and then dried using a method such as hot air drying to obtain polyvinylacetate.
이렇게 얻어진 폴리비닐아세테이트(Polyvinylacetate) 0.5g과 증류수 100㎖를 반응기에 투입하고, 반응기를 가열하여 75℃ 정도의 온도가 되게 하여 30분∼1시간 동안 유지한다. 반응기의 온도를 상온으로 냉각시킨 다음, 40％ 수산화나트륨(NaOH) 용액 2㎖를 투입하고, 20분∼1시간 정도 교반한다. 교반 후, 1시간 30분∼2시간 정도 방치한 후, 결과물에 황산(H2SO4)을 투입하여 반응시키면, 폴리비닐알콜(PVA)을 얻을 수 있다. 0.5 g of polyvinylacetate thus obtained and 100 ml of distilled water were added to the reactor, and the reactor was heated to a temperature of about 75 ° C. and maintained for 30 minutes to 1 hour. After the reactor was cooled to room temperature, 2 ml of 40% sodium hydroxide (NaOH) solution was added thereto, followed by stirring for 20 minutes to 1 hour. After stirring, the mixture is left for 1 hour 30 minutes to 2 hours, and then sulfuric acid (H 2 SO 4 ) is added to the resultant to react, thereby obtaining polyvinyl alcohol (PVA).
이렇게 얻어진 폴리비닐알콜(PVA) 11∼13.5중량%를 폴리비닐아세트아미드(PNVA) 11∼13.5중량%와 함께 배합한다. 폴리비닐알콜(PVA)과 폴리비닐아세트아미드(PNVA)를 가장 먼저 배합하는 이유는 폴리머 용액의 안정성을 높이기 위함이다.11-13.5 weight% of polyvinyl alcohol (PVA) obtained in this way is mix | blended with 11-13.5 weight% of polyvinyl acetamide (PNVA). The first reason to combine polyvinyl alcohol (PVA) and polyvinylacetamide (PNVA) is to increase the stability of the polymer solution.
상기 폴리비닐알콜(PVA)과 폴리비닐아세트아미드(PNVA)의 배합이 완료되면, 이 배합물에 폴리아크릴아미드(PAAM) 11∼13.5중량%와, 질산(Nitric acid) 11∼13.5중량%를 투입하는 데, 이때 폴리머 용액이 겔화가 되지 않도록 주의하여야 한다. 그리고 상기 폴리아크릴아미드(PAAM)과 질산(Nitric acid)을 투입하는 것은 질산(Nitric acid)이 폴리머 용액 내에서 산화-환원 반응으로 전자받게로 작용함으로서 전기 전도도와 폴리머 용액 내의 폴리머릭(Polymeric) 화합물들의 결합력을 일정하게 하기 위함이다. When the blending of the polyvinyl alcohol (PVA) and polyvinyl acetamide (PNVA) is completed, 11 to 13.5 wt% of polyacrylamide (PAAM) and 11 to 13.5 wt% of nitric acid are added to the blend. At this time, care should be taken not to gel the polymer solution. In addition, the polyacrylamide (PAAM) and nitric acid (nitric acid) is added to the nitric acid (Nitric acid) acts as an electron-receiving reaction by the oxidation-reduction reaction in the polymer solution, the electrical conductivity and the polymer (Polymeric) compound in the polymer solution This is to keep their bond strength constant.
폴리아크릴아미드(PAAM)와 질산(Nitric acid)이 투입된 혼합물에 노말 메틸 피롤리돈(Normal methyl pyrolidone; NMP) 용매(Solvent) 30∼50중량%를 투입하여 교반을 한다. 이는 전도성 폴리머 용액 내의 폴리머릭(Polymeric) 화합물들과 반응하여 적당한 점성을 유지하기 위함이다. 이때 교반기의 회전속도는 600∼1500 rpm 정도로 한다. 30-50% by weight of a normal methyl pyrolidone (NMP) solvent (Solvent) is added to a mixture containing polyacrylamide (PAAM) and nitric acid, followed by stirring. This is to maintain the proper viscosity by reacting with the polymeric compounds in the conductive polymer solution. At this time, the rotation speed of the stirrer is about 600 to 1500 rpm.
상기 노말 메틸 피롤리돈(Normal methyl pyrdlidone; NMP) 용매가 혼합되면, 메타크릴산메틸에스테르(CH2=C(CH3)CO2CH3; MMA) 5∼20중량%를 투입하여 다시 교반을 한다. 이때 교반기의 회전속도는 600∼1500 rpm 정도로 한다. 상기 메타크릴산메틸에스테르(CH2=C(CH3)CO2CH3; MMA)는 폴리머 용액의 폴리머릭(Polymeric) 화합물들과 직접 결합하며, 필름 제조 시 투과율 및 전기 전도성에 영향을 주는 것일 뿐만 아니라, 폴리머 용액 내에 수지 조성을 갖게 하기 위한 것이다. When the normal methyl pyrdlidone (NMP) solvent is mixed, 5-20% by weight of methyl methacrylate (CH 2 = C (CH 3 ) CO 2 CH 3 ; MMA) is added thereto, followed by stirring again. do. At this time, the rotation speed of the stirrer is about 600 to 1500 rpm. The methacrylic acid methyl ester (CH 2 = C (CH 3 ) CO 2 CH 3 ; MMA) is directly bonded to the polymer (Polymeric) compounds of the polymer solution, and affects the transmittance and electrical conductivity during film production In addition, it is for making a resin composition in a polymer solution.
본 발명의 바람직한 실시예에 따른 폴리머 용액을 제조하기 위한 위의 공정들은 상온(10℃∼30℃)에서 실시할 수 있다. The above process for preparing a polymer solution according to a preferred embodiment of the present invention can be carried out at room temperature (10 ℃ ~ 30 ℃).
상술한 과정을 거쳐 폴리머 용액을 얻을 수 있다. 본 발명의 바람직한 실시예에 따른 폴리머 용액은 수용성 폴리머계의 일종이다. The polymer solution can be obtained through the above process. Polymer solution according to a preferred embodiment of the present invention is a kind of water-soluble polymer.
이하에서, 상기 폴리머 용액을 이용하여 투명 전도성 폴리머 필름을 제조하는 방법을 설명한다. Hereinafter, a method of manufacturing a transparent conductive polymer film using the polymer solution will be described.
상기 폴리머 용액을 노즐을 이용하여 아크릴 필름과 같은 코팅하려는 대상 위에 분사하는 데, 이때 폴리머 용액의 건조를 열풍 건조 등의 방법을 이용하여 80℃ 내지 110℃에서 행하여 투명 전도성 폴리머 필름을 형성한다. 건조 온도 조건을 80℃∼110℃ 함으로써 투명 전도성 폴리머 필름을 제조하는데, 상기 온도 조건이 80℃ 미만이 되면, 투명 전도성 폴리머 필름이 충분히 필름의 형태를 취하지 못하고 110℃을 초과하게 되면 과도한 온도에 의한 필름의 손상으로 경제적이지 못하므로, 그 온도를 80℃～110℃로 하는 것이 바람직하다. The polymer solution is sprayed onto a target to be coated such as an acrylic film using a nozzle, wherein the drying of the polymer solution is performed at 80 ° C. to 110 ° C. using a method such as hot air drying to form a transparent conductive polymer film. The transparent conductive polymer film is manufactured by drying temperature conditions of 80 ° C to 110 ° C. When the temperature condition is less than 80 ° C, the transparent conductive polymer film does not sufficiently take the form of the film and exceeds 110 ° C. Since it is not economical by damaging a film, it is preferable to make the temperature into 80 degreeC-110 degreeC.
이상, 본 발명의 바람직한 실시예를 들어 상세하게 설명하였으나, 본 발명은 상기 실시예에 한정되는 것은 아니며, 본 발명의 기술적 사상의 범위내에서 당 분야에서 통상의 지식을 가진 자에 의하여 여러 가지 변형이 가능하다.As mentioned above, although preferred embodiment of this invention was described in detail, this invention is not limited to the said embodiment, A various deformation | transformation by a person of ordinary skill in the art within the scope of the technical idea of this invention is carried out. This is possible.
도 1은 비닐아세테이트로부터 이멀젼 중합을 통해 폴리비닐아세티이트를 제조하고, 폴리비닐아세티이트를 가수분해하여 폴리비닐알콜을 얻는 과정을 설명하기 위하여 도시한 도면이다. FIG. 1 is a view illustrating a process for preparing polyvinylacetate through emulsion polymerization from vinyl acetate and obtaining polyvinyl alcohol by hydrolyzing polyvinylacetate.
Claims (9)
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| PCT/KR2008/004024 WO2009008658A2 (en) | 2007-07-10 | 2008-07-09 | Polymer solution, manufacturing method thereof, and manufacturing method of transparent conductive polymer film |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| KR20000008569A (en) * | 1998-07-14 | 2000-02-07 | 남창우 | Coating solution compound and coating compound containing it |
| KR20010101560A (en) * | 1999-11-17 | 2001-11-14 | 도요 고세이 고교 가부시키가이샤 | Coating solution for forming transparent and conductive tin oxide film and method for preparing transparent and conductive tin oxide film, and transparent and conductive tin oxide film |
| JP2002161246A (en) | 2000-11-24 | 2002-06-04 | Toto Ltd | Composition for forming film and member made by application thereof |
| KR20020054537A (en) * | 2000-12-28 | 2002-07-08 | 안복현 | Conductive polymer cathode ray tube black coating layer and method for producing thereof |
| KR100390578B1 (en) | 1998-12-17 | 2003-12-18 | 제일모직주식회사 | High refractive index conductive polymer thin film transparent film coating liquid composition |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20000008569A (en) * | 1998-07-14 | 2000-02-07 | 남창우 | Coating solution compound and coating compound containing it |
| KR100390578B1 (en) | 1998-12-17 | 2003-12-18 | 제일모직주식회사 | High refractive index conductive polymer thin film transparent film coating liquid composition |
| KR20010101560A (en) * | 1999-11-17 | 2001-11-14 | 도요 고세이 고교 가부시키가이샤 | Coating solution for forming transparent and conductive tin oxide film and method for preparing transparent and conductive tin oxide film, and transparent and conductive tin oxide film |
| JP2002161246A (en) | 2000-11-24 | 2002-06-04 | Toto Ltd | Composition for forming film and member made by application thereof |
| KR20020054537A (en) * | 2000-12-28 | 2002-07-08 | 안복현 | Conductive polymer cathode ray tube black coating layer and method for producing thereof |
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