TWI383891B - Transparent conducting pet film via oxidation polymerization and the manufacturing method thereof - Google Patents
Transparent conducting pet film via oxidation polymerization and the manufacturing method thereof Download PDFInfo
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本發明係關於一種具有導電性及可撓性的透明聚合物薄膜及其製造方法，特別是指一種利用聚吡咯PET薄膜所製成之具導電性與可撓性的透明聚合物薄膜及其製造方法。The invention relates to a transparent polymer film with conductivity and flexibility and a manufacturing method thereof, in particular to a transparent polymer film made of polypyrrole PET film and having conductivity and flexibility and manufacturing thereof. method.
近年來，由於電子資訊產品隨著時代發展逐漸趨向於往輕量化及微型化的方向發展，因此對於所使用的材料性質，在重量及加工性的要求上，也日益增高。一般來說，金屬材料相較於高分子材料，具有重量重、加工不易以及不耐腐蝕的缺點，因此近年來的技術研究上，就有一部分的研究，是針對如何使用高分子材料來取代現有的金屬材料這方面而加以進行。高分子材料要應用到電子資訊產品上取代現有的金屬材料，所遇到的第一個難題，就是高分子材料本身並不具有如同金屬材料的良好導電性。然而隨著進年來導電性高分子研究的發展，由最先發現的聚吡咯、聚硫氮、聚乙炔等導電性高分子，到後來衍生出許多不同的環狀及雜環結構導電性高分子，導電性高分子在對於電子資訊產品應用上，已有相當程度的實用性。In recent years, as electronic information products have gradually developed in the direction of lighter weight and miniaturization with the development of the times, the requirements for weight and processability of the materials used have also increased. In general, metal materials have the disadvantages of heavy weight, difficult processing, and corrosion resistance compared to polymer materials. Therefore, in recent years, some researches have been conducted on how to use polymer materials to replace existing ones. The metal material is carried out in this respect. The first problem encountered in the application of polymer materials to electronic information products to replace existing metal materials is that the polymer materials themselves do not have good electrical conductivity as metal materials. However, with the development of research on conductive polymers in the past years, many conductive polymers such as polypyrrole, polysulfide, and polyacetylene have been discovered, and many different cyclic and heterocyclic conductive polymers have been derived. Conductive polymers have a considerable degree of practicality in the application of electronic information products.
在習知技術中，導電性高分子被嘗試用以在聚對苯二甲酸乙二酯(Polyethylene terephthalate,PET)的表面進行聚合，以期望能在聚對苯二甲酸乙二酯(Polyethylene terephthalate,PET)表面形成具有良好導電性的聚吡咯薄膜。由於聚對苯二甲酸乙二酯本身係為一種高分子加工中常見的材料，具有良好的韌性、抗衝擊強度以及耐熱耐磨。通常的情況下，製造出來的聚對苯二甲酸乙二酯可以用來製作為聚酯纖維、絕緣膜、容器或是電器零部件，且原料本身為透明無色，亦可以加入染料製造出所需要的顏色。在習知技術中對於聚對苯二甲酸乙二酯的表面上進行導電性高分子聚合的做法上，其困難點在於，聚對苯二甲酸乙二酯表面上的自由能很低，換言之，也就是聚對苯二甲酸乙二酯表面具有很強的疏水性，因此一般加工塗佈方法或是合成方式皆無法輕易在聚對苯二甲酸乙二酯(Polyethylene terephthalate,PET)表面上形成導電薄膜。為了改善此一缺點，使聚對苯二甲酸乙二酯表面能夠具有良好的界面性質，以順利產生導電性高分子的表面聚合，目前一般習知技術中多半採用電漿改質、化學氧化改質以及紫外線臭氧改質，來進行聚對苯二甲酸乙二酯表面的界面性質改良。In the prior art, conductive polymers have been tried to polymerize on the surface of polyethylene terephthalate (PET) in order to be able to be used in polyethylene terephthalate (Polyethylene terephthalate, The PET) surface forms a polypyrrole film with good electrical conductivity. Since polyethylene terephthalate itself is a common material in polymer processing, it has good toughness, impact strength and heat resistance. Under normal circumstances, the manufactured polyethylene terephthalate can be used to make polyester fiber, insulating film, container or electrical parts, and the raw material itself is transparent and colorless, and it can also be added to the dye to produce the required colour. In the prior art, the conductive polymer polymerization on the surface of polyethylene terephthalate is difficult in that the free energy on the surface of polyethylene terephthalate is low, in other words, That is to say, the surface of polyethylene terephthalate has a strong hydrophobicity, so it is generally impossible to form a conductive layer on the surface of polyethylene terephthalate (PET) by a general processing method or a synthetic method. film. In order to improve this disadvantage, the surface of the polyethylene terephthalate can have good interfacial properties to smoothly produce surface polymerization of the conductive polymer. At present, most of the conventional techniques use plasma modification and chemical oxidation. Quality and UV ozone modification to improve the interface properties of polyethylene terephthalate surface.
使用前述之表面電漿改質、化學氧化改質以及紫外線臭氧改質等方法，進行聚對苯二甲酸乙二酯的表面改質後，可以使得聚對苯二甲酸乙二酯的表面，具有較佳的親水性。然而在使用電漿改質或前述其他改質方法進行聚對苯二甲酸乙二酯表面的界面性質改良時，存在有可能過度氧化或蝕刻，進而損害聚對苯二甲酸乙二酯表面的風險。再者，使用電漿改質或前述其他改質方法進行改質，聚對苯二甲酸乙二酯表面的界面性質，可能會因處理後置放過久，而造成表面官能基的變化。因此，如何能夠提供一種有效在聚對苯二甲酸乙二酯的表面進行改質，並且直接在改質後的表面上進行導電性高分子聚合的方式，以生產出具有良好導電性的聚對苯二甲酸乙二酯的方法及其製品，為本發明所欲揭露之重點。After the surface modification of polyethylene terephthalate is carried out by using the above-mentioned surface plasma modification, chemical oxidation modification, and ultraviolet ozone modification, the surface of the polyethylene terephthalate can be made to have Preferred hydrophilicity. However, when using plasma modification or other modification methods described above to improve the interface properties of the polyethylene terephthalate surface, there is a possibility of excessive oxidation or etching, thereby damaging the risk of the polyethylene terephthalate surface. . Furthermore, the modification of the plasma or the other modification methods described above, the interface properties of the polyethylene terephthalate surface may be caused by the long-term placement after treatment, resulting in changes in surface functional groups. Therefore, it is possible to provide a method of efficiently modifying the surface of polyethylene terephthalate and directly performing polymerization of a conductive polymer on the surface after reforming to produce a polymer pair having good conductivity. The method of ethylene phthalate and its products are the focus of the present invention.
為了解決前述的問題，本發明利用低溫電漿的方式，進行聚對苯二甲酸乙二酯薄膜的表面親水性改質。在完成表面改質之後，接著在聚對苯二甲酸乙二酯薄膜的表面進行一層以上的自組裝薄膜(Selfassembly membranes,SAMs)的塗佈程序，藉由使用不同層數以及不同自組裝薄膜成份，可以有效控制聚對苯二甲酸乙二酯薄膜的表面特性。最後再在表面上進行聚吡咯的聚合程序，以製造出具有導電性及可撓性的透明聚合物薄膜。In order to solve the aforementioned problems, the present invention performs surface hydrophilicity modification of a polyethylene terephthalate film by means of low temperature plasma. After the surface modification is completed, a coating process of one or more self-assembled films (SAMs) is performed on the surface of the polyethylene terephthalate film by using different layers and different self-assembled film components. The surface characteristics of the polyethylene terephthalate film can be effectively controlled. Finally, a polymerization procedure of polypyrrole is carried out on the surface to produce a transparent polymer film having conductivity and flexibility.
本發明之其中一種實施例係為具有導電性的高分子薄膜，其中該高分子薄膜包含：一基材，其係由透明之聚對苯二甲酸乙二酯薄膜所組成；一複數層自組裝高分子聚電解質薄膜，其中該複數層自組裝薄膜係形成於前述透明聚對苯二甲酸乙二酯薄膜的表面上，並由陽離子自組裝薄膜層與陰離子自組裝薄膜層所組成；以及一導電性高分子層，該導電性高分子層係聚合於前述之複數層自組裝薄膜之上，且摻雜有掺雜物。其中該透明聚對苯二甲酸乙二酯薄膜，可進一步添加各種染色原料，且該透明聚對苯二甲酸乙二酯薄膜之表面係經由低溫電漿處理，以增加表面之親水性。該高分子複數層自組裝薄膜係以陽離子自組裝薄膜層與陰離子自組裝薄膜層交替方式而形成。且陽離子自組裝薄膜層較佳的情況下係可由聚丙烯胺氯化氫或聚二甲基二烯丙基氯化銨所構成，陰離子自組裝薄膜層則可由聚丙烯酸或聚苯乙烯磺酸鈉所構成。該自組裝薄膜層的厚度可為50nm至1000nm，層數則為1至20層，且自組裝薄膜層的頂端表面聚合有導電性高分子層，其中該導電性高分子層在較佳的使用狀態下係為聚吡咯層，且其中該掺雜物可為鹽酸、硫酸或其他無機鹽類。One embodiment of the present invention is a conductive polymer film, wherein the polymer film comprises: a substrate composed of a transparent polyethylene terephthalate film; a plurality of layers self-assembling a polymer polyelectrolyte film, wherein the plurality of self-assembled films are formed on a surface of the transparent polyethylene terephthalate film, and are composed of a cationic self-assembled film layer and an anionic self-assembled film layer; and a conductive The polymer layer is polymerized on the plurality of self-assembled films and doped with a dopant. The transparent polyethylene terephthalate film may further be added with various dyeing materials, and the surface of the transparent polyethylene terephthalate film is treated by low temperature plasma to increase the hydrophilicity of the surface. The polymer multilayer self-assembled film is formed by alternating a cationic self-assembled film layer and an anionic self-assembled film layer. The cationic self-assembled film layer is preferably composed of polyacrylamide hydrogen chloride or polydimethyldiallylammonium chloride, and the anionic self-assembled film layer may be composed of polyacrylic acid or sodium polystyrene sulfonate. . The self-assembled film layer may have a thickness of 50 nm to 1000 nm, and the number of layers is 1 to 20 layers, and the top surface of the self-assembled film layer is polymerized with a conductive polymer layer, wherein the conductive polymer layer is preferably used. In the state, it is a polypyrrole layer, and wherein the dopant may be hydrochloric acid, sulfuric acid or other inorganic salts.
本發明之另一種實施例係為一種具有導電性的高分子薄膜之製造方法，其中該製造方法係包含下列步驟：將基材預先經由低溫電漿處理，以增加表面之親水性；於該基材之表面形成複數層自組裝薄膜，其中該複數層自組裝薄膜係包含陽離子自組裝薄膜層與陰離子自組裝薄膜層；於該複數層自組裝薄膜表面聚合成一含有摻雜物的導電性高分子層。其中該基材較佳的情況下，係為聚對苯二甲酸乙二酯薄膜，並可進一步於聚對苯二甲酸乙二酯薄膜內添加染色原料，同時亦可以使用聚甲基丙烯酸甲酯(PMMA)或聚碳酸酯(PC)做為基材的原料，亦可使用如聚丙烯(PP)、聚氯乙烯(PVC)、聚對苯二甲酸酯(PET)、聚苯乙烯(PS)、聚乙烯(PE)、低密度聚乙烯(LDPE)、中密度聚乙烯(MDPE)、高密度聚乙烯(HDPE)等不同的材質作為基材的原料。該高分子複數層自組裝薄膜係以陽離子自組裝薄膜層與陰離子自組裝薄膜層交替方式而形成。又，該陽離子自組裝薄膜層較佳的情況下係由聚丙烯胺氯化氫或聚二甲基二烯丙基氯化銨所構成，該陰離子自組裝薄膜層係由聚丙烯酸或聚苯乙烯磺酸鈉所構成。同時高分子聚電解質的種類可包含由聚丙烯胺氯化氫(Poly allylamine hydrochloride,PAH)、聚二甲基二烯丙基氯化銨(Poly diallydimethylammonium chloride,PDDA or PDADMA)、聚丙烯酸(Poly acylic acid,PAA)、聚苯乙烯磺酸鈉(Poly sodium 4-styrenesulfonate,PSS)、聚N-甲基-2-乙烯吡啶(Poly(N-methyl-2-vinyl pyridinium),PM2VP)以及聚丁基紫原(Poly(butyl viologen),PBV)中任一種單獨或共聚之高分子聚電解質所形成的陰陽離子自組裝薄膜。Another embodiment of the present invention is a method for producing a conductive polymer film, wherein the method comprises the steps of: pretreating a substrate through a low temperature plasma to increase the hydrophilicity of the surface; a plurality of self-assembled films are formed on the surface of the material, wherein the plurality of self-assembled films comprise a cationic self-assembled film layer and an anionic self-assembled film layer; and the surface of the plurality of self-assembled films is polymerized into a conductive polymer containing a dopant Floor. Wherein the substrate is preferably a polyethylene terephthalate film, and further, a dyeing raw material may be added to the polyethylene terephthalate film, and polymethyl methacrylate may also be used. (PMMA) or polycarbonate (PC) as a raw material for the substrate, such as polypropylene (PP), polyvinyl chloride (PVC), polyterephthalate (PET), polystyrene (PS) ), polyethylene (PE), low density polyethylene (LDPE), medium density polyethylene (MDPE), high density polyethylene (HDPE) and other materials are used as raw materials for the substrate. The polymer multilayer self-assembled film is formed by alternating a cationic self-assembled film layer and an anionic self-assembled film layer. Further, the cation self-assembled film layer is preferably composed of polyacrylamide hydrogen chloride or polydimethyldiallyl ammonium chloride, and the anion self-assembled film layer is made of polyacrylic acid or polystyrene sulfonic acid. Made up of sodium. At the same time, the type of the polymer polyelectrolyte may include poly allylamine hydrochloride (PAH), poly diallydimethylammonium chloride (PDDA or PDADMA), polyacrylic acid (Poly acylic acid, PAA), sodium polystyrene sulfonate (PSS), poly(N-methyl-2-vinyl pyridinium, PM2VP), and polybutyl zirconia ( An anion-cation self-assembled film formed by any one of poly(butyl viologen), PBV) alone or copolymerized polymer polyelectrolyte.
為瞭解本發明之目的、特徵及功效，茲藉由下述具體之實施例，並配合所附之圖式，對本發明做一詳細說明，說明如後：參照第一圖所揭露之導電性高分子薄膜製造流程圖。首先，以透明或經染色之聚對苯二甲酸乙二酯薄膜做為基材，並進行表面潔淨程序，該表面潔淨程序係利用去離子水清洗表面後再加以乾燥。之後，將經由表面潔淨程序處理後的聚對苯二甲酸乙二酯薄膜置入低溫電漿環境中，以50ml/min的流速通入氧氣，並將功率保持在800W的環境下，進行五分鐘的表面處理，使聚對苯二甲酸乙二酯薄膜能夠具有較佳的表面親水性。接著配製陽離子水溶液與陰離子水溶液，其中陽離子水溶液其配製濃度為0.01M，且PH值控制在約7.5左右，陰離子水溶液其配製濃度為0.01M，且PH值控制在約3.5左右。接著視所需要的陽離子自組裝薄膜層與陰離子自組裝薄膜層的層數、排列方式以及吸附厚度進行陽離子水溶液與陰離子水溶液的浸泡。在完成複數層自組裝薄膜後，接著進行導電性高分子在複數層自組裝薄膜表面上的聚合。在較佳的情況下，可選用聚吡咯做為複數層自組裝薄膜表面上的導電性高分子層，該聚吡咯導電性高分子層的製造方法，是利用氯化鐵(Ferric chloride,FeCl3 )做為催化劑，首先配置濃度為1M的鹽酸(HCl)水溶液作為掺雜物，再加入5-10wt%的氯化鐵，均勻攪拌後，置入具有複數層自組裝薄膜的聚對苯二甲酸乙二酯薄膜基材，基材的厚度並無特別限制，視使用的目的不同而可做各種厚度的選擇。最後加入聚吡咯單體進行四小時的聚合反應，其中聚吡咯單體係與氯化鐵以1mmole比2.2mmole的比例進行添加。之後再利用去離子水清洗以移除表面殘留的未反應物，完成後則進行乾燥，即可得到具有如同本發明所揭露之具導電性與可撓性的透明聚合物薄膜。In order to understand the object, features and effects of the present invention, the present invention will be described in detail by the following specific embodiments and the accompanying drawings, which are illustrated as follows: Molecular film manufacturing flow chart. First, a transparent or dyed polyethylene terephthalate film is used as a substrate, and a surface cleaning process is performed. The surface cleaning process is performed by washing the surface with deionized water and then drying. Thereafter, the polyethylene terephthalate film treated by the surface cleaning process was placed in a low-temperature plasma environment, oxygen was introduced at a flow rate of 50 ml/min, and the power was maintained at 800 W for five minutes. The surface treatment enables the polyethylene terephthalate film to have better surface hydrophilicity. Then, a cationic aqueous solution and an anionic aqueous solution are prepared. The cationic aqueous solution is prepared at a concentration of 0.01 M, and the pH is controlled to be about 7.5. The anionic aqueous solution is prepared at a concentration of 0.01 M, and the pH is controlled to about 3.5. Then, the cation aqueous solution and the anionic aqueous solution are immersed according to the required number of layers, arrangement, and adsorption thickness of the cation self-assembled film layer and the anion self-assembled film layer. After completing the plurality of layers of the self-assembled film, polymerization of the conductive polymer on the surface of the plurality of layers of the self-assembled film is performed. In a preferred case, polypyrrole can be used as the conductive polymer layer on the surface of the plurality of self-assembled films. The method for producing the polypyrrole conductive polymer layer is to use ferric chloride (FeCl 3 , FeCl 3 ). As a catalyst, firstly, a 1M hydrochloric acid (HCl) aqueous solution is used as a dopant, and then 5-10 wt% of ferric chloride is added, uniformly stirred, and then placed into a polylayer of a polylayer having a plurality of self-assembled films. The thickness of the substrate of the ethylene glycol film substrate is not particularly limited, and various thicknesses can be selected depending on the purpose of use. Finally, a polypyrrole monomer was added for polymerization for four hours, in which a polypyrrole single system and ferric chloride were added at a ratio of 1 mmole to 2.2 mmole. Thereafter, it is washed with deionized water to remove unreacted materials remaining on the surface, and after completion, it is dried to obtain a transparent polymer film having conductivity and flexibility as disclosed in the present invention.
參照第二圖所揭露之複數層自組裝薄膜結構圖。其中最底下係為透明或經染色之聚對苯二甲酸乙二酯薄膜基材，藉由前述之製造方法，可以依照所需要的層數、排列方式以及吸附厚度控制陽離子水溶液與陰離子水溶液的浸泡程序與時間，以得到預期的結構。該浸泡時間的範圍可為十分鐘至十二小時，較佳的情況下，是以二十分鐘至兩小時為浸泡的時間。其中陽離子水溶液較佳的情況為聚丙烯胺氯化氫(Poly allylamine hydrochloride,PAH)或聚二甲基二烯丙基氯化銨(Poly diallydimethylammonium chloride,PDDA)水溶液，陰離子水溶液較佳的情況為聚丙烯酸(Poly acylic acid,PAA)或聚苯乙烯磺酸鈉(Poly sodium 4-styrenesulfonate,PSS)水溶液。其中聚丙烯胺氯化氫或聚二甲基二烯丙基氯化銨陽離子水溶液與聚丙烯酸或聚苯乙烯磺酸鈉陰離子水溶液之間可以任意搭配，以形成具有不同組成、層數、排列方式之複數層自組裝薄膜結構。之後，再利用前述之聚吡咯導電性高分子層的製造方法，在完成預定結構之複數層自組裝薄膜結構表面上，形成一定厚度的聚吡咯導電性高分子層，其中該複數層自組裝薄膜結構及聚吡咯導電性高分子層之厚度可為50nm至1000nm，較佳的情況下則為100nm至300nm之間，聚對苯二甲酸乙二酯薄膜基材的厚度則無特別限制，可視應用上之實際需要而加以調整。Referring to the second layer, the structure of the self-assembled film of the plurality of layers is disclosed. The bottom layer is a transparent or dyed polyethylene terephthalate film substrate. By the above-mentioned manufacturing method, the cation solution and the anion aqueous solution can be controlled according to the required number of layers, the arrangement and the adsorption thickness. Program and time to get the expected structure. The soaking time can range from ten minutes to twelve hours, and preferably from twenty minutes to two hours. Preferably, the aqueous cationic solution is an aqueous solution of polyalylamine hydrochloride (PAH) or poly diallydimethylammonium chloride (PDDA), and the aqueous anionic solution is preferably polyacrylic acid. Poly acylic acid (PAA) or an aqueous solution of sodium polystyrene sulfonate (PSS). The polyacrylamide hydrogen chloride or polydimethyldiallylammonium chloride cation aqueous solution and the polyacrylic acid or sodium polystyrene sulfonate anion aqueous solution can be arbitrarily matched to form a plurality of different compositions, layers and arrangements. Layer self-assembled film structure. Then, using the above-described method for producing a polypyrrole conductive polymer layer, a polypyrrole conductive polymer layer having a certain thickness is formed on a surface of a plurality of self-assembled film structures having a predetermined structure, wherein the plurality of self-assembled films The thickness of the structure and the polypyrrole conductive polymer layer may be from 50 nm to 1000 nm, preferably from 100 nm to 300 nm, and the thickness of the polyethylene terephthalate film substrate is not particularly limited. Adjusted to the actual needs.
參照第三圖所揭露之導電高分子表面聚合示意圖。圖示中選用聚吡咯做為複數層自組裝薄膜表面上的導電性高分子層，首先以濃度為1M的鹽酸(HCl)水溶液作為掺雜物，並加入5-10wt%的氯化鐵(Ferric chloride,FeCl3 )做為催化劑，均勻攪拌後，置入具有已置備有複數層自組裝薄膜的聚對苯二甲酸乙二酯薄膜基材，最後加入與氯化鐵以1mmole比2.2mmole比例添加的聚吡咯單體，並進行四小時的聚合反應。待聚合完成後，再利用去離子水清洗以移除表面殘留的未反應物，完成後則進行乾燥，即可得到具有如同本發明所揭露之具導電性與可撓性的透明聚合物薄膜。Referring to the third embodiment, the schematic diagram of the surface polymerization of the conductive polymer is disclosed. In the figure, polypyrrole is used as the conductive polymer layer on the surface of the multi-layer self-assembled film. First, a 1M hydrochloric acid (HCl) aqueous solution is used as a dopant, and 5-10 wt% of ferric chloride is added (Ferric Chloride, FeCl 3 ) as a catalyst, uniformly stirred, placed into a polyethylene terephthalate film substrate having a plurality of layers of self-assembled film, and finally added with iron chloride at a ratio of 1 mmole to 2.2 mmole The polypyrrole monomer was subjected to a polymerization reaction for four hours. After the polymerization is completed, it is washed with deionized water to remove unreacted materials remaining on the surface, and dried after completion to obtain a transparent polymer film having conductivity and flexibility as disclosed in the present invention.
同時，在本發明的導電高分子表面聚合過程中，可以進行不同種類的摻雜物的替換，其中例如前述之濃度為1M的鹽酸(HCl)水溶液，亦可以使用硫酸(H2 SO4 )水溶液加以代替。再者，為了提高導電性高分子層的透明度，可以在聚吡咯的聚合過程中，添加聚苯乙烯磺酸鈉(Poly sodium 4-styrenesulfonate)對聚吡咯單體進行捕抓，以減少聚吡咯的吸附量，進而提高導電性高分子薄膜整體的透明度。其中聚苯乙烯磺酸鈉與聚吡咯單體係以2:1至0.1:1的比例範圍進行添加，較佳的情況下係以0.5:1至1:1的比例範圍進行添加。同時，鹵化無機鹽類的添加亦可以達到相同的提高導電性高分子層透明度之效果。其中，以氯化鈉(NaCl)、氯化鋰(LiCl)、氯化鉀(KCl)以及溴化鉀(KBr)效果為最佳。鹵化無機鹽類與聚吡咯單體係以1:1至0.1:1的比例範圍進行添加，較佳的情況下係為以0.5:1的比例進行添加，即可達到有效增加導電性高分子層透明度的效果。Meanwhile, in the surface polymerization process of the conductive polymer of the present invention, substitution of different kinds of dopants may be performed, wherein, for example, the aforementioned hydrochloric acid (HCl) aqueous solution having a concentration of 1 M, an aqueous solution of sulfuric acid (H 2 SO 4 ) may also be used. Replace it. Furthermore, in order to increase the transparency of the conductive polymer layer, polypyrrole monomer may be trapped during the polymerization of polypyrrole by adding poly sodium 4-styrenesulfonate to reduce polypyrrole. The amount of adsorption further increases the transparency of the entire conductive polymer film. The sodium polystyrene sulfonate and the polypyrrole single system are added in a ratio ranging from 2:1 to 0.1:1, preferably in a ratio ranging from 0.5:1 to 1:1. At the same time, the addition of halogenated inorganic salts can also achieve the same effect of improving the transparency of the conductive polymer layer. Among them, sodium chloride (NaCl), lithium chloride (LiCl), potassium chloride (KCl), and potassium bromide (KBr) are most effective. The halogenated inorganic salt and the polypyrrole single system are added in a ratio ranging from 1:1 to 0.1:1, preferably in a ratio of 0.5:1, to effectively increase the conductive polymer layer. The effect of transparency.
本發明使用電子顯微鏡、原子力顯微鏡、化學分析電子光譜儀、膜厚儀、透光度儀以及四點探針儀進行複數層自組裝薄膜結構之表面型態鑑定、組成鑑定以及導電性測試，其測試及結果如下：The invention uses an electron microscope, an atomic force microscope, a chemical analysis electronic spectrometer, a film thickness meter, a transmittance meter and a four-point probe instrument to perform surface type identification, composition identification and conductivity test of a plurality of self-assembled thin film structures, and the test thereof And the results are as follows:
使用氧電漿預先處理基材表面，並以聚丙烯胺氯化氫與聚苯乙烯磺酸鈉交替形成複數層自組裝薄膜結構，最外層為聚丙烯胺氯化氫與聚苯乙烯磺酸鈉陽離子層，最後於複數層自組裝薄膜結構上形成聚吡咯的表面聚合層。The surface of the substrate is pretreated with oxygen plasma, and a plurality of layers of self-assembled film structure are alternately formed by polyacrylamide hydrogen chloride and sodium polystyrene sulfonate, and the outermost layer is a polyacrylamide hydrogen chloride and a polystyrene sulfonate sodium cation layer, and finally A surface polymerization layer of polypyrrole is formed on the plurality of self-assembled film structures.
使用氧電漿預先處理基材表面，並以聚二甲基二烯丙基氯化銨與聚苯乙烯磺酸鈉交替形成複數層自組裝薄膜結構，最外層為聚二甲基二烯丙基氯化銨陽離子層，最後於複數層自組裝薄膜結構上形成聚吡咯的表面聚合層。The surface of the substrate is pretreated with oxygen plasma, and a plurality of layers of self-assembled film structure are alternately formed by using polydimethyldiallylammonium chloride and sodium polystyrene sulfonate, and the outermost layer is polydimethyldiallyl. The ammonium chloride cation layer finally forms a surface polymerization layer of polypyrrole on the plurality of self-assembled film structures.
使用氧電漿預先處理基材表面，並以聚二甲基二烯丙基氯化銨與聚丙烯酸交替形成複數層自組裝薄膜結構，最外層為聚二甲基二烯丙基氯化銨陽離子層，最後於複數層自組裝薄膜結構上形成聚吡咯的表面聚合層。The surface of the substrate is pretreated with oxygen plasma, and a plurality of layers of self-assembled film structure are formed by alternately forming polydimethyldiallylammonium chloride and polyacrylic acid, and the outermost layer is polydimethyldiallyl ammonium chloride cation. The layer finally forms a surface polymerization layer of polypyrrole on the plurality of self-assembled film structures.
使用氧電漿預先處理基材表面，並以聚丙烯胺氯化氫與聚丙烯酸交替形成複數層自組裝薄膜結構，最外層為聚丙烯胺氯化氫陰離子層，最後於複數層自組裝薄膜結構上形成聚吡咯的表面聚合層。The surface of the substrate is pretreated with oxygen plasma, and a plurality of self-assembled thin film structures are formed by alternating polyacrylamide hydrogen chloride and polyacrylic acid. The outermost layer is a polyacrylamide hydrogen chloride anion layer, and finally a polypyrrole is formed on the plurality of self-assembled thin film structures. Surface polymerization layer.
使用氧電漿預先處理基材表面，並以聚丙烯胺氯化氫與聚苯乙烯磺酸鈉交替形成複數層自組裝薄膜結構，最外層為聚丙烯胺氯化氫與聚苯乙烯磺酸鈉陽離子層，最後於複數層自組裝薄膜結構上形成聚吡咯的表面聚合層。The surface of the substrate is pretreated with oxygen plasma, and a plurality of layers of self-assembled film structure are alternately formed by polyacrylamide hydrogen chloride and sodium polystyrene sulfonate, and the outermost layer is a polyacrylamide hydrogen chloride and a polystyrene sulfonate sodium cation layer, and finally A surface polymerization layer of polypyrrole is formed on the plurality of self-assembled film structures.
使用氧電漿預先處理基材表面，並以聚二甲基二烯丙基氯化銨與聚苯乙烯磺酸鈉交替形成複數層自組裝薄膜結構，最外層為聚二甲基二烯丙基氯化銨陽離子層，最後於複數層自組裝薄膜結構上形成聚吡咯的表面聚合層。The surface of the substrate is pretreated with oxygen plasma, and a plurality of layers of self-assembled film structure are alternately formed by using polydimethyldiallylammonium chloride and sodium polystyrene sulfonate, and the outermost layer is polydimethyldiallyl. The ammonium chloride cation layer finally forms a surface polymerization layer of polypyrrole on the plurality of self-assembled film structures.
使用氧電漿預先處理基材表面，並以聚二甲基二烯丙基氯化銨與聚丙烯酸交替形成複數層自組裝薄膜結構，最外層為聚二甲基二烯丙基氯化銨陽離子層，最後於複數層自組裝薄膜結構上形成聚吡咯的表面聚合層。The surface of the substrate is pretreated with oxygen plasma, and a plurality of layers of self-assembled film structure are formed by alternately forming polydimethyldiallylammonium chloride and polyacrylic acid, and the outermost layer is polydimethyldiallyl ammonium chloride cation. The layer finally forms a surface polymerization layer of polypyrrole on the plurality of self-assembled film structures.
使用氧電漿預先處理基材表面，並以聚丙烯胺氯化氫與聚丙烯酸交替形成複數層自組裝薄膜結構，最外層為聚丙烯胺氯化氫陰離子層，最後於複數層自組裝薄膜結構上形成聚吡咯的表面聚合層。The surface of the substrate is pretreated with oxygen plasma, and a plurality of self-assembled thin film structures are formed by alternating polyacrylamide hydrogen chloride and polyacrylic acid. The outermost layer is a polyacrylamide hydrogen chloride anion layer, and finally a polypyrrole is formed on the plurality of self-assembled thin film structures. Surface polymerization layer.
使用氧電漿預先處理基材表面，並以聚丙烯胺氯化氫與聚苯乙烯磺酸鈉交替形成複數層自組裝薄膜結構，最外層之表面為聚丙烯胺氯化氫與聚苯乙烯磺酸鈉陽離子層。並以1：1、1：0.7、1：0.5之聚吡咯與聚苯乙烯磺酸鈉比例進行聚苯乙烯磺酸鈉的添加，以降低聚吡咯於基材的附著量。The surface of the substrate is pretreated with oxygen plasma, and a plurality of layers of self-assembled film structure are alternately formed by polyacrylamide hydrogen chloride and sodium polystyrene sulfonate. The outermost surface is a polyacrylamide hydrogen chloride and sodium polystyrene sulfonate cationic layer. . The addition of sodium polystyrene sulfonate was carried out at a ratio of polypyrrole to sodium polystyrene sulfonate of 1:1, 1:0.7, 1:0.5 to reduce the adhesion of polypyrrole to the substrate.
使用氧電漿預先處理基材表面，並以聚丙烯胺氯化氫與聚苯乙烯磺酸鈉交替形成複數層自組裝薄膜結構，最外層之表面為聚丙烯胺氯化氫與聚苯乙烯磺酸鈉陽離子層。並以1：0.5之比例添加氯化鈉(NaCl)、氯化鋰(LiCl)、氯化鉀(KCl)及溴化鉀(KBr)，以降低聚吡咯於基材的附著量。The surface of the substrate is pretreated with oxygen plasma, and a plurality of layers of self-assembled film structure are alternately formed by polyacrylamide hydrogen chloride and sodium polystyrene sulfonate. The outermost surface is a polyacrylamide hydrogen chloride and sodium polystyrene sulfonate cationic layer. . Sodium chloride (NaCl), lithium chloride (LiCl), potassium chloride (KCl) and potassium bromide (KBr) were added in a ratio of 1:0.5 to reduce the amount of polypyrrole attached to the substrate.
雖本發明以一較佳實施例揭露如上，但並非用以限定本發明實施之範圍。任何熟習此項技藝者，在不脫離本發明之精神和範圍內，當可作些許之更動與潤飾，即凡依本發明所做的均等變化與修飾，應為本發明專利範圍所涵蓋，其界定應以申請專利範圍為準。The present invention has been described above in terms of a preferred embodiment, and is not intended to limit the scope of the invention. Any change and modification that may be made in accordance with the present invention, which is within the spirit and scope of the present invention, should be covered by the scope of the present invention. The definition shall be based on the scope of the patent application.
第一圖 導電性高分子薄膜製造流程Figure 1 Conductive polymer film manufacturing process
第二圖 複數層自組裝薄膜結構Figure 2 Complex layer self-assembled film structure
第三圖 導電高分子表面聚合示意圖Figure 3 Schematic diagram of surface polymerization of conductive polymer
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