TWI427644B - Method for making transparent conductive film - Google Patents
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- TWI427644B TWI427644B TW100120521A TW100120521A TWI427644B TW I427644 B TWI427644 B TW I427644B TW 100120521 A TW100120521 A TW 100120521A TW 100120521 A TW100120521 A TW 100120521A TW I427644 B TWI427644 B TW I427644B
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Description
本發明係關於一種奈米材料備製技術，尤其是一種透明導電膜結構及其製造方法。The present invention relates to a nanomaterial preparation technology, and more particularly to a transparent conductive film structure and a method of fabricating the same.
透明導電膜(transparent conductive films)在觸控面板、液晶顯示器、太陽能電池、有機發光二極體等產業上均扮演著相當重要的角色。目前工業上使用於製造透明導電膜的材料一般為銦錫氧化物(indium tin oxide,ITO)，其係可使該透明導電膜具備低電阻及高光線穿透率之特性。然而，ITO具有彎曲性低(脆性高)及其所使用的銦金屬原料產量稀少的問題存在。Transparent conductive films play an important role in industries such as touch panels, liquid crystal displays, solar cells, and organic light-emitting diodes. The material currently used in the manufacture of a transparent conductive film in the industry is generally indium tin oxide (ITO), which enables the transparent conductive film to have low resistance and high light transmittance. However, ITO has a problem that the flexibility is low (high brittleness) and the production of indium metal raw materials used is scarce.
過去二十幾年期間，奈米碳管已經廣泛地被研究用來取代ITO，成為具有相當發展潛力之透明導電膜材料。從研究結果顯示，奈米碳管透明導電膜的導電特性除決定於奈米碳管的外殼層數(sheet numbers)、奈米碳管的合成方法和所形成的透明導電膜的表面型態外，其後處理程序往往是導電特性提升的重要關鍵。常用於製造奈米碳管透明導電膜有數種方法，包括過濾法(filtration)、噴塗法(airbrushing)、浸沾塗佈法(dip coating)及繞線棒塗佈法(wire-wound rod coating)等等。然而，上述方法所製造出的奈米碳管的透明導電膜，其表面強度相當薄弱，原因是奈米碳管間及其所形成的導電層與透明基材間僅存在很微弱的吸引力，如此脆弱的薄膜不利於後處理程序，使薄膜導電特性不易提升，限制了奈米碳管透明導電膜的實際應用上的發展。In the past two decades, nanocarbon tubes have been extensively studied to replace ITO, becoming a transparent conductive film material with considerable development potential. From the research results, the conductive properties of the carbon nanotube transparent conductive film are determined by the sheet number of the carbon nanotubes, the synthesis method of the carbon nanotubes, and the surface type of the formed transparent conductive film. Then, the processing procedure is often the key to the improvement of the conductive characteristics. There are several methods commonly used in the manufacture of carbon nanotube transparent conductive films, including filtration, airbrushing, dip coating, and wire-wound rod coating. and many more. However, the transparent conductive film of the carbon nanotube produced by the above method has a relatively weak surface strength because the carbon nanotubes and the conductive layer formed therebetween and the transparent substrate have only a weak attraction. Such a fragile film is not conducive to the post-treatment process, so that the conductive properties of the film are not easily improved, which limits the practical application of the carbon nanotube transparent conductive film.
近年來，利用奈米銀絲製作透明導電膜也展現出優異的透明性及導電性。然而，如同奈米碳管透明導電膜一樣，機械物性仍有待提升。圖1為傳統透明導電膜之剖面示意圖。少數已公開的研究結果，利用黏著劑提升透明導電膜的強度，藉以改善透明導電膜的機械強度，但因導電材料(如奈米碳管或銀絲等)間及其所形成的導電層5與透明基材1間的連結處會引起較高的阻抗，造成整體薄膜導電度下降。In recent years, the use of nano-silver to produce a transparent conductive film also exhibits excellent transparency and electrical conductivity. However, like the carbon nanotube transparent conductive film, mechanical properties still need to be improved. 1 is a schematic cross-sectional view of a conventional transparent conductive film. A few published research results have used adhesives to increase the strength of transparent conductive films, thereby improving the mechanical strength of transparent conductive films, but due to conductive layers (such as carbon nanotubes or silver wires) and conductive layers formed therebetween The junction with the transparent substrate 1 causes a higher impedance, resulting in a decrease in the overall film conductivity.
此外，透明導電膜的表面阻抗(sheet resistance)與光線穿透率(transmittance)，兩者通常無法同時兼顧。減少導電材料在導電層5中的含量，雖然會造成光線穿透率上升，但同時也會造成表面阻抗的增加。對於奈米碳管而言，在光線穿透率超過70%以上的範圍，其光線穿透率微幅的增加會使薄膜的表面阻抗電阻產生極大的上升變化。因此，要製作高穿透率的透明導電膜是相當不容易的事情。再者，雖然可藉由正型摻雜(p-type doping)模式，明顯地提升透明導電膜的導電性，但對於光線穿透率的增加及機械性質不佳的問題，仍沒有正面的幫助。In addition, the surface resistance of the transparent conductive film and the transmittance of the light are generally not at the same time. Reducing the content of the conductive material in the conductive layer 5, although causing an increase in light transmittance, also causes an increase in surface impedance. For the carbon nanotubes, in the range where the light transmittance exceeds 70%, the slight increase in the light transmittance causes a large increase in the surface resistance resistance of the film. Therefore, it is quite difficult to produce a transparent conductive film having a high transmittance. Furthermore, although the conductivity of the transparent conductive film can be remarkably improved by the p-type doping mode, there is still no positive help for the increase of the light transmittance and the poor mechanical properties. .
鑑於目前的透明導電膜製作過程中，在導電層中減少導電材料的含量，無法使光線穿透率有效提升及造成表面阻抗增加，同時存在後處理程序上的問題等諸多缺點及限制，本發明係提供一種透明導電膜結構及其製造方法，其中在導電層表面上塗佈一透明耐磨層，形成一透明導電膜結構，藉由在透明耐磨層厚度之控制，有效提升整體透明導電薄膜的光線穿透率(transmittance)及抗刮性(anti-scratch)。In view of the current transparent conductive film fabrication process, the content of the conductive material is reduced in the conductive layer, the light transmittance is not effectively improved, and the surface impedance is increased, and there are many disadvantages and limitations such as problems in the post-processing procedure, and the present invention Providing a transparent conductive film structure and a manufacturing method thereof, wherein a transparent wear-resistant layer is coated on the surface of the conductive layer to form a transparent conductive film structure, and the transparent transparent conductive film is effectively improved by controlling the thickness of the transparent wear-resistant layer Light transmission (transmittance) and anti-scratch (anti-scratch).
本發明所提供的技術手段在於提供一種透明導電膜結構之製造方法，其係包括有下列步驟：提供一基材；將該基材浸入一導電材料塗液，以浸沾塗佈、旋轉塗佈、繞線棒塗佈、過濾或是其他塗佈方式於該基材表面形成一導電層；對該導電層進行一後處理程序，形成一經後處理的導電層；於該經後處理的導電層表面上塗佈一層透明耐磨塗液，藉由烘烤將塗液中溶劑去除，形成一透明耐磨層，以製得該透明導電膜結構。The technical means provided by the present invention is to provide a method for manufacturing a transparent conductive film structure, which comprises the steps of: providing a substrate; dipping the substrate into a conductive material coating solution, dip coating, spin coating Forming a conductive layer on the surface of the substrate by wire coating, filtering or other coating methods; performing a post-processing procedure on the conductive layer to form a post-treated conductive layer; and the post-treated conductive layer The surface is coated with a transparent wear-resistant coating liquid, and the solvent in the coating liquid is removed by baking to form a transparent wear-resistant layer to obtain the transparent conductive film structure.
較佳的，該透明耐磨層的厚度介於約50奈米至500奈米之間。Preferably, the transparent wear layer has a thickness of between about 50 nanometers and 500 nanometers.
較佳的，該透明耐磨層可為兩層結構，即在該透明耐磨層與導電層間更設置有一附屬透明耐磨層，且該附屬透明耐磨層的厚度介於約50奈米至500奈米之間。Preferably, the transparent wear layer may have a two-layer structure, that is, an auxiliary transparent wear layer is further disposed between the transparent wear layer and the conductive layer, and the thickness of the subsidiary transparent wear layer is about 50 nm to Between 500 nm.
較佳的，所述之透明導電膜結構之製造方法中，該基材係包含有玻璃、聚丙烯酸酯(polyacrylate)、聚碳酸酯(polycarbonate)、聚乙烯(polyethylene)、聚乙烯對苯二甲酸酯(polyethylene terephthalate)或三醋酸纖維素(triacetyl cellulose)等材料。Preferably, in the manufacturing method of the transparent conductive film structure, the substrate comprises glass, polyacrylate, polycarbonate, polyethylene, polyethylene terephthalic. A material such as polyethylene terephthalate or triacetyl cellulose.
較佳的，所述之透明導電膜結構之製造方法，其中該導電材料係包含奈米碳管、銀絲或其等材料之組合。奈米碳管係單壁奈米碳管、雙壁奈米碳管或多壁奈米碳管，更佳的，該奈米碳管為單壁奈米碳管或雙壁奈米碳管。Preferably, the method for manufacturing a transparent conductive film structure, wherein the conductive material comprises a combination of a carbon nanotube, a silver wire or the like. The carbon nanotubes are single-walled carbon nanotubes, double-walled carbon nanotubes or multi-walled carbon nanotubes. More preferably, the carbon nanotubes are single-walled carbon nanotubes or double-walled carbon nanotubes.
較佳的，所述之透明導電膜結構之製造方法，其中該導電材料塗液係由導電材料、界面活性劑及去離子水混合製備而成。Preferably, the method for manufacturing a transparent conductive film structure, wherein the conductive material coating liquid is prepared by mixing a conductive material, a surfactant, and deionized water.
較佳的，所述之透明導電膜結構之製造方法，其中該後處理程序係將該含有導電層的基材浸漬於一後處理溶液中。Preferably, the method for manufacturing a transparent conductive film structure, wherein the post-treatment procedure is to immerse the substrate containing the conductive layer in a post-treatment solution.
較佳的，所述之透明導電膜結構之製造方法，其中該後處理溶液係包含有硫酸、鹽酸、硝酸、過氧化氫、氫氯金酸(hydrogen tetrachloroaurate)、氯化亞碸(thionyl chloride)之溶液，或是上述材料之混合溶液，但並不以此為限。Preferably, the method for manufacturing a transparent conductive film structure, wherein the post-treatment solution comprises sulfuric acid, hydrochloric acid, nitric acid, hydrogen peroxide, hydrogen tetrachloroaurate, thionyl chloride The solution, or a mixed solution of the above materials, is not limited thereto.
較佳的，所述之透明導電膜結構之製造方法，其中該透明耐磨塗液係包含有透明耐磨樹脂和溶劑。Preferably, the method for manufacturing a transparent conductive film structure, wherein the transparent wear-resistant coating liquid comprises a transparent wear-resistant resin and a solvent.
較佳的，所述之透明導電膜結構之製造方法，其中該透明耐磨樹脂係包含有熱硬化樹脂或光硬化樹脂；其中該熱硬化樹脂係為四甲氧基矽烷(Tetramethyloxysilane)、四乙氧基矽烷(Tetraethyloxysilane，TEOS)、聚乙氧基矽烷(polyethoxysiloxane，PES)、壓克力樹脂(acrylic resin)、聚胺酯樹脂(polyurethane resin，PU resin)或環氧樹脂(epoxy resin)等材料，或上述材料之混合物；其中該光硬化樹脂係包含有單體及寡聚物。Preferably, the transparent conductive film structure comprises a thermosetting resin or a photocurable resin; wherein the thermosetting resin is Tetramethyloxysilane, Tetraethyl a material such as Tetraethyloxysilane (TEOS), polyethoxysiloxane (PES), acrylic resin, polyurethane resin (PU resin) or epoxy resin, or a mixture of the above materials; wherein the photohardenable resin comprises a monomer and an oligomer.
較佳的，所述之透明導電膜結構之製造方法，其中該單體之組成材料係包含有丙烯酸異丁酯(isobutyl acrylate)、丙烯酸2-乙基己酯(2-ethylhexyl acrylate)、1,6-六二醇二丙烯酸酯(1,6-hexanediol diacrylate，HDDA)、二丙二醇二丙烯酸酯(tripropylene glycol diacrylate，TPG)、三羥甲基丙烷三丙烯酸酯(trimethylolpropane triacrylate，TMPTA)、二異戊四醇六丙烯酸酯(dipentaerythritol pentaacrylate，DPHPA)、季戊四醇三丙烯酸(pentaerythritol triacrylate，PETA)、二季戊四醇六丙烯酸酯(dipentaerythritol hexaacrylate，DPHA)或上述材料之混合物；其中該寡聚物之組成材料係包含有胺酯(甲基)丙烯酸酯寡聚物(urethane(meth)acrylate oligomer)、聚酯(甲基)丙烯酸酯寡聚物(polyester(meth)acrylate oligomer)、環氧(甲基)丙烯酸酯寡聚物(epoxy(meth)acrylate oligomer)或上述材料之混合物。Preferably, the method for manufacturing a transparent conductive film structure, wherein the constituent material of the monomer comprises isobutyl acrylate, 2-ethylhexyl acrylate, 1, 1,6-hexanediol diacrylate (HDDA), tripropylene glycol diacrylate (TPG), trimethylolpropane triacrylate (TMPTA), diisoamyl Dipentaerythritol pentaacrylate (DPHPA), pentaerythritol triacrylate (PETA), dipentaerythritol hexaacrylate (DPHA) or a mixture thereof; wherein the oligomeric constituent material comprises Urethane (meth) acrylate oligomer, polyester (meth) acrylate oligomer, epoxy (meth) acrylate oligomer Epoxy (meth) acrylate oligomer or a mixture of the above materials.
較佳的，所述之透明導電膜結構之製造方法，其中該透明耐磨塗液所包含之溶劑係包含有異丙醇、丁酮、甲基異丁基酮、醋酸乙酯、醋酸丁酯、甲苯、環己酮、甲醇、乙醇、丙二醇***醋酸酯、水或上述材料之混合物。Preferably, the method for manufacturing a transparent conductive film structure, wherein the transparent wear-resistant coating liquid comprises a solvent comprising isopropyl alcohol, methyl ethyl ketone, methyl isobutyl ketone, ethyl acetate, butyl acetate , toluene, cyclohexanone, methanol, ethanol, propylene glycol ethyl ether acetate, water or a mixture of the above materials.
本發明所提供的技術手段在於提供一種透明導電膜結構，其係由一種如前所述之透明導電膜結構之製造方法所製成。The technical means provided by the present invention is to provide a transparent conductive film structure which is produced by a method for manufacturing a transparent conductive film structure as described above.
本發明所提供之透明導電膜結構及其製造方法，可以獲得的優點和功效增進有：The transparent conductive film structure provided by the present invention and the manufacturing method thereof can be improved in advantages and effects:
1.本發明所製造出的高導電性及高光線穿透率的透明導電膜結構，其抗刮性、光線穿透率及導電性質，藉由添加該透明耐磨層於該導電層表面產生明顯的改善功效，隨著透明耐磨層厚度增加，其抗刮性質也增強。1. The highly conductive and high light transmittance transparent conductive film structure produced by the invention has scratch resistance, light transmittance and conductive property, and is formed on the surface of the conductive layer by adding the transparent wear resistant layer. Significant improvement in efficacy, as the thickness of the transparent wear layer increases, its scratch resistance is also enhanced.
2.當該透明耐磨層的厚度達較佳厚度時介於50奈米至500奈米，透明導電膜的光線穿透率快速的上升，而表面阻抗僅些微增加。因此，在相同光線穿透率下，本發明之透明導電膜結構具有較低之表面阻抗；特別地，當光線穿透率大於80%時，其透明導電膜的導電度大幅提升，呈現出較佳的導電性質。2. When the thickness of the transparent wear-resistant layer is between 50 nm and 500 nm, the light transmittance of the transparent conductive film rises rapidly, and the surface resistance increases only slightly. Therefore, the transparent conductive film structure of the present invention has a low surface resistance at the same light transmittance; in particular, when the light transmittance is greater than 80%, the conductivity of the transparent conductive film is greatly improved, showing a comparative Good conductive properties.
本發明利用該透明耐磨層與導電層，所提供的高導電性、高光線穿透率及高抗刮性，可以改良習用透明導電膜的限制及缺點，可廣泛應用於觸控面板、液晶顯示器、太陽能電池、有機發光二極體等產業上。The transparent wear-resistant layer and the conductive layer provide high conductivity, high light transmittance and high scratch resistance, and can improve the limitations and disadvantages of the conventional transparent conductive film, and can be widely applied to touch panels and liquid crystals. Display, solar cells, organic light-emitting diodes and other industries.
本發明將由下列的實施例作進一步的說明，熟知本發明之技藝者，可以做些許的改良與修飾，但不脫離本發明的範疇。The invention will be further clarified by the following examples, and those skilled in the art can make some modifications and changes without departing from the scope of the invention.
請參見圖2及圖3所示，為本發明一較佳實施例之製造方法和透明導電膜結構。首先提供一透明基材10(S1)，此透明基材10為具有透光性之基材，其組成材料可以是玻璃、聚丙烯酸酯(polyacrylate)、聚碳酸酯(polycarbonate)、聚乙烯(polyethylene)、聚乙烯對苯二甲酸酯(polyethylene terephthalate)或三醋酸纖維素(triacetyl cellulose)等材料。Referring to FIG. 2 and FIG. 3, a manufacturing method and a transparent conductive film structure according to a preferred embodiment of the present invention are shown. First, a transparent substrate 10 (S1) is provided. The transparent substrate 10 is a light transmissive substrate, and the constituent material thereof may be glass, polyacrylate, polycarbonate, or polyethylene. ), polyethylene terephthalate or triacetyl cellulose.
接著進行透明基材的前處理(S2)，其係以清水沖洗透明基材10，並將洗淨後的透明基材10浸泡於一鹼性溶液中，並在攝氏溫度50至60度的環境下靜置1至5分鐘。然後將透明基材10從鹼性溶液中取出，並使透明基材10乾燥後備用。Next, a pretreatment (S2) of the transparent substrate is performed, which rinses the transparent substrate 10 with water, and immerses the washed transparent substrate 10 in an alkaline solution at an environment temperature of 50 to 60 degrees Celsius. Let it sit for 1 to 5 minutes. The transparent substrate 10 is then taken out of the alkaline solution, and the transparent substrate 10 is dried and ready for use.
於透明基材10乾燥後，以浸沾式塗佈(dip coating)、旋轉塗佈(spin coating)、繞線棒塗佈(wire-wound rod coating)、狹縫式塗佈(slot coating)或是凹版塗佈(gravure coating)等方式，塗佈一導電材料塗液於透明基材10上(S3)，此導電材料塗液中混合有一導電材料、界面活性劑及去離子水。其中該導電材料係包含奈米碳管、銀絲等。奈米碳管係包含有單壁奈米碳管、雙壁奈米碳管或多壁奈米碳管，更佳的，該奈米碳管為單壁奈米碳管或是雙壁奈米碳管。界面活性劑可以是十二烷基硫酸鈉(sodium dodecylsulphate)、十二烷基苯磺酸鈉(sodium dodecylbenzenesulfonate)、十二烷基硫酸鋰(lithium dodecylsulphate)、膽酸鈉(sodium cholate)、采酮-X100(Triton-X100)或及其混合物。After the transparent substrate 10 is dried, by dip coating, spin coating, wire-wound rod coating, slot coating or It is a gravure coating method, and a conductive material coating liquid is applied on the transparent substrate 10 (S3), and the conductive material coating liquid is mixed with a conductive material, a surfactant, and deionized water. Wherein the conductive material comprises a carbon nanotube, a silver wire or the like. The carbon nanotube system comprises a single-walled carbon nanotube, a double-walled carbon nanotube or a multi-walled carbon nanotube. More preferably, the carbon nanotube is a single-walled carbon nanotube or a double-walled nanotube. Carbon tube. The surfactant may be sodium dodecylsulphate, sodium dodecylbenzenesulfonate, lithium dodecylsulphate, sodium cholate, and ketol -X100 (Triton-X100) or a mixture thereof.
然後，將此塗佈有導電材料塗液之透明基材10置於80℃至100℃烘箱中烘烤5至10分鐘，使去離子水從導電材料塗液中揮發，形成導電層20於透明基材10上。Then, the transparent substrate 10 coated with the conductive material coating liquid is baked in an oven at 80 ° C to 100 ° C for 5 to 10 minutes to volatilize deionized water from the conductive material coating liquid to form the conductive layer 20 in a transparent manner. On the substrate 10.
將上述製備之具有導電層之基材浸漬於一後處理溶液中5分鐘至2個小時之間，進行後處理程序，最後用去離子水沖洗乾淨並置入烘箱中以60℃烘乾(S4)。該後處理溶液可以是硫酸、鹽酸、硝酸、過氧化氫、氫氯金酸(hydrogen tetrachloroaurate)、氯化亞碸(thionyl chloride)等溶液，或是上述材料之混合溶液。The substrate prepared with the conductive layer prepared above is immersed in a post-treatment solution for 5 minutes to 2 hours, subjected to a post-treatment procedure, finally rinsed with deionized water and placed in an oven to be dried at 60 ° C (S4 ). The post-treatment solution may be a solution of sulfuric acid, hydrochloric acid, nitric acid, hydrogen peroxide, hydrogen tetrachloroaurate, thionyl chloride or the like, or a mixed solution of the above materials.
然後，將上述後處理過後之薄膜，於該導電層20上，以浸沾式塗佈(dip coating)、旋轉塗佈(spin coating)、繞線棒塗佈(wire-wound rod coating)、狹縫式塗佈(slot coating)或是凹版塗佈(gravure coating)等方式，塗佈一層透明耐磨塗液，藉由烘烤將塗液中溶劑去除，並藉由熱硬化或是紫外光硬化等方式，形成一透明耐磨層30，以製得透明導電膜(S5)。其中該透明耐磨塗液係由透明耐磨樹脂和溶劑所組成。透明耐磨樹脂係使用熱硬化樹脂或光硬化樹脂，其中熱硬化樹脂可以是四甲氧基矽烷(Tetramethyloxysilane)、四乙氧基矽烷(Tetraethyloxysilane，TEOS)、聚乙氧基矽烷(polyethoxysiloxane，PES)、壓克力樹脂(acrylic resin)、聚胺酯樹脂(polyurethane resin，PU resin)或環氧樹脂(epoxy resin)等材料，或是上述材料之混合物。而光硬化樹脂則包含有單體及寡聚物，單體之組成材料可以是丙烯酸異丁酯(isobutyl acrylate)、丙烯酸2-乙基己酯(2-ethylhexyl acrylate)、1,6-六二醇二丙烯酸酯(1,6-hexanediol diacrylate，HDDA)、二丙二醇二丙烯酸酯(tripropylene glycol diacrylate，TPG)、三羥甲基丙烷三丙烯酸酯(trimethylolpropane triacrylate，TMPTA)、二異戊四醇六丙烯酸酯(dipentaerythritol pentaacrylate，DPHPA)、季戊四醇三丙烯酸(pentaerythritol triacrylate，PETA)、二季戊四醇六丙烯酸酯(dipentaerythritol hexaacrylate，DPHA)或上述材料之混合物。而寡聚物之組成材料則可以是胺酯(甲基)丙烯酸酯寡聚物(urethane (meth)acrylate oligomer)、聚酯(甲基)丙烯酸酯寡聚物(polyester (meth)acrylate oligomer)、環氧(甲基)丙烯酸酯寡聚物(epoxy (meth)acrylate oligomer)或上述材料之混合物。其中該透明耐磨塗液所包含之溶劑可以是異丙醇、丁酮、甲基異丁基酮、醋酸乙酯、醋酸丁酯、甲苯、環己酮、甲醇、乙醇、丙二醇***醋酸酯、水或上述材料之混合物。Then, the post-treated film is applied to the conductive layer 20 by dip coating, spin coating, wire-wound rod coating, and narrow coating. Slot coating or gravure coating, coating a transparent wear-resistant coating solution, removing the solvent in the coating solution by baking, and hardening by heat or ultraviolet light Alternatively, a transparent wear-resistant layer 30 is formed to produce a transparent conductive film (S5). The transparent wear-resistant coating liquid is composed of a transparent wear-resistant resin and a solvent. The transparent wear resistant resin is a thermosetting resin or a photocurable resin, wherein the thermosetting resin may be Tetramethyloxysilane, Tetraethyloxysilane (TEOS), or polyethoxysiloxane (PES). , a material such as an acrylic resin, a polyurethane resin (PU resin) or an epoxy resin, or a mixture of the above materials. The photohardenable resin comprises a monomer and an oligomer, and the constituent material of the monomer may be isobutyl acrylate, 2-ethylhexyl acrylate, 1,6-six-two. 1,6-hexanediol diacrylate (HDDA), tripropylene glycol diacrylate (TPG), trimethylolpropane triacrylate (TMPTA), diisoamyltetraol hexaacrylic acid Dipentaerythritol pentaacrylate (DPHPA), pentaerythritol triacrylate (PETA), dipentaerythritol hexaacrylate (DPHA) or a mixture of the above. The constituent material of the oligomer may be an urethane (meth) acrylate oligomer, a polyester (meth) acrylate oligomer, or a polyester (meth) acrylate oligomer. Epoxy (meth) acrylate oligomer or a mixture of the above materials. The solvent contained in the transparent wear-resistant coating liquid may be isopropanol, methyl ethyl ketone, methyl isobutyl ketone, ethyl acetate, butyl acetate, toluene, cyclohexanone, methanol, ethanol, propylene glycol ethyl ether acetate, Water or a mixture of the above materials.
請參見圖4，本發明另一較佳實施例與前述實施例製作過程類似，不同之處在於，於該導電層20上設置有兩層透明耐磨層，即為該透明耐磨層30與該導電層20間再設置一附屬透明耐磨層40，該透明耐磨層30的厚度介於約50奈米至500奈米之間，最佳的，其厚度介於約80奈米至150奈米之間；該附屬透明耐磨層的厚度介於約50奈米至500奈米之間，最佳的，其厚度介於約80奈米至150奈米之間；其中該透明耐磨層30折射率小於該導電層20折射率，該透明耐磨層30的折射率介於1.2至1.5之間，該附屬耐磨層40的折射率介於1.5至2之間。Referring to FIG. 4, another preferred embodiment of the present invention is similar to the manufacturing process of the foregoing embodiment, except that two transparent wear-resistant layers are disposed on the conductive layer 20, that is, the transparent wear-resistant layer 30 and An auxiliary transparent wear layer 40 is further disposed between the conductive layers 20, and the transparent wear layer 30 has a thickness of between about 50 nm and 500 nm. Preferably, the thickness is between about 80 nm and 150. Between the nanometers; the thickness of the subsidiary transparent wear-resistant layer is between about 50 nm and 500 nm, and most preferably, the thickness is between about 80 nm and 150 nm; wherein the transparent wear-resistant layer The refractive index of layer 30 is less than the refractive index of the conductive layer 20, the refractive index of the transparent wear layer 30 is between 1.2 and 1.5, and the refractive index of the subsidiary wear layer 40 is between 1.5 and 2.
為使從事該領域技術人員更能理解本發明之精神、技術特徵以及優點所在，以下，即藉由一實例來說明本發明透明導電膜之詳細製備過程以及其測試結果。本發明提供一種製程簡單、抗磨及導電性佳之透明導電膜結構及其製作方法。In order to make the spirit, technical features and advantages of the present invention more comprehensible to those skilled in the art, the detailed preparation process of the transparent conductive film of the present invention and the test results thereof will be described below by way of an example. The invention provides a transparent conductive film structure with simple process, anti-wear and good conductivity and a manufacturing method thereof.
將一玻璃透明基材，以清水沖洗，並將洗淨後的透明基材浸泡於氫氧化鉀溶液中，並在55℃的環境下靜置2分鐘後，將透明基材從氫氧化鉀溶液中取出並乾燥備用。A glass transparent substrate was rinsed with water, and the washed transparent substrate was immersed in a potassium hydroxide solution and allowed to stand in an environment of 55 ° C for 2 minutes, and then the transparent substrate was removed from the potassium hydroxide solution. Remove and dry for use.
本實施例中使用浸漬塗佈法(dip-coating)結合一黏著促進劑(adhesion promoter)，製備導電層，取1 g奈米碳管(SWCNT，Carbon Solutions)和、10 g辛基酚乙氧基化物(Octyl phenol ethoxylate,J.T.Baker)和去離子水混合攪拌一小時。將前述清洗過後之玻璃基材浸入調配好的奈米碳管水溶液中。2分鐘後取出乾燥，然後再浸入上述奈米碳管水溶液中。如此重複多次，以達到所需之奈米碳管層厚度。In this embodiment, a dip-coating method is used in combination with an adhesion promoter to prepare a conductive layer, and 1 g of carbon nanotubes (SWCNT, Carbon Solutions) and 10 g of octylphenol ethoxylate are prepared. The complex (Octyl phenol ethoxylate, JT Baker) was mixed with deionized water for one hour. The cleaned glass substrate is immersed in a prepared aqueous solution of carbon nanotubes. After 2 minutes, it was taken out and dried, and then immersed in the above aqueous solution of carbon nanotubes. This is repeated several times to achieve the desired carbon nanotube layer thickness.
將前述之完成浸沾塗佈程序後奈米碳管薄膜樣品浸入硫酸溶液中30分鐘進行後處理程序，最後用去離子水沖洗乾淨並置入烘箱中以60℃烘乾。The carbon nanotube film sample was immersed in a sulfuric acid solution for 30 minutes after the completion of the dip coating procedure, and was subjected to a post-treatment procedure, finally rinsed with deionized water and placed in an oven to be dried at 60 °C.
取0.1M,3 g的鹽酸加入30 g含有聚乙氧基矽烷(PES,Colcoat)的乙醇溶液中進行酸催化，配置成含有不同重量百分濃度PES的乙醇溶液(如表1所示NO.1至6，該PES之含量佔該乙醇溶液之整體重量百分濃度約0.33至23.33wt%之間)，各別將不同PES濃度的溶液以100℃加熱3小時，之後再冷卻至室溫，將前述之已經完成後處理程序的樣品浸入上述不同PES濃度的溶液中並隨後立即拉起，最後將已經完成浸沾塗佈的樣品置入烘箱中以60℃烘乾10分鐘，再以100℃烘乾6小時。Take 0.1M, 3 g of hydrochloric acid into 30 g of ethanol solution containing polyethoxy decane (PES, Colcoat) for acid catalysis, and configure it into ethanol solution containing different weight percentages of PES (as shown in Table 1 NO. 1 to 6, the content of the PES is between about 0.33 and 23.33 wt% of the total weight concentration of the ethanol solution, and the solution of different PES concentrations is heated at 100 ° C for 3 hours, and then cooled to room temperature. The aforementioned sample which has been subjected to the post-treatment procedure is immersed in the solution of the above different PES concentrations and then pulled up immediately, and finally the sample which has been subjected to the dip coating is placed in an oven and dried at 60 ° C for 10 minutes, and then at 100 ° C. Dry for 6 hours.
樣品之光線穿透率以UV-VIS分光光度計(Lambda 850,Perkin-Elmer)進行測量，每樣品表面以四點位置進行定性偵測，其誤差範圍為5%之間。表面阻抗以四點探針偵測儀(four-pin probe meter,Loresta-GP,Mitsubishi Chemical)進行量測偵測而獲得，其中使用探針型號為MCP-T610。樣品之抗刮性(anti-scratch)以磨耗試驗機(Model 339,Fu-Chien Enterprise Co)進行量測，以棉布於250g荷重下，進行10回合抗刮性測試；彎曲度試驗，如前所述製備樣品的方法，當中將前述玻璃基材以聚對苯二甲酸乙二酯(polyethylene terephthalate,PET)取代，進行以PET為基材下的彎曲度試驗，測試樣品大小為1x5公分，將一短邊彎折碰觸另一短邊，再攤平，如此程序視為彎曲測試一次。The light transmittance of the sample was measured by a UV-VIS spectrophotometer (Lambda 850, Perkin-Elmer), and the surface of each sample was qualitatively detected at a four-point position with an error range of 5%. The surface impedance was obtained by measuring with a four-pin probe meter (Loresta-GP, Mitsubishi Chemical) using a probe model of MCP-T610. The anti-scratch of the sample was measured by an abrasion tester (Model 339, Fu-Chien Enterprise Co), and the cotton cloth was subjected to a 10-round scratch resistance test under a load of 250 g; the bending test, as before The method for preparing a sample, wherein the glass substrate is replaced by polyethylene terephthalate (PET), and a bending test under PET is performed, and the sample size is 1×5 cm, and the test sample has a size of 1×5 cm. The short side bends to touch the other short side and then flattens out, so the program is regarded as a bending test once.
實驗結果如表1所示。從表1可以發現，在經過抗刮測試前後的結果，無PES透明耐磨層之樣品(比較樣品1)，奈米碳管層在抗刮測試的過程中會被刮除，因此，無法量測到表面阻抗。而具有PES透明耐磨層的樣品(樣品1至樣品5)，相較於比較樣品1，在耐磨測試前，表面阻抗只有些微上升。隨著PES濃度增加，耐磨測試前後表面阻抗值幾乎沒有變化，顯示，PES透明耐磨層以有效保護奈米碳管層。特別地，當PES在特定濃度時(16.67wt%，樣品4)，光線穿透率明顯上升。The experimental results are shown in Table 1. It can be found from Table 1 that, before and after the scratch-resistance test, the sample without the PES transparent wear-resistant layer (Comparative Sample 1), the carbon nanotube layer is scraped off during the scratch-resistant test, and therefore, cannot be measured. The surface impedance was measured. For the samples with the PES transparent wear layer (samples 1 to 5), the surface impedance only slightly increased before the abrasion test compared to the comparative sample 1. As the PES concentration increases, the surface impedance values before and after the abrasion test hardly change, indicating that the PES transparent wear layer effectively protects the carbon nanotube layer. In particular, when the PES was at a specific concentration (16.67 wt%, sample 4), the light transmittance was significantly increased.
彎曲測試結果如圖5所示。於500次彎曲測試後，比較樣品1表面阻抗增加幅度大於40%(R/R0 ：1.0提升至約1.45)，然而，樣品4表面阻抗增加幅度小於30%(R/R0 ：1.0提升至約<1.30)。The bending test results are shown in Figure 5. After 500 bend tests, the surface impedance of Sample 1 was increased by more than 40% (R/R 0 : 1.0 increased to about 1.45), however, the surface impedance of Sample 4 increased by less than 30% (R/R 0 : 1.0 was raised to About <1.30).
1‧‧‧透明基材1‧‧‧Transparent substrate
5‧‧‧導電層5‧‧‧ Conductive layer
10‧‧‧透明基材10‧‧‧Transparent substrate
20‧‧‧導電層20‧‧‧ Conductive layer
30‧‧‧透明耐磨層30‧‧‧Transparent wear layer
40‧‧‧附屬透明耐磨層40‧‧‧Attached transparent wear layer
圖1係為習知技術之透明導電膜之剖面示意圖。1 is a schematic cross-sectional view of a transparent conductive film of the prior art.
圖2係為本發明透明導電膜結構之製造流程圖。2 is a flow chart showing the manufacture of the transparent conductive film structure of the present invention.
圖3係為本發明一較佳實施例之剖面示意圖。3 is a schematic cross-sectional view of a preferred embodiment of the present invention.
圖4係為本發明另一較佳實施例之剖面示意圖。4 is a schematic cross-sectional view showing another preferred embodiment of the present invention.
圖5係為樣品在不同彎曲測試次數下所對應的相對表面阻抗關係圖。(1：比較樣品1；2：樣品4；R0 ：初始電阻；R：測試後電阻)Figure 5 is a graph showing the relative surface impedance of the sample at different bending test times. (1: Comparative sample 1; 2: Sample 4; R 0 : initial resistance; R: resistance after test)
10．．．透明基材10. . . Transparent substrate
20．．．導電層20. . . Conductive layer
30．．．透明耐磨層30. . . Transparent wear layer
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| TW200912965A (en) * | 2007-06-15 | 2009-03-16 | Inktec Co Ltd | Transparent conductive layer and preparation method thereof |
| TW200924203A (en) * | 2007-04-20 | 2009-06-01 | Cambrios Technologies Corp | Composite transparent conductors and methods of forming the same |
| TW201106383A (en) * | 2009-05-14 | 2011-02-16 | Dupont Teijin Films Us Ltd | Transparent conductive composite films |
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| TW200924203A (en) * | 2007-04-20 | 2009-06-01 | Cambrios Technologies Corp | Composite transparent conductors and methods of forming the same |
| TW200912965A (en) * | 2007-06-15 | 2009-03-16 | Inktec Co Ltd | Transparent conductive layer and preparation method thereof |
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