TWI479512B - Method for preparing conductive board containing patterned nano-carbon tube film and conductive board containing said patterned nano-carbon tube film - Google Patents
Method for preparing conductive board containing patterned nano-carbon tube film and conductive board containing said patterned nano-carbon tube film Download PDFInfo
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Description
本發明是有關於一種製備一具有奈米碳管膜的導電板的方法，特別是指一種製備一具有一預定圖案奈米碳管膜的導電板的方法。The present invention relates to a method of preparing a conductive plate having a carbon nanotube film, and more particularly to a method of preparing a conductive plate having a predetermined pattern of carbon nanotube film.
氧化銦錫(Indium tin oxide，簡稱ITO)透明導電膜具有高透光性及良好導電性，因此被廣泛應用於觸控面板及發光二極體等領域。然，一般ITO透明導電膜的製程需經高溫處理且製程繁雜，以及氧化銦錫成本高，不符合業者的使用及成本效益。因此，逐漸地被奈米碳管或導電高分子材料所取代。Indium tin oxide (ITO) transparent conductive film has high light transmittance and good electrical conductivity, and thus is widely used in the fields of touch panels and light-emitting diodes. However, the general ITO transparent conductive film process requires high temperature treatment and complicated process, and the cost of indium tin oxide is high, which is not in accordance with the use and cost effectiveness of the industry. Therefore, it is gradually replaced by a carbon nanotube or a conductive polymer material.
目前製備一具有一預定圖案奈米碳管膜的導電板的方法可採用雷射燒結法或光阻微影製程法。At present, a method of preparing a conductive plate having a predetermined pattern of carbon nanotube film can be performed by a laser sintering method or a photoresist lithography process.
該雷射燒結法是將奈米碳管鋪設在一基板上，形成一奈米碳管膜，接著透過雷射裝置，使該奈米碳管膜形成圖案，即可獲得一具有一預定圖案奈米碳管膜的導電板。然，該雷射裝置設備成本高，且因該奈米碳管膜形成圖案化需要於高能量的環境下，伴隨著基板材質亦需耐高溫之要求，因而導致基板的選用易受限制，再者，奈米碳管與基板間的附著性更需考量，避免奈米碳管脫離該基板影響後續效能。因此，於使用及成本效益上，不符合業者所需。In the laser sintering method, a carbon nanotube is laid on a substrate to form a carbon nanotube film, and then the carbon nanotube film is patterned by a laser device to obtain a predetermined pattern. Conductive plate of carbon nanotube film. However, the laser device has high cost, and the patterning of the carbon nanotube film needs to be in a high-energy environment, and the substrate material also needs to have high temperature resistance, so that the selection of the substrate is restricted, and then The adhesion between the carbon nanotubes and the substrate needs to be considered, so that the removal of the carbon nanotubes from the substrate affects the subsequent performance. Therefore, it is not in line with the needs of the operators in terms of use and cost effectiveness.
而光阻微影製程法是將一包含奈米碳管、黏著劑、光阻劑及溶劑的奈米碳管溶液鋪設在一基板上，經預加熱處 理後，形成一奈米碳管膜，接著對該奈米碳管膜進行曝光及顯影處理，使該奈米碳管膜形成圖案，即可獲得一具有一預定圖案奈米碳管膜的導電板。然該方法因奈米碳管、黏著劑與光阻劑的混合會有分散均勻性的問題，且奈米碳管是被包覆在黏著劑及光阻劑中，使得奈米碳管彼此間不易接觸，會造成電子傳遞的效果不佳，致使奈米碳管膜的導電性下降。The photoresist lithography process is to deposit a carbon nanotube solution containing a carbon nanotube, an adhesive, a photoresist and a solvent on a substrate, and preheating. After the formation, a carbon nanotube film is formed, and then the carbon nanotube film is exposed and developed to form a pattern of the carbon nanotube film to obtain a conductive film having a predetermined pattern of carbon nanotube film. board. However, this method has the problem of dispersion uniformity due to the mixing of the carbon nanotubes, the adhesive and the photoresist, and the carbon nanotubes are coated in the adhesive and the photoresist, so that the carbon nanotubes are mutually It is difficult to contact, which may result in poor electron transfer, resulting in a decrease in the conductivity of the carbon nanotube film.
另，US2009/0056854揭示一種可提升奈米碳管與基板間的附著性的方法。該方法是將一奈米碳管溶液塗佈於一具有孔隙的基板，且該具有孔隙的基板可將奈米碳管溶液中的各液體成分移除，僅保留奈米碳管於該基板的表面上，再經由滾輪加壓方式，將部分奈米碳管嵌入在基板的表面中，以提升奈米碳管與基板間的附著性。然，該方式中的基板的選用仍易受限制。再者，於該案中提及可將含有奈米碳管的基板的奈米碳管轉印至一透明基材上，且透過加壓方式將該與奈米碳管接觸之透明基材表面軟化，使該奈米碳管嵌入該透明基材的表面中，並轉印至該透明基材上。然，該方式中的透明基材的選用易受限制，需滿足加壓時表面可軟化的需求，且加壓的製程參數控制也較嚴苛，以及透明基板經軟化後會形變而使表面變為不平整，不符合業者所需。In addition, US 2009/0056854 discloses a method for enhancing the adhesion between a carbon nanotube and a substrate. The method is to apply a carbon nanotube solution to a substrate having pores, and the substrate having pores can remove each liquid component in the carbon nanotube solution, and only retain the carbon nanotubes on the substrate. On the surface, a part of the carbon nanotubes are embedded in the surface of the substrate via a roller pressurization method to enhance the adhesion between the carbon nanotubes and the substrate. However, the selection of substrates in this manner is still susceptible. Furthermore, in this case, it is mentioned that the carbon nanotubes of the substrate containing the carbon nanotubes can be transferred onto a transparent substrate, and the surface of the transparent substrate which is in contact with the carbon nanotubes is pressurized. Softening, the carbon nanotubes are embedded in the surface of the transparent substrate and transferred onto the transparent substrate. However, the selection of the transparent substrate in the method is limited, and the surface softening requirement during pressurization is required, and the process parameters of the pressurization are also controlled more severely, and the transparent substrate is deformed by softening to change the surface. For the unevenness, it does not meet the needs of the industry.
有鑑於上述，仍有需要發展出一種製程簡單且成本低廉之製備一具有一預定圖案奈米碳管膜的導電板的方法，以符合業者所需。In view of the above, there is still a need to develop a method for preparing a conductive plate having a predetermined pattern of carbon nanotube film, which is simple in process and low in cost, to meet the needs of the industry.
因此，本發明之第一目的，即在提供一種製程簡單且成本低廉的製備一具有一預定圖案奈米碳管膜的導電板的方法。Accordingly, a first object of the present invention is to provide a method of preparing a conductive plate having a predetermined pattern of carbon nanotube film in a simple and inexpensive process.
於是，本發明製備一具有一預定圖案奈米碳管膜的導電板的方法，包含以下步驟：提供一黏著基板，包括一基板本體及一形成在該基板本體上且具有一預定圖案的黏著部；利用一奈米碳管組份，與該具有一預定圖案的黏著部接觸，並於該黏著部上形成一具有一預定圖案的奈米碳管膜；接著，施予一固化處理，將該具有一預定圖案的黏著部固化，即可獲得一具有一預定圖案奈米碳管膜的導電板，其中，該具有一預定圖案的奈米碳管膜之預定圖案與該具有一預定圖案的黏著部之預定圖案相同。Thus, the present invention provides a method of preparing a conductive plate having a predetermined pattern of carbon nanotube film, comprising the steps of: providing an adhesive substrate comprising a substrate body and an adhesive portion formed on the substrate body and having a predetermined pattern Using a carbon nanotube component, contacting the adhesive portion having a predetermined pattern, and forming a carbon nanotube film having a predetermined pattern on the adhesive portion; and then applying a curing treatment, The adhesive portion having a predetermined pattern is cured to obtain a conductive plate having a predetermined pattern of carbon nanotube film, wherein the predetermined pattern of the carbon nanotube film having a predetermined pattern and the adhesion with the predetermined pattern The predetermined pattern of the department is the same.
本發明之第二目的，即在提供一種具有一預定圖案奈米碳管膜的導電板。A second object of the present invention is to provide a conductive plate having a predetermined pattern of carbon nanotube film.
於是，本發明具有一預定圖案奈米碳管膜的導電板，包含：一基板，包括一基板體及一形成在該基板體上且具有一預定圖案的黏著固化部；及一具有一預定圖案的奈米碳管膜，形成於該具有一預定圖案的黏著固化部上，且該具有一預定圖案的奈米碳管膜之預定圖案與該具有一預定圖案的黏著固化部之預定圖 案相同。Thus, the present invention has a conductive plate of a predetermined pattern of carbon nanotube film, comprising: a substrate comprising a substrate body and an adhesive curing portion formed on the substrate body and having a predetermined pattern; and a predetermined pattern a carbon nanotube film formed on the adhesive curing portion having a predetermined pattern, and a predetermined pattern of the carbon nanotube film having a predetermined pattern and a predetermined pattern of the adhesive curing portion having a predetermined pattern The case is the same.
本發明之功效在於：該製備一具有一預定圖案奈米碳管膜的導電板的方法是透過該具有一預定圖案的黏著部來形成該具有一預定圖案的奈米碳管膜，不僅製程簡單且成本低廉，並能有效地將該具有一預定圖案的奈米碳管膜固定在該黏著基板上。The invention has the effect that the method for preparing a conductive plate having a predetermined pattern of carbon nanotube film is to form the carbon nanotube film having a predetermined pattern through the adhesive portion having a predetermined pattern, which is not only simple in process The invention is low in cost and can effectively fix the carbon nanotube film having a predetermined pattern on the adhesive substrate.
在本發明被詳細描述之前，要注意的是，在以下的說明內容中，類似的元件是以相同的編號來表示。Before the present invention is described in detail, it is noted that in the following description, similar elements are denoted by the same reference numerals.
本發明製備一具有一預定圖案奈米碳管膜的導電板的方法，包含以下步驟：提供一黏著基板，包括一基板本體及一形成在該基板本體上且具有一預定圖案的黏著部；利用一奈米碳管組份，與該具有一預定圖案的黏著部接觸，並於該黏著部上形成一具有一預定圖案的奈米碳管膜；接著，施予一固化處理，將該具有一預定圖案的黏著部固化，即可獲得一具有一預定圖案奈米碳管膜的導電板，其中，該具有一預定圖案的奈米碳管膜之預定圖案與該具有一預定圖案的黏著部之預定圖案相同。The invention provides a method for preparing a conductive plate having a predetermined pattern of carbon nanotube film, comprising the steps of: providing an adhesive substrate comprising a substrate body and an adhesive portion formed on the substrate body and having a predetermined pattern; a carbon nanotube component, in contact with the adhesive portion having a predetermined pattern, and forming a carbon nanotube film having a predetermined pattern on the adhesive portion; and then applying a curing treatment, which has a The adhesive portion of the predetermined pattern is solidified to obtain a conductive plate having a predetermined pattern of carbon nanotube film, wherein the predetermined pattern of the carbon nanotube film having a predetermined pattern and the adhesive portion having a predetermined pattern The predetermined pattern is the same.
本發明製備一具有一預定圖案奈米碳管膜的導電板的方法是透過具有一預定圖案的黏著部來形成一具有一預定圖案的奈米碳管膜，其中，該具有一預定圖案的奈米碳管膜之預定圖案與該具有一預定圖案的黏著部之預定圖案相 同，不僅製程簡單且成本低廉。若直接將奈米碳管分散於水或有機溶劑中得一分散液後塗佈在基材上，因該奈米碳管分散液本身黏度低，難以維持固定之圖案並固著於基材上，且塗佈後，將奈米碳管分散液中的溶劑單純以自然揮發法或加熱法移除，奈米碳管彼此間堆積不緊密，導電效果不佳。本發明的奈米碳管組份以真空抽濾方式成為乾燥固態，在真空吸力作用下，彼此間堆積較緊密，並利用該具有一預定圖案之黏著部，使該具有一預定圖案的奈米碳管膜牢固黏附於該黏著基板上。The method for preparing a conductive plate having a predetermined pattern of carbon nanotube film is to form a carbon nanotube film having a predetermined pattern through an adhesive portion having a predetermined pattern, wherein the nano tube having a predetermined pattern a predetermined pattern of the carbon nanotube film and a predetermined pattern of the adhesive portion having a predetermined pattern The same, not only the process is simple and the cost is low. If the carbon nanotube is directly dispersed in water or an organic solvent to obtain a dispersion and then coated on the substrate, the carbon nanotube dispersion itself has low viscosity, and it is difficult to maintain a fixed pattern and fix it on the substrate. After the coating, the solvent in the carbon nanotube dispersion is simply removed by natural evaporation or heating, and the carbon nanotubes are not closely packed with each other, and the conductivity is not good. The carbon nanotube component of the present invention is vacuum-filtered into a dry solid state, and is densely packed with each other under vacuum suction, and the adhesive having a predetermined pattern is used to make the nanometer having a predetermined pattern. The carbon tube film is firmly adhered to the adhesive substrate.
該奈米碳管組份與該具有一預定圖案的黏著部接觸時，依據所施予接觸的壓力，可將該奈米碳管組份全部形成在該具有一預定圖案的黏著部的表面上，而形成該具有一預定圖案奈米碳管膜，或者是使該奈米碳管組份的一端嵌入於該具有一預定圖案的黏著部中，另一端自該黏著部表面凸出，而形成至少一部份之奈米碳管組份不與黏著部接觸之一具有一預定圖案奈米碳管膜。其中，該奈米碳管組份的一端嵌入於該具有一預定圖案的黏著部中，更可使該具有一預定圖案奈米碳管膜不會從該黏著基板上脫落，且另一端自該黏著部表面凸出，可使該奈米碳管組份彼此接觸，維持導電性。When the carbon nanotube component is in contact with the adhesive portion having a predetermined pattern, the carbon nanotube component may be entirely formed on the surface of the adhesive portion having a predetermined pattern according to the pressure of the applied contact. Forming the carbon nanotube film having a predetermined pattern, or embedding one end of the carbon nanotube component in the adhesive portion having a predetermined pattern, and the other end protruding from the surface of the adhesive portion to form At least a portion of the carbon nanotube component has a predetermined pattern of carbon nanotube film that is not in contact with the adhesive portion. Wherein, one end of the carbon nanotube component is embedded in the adhesive portion having a predetermined pattern, so that the carbon nanotube film having a predetermined pattern does not fall off the adhesive substrate, and the other end The surface of the adhesive portion is convex, and the carbon nanotube components are brought into contact with each other to maintain electrical conductivity.
該固化處理可將該具有一預定圖案的黏著部固化，還可防止該黏著部黏附其他物質。較佳地，該固化處理步驟是擇自於光固化處理、熱固化處理，或此等一組合。The curing treatment can cure the adhesive portion having a predetermined pattern, and can prevent the adhesive portion from adhering to other substances. Preferably, the curing treatment step is selected from a photocuring treatment, a thermal curing treatment, or a combination thereof.
該基板本體並無特別的限制，只要能承載該具有一預 定圖案的黏著部即可。該基板本體是擇自於玻璃基板或塑膠基板。該玻璃基板包含但不限於應用在顯示裝置或觸控裝置中的無鹼玻璃、鈉鈣玻璃、強化玻璃(Pyrex玻璃)、石英玻璃、表面上已附著透明導電膜的玻璃或表面上已附著彩色層的玻璃等之基板及用於固體攝影元件等之光電變換元件基板(如：矽基板)等。該塑膠基板可選自應用在軟性電子裝置(如電子紙或紙喇叭)中的軟性基板，如聚對苯二甲酸乙二醇酯(polyethylene terephthalate，簡稱PET)基板、聚醯亞胺(polyimide，簡稱PI)基板、聚碳酸酯(polycarbonate，簡稱PC)基板等。The substrate body is not particularly limited as long as it can carry the The adhesive part of the pattern can be used. The substrate body is selected from a glass substrate or a plastic substrate. The glass substrate includes, but is not limited to, an alkali-free glass, a soda-lime glass, a tempered glass (Pyrex glass), a quartz glass, a glass having a transparent conductive film attached to the surface, or a surface on which a color is attached to the display device or the touch device. A substrate such as a layer of glass or a photoelectric conversion element substrate (for example, a germanium substrate) used for a solid-state imaging device or the like. The plastic substrate may be selected from a flexible substrate used in a flexible electronic device such as an electronic paper or a paper horn, such as a polyethylene terephthalate (PET) substrate, or a polyimine (polyimide, Referring to PI) substrate, polycarbonate (PC) substrate, and the like.
該具有一預定圖案的黏著部中的預定圖案可以依據該具有一預定圖案奈米碳管膜的應用進行變化，較佳地，該預定圖案為二維陣列，如圖1所示。The predetermined pattern in the adhesive portion having a predetermined pattern may vary depending on the application having the predetermined pattern of the carbon nanotube film. Preferably, the predetermined pattern is a two-dimensional array, as shown in FIG.
較佳地，該黏著基板11中具有一預定圖案的黏著部13的製備方式是擇自於經由網印處理或經由曝光處理所獲得。Preferably, the adhesive portion 13 having a predetermined pattern in the adhesive substrate 11 is prepared from the screen printing process or via the exposure process.
詳細地說，如圖2所示，該網印處理是包含以下步驟：提供一具有一預定圖案的母模14，可脫離地設置在該基板本體12上；提供一黏著組成物15並塗佈於該具有一預定圖案的母模14上；移除該具有一預定圖案的母模14，以在基板本體12上形成一具有一預定圖案的黏著部13。In detail, as shown in FIG. 2, the screen printing process comprises the steps of: providing a master mold 14 having a predetermined pattern, detachably disposed on the substrate body 12; providing an adhesive composition 15 and coating The master mold 14 having a predetermined pattern is removed; the master mold 14 having a predetermined pattern is removed to form an adhesive portion 13 having a predetermined pattern on the substrate body 12.
該黏著組成物15需同時具有黏性及光/熱可固化性，較佳為具有可曝光顯影性，以能黏住奈米碳管組份並經熱或光可固化定形，避免於實際應用時因施加外力而使該預定 圖案變形，造成短路或斷路等不良電性。該黏著組成物15包含但不限於環氧樹脂類化合物或聚丙烯酸酯類化合物。該黏著組成物15也可是將一用於黏著的組成物塗佈於該具有一預定圖案的母模14後經曝光所形成。較佳地，該用於黏著的組成物包含1,6-己二醇二丙烯酸酯(1,6-hexanediol diacrylate，簡稱HDDA)及丙烯酸丁酯(butyl acrylate，簡稱BA)。The adhesive composition 15 needs to have both viscous and light/heat curability, and preferably has an exposable developability to adhere to the carbon nanotube component and be shaped by heat or light to avoid practical application. When the external force is applied to make the reservation The pattern is deformed, causing poor electrical properties such as short circuit or open circuit. The adhesive composition 15 includes, but is not limited to, an epoxy resin compound or a polyacrylate compound. The adhesive composition 15 may also be formed by applying a composition for adhesion to the master mold 14 having a predetermined pattern and then exposing it. Preferably, the composition for adhesion comprises 1,6-hexanediol diacrylate (HDDA) and butyl acrylate (BA).
該1,6-己二醇二丙烯酸酯照光後具有固化及聚合的特性，且照光後不易被溶劑移除，有助於形成該黏著部的預定圖案。而該丙烯酸丁酯照光後具有黏性，有助於使該黏著部具有黏性。The 1,6-hexanediol diacrylate has the characteristics of curing and polymerization after being irradiated, and is not easily removed by the solvent after illumination, and contributes to the formation of a predetermined pattern of the adhesive portion. The butyl acrylate is viscous after illuminating, which helps to make the adhesive portion viscous.
詳細地說，如圖3所示，該曝光處理是包含以下步驟：塗佈一用於黏著的組成物16在該基板本體12上；透過一具有一預定圖案的光罩17對該用於黏著的組成物16進行曝光，使該用於黏著的組成物16經曝光的區域產生黏性，而未曝光區域使用可溶解該用於黏著的組成物16的試劑移除，即可在基板本體12上形成一具有一預定圖案的黏著部13。該曝光處理中的該用於黏著的組成物16如同上述，故不再贅述。In detail, as shown in FIG. 3, the exposure process includes the steps of: coating a composition 16 for adhesion on the substrate body 12; and bonding the film through a mask 17 having a predetermined pattern. The composition 16 is exposed such that the exposed areas of the adherent composition 16 are viscous, and the unexposed areas are removed using an agent that dissolves the composition 16 for adhesion, i.e., on the substrate body 12 An adhesive portion 13 having a predetermined pattern is formed thereon. The composition 16 for adhesion in the exposure process is as described above, and therefore will not be described again.
較佳地，該奈米碳管組份形成於該具有一預定圖案的黏著部上的方式是經由轉印處理所形成。Preferably, the carbon nanotube component is formed on the adhesive portion having a predetermined pattern by a transfer process.
該轉印處理指的是將該奈米碳管組份形成於一暫時基板上，接著與該具有一預定圖案的黏著部接觸，透過轉印處理，將奈米碳管組份轉印至該具有一預定圖案的黏著部 上。該暫時基板包含但不限於滾輪裝置上的基板、上述的基板本體，或濾紙。The transfer process refers to forming the carbon nanotube component on a temporary substrate, and then contacting the adhesive portion having a predetermined pattern, and transferring the carbon nanotube component to the transfer process through the transfer process. Adhesive portion having a predetermined pattern on. The temporary substrate includes, but is not limited to, a substrate on a roller device, the above-described substrate body, or a filter paper.
該奈米碳管組份包含多數個擇自於由下列所構成之群組：未改質的奈米碳管、經改質的奈米碳管、奈米碳管複合材，及此等一組合。較佳地，該奈米碳管組份是奈米碳管複合材。The carbon nanotube component comprises a plurality of groups selected from the group consisting of unmodified carbon nanotubes, modified carbon nanotubes, carbon nanotube composites, and the like. combination. Preferably, the carbon nanotube component is a carbon nanotube composite.
該未改質的奈米碳管可單獨或混合使用，且該未改質的奈米碳管包含但不限於單層奈米碳管(single-walled CNTs)、雙層奈米碳管(double-walled CNTs)、多層奈米碳管(multiple-walled CNTs)或奈米碳繩(rope CNTs)等。The unmodified carbon nanotubes may be used singly or in combination, and the unmodified carbon nanotubes include, but are not limited to, single-walled CNTs, double-layered carbon nanotubes (double) -walled CNTs), multiple-walled CNTs or rope CNTs.
該經改質奈米碳管並無特別限制，可採用以往所使用的，例如，由一改質劑與一未改質的奈米碳管反應所製得的經改質奈米碳管。該改質劑為一包含至少一種由下列所構成群組的基團的改質劑，且該基團為酸酐基、羧基、羥基、醯基及胺基。該改質劑可單獨或混合使用，且該改質劑包含但不限於順丁烯二酸酐(maleic anhydride)、甲基丙烯酸-2-羥基乙酯(2-hydroxyethyl methacrylate)，或亞胺乙二酸(iminodiacetic acid)與縮水甘油甲基丙烯酸酯(glycidyl methacrylate)反應後的化合物等。The modified carbon nanotube is not particularly limited, and may be a conventionally modified nanocarbon tube obtained by reacting a modifier with an unmodified carbon nanotube. The modifier is a modifier comprising at least one group consisting of the following groups, and the group is an acid anhydride group, a carboxyl group, a hydroxyl group, a thiol group, and an amine group. The modifier may be used singly or in combination, and the modifier includes, but is not limited to, maleic anhydride, 2-hydroxyethyl methacrylate, or imine ethylene. A compound obtained by reacting an acid (iminodiacetic acid) with glycidyl methacrylate.
該奈米碳管複合材並無特別限制，可採用例如含有奈米碳管及金屬源的複合材。該奈米碳管可以是未改質的奈米碳管或經改質奈米碳管，而該金屬源可以依據後續應用(如導電度)進行不同的選擇，可以是金屬或金屬氧化物。該金屬包含但不限於銀、錫及鎘。The carbon nanotube composite material is not particularly limited, and for example, a composite material containing a carbon nanotube and a metal source can be used. The carbon nanotubes can be unmodified carbon nanotubes or modified carbon nanotubes, and the metal source can be selected differently depending on the subsequent application (such as conductivity), and can be a metal or a metal oxide. The metal includes, but is not limited to, silver, tin, and cadmium.
較佳地，該含有奈米碳管及金屬源的複合材包括複數個經改質奈米碳管，每一個經改質奈米碳管含有複數個官能基團；及複數個奈米金屬團，每一個奈米金屬團是連結於每一個經改質奈米碳管中之至少一官能基團上，且兩相鄰的經改質奈米碳管是透過至少一個奈米金屬團而彼此相互連結。透過經改質奈米碳管上的官能基團，使金屬團均勻分佈並吸附在經改質奈米碳管的官能基團上而不聚集或堆積，同時，透過金屬團連結使該等經改質奈米碳管彼此間緊密堆疊，提升電子傳遞效率，繼而使該含有奈米碳管及金屬的複合材具有較佳的導電性。Preferably, the composite material comprising a carbon nanotube and a metal source comprises a plurality of modified carbon nanotubes, each of the modified carbon nanotubes comprising a plurality of functional groups; and a plurality of nano metal clusters Each nano metal cluster is bonded to at least one functional group in each of the modified carbon nanotubes, and the two adjacent modified carbon nanotubes pass through at least one nano metal cluster and are mutually Connected to each other. Through the functional groups on the modified carbon nanotubes, the metal clusters are uniformly distributed and adsorbed on the functional groups of the modified carbon nanotubes without being aggregated or accumulated, and at the same time, the metal groups are connected to each other. The modified carbon nanotubes are closely stacked with each other to improve the electron transfer efficiency, and then the composite containing the carbon nanotubes and the metal has better conductivity.
較佳地，該等官能基團為一可提供電子的基團。較佳地，該等官能基團包含至少一種由下列所構成群組的基團：酸酐基、羧基、羥基、醯基及胺基。更佳地，該等官能基團為酸酐基。較佳地，該金屬團包含至少一種由下列所構成群組的金屬：銀、錫及鎘。Preferably, the functional groups are a group capable of providing an electron. Preferably, the functional groups comprise at least one group consisting of an acid anhydride group, a carboxyl group, a hydroxyl group, a thiol group and an amine group. More preferably, the functional groups are anhydride groups. Preferably, the metal cluster comprises at least one metal consisting of the following: silver, tin and cadmium.
該含有奈米碳管及金屬源的複合材的製備方法，包含以下步驟：步驟(a)：提供複數個的經改質奈米碳管，每一個經改質奈米碳管含有複數個官能基團；步驟(b)：提供複數個金屬離子，與該等經改質奈米碳管上的官能基團連結並獲得一混合物；步驟(c)：將該混合物加入一還原劑中以使該等金屬離子進行還原反應，形成複數個具有奈米金屬粒子的奈米碳管； 步驟(d)：將該等具有奈米金屬粒子的奈米碳管施予一加熱處理，即可獲得該含有奈米碳管及金屬源的複合材。The method for preparing a composite material comprising a carbon nanotube and a metal source comprises the following steps: Step (a): providing a plurality of modified carbon nanotubes, each of which has a plurality of functionalized carbon nanotubes a group; a step (b): providing a plurality of metal ions, linking with the functional groups on the modified carbon nanotubes to obtain a mixture; and step (c): adding the mixture to a reducing agent to The metal ions are subjected to a reduction reaction to form a plurality of carbon nanotubes having nano metal particles; Step (d): The carbon nanotubes having nano metal particles are subjected to a heat treatment to obtain the composite material comprising a carbon nanotube and a metal source.
該加熱處理主要是使奈米金屬粒子彼此相互熔融，繼而使該等經改質奈米碳管彼此緊密堆疊，提升電子傳遞效率，繼而使該含有奈米碳管及金屬源的複合材具有較佳的導電性。The heat treatment mainly dissolves the nano metal particles with each other, and then the heat-exchanged carbon nanotubes are closely stacked with each other to improve the electron transfer efficiency, and then the composite material containing the carbon nanotubes and the metal source is more Good conductivity.
較佳地，還包含一於步驟(c)前進行的清洗處理步驟。該清洗處理步驟可採以往的方式，目的在於清洗掉未連結在經改質奈米碳管的官能基團上的金屬離子，以利步驟(c)能僅將連結在經改質奈米碳管的官能基團上的金屬離子還原成奈米等級的金屬粒子。Preferably, a cleaning treatment step performed before step (c) is further included. The cleaning treatment step can be carried out in a conventional manner, in order to wash away the metal ions not attached to the functional groups of the modified carbon nanotubes, so that the step (c) can only be bonded to the modified nanocarbon. The metal ions on the functional groups of the tube are reduced to metal particles of the nanometer grade.
該金屬離子並無特別的限制，依含有奈米碳管及金屬源的複合材所需的特性(如導電性)進行選擇即可，較佳地，該金屬離子包含至少一種由下列所構成群組的化合物：銀離子、錫離子及鎘離子。該還原劑可單獨或混合使用，且該還原劑包含至少一種由下列所構成群組的化合物：硼氫化鈉(NaBH4 )、次磷酸鈉(NaH2 PO2 ．H2 O)、二鹽酸肼(N2 H4 ．2HCl)及水合肼(N2 H4 ．H2 O)。The metal ion is not particularly limited, and may be selected according to characteristics (such as conductivity) of a composite material containing a carbon nanotube and a metal source. Preferably, the metal ion contains at least one group consisting of the following Group of compounds: silver ions, tin ions and cadmium ions. The reducing agent may be used singly or in combination, and the reducing agent comprises at least one compound consisting of sodium borohydride (NaBH 4 ), sodium hypophosphite (NaH 2 PO 2 .H 2 O), bismuth dihydrochloride (N 2 H 4 .2 HCl) and hydrazine hydrate (N 2 H 4 .H 2 O).
該加熱處理可採用以往的方式，以能使奈米金屬粒子彼此間相互熔融的方式即可。較佳地，該加熱處理的操作溫度範圍120℃~200℃。This heat treatment may be carried out in a conventional manner so that the nano metal particles can be mutually melted. Preferably, the heat treatment has an operating temperature range of 120 ° C to 200 ° C.
本發明之具有一預定圖案奈米碳管膜的導電板可應用於顯示裝置(如液晶顯示裝置)或觸控裝置(如觸控面板)中。且本發明具有一預定圖案奈米碳管膜的導電板中的具有一 預定圖案奈米碳管膜不會從基板上脫落，且具有較佳的導電性。The conductive plate of the present invention having a predetermined pattern of carbon nanotube film can be applied to a display device (such as a liquid crystal display device) or a touch device (such as a touch panel). And the present invention has a predetermined pattern of carbon nanotube film having a conductive plate The predetermined pattern carbon nanotube film does not fall off the substrate and has better conductivity.
本發明之具有一預定圖案奈米碳管膜的導電板的第一較佳實施例如圖4所示。於圖4中，該具有一預定圖案奈米碳管膜的導電板，包含：一基板2，包括一基板體21及一形成在該基板體21上且具有一預定圖案的黏著固化部22；及一具有一預定圖案的奈米碳管膜23，形成於該具有一預定圖案的黏著固化部22上，且該具有一預定圖案的奈米碳管膜23之預定圖案與該具有一預定圖案的黏著固化部22之預定圖案相同。A first preferred embodiment of the conductive plate of the present invention having a predetermined pattern of carbon nanotube film is shown in FIG. In FIG. 4, the conductive plate having a predetermined pattern of carbon nanotube film, comprising: a substrate 2, comprising a substrate body 21 and an adhesive curing portion 22 formed on the substrate body 21 and having a predetermined pattern; And a carbon nanotube film 23 having a predetermined pattern formed on the adhesive curing portion 22 having a predetermined pattern, and the predetermined pattern of the carbon nanotube film 23 having a predetermined pattern and the predetermined pattern The predetermined pattern of the adhesive curing portion 22 is the same.
該基板體21如同上述基板本體12，故不再贅述。而該具有一預定圖案的黏著固化部22是由上述該具有一預定圖案的黏著部13經固化處理所形成，故不再贅述。該具有一預定圖案的奈米碳管膜23是由上述奈米碳管組份所形成，故不再贅述。The substrate body 21 is like the above-described substrate body 12, and therefore will not be described again. The adhesive curing portion 22 having a predetermined pattern is formed by the above-described curing process of the adhesive portion 13 having a predetermined pattern, and therefore will not be described again. The carbon nanotube film 23 having a predetermined pattern is formed of the above-described carbon nanotube component, and therefore will not be described again.
該具有一預定圖案奈米碳管膜的導電板，還包含一具有一預定圖案的混合層，形成在該具有一預定圖案的黏著固化部22及該具有一預定圖案的奈米碳管膜23之間。The conductive plate having a predetermined pattern of carbon nanotube film further comprising a mixed layer having a predetermined pattern formed in the adhesive curing portion 22 having a predetermined pattern and the carbon nanotube film 23 having a predetermined pattern between.
該具有一預定圖案的混合層是由上述製備一具有一預定圖案奈米碳管膜的導電板的方法中，該奈米碳管組份的一端嵌入於該具有一預定圖案的黏著部中所形成。依據所施予接觸的壓力，使該奈米碳管組份的一端嵌入於該具有一預定圖案的黏著部中，而另一端自該黏著部表面凸出。 其中，該奈米碳管組份的一端嵌入於該具有一預定圖案的黏著部中，更可使該具有一預定圖案奈米碳管膜不會從黏著基板上脫落，且另一端自該黏著部表面凸出，可使該奈米碳管組份彼此接觸，維持導電性The mixed layer having a predetermined pattern is a method of preparing a conductive plate having a predetermined pattern of carbon nanotube film, wherein one end of the carbon nanotube component is embedded in the adhesive portion having a predetermined pattern form. One end of the carbon nanotube component is embedded in the adhesive portion having a predetermined pattern and the other end is projected from the surface of the adhesive portion in accordance with the pressure applied thereto. Wherein, one end of the carbon nanotube component is embedded in the adhesive portion having a predetermined pattern, so that the carbon nanotube film having a predetermined pattern does not fall off from the adhesive substrate, and the other end is adhered to the adhesive substrate. The surface of the portion protrudes to allow the carbon nanotube components to contact each other to maintain conductivity
本發明將就以下實施例來作進一步說明，但應瞭解的是，該實施例僅為例示說明之用，而不應被解釋為本發明實施之限制。The present invention will be further illustrated by the following examples, but it should be understood that this embodiment is intended to be illustrative only and not to be construed as limiting.
將一具有由多數個彼此間隔且呈二維排列之方形孔所構成之預定圖案的網狀模設置在一以聚對苯二甲酸乙二醇酯為材質的基板本體上，接著將一包含重量比1：1的1,6-己二醇二丙烯酸酯及丙烯酸丁酯的用於黏著的組成物塗佈於該網狀模上，之後，移除該網狀模，接著，經使用365nm的光照射30秒後，該基板本體的表面上就會形成一具有該預定圖案的黏著部，即可獲得一黏著基板。Locating a mesh mold having a predetermined pattern of a plurality of square holes spaced apart from each other and arranged in two dimensions on a substrate body made of polyethylene terephthalate, and then including a weight A composition for adhesion of 1,6-hexanediol diacrylate and butyl acrylate is coated on the mesh mold, and then the mesh mold is removed, and then, 365 nm is used. After 30 seconds of light irradiation, an adhesive portion having the predetermined pattern is formed on the surface of the substrate body to obtain an adhesive substrate.
將含有多數個未改質的奈米碳管之奈米碳管組份形成於一濾紙上，接著，將該將奈米碳管組份疊置於該具有該預定圖案的黏著部上並對其下壓，接著，將該濾紙移除，則每個未改質的奈米碳管之一端將嵌入該具有預定圖案的黏著部中，另一端將自該具有預定圖案的黏著部的表面凸出，即可形成一具有該預定圖案的混合部及一具有該預定圖案的奈米碳管膜，之後，經70℃的溫度固化後，即可獲得該具有該預定圖案的奈米碳管膜的導電板。Forming a carbon nanotube component containing a plurality of unmodified carbon nanotubes on a filter paper, and then stacking the carbon nanotube component on the adhesive portion having the predetermined pattern and Pressing down, and then removing the filter paper, one end of each unmodified carbon nanotube will be embedded in the adhesive portion having a predetermined pattern, and the other end will be convex from the surface of the adhesive portion having the predetermined pattern Forming, a mixing portion having the predetermined pattern and a carbon nanotube film having the predetermined pattern, and then curing the temperature at 70 ° C to obtain the carbon nanotube film having the predetermined pattern Conductive plate.
將一包含重量比1：1的1,6-己二醇二丙烯酸酯及丙烯酸丁酯的用於黏著的組成物塗佈於一以聚對苯二甲酸乙二醇酯為材質的基板本體上，接著利用一具有二維陣列圖案的光罩，使部分該用於黏著的組成物曝光產生黏性，該曝光波長為365nm、曝光時間為30秒，接著，將未曝光區使用乙醇溶解該用於黏著的組成物後，於該基板本體上形成一具有二維陣列圖案的黏著部，即可獲得一黏著基板。Applying a composition for adhesion comprising 1,6-hexanediol diacrylate and butyl acrylate in a weight ratio of 1:1 to a substrate body made of polyethylene terephthalate Then, using a photomask having a two-dimensional array pattern, a portion of the composition for adhesion is exposed to produce viscosity, the exposure wavelength is 365 nm, and the exposure time is 30 seconds. Then, the unexposed area is dissolved by using ethanol. After the adhesive composition, an adhesive portion having a two-dimensional array pattern is formed on the substrate body to obtain an adhesive substrate.
將含有多數個未改質的奈米碳管之奈米碳管組份形成於一濾紙上，接著，該將奈米碳管組份疊置於該具有該預定圖案的黏著部上並對其下壓，接著，將該濾紙移除，則每個未改質的奈米碳管之一端將嵌入該具有預定圖案的黏著部中，另一端將自該具有預定圖案的黏著部的表面凸出，即可形成一具有該二維陣列圖案的混合部及一具有該二維陣列圖案的奈米碳管膜，之後，經70℃的溫度固化後，即可獲得該具有該二維陣列圖案的奈米碳管膜的導電板。Forming a carbon nanotube component containing a plurality of unmodified carbon nanotubes on a filter paper, and then stacking the carbon nanotube component on the adhesive portion having the predetermined pattern and Pressing down, and then removing the filter paper, one end of each unmodified carbon nanotube will be embedded in the adhesive portion having a predetermined pattern, and the other end will protrude from the surface of the adhesive portion having the predetermined pattern Forming a mixing portion having the two-dimensional array pattern and a carbon nanotube film having the two-dimensional array pattern, and then curing the temperature at 70 ° C to obtain the two-dimensional array pattern Conductive plate of carbon nanotube film.
將一具有由多數個彼此間隔且呈二維排列之方形孔所構成之預定圖案的網狀模設置在一以聚對苯二甲酸乙二醇酯為材質的基板本體上，接著將一包含重量比1：1的1,6-己二醇二丙烯酸酯及丙烯酸丁酯的用於黏著的組成物塗佈於該網狀模上，之後，移除該網狀模，接著，經使用365nm的光照射30秒後，該基板本體的表面上就會形成一具有該預定圖案的黏著部，即可獲得一黏著基板。Locating a mesh mold having a predetermined pattern of a plurality of square holes spaced apart from each other and arranged in two dimensions on a substrate body made of polyethylene terephthalate, and then including a weight A composition for adhesion of 1,6-hexanediol diacrylate and butyl acrylate is coated on the mesh mold, and then the mesh mold is removed, and then, 365 nm is used. After 30 seconds of light irradiation, an adhesive portion having the predetermined pattern is formed on the surface of the substrate body to obtain an adhesive substrate.
將含有多數個未改質的奈米碳管之奈米碳管組份形成 於一濾紙上，且將該含有奈米碳管組份的濾紙設置在滾輪裝置的滾輪上，接著，轉動滾輪，將該奈米碳管組份與該黏著基板上的具有預定圖案的黏著部接觸，則每個未改質的奈米碳管之一端將嵌入該具有預定圖案的黏著部中，另一端將自該具有預定圖案的黏著部的表面凸出，即可形成一具有該預定圖案的混合部及一具有該預定圖案的奈米碳管膜，之後，經70℃的溫度固化後，即可獲得具有該預定圖案的奈米碳管膜的導電板。Forming a carbon nanotube component containing a plurality of unmodified carbon nanotubes On a filter paper, and the filter paper containing the carbon nanotube component is placed on the roller of the roller device, and then the roller is rotated to bond the carbon nanotube component with the predetermined pattern on the adhesive substrate. In contact, one end of each unmodified carbon nanotube will be embedded in the adhesive portion having a predetermined pattern, and the other end will protrude from the surface of the adhesive portion having the predetermined pattern to form a predetermined pattern. The mixing portion and a carbon nanotube film having the predetermined pattern are then cured at a temperature of 70 ° C to obtain a conductive plate of the carbon nanotube film having the predetermined pattern.
本發明製備具有一預定圖案奈米碳管膜的導電板的方法是透過具有一預定圖案的黏著部來形成，不僅製程簡單且成本低。且本發明具有一預定圖案奈米碳管膜的導電板中的具有一預定圖案奈米碳管膜不會從基板上脫落，且具有較佳的導電性，故確實能達成本發明之目的。The method of the present invention for preparing a conductive plate having a predetermined pattern of carbon nanotube film is formed by an adhesive portion having a predetermined pattern, which is not only simple in process but also low in cost. Moreover, the carbon nanotube film having a predetermined pattern in the conductive plate having a predetermined pattern of the carbon nanotube film does not fall off from the substrate, and has better conductivity, so that the object of the present invention can be achieved.
惟以上所述者，僅為本發明之較佳實施例而已，當不能以此限定本發明實施之範圍，即大凡依本發明申請專利範圍及發明說明內容所作之簡單的等效變化與修飾，皆仍屬本發明專利涵蓋之範圍內。The above is only the preferred embodiment of the present invention, and the scope of the invention is not limited thereto, that is, the simple equivalent changes and modifications made by the scope of the invention and the description of the invention are All remain within the scope of the invention patent.
11‧‧‧黏著基板11‧‧‧Adhesive substrate
12‧‧‧基板本體12‧‧‧Substrate body
13‧‧‧具有一預定圖案的黏著部13‧‧‧Adhesive parts with a predetermined pattern
14‧‧‧具有一預定圖案的母模14‧‧‧Female model with a predetermined pattern
15‧‧‧黏著組成物15‧‧‧Adhesive composition
16‧‧‧用於黏著的組成物16‧‧‧Composition for adhesion
17‧‧‧具有一預定圖案的光罩17‧‧‧Photomask with a predetermined pattern
2‧‧‧基板2‧‧‧Substrate
21‧‧‧基板體21‧‧‧ substrate body
22‧‧‧具有一預定圖案的黏著固化部22‧‧‧Adhesive curing part with a predetermined pattern
23‧‧‧具有一預定圖案的奈米碳管膜23‧‧‧Non carbon nanotube film with a predetermined pattern
圖1是一示意圖，說明本發明預定圖案；圖2是一示意圖，說明本發明具有一預定圖案的黏著部的製備方式；圖3是一示意圖，說明本發明具有一預定圖案的黏著部的製備方式；及圖4是一示意圖，說明本發明第一較佳實施例之具有 一預定圖案奈米碳管膜的導電板。1 is a schematic view showing a predetermined pattern of the present invention; FIG. 2 is a schematic view showing the preparation of an adhesive portion having a predetermined pattern of the present invention; and FIG. 3 is a schematic view showing the preparation of an adhesive portion having a predetermined pattern of the present invention. And FIG. 4 is a schematic view showing the first preferred embodiment of the present invention A conductive plate of a predetermined pattern of carbon nanotube film.
2‧‧‧基板2‧‧‧Substrate
21‧‧‧基板體21‧‧‧ substrate body
22‧‧‧具有一預定圖案的黏著固化部22‧‧‧Adhesive curing part with a predetermined pattern
23‧‧‧具有一預定圖案的奈米碳管膜23‧‧‧Non carbon nanotube film with a predetermined pattern
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| TW200802708A (en) * | 2006-04-03 | 2008-01-01 | Motorola Inc | Semiconductor device having carbon nanotube interconnects and method of fabrication |
| TW201102701A (en) * | 2009-07-15 | 2011-01-16 | Innolux Display Corp | Conductive plate and touch plate applied by the same |
| TWI357632B (en) * | 2008-04-18 | 2012-02-01 | Zhen Ding Technology Co Ltd | Circuit substrate and method for manufacturing the |
| TW201214470A (en) * | 2010-09-30 | 2012-04-01 | Far Eastern New Century Corp | Transparent conductive film having high optical transmittance and method for manufacturing the same |
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| JP2007287478A (en) * | 2006-04-17 | 2007-11-01 | Mitsubishi Gas Chem Co Inc | Manufacturing method of oriented carbon nanotube wiring |
| JP5266889B2 (en) * | 2008-06-04 | 2013-08-21 | ソニー株式会社 | Method for manufacturing light transmissive conductor |
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| TW200802708A (en) * | 2006-04-03 | 2008-01-01 | Motorola Inc | Semiconductor device having carbon nanotube interconnects and method of fabrication |
| TWI357632B (en) * | 2008-04-18 | 2012-02-01 | Zhen Ding Technology Co Ltd | Circuit substrate and method for manufacturing the |
| TW201102701A (en) * | 2009-07-15 | 2011-01-16 | Innolux Display Corp | Conductive plate and touch plate applied by the same |
| TW201214470A (en) * | 2010-09-30 | 2012-04-01 | Far Eastern New Century Corp | Transparent conductive film having high optical transmittance and method for manufacturing the same |
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