201024208 六、發明說明： 【發明所屬之技術領域】 本發明是有關於一種導電薄膜的製造方法，特別是指 一種轉印式奈米碳管導電薄膜的製造方法。 a 【先前技術】 隨著液晶螢幕的廣泛應用與發展，透曰月導電材料的開 發-直是熱門的研究主題，應用於顯示器與觸控面板的透明 導電薄膜則應具備下列基本特性：⑴在可見光範圍的光透 過率與導電率皆高，⑺須能被製為表面平滑的薄膜，且能 承受電漿製程環境，（3)容易钱刻’以形成預定的圖樣 (pattern)，（4)可大面積均勻化，（5)低生產成本，（6)無毒並 旎回收再生。氧化銦錫（indium tin 〇xide，簡稱為ιτ〇)由於 兼具低薄膜片電阻與可見光透光率在80%〜90%的特性，已 成為透明導電薄膜最主要的原料來源，然而ΙΤ〇原料中的 銦屬於稀有金屬，產量有限，造成供給不穩定及原料成本節 節高升，因此，開發新的替代性材料已成為主要的課題。此 外，針對近來業界積極投入的觸控式面板與可撓曲面板，由 於ΙΤΟ薄膜不夠柔軟，在使用上相對具有耐用性相對較差 與可靠性相對較低的缺點。 針對ΙΤΟ的來源不足與其應用極限等問題，奈米碳管 為近來研究開發出來的一種熱門的替代性材料，主要是鑑於 奈米碳管材料有許多極優異的光、電、磁與機械特性，且其 巨觀物性與化性和材料本身微觀的排列方式與數量有直接關 係，而能影響到可應用的產品端，目前並已開發出可投入商 201024208 業化應用的單壁奈米礙管（single-walled carbon nanotubes， 簡稱為SWNT)導電薄膜。 單壁式奈米碳管導電薄膜主要是採用濾膜法與喷灑法 製成。其中，濾膜法是先以雷射法合成SWNT，並以高濃度 的硝酸溶液酸洗後，將其加入含有特定界面活性劑的溶劑形 成奈米碳管溶液中，再以特定的濾紙過濾使該等奈米碳管停 駐於濾紙表面形成奈米碳管濾膜，接著，將該奈米碳管濾膜 貼至透明基板上，再利用丙酮除去濾紙部分，只留下奈米碳 管，就能製得單壁式奈米碳管導電薄膜（“ Transparent， Conductive Carbon Nanotube Films” ，Z.Wu etc., Science 2004，305，1273、” Effect of SOC12 Treatment on Electrical and Mechanical Properties of Single-Wall Carbon Nanotube Networks”，U.Dettlaff-Weglikowska etc.，J. Am. Chem. Soc.， 2005, 127, 5125-5131)。 以喷灑法製備單壁式奈米碳管導電薄膜的製造方法則 是將預定量的單壁式奈米碳管加入並分散於含有特定界面活 性劑的溶劑中形成奈米碳管溶液，將該奈米碳管溶液離心後 ，取溶液上層50%的部分喷灑於表面溫度維持在100°C的聚 對苯二甲酸乙二醋（poly(ethylene terephthalate)，簡稱為 PET)基材上，接著，以去離子水清洗並烘乾，就能製得單 壁式奈米碳管導電薄膜（“ Effect of Acid Treatment on Carbon Nanotube-Based Flexible Transparent Conducting Films”，J· Am. Chem. Soc.，2007, 129, 7758-7759)。 雖然學界與業界的積極研究開發，已發展出各種互有 201024208 優劣的透明導電薄膜，而且其中的單壁式奈米碳管導電薄膜 的製造技術也進入準備商業化的階段’並有可取代IT〇薄 膜的趨勢’但相關配套的製程技術並非短時間就能成功，為 因應未來需求，並創造出更多更人性化的人機介面產品及軟 性電子產品，與觸控面板、可撓曲面板、透明電極等有關的 液晶顯示器的製程技術也將有所變革，其中，材料技術的成 熟度將疋關鍵的要素，因此，仍有持續開發不同類型的材料 技術的需求’以提供更多元的選擇與應用。 除了持續開發出新的，以及低成本的應用材料，為因 應商業上大量製造生產的需求，還應對應地設計能供實務 應用且能提高生產效率的製造技術，以降低整體生產成本 〇 【發明内容】 因此，本發明的目的，是在提供一種製程相對較簡化 ’且能符合大量製造生產需求的轉印式奈米碳管導電薄膜 的製造方法。 於是’本發明轉印式奈米碳管導電薄膜的製造方法， 包含下列步驟： (i) 配製一奈米碳管溶液，將預定量的奈米碳管組份加 入一預定量的溶劑中調配成黏度值介於idOc.p的奈米碳管 溶液，且該奈米碳管組份具有多數個多層壁奈米破管； (ii) 霧化’施加一超音波霧化頻率於該奈米碳管溶液， 使該奈米碳管溶液霧化成多數個分散且挾帶有該等奈米碳 管的霧化顆粒’並提供一攜帶氣體使該等霧化顆粒沿—預 201024208 疋路徑傳送’其中’該等霧化顆粒的粒徑是介於0.5/zm〜50 β m ； (iii)旋轉塗佈，將該等霧化顆粒引導至一放置有一第 基材片的基座，該基座藉由高速旋轉與低速旋轉的周期 變換’使該等霧化顆粒均句地塗佈於該第—基材片表面， 並形成多層導電薄膜；及 dv)轉印’使一表面能低於該第一基材片的表面能之 轉印片接觸該第一基材片上的導電薄膜，並施加壓力 200kg/cm，使該第一基材片上位於最上層的導電薄臈附 著到該轉印片上，再準備一表面能高於該轉印片的表面能 的第二基材片，使該轉印片接觸該第二基材片，並施加壓 力1 2G0kg/em ’使附著至該轉印片上的導電薄膜轉印到該 第二基材片上。 本發明的有益效果在於：除了能以多層壁奈米碳管為 導電薄膜的原料以減少原料成本，及結合超音波霧化與旋 轉塗佈技術以簡化該等奈米碳管製成多層導電薄膜的製程 卜還能藉由轉印方式將所製成的多層導電薄膜分別轉印 到不同的第二基材片上，藉以進行量化生產’使本發明具 有能降低成本、製程技術相對較簡單，及可供進行商業化 量產的優點。 【實施方式】 有關本發明之前述及其他技術内容、特點與功效，在 以下配合參考圖式之一個較佳實施例的詳細說明中，將可 清楚的呈現。 201024208 參閱圖1、圖2與圖3,本發明轉印式奈米碳管導電薄 膜的製造方法的較佳實施例包含下列步驟： 步驟101是純化，是分別以高濃度鹽酸溶液酸洗、沉 澱法水洗及真空乾燥處理以純化一奈米碳管組份中的多數 個多層壁奈米碳管，純化處理的主要目的在去除該等奈米 碳管原料中的氧化鐵、不定型碳、表面官能基等附著或混 摻在該等奈米碳管原料中的雜質，以提高多層壁奈米碳管 的導電度，進而使該等奈米碳管能表現出較佳的光電特質 〇 步驟102是配製一奈米碳管溶液20，將1重量份的的 奈米碳管組份及1重量份的界面活性劑組份分別加入 1000〜1000000重量份的溶劑中調配成黏度值介於1〜50c.p 的奈米碳管溶液20,且該奈米碳管組份具有多數個多層壁 奈米碳管。 該界面活性劑組份是用以防止該等多層壁奈米碳管聚 集，且為一選自下列群組中的物質：醇之硫酸酯鹽（sulfated alcohol，通式為 R〇S〇3-M+)、烧基績酸鹽（alkylsulfonate， 通式為 RSCVM')、α-稀烴確酸鹽（alpha-olefinsulphonate， 簡稱為AOS，通式為RCH=CH(CH2)n-S03M)、第四級銨鹽 ’ R，、卜 R-lji-R" Cl- (Quaternary ammonium salt，通式為、R”’ ^ )、環氧乙烧 系（亦稱聚乙二醇系，polyoxyethylene，簡稱為POE)、聚氧 乙烯烷基醚（又稱為脂肪醇聚氧乙烯醚、醚醇，alcohol ethoxylate，簡稱為 AE，通式為 R0(CH2CH20)nH)，及其等 201024208 之組合。 較佳地’該界面活性劑為一選自下列群組中的物質： C4〜C1S之直鏈烷基磺酸鈉（通式為RS〇3-Na+)、c4〜c18之直 鍵烷基績酸鉀（通式為RS〇3_K+)、C4〜C18之直鏈烧基硫酸鈉 (通式為ROS〇3_Na+)、C4〜c18之直鏈烷基硫酸鉀（通式為 ROSCVK+)、C4〜CU之直鏈烷基苯磺酸鈉（通式為RC6h4 S03Na+)、C4~C18之直鏈烷基苯磺酸鉀（通式為11(：61148〇3-K+)、C4〜Cu之直鏈烷基苯硫酸鈉（通式為R〇C6H4S〇3-Na+) 、c4〜c18之直鍵烧基苯硫酸鉀（通式為rOC6h4s〇3-k+)、 C2〜c16之直鏈烷基四級銨鹽、α_烯烴磺酸鹽（簡稱為A〇s， 通式為 RCH=CH(CH2)n-S03M’ 其中，n=14~16，且 Μ 為驗 金族離子）、烷基為C2〜CU之聚氧乙烯烷基醚（簡稱為ΑΕ, 通式為R0(CH2CIi20)nH，η=5〜30)，及其等之組合。藉此 ，可達到較佳的分散效果，在本實施例中，是選用 十二院基續酸納（sodium dodecyl sulfate，簡稱為SDS)作為 該界面活性劑。 其中’該溶劑為一選自下列群組中的液體：水、乙醇 、異丙醇及丙酮。配製時，於溶劑中添加該多層壁奈米碳 管組份與該界面活性劑後，可先以功率75〇w的探頭式超音 波震盈分散器（機型：Sonics & Materials，Inc.「SONICS® VCX750」）對該MWNT溶液以2〇%功率作用5分鐘，及 30%功率作用5分鐘，以防止該等多層壁奈米碳管聚集並呈 均勻分散的狀態。 步驟103是霧化，施加一超音波霧化頻率於該奈米碳 201024208 管溶液20，使該奈米碳管溶液2〇霧化成多數個分散且挾帶 有該等奈米碳管的霧化顆粒21，並提供一攜帶氣體22使該 等霧化顆粒21沿一預定路徑傳送。其中，該奈米碳管溶皱 20是盛裝於一霧化容器23中，且該溶液的液面是藉由—虹 吸管24維持在固定高度，藉此，使產生該超音波頻率的超 音波元件25恆位於液面下固定深度處，以控制該溶液液面 所承受的能量固定，及所產生的霧化顆粒21的粒徑能維持 一致。其中，該虹吸管24是連接在該霧化容器23與—貯 液容器28之間，該貯液容器28是置於一升降座29上，以 觉連動而上下位移，並能藉此控制該霧化容器23中的液面 高度。 較佳地’該超音波霧化頻率為2〇ΚΗζ〜2.45MHz，在本 實施例中則是採用1·65ΜΗζ的超音波霧化頻率（在本實施例 中所用的超音波霧化器的機型為：普崴電子Pr〇_Wave201024208 VI. Description of the Invention: [Technical Field] The present invention relates to a method for producing a conductive film, and more particularly to a method for producing a transfer type carbon nanotube conductive film. a [Prior Art] With the wide application and development of LCD screens, the development of conductive materials is a hot research topic. Transparent conductive films used in displays and touch panels should have the following basic characteristics: (1) The light transmittance and conductivity in the visible light range are high, (7) must be made into a smooth surface film, and can withstand the plasma process environment, (3) easy to engrave 'to form a predetermined pattern, (4) It can be homogenized over a large area, (5) low production cost, and (6) non-toxic and recycled. Indium tin 〇xide (abbreviated as ιτ〇) has the characteristics of low film resistance and visible light transmittance of 80% to 90%, and has become the most important source of raw materials for transparent conductive films. Indium is a rare metal, and its production is limited, resulting in unstable supply and high raw material costs. Therefore, the development of new alternative materials has become a major issue. In addition, the touch panels and flexible panels that have been actively invested in the industry in recent years are disadvantageous in that the film is not sufficiently soft and relatively durable in use and relatively low in reliability. In view of the lack of sources of antimony and its application limit, carbon nanotubes are a popular alternative material developed recently, mainly because of the excellent optical, electrical, magnetic and mechanical properties of nanocarbon tubes. Moreover, its macroscopic physical properties and chemical properties are directly related to the microscopic arrangement and quantity of the materials themselves, and can affect the applicable product end. At present, the single-walled nano-intrusion can be developed for the commercial application of 201024208. (Single-walled carbon nanotubes, abbreviated as SWNT) conductive film. The single-walled carbon nanotube conductive film is mainly made by a filter method and a spray method. Among them, the filter method is to first synthesize SWNT by laser method, pickle it with a high concentration of nitric acid solution, add it to a solvent containing a specific surfactant to form a carbon nanotube solution, and then filter it with a specific filter paper. The carbon nanotubes are parked on the surface of the filter paper to form a carbon nanotube filter membrane. Then, the carbon nanotube membrane is attached to the transparent substrate, and the filter paper portion is removed by acetone, leaving only the carbon nanotubes. A single-walled carbon nanotube conductive film ("Transparent, Conductive Carbon Nanotube Films", Z. Wu et., Science 2004, 305, 1273," Effect of SOC12 Treatment on Electrical and Mechanical Properties of Single-Wall Carbon Nanotube Networks", U. Dettlaff-Weglikowska et., J. Am. Chem. Soc., 2005, 127, 5125-5131). The method for preparing a single-walled carbon nanotube conductive film by spraying method is to add a predetermined amount of single-walled carbon nanotubes to a solvent containing a specific surfactant to form a carbon nanotube solution, and After centrifugation of the carbon nanotube solution, a 50% portion of the upper layer of the solution was sprayed onto a poly(ethylene terephthalate, abbreviated as PET) substrate having a surface temperature maintained at 100 ° C. Then, by washing and drying with deionized water, a single-walled carbon nanotube conductive film ("Issue of Acid Treatment on Carbon Nanotube-Based Flexible Transparent Conducting Films", J. Am. Chem. Soc., 2007, 129, 7758-7759). Although the academic and industry's active research and development, has developed a variety of transparent conductive film with the advantages of 201024208, and the manufacturing technology of the single-walled carbon nanotube conductive film has also entered the stage of preparation for commercialization' and has the ability to replace IT. The trend of 〇 film 'but the related process technology can not be successful in a short time, in order to meet future needs, and create more humane interface products and soft electronic products, with touch panels, flexible panels The process technology of liquid crystal displays, such as transparent electrodes, will also change. Among them, the maturity of material technology will be a key factor. Therefore, there is still a need to continuously develop different types of material technologies to provide more yuan. Choice and application. In addition to the continuous development of new and low-cost application materials, in order to meet the needs of commercial mass production, we should also design manufacturing technologies that can be used for practical applications and improve production efficiency to reduce overall production costs. SUMMARY OF THE INVENTION Accordingly, it is an object of the present invention to provide a method of manufacturing a transfer type carbon nanotube conductive film which is relatively simple in process and which can meet a large number of manufacturing and production requirements. Thus, the method for producing a transfer type carbon nanotube conductive film of the present invention comprises the following steps: (i) preparing a carbon nanotube solution, and adding a predetermined amount of the carbon nanotube component to a predetermined amount of solvent. a carbon nanotube solution having a viscosity value of idOc.p, and the carbon nanotube component has a plurality of multi-walled nanotubes; (ii) atomization 'applying an ultrasonic atomization frequency to the nanometer a carbon tube solution that atomizes the nanocarbon tube solution into a plurality of atomized particles dispersed with the carbon nanotubes and provides a carrier gas to transport the atomized particles along the path of the pre-201024208 ' Wherein the particle size of the atomized particles is between 0.5/zm and 50 β m; (iii) spin coating, directing the atomized particles to a susceptor on which a substrate sheet is placed, the susceptor The atomized particles are uniformly applied to the surface of the first substrate sheet by a periodic conversion of high-speed rotation and low-speed rotation, and a multilayer conductive film is formed; and dv) transfer enables a surface energy to be lower than the The transfer sheet of the surface energy of the first substrate sheet contacts the conductive film on the first substrate sheet, And applying a pressure of 200 kg/cm to adhere the uppermost conductive thin layer on the first substrate sheet to the transfer sheet, and preparing a second substrate sheet having a surface energy higher than the surface energy of the transfer sheet. The transfer sheet contacts the second substrate sheet, and a pressure of 1 2 G0 kg/em ' is applied to transfer the conductive film attached to the transfer sheet onto the second substrate sheet. The invention has the beneficial effects of reducing the raw material cost by using the multi-layered wall carbon nanotube as the raw material of the conductive film, and combining the ultrasonic atomization and spin coating technology to simplify the formation of the multilayer conductive film of the carbon nanotubes. The process can also transfer the prepared multilayer conductive film to different second substrate sheets by transfer method, thereby performing quantitative production, so that the invention has the advantages of reducing cost and relatively simple process technology, and The advantages of commercial mass production. The above and other technical contents, features, and advantages of the present invention will be apparent from the following detailed description of the preferred embodiments. 201024208 Referring to FIG. 1, FIG. 2 and FIG. 3, a preferred embodiment of the method for manufacturing a transfer type carbon nanotube conductive film of the present invention comprises the following steps: Step 101 is purification, which is respectively pickled and precipitated with a high concentration hydrochloric acid solution. Method for washing and vacuum drying to purify a plurality of multi-walled carbon nanotubes in a carbon nanotube component. The main purpose of the purification treatment is to remove iron oxide, amorphous carbon and surface in the carbon nanotube raw materials. Functional groups or the like are attached or mixed with impurities in the carbon nanotube raw materials to improve the conductivity of the multilayered carbon nanotubes, thereby enabling the carbon nanotubes to exhibit better photovoltaic characteristics. Step 102 Is to prepare a carbon nanotube solution 20, 1 part by weight of the carbon nanotube component and 1 part by weight of the surfactant component are respectively added to 1000~1000000 parts by weight of the solvent to prepare a viscosity value of 1~ 50c.p of the carbon nanotube solution 20, and the carbon nanotube component has a plurality of multi-layered wall carbon nanotubes. The surfactant component is used to prevent the aggregation of the multi-layered wall carbon nanotubes, and is a substance selected from the group consisting of a sulfated alcohol (formula: R〇S〇3- M+), alkylsulfonate (formula: RSCVM'), alpha-olefinsulphonate (abbreviated as AOS, general formula RCH=CH(CH2)n-S03M), fourth Ammonium salt 'R,, R-lji-R" Cl- (Quaternary ammonium salt, general formula, R"' ^), epoxy ethene (also known as polyethylene glycol, polyoxyethylene, POE for short) , a polyoxyethylene alkyl ether (also known as fatty alcohol polyoxyethylene ether, ether alcohol, alcohol ethoxylate, abbreviated as AE, of the formula R0 (CH2CH20) nH), and combinations thereof, such as 201024208. Preferably' The surfactant is a substance selected from the group consisting of sodium C4~C1S linear alkyl sulfonate (formula: RS〇3-Na+), c4~c18 direct bond alkyl acid potassium (pass) The formula is RS〇3_K+), C4~C18 linear sodium sulphate (formula ROS〇3_Na+), C4~c18 linear alkyl sulphate (formula of ROSCVK+), C4~CU linear alkane base Sodium benzenesulfonate (formula: RC6h4 S03Na+), potassium C4~C18 linear alkylbenzenesulfonate (linear formula of 11(:61148〇3-K+), C4~Cu linear sodium alkylbenzeneate ( The formula is R〇C6H4S〇3-Na+), c4~c18 of direct-bonding potassium phenyl sulfate (formula: rOC6h4s〇3-k+), C2~c16 linear alkyl quaternary ammonium salt, α-olefin a sulfonate (abbreviated as A〇s, a formula of RCH=CH(CH2)n-S03M' wherein n=14~16, and Μ is a gold-requiring ion), and an alkyl group having a polyoxyethylene of C2~CU An alkyl ether (abbreviated as hydrazine, a formula of R0(CH2CIi20)nH, η=5~30), and combinations thereof, thereby achieving a better dispersion effect. In this embodiment, ten is selected. The second hospital is sodium dodecyl sulfate (SDS) as the surfactant. The solvent is a liquid selected from the group consisting of water, ethanol, isopropanol and acetone. After adding the multi-layered wall carbon nanotube component and the surfactant to the solvent, the probe-type ultrasonic shock diffuser with a power of 75 〇w can be used first (model: Sonics & Materials, Inc. "SONICS® VCX750" ") on the MWNT 2〇% power to effect solution for 5 minutes, and 30% power is applied for five minutes, to prevent such aggregation and form a multilayer SWNTs uniformly dispersed. Step 103 is atomization, applying an ultrasonic atomization frequency to the nanocarbon 201024208 tube solution 20, atomizing the carbon nanotube solution 2 into a plurality of dispersed and atomized carbon nanotubes. The particles 21 and a carrier gas 22 are provided to transport the atomized particles 21 along a predetermined path. Wherein, the carbon nanotube wrinkle 20 is contained in an atomizing container 23, and the liquid level of the solution is maintained at a fixed height by the siphon tube 24, thereby generating an ultrasonic component of the ultrasonic frequency. 25 is constant at a fixed depth below the liquid surface to control the energy of the liquid surface of the solution to be fixed, and the particle size of the atomized particles 21 produced can be maintained consistently. Wherein, the siphon tube 24 is connected between the atomization container 23 and the liquid storage container 28, and the liquid storage container 28 is placed on a lifting seat 29 to be vertically displaced by the linkage, and the mist can be controlled thereby. The liquid level in the container 23. Preferably, the ultrasonic atomization frequency is 2 〇ΚΗζ to 2.45 MHz, and in this embodiment, the ultrasonic atomization frequency of 1.65 ( is used (the ultrasonic atomizer used in the embodiment) Type: Pu'er Electronics Pr〇_Wave
Electronic Corp M165D25、M165D20)，而該等霧化顆粒 21 的粒徑則是介於〇.5/zm〜50/zm，且較佳是介於〜7#m ，在本實施例中’則是配合超音波霧化頻率使該等霧化顆 粒21的粒徑實質上維持在3/zm左右。 為了符合所要求的粒徑大小，可透過下列公式推算該 超音波的頻率範圍，以較快速地調整到所要求的霧化顆粒 尺寸：Electronic Corp M165D25, M165D20), and the particle size of the atomized particles 21 is between 〇.5/zm~50/zm, and preferably between ~7#m, in the present embodiment, 'is The particle diameter of the atomized particles 21 is substantially maintained at about 3/zm in conjunction with the ultrasonic atomization frequency. In order to meet the required particle size, the frequency range of the ultrasonic wave can be estimated by the following formula to adjust to the required atomized particle size more quickly:
(8πΤ V 〇=« -γγ(8πΤ V 〇=« -γγ
Ipf J 其中’D為霧化顆粒的粒徑，τ為表面張力係數（N/cm) ，P為溶液密度（g/cm3)，f為超音波霧化頻率（Hz)，及α為 201024208 0.34 的常數值。（Ultrasonics Volume 22, Issue 6，November 1984, Pages 259-260) 較佳地，該攜帶氣體22的流速為lL/min〜200L/min， 在本實施例中，該攜帶氣體22的流速則是設定為22L/min ，且該攜帶氣體21為氮氣。 步驟104是旋轉塗佈，將該等霧化顆粒21引導至一放 置有一第一基材片26的基座27上方，該基座27並藉由高 速旋轉與低速旋轉的周期變換，使該等霧化顆粒均勻地塗 佈於該第一基材片26表面，並形成多層導電薄膜。 進行旋轉途佈時，配合調整該基座27的低速、中速與 高速轉速，該等霧化顆粒21是分別對該基座27進行一次 濕潤旋轉塗佈、一次初步成膜旋轉塗佈與多次的再成膜旋 轉塗佈5以在該基座27形成多層導電薄膜。進行該再成膜 旋轉塗佈時，該基座27是依序經由一低速轉速、一中速轉 速及一高速轉速的周期變換旋轉，且該低速、中速與高速 轉速的比率為2〜3 : 3〜6 : 8〜40。在本實施例中，該低速轉 速較佳為300 r.p.m.〜450r.p.m.，該中速轉速較佳是控制在 450 r.p.m.〜900 r.p.m.，及該高速轉速較佳是 1200 r.p.m.~6000_r.p.m.。 步驟105是清洗，是將具有多層導電薄膜的第一基材 片26先置於去離子水中潤洗5〜30分鐘，並浸泡2小時換 水，重複5次，再浸泡乙醇2小時，再於溫度60°C下抽真 空，藉此可去除殘留在該等導電薄膜中的界面活性劑，以 免殘留雜質造成該等導電薄膜的導電度降低 10 201024208 步驟106是轉印，使一表面能低於該第一基材片26的 表面能的轉印片30接觸塗佈在該第一基材片26上的導電 薄膜 100，並於溫度 50 °C ~11〇 °C下，施加壓力 lkg/cm2〜200kg/cm2，使該第一基材片26上位於最上層的導 電薄膜100附著到該轉印片30上，再準備一表面能高於該 轉印片30的表面能的第二基材片31，使該轉印片30接觸 該第二基材片31，並於溫度50°C〜110°C下，施加壓力 lkg/cm2〜200kg/cm2，使附著至該轉印片30上的導電薄膜 100轉印到該第二基材片31上，就能製得結合在該第二基 材片3 1的奈米碳管導電薄膜成品。 在該實施例中，是在溫度70°C下施加壓力l〇〇kg/cm2 一段時間，以使位於該第一基材片26最上層的導電薄膜 100轉而附著到該轉印片30上。其中，該第一基材片26的 材質是選用聚對苯二甲酸乙二醋（P〇ly(ethylene terephthalate)，簡稱為PET)，該轉印片30的材質則為聚二 曱基石夕氧烧(poly(dimethylsiloxane)，簡稱為 PDMS)。 較佳地，該第二基材片3 1則為一選自下列群組中的材 質所製成：聚對苯二甲酸乙二酯（PET)、玻璃、聚曱基丙烯 酸曱醋（p〇ly(methyl methacrylate)，簡稱為 PMMA)、聚碳酸 酉旨（polycarbonate，簡稱為 PC)、聚丙浠（polypropylene，簡 稱為PP)及聚乙烯（polyethylene，簡稱為PE)。此外，該第 一基材片26除了以PET為材質外，也能採用前述與該第二 基材片31相同的材質製成。 接著再重複執行步驟106,並不斷提供新的第二基材片 11 201024208 31，使位於該第一基材片26上的多層導電薄膜分次轉印至 不同的第二基材片31上，直到該第一基材片26上的多層 導電薄膜100被轉印完為止。 步驟107是熱壓，轉印到該第二基材片31上導電薄膜 100須再經熱壓處理以穩定導電結構，熱壓條件為在溫度 50°C〜90°C下施加壓力50-200kg/cm2、熱壓時間為10秒至 30分鐘，且較佳地，熱壓前需先以鐵氟龍薄膜作為離型材 質覆蓋在該導電薄膜上，熱壓結束後就能在不破壞導電薄 膜的情況下將鐵氟龍薄膜撕離。 <具體例> (1) 純化lg的多層壁奈米碳管（MWNT):先配製6M的 濃鹽酸溶液250ml，再將lg的MWNT投入該鹽酸溶液中， 並攪拌24小時，再以沉澱法水洗6次，接著，再重新配製 6M鹽酸250ml，再以前述的酸洗及水洗方式繼續純化 MWNT，如此重覆三次，純化完成的MWNT分別在溫度80 °C，12小時及溫度250°C，24小時的條件下進行真空乾燥 ，再置入氮氣烘箱中以溫度400°C烘乾。 (2) 配置10mg/L的MWNT水溶液：於1L的去離子水中 投入10mg的MWNT及10mg的SDS，可先以功率750W的 探頭式超音波震盪分散器（機型：Sonics & Materials, Inc.「 SONICS® VCX750」）對該MWNT溶液以20%功率作用5分 鐘，及30%功率作用5分鐘，以防止該等多層壁奈米碳管 聚集並維持均勻分散的狀態。 (3) 霧化：將超音波震動片置於液面下3.0cm的深度處 12 201024208 ，並使溶液的溫度維持在30〇c，提供l 65MHz的超音波霧 化頻率作用於該奈米碳管溶液，則可達到25〜30ml/hr的霧 化率，且霧化顆粒的粒徑約為3em，利用一與盛裝 溶液的容器相連通的輸氣管送入攜帶氣體，該攜帶氣體的 流速為22L/min。 (4)旋轉塗佈.該攜帶氣體將該等霧化顆粒引導到一旋 轉塗佈機的基座上，放置於該基座的第一基材片為ρΕτ材 春 質’且是與該基座同步旋轉，進行旋轉塗佈前，該第一基 材片是先於500 r.p.m.的轉速下以去離子水清洗4〇秒，再於 800 r.p.m.的轉速下以酒精清洗60秒，再進行該等超音波霧 化顆粒的旋轉塗佈。 進行超音波霧化顆粒的旋轉塗佈時，是先經一次濕潤 旋轉塗佈與一次初步成膜旋轉塗佈的預處理，再重複進行 多次周期性的再成膜旋轉塗佈《其中’進行濕潤旋轉塗佈 的轉速為300 r.p.m與450r.p.m·相交替數次，進行初步成膜 • 旋轉塗佈的轉速則為自450 r.p.m.依階梯式上升到 6000r.p.m.後，再進入周期性的再成膜旋轉。塗佈進行的過 程中，該基座是以如圖4所示的階段式周期進行連續旋轉 ，且區間（I)表示濕潤旋轉塗佈的轉速變化，區間（11)表示初 步成膜旋轉塗佈時的階梯式轉速變化，區間（III)、（IV)、 皆為再成膜旋轉塗佈時的階梯式轉速變化，藉此，使該等 霧化顆粒能較均勻地塗佈至該第一基材片表面，且能透過 再成膜旋轉塗佈的次數控制導電薄膜的成膜層數，及利用 高低轉速的周期變換與時間長短控制成膜厚度。 13 201024208 在圖4中’不同階段別分別以不同字母表示，並將其 所代表的轉速與時間整理如下表1。 泰1-旋轉塗佈各周期不同階段別所設定的轉速與旋轉時間 a b c d e f g h i i 轉速（r.p.m..) 300 450 450 600 750 900 1200 2500 4500 j 6000 時間（秒） 30 20 20 20 20 20 60 60 60 180 旋轉塗佈的時間是控制在1 〇分鐘〜240分鐘，並能藉由 再成膜旋轉塗佈（即階段a到f的過程）的次數決定所形成的 多層壁奈米碳管導電薄膜的層數。每一層薄膜的厚度則再 以階段a到f其中的階段c_f的時間控制。如果需要進行多 參 次轉印，進行再成膜旋轉塗佈的次數要相應地增加，塗佈 時間通常必須超過30分鐘，為了確保轉印結果的再現性， 成膜層數應要超過5層，最佳是形成1〇層以上的薄膜，可 得到較穩定的轉印品質。 ❹ 值得說明的是，每一次再成膜旋轉塗佈時，當轉速範 圍在1_啊以下的低速或中速時，主要是進行渔潤與表 面塗佈，當轉速範圍在4500rpm α上的高速時則為乾燥步 驟’藉由操作轉速純速到高衫成—次再成膜旋轉塗佈 ’可形成-層薄膜，若重複進行從關塗饰與乾燥的再成 膜旋轉塗佈射形成多層薄膜，因此可藉由再成膜旋轉塗 佈的次數控制層數。減目前實驗結果，當成制數超過$ 層以上時，轉印後的導電薄琪是均其 圍可控制在±2.5〇/〇以内。 千茭動軏 (5)清洗：以前述步驟1〇5 一基材片上的多層導電薄膜， 所述的方式清洗形成在該第 以去除殘留在該等導電薄膜 14 201024208 中的界面活性劑。 (6)轉印：參閲圖6，進行轉印時，是將形成有多層導電 薄膜501㈣第一基材# 5〇2置於—熱廢機的上下麼模之 間，將該上下壓模的溫度升溫至7〇<t，並維持恆溫】小時 ，另外裁剪二片5 cmx5 cm的PET薄片5〇4，並分別以去離 子水、乙醇、去離子水、丙酮、去離子水的清洗順序潤洗 該等PET薄片5〇4,再分別於該第一基材片5〇2上方提供 PDMS轉印# 505，及於其下方放置二片pET薄片5〇4 式夾住已設置有該等導電薄膜501的第一基材片5〇2，再取 10 cnixlO cm的不銹鋼夾具503上下疊合於該pDMS轉印片 505與該二PET薄片504外，並置於該熱壓機的上下壓模 之間，並施加10kg/cm2壓力熱壓3〇分鐘，使該第一基材片 502上位於最上層的導電薄膜5〇1附著到該轉印片5〇5上， 再準備一表面能高於該轉印片505的表面能的第二基材片 5〇6放到該轉印片505下方，使該轉印片5〇5接觸該第二基 材片506,並於溫度70。(：下，施加壓力10kg/cm2,使附著 於該轉印片505上的導電薄膜501轉印到該第二基材片5〇6 上》 (7)熱壓：參閱圖7，轉印到該第二基材片5〇6上的導電 薄膜501須再經熱壓處理以穩定導電結構，熱壓前須另外 裁剪四片5 cmx5 cm的pet薄片507，並分別以去離子水、 乙醇、去離子水、丙酮、去離子水的清洗順序潤洗該等 PET薄片507,再以上下各二片的方式夾住已設置有轉印有 §^導電薄膜501的第二基材片506，再取l〇cmxi〇cm的不 15 201024208 銹鋼夾具508上下疊合於pet薄片507外，此外，在上方 的不銹鋼夾具與PET薄片507之間還設置一 PDMS薄片 509’最後’將前述相疊合的組合體一起置於該熱壓機的上 下壓模之間，並施加l〇〇kg/cm2的壓力熱壓30分鐘，如此 就能製得結合在該第二基材片5〇6的奈米碳管導電薄膜成 品。其中，設置該PDMS薄片509有協助熱壓平整的功能 〇 <耐曲撓性測試> 參閱圖5 ’將所製得的附有導電薄膜的第二基材片裁成 lcmx2cm的試片41，並量測該試片41未受彎折前的導電度 。接著’將該試片41較長邊的二相反側分別固定至一固定 夾座42 ’及一與該固定夾座42相間隔的活動夾座43，再 使該活動夾座43靠向該固定夾座41位移至該試片41長邊 二相反侧的間距為1 cm ’再進一步位移到該試片4〗長邊的 二相反侧的間距為0.5cm為止，該試片41會隨著該活動夾 座43的活動而曲撓彎折，再使該活動夾座43遠離該固定 夾座42位移，使該試片41回復為平直狀態，量測該試片 41受彎折後的片電阻，並重複前述使該試片41曲撓彎折的 動作’且該試片41每次回復到平直狀態後都再測一次片電 阻’藉由片電阻的變化可相應地反應出導電度的變化，片 電阻值越穩定表示導電度值也越穩定。Ipf J where 'D is the particle size of the atomized particles, τ is the surface tension coefficient (N/cm), P is the solution density (g/cm3), f is the ultrasonic atomization frequency (Hz), and α is 201024208 0.34 Constant value. (Ultrasonics Volume 22, Issue 6, November 1984, Pages 259-260) Preferably, the flow rate of the carrier gas 22 is from 1 L/min to 200 L/min. In the present embodiment, the flow rate of the carrier gas 22 is set. It is 22 L/min and the carrier gas 21 is nitrogen. Step 104 is spin coating, and the atomized particles 21 are guided onto a susceptor 27 on which a first substrate sheet 26 is placed, and the susceptor 27 is rotated by a high-speed rotation and a low-speed rotation cycle. The atomized particles are uniformly coated on the surface of the first substrate sheet 26, and a multilayer conductive film is formed. When the rotating cloth is rotated, the low speed, the medium speed and the high speed speed of the base 27 are adjusted, and the atomized particles 21 are subjected to a wet spin coating, a preliminary film forming spin coating, and a plurality of the atomizing particles 21, respectively. The secondary re-filming spin coating 5 forms a multilayer conductive film on the susceptor 27. When the re-filming spin coating is performed, the susceptor 27 is sequentially rotated by a period of a low speed, a medium speed, and a high speed, and the ratio of the low speed, the medium speed, and the high speed is 2 to 3. : 3~6: 8~40. In this embodiment, the low speed rotation speed is preferably 300 r.p.m. to 450 r.p.m., and the medium speed is preferably controlled at 450 r.p.m. to 900 r.p.m., and the high speed is preferably 1200 r.p.m.~6000_r.p.m. Step 105 is cleaning. The first substrate sheet 26 having a plurality of conductive films is firstly rinsed in deionized water for 5 to 30 minutes, and soaked for 2 hours for water exchange, repeated 5 times, and then soaked in ethanol for 2 hours, and then at a temperature. Vacuuming at 60 ° C, thereby removing the surfactant remaining in the conductive film to prevent residual impurities from causing the conductivity of the conductive film to decrease 10 201024208 Step 106 is transfer, so that a surface energy is lower than the The surface transfer sheet 30 of the first substrate sheet 26 is in contact with the conductive film 100 coated on the first substrate sheet 26, and is applied at a temperature of 50 ° C to 11 ° C to apply a pressure of lkg/cm 2 . 200 kg/cm 2 , the uppermost conductive film 100 on the first substrate sheet 26 is attached to the transfer sheet 30, and a second substrate sheet having a surface energy higher than the surface energy of the transfer sheet 30 is prepared. 31, the transfer sheet 30 is brought into contact with the second base material sheet 31, and a pressure of lkg/cm2 to 200 kg/cm2 is applied at a temperature of 50 ° C to 110 ° C to cause electrical conduction to the transfer sheet 30. The film 100 is transferred onto the second substrate sheet 31 to obtain a carbon nanotube guide bonded to the second substrate sheet 31. Finished electrical film. In this embodiment, a pressure of 1 〇〇kg/cm 2 is applied at a temperature of 70 ° C for a period of time to cause the conductive film 100 located at the uppermost layer of the first substrate sheet 26 to be attached to the transfer sheet 30. . The material of the first substrate sheet 26 is made of polyethylene terephthalate (PET), and the material of the transfer sheet 30 is polyfluorene. Burn (poly(dimethylsiloxane), abbreviated as PDMS). Preferably, the second substrate sheet 31 is made of a material selected from the group consisting of polyethylene terephthalate (PET), glass, and polyacrylic acid vinegar (p〇). Ly (methyl methacrylate), abbreviated as PMMA), polycarbonate (referred to as PC), polypropylene (polypropylene, abbreviated as PP) and polyethylene (referred to as PE). Further, the first base material sheet 26 can be made of the same material as the second base material sheet 31 in addition to PET. Then, step 106 is repeated, and a new second substrate sheet 11 201024208 31 is continuously provided, and the multilayer conductive film located on the first substrate sheet 26 is successively transferred onto the different second substrate sheets 31. Until the multilayer conductive film 100 on the first substrate sheet 26 is transferred. Step 107 is hot pressing, and the conductive film 100 transferred onto the second substrate sheet 31 is subjected to hot pressing treatment to stabilize the conductive structure, and the hot pressing condition is to apply a pressure of 50-200 kg at a temperature of 50 ° C to 90 ° C. /cm2, the hot pressing time is 10 seconds to 30 minutes, and preferably, the Teflon film is first coated on the conductive film as a release material before hot pressing, and the conductive film can be destroyed without being destroyed after the hot pressing. In the case of tearing off the Teflon film. <Specific Example> (1) Purification of lg multi-walled nanotubes (MWNT): 250 ml of a 6 M concentrated hydrochloric acid solution was first prepared, and lg of MWNT was put into the hydrochloric acid solution, and stirred for 24 hours, followed by precipitation. The method was washed 6 times, then reconstituted with 250 ml of 6M hydrochloric acid, and then the MWNT was further purified by the above-mentioned pickling and washing, so as to be repeated three times, and the purified MWNT was respectively at a temperature of 80 ° C, 12 hours and a temperature of 250 ° C. Vacuum drying was carried out under conditions of 24 hours, and then placed in a nitrogen oven to dry at a temperature of 400 °C. (2) Configure 10mg/L MWNT aqueous solution: Put 10mg MWNT and 10mg SDS in 1L deionized water, firstly use 750W probe type ultrasonic oscillating disperser (model: Sonics & Materials, Inc. "SONICS® VCX750") was applied to the MWNT solution at 20% power for 5 minutes and 30% power for 5 minutes to prevent the multi-walled nanotubes from collecting and maintaining a uniformly dispersed state. (3) Atomization: The ultrasonic vibration plate is placed at a depth of 3.0 cm below the liquid surface 12 201024208, and the temperature of the solution is maintained at 30 〇c, and a supersonic atomization frequency of 65 MHz is applied to the nano carbon. The tube solution can reach an atomization rate of 25 to 30 ml/hr, and the atomized particles have a particle diameter of about 3 cm. The carrier gas is fed into the gas pipe connected to the container containing the solution, and the flow rate of the carrier gas is 22L/min. (4) spin coating. The carrier gas guides the atomized particles onto a susceptor of a spin coater, and the first substrate sheet placed on the susceptor is a sputum material and is associated with the base The seat is rotated synchronously. Before the spin coating, the first substrate sheet is washed with deionized water for 4 seconds at 500 rpm, and then washed with alcohol at 800 rpm for 60 seconds. Spin coating of ultrasonic atomized particles. When the spin coating of the ultrasonic atomized particles is performed, the pretreatment by one wet spin coating and one preliminary film spin coating is repeated, and then a plurality of periodic re-filming spin coatings are repeatedly performed. Wet spin coating speed is 300 rpm and 450r.pm· alternates several times for preliminary film formation • The speed of spin coating is stepped up to 6000r.pm from 450 rpm, and then enters the periodic cycle. Film formation is rotated. During the coating process, the susceptor is continuously rotated in a staged cycle as shown in FIG. 4, and the interval (I) represents the change in the rotational speed of the wet spin coating, and the interval (11) represents the preliminary film forming spin coating. In the case of the stepwise rotation speed change, the sections (III) and (IV) are all the stepwise rotation speeds during the recoating spin coating, whereby the atomized particles can be uniformly applied to the first The surface of the substrate sheet is controlled by the number of times of spin coating of the film, and the number of film formation layers of the conductive film is controlled, and the film thickness is controlled by the period change of the high and low rotation speeds and the length of time. 13 201024208 In Figure 4, the different stages are indicated by different letters, and the speed and time they represent are organized as shown in Table 1. The speed and rotation time set by the different stages of the spin-coating cycle are abcdefghii speed (rpm.) 300 450 450 600 750 900 1200 2500 4500 j 6000 time (seconds) 30 20 20 20 20 20 60 60 60 180 The cloth time is controlled from 1 minute to 240 minutes, and the number of layers of the multilayered walled carbon nanotube conductive film formed can be determined by the number of times of re-filming spin coating (i.e., the process of stages a to f). The thickness of each layer of film is then controlled by the time of stage c_f of stages a to f. If multi-parallel transfer is required, the number of re-filming spin coatings should be increased accordingly, and the coating time must usually exceed 30 minutes. In order to ensure the reproducibility of the transfer results, the number of film formation layers should exceed 5 layers. It is preferable to form a film of one layer or more, and a relatively stable transfer quality can be obtained.值得 It is worth noting that each time the film is coated by spin coating, when the speed range is below 1_ah, the low speed or medium speed is mainly for the fishing and surface coating, when the speed range is 4500rpm α. In the case of the drying step, the film can be formed by the operation speed from the pure speed to the high-coating, and the film can be formed by spin coating of the coating and drying. Since the film is used, the number of layers can be controlled by the number of times of spin coating. Subtracting the current experimental results, when the number of products exceeds more than $ layer, the conductive thin film after transfer can be controlled within ±2.5〇/〇.千茭动軏 (5) Cleaning: The above-mentioned step 1〇5, a multilayer conductive film on a substrate sheet, is cleaned in the manner described above to remove the surfactant remaining in the conductive film 14 201024208. (6) Transfer: Referring to FIG. 6, when performing transfer, a plurality of conductive films 501 (four) first substrate #5〇2 are placed between the upper and lower molds of the hot waste machine, and the upper and lower molds are pressed. The temperature is raised to 7 〇 < t, and the temperature is kept constant for an hour, and two 5 cm x 5 cm PET sheets 5 〇 4 are separately cut and washed with deionized water, ethanol, deionized water, acetone, deionized water, respectively. The PET sheets 5〇4 are sequentially rinsed, and then PDMS transfer #505 is provided above the first substrate sheet 5〇2, and two pET sheets are placed under the bottom sheet 5〇4. The first substrate sheet 5〇2 of the conductive film 501 is further stacked on the pDMS transfer sheet 505 and the second PET sheet 504 by a 10 cnixlO cm stainless steel jig 503, and placed on the upper and lower sides of the hot press. Between the molds, and applying a pressure of 10 kg/cm 2 for 3 minutes, the uppermost conductive film 5〇1 of the first substrate sheet 502 is attached to the transfer sheet 5〇5, and a surface energy is prepared. A second substrate sheet 5〇6 higher than the surface energy of the transfer sheet 505 is placed under the transfer sheet 505, and the transfer sheet 5〇5 is brought into contact with the second substrate sheet 5. 06, and at a temperature of 70. (: Next, a pressure of 10 kg/cm 2 was applied to transfer the conductive film 501 attached to the transfer sheet 505 onto the second substrate sheet 5 〇 6 (7) Hot pressing: Referring to Fig. 7, transfer to The conductive film 501 on the second substrate sheet 5〇6 is subjected to hot pressing treatment to stabilize the conductive structure, and four pieces of 5 cm×5 cm pet sheets 507 are additionally cut before hot pressing, and respectively, deionized water, ethanol, and The PET sheet 507 is rinsed in the order of cleaning the ionized water, acetone, and deionized water, and the second substrate sheet 506 on which the conductive film 501 is transferred is sandwiched between the two sheets, and then taken. L〇cmxi〇cm的不15 201024208 The stainless steel clamp 508 is superimposed on the pet sheet 507, and a PDMS sheet 509' is finally disposed between the upper stainless steel jig and the PET sheet 507. The assembly is placed together between the upper and lower stampers of the hot press, and subjected to a pressure hot pressing of 1 〇〇kg/cm 2 for 30 minutes, so that the nano bonded to the second substrate sheet 5 〇 6 can be obtained. A carbon tube conductive film product, wherein the PDMS sheet 509 is provided with a function of assisting hot pressing and flatness <flexibility resistance measurement Test> Referring to Fig. 5', the prepared second substrate sheet with the conductive film was cut into a test piece 41 of 1 cm x 2 cm, and the conductivity of the test piece 41 before being bent was measured. The two opposite sides of the longer side of the test piece 41 are respectively fixed to a fixed holder 42' and a movable holder 43 spaced apart from the fixed holder 42, and the movable holder 43 is displaced toward the fixed holder 41. The distance to the opposite side of the long side 2 of the test piece 41 is 1 cm', and further displaced to the opposite side of the long side of the test piece 4, the distance between the two sides is 0.5 cm, and the test piece 41 follows the movable holder 43. The movement is flexed and bent, and the movable clamp 43 is displaced away from the fixed clamp 42 to return the test piece 41 to a flat state, and the sheet resistance of the test piece 41 after being bent is measured and repeated. The above-described operation of bending the test piece 41 by bending and re-measuring the sheet resistance once the test piece 41 returns to the flat state can reflect the change of the conductivity correspondingly by the change of the sheet resistance. The more stable the resistance value, the more stable the conductivity value.
分別以刖述具體例的製造方法藉由轉印與熱壓在一 PET基材表面形成奈米碳管導電薄膜（以CNT/PET表示，在 此是選擇第1次轉印的奈米破管導電薄膜），及在另一 pET 201024208 基材上形成ITO薄膜（以ITO/PET表示），再分別將 CNT/PET、ITO/PET皆裁剪為如前所述尺寸的試片分別進行 耐曲撓性測試，其中，ITO/PET試片未受曲撓前的原始片電 阻為 ΙΤΟ/ΡΕΤ = 120Ω/[1，（其中，口=。1112，即 Ω/〇 = Ω/£；ιη2) 、CNT/PET与100 Ω/□，由於前面幾次的曲撓，會使 ITO/PET與CNT/PET的片電阻皆呈不穩定的變化，無法作 明確的比較，因此，先分別將ITO/PET與CNT/PET的試片 各折彎50次使其片電阻（導電度）穩定後，再正式進入耐曲 撓性測試。其中，預先折彎50次後穩定的片電阻值分別為 ITO/PET =5ΚΩ/口，CNT/PET =3ΚΩ/□，測試結果如下表 所示，其中，表1中的曲撓次數並未包含預先折彎50次的 次數 表1-耐曲撓性測試結果 曲撓次數 50次 100次 250次 500次 折測結果 50次後 穩定的片電阻 片電阻 (Ω/口) 上升 比率 片電阻 (Ω/口） 上升 比率 片電阻 (Ω/口） 上升 比率 片電阻 (Ω/D ) 上升 比率 ΙΤΟ/ΡΕΤ= 5ΚΩ /□ 6.4Κ 28% 6.5Κ 30% 6.8Κ 36% 6.8Κ 36% CNT/PET =3ΚΩ/ϋ 3.4Κ 13% 3.4Κ 13% 3.6Κ 20% 3.7Κ 23% 測試結果顯示CNT/PET試片曲撓50次與100次後的片 電阻皆上升約10%，曲撓250次後的片電阻上升20%，曲 撓500次後的片電阻約上升20%，與ITO/PET相同曲撓次 數後的片電阻相較，顯示其片電阻的上升比率較小，並可 據此推知其導電度的下降比率也會小於ITO/PET的導電度 變化，顯示本發明的導電薄膜具有較佳的耐曲撓性。 17 201024208 CNT/PET經原始轉印後未曲撓前的片電阻約為j 〇〇 Ω， 當以55〇nm波長光線照射時，所量測得的光穿透率為 81.292%，與一般可供應用的導電薄膜在55〇nm時的光穿透 率規格70%〜90%相較，顯示本發明製造方法所製得的奈米 碳管導電薄膜已具有實際應用的價值。 <轉印到該第二基材片上的導電薄膜的耐曲撓性測試及 經550nm波長光線照射的穿透率> 所用的母片（即前述的第一基材片）上的奈米碳管導電薄 膜是經旋轉塗佈120分鐘所製得，完成旋轉塗佈後，再以 φ 轉印的方式，將該母片上的多層奈米碳管導電薄膜分別轉 印到不同的第二基材片上’該等第二基材片的導電薄膜分 別以前述的耐曲撓性測試量測其曲撓5〇次後的片電阻值， 由於前面幾次的曲撓，會使轉印到該等第二基材片的導電 薄膜的片電阻皆呈不穩定的變化’所以同樣要經預先折彎 5〇次處理’以使該等第二基材片上之導電薄膜的片電阻值 穩定’再正式進行财曲撓性測試，並以曲挽5〇次後的片電 阻，別與其預先折f 50次達到穩㈣的片電阻值㈣較，❹ 心十算其上升比率°其中，該等第二基材片預先折f 5G次 後穩定的片電阻值分別為CNT/PET%3KQ/a。結果如下表 所不，顯示轉印至第9次時，其曲撓5〇次的片電阻值已有 明顯上升’且轉印至第1〇次時，其曲撓Μ次的片電阻值 更大幅度上升，顯示轉印至第1G次時該母片上的奈米碳管 導電薄膜已接近耗盡，導致轉印後的片電阻值已不穩定， 只有前8次轉印結果才有較佳的再現性。 18 201024208 轉印第1次 且曲撓50次 耐曲撓性測試結果 轉印第2次 且曲撓50次 轉印第3次 曰娃夕π 士 轉印第4次A carbon nanotube conductive film is formed on the surface of a PET substrate by transfer and hot pressing in a manufacturing method of a specific example (represented by CNT/PET, where the first transfer of the nanotube is selected) Conductive film), and forming an ITO film (indicated by ITO/PET) on another pET 201024208 substrate, and then cutting the CNT/PET and ITO/PET into test pieces of the above-mentioned size for resistance to flexing Sex test, in which the original sheet resistance of the ITO/PET test piece before being subjected to bending is ΙΤΟ/ΡΕΤ = 120 Ω / [1, (where, mouth = 11.11, ie Ω / 〇 = Ω / £; ιη2), CNT /PET and 100 Ω / □, due to the previous few flexing, the sheet resistance of ITO / PET and CNT / PET are unstable changes, can not make a clear comparison, therefore, first ITO / PET and After the CNT/PET test piece was bent 50 times to stabilize the sheet resistance (conductivity), it was officially entered into the flexural resistance test. Among them, the sheet resistance values stabilized after pre-bending for 50 times are ITO/PET = 5 Κ Ω / port, CNT / PET = 3 Κ Ω / □, the test results are shown in the following table, wherein the number of bends in Table 1 does not include The number of times of pre-bending 50 times Table 1 - Flexural resistance test results The number of flexing times 50 times 100 times 250 times 500 times of the results 50 times after stable sheet resistance resistance (Ω / port) Rising ratio sheet resistance (Ω / Port) Rising ratio sheet resistance (Ω/port) Rising ratio sheet resistance (Ω/D) Rising ratio ΙΤΟ/ΡΕΤ = 5ΚΩ /□ 6.4Κ 28% 6.5Κ 30% 6.8Κ 36% 6.8Κ 36% CNT/PET = 3ΚΩ/ϋ 3.4Κ 13% 3.4Κ 13% 3.6Κ 20% 3.7Κ 23% The test results show that the sheet resistance of the CNT/PET specimens after bending for 50 times and 100 times is about 10%, after 250 bends. The sheet resistance is increased by 20%, and the sheet resistance after bending for 500 times is increased by about 20%. Compared with the sheet resistance after the same number of bends of ITO/PET, the sheet resistance is small, and it can be inferred from this. The rate of decrease in conductivity is also smaller than the change in conductivity of ITO/PET, indicating that the conductive film of the present invention has better flex resistance. 17 201024208 The sheet resistance of CNT/PET before the original transfer is not j 〇〇 Ω. When irradiated with light of 55 〇 nm, the measured light transmittance is 81.292%. The conductive film for supply has a light transmittance specification of 70% to 90% at 55 〇 nm, and shows that the carbon nanotube conductive film produced by the manufacturing method of the present invention has practical application value. <Tear resistance test of conductive film transferred onto the second substrate sheet and transmittance of light irradiation by 550 nm wavelength> Nano on the mother sheet (i.e., the aforementioned first substrate sheet) used The carbon tube conductive film is obtained by spin coating for 120 minutes. After the spin coating is completed, the multilayer carbon nanotube conductive film on the mother sheet is transferred to different second bases by φ transfer. On the sheet, the conductive film of the second substrate sheet is measured by the aforementioned flexural resistance test, and the sheet resistance value after 5 bends is measured, and the transfer is performed due to the previous several bends. The sheet resistance of the conductive film of the second substrate sheet is unstable, so it is also treated by pre-bending 5 times to stabilize the sheet resistance of the conductive film on the second substrate sheet. Formally carry out the flexibility test of the financial flexure, and the sheet resistance after 5 strokes of the curve is not the same as the sheet resistance value (4) of the stable (four) before the f 50 times, and the increase ratio of the tenth is calculated. The sheet resistance values of the two substrate sheets which were stabilized by 5 g times beforehand were CNT/PET%3KQ/a, respectively. The results are shown in the following table. It is shown that when the transfer is carried out to the ninth time, the sheet resistance value of the bend of 5 turns has been significantly increased', and when the transfer is performed to the first pass, the sheet resistance value of the twist is higher. Significantly increased, showing that the carbon nanotube conductive film on the mother sheet is nearly depleted when transferred to the first G, resulting in unstable sheet resistance after transfer, only the first 8 transfer results are better. Reproducibility. 18 201024208 Transfer 1st time and bend 50 times Flexibility test results Transfer 2nd time and bend 50 times Transfer 3rd 曰 夕 夕 π Transfer 4th
片電阻 (Ω/Ρ) 上升比率 片電阻 (Ω/Ρ) 3.2K 上升比率 10% 片電阻 (Ω /□) 3.5Κ 上升比率 片電阻 (Ω/口） 上升比率 3.6K 10% 轉印第9次 且曲撓50次 片電阻 (Ω/Ρ)Chip resistance (Ω/Ρ) Rising ratio chip resistance (Ω/Ρ) 3.2K Rising ratio 10% Chip resistance (Ω /□) 3.5Κ Rising ratio sheet resistance (Ω/port) Rising ratio 3.6K 10% Transfer number 9 And flexing 50 times of sheet resistance (Ω/Ρ)
4.9K 上升比率 30% 轉印第1 〇次 且曲撓50次 片電阻 (Ω/Ρ)4.9K rise ratio 30% transfer 1st pass and bend 50 times chip resistance (Ω/Ρ)
6.8K 上升比率 >50% 10% 轉印第11次 且曲撓50次 片電阻 (Ω /□) 237Κ 上升比率 3.7Κ 10% 轉印第12次 且曲撓50次 片電阻 (Ω/口） 上升比率 >50% 253Κ > 50% 由實驗結果顯示，由於轉印第1〇次與第12次已接近 耗盡導電薄膜的狀態，使轉印到第二基材片上的導電薄膜 結構可能較不均勻穩定，而影響其光電性質，所以最後二 次轉印結果不納人考慮。由轉印第i :欠至第8次的結果來 看’其曲撓50次後的片電阻值CNT/pET的範圍是介於π Ω〜4ΚΩ，分別和其㈣折f 5Q次後達到穩定後的片電阻 值相比’其上升比率都維持纟祕，顯示該等奈米碳管導 電薄膜分別轉印到該第二基材片I，仍然具有穩定的片電 阻值，即減維持穩定料電度，*妹㈣再現性，並 具有可適於發展為工業大量製造生產的模式。此外，轉印 第1次至第8次且曲接5 〇 +你 jj.. -人後，其在550nm波長下穿透率 值經㈣皆是介於78%〜83%，顯示經轉印後製得的奈米碳 管導電薄膜仍能具有較佳的光穿透率而適於應用至相關的 19 201024208 光電材料上。 歸納上述’本發明轉印式奈米碳管導電薄膜的製造方 法，可獲致下述的功效及優點，故能達到本發明的目的： 〃-、本發明除了能夠以超音波霧化配合旋轉塗佈以較 簡單的方式在該第-基材片26形成多層數或厚度較厚的導 電薄膜外，還能再將多層的導電薄膜分別轉印到數片第二 基材片η，以製成多數片與該第二基材片31相結合，並= 供直接使用的導電薄媒，藉此，能提高導電薄媒的製造數 量與產出效率’使本發明具有適合進行商業上量化生產的❿ 實用價值。 二、由測試結果顯由本發明所製出且分別被轉印 到該第二基材片的導電薄膜仍然能維持m穿透率與 導電率’並有可耐撓曲的品f特性而適於作為電子相關產 扣的原料’使本發明製造方法所製出的導電薄膜具有可挽 曲、可透光及可導電的性皙，栌鈞、去π 質此夠達到可撓曲導電薄膜的 應用標準’而適於應用至相關電子產品上。 Φ 、惟以上所述者，僅為本發明之較佳實施例而已，當不 用b以此限定本發明實絲 益 銘閉“ 月實施之範圍，即大凡依本發明申請專利 範圍及發明說明内容所你飭 屬本…… 等效變化與修飾，皆仍 厲本發明專利涵蓋之範圍内。 【圖式簡單說明】 y是-說明本發明奈米碳管導電薄膜的製造方法― 較佳實施例的流程圓； 圖2疋7F意圖，說明在該較佳實施例中所使用的裝 20 201024208 置的組合情形； 圖3是一示意圖’說明在該較佳實施例中，利用一轉 印片將形成在一第一基材片的多層導電薄膜轉印到一第二 基材片的情形； 圖4是一曲線示意圖，說明該較佳實施例進行旋轉塗 佈時，不同時間所設定轉速的變化情形； +圖5是-示意圖’說明以本發明製造方法所製出的導 電薄膜試片進行曲撓性測試的過程； 圖6是一示意圖，說明將該第一基材片上最上層的多 層導電薄膜轉印到該第二基材片的過程；及 圖7是一示意圖，說明對轉印到該第 薄臈進行熱壓的情形^ #的導電 21 201024208 【主要元件符號說明】 20•.… •…奈米碳管溶液 41…… •…導電薄膜試片 21…… •…霧化顆粒 42…… …·固定夾座 22···.· •…攜帶氣體 43…… 23…… •…霧化容器 501 ··· •…導電薄膜 24…… —虹吸管 502 ··· …·第一基材片 25…… •…超音波元件 503 ··· …·不銹鋼夾具 26···.· •…第一基材片 504 ··· _··.ΡΕΤ 薄片 27·..·· •…基座 505… •…轉印片 28·..·· •…貯液容器 506… •…第二基材片 29···.· •…升降座 507… •••PET薄片 30·.··· •…轉印片 508… •…不銹鋼夾具 31 ····. •…第二基材片 509… ••••PDMS 薄片 100… •…導電薄膜6.8K rise ratio >50% 10% Transfer 11th time and bend 50th sheet resistance (Ω /□) 237Κ Increase ratio 3.7Κ 10% Transfer 12th time and bend 50th sheet resistance (Ω/口) Rising ratio >50% 253Κ > 50% The experimental results show that the conductive film structure transferred onto the second substrate sheet is transferred due to the state in which the first and second passes of the transfer are nearly exhausted. It may be less uniform and stable, but affect its photoelectric properties, so the final secondary transfer results are not considered. From the result of transfer i: from the 8th to the 8th time, the range of the sheet resistance value CNT/pET after 50 bends is between π Ω and 4 Κ Ω, and it is stabilized after (f) f 5Q times. The subsequent sheet resistance value is kept secret compared to the 'the rising ratio thereof. It is shown that the carbon nanotube conductive films are respectively transferred to the second substrate sheet I, and still have a stable sheet resistance value, that is, the holding stable material is maintained. Electricity, * sister (four) reproducibility, and has a model that can be adapted to develop into industrial mass production. In addition, transfer the first to the eighth and splicing 5 〇 + you jj.. - after the person, its transmittance at 550nm wavelength (four) are between 78% ~ 83%, showing transfer The post-produced carbon nanotube conductive film can still have better light transmittance and is suitable for application to the related 19 201024208 photoelectric material. By summarizing the above-mentioned "manufacturing method of the transfer type carbon nanotube conductive film of the present invention, the following effects and advantages can be obtained, so that the object of the present invention can be attained: 〃-, the present invention can be applied by ultrasonic atomization in combination with spin coating. The cloth is formed in a relatively simple manner by forming a plurality of layers or thick conductive films on the first substrate sheet 26, and further transferring the plurality of conductive films to the plurality of second substrate sheets η. A plurality of sheets are combined with the second substrate sheet 31, and = a conductive thin medium for direct use, whereby the number of manufacturing and output efficiency of the conductive thin medium can be improved, making the present invention suitable for commercial quantitative production. ❿ Practical value. 2. The conductive film produced by the present invention and transferred to the second substrate sheet by the test results can still maintain the m transmittance and conductivity 'and has the property of flexing resistance and is suitable for As a raw material for electronic related production and production, the conductive film produced by the manufacturing method of the present invention has the properties of being bendable, permeable, and electrically conductive, and the 栌钧 and π qualities are sufficient to achieve the flexible conductive film. Standard 'is suitable for application to related electronic products. Φ, except for the above, is only a preferred embodiment of the present invention, and does not use b to limit the scope of the present invention to the extent of the implementation of the month, that is, the scope of the patent application and the description of the invention according to the present invention. Equivalent changes and modifications are still within the scope of the invention patent. [Simplified illustration] y is - illustrating the method of manufacturing the carbon nanotube conductive film of the present invention - preferred embodiment Figure 2疋7F is intended to illustrate the combination of the assembly 20 201024208 used in the preferred embodiment; Figure 3 is a schematic view illustrating the use of a transfer sheet in the preferred embodiment. A case where a plurality of conductive films formed on a first substrate sheet are transferred to a second substrate sheet; and FIG. 4 is a schematic view showing changes in the rotational speeds set at different times during spin coating of the preferred embodiment. 5; FIG. 5 is a schematic view showing the process of performing a flexural test on the conductive film test piece produced by the manufacturing method of the present invention; FIG. 6 is a schematic view showing the uppermost layer of the first base material sheet being electrically conductive. The process of transferring the film to the second substrate sheet; and FIG. 7 is a schematic view showing the case where the transfer to the first thin crucible is performed by the hot pressing of the first surface. # 201024208 [Explanation of main component symbols] 20•.... •...Nanocarbon tube solution 41... •...Conductive film test piece 21... •...Atomized particle 42... ...·Fixed holder 22······... Carrying gas 43... 23... •... Atomization container 501 ····...Electrical film 24...-Siphon tube 502 ·····First substrate sheet 25...•...Ultrasonic element 503 ·····Stainless steel fixture 26····· ...first substrate sheet 504 ··· _··.ΡΕΤ Sheet 27·..···...Base 505...•...Transfer sheet 28·..·...•...Liquid container 506...•...Second Substrate sheet 29·····•... Lifting seat 507... •••PET sheet 30······...Transfer sheet 508...•...Stainless steel fixture 31 ·····....Second substrate sheet 509... ••••PDMS sheet 100... •...conductive film
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