201024002 九、發明說明： 【發明所屬之技術領域】 本發明係有關於一種奈米金屬 之製備技術，特別是關 於種不米娘線之製傷組成物及奈米銀線之製備方法。 【先前技術】 不米金屬擁具有許多獨特的物性，因此被廣範應用在 如紡織衣物作為抗菌，或在光電應用上，其中奈米銀線更 在m米級電子元件上扮演著内部導電連結的重要角 色特别在添加於向分子樹脂的配方中，預期奈米銀線的 導電性將優於奈米銀粒子，同時也可以有效地降低奈米銀 線的添加比例’由此得知奈米銀線的重要性。 奈来銀線的製備法目前主要有模板法及溶液化學法兩 種’利_板法雖然可以得到奈米線狀物質，但是在製作 過程中必須經過銀的填充還原與電解沉積等複雜的製程， 且此技術無法大量製造所需的奈米銀線。有關溶液化學法 製備奈米銀線，目前雖然已有許多化學合成奈米銀線的方 法被發表，不過從所發表的文獻中發現其大都採用高溫製 程（大於160°C)，並且需要3至4道合成步驟，且使用貴 金屬作觸媒(如鈀、鉑等）來達到合成奈米銀線◊實際工業 應用上高溫製程將不利於生產，而使用貴金屬觸媒如鈀、 鉑等也將增加生產成本，亦不利於實際量產應用。舉例來 說，Younan Xiaet al.於2002年在nano Lett.揭示使用大量 的乙二醇與PtCU混合在160。(：下可得到pt奈米顆粒，之 後再將此奈米顆粒與硝酸銀及聚乙烯η比洛烧_ (PVP)混合 5 201024002 在160°C持續反應，得到奈米銀線，不過由於此方法需使 用大量的多元醇作為溶劑，以昂責的PtCl2作為形成晶粒的 物種，且必須在高於160。(：的條件下方能形成奈米銀線。 因此’此技術不易將奈米銀線的應用於大量生產，商業價 值較低。201024002 IX. Description of the Invention: [Technical Field] The present invention relates to a technique for preparing a nano metal, and more particularly to a method for preparing a wound-forming composition of a seed and a nano-silver wire. [Prior Art] The non-metallic metal has many unique physical properties, so it is widely used in textile clothing as antibacterial, or in optoelectronic applications, in which the nano silver wire acts as an internal conductive link on the m-meter electronic component. The important role is especially in the formulation added to the molecular resin. It is expected that the conductivity of the nano silver wire will be better than that of the nano silver particles, and it can also effectively reduce the addition ratio of the nano silver wire. The importance of the silver line. The preparation method of the Neil silver wire is mainly composed of two methods: the template method and the solution chemical method. Although the nano-line material can be obtained, it must undergo complicated processes such as silver reduction and electrolytic deposition during the production process. And this technology cannot make the required nano silver wire in large quantities. Regarding the preparation of nano silver wires by solution chemistry, although many methods for chemically synthesizing nano silver wires have been published, it has been found from the published literature that most of them use high temperature processes (greater than 160 ° C) and require 3 to 4 synthetic steps, and use precious metals as catalysts (such as palladium, platinum, etc.) to achieve synthetic nano silver wire. The high temperature process in practical industrial applications will be detrimental to production, and the use of precious metal catalysts such as palladium, platinum, etc. will also increase. Production costs are also not conducive to actual mass production applications. For example, Younan Xia et al. in 2002 at nano Lett. revealed the use of a large amount of ethylene glycol mixed with PtCU at 160. (: pt nanoparticle can be obtained, and then the nanoparticle is mixed with silver nitrate and polyethylene η 洛洛烧_ (PVP) 5 201024002 Continuous reaction at 160 ° C, to obtain nano silver wire, but due to this method A large amount of polyol is used as a solvent, and PtCl2 is used as a grain-forming species, and a nano silver wire must be formed under conditions higher than 160. Therefore, this technique is not easy to use nano silver wire. Applied to mass production, the business value is low.
CN1843670提到可不使用昂貴的ptCl2,但其仍需使用 多元醇（如乙二醇、丙二醇或乙醯丙酮等）有機溶劑來進行 奈米線的製備，且反應溫度仍需在120oC〜160。(：之間，此 奈米線的製備之技術商業價值仍不高。 CN1424163揭示使用鈦酸丁基作為觸媒可將反應溫度 降低至85°C，不過此技術需使用如二甲基甲醯胺(dmf)、 乙醯丙酮等有害的有機溶劑作為溶媒，因此在生產性上不 利於商業製造。此外，由於此技術所用的鈦酸丁基會造成 產物中的金屬雜質，因此此技術若使用於電子元件，會因 金屬離子的干擾形成雜訊。 【發明内容】 根據上述問題，本發明提供一種奈米銀線之製備組成 物至乂〇括具正價之銀鹽、一酶類衍生物之還 及-具有可促使銀鹽轉換為銀線之有機促進劑。 本發明另提供一種奈米銀線之製備方法，至少包括以 :步驟：將-具正-價銀鹽和衍生物之還原劑加入 轉換為一銀線。 力入-有機促進劑’使銀鹽 為了讓本發明之上述目的、特徵及優點能更明顯易 6 201024002 懂，以下配合所附圖式，作詳細說明如下： 【實施方式】 以下描述本發明一實施例奈米銀線的製備組成物和太 米銀線之製備方法，在本實施例中，奈米銀線的製備組二 物包括具正一價銀離子鹽類（例如硝酸銀及其銀鹽混人 物）、具有裱保性的醣類衍生物(Fructose)作為還原劑（醣類 衍生物可選自果糖QHuO6、葡萄糖、半乳糖或其混合物）， 可調控銀鹽轉換為銀線之有機促進劑，本實施例之有機促 進劑係為有機鹼和有機酸，其中有機鹼以二曱基〇比啶 (Lutidine)較佳，有機酸以包含至少一 c〇〇H官能基之有機 化合物較佳，例如抗壞血酸(asc〇rbic acid)、草酸、摔檬酸 等。 本實施例係使用在生產上具有環保性的醣類衍生物作 為還原劑’由於醣類衍生物可直接溶解在水中’因此本實 施例可在低溫製程和水溶液中進行，此外，本實施例特別 0 應用有機驗或有機酸之有機促進劑，進行奈米銀線的製 備’所得的奈米銀線可進一步進行奈米銀線油墨的製備並 具有高導電性與安定性。在本發明一較佳實施例中，形成 銀線之反應溫度約為70°C〜90。〇奈米銀線之alfa(a)值大 於50(奈米銀之alfa(線徑d與線長1的比值大於25即為奈 米銀線）’銀鹽混合物是硝酸銀與低還原電位之銀鹽混合 物，其中低還原電位之銀鹽所佔有之比例介於0.005%〜5% 之間’低還原電位之銀鹽其標準還原電位介於 +0.222〜-0.151伏特之間，硝酸銀和醣類衍生物之比例約為 201024002 0.5〜2 ’有機促進劑的濃度約為〇. 〇iM〜1M，低還原電位之 銀鹽可以是氯化銀、溴化銀或磺化銀等。另外，在本發明 一最佳實施例中’硝酸銀和醣類衍生物之比例約為 0.5〜2.Owt%其中較佳的比例為1.2-1.gwt%，有機促進劑的 濃度約為0.01-0.05M’其中較佳的比例為〇.〇l5-(K025M奈 米銀線之alfa值大於100。 以下列舉本發明之實施範例和比較範例： 【實施範例一】線狀奈米銀的製備 參 將葡萄糖15.88g(ACROS ’純度98%)置於2000ml之四 頸反應瓶中，依序加入1000ml的去離子水及硝酸銀 3〇g(昭和純藥，純度98%)及安定劑聚乙烯吡咯烷酮(PVP) 3〇g(日本觸媒）於上述四頸反應瓶中，設定攪拌轉數為 3〇〇rpm，持續攪拌使其溶解，並於常溫下將預先配置好之 有機驗二甲基11比唆(Lutidine)水溶液250ml(濃度為5.0wt%) f於250ml的等壓加料管中，調整滴入速度為每分鐘2ml， 搏續滴入四頸反應瓶中直到滴完約3小時，完成之後進行 參 離心純化及以去離子水清洗。經掃瞄式電子顯微鏡(SEM)和 梦透式電子顯微鏡(TEM)檢視之結果，本範例可反應形成報 条米線。 【比較例一】將有機鹼改為無機鹼 將葡萄糖15.88g (ACROS，純度98%)置於2000ml支 四頸反應瓶中，依序加入l〇〇〇ml的去離子水及硝酸銀3〇g (日召和純藥’純度98%)及安定劑聚乙烯吡咯烷酮(PVP)3〇g (日本觸媒）於四頸反應瓶中，設定攪拌轉數為300rpm持續 8 201024002 撲摔使其溶解，並於常溫下將預先配置好之無機鹼氫氧化 納水溶液250ml(濃度為5.0wt%)置於25〇ml的等壓加料管 中，調整滴入速度為每分鐘2ml並持續滴入四頸反應瓶中 直到滴完約3小時，完成之後進行離心純化及以去離子水 清洗。經掃瞄式電子顯微鏡(SEM)和穿透式電子顯微鏡(TEM) 檢視之結果，本比較範例無法形成銀奈米線，僅能形成顆 粒狀的銀奈米粒子。 0 【實施範例二】 將果糖2.11g (ACROS，純度98%)置於5〇〇ml之四頸 反應瓶中，依序加入100ml的去離子水及抗壞血酸(asc〇rbic acid) O.lg (TCI，純度98%)於四頸反應瓶中，設定授拌轉 數為lOOrpm持續攪拌使其溶解，並升溫至内溫8〇〇c，將 預先配置好之硝酸銀水溶液l〇〇ml(濃度為2 〇%)及pvp安 定劑之水溶液100ml (濃度為4wt%)分別置於！5〇ml的等壓 加料管中並調整滴入速度為每分鐘2ml，持續滴入四頸反 ❹應瓶中直到滴完約1-2小時。完成後關閉加熱器並降溫至 至溫’之後進行離心純化及以去離子水清洗。本範例可反 應形成銀奈米線。 【實施範例三】 本實施範例三和實施範例二的操作條件之差異為將抗 壞血酸(ascorbic acid)由原先的〇.lg(TCI，純度98%)提昇 為〇.2g ’其它條件和實施範例二的操作條件相同。本實施 範例製備之奈米銀線經掃描式電子顯微鏡(S E Μ)分析得到 線徑介於120〜270nm，其alfa值介於58〜130之間。 9 201024002 由上述實絲财得到本發明確可形成 得注意的是，！知技術雖然也有揭示以葡萄：;乍：線’值 之銀鏡反應技但該技術係使用無機酸或42原劑 =上述結果可得知使用― 另外，相對於先前技術必須 原劑，使用昂貴的責金屬作為觸媒ί還 ❿ 才能得到奈米銀線’本發明利3 生產上具㈣純的_衍生物(F_se)作 以去離子水作為溶媒，同销由有機 下)有效製備奈米銀線，且=二 至=2發明銀奈米線的製備組成物和製備方法 咖㈣奈料 ^本發明係制_衍生物，因此財環保性。 3. 本發明可於低溫製程下製備奈米銀線。 4. 本發義使用去離子水作為溶媒，避免 这成過多的有機廢溶劑的產生，符合環保之 ， 雖然本發明已揭露較佳實施; 定本發明，任錢悉此項科者，在不^其並非用以限 和範圍内，當可做些許更動二=;發明之精神 園當視後附之申請專職®所界定為準。*明之保護範 201024002CN1843670 mentions that expensive ptCl2 may not be used, but it still requires the use of a polyol (e.g., ethylene glycol, propylene glycol or acetamidine) organic solvent for the preparation of the nanowire, and the reaction temperature still needs to be 120oC~160. (Between: the technical value of the preparation of this nanowire is still not high. CN1424163 discloses that the use of titanate as a catalyst can reduce the reaction temperature to 85 ° C, but this technique requires the use of dimethylformamide A harmful organic solvent such as (dmf) or acetamidine is used as a solvent, and thus is not economically advantageous for commercial production. Further, since the butyl titanate used in the technique causes metal impurities in the product, the technique is used if The electronic component may form a noise due to the interference of metal ions. SUMMARY OF THE INVENTION According to the above problems, the present invention provides a composition for preparing a nano silver wire to include a silver salt of a normal price and an enzyme derivative. Also-having an organic promoter capable of promoting the conversion of a silver salt into a silver wire. The present invention further provides a method for preparing a nano silver wire, comprising at least the steps of: a reducing agent having a positive-valent silver salt and a derivative Adding to a silver wire. Force-organic accelerator' makes the silver salt in order to make the above objects, features and advantages of the present invention more obvious. 6 201024002 Understand, the following is a detailed description [Embodiment] The following describes a preparation method of a nano silver wire according to an embodiment of the present invention and a method for preparing a silver silver wire. In the present embodiment, the preparation group of the nano silver wire includes a positive monovalent silver. An ionic salt (such as a mixture of silver nitrate and its silver salt), a saccharide derivative (Fructose) as a reducing agent (the sugar derivative may be selected from the group consisting of fructose QHuO6, glucose, galactose or a mixture thereof). An organic promoter for regulating the conversion of a silver salt to a silver wire. The organic accelerator of the present embodiment is an organic base and an organic acid, wherein the organic base is preferably a ruthenium group, and the organic acid comprises at least one c. The H-functional organic compound is preferably, for example, ascorbic acid, oxalic acid, citric acid, etc. In this embodiment, a sugar derivative which is environmentally friendly in production is used as a reducing agent 'because of sugars The derivative can be directly dissolved in water'. Therefore, this embodiment can be carried out in a low-temperature process and an aqueous solution. In addition, in this embodiment, the organic test or the organic acid organic accelerator is used in particular, and the nano silver wire is produced. The resulting nano silver wire can be further prepared for nano silver ink and has high electrical conductivity and stability. In a preferred embodiment of the invention, the reaction temperature for forming the silver wire is about 70 ° C to 90 °. The alfa(a) value of the silver nanowire is greater than 50 (the alfa of nano silver (the ratio of the diameter d to the length of the line 1 is greater than 25 is the nano silver wire). The silver salt mixture is silver nitrate and silver with a low reduction potential. a salt mixture in which a silver salt having a low reduction potential occupies between 0.005% and 5%. A low reduction potential silver salt has a standard reduction potential between +0.222 and -0.151 volts, and is derived from silver nitrate and sugar. The ratio of the substance is about 201024002 0.5~2 'The concentration of the organic accelerator is about 〇. 〇iM~1M, and the silver salt of the low reduction potential may be silver chloride, silver bromide or silver sulfonate. Further, in a preferred embodiment of the present invention, the ratio of the silver nitrate to the saccharide derivative is about 0.5 to 2. 0 wt%, wherein the preferred ratio is 1.2 to 1. gwt%, and the concentration of the organic accelerator is about 0.01 - The preferred ratio of 0.05M' is 〇.〇l5-(the calf value of the K025M nano silver wire is greater than 100. The following describes the examples and comparative examples of the present invention: [Example 1] Preparation of linear nano silver 15.88 g of glucose (ACROS 'purity 98%) was placed in a 2000 ml four-necked reaction flask, and 1000 ml of deionized water and silver nitrate 3 〇g (Showa Pure Chemical, purity 98%) and stabilizer Sterling polyvinylpyrrolidone were sequentially added ( PVP) 3〇g (Japanese catalyst) in the above four-neck reaction flask, set the stirring rotation number to 3 rpm, continue to stir to dissolve, and pre-configured organic dimethyl 11 ratio at room temperature 250 ml of Lutidine aqueous solution (concentration: 5.0 wt%) f in a 250 ml isobaric feeding tube, adjust the dropping rate to 2 ml per minute, and drip into the four-neck reaction flask until the completion of the dripping for about 3 hours. Perform centrifugation purification and wash with deionized water. Scanned electron microscope (SEM) and dream The results of electron microscopy (TEM) examination, this example can be reacted to form a reporter rice noodle. [Comparative Example 1] The organic base was changed to an inorganic base to convert 15.88 g of glucose (ACROS, purity 98%) into 2000 ml of four-neck reaction. In the bottle, add l〇〇〇ml of deionized water and silver nitrate 3〇g (Japanese and pure medicine 'purity 98%) and stabilizer Styropyrrolidone (PVP) 3〇g (Japanese catalyst) in four In the neck reaction bottle, set the stirring rotation number to 300 rpm for 8 201024002 to make it dissolve, and at a normal temperature, pre-configured 250 ml of the inorganic alkali sodium hydroxide aqueous solution (concentration: 5.0 wt%) in 25 〇 ml, etc. In the pressure feeding tube, the dropping speed was adjusted to 2 ml per minute and continuously dropped into the four-neck reaction flask until the completion of the dropping for about 3 hours, after which the centrifugation was carried out and washed with deionized water. Scanning electron microscope (SEM) As a result of inspection by transmission electron microscopy (TEM), this comparative example could not form a silver nanowire and could only form granular silver nanoparticles. 0 [Example 2] Fructose 2.11 g (ACROS, purity 98%) ) placed in a 5 〇〇 ml four-neck reaction flask, sequentially added to 100 Mol of deionized water and ascorbic acid (asc〇rbic acid) O.lg (TCI, purity 98%) in a four-necked reaction flask, set the number of mixing revolutions to 100 rpm, continue to stir to dissolve, and raise the temperature to 8 内〇c, 100ml (concentration: 4wt%) of a pre-configured silver nitrate aqueous solution l〇〇ml (concentration of 2%) and pvp stabilizer (100% by weight) are placed separately! 5 〇 ml of the equal pressure feeding tube and adjust the dropping speed to 2 ml per minute, and continue to drip into the four-necked sputum bottle until the lapse of about 1-2 hours. After completion, the heater was turned off and allowed to cool to temperature, then centrifuged and rinsed with deionized water. This example can react to form a silver nanowire. [Example 3] The difference between the operating conditions of the third embodiment and the second embodiment is that the ascorbic acid is upgraded from the original 〇.lg (TCI, purity 98%) to 〇.2g 'other conditions and the second embodiment The operating conditions are the same. The nano silver wire prepared in this example was analyzed by a scanning electron microscope (S E Μ) to obtain a wire diameter of 120 to 270 nm and an alfa value of 58 to 130. 9 201024002 From the above-mentioned real money, the invention can be formed with attention! Although the technology has also revealed the silver mirror reaction technique of grape:; 乍: line 'value, but the technology uses inorganic acid or 42 original agent = the above results can be used to know - in addition, compared with the prior art, the original agent must be used expensive. Responsible for the use of metal as a catalyst ί ❿ 才能 得到 才能 才能 才能 才能 才能 才能 才能 才能 才能 才能 才能 才能 才能 才能 才能 才能 才能 才能 才能 奈 才能 奈 奈 奈 奈 奈 奈 奈 ' ' 本 本 ' 本 本 本 本 本 本 本 本 本 本 本 本Line, and = 2 to = 2 Preparation of silver nanowires and preparation method Coffee (four) Nai material ^ This invention is a system of derivatives, and therefore environmentally friendly. 3. The invention can prepare nano silver wire in a low temperature process. 4. The present invention uses deionized water as a solvent to avoid the generation of excessive organic waste solvent, which is environmentally friendly. Although the present invention has been disclosed as a preferred embodiment, the present invention is not limited to those of the subject. It is not intended to be within the scope of the limitation. When a change is made, the spirit of the invention is determined by the application of the full-time application. *Mingzhi protection fan 201024002
【圖式簡單說明】 無。 【主要元件符號說明】 無。 11[Simple description of the diagram] None. [Main component symbol description] None. 11