201223876 六、發明說明： 【發明所屬之技術領域】 本發明係有關於-種高濃度奈米銀膠體及其奈米银膠 體前驅物之製備方法，特別是關於—種利用溶液相途捏製 備出南濃度奈米銀膠體及其奈米銀膠體前驅物。 【先前技術】 综觀目前從事奈米銀膠體製備技術，多將技術重點著 重在粒子尺寸的改良，但因為生產成本面的受限，所以讀 些方法無法大規模量產。再者，目前的製備方法，並非每 種方式皆適合工業之應用。因為若製程設備成本過高或是 製備程序太複雜，皆不適合大規模生產。其中最有可能大 規模生產化的為”溶液相化學還原法”。因為化學還原^ 須透過複雜或昂貴的儀器即可製得相當產量的奈米級缸 子’如果能改善純度問題，此法對於工業應用十分有利。 因應用來分散膠體用的界面活性劑（或稱分散劑）類型不 同’銀膠體可分水溶錢油溶性料。由於水溶性溶劑 (例如水、醇類）和油溶性溶劑（例如烷類、苯類）二； 截然不同的性質，但是傳統製備途徑通常僅為針對單—溶 劑所設計之方法，若將系統換為另一相溶劑則不相容而無 去適用㉟s之’原水溶性膠體的製程就無法製備油溶性 膠體，反之亦然。 在2003年時，人利用CMC做為分散劑以 檸檬酸做為還原劑，製備出低於5〇⑽之奈米銀粒子。利用 冷康乾燥法，將所合成的奈米銀懸浮液漢縮至銀微粒漠度 201223876 至wt% (此時銀微粒粒徑增加至i2〇 nm左右），利用喷 可噴出銀微粒組成之線路。不過這樣形成的線路 卢j導電，由電子顯微鏡觀察，發現這些銀微粒因為濃 又太低，並無法形成連續接觸。此外’在漠縮的過程前， 浮液並沒有經過純化的步驟，因此後來的 也曰、二J3有·多未反應完的銀離子與還原劑等，這 線路無法導電的原因之_。由此實驗，顯示了若 要r喷墨方式得到導電之線路，在導電 之要求：⑴導電金屬之含量需夠高，： 益===3Gwt.%之間，⑵純度必須盡量提高: 無足以影響導電特性之雜質存在。 粒，時心1等人則是以2·4 nm大小之奈米金微 導電啥:本，令，而形成導電墨水。利用雷射光加埶 / 钟之區域’可得到導電之導線。不過在電子顯 微鏡的分析中，發現這樣的導 ‘‘·、 揮發速率過快，造成線路二 法形成連續相。這對於導編微粒無 會造成不·影響。k轨值與導線之均-性，皆 太平資，人的研究中’導電墨水的組成為10 wt.%之 j銀刀政於咖plneol之令，奈米銀粒徑為5·7⑽ 於在這個研究之巾，如化雜 :墨水液滴喷覆到基材上時，溶劑即二 =開•短時間之内即可形成直^ 、⑽⑽左右之圓板。_這些奈祕燒結而叙圓板互ς 201223876 連接，最終可形成電阻率約為3xl0娘伽之導電之線路， =線可製作出一些電子元件。不過這樣的方式，必須 =基材的高溫，勢必增加設備的複雜度與操作的成本； 由於是以逐_方式漸漸連接成導電祕，這樣的 方^也需要較長的製作時間。更大的問題是，由於導線是 以早獨液滴的方式乾燥，這樣的過程之中，容易造成c〇ffee ^現象，即圓板外緣較厚，而中心部分㈣，這對於導 線之電阻有極大的影響。料，可以想像的—點是由於 ㈣早獨錢’液滴之_界面明顯，勢必造成電阻值提 =若無經過-定的高溫處理使其邊界消失，這樣的導線 其電阻值也會較高。 ^述技術，無論在網版印刷或是噴墨印卿域應用， 最重要的核碰術都是導電油墨（墨水）。 =與表面張力、高體積分率之金屬‘、長‘ 於喷墨應用要求更是嚴苛。這是===:其對 細複雜’金屬微粒必須足夠微小免嘴:°又二軚為精 也必須長期就，以避免金屬彳” 大’進-步阻塞喷嘴。另外，為了實際的；:素而導: 油墨必須具有適當的黏度，一般而言介於w。乍導電 大的黏度时造成金屬料液無法糊地許姑過 同的基材’亦必須調成導電油墨 是x康不 的表面沾濕性與附著力。最後，以獲得適當 ♦電/由墨中金屬微粒所佔 201223876 的體積分率也是影響導電線路電性重要因素。因為在喷覆 後於溶劑揮發過程，不可避免有體積收縮的現象發生。一 旦金屬微粒體積分率不足（亦即溶劑體積分率太高），收 縮後的導線會有斷裂的情形產生。此外，過低分率的金屬 微粒即使仍維持連續接觸’但會因為過高的電阻而無法展 現導電的特性。 【發明内容】 鑒於上述習知技術之缺點，本發明之主要目的在於提 供高濃度奈米銀膠體溶液及其奈米銀膠體前驅物之製備方 法，整合一奈米銀膠體前驅物、一還原劑、一分散劑、一 催化劑等，以解決以往奈米銀膠體純化不足及受限於高濃 度分散劑添加時所造成溶液黏度過高易造成勻相反應物分 散不及或不均等問題。 為了達到上述目的，根據本發明所提出之一方案，提 供一種奈米銀膠體前驅物之製備方法，其步驟包括：提 供一反應A溶液及一反應B溶液，其中，反應a溶液包含一 銀鹽及-尿素，反應崎液係為—催化劑；（2)將反應A溶液 及反應B溶液進行混合以得_前驅物沉殿物 ;(3)利用一離 〜法分離出該前驅物沉㈣，並將該前驅物沉麟分散於 P去離子水中；（4)利用一離心法自步驟(3)該去離子水中分 離出^驅物沉澱物’並將該前驅物沉殿物分散於一乙醇 冷液中。經上述製備錢可得—奈米銀膠體前驅物。 為了達到上述目的，根據本發明所提出之另一方案， 201223876 &供種奈米銀膠體之製備方法，其步驟包括：⑴將前述 之奈米銀膠體前驅物製備方法所製備出奈米銀膠體前驅物 與一c溶液混合而得一混合液，其中，c溶液係為一分散劑 溶液；（ii)將一D溶液與⑴中混合液進行混合以得一奈米銀 膠體沉澱物，其中，D溶液係為一還原劑溶液；（iU)利用一 離心法分離出該奈米銀膠體沉澱物，並將該奈米銀膠體沉 澱物分散於一乙醇溶液中；（iv)利用一離心法自步驟(沿)該 乙醇溶液中分離出該奈米銀膠體沉澱物，並將該奈米銀膠 體沉殿物分散於一正己院溶液中。藉此，可得到高濃产、 高純度、粒徑大小均勻的奈米銀膠體，降低影響導電特性 之雜質存在，並使奈米銀粒子均勻分布於奈米銀膠體溶液 中。 上述合成反應中所使用的銀鹽，並無特別限定，硝酸 銀、硫酸銀、過氣酸銀等其它含銀之鹽類化合物皆可鸡用 於本發明所提供之製造方法。 上述合成反應中所使用的分散劑，是用來避免粒子發 生聚集的保護機制，通常是藉由保護劑中活性劑的吸附增 加粒子表面帶電，利用電荷同性相斥的原理，抑制粒子發 生聚集。另一種方法為保護劑在粒子間提供障礙物，抑制 粒子運動的此力，減少發生碰撞的機率。常用的保護劑包 括十二烷基苯磺酸鈉(sodium dodecyl sulphate, SDS)、聚乙 烯吡咯烷酮（polyvinyl pyr〇llid〇ne，PVP)、聚乙烯基醇 (polyvinyl alcohol, PVA)及辛癸胺分子(〇da)，但不以 201223876 此為限。 還原劑用於氧化還原反應中將奈米銀膠體前驅物中的 銀離子還原至原子態，一般常用者為氫硼酸鈉（s〇dium201223876 VI. Description of the Invention: [Technical Field] The present invention relates to a method for preparing a high-concentration nano-silver colloid and a nano-silver colloid precursor thereof, in particular, a method for preparing a solution by using a solution South-concentrated nano-silver colloid and its nano-silver colloid precursor. [Prior Art] Looking at the current nano-silver colloid preparation technology, the focus of the technology is on the improvement of particle size. However, due to the limited production cost, some methods cannot be mass-produced. Furthermore, the current preparation methods are not suitable for industrial applications in every way. Because if the cost of the process equipment is too high or the preparation process is too complicated, it is not suitable for mass production. Among them, the most likely to be produced on a large scale is the "solution phase chemical reduction method". Because chemical reductions require a complex or expensive instrument to produce a comparable yield of nano-scale cylinders, this method is advantageous for industrial applications if it improves purity. The type of surfactant (or dispersant) used to disperse the colloid is different. The silver colloid can be divided into water-soluble oil-soluble materials. Due to the very different properties of water-soluble solvents (such as water, alcohols) and oil-soluble solvents (such as alkanes, benzenes), the traditional preparation route is usually only for the single-solvent method, if the system is changed It is not compatible with the solvent of the other phase, and it is not possible to prepare the oil-soluble colloid by the process of applying the original water-soluble colloid of 35s, and vice versa. In 2003, humans used CMC as a dispersant to prepare cerium silver particles of less than 5 Å (10) using citric acid as a reducing agent. Using the cold-drying method, the synthesized nano-silver suspension is condensed to a silver particle infiltration degree of 201223876 to wt% (when the particle size of the silver particles is increased to about i2〇nm), and the line composed of the silver particles can be sprayed by spraying. . However, the line thus formed was electrically conductive, and it was observed by an electron microscope that these silver particles were too concentrated and too low to form continuous contact. In addition, before the process of the shrinking process, the floating liquid did not undergo the purification step, so the subsequent sputum, the second J3 had many unreacted silver ions and a reducing agent, and the reason why the line could not conduct electricity. From this experiment, it is shown that if the r inkjet method is used to obtain a conductive line, the requirements for electrical conduction are as follows: (1) The content of the conductive metal needs to be high enough: (b) ===3 Gwt.%, (2) the purity must be increased as much as possible: Impurities that affect the conductivity properties are present. The grain, the heart 1 and the like are made of nanometer gold micro-conducting enamel of 2·4 nm size, and the conductive ink is formed. Conductive wires can be obtained by using laser light to add the area of the 埶 / clock. However, in the analysis of electron microscopy, it was found that such a derivative ‘··, the volatilization rate is too fast, causing the line two method to form a continuous phase. This does not affect the guiding of the particles. The k-track value and the uniformity of the wire are all too flat. In the human study, the composition of the conductive ink is 10 wt.%, and the silver particle size is 5·7 (10). The towel of this study, such as the chemical: when the ink droplets are sprayed onto the substrate, the solvent is two = open; within a short time, a circular plate of about (10) (10) can be formed. _ These secrets are sintered and the circular plates are interchangeable. 201223876 The connection can finally form a conductive line with a resistivity of about 3xl0, and the = line can make some electronic components. However, in this way, it is necessary to = the high temperature of the substrate, which will inevitably increase the complexity of the equipment and the cost of operation; since it is gradually connected to the conductive secret in a _ way, such a method also requires a long production time. The bigger problem is that since the wire is dried in the form of early single droplets, it is easy to cause c〇ffee ^ phenomenon, that is, the outer edge of the disk is thicker, and the central portion (four), which is the resistance of the wire. Has a great impact. Material, can be imagined - the point is because (4) early alone money 'droplet' interface is obvious, it is bound to cause the resistance value to be raised = if there is no high-temperature treatment to make its boundary disappear, such a wire will have a higher resistance value . The technology, whether in screen printing or inkjet printing, the most important nuclear collision is conductive ink (ink). = Metals with surface tension, high volume fraction, and long requirements are more demanding for inkjet applications. This is ===: its fine-complex 'metal particles must be small enough to avoid the mouth: ° and the second is fine must also be long-term to avoid metal 彳" large 'in-step blocking nozzle. In addition, for the actual;:素素: The ink must have a suitable viscosity, generally in the w. 乍 conductive large viscosity caused by the metal liquid can not paste the same substrate ' must also be adjusted into conductive ink is x Kang not Surface wettability and adhesion. Finally, to obtain the appropriate ♦ electricity / by the metal particles in the ink accounted for the volume fraction of 201223876 is also an important factor affecting the electrical conductivity of the conductive circuit. Because after the spray in the solvent evaporation process, there is inevitably The phenomenon of volume shrinkage occurs. Once the volume fraction of the metal particles is insufficient (that is, the solvent volume fraction is too high), the contracted wire may be broken. In addition, the metal particles having too low a fractional rate maintain continuous contact even' However, due to the excessive resistance, the conductive characteristics cannot be exhibited. SUMMARY OF THE INVENTION In view of the above disadvantages of the prior art, the main object of the present invention is to provide a high concentration nano silver colloid solution. The preparation method of the nano silver colloid precursor integrates a nano silver colloid precursor, a reducing agent, a dispersing agent, a catalyst, etc., to solve the problem that the conventional nano silver colloid is insufficiently purified and limited by the high concentration dispersing agent. In order to achieve the above object, in accordance with one aspect of the present invention, a method for preparing a nano silver colloid precursor is provided, the steps of which include: Providing a reaction A solution and a reaction B solution, wherein the reaction a solution comprises a silver salt and a urea, and the reaction Nagas solution is a catalyst; (2) the reaction A solution and the reaction B solution are mixed to obtain a precursor. (3) separating the precursor sink (4) by using a separation method, and dispersing the precursor Shenlin in P deionized water; (4) using a centrifugation method from the step (3) in the deionized water Separating the precipitate of the precursor and dispersing the precursor in an ethanol cold liquid. The above-mentioned preparation of the money-nano silver colloid precursor. In order to achieve the above object, according to the present invention A solution, 201223876 & a method for preparing a nano silver colloid, the steps comprising: (1) mixing a nano silver colloid precursor prepared by the method for preparing a nano silver colloid precursor with a c solution to obtain a mixture a liquid, wherein the c solution is a dispersant solution; (ii) mixing a D solution with the (1) mixture to obtain a nano silver colloidal precipitate, wherein the D solution is a reducing agent solution; (iU Separating the nano silver colloidal precipitate by a centrifugation method, and dispersing the nano silver colloidal precipitate in an ethanol solution; (iv) separating the ethanol solution from the step by a centrifugation method Nano silver colloidal precipitate, and the nano silver colloidal sediment is dispersed in a positive chamber solution. Thereby, a high-concentration, high-purity, uniform particle size nano silver colloid can be obtained, which reduces the influence of conductivity. The characteristic impurities exist and the nano silver particles are uniformly distributed in the nano silver colloidal solution. The silver salt used in the above synthesis reaction is not particularly limited, and other silver-containing salt compounds such as silver nitrate, silver sulfate, and silver peroxylate can be used in the production method of the present invention. The dispersing agent used in the above synthesis reaction is a protection mechanism for avoiding aggregation of particles. Usually, the surface of the particles is charged by the adsorption of the active agent in the protective agent, and the principle of repulsive repulsion of the charges is used to suppress the aggregation of the particles. Another method is to provide an obstacle between the particles, to inhibit the movement of the particles, and to reduce the probability of collision. Commonly used protective agents include sodium dodecyl sulphate (SDS), polyvinylpyrrolidone (PVP), polyvinyl alcohol (PVA) and octopamine molecules. (〇da), but not limited to 201223876. The reducing agent is used in the redox reaction to reduce the silver ions in the nano silver colloid precursor to the atomic state, and is generally used as sodium borohydride (s〇dium).
Borohydride)(NaBH4)、聯氨（hydrazine)(M4)、甲搭 (F〇nmldehyde)(HCHO)、葡萄糖（G1UCOS)(C6HI2〇6 · h2〇)、 檸檬酸鈉（Trisodium Citrate)(2Na3aH5〇7 · llHzO)等，但 不以此為限。 催化劑在化學反應中係用以增加反應速率，本發明中 在鹼性的環境裡還原劑有較大的氧化還原驅動力，因此， 本發明中催化劑的條件為能提供鹼性環境的氫氧離子(〇H_ )° 為了達到上述目的，根據本發明所提出之另一方案， 提供一種奈米銀膠體之製備方法，其步驟包括：（1)將前述 之奈米銀膠體前驅物製備方法所製備出奈米銀膠體前驅物 與一E溶液混合而得一混合液，其中，該E溶液係為一分散 劑溶液(2)將一 F溶液與（1)中該混合液進行混合以得一奈米 銀膠體沉殿物’射，該F溶液係為—還原劑溶液；（3)利用 一離心法分離出該奈米銀膠體沉澱物，並將該奈米銀膠體 沉澱物分散於一丙酮溶液中;(4)利用一離心法分離出該奈米 銀膠體沉澱物，並將該奈米銀膠體沉澱物溶於一水溶液或 -有機溶射。藉此，可制綠度、高純度、粒徑大小 均勻的奈求銀膠體，降低影響導電特性之雜質存在，並使 奈米銀粒子均勻分布於奈米銀膠體溶液中。 201223876 以上之概述與接下來的詳細說明及附圖，皆是為了能 進一步說明本發明為達預定目的所採取的方式、手段及功 效。而有關本發明的其他目的及優點，將在後續的說明及 圖示中加以闡述。 【實施方式】 以下係藉由特定的具體實例說明本發明之實施方式， 熟悉此技藝之人士可由本說明書所揭示之内容輕易地瞭解 本發明之其他優點與功效。 ® 請參考第一圖’為本發明一種奈米銀膠體前驅物之製 備方法流程圖。如圖所示，本發明提供一種奈米銀膠體前 驅物之製備方法，其步驟包括:(1)首先提供一反應A溶液及 一反應B溶液，其中，該反應A溶液包含一銀鹽及一尿素， 該反應B溶液係為一催化劑溶液81〇1 ; (2)該反應人溶液及該 反應B溶液進行混合以得一前驅物沉殿物si〇2 ; (3)利用一 離心法分離出該前驅物沉澱物，並將該前驅物沉澱物分散 • 於一去離子水中Sl〇3 ;⑷利用一離心法自步驟⑶該去離子 水中分離出該前驅物沉澱物，並將該前驅物沉殿物分散於 一乙醇溶液中S104。 反應八溶液包含-銀鹽及-尿素。本發明所使用的銀 鹽，並無特別限定，硝酸銀、硫酸銀、過氣酸銀等其它含 銀之鹽類化合物皆可適用於本發明所提供之製造方法，例 如’本實施例中的反應A溶液中的銀鹽為—硝酸銀溶液，a 溶液30ml包含3.4g硝酸銀和4.8g尿素。 201223876 錢A溶液切尿素，主要的目的是當作氧化還原反應 中的還原劑，在氧化還原的反應下’尿素與反應麟液中的 琐酸銀離子反應後，將可得—奈米銀前驅物涵物。在本 實施例中溶液中’尿素和該銀鹽的莫耳分率比的範圍 為2-8比1時’皆有奈米銀前驅物沉殿物產出，其中，本實 施例使用尿素和該銀鹽的莫耳分率比為*比H、具有較大 量的奈米銀前驅物沉澱物產出。 催化劑在化學反應中係用以增加反應速率，本發明中 在驗性的環境裡還原劑有較大的氧化還原驅動力，因此， 本毛明中催化劑的條件為能提4共驗性王裒境的氫氧離子（⑽） 皆可，例如，本實施例中反應Β溶液的催化劑為一氫氧化鈉 溶液。 上述步驟(2)該反應a溶液及該反應Β溶液進行混合以得 -前驅物職物S1G2中，為了使反應a溶液及反應B溶液得 以均勻混合，本發明使用一授拌法，在反應A溶液及反應β 浴液混合時不停攪拌，例如，本實施例中可利用一磁石攪 摔法，同時搜拌該混合液至少持續5分鐘，以促進前驅物沉 殿物產出。 上述步驟(2)該反應A溶液及該反應B溶液進行混合以得 一前驅物沉澱物31〇2中，反應A溶液及反應B溶液經攪拌均 勻混合後反應產出一前驅物沉澱物，這沉澱物係包含一氰 酸銀及一碳酸銀。為了得到良好品質的固態奈米銀膠體前 驅物，本發明利用一分離法分離出前驅物沉澱物，將該前 201223876 驅物沉殿物離，把前驅物麟物及溶液分離開來， 再將該前驅物沉料分散於擁子水巾，如此—來，利用 離、，法及去離水’將可有效純化奈米銀雜前驅物，提高 不米銀膠體則驅物的品質^上述湘離心法及去離水純化 不米銀膠體前驅物的步驟不限—次，重複多次，將可得到 巧、、屯=之固祕米銀膠體前驅物。最後，將該固態奈米銀 膠體刚驅物溶於乙醇巾，即可得到高品質之奈米銀勝體前 驅物在本實施例中，使用的乙醇溶液為—995%之高濃度 乙醇溶液。 七明芩考第二圖，為本發明一種奈米銀膠體之製備方法 Ά圖士。圖所不’本發明提供一種奈米銀膠體溶液之製 備方法’其步驟包括:(i)將上述依奈練膠體前驅物製備方 =所製備出的—奈米銀膠體前驅物與-c溶液混合而得-混 σ液其中，戎c溶液係為一具有分散劑溶液S2〇1;(ii)將一 =办液與⑴中該混合液進行混合以得一奈米銀膠體沉澱物， 其^中，戎D溶液係為一還原劑水溶液s2〇2;(iii)利用一離心法 :維出4奈米銀膠體m物，並將該奈米銀膠體沉澱物分 政於-乙醇溶液巾S2Q3; (iv)湘—離心、法自步驟㈣該乙 醇各液中分離出該奈米銀膠體沉澱物，並將該奈米銀膠體 沉澱物分散於一正己烷溶液中S204。 上述第二圖步驟(i)奈米銀膠體前驅物製備方法所製備 出的一奈米銀膠體前驅物與一C溶液混合而得一混合液§20i =，為了達到均勻混合，本發明使用一攪拌法，在奈米銀 勝體則驅物與C溶液混合時不停攪拌(例如可利用一磁石授 11 201223876 拌法）’並持續攪拌一段時間，本實施例中，攪掉時間最少 10分鐘’以達到充分混合反應。 上述步驟(i)中’ c溶液為包含分散劑溶液，在本發明中 C溶液當作分散劑，是用來避免粒子發生聚集的保護機制， 本實施例中，使用一油溶性的辛癸胺分子（ODA)當作一 分散劑，因此C溶液當中包含分散劑的辛癸胺分子 (ODA) ’而0DA分子和奈米銀膠體前驅物中的銀鹽，具 有莫耳分比為1比4的比例。 上述步驟(i i)中將一 D溶液與(i)中該混合液進行混合以 得一奈米銀膠體沉澱物，其中，該D溶液係為一還原劑水溶 液S202中，D溶液是用來將奈米銀膠體前驅物中的銀離子還 原至原子態，一般常用者為氫硼酸鈉（s〇dium BorohydrideXNaBH4)、聯氨（hydrazine)(N2H〇、曱醛 (FooialdehydeXHCHQ)、葡萄糖（Gluc〇s)(C6Hl2〇6 · H2〇)、 檸檬酸鈉（Trisodium Citrate)(2Na3C6H5〇7 · 11Η2〇)、乙二 醇等’本實施例中’使用葡萄糖（Gluc〇s)(C6Hi2〇6 · H2〇)當 作還原劑，並且在還原劑_葡萄糖加入時，必須以2_ 20ml/min流速緩慢注入，混合期間溶液的顏色從黃色漸漸 轉變成紅棕色至最終的黑色，並待還原劑_㈣糖注入完成 後給予1〜5小時反應時間（靜置卜5小時），一奈米銀膠體沉 澱物在此期間内逐漸產生。 奈米銀膠體沉殿物產生後，可利用一離心法分離出該 奈米銀膠體沉叙物，本實施例中，以轉速1〇〇〇_1〇〇〇〇rpm之 離心法處理2分鐘以取得奈麵膠敝殿物，之後再分散於 201223876 乙醇中，上述步驟為一純化步驟，藉以排除其他雜質，可 重複以上步驟多次以洗去多餘的〇DA分子及鹽類，最後得到 純化後的奈米銀膠體。Borohydride) (NaBH4), hydrazine (M4), F〇nmldehyde (HCHO), glucose (G1UCOS) (C6HI2〇6 · h2〇), Trisodium Citrate (2Na3aH5〇7) · llHzO), etc., but not limited to this. The catalyst is used in a chemical reaction to increase the reaction rate. In the present invention, the reducing agent has a large redox driving force in an alkaline environment. Therefore, the condition of the catalyst in the present invention is a hydroxide ion which provides an alkaline environment. (〇H_)° In order to achieve the above object, according to another aspect of the present invention, a method for preparing a nano silver colloid is provided, the steps comprising: (1) preparing the foregoing nano silver colloid precursor preparation method The nano silver colloid precursor is mixed with an E solution to obtain a mixed solution, wherein the E solution is a dispersant solution (2), and the F solution is mixed with the mixed solution in (1) to obtain a mixture. The silver-silver colloidal material is shot, the F solution is a reducing agent solution; (3) the nano silver colloidal precipitate is separated by a centrifugation method, and the nano silver colloid precipitate is dispersed in an acetone solution. (4) separating the nano-silver colloidal precipitate by a centrifugation method, and dissolving the nano-silver colloidal precipitate in an aqueous solution or - organic spray. Thereby, it is possible to produce a silver colloid having a greenness, a high purity, and a uniform particle size, thereby reducing the presence of impurities affecting the conductive properties, and uniformly distributing the nano silver particles in the nano silver colloidal solution. 201223876 The above summary, the following detailed description and the accompanying drawings are intended to further illustrate the manner, the Other objects and advantages of the present invention will be described in the following description and drawings. [Embodiment] The embodiments of the present invention are described below by way of specific examples, and those skilled in the art can readily understand other advantages and effects of the present invention from the disclosure. ® Please refer to the first figure' for a flow chart of a method for preparing a nano silver colloid precursor. As shown in the figure, the present invention provides a method for preparing a nano silver colloid precursor, the steps comprising: (1) first providing a reaction A solution and a reaction B solution, wherein the reaction A solution comprises a silver salt and a Urea, the reaction B solution is a catalyst solution 81〇1; (2) the reaction human solution and the reaction B solution are mixed to obtain a precursor sinking substance si〇2; (3) separated by a centrifugation method Precipitating the precursor and dispersing the precursor precipitate in a deionized water Sl3; (4) separating the precursor precipitate from the deionized water in step (3) by a centrifugation method, and sinking the precursor The temple is dispersed in an ethanol solution in S104. The reaction eight solution contains - silver salt and - urea. The silver salt used in the present invention is not particularly limited, and other silver-containing salt compounds such as silver nitrate, silver sulfate, and silver peroxy acid can be suitably used in the production method provided by the present invention, for example, the reaction in the present embodiment. The silver salt in solution A was a silver nitrate solution, and 30 ml of a solution contained 3.4 g of silver nitrate and 4.8 g of urea. 201223876 The money A solution cuts urea, the main purpose is to act as a reducing agent in the redox reaction. Under the redox reaction, 'the reaction between urea and silver citrate in the reaction lining liquid will be available. Objects. In the present embodiment, the ratio of the molar ratio of urea to the silver salt in the solution is in the range of 2-8 to 1 'all of which are produced by nano silver precursors, wherein the present embodiment uses urea and The molar ratio of the silver salt is * ratio H, and a larger amount of nano silver precursor precipitate is produced. The catalyst is used in the chemical reaction to increase the reaction rate. In the present invention, the reducing agent has a large redox driving force in the environment, and therefore, the condition of the catalyst in the present invention is that the catalyst can be improved. The hydroxide ion ((10)) may be used. For example, the catalyst for reacting the ruthenium solution in this embodiment is a sodium hydroxide solution. In the above step (2), the reaction a solution and the reaction hydrazine solution are mixed to obtain a precursor substance S1G2. In order to uniformly mix the reaction a solution and the reaction B solution, the present invention uses a mixing method in the reaction A. The solution and the reaction β bath are mixed continuously without stirring. For example, in the present embodiment, a magnet stirring method can be utilized, and the mixture is mixed for at least 5 minutes to promote the production of precursors. In the above step (2), the reaction A solution and the reaction B solution are mixed to obtain a precursor precipitate 31〇2, and the reaction A solution and the reaction B solution are uniformly mixed by stirring to produce a precursor precipitate. The precipitate contains silver cyanate and silver carbonate. In order to obtain a good quality solid nano silver colloid precursor, the present invention separates the precursor precipitate by a separation method, separates the former 201223876 flooding material, separates the precursor material and the solution, and then separates The precursor sinking material is dispersed in the water towel of the bottle, so that the use of the separation, the method and the removal of the water will effectively purify the nano silver precursor, and improve the quality of the non-silver colloid. The method and the step of purifying the non-silver colloid precursor from the water are not limited, and the repetition is repeated several times to obtain the solid silver colloid precursor of Qiao, 屯=. Finally, the solid nano-silver colloidal precursor is dissolved in an ethanol towel to obtain a high-quality nano silver precursor precursor. In this embodiment, the ethanol solution used is a high-concentration ethanol solution of -995%. The seventh figure of Qiming is a preparation method of a nano silver colloid of the present invention. The present invention provides a method for preparing a nano silver colloidal solution, the steps of which include: (i) preparing the above-mentioned lysine colloid precursor for preparation - the preparation of the nano silver colloid precursor and the -c solution Mixing the mixed σ liquid, wherein the 戎c solution is a dispersant solution S2〇1; (ii) mixing the liquid solution with the liquid mixture in (1) to obtain a nano silver colloidal precipitate, ^, 戎D solution is a reducing agent aqueous solution s2 〇 2; (iii) using a centrifugation method: vitamin 4 nano silver colloidal m material, and the nano silver colloidal precipitate is divided into - ethanol solution towel S2Q3; (iv) Xiang-centrifugation, the method separates the nano-silver colloidal precipitate from the ethanol solution in step (4), and disperses the nano-silver colloidal precipitate in a n-hexane solution in S204. In the second step (i), the nano silver colloid precursor prepared by the nano silver colloid precursor preparation method is mixed with a C solution to obtain a mixed liquid §20i =, in order to achieve uniform mixing, the present invention uses one Stirring method, when the nano silver body is mixed with the C solution, stirring is continued (for example, a magnet can be used for 11 201223876 mixing method)' and stirring is continued for a while, in this embodiment, the stirring time is at least 10 minutes. 'To achieve a thorough mixing reaction. In the above step (i), the 'c solution is a solution containing a dispersant. In the present invention, the C solution is used as a dispersant, and is a protection mechanism for preventing aggregation of particles. In this embodiment, an oil-soluble octopamine is used. The molecule (ODA) acts as a dispersing agent, so the C salt contains the dispersant of the octylamine molecule (ODA)' and the 0DA molecule and the silver salt of the nano-silver colloidal precursor have a molar ratio of 1 to 4. proportion. In the above step (ii), a D solution is mixed with the mixed solution in (i) to obtain a nano silver colloidal precipitate, wherein the D solution is a reducing agent aqueous solution S202, and the D solution is used for The silver ions in the nano-silver colloidal precursor are reduced to the atomic state. Generally, sodium borohydride (s〇dium Borohydride XNaBH4), hydrazine (N2H〇, furfural XHCHQ, glucose (Gluc〇s)) are commonly used. (C6Hl2〇6 · H2〇), sodium citrate (Trisodium Citrate) (2Na3C6H5〇7 · 11Η2〇), ethylene glycol, etc. 'In this example, 'Gluc〇s' (C6Hi2〇6 · H2〇) As a reducing agent, and when the reducing agent _ glucose is added, it must be slowly injected at a flow rate of 2-20 ml/min. During the mixing, the color of the solution gradually changes from yellow to reddish brown to the final black, and the reducing agent _(tetra) is injected. After 1~5 hours of reaction time (quiet 5 hours), a nano-silver colloidal precipitate is gradually produced during this period. After the nano-silver colloidal substance is produced, the nanometer can be separated by a centrifugation method. Silver colloidal sinking, in this embodiment, The rotation method of 1〇〇〇_1〇〇〇〇rpm was carried out for 2 minutes to obtain the Naijiao capsule, and then dispersed in 201223876 ethanol. The above step is a purification step to exclude other impurities, and the above can be repeated. The steps are repeated several times to wash away excess 〇DA molecules and salts, and finally the purified nano silver colloid is obtained.
純化後的奈米銀膠體，去除多餘的〇以分子及鹽類後， 具有良好的導電性，將該奈米銀膠體溶於一正己烷溶液， 即可得一面濃度奈米銀膠體溶液，為使該奈米銀膠體均勻 分布於正己烷溶液中，本實施例採取超音波震盪法處理， 利用超音波震盪固態奈米銀膠體直至其充分分散於奈米銀 膠體溶液。由於正己烷溶液為一油性溶液，因此可得一高 濃度奈米銀油溶性膠體。 酉同溶液中S303(4)利用一 凊參考第二圖，為本發明另一種奈米銀膠體之製備方 法流程圖。如圖所示，本發明提供一種奈米銀膠體溶液之 製備方法’其步驟包括：⑴將前述之奈米銀膠體前驅物製備 方法所製備出奈米銀膠體前驅物與—E溶液混合而得一混合 液’其中’該E溶液係為—分散劑溶液S3Q1;(·—f溶液與 U)中1“液進行混合以得—奈米銀膠體沉殿物，其中， _容液係為-還原劑溶液戰⑶利用一離心法分離出該 ί米銀膠體沉殿物，並將該奈米銀膠體沉澱物分散於一兩 離心法分離出該奈米銀膠體沉殿 物並將f米銀沉殿物溶於一水溶液或一有機溶劑中。 機制上分^丨^㈣纽子發^集的倮護 (pvp)當作-分容㈣聚乙烯鱗_分子 本發明 上述實施例中的催化劑是用來增加反應速率， 13 201223876 中在驗性的環&裡還原劑有較大的氧化還原驅動力，因 此’本發明中催化劑的條件為能提供驗性環境的氫氧離子 (OH)皆可，而本實施例中的摧化劑為一氣氧化納水溶液。 上述F >谷液中的還原劑是用來將奈米銀膠體中的銀離子 還原至原子態，一般常用者為氫硼酸鈉（Sodium BorohydrideXNaBH4)、聯氨、甲醛 (FonnaldehydeXHCHO)、葡萄糖（Gluc〇s)(C6Hi2〇6 · H2〇)、 豕酸鈉（Trisodium Citrate)(2Na3C6H5〇7 · IIH2O)、乙二 醇等，本實施例中，使用甲醛（F〇rmal,dehyde)(HCH〇)當作 _ 還原劑，在還原劑-甲搭加入反應時，奈米銀膠體中的銀離 子會還原至固態原子態，因此一奈米銀膠體沉殿物逐漸產 出，為讓沉澱物充分產出，必須待混合後靜置一段時間， 在本貝施例中給予1〇〜分鐘反應時間後，可得到一充份反 應之奈米銀膠體沉澱物。 奈米銀膠體沉澱物產生後，可利用一離心法分離出該 沉澱物，本實施例中，以轉速lOOO-lOOOOrpm之離心法處理 2刀！里以取知’儿殿物，之後再分散於丙酮溶液中，上述步驟 φ 為一純化步驟，藉以排除其他雜質，可重複以上步驟多次 以洗去夕餘的PVP分子及鹽類，最後得到純化後的奈米銀膠 體。 " 純化後的奈米銀膠體’去除多餘的pvp分子及鹽類後， 具有良好的導電性，將該奈米銀膠體溶於一有機溶液或水 溶液中，即可得一高濃度奈米銀膠體，為使該奈米銀膠體 均勻分布於有機溶液或水溶液中’本實施例採取超音波震 14 201223876 盪法處理，利用超音波震盪固態奈米銀膠體直至其充分分 散於奈米銀膠體溶液。由於有機溶液或水溶液為一水性溶 液’因此可得一高濃度奈米銀水溶性膠體。 以往相關技術’以銀離子（例如水相中常用之硝酸銀 或油相中常用之脂肪酸銀）做為前驅物系統，同質相（液 相）化學還原反應幾乎為瞬間反應，此時由於反應過於快 速’粒徑分佈控制會受產物析出速率和分散劑吸附速率等 質傳問題所影響而較為困難。此外，為了降低生成粒子尺 寸’習知技術通常藉由高劑量分散劑的添加來達成目的， 但卻因此增加後續純化步驟的困難度，過多殘留於膠體的 刀月欠劑可能造成未來應用上的問題（例如導電用途）.而 本發明的優點為所合成之固態銀前驅物在還原劑存在下所 還原触為-異質相（固-液相）反應，轉化成金屬銀速率 ㈣前者較為緩慢。-旦金屬析出速率降低，僅需提供足 量分散劑即能幫帅子分散黯，所㈣量婦先前技術 揭露者為大低。以往魏於高濃4賴·加時所造 成溶液黏度過高易造成勻相反應物分散不及或不均的問 題’使得反練濃度受到關，現今树明⑽成功克服 此技術_，使單減讀朗含量可提升至相當高程 本發雜先前其他緣工#技術較有㈣突破及創 新。 本發明所提出的製備方法所製備出的高濃度奈米銀水 f生及油溶性膠體。單位批次製程膠體金屬含量高，生成 子尺寸微細，其中局浪度奈米銀水溶性膠體銀含量可為 15 201223876 =8g/L ’平均粒徑為22nm ;高濃度奈米銀油溶性膠體銀含 曰，；6§几平均粒徑為6nm。本發明之精髓為提出一 ，製備©%轉驅物的方法，藉此可進—步於二種溶液相 還原口成銀龍。換言之，在幾乎㈣設備條件下，配合 適當保魏（分㈣）與溶射合錢、㈣浮水溶性或油溶 性f體溶液。此外，由於乾燥後_態銀前驅物可再分散 於溶劑巾，因此乾雜末除了餅保存也增添躺時便利 性。 根據本發明上述實施例所製備出高濃度奈米銀水溶性 膠體及=濃度奈纽油雜频，分別可製作成高濃度奈 米銀水/谷性導電墨水及高濃度奈米銀油溶性導電墨水。在 電性表現方面，以金屬微粒為主之導電材料通常會藉助敎 處理來幫雜子燒結來降低_餘率。考第四圖， 為本發明不同導電墨水製程溫度與薄膜阻抗示意圖。如圖 所示相車乂銀塊材電阻礼6以Q_cm，於本發明中使用哪 為分散劑之高濃度奈米财紐導電墨水，經過清洗純化 後（PVP你固體總含量約5wt%)之乾燥薄膜於綱。。及2抓 熱處理3G分鐘後電阻率分別約為u w Q_cn^4. w Ω—cm ; 使用0DA為分散劑之高濃度奈米銀油溶性導電墨水，經過清 洗純化後（0DA佔固體總含量約1Gwt%)之乾燥薄膜於細。c 及250°C熱處理3G分鐘後電阻率分別約為23w_ci^ 2/ζΩ cm 一者墨水在適當溫度熱處理後皆可得到優異導 電性質。在導電祕佈位細上，除了網版印刷佈位技術 外銀墨水可藉由彼此互溶的多重溶劑組合來調整包括黏 201223876 面T力等吐質’使之適用於噴墨硬體設備來直接啥 =。=銀墨水由於較水溶性奈米銀墨水在較= )鱗理下可得顺低且更近乎塊材之電阻率， 因此可為低軟化溫度的透明可撓式基板（例如p〇lyimide) 上導電線路佈位的材料。The purified nano silver colloid has good conductivity after removing excess bismuth molecules and salts. The nano silver colloid is dissolved in a n-hexane solution to obtain a one-side concentration nano-n-colloid solution. The nano silver colloid is uniformly distributed in the n-hexane solution. In this embodiment, the ultrasonic vibration method is used to oscillate the solid nano silver colloid by ultrasonic wave until it is sufficiently dispersed in the nano silver colloidal solution. Since the n-hexane solution is an oily solution, a high concentration of nano silver oil-soluble colloid can be obtained. In the same solution, S303 (4) utilizes a reference to the second figure, which is a flow chart of a method for preparing another nano silver colloid of the present invention. As shown in the figure, the present invention provides a method for preparing a nano silver colloidal solution, the steps of which include: (1) mixing the nano silver colloid precursor prepared by the preparation method of the nano silver colloid precursor with the -E solution. a mixed liquid 'where' the E solution is - dispersant solution S3Q1; (· - f solution and U) 1 "liquid mixed to obtain - nano silver colloidal sinking matter, wherein _ liquid system is - The reducing agent solution warfare (3) separates the glutinous silver colloidal sinking matter by a centrifugation method, and disperses the nano silver colloidal precipitate in a centrifugation method to separate the nano silver colloidal sinking matter and f-silver The sulphate is dissolved in an aqueous solution or an organic solvent. The mechanism is divided into 丨^(4) 子 发 倮 ( ( ( p ( ( 四 四 四 四 四 四 四 四 四 四 四 四 四 四 四 四 四 四 四 四 四 四 四 四 四 四It is used to increase the reaction rate. In 2012 20128876, the reducing agent in the ring and the detector has a large redox driving force, so the condition of the catalyst in the present invention is the hydroxide ion (OH) capable of providing an experimental environment. Yes, and the catalyzing agent in this embodiment is an aqueous gas oxide nano solution. The reducing agent in the above F > trough liquid is used to reduce the silver ions in the nano silver colloid to the atomic state, generally used as sodium borohydride (Sodium Borohydride XNaBH4), hydrazine, formaldehyde (Fonnaldehyde XHCHO), glucose (Gluc 〇s) (C6Hi2〇6 · H2〇), sodium citrate (Trisodium Citrate) (2Na3C6H5〇7 · IIH2O), ethylene glycol, etc. In this example, formaldehyde (F〇rmal, dehyde) (HCH〇) is used. As a reducing agent, when the reducing agent-addition reaction is added, the silver ions in the nano-silver colloid are reduced to a solid atomic state, so that a nano-silver colloidal material is gradually produced, so that the precipitate is fully produced. The mixture must be allowed to stand for a period of time after mixing. After a reaction time of 1 〇 to 1 minute in the present embodiment, a solid silver colloid precipitate can be obtained. After the nano silver colloid precipitate is produced, The precipitate is separated by a centrifugation method. In this embodiment, the 2 knives are treated by centrifugation at a rotation speed of 1000-100 rpm to obtain the 'children's matter, and then dispersed in the acetone solution. The above step φ is a purification. Steps to exclude other impurities Repeat the above steps several times to wash away the PVP molecules and salts in the evening, and finally obtain the purified nano silver colloid. " The purified nano silver colloid has good after removing excess pvp molecules and salts. Conductivity, the nano silver colloid is dissolved in an organic solution or an aqueous solution to obtain a high concentration of nano silver colloid, in order to uniformly distribute the nano silver colloid in an organic solution or an aqueous solution. Sonic vibration 14 201223876 Swing treatment, using ultrasonic waves to oscillate solid nano silver colloid until it is fully dispersed in the nano silver colloidal solution. Since the organic solution or the aqueous solution is an aqueous solution, a high concentration of nanosilver water-soluble colloid can be obtained. In the related art, silver ions (such as silver nitrate commonly used in the aqueous phase or silver fatty acid commonly used in the oil phase) are used as precursor systems, and the homogeneous phase (liquid phase) chemical reduction reaction is almost instantaneous reaction, at which time the reaction is too fast. 'Particle size distribution control is more difficult due to quality problems such as product precipitation rate and dispersant adsorption rate. In addition, in order to reduce the size of the generated particles, the prior art usually achieves the purpose by adding a high-dose dispersant, but thus increases the difficulty of the subsequent purification step, and excessive stagnation agent remaining in the colloid may cause future applications. The problem (for example, conductive use). The advantage of the present invention is that the synthesized solid silver precursor is reduced in the presence of a reducing agent to a heterogeneous phase (solid-liquid phase) reaction, and converted to a metallic silver rate (iv). Once the rate of metal precipitation is reduced, it is only necessary to provide a sufficient amount of dispersing agent to disperse the cockroaches, and (4) the technologists of the women are exposed. In the past, the problem that the viscosity of the solution caused by the high viscosity of the solution was too high, which caused the dispersion of the homogeneous reactants to be inconsistent or uneven, which made the concentration of the back-flushing off. Nowadays, Shuming (10) successfully overcomes this technology. Read the lang content can be upgraded to a fairly high level. This is a hybrid. Previously, other cultivators #技术有有(四) breakthroughs and innovations. The high-concentration nano-silver water and oil-soluble colloid prepared by the preparation method proposed by the invention. The unit batch process has high colloidal metal content and fine sub-size. The water-soluble colloidal silver content of local wave nano-silver can be 15 201223876 =8g/L 'average particle size is 22nm; high concentration nano silver oil-soluble colloidal silver Containing ruthenium; 6 § several average particle size of 6nm. The essence of the present invention is to provide a method for preparing a %% transfer product, whereby the two solutions can be further reduced to form a silver dragon. In other words, under almost (four) equipment conditions, it is suitable to cooperate with Wei (division (4)) and solvent, and (4) float water-soluble or oil-soluble f-body solution. In addition, since the dried silver precursor can be redispersed in the solvent towel after drying, the dry miscellaneous addition of the cake also increases the convenience of lying. According to the above embodiments of the present invention, a high-concentration nano-silver water-soluble colloid and a concentration of nai oil miscellaneous frequency are prepared, respectively, and can be prepared into a high-concentration nano silver water/gluten conductive ink and a high-concentration nano silver oil-soluble conductive ink. In terms of electrical performance, conductive materials based on metal particles are usually treated with ruthenium to help the sintering of the dopants to reduce the _ residual ratio. The fourth figure is a schematic diagram of process temperature and film impedance of different conductive inks according to the present invention. As shown in the figure, the car block silver block resistor 6 is Q_cm, which is a high-concentration nano-coin conductive ink which is a dispersant used in the present invention, after washing and purification (PVP your total solid content is about 5wt%) drying The film is in the class. . And 2 after heat treatment for 3G minutes, the resistivity is about uw Q_cn^4. w Ω-cm; using high-concentration nano-silver oil-soluble conductive ink with 0DA as dispersant, after washing and purification (0DA accounts for about 1Gwt total solid content) %) The dried film is fine. After heat treatment at c and 250 °C for 3G minutes, the resistivity is about 23w_ci^ 2/ζΩ cm. The ink can be excellently conductive after heat treatment at an appropriate temperature. In addition to the screen printing technology, in addition to the screen printing technology, the silver ink can be adjusted by the combination of multiple solvents that are mutually soluble, including the adhesion of 201223876 T-force, making it suitable for inkjet hardware devices.啥=. = Silver ink can be a low-softening temperature transparent flexible substrate (such as p〇lyimide) because the water-soluble nano silver ink can be lower and closer to the resistivity of the bulk material. The material of the conductive line.
>上述之實_僅為例稀說明本發明之特點及其功 而非用於限制本發明之實質技術内容的顧。任何熟 習此技*之人均可在*違背本發明之精神及料下，對 上述實施贿娜飾與變化。附t，本發狀權利保護範 圍，應如後述之申請專利範圍所列。 【圖式簡單說明】 第1圖係為本㈣—種奈綠賴前驅物之製财法流程圖; 第2圖係為本發明-種奈米轉體之製備方法流程圖； 第3圖係為本發明另—種奈米轉體之f備方法流程圖； 第4圖係為本發明不同導電墨水製程溫度與薄膜阻抗示意 【主要元件符號說明】 步驟 S101-S104 17 201223876 S201-S204 步驟 S301-S304 步驟The above description is merely illustrative of the features and advantages of the present invention and is not intended to limit the technical scope of the present invention. Anyone who is familiar with this technology* can implement the above-mentioned implementation and changes in the spirit of the invention. With t, the scope of protection of this issue shall be as listed in the scope of application of the patents described later. [Simple description of the diagram] Figure 1 is a flow chart of the production method of (4) - the precursor of the green-green precursor; Figure 2 is a flow chart of the preparation method of the nano-transfer of the invention; The flow chart of the method for preparing the nano-rotating body of the present invention is the flow chart of the method for preparing the nano-rotating body of the present invention; FIG. 4 is a schematic diagram of the process temperature and film impedance of the different conductive inks of the present invention. [Summary of the main component symbols] Step S101-S104 17 201223876 S201-S204 Step S301 -S304 step
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