200406272 玫、發明說明： 【發明所屬之技術領域】 本發明係關於一種含有奈米金屬微粒的添加劑及其 製造方法，特別是關於一種可直接於黏稠的有機溶劑系統 中合成含有奈米金屬微粒的製造方法及該添加劑。 【先前技術】 近年來，隨著在奈米科技上的研究進展，已經發現金 屬顆粒奈米化之後，能展現出許多異於以往的特性，其光 學、磁性、熱傳、擴散以及機械等性質均與微米級的金屬 顆粒大不相同，因此也具有更多方面的應用潛力。 不米金屬微粒具有廣泛的應用性，例如，以奈米金屬 微粒作為催化劑，因其具有高的表面積與體積的比值與不 同的表面原子的排列結構，因此可以大幅提昇反應速度， 甚至產生新的催化性質。再者，如奈米金顆粒可以應用於 生醫檢測元件上，又因其具有生物相容性，因此可應用於 新一代的生醫材料。此外，如奈米銀顆粒，其具有極佳之 電導特性而且使用量低，因此可作為導電塗佈材料。又因 為奈米銀顆粒具有抗菌效果，因此可作為塗料或是化纖的 添加劑，提供塗有塗料的物品表面或衣物的抗菌效果。除 I上述的諸多應用之外，相關領域的研究者仍持續投入研 九’利用奈米金屬微粒的特性，開發出新用途。 目前有許多方法可以生產奈米金屬微粒，因為化學還 原合成法具有產能高，操作容易，以及成本低等優點，因 被廣泛的使用。例如j 1998，/μ 200406272 8379-8388中揭示製造奈米銀顆粒的方法，其係利用相轉 移催化劑，將銀的前驅物及其他相關試劑，轉移至有機溶 劑中，再進行銀前驅物之還原與後續的合成步驟。但是此 方法的步驟繁複，因此不適於工業上的生產。另外，如美 國專利US5,759,230，其係將二氯化鈀（Pdcl2)或硝酸銀 (AgN〇3)在乙醇中進行反應，藉以合成顆粒大小為1〇打㈤ 的鈀或是40 nm的銀，但是其反應温度高達12〇_2〇(rc。 ,如美國專利US6，103，868揭示另一種製備奈米金屬顆 粒=方法，其係將金屬鹽類水溶液與含有界面活性劑的有 機溶劑混合，而後加入還原劑進行還原反應，藉此得到奈 米金屬顆粒。為了使前述方法的反應效果更好，仍需使用 相轉移劑，且此方法的反應時間甚長。 上述的方法中，除了有反應溫度高，步驟繁複，或是 反應時間長等缺點。同時，若需要在黏稠的溶劑介質，如 油f生塗料油墨、導電油墨，或聚合物反應液中添加奈米 金屬微粒，前述等方法所合成的奈米金屬微粒，將無法直 接添加於黏祠的溶杳丨介暂击 例幻/合丨貝中，而且可能造成散佈不均及聚 集結塊專問題。此夕卜 羽a 此外I知的合成方式所製成的產品，其 中的奈米金屬微粒含量不高，相對上成本較高。 再者提问奈米金屬微粒含量（濃度），同時確保粒 、，持好的分散性，對於實驗室以及產業之規模而言，已 常具有挑戰性之課題；更遑論要求克服粒徑均勾性 工J以及確保添加之後粒子的分散性等問題。 因此：右能發展出-種反應溫度低，反應時間短，製 王間更，同時可直接於黏稍的溶劑系統中合成含奈米金屬 200406272 a λ 微粒之高濃度添加劑，一 ^ 方面將因添加劑中的奈米金屬微 高’使得運輸更方便，而且可降低成本。此 料、μ Υ 微粒添加劑將可直接添㈣如油性塗 _ ^ 電’由墨，或聚合物反應液等黏稠的溶劑介質， 因而擴展奈米金屬的應用性。 、 本發明即克服以上諸吝 ^ 居夕ρ早破，而發展出可應用於生產 夕樣奈米金屬為例的添加劑的製程。 【發明内容】 "、目的之一為提供一種含有高濃度奈米金屬 微粒的添加劑’此種添加劑可以直接添加料式非親水相 之塗料或其匕；I貝巾；同時’其所含有之奈米金屬微粒能 始終均勻分散於被添加的介質中，發揮其功能以及提供大 量之總表面積。 本發月的另目的為提供一種製備含有奈米金屬微 粒添加劑的方法，此方法之反應溫度低，反應時間短，且 製私ΡΪ單’因J：匕能有安丈降低生產成本，並且可應用於多種 奈米金屬粒添加劑的製備。 本發明是藉由一特定的反應物組成進行還原反應而 達成。此反應物之組成包含金屬鹽類（奈米金屬顆粒之前 驅物）、穩定劑、還原劑、溶劑以及增稠劑。舉例而言， 若以合成大約1 0 wt%之奈米銀添加劑為例，此反應物組成 之重里百分比較佳為9-1 0%的金屬鹽類（奈米金屬顆粒之 前驅物），0.1-15%的穩定劑，〇1_15%的還原劑，4〇_89% 的溶劑以及〇·1-20%的增稠劑。 本發明所使用之合成方法如第一圖之流程圖所示。首 200406272 =將作為奈米金屬粒子之前驅物的金屬鹽類與穩 劑以及增稠齋丨所# 士、& / 合 /成的黏稠浴劑系統混合並持續攪拌，再 入:原制加入前述混合物中，利用化學還原法並於室溫τ 合成金屬奈半下 、、7 ，並使八均勻分散於黏稠的溶劑*** 中，而成為含有奈米金屬微粒的添加劑。 、 前述合歧應中所使料金屬鹽類，並 =使用金鋇、：、 鎂、錳、鎳、錫、鎢等金屬鹽類，可以利用單一 金屬鹽類製成含有單種夺乎 早 種不…卡金屬的添加劑，也可混用兩種 5 以上之金屬鹽類，製成含有雙金屬或合金之奈米金 添加劑。以合成奈米銀粒為例，確酸銀、氯化銀、漠化 =、'過氯酸銀、氯酸銀等，以及其餘含銀之鹽類化合物皆 可適用於本發明所提供的製造方法。 上述所使用之穩定劑係作為控制奈米粒子粒护之主 要成分，此成分可列舉如四級胺鹽及其衍生物、非 界面活性劑、陽離子介面活性劑、硫酸酯類化合物、三 膦化合物（trialkyl phosphines)或其共聚合物所組成之 群的其中之一，或其二者以上之混合物。 、 再者，本發明所使用之還原劑係用以將金屬 :中之金屬離子還原為金屬原子。此還原劑並無特別： 疋，可列舉如硼系化合物、亞硫酸系化合物、次磷酸 合物、胺類化合物、過氧系化合物之還原劑及 ？ 生物等。 何 使用於本發明中之溶劑，並無特別限制，但因考戾 發明所合成之添加劑’需能直接添加於黏稠的溶劑：質 200406272 中，因此最好使用待添加物中所含有的溶劑。例如，待添 加溶劑介質為塗料時，可選用苯類、酮類、醚類、烷類、 醇類、酯類、石油系溶劑、㈣溶劑."等有機溶劑及其衍 生物’或其混合兩種或兩種以上之混合溶料作為反應溶 劑。又如，若希望於化纖原料中添加奈米銀顆粒時，可以 選擇以甲苯作為反應溶劑來製造奈米銀添加劑。因甲苯與 化纖材料（例如：PET或PBT )具有甚佳之溶解性，因此^ 當添加劑進入化纖原料之混煉製程時，具有極佳的分散 性，並且可維持化纖原料成品之物性，相較於水性奈米銀 添加劑而言，更具實際上的應用價值。 本發明中所使用的增稠劑，其主要功能在於增進奈米 粒子之懸浮，同時進一步避免粒子之聚集與不可^分二^ 負面性質。本發明所使用之增稠劑可為有機合成腊、氫化 油脂、矽酸系之化合物及其衍生物等。 以下將以具體實施例’更進一步詳細說明本發明。下 述實施例係用以闡明本發明，並非用以限定本發明之範 圍’任何熟習此技藝者’在不脫離本發明之精神和範圍 内，當可做些許更動與潤#，因此本發明之保護範圍 後附之申請專利範圍所界定者為準。 田 【實施方式】 直々例1製備含有奈米銀添加劑的方法 首先說明製備含有奈米銀添加劑之反應物組成，1組 成成分典型之相對重量百分比為：9_10%的銀鹽類：合 物’ 0.1-15%的穩定劑，0.M5%的還原劑，4〇_89%的溶二 以及0 · 1 - 2 0 %的增稿劑。 200406272 上述銀鹽類化合物可以是硝酸銀、氣化銀、溴化銀、 迻氯馱銀或是氣酸銀，其他之銀鹽類化合物也可適用於本 方法。 先在反應槽中加入甲苯、溴化四-十二基胺和硝酸銀， 攪拌以加速溶解與分散。爾後，加入聚醯胺蠛以增加 合J黏稠度，並於室溫中以適當的速率攪拌使其均勻分 散0 八、、’、夷授拌别述之反應物，同時加入亞硫酸鈉，反應完 全後’即可得到納米銀粒子。 “ 第一圖為將依照上述方法所合成的奈米銀添加劑，經 稀釋後所得之穿透式電鏡（TEM)影像圖，分析此標準樣品 之粒=，結果顯示此奈米銀粒子之直徑分佈為5·2 ± 1〇 。f準差小於20%。由此可知，本發明所提供的方法， σ 、製備出粒徑相當均勻的奈米粒子，粒徑可操控於1〜π nm之間。 、 旦八另外，將依照上述方法所合成的奈米銀添加劑，以微 厂刀散於甲苯中，所測得之吸收光譜圖如第三圖所示。其 =屬奈米粒子的吸收光譜可以提供粒子結構的對稱性 、¥維或二維之金屬奈米粒子）及粒子的分散性等資 :第Γ般而言，吸收波峰峰寬越窄，粒子的分佈越均勻。' 子之2圖所示，波長400 nm〜450 nm之波帶即為奈米銀粒 類化人Γ電漿共振吸收區域，由此可知，反應物中的銀鹽 了 & ,經還原反應後，生成奈米銀粒子，且由其波形 °知’奈米銀粒子的分佈十分均勻。 上述合成反應之結果可知，藉由此方法可以合成 10 200406272 卜50 nm粒徑範圍之内的奈米銀粒子，且其粒徑分佈相當 均句。另外，所生成的奈米銀粒子可以均自分佈於含有增 稍：的黏稠溶劑系統中’因A，能夠直接添加於黏稍的溶 劑介質中，而不會造成分佈不均的現象。 奈米銀添加劑應用於油性塗料以製備具有抑菌 性之油性塗料 依照實施例i的方法合成奈米銀添加劑，將此奈米銀 二二劑加入市售的油性pu漆中，其添加量以重量百分比 2 ’分別製備添加量為〇.()1%以及Q•⑽1%的兩組樣品， 具製備後之樣品如第四圖所示。 將上？之兩組樣品與未添加奈米銀添加劑之比較樣 :杳仃抑囷試驗，此試驗係委由台灣中國紡織中心生化檢 進行。所使狀測試8株為切料及金黃色葡 2困1測試菌株分別培料比較樣品及測試樣品中， 二」：异試驗時之最初菌數及培# 24小時後之菌數，並 计异L〇g(菌數比），其結果如表二及表三所示。 表:為添加奈米銀之油性PU漆對大腸桿菌的抑菌效 對大腸桿菌具有抑g效果。 添加里為請時即 抑菌ir:矣加奈米銀之油性叩漆對金黃色葡萄球菌的 子金貝色匍萄球菌具有抑菌效果。 以直結果可知’本發明所提供之奈米銀添加劑可 乂直接添加於如油性ρυ漆之# 油性PU漆產生良好的抑菌甚至抗菌效果。、中κ吏 200406272 如同實施例2所示的應用實例，也可將奈米銀添加劑 加入化纖材料中，如此將可製成具有抑菌或抗菌效果的衣 物0 兔I例3_製備含有奈米鉑添加劑的方法 除了將硝酸銀改為氯化鉑作為奈米金屬的前驅物 外，其如均依照實施例1的方法進行，製備含有奈米鉑的 金屬添加劑。 第五圖為將依照上述方法所合成的奈米鉑添加劑，經 稀釋後所得之穿透式電鏡影像圖，分析此標準樣品之粒 徑，並將平均粒徑之分佈列於表一。由表一可知，本實施 例所提供的方法，可以製備出粒徑相當均勻的奈米二： 子。 此外，利用能量分析儀（EDS)確認上述添加劑中所 含有之奈米金屬的成分為鉑’此能量分析儀圖譜如 所示。 置施例4製備含有奈米添加劑的方法 除了將銀鹽類化合物改為氣化鈀作為奈米金屬的前 驅物外’其如均依照實施例丨的方法進行，製備含有奈米 把的金屬添加劑。 、 乐七圆马將依照 •…久…不不此添加劑， 稀釋後所得之穿透式電鏡影像圖，分析此標準樣品, 徑’並將平均粒徑之分佈列於表_。由表一可知 例所提供的方法，可以製備出粒徑相當均句的奈米: 子0 12 200406272 此外、，利用能量分析儀（EDS)確認上述添加劑中所 3有之不米金屬的成分為銘，此能量分析儀圖譜如 所示。 不口 實施_例5製備含有奈米伽添加劑的方法 除了將銀鹽類化合物改為氣化㈣為奈米金屬的前 驅物外’其如均依照實施例i的方法進行， 铷的金屬添加劑。 占另不木 第九圖為將依照上述方法所合成的奈米如添加劑，經 稀釋後所得之穿透式電鏡影像圖，分析此標準樣品之粒 徑，並將平均粒徑之分佈列於表—。由表-可知，本實施 例所提供的方法，可以製備出 表侑出粒徑相當均勻的奈米铷粒 子。 此^利Μ量分析儀（EDS)確認上述添加劑中所 各有之^金屬的成分為*，此能量分析儀圖譜 所示。 π I 口 [拖例6.製備含有奈米金添加劑的方法 將銀鹽類化合物改為過氣酸金作為奈米金屬的 則 其如均依照實施例1的方法進行，製備含有$ 米金的金屬添加劑。 不 第:一圖為將依照上述方法所合成的奈米金添加 劑’經稀釋後所得之穿透式電鏡影像Β，分析此標準樣品 =拉徑’麵平均粒徑之分佈列於表一。由表一可知，本 實加例所提供的方法可以盤j借屮 粒子。 幻万4 了以衣備出粒徑相當均勻的奈米金 13 200406272 此外，利用能量分析儀（EDS )確認上述添加劑中所 含有之奈米金屬的成分為金，此能量分析儀圖譜如第十二 圖所示。 由上述的說明及實施例中，本發明所提供的方法可以 應用於製備添加於黏稠溶劑介質中的奈米金屬添加劑，且 此添加劑中所含之奈米金屬濃度高，粒徑均勻，能均勻散 佈於添加劑中，因此能直接添接於黏稠溶劑介質中。 此外，本發明之合成方法簡單，可於室溫下反應，反 應時間短，因此能簡化生產流程，降低製造成本。 再者’本發明之應用性廣泛，能製備出含有不同的奈 米金屬微粒之添加劑。並且，根據使用者的需求，於添加 奈米金屬微粒後，可使原來的被添加物質產生不同的特性 或其他附加價值。 14 【圖式簡單說明】 I圖本發明合成奈米金屬粒子添加劑之示意流程圖。 第二圖為將依照本發明之方法所合成的奈米銀添加劑，經 稀釋後所得之穿透式電鏡影像圖，刻度尺所示為 62.5 nm 〇 第三圖為依照本發明之方法所合成的奈米銀添加劑，以微 量分散於甲笨中所測得之吸收光譜圖。 第四圖為將依照本發明之方法所合成的奈米銀添加劑加 入油性PU漆中所調配出之樣品照片。（a)係奈米銀 添加劑為0.001 wt%的油性pu漆；（b)係奈米銀添 加劑為0·01 wt%的油性pu漆。 第五圖為將依照本發明之方法所合成的奈米鉑添加劑，經 稀釋後所得之穿透式電鏡影像圖，刻度尺所示為 62.5 nm 〇 第，、圖為依照本發明之方法所合成的奈米鉑添加劑之能 里分析儀（EDS )成份分析圖譜。成分鉑為唯一偵 測之元素，圖譜中所含鋼與碳源自於樣品基材。 第七圖為將依照本發明之方法所合成的奈米鈀添加劑，經 稀釋後所得之穿透式電鏡影像圖，刻度尺所示為 1 00 nm 〇 第八圖為依照本發明之方法所合成的奈米鈀添加劑之能 里分析儀（EDS )成份分析圖譜。成分鈀為唯一偵 測之το素’圖譜中所含鋼與碳源自於樣品基材。 15 200406272200406272 Rose, description of the invention: [Technical field to which the invention belongs] The present invention relates to an additive containing nano metal particles and a method for manufacturing the same, and particularly to a method for synthesizing nano metal particles containing directly in a viscous organic solvent system. Manufacturing method and the additive. [Previous technology] In recent years, with the research and development of nanotechnology, it has been found that metal nanoparticles can exhibit many characteristics that are different from the past, such as optical, magnetic, heat transfer, diffusion, and mechanical properties. They are all very different from micron-sized metal particles, so they also have more application potential. Micron metal particles have a wide range of applications. For example, nanometer metal particles are used as catalysts. Because of their high surface area to volume ratio and different surface atom arrangement, they can greatly increase the reaction speed and even generate new ones. Catalytic properties. Furthermore, nanogold particles can be applied to biomedical detection elements, and because of their biocompatibility, they can be applied to a new generation of biomedical materials. In addition, nano-silver particles, such as nano-silver particles, have excellent electrical conductivity and low usage, so they can be used as conductive coating materials. Because of the antibacterial effect of nano silver particles, it can be used as an additive for coatings or chemical fibers to provide antibacterial effects on the surface of coated articles or clothing. In addition to the many applications mentioned above, researchers in related fields continue to invest in research and development of new applications that utilize the properties of nanometer metal particles. At present, there are many methods for producing nano metal particles, because the chemical reduction synthesis method has the advantages of high productivity, easy operation, and low cost, and is widely used. For example, j 1998, / μ 200406272 8379-8388 discloses a method for manufacturing nano silver particles, which uses a phase transfer catalyst to transfer silver precursors and other related reagents to an organic solvent, and then reduces the silver precursors. With subsequent synthesis steps. However, the steps of this method are complicated and therefore unsuitable for industrial production. In addition, for example, U.S. Patent No. 5,759,230, which reacts palladium dichloride (Pdcl2) or silver nitrate (AgNO3) in ethanol to synthesize palladium with a particle size of 10 ㈤ or silver at 40 nm. However, the reaction temperature is as high as 120 ° C. For example, U.S. Patent No. 6,103,868 discloses another method for preparing nano metal particles, which is a method of mixing an aqueous solution of a metal salt with an organic solvent containing a surfactant, Then, a reducing agent is added to carry out the reduction reaction, thereby obtaining nano metal particles. In order to make the reaction effect of the foregoing method better, a phase transfer agent is still required, and the reaction time of this method is very long. In the above method, in addition to the reaction High temperature, complicated steps, or long reaction time. At the same time, if it is necessary to add nano metal particles in viscous solvent media, such as oil paint ink, conductive ink, or polymer reaction solution, the above methods and other methods Synthesized nano metal particles will not be directly added to the solution of sticky temples. Temporary hits / combinations, and may cause problems of uneven distribution and agglomeration. Xi Xibu a In addition, the product made by the known synthesis method has a low content of nano metal particles, which is relatively expensive. Also ask the content (concentration) of nano metal particles, and at the same time ensure that the particles are well dispersed. For the scale of laboratories and industries, it has always been a challenging subject; not to mention that it is necessary to overcome the problems of uniformity of particle size and ensure the dispersion of particles after addition. Therefore: Right can develop The reaction temperature is low, the reaction time is short, and the king is better. At the same time, it can directly synthesize nano-metals with a concentration of 200406272 a λ particles in a slightly viscous solvent system. In one aspect, the nano-metals in the additives will be slightly high. 'Make transportation more convenient and reduce costs. This material and μ 微粒 particulate additives can be directly added such as oily coating _ ^ electricity' from ink, or polymer solvent liquid and other viscous solvent media, thus expanding the nano metal Applicability. The present invention is to overcome the above-mentioned premature rupture of Ju Xi ρ, and to develop a process that can be applied to the production of additives such as nano-metals. [Content of the Invention] " One of the objectives is to provide an additive containing a high concentration of nano metal particles. 'This additive can be directly added to the coating of non-hydrophilic phase or its dagger; I towel; and' the nano metal particles contained in it It can always be uniformly dispersed in the added medium, exert its function and provide a large amount of total surface area. Another purpose of this month is to provide a method for preparing an additive containing nano metal particles. The method has a low reaction temperature and a short reaction time. In addition, the production of the private PZ sheet can reduce production costs due to J: dangle, and can be applied to the preparation of a variety of nano metal particle additives. The present invention is achieved by performing a reduction reaction with a specific reactant composition. This The composition of the reactant includes metal salts (precursors of nanometer metal particles), stabilizers, reducing agents, solvents, and thickeners. For example, if the synthesis of about 10 wt% nano silver additives is taken as an example, the weight percentage of this reactant composition is preferably 9-10% metal salts (precursors of nano metal particles), 0.1 -15% stabilizer, 0.01-15% reducing agent, 40-89% solvent and 0.1-20% thickener. The synthesis method used in the present invention is shown in the flowchart of the first figure. First 200406272 = Mix metal salts that are precursors of nanometer metal particles with stabilizers and thickeners In the aforementioned mixture, the metal nano-semi-lowers, 7 and 7 were synthesized by a chemical reduction method at room temperature τ, and the eight were uniformly dispersed in a viscous solvent system to become an additive containing nano-metal particles. 1. The metal salts used in the aforementioned amalgamation and the use of metal salts such as gold, barium, magnesium, manganese, nickel, tin, tungsten, etc., can be made from a single metal salt containing a single species that is earlier than the previous species. Additives that do not ... card metals can also be mixed with two or more metal salts of 5 to make nano gold additives containing bimetals or alloys. Taking the synthesis of silver nanoparticles as an example, it is confirmed that silver acid, silver chloride, desertification =, 'silver perchlorate, silver chlorate, etc., and other silver-containing salt compounds can be applied to the manufacturing provided by the present invention. method. The stabilizer used above is the main component for controlling the protection of nano particles. This component can be exemplified by quaternary amine salts and their derivatives, non-surfactants, cationic surfactants, sulfate compounds, and triphosphine compounds. (Trialkyl phosphines) or one of its groups, or a mixture of two or more thereof. Furthermore, the reducing agent used in the present invention is used to reduce metal ions in metal: to metal atoms. This reducing agent is not particularly: 疋, examples include boron-based compounds, sulfurous acid-based compounds, hypophosphite compounds, amine compounds, peroxy compounds, and? Creatures etc. There are no particular restrictions on the solvent used in the present invention, but the additive synthesized by the invention needs to be directly added to the viscous solvent: qualitative 200406272, so it is best to use the solvent contained in the to-be-added. For example, when the solvent medium to be added is paint, benzenes, ketones, ethers, alkanes, alcohols, esters, petroleum solvents, fluorene solvents, and other organic solvents and their derivatives' or their mixtures can be selected. Two or more mixed solvents are used as reaction solvents. As another example, if it is desired to add nano-silver particles to a chemical fiber raw material, toluene can be selected as a reaction solvent to produce nano-silver additives. Because toluene has good solubility with chemical fiber materials (such as PET or PBT), ^ When the additive enters the mixing process of chemical fiber raw materials, it has excellent dispersibility, and can maintain the physical properties of the finished chemical fiber raw materials, compared to For water-based nanosilver additives, it has more practical application value. The main function of the thickener used in the present invention is to improve the suspension of nano particles, and at the same time to further avoid the aggregation of particles and the inseparable negative properties. The thickener used in the present invention may be organic synthetic wax, hydrogenated fats and oils, silicic acid-based compounds and derivatives thereof, and the like. Hereinafter, the present invention will be described in further detail with specific examples'. The following examples are intended to clarify the present invention and are not intended to limit the scope of the present invention. 'Any person skilled in the art' can make some changes and embellishments without departing from the spirit and scope of the present invention. The scope of the patent application attached to the scope of protection shall prevail. [Embodiment] Straight Example 1 Method for preparing nano-silver-containing additives First, the preparation of the reactant composition containing nano-silver additives will be described. The typical relative weight percentage of 1 component is: 9-10% silver salts: compound '0.1 -15% stabilizer, 0. M5% reducing agent, 40-89% dissolve and 0. 1-20% of the supplement. 200406272 The above silver salt compounds can be silver nitrate, silver gasified, silver bromide, silver chlorosulfonate, or silver gas acid. Other silver salt compounds can also be applied in this method. First add toluene, tetra-dodecylamine bromide and silver nitrate to the reaction tank, and stir to accelerate dissolution and dispersion. Then, add polyamidine to increase the viscosity of the mixture, and stir it at an appropriate rate at room temperature to disperse it uniformly. At the same time, add sodium sulfite. After the reaction is complete, 'You can get nano silver particles. "The first picture is a transmission electron microscopy (TEM) image of the nanosilver additive synthesized in accordance with the method described above, and the particle size of this standard sample is analyzed. The results show that the diameter distribution of the nanosilver particles is 5 · 2 ± 10.0. The f standard deviation is less than 20%. It can be seen that the method provided by the present invention can prepare nano particles with fairly uniform particle size, and the particle size can be controlled between 1 and π nm. In addition, the nano-silver additive synthesized in accordance with the above method is dispersed in toluene with a micromill knife, and the measured absorption spectrum is shown in the third figure. It is the absorption spectrum of the nano-particles. Provides the symmetry of particle structure, ¥ dimensional or two-dimensional metal nano particles) and particle dispersibility, etc .: Generally speaking, the narrower the width of the absorption peak, the more uniform the particle distribution. '子 之 2 图As shown, the wavelength band of 400 nm to 450 nm is the nano-silver-like human Γ plasma resonance absorption region. It can be seen that the silver salt in the reactant is & after reduction reaction, it generates nanometer. Silver particles, and from its waveform, the distribution of nano silver particles is very uniform From the results of the above synthesis reaction, it can be known that by this method, nano-silver particles with a particle size range of 10 200406272 and 50 nm can be synthesized, and the particle size distribution is quite uniform. In addition, the generated nano-silver particles can be uniform Self-distributed in a viscous solvent system containing a thinner: Because of A, it can be added directly to a thin solvent medium without causing uneven distribution. Nanosilver additives are used in oily coatings to prepare antibacterial agents. Oily coatings based on the method of Example i to synthesize nano silver additives, this nano silver two second agent is added to the commercially available oil-based pu paint, the added amount is 2% by weight, respectively, the added amount is 0. () 1 % And Q • ⑽1% of the two groups of samples, the sample after preparation is shown in the fourth figure. Comparison of the two groups of samples with and without the addition of nano-silver additives: 杳 仃 inhibition test, this test is The test was carried out by the Biochemical Inspection of China Textile Center in Taiwan. The tested 8 strains were cut materials and golden yellow starch. 2 test strains were used for comparison and test samples. 2 ": the initial bacterial count and training in the different tests. 24 hours After the number of bacteria and iso L〇g meter (ratio of cell count), and the results shown in Table II and Table III. Table: The antibacterial effect of oily PU paint with nano silver added on E. coli has a g-inhibitory effect on E. coli. Please add it immediately. Bacteriostatic ir: oily paint with silver and nanometer has antibacterial effect on Staphylococcus aureus, Staphylococcus aureus. From the direct results, it can be known that the nanosilver additive provided by the present invention can be directly added to oily ρυpaint # oily PU paint to produce good antibacterial and even antibacterial effects. ， 中 κ200200406272 As the application example shown in Example 2, nano silver additives can also be added to the chemical fiber material, so that it can be made into clothing with antibacterial or antibacterial effect. 0 Rabbit I Example 3_ Preparation of nano The method for the platinum additive is to change the silver nitrate to platinum chloride as the precursor of the nano metal, and it is performed according to the method of Example 1 to prepare a metal additive containing nano platinum. The fifth figure is a transmission electron microscope image of the nano-platinum additive synthesized in accordance with the above method after dilution. The particle size of this standard sample is analyzed, and the average particle size distribution is listed in Table 1. As can be seen from Table 1, the method provided in this embodiment can prepare nanometer particles with a fairly uniform particle size. In addition, the energy analyzer (EDS) was used to confirm that the component of the nano metal contained in the additive was platinum '. The spectrum of the energy analyzer is shown below. The method for preparing nanometer-containing additives in Example 4 except that the silver salt compounds were changed to vaporized palladium as a precursor of nanometer metals. It was performed in accordance with the method of Example 丨 to prepare a metal additive containing nanometers. . 7. Leqiyuanma will analyze the standard sample according to the transmission electron microscope image obtained by diluting the additive with the long-lasting ... but this additive, and the diameter distribution will be listed in Table_. According to the method provided in Table 1, the nano particles with fairly uniform particle diameters can be prepared: 子 0 12 200406272 In addition, using an energy analyzer (EDS), it is confirmed that the composition of the three metals in the additive is 3 Ming, the spectrum of this energy analyzer is shown below. Example 5-Method for preparing nanogamma-containing additives Except changing the silver salt compounds to the precursors of gasification of gadolinium to nano-metals, it was carried out in accordance with the method of Example i, the metal additives of gadolinium. The ninth figure of Zhanbeimu is a transmission electron microscope image of the nanometer additive synthesized in accordance with the above method after dilution. The particle size of this standard sample is analyzed, and the average particle size distribution is listed in the table. —. It can be seen from Table-that the method provided in this embodiment can prepare nano-sized particles having a relatively uniform particle size. The EDS analyzer confirms that the metal composition of each of the additives mentioned above is *, as shown in the spectrum of the energy analyzer. π I 口 [Example 6. Preparation of nano-gold-containing additive method The silver salt compounds are changed to peroxy acid gold as the nano-metal, and if they are performed in accordance with the method of Example 1, preparation of $ -gold Metal additives. No. The first picture shows the transmission electron microscope image B of the nano-gold additive ′ synthesized according to the above method after dilution. The distribution of the average particle size of the standard sample = pull-diameter surface is shown in Table 1. As can be seen from Table 1, the method provided in this example can be used to borrow particles. Magic Wan 4 has nano-gold with uniform particle size. 13 200406272 In addition, the energy analyzer (EDS) was used to confirm that the composition of the nano-metal contained in the additive was gold. The spectrum of the energy analyzer is as follows: As shown in the second figure. From the above description and examples, the method provided by the present invention can be applied to the preparation of nano metal additives added in a thick solvent medium, and the nano metal metal contained in the additive has a high concentration, a uniform particle size, and can be uniform. It is interspersed in additives, so it can be directly added to viscous solvent media. In addition, the synthesis method of the present invention is simple, can be reacted at room temperature, and the reaction time is short, so the production process can be simplified and the manufacturing cost can be reduced. Furthermore, the present invention has a wide range of applications and can prepare additives containing different nano-metal particles. In addition, according to the needs of users, after adding nano metal particles, the original added substance can have different characteristics or other added value. 14 [Schematic description] Figure I is a schematic flowchart of the synthesis of nano metal particle additives according to the present invention. The second figure is a transmission electron microscope image of the nanosilver additive synthesized in accordance with the method of the present invention after dilution. The scale shows 62.5 nm. The third figure is synthesized according to the method of the present invention. Nano-silver additive, absorption spectrum measured in micro-dispersion in methylbenzyl. The fourth figure is a photo of a sample prepared by adding the nano silver additive synthesized according to the method of the present invention to an oily PU paint. (A) Nano-silver additive is 0.001 wt% oily pu paint; (b) Nano-silver additive is 0.01 wt% oily pu paint. The fifth figure is a transmission electron microscope image of the nano-platinum additive synthesized in accordance with the method of the present invention after dilution. The scale shows 62.5 nm. The figure and the figure are synthesized according to the method of the present invention. Component analysis chart of Nanometer Platinum Additive Energy Analyzer (EDS). The component platinum is the only detectable element, and the steel and carbon contained in the map are derived from the sample substrate. The seventh figure is a transmission electron microscope image of the nano-palladium additive synthesized according to the method of the present invention after dilution. The scale shows 100 nm. The eighth figure is synthesized according to the method of the present invention. Composition analysis of nanometer palladium additive energy analyzer (EDS). The component palladium is the only το prime ’spectrum detected. The steel and carbon are derived from the sample substrate. 15 200406272
第九圖為將依照本發明之方法&人丄、μ太上& I 々杏所合成的奈米#σ添加劑，經 稀釋後所得之穿读4 $ 牙透式電鏡影像圖，刻度尺所示為 1 00 nm 〇 第十圖，依妝本發明之方法所合成的奈米铷添加劑之^ ®分析儀（EDS )成份分析圖譜。成分麵為唯一 ^ 測之疋素，圖譜中所含鋼與碳源自於樣品基材。 第十一圖 為將依照本發明之方法所合成的奈米金添加The ninth figure is a penetrating electron microscope image of a nanometer # σ additive synthesized by the method & human 丄, μ 太 上 & I 々 杏, after dilution, and a scale Shown is the 10th graph of 100 nm. The composition analysis chart of the nanometer 铷 additive analyzer (EDS) synthesized by the method of the present invention. The composition side is the only test element, and the steel and carbon contained in the map are derived from the sample substrate. Figure 11 shows the nanogold synthesized by the method of the present invention.
剔，經稀釋後所得之穿透式電鏡影像圖，刻度 尺所示為62.5 nm。 第十二圖$依照本發明之方法所合成的奈米金添加劑之 能量分析儀（EDS)成份分析圖譜。成分金為唯 侦測之元素，圖譜中所含銅與碳源自於樣品 基材。 16 200406272 表一、依照本發明之方法所合成之各種奈米金屬添加劑中 戶斤含奈米金屬粒子之平均直徑 奈米金屬種類 奈米銀 奈米齡 平均直徑（nm) 5·2 士 1.0 4·4 ± 0.7 4 奈米把 5·3±1·0 5 奈米物 5.7 ± 1.7 6 奈米金 6.2 ±2.0 貫施例 1 3 表二、添加奈米銀之油性PU漆對大腸桿菌的抑菌效果 奈米銀添加 劑之添加量 最初菌數 培養24小時 後之菌數 ~---1 aL〇g(菌數比） 比較樣品（無 添加） 1.35x10s 1.94 xl〇6 - 2.84x10s 8.93 xlO6 0.01% 1.35xl05 <20 >4.99 0.001% 2.84xl05 <20 >5.65 aLog(菌數比）之值大於2，表示具有抑菌效果。 17 200406272 添加奈米銀之油性PU漆對金黃色葡萄球菌的抑菌 效果 奈米銀添加 劑之添加量 最初菌數 培養24小時 後之菌數 aLog(菌數比） 比較樣品（盔 添加） 2.93xl04 1.35 xlO4 - 0.01% 2.93χ104 <20 >2.83 0.001% 2·93χ104 2-lOxlO4 1.81 aLog(菌數比）之值大於2，表示具有抑菌效果。 18The image of the transmission electron microscope obtained after picking and diluting. The scale shows 62.5 nm. Twelfth figure: An analysis chart of the energy analyzer (EDS) of the nanogold additive synthesized according to the method of the present invention. The component gold is the only detectable element, and the copper and carbon contained in the map are derived from the sample substrate. 16 200406272 Table 1. The average diameter of nano-containing metal particles in various nano-metal additives synthesized according to the method of the present invention. Nano-metal type. Nano-silver nano-age average diameter (nm) 5 · 2 ± 1.0 4 4 ± 0.7 4 Nanometers 5 · 3 ± 1 · 0 5 Nanometers 5.7 ± 1.7 6 Nanometers 6.2 ± 2.0 Implementation Example 1 3 Table 2. Inhibition of E. coli by oily PU paint with nanometer silver added Bacterial effect Addition amount of nano-silver additive The initial number of bacteria after 24 hours of culture ~~ -1 aL〇g (number of bacteria) Comparative sample (no addition) 1.35x10s 1.94 xl〇6-2.84x10s 8.93 xlO6 0.01 % 1.35xl05 < 20 > 4.99 0.001% 2.84xl05 < 20 > 5.65 The value of aLog (bacteria number ratio) is greater than 2, indicating a bacteriostatic effect. 17 200406272 Antibacterial effect of oily PU paint with nano-silver on Staphylococcus aureus Addition of nano-silver additive The number of bacteria aLog (ratio of bacteria number) after 24 hours of initial culture Comparative sample (addition of helmet) 2.93xl04 1.35 xlO4-0.01% 2.93x104 < 20 > 2.83 0.001% 2.93x104 2-lOxlO4 1.81 The value of aLog (bacteria number ratio) is greater than 2, indicating a bacteriostatic effect. 18