200902192 九、發明說明： [發明所屬之技術領域】 2發明是有關於一種製備含有多數奈米金屬粒子之 複日材料的方法，特別是指—種利用 的、锋贈士为戍丁聚醣 广來I備含有多數奈米金屬粒子之複合材料的方 以及—種製備該等奈米金屬粒子的方法。 【先前技術】 #奈米材料是目前熱門的研究之-，隨著粒子尺 鲶小’其表面位能會增力口 ’造成例如光學、機械、電 、磁、熱力學、化學等的材料性質也隨之改變，進而 產生許多的「奈米特性」。以現在流行的奈米銀粒子為 例，由於奈米銀粒子的尺寸縮小’導致其表面能增加 二，得奈米銀粒子具有很大的活性而可被用於殺菌、 抗菌或除臭等’此外’ x因其燒結溫度低，且具有低 電^及㈣關性質單的減龍可以應用 在導電用途及各種初期電路製作，因此，目前各方都 積極地研究製備含有多數奈米金屬粒子的複合材料及 奈米金屬粒子的方法。 已知幾丁聚醣對金屬離子具有吸附效果，加上幾 丁來醣無毋性’具有生物分解性及生物相容性等特性 ，且又是一價格便宜的天然高分子，因此是目前被利 用於製造奈米金屬粒子的方法之一。幾丁聚醣乃是由 ^ 丁質經高度去乙醯化而得的多醣類聚合物，一般常 見的去乙醯化程度為70%至90%之間，其之所以能吸 200902192 附金屬離子的原理在於：脫去乙酿基後裸露的胺美合 使幾丁聚醣具有整合金屬離子的特性。如陳紅婉^ 耀國等人發表的「以幾丁聚醣製備奈米銀之研究及 施詔銘和凃耀國等人發表的「以幾丁聚醣製備：二金 之研究」的論文中所記載的，目前 ^ , 刖刊用幾丁聚醣製備 不、米銀或金粒子的步驟為··⑷將溶有幾丁聚醋的醋酸 水溶液加入-氫氧化納水溶液中，以形成—幾丁聚酷 懸浮液；⑻將該幾丁聚酷懸浮液與—硝酸銀水溶液或 一氯化金水溶液反應形成—驗性幾丁聚醣.金屬複合物 懸夺液，並靜置歷時-段時間，藉由水溶液中的陰離 子提供電子給金屬離子，使金屬離子還原成奈米金屬 粒子，以及⑷以酸水解法或熱裂解法將該幾丁聚醣從 該複合物中移除，進而得到奈米金屬粒子。在論文「 以幾丁聚骑製備奈米銀之研究」t，以熱裂解製得的 銀粒子的粒徑是介们⑽至⑽聰之間，而在論文「 m醣製備奈米金之研究」中’以酸水解法製得 的粒徑是介於15_至1〇〇·之間，以熱裂解 “的金粒子的粒徑由於粒子密集排列，僅能推估里 粒徑約為5nm左右。 '、 然而’雖然習知技術已經能製得奈米級的金屬粒 子’但是由於該幾丁聚醣懸浮於水溶液巾時， 聚醣之部分片段或全邻 …王侧又可能會彼此糾結，致使螯 广4丁聚酿上的金或銀離子的排列是無規則性， 因而不易控制還原成金或銀极子的顆粒大小。尤其是 200902192 =解法製得的奈米金屬粒子的大小均—性更是難以 ；：制：且需要使用化學還原劑，目而容易造成環境上 的污染，此外，後靖、萝+ a 士 、’、還品要有一處理大量溶液的步驟 ’ ¥致製備成本高。再去，F^ 再者，上述的二篇論文皆是利用 * ,曰供電子給金屬離子的原理來將金屬離子還原 、丁米金屬粒子’所以最好是使用強驗性溶液，故在 操作時還有會安全性 的問喊。因此，目前仍是有需要 發展出一種安令、彻、、_ * ,, 女王低π染性且能製備含有多數大小一 致且排列規則之奈米金屬粒子之複合材料的方法。 【發明内容】 繁於習知技術在利用幾丁聚聽懸浮液製備奈米金 屬粒子時會產生的缺點，申請人思及若是能想出一種 使幾丁聚st (尤其是其中的胺基）不會糾結在一起的 方法’應該就能解決習知無法製備出含有大小均一及 排列規則的奈米金屬粒子之複合材料的問題，於是申 請人利用先製備出一含有幾丁聚骑的薄膜，再將該薄 膜置於-含有多數金屬離子的溶液中’使該等金屬離 子與薄膜中的幾丁聚聽主鏈之胺基螯合，藉此使得該 等金屬離子的排列會較有規則性，當然，再配合上適 當的光照處理而還原得到的奈米金屬粒子的排列也會 較為整齊，粒徑也會較為均—。 於是，本發明之第—目的即在提供—種製備含有 多數奈米金屬粒子之複合材料的方法，其係包含下列 步驟：⑷提供-含有多數金屬離子的第—溶液；⑻提 200902192 供一含有幾丁聚醣的薄膜；（c)將兮本 v )將該步驟（b)之含有幾丁 聚醣的薄膜置於該步驟（a)之第_ 办液中，以形成—螯 合有該等金屬離子的整合膜’以及⑷對該步驟⑷之整 合膜施予-光照處理’藉此將該等金屬離子還原成太 米金屬粒子’ $而得到該含有多數奈来金屬粒子的複 合材料。 本發明之第二目的即在提供_種製備奈米金屬粒子200902192 IX. Description of the invention: [Technical field to which the invention pertains] 2 The invention relates to a method for preparing a multi-day material containing a plurality of nano metal particles, in particular, a method for utilizing A method of preparing a composite material containing a plurality of nano metal particles and a method of preparing the nano metal particles. [Prior Art] #奈米材料 is a popular research--the material properties such as optical, mechanical, electrical, magnetic, thermodynamic, chemical, etc. are also caused by the small particle size of the particle. It changes, and a lot of "nano characteristics" are produced. Taking the popular nano silver particles as an example, the size of the nano silver particles is reduced, resulting in an increase in surface energy. The nano silver particles have great activity and can be used for sterilization, antibacterial or deodorization. In addition, because x has a low sintering temperature and has a low electrical and (four) nature, the reduced dragon can be used in conductive applications and various initial circuit fabrications. Therefore, all parties are actively studying the preparation of nanoparticles containing most nano-particles. A method of composite materials and nano metal particles. It is known that chitosan has an adsorption effect on metal ions, and it has the characteristics of biodegradability and biocompatibility, and is an inexpensive natural polymer, so it is currently One of the methods used in the manufacture of nano metal particles. Chitosan is a polysaccharide polymer obtained by highly deacetylating the chitin. The common degree of deacetylation is between 70% and 90%. The reason why it can absorb 200,902,192 metal The principle of the ion is that the naked amine merging after removing the ethyl ketone makes the chitosan have the property of integrating metal ions. For example, Chen Hongqi, Yao Guo and others published the study on the preparation of nano silver from chitosan and the papers in "Study on Chitosan Preparation: Two Gold" published by Shi Yuming and Tu Yaoguo. At present, the procedure for preparing non-silver or gold particles with chitosan is (4) adding an aqueous solution of acetic acid in which several butyl vinegar is dissolved to an aqueous solution of sodium hydroxide to form a few a suspension; (8) reacting the chitosan suspension with an aqueous solution of silver nitrate or an aqueous solution of gold monochloride to form a chitosan-metal complex suspension, which is allowed to stand for a period of time, by an aqueous solution. The anion in the electron supply electrons to the metal ions to reduce the metal ions to the nano metal particles, and (4) the chitosan is removed from the composite by acid hydrolysis or thermal cracking to obtain nano metal particles. In the paper "Study on the preparation of nano silver by a few chisels" t, the particle size of the silver particles prepared by thermal cracking is between (10) and (10) Cong, and in the paper "M-sugar preparation of nano gold" The particle size obtained by the acid hydrolysis method is between 15 Å and 1 〇〇·, and the particle size of the gold particles by thermal cracking can only be estimated as the particle size is about 5 nm due to the dense arrangement of the particles. Left and right. 'However, although the conventional technology has been able to produce nano-sized metal particles', but because the chitosan is suspended in the aqueous solution, some fragments of the glycans or the entire neighbors... may be entangled with each other. Therefore, the arrangement of gold or silver ions on the chewing powder is irregular, so it is difficult to control the particle size of the gold or silver poles. Especially, the size of the nano metal particles prepared by the solution is 200902192 = Sex is more difficult;: system: and need to use chemical reducing agent, it is easy to cause environmental pollution, in addition, Hou Jing, Luo + a, ', also have a step to handle a large number of solutions' ¥ to the cost of preparation High. Go again, F^ Again, the above two papers It is the use of *, 曰 electrons to the metal ion principle to reduce metal ions, butadiene metal particles 'so it is best to use a strong solution, so there will be security in the operation of the call. Therefore, currently There is still a need to develop a method for the preparation of a composite material containing a majority of uniform size and regular arrangement of nano metal particles, which is capable of producing a composite material having a majority of uniform size and regular arrangement of nano metal particles. Knowing the shortcomings of the technology in the preparation of nano metal particles by using chitosan suspension suspension, the applicant thinks that if one can think of a way to make the chitin poly (especially the amine group therein) not entangled together 'It should be possible to solve the problem that it is impossible to prepare a composite material containing nano metal particles of uniform size and arrangement order, so the applicant uses a film containing a few chines to prepare a film, and then the film is placed - In a solution containing a plurality of metal ions, 'the metal ions are chelated with the amine groups of the chitosan backbone in the film, whereby the arrangement of the metal ions is more regular, of course, The arrangement of the nano metal particles obtained by the combination with the appropriate light treatment is also relatively uniform, and the particle size is also relatively uniform. Thus, the first object of the present invention is to provide a preparation of a plurality of nano metal particles. A method of composite material comprising the steps of: (4) providing a first solution containing a plurality of metal ions; (8) providing a film containing chitosan; (c) preparing a film of the chitosan; (c) preparing the step (b) The chitosan-containing film is placed in the first step of the step (a) to form an integrated film that sequesters the metal ions, and (4) the integrated film is applied to the step (4) - illumination treatment 'There is a reduction of the metal ions to the tow metal particles' to obtain the composite material containing the majority of the nanoparticles. The second object of the present invention is to provide a nano metal particle for preparation.
的方法，其係令如上所述的製備方法所製得的複合材料 在-溫度介於载至靴的環境下進行熱裂解，以 分離出該等奈米金屬粒子。 本發明製備含有多數奈米金屬粒子之複合材料， 由於將含有幾丁聚醣的水溶液先製成膜，免去了該幾 丁聚醣的分子鏈在水溶液中會糾結在—起的情形，使 得該幾丁聚醣分子鏈上的胺基得以分散，如此一來， 螯合於其上的金屬離子也能規則地排列，相對地，以 光照還原法還原後所得到的奈米金屬粒子的排列也較 為規則，且粒徑可被控制在5nm至14〇nm之間，此外 還可以藉由在該薄膜中摻混不同比例的水溶性高分子 ，或是使用不同去乙醯化的幾丁聚醣，或是控制光照 強度及時間，而使粒徑大小較為均一，因此本發明製 備多數奈米金屬粒子之複合材料確實可以達到本發明 之目的，且更進一步可以藉由熱裂解該複合材料而分 離出該複合材料上的多數奈米金屬粒子。 【實施方式】 8 200902192 本發明製備含有多數牟半么 卡 不水金屬粒子之複合材料的 万法’係包含下列步驟： ⑷提供—含有多數金屬離子的第-溶液’· (b) 提供—含有幾丁聚醣的薄膜； (c) 將該步驟（b)之含右绻丁 广、 有成丁聚醣的薄膜置於該步驟 (a)之第一溶液中，以形 哪 八妝 攻螯合有該等金屬離子的螯 合膜；以及 (d) 對該步驟（c)之螯合胺 m ρ 坌口膜施予一光照處理，藉此將 3亥專金屬離子還原成奈米金 夕红4 I屬粒子，進而得到該含有 夕不'米金屬粒子的複合材料。 選擇性地，該步驟⑷之料金屬離子是如金離子 、銀離子及㈣子等貴重金屬離子，㈣制該步驟 之含有幾丁聚醣的薄膜螯合該等貴重金屬離子，進 而形成的含有多數I半+Μ 枯古 ’…、屬粒子的複合材料的應用價 r、呵，：用於抗菌及殺菌等用途。選擇性地，該步驟 a之該等金屬離子是如㈣子及汞離子等重金屬離子 ’此時該步驟（a)之第—、、宠该可θ ^ r ;弟/合液可以是一含有重金屬離子 的廢水’而利用該步驟（b) 之3有成丁聚醣的薄膜螯合 住該荨重金屬離子時，藉此 離子。 稭此了除去該廢水中的重金屬 較佳地，該步驟⑷之該等金屬離子是選自於金離 不銀離子、鋼離子、锡離子、辞離子、麵離子、鐘 子、鎂離子、汞離子，或此等之一組合。 較佳地’該步驟⑻之第一溶液是藉由將含有該等 200902192 金屬離子的化合物溶於一水〉谷液中而製得的，例如： 醋酸銀、硫酸鹽、磷酸銀、氧化銀、氟化銀、四氟化 金。在本案具體例中，該等金屬離子是銀離子，該化 合物是硝酸銀。 較佳地，該步驟（b)之含有幾丁聚醣的薄膜是藉由 對一含有幾丁聚醣的第二溶液施予一烘乾處理而製得 的。更佳地’該步驟（b)之含有幾丁聚醣的第二溶液是 藉由將該幾丁聚醣溶於一酸性溶液中而製得的，該酸 性溶液是選自於醋酸、硝酸、鹽酸、填酸、甲酸，或 此荨之組合。 較佳地，該步驟（b)之供乾處理的溫度是介於6〇。〇 至loot：之間。更佳地，該步驟（b)之烘乾處理的溫度 是介於60°c至70°c之間。 選擇性地，該步驟（b)之第二溶液還含有一高分子 組份，該高分子組份包括至少一能溶於水的高分子。 較佳地，該步驟（b)之高分子組份中的至少一能溶於水 醇、聚丙烯醇、聚丙烯酸、 、聚氨酯、澱粉、曱基纖維 海藻酸鹽、明膠、聚乙烯基 聚（2-羥乙基異丁烯酸）。在本 的高分子是選自於聚乙烯 聚甲基丙烯酸、聚乙二醇 素、黃原膠、膠原蛋白、 π比略烧_、聚丙烯酿胺、 案具體例中所使用的高分子是聚乙烯醇 較佳地，該步驟⑻之第二溶液是藉由將該幾丁聚 酶與該高分子組份溶於―酸性溶液中而製㈣，該酸 性溶液係如上述。 10 200902192 該高分子組份是用以分散幾丁聚醣，且申請人由 實驗传知隨著高分子组份的含量增加’最後製得的奈 米金屬粒子的粒徑會愈小，也就是說可以藉由調控幾 丁聚騎血其八7 / 回刀子組份的摻混比例來控制奈米金屬粒子 的粒徑大小》 、 ’ 十 也以該幾丁聚醣與該高分子組份她曹晉外 ，該步驟㈨之第二溶液中的該幾丁聚糖的重== 、t%至100wt%之間。更佳地，以該幾丁聚醣與該高 分子組份總重量計，該步驟⑻之第二溶液中的該幾丁 聚·的重量是介於20wt%至100wt%之間。最佳地， T該幾丁聚糖與該高分子組份總重量計，該步驟⑻之 第二溶液中的該幾丁聚醣的重量是介於40wt%至 100wt% 之間。 選擇性地，該步驟（b)之含有幾丁聚畴的薄膜是形 成於—布料上，且該步驟⑷係將該含有幾丁聚醣的薄 膜與該布料_同置於該步驟⑷之第—溶液中。 較佳地，該步驟⑻之幾丁聚糖為去乙酿度是介於 70%及95%的幾丁聚醣。更佳地，該步驟⑼之幾丁聚 醣為去乙醯度是介於8〇% & 95%的幾丁聚醣。 較佳地，該步驟⑷還進—步對該螯合膜施予一供 乾處理’進而得到一經烘乾且f合有多數金屬離子的 螯合膜。 較佳地，該步驟⑷之供乾處理的溫度是介於⑽ 至1 oo°c之間。更佳地，竽牛 佳 3步驟⑷之奴乾處理的溫度是 11 200902192 介於60°C至70°C之間。 較佳地，該步驟（d)之光照處理是藉由令一紫外光 照射該螯合膜而達成，或是藉由以—日光燈照射該螯 合膜而達成。不過直接將該螯合膜放置在室内或室外 任何有日光照射到的地方皆可以還原出奈米金屬粒子 ，較佳地，是在一波長介於150nm至6〇〇nm之間的光 照下，更佳地，是在一波長介於2〇〇nm至4〇〇nm之間 的光照下。在本案具體例中是使用波長為245nm的紫 外光。此外，藉由變化光照還原條件，例如光照強度 和照射時間，可以控制製備出的奈米金屬粒子的粒徑 。舉例來說’該步驟（b)之含有幾丁聚醣的薄膜是由 100wt%的幾丁聚醣所構成時，在紫外光照射i小時下 還原出的奈米金屬粒子的粒徑是介於1011111至14011111之 間，但是改由日光燈照射4天後還原出的奈米金屬粒 子的粒徑則可介於1 〇nrn至3Onm之間。 較佳地，該步驟（d)之奈米金屬粒子的粒徑是介於 5nm至140nm之間。在本案之一具體例中，該等奈米 金屬粒子的粒徑是介於l〇nm至30nm之間，在本案之 另一具體例中，該等奈米金屬粒子的粒徑是介於i 至5〇nm之間，在本案之又一具體例中，該等奈米金屬 粒子的粒徑是介於5nm至20nm之間。 如上所述的製備方法還可以被進一步用於製備/ 種抗菌噴劑，該抗菌喷劑是藉由在如上所述的製備含 有多數奈米金屬粒子之複合材料的方法中的步驟（幻後 12 200902192 進行一步驟（d，）而製得，該步驟（d，）是將該步驟（d)之含 有多數奈米金屬粒子的複合材料溶於一酸性溶液中， 該酸性溶液是選自於稀醋酸、稀磷酸，或此等之組合 〇 較佳地’該稀醋酸或稀磷酸的濃度是介於0.2wt% 至2wt%之間。 此外’本發明製備奈米金屬粒子的方法係令如上 所述的製備方法所製得的複合材料在一溫度介於4〇〇。匸 至800 C的環境下進行熱裂解，以分離出該等奈米金屬 粒子。 本發明將就以下實施例來作進一步說明，但應瞭 解的是，該等實施例僅為例示說明之用，而不應被解 釋為本發明實施之限制。 <化學品> 1. 幾丁聚醋（chitosan):購自於誠麗實業股份有限公 司，去乙醯度為95%之β型幾丁聚醣，分子量約& 萬，以下以幾丁聚醣Α代表。 2. 幾丁聚醣（chitosan):購自於誠麗實業股份有限公 司，去乙醯度為80%之β型幾丁聚醣，分子量約3之 萬，以下以幾丁聚醣Β代表。 3·醋酸（Acetic Acid，CH3C00H):購自於聯工化學 (Union chemical) ° 4.硝酸銀（silver nitrate solution ; AgN03):蹲自於 本昭和株式會社，濃度為〇.〇lln〇i/;i。 製備一含有幾丁聚醣的薄膜 13 200902192 〈製備例1〜5> 製備例1〜5的操作步驟如下： (1)取如下表〗$ 广衣1所不的不同量的聚乙烯醇粉末，加 入2% 、70 c的醋酸水溶液内，並攪拌溶解成 一透明溶液。 ⑺將該透明溶液冷卻至5(rc，再加入如下表丨所 不的不同置的95%去乙醯度之幾丁聚醣粉末， 並攪拌溶解，即得到一 5wt%的幾丁聚醣/聚乙 烯醇摻混液’其中各製備例中的該幾丁聚醣與 該糸乙烯醇的摻混比例，如下表1所示。 (3)以玻璃針筒吸取1〇ml幾丁聚醣/聚乙烯醇摻混 液至一培養皿中，靜置消泡3小時。 (4) 放入一溫度為6〇。〇的烘箱中24小時。 (5) 放入70t真空烘箱24小時，以去除殘留的水 分，即可得到一厚度約為〇.5mm之含有幾丁聚 醣的薄膜。 Λ <製備例6 > 製備例6的操作步驟與製備例1相同， + Μ的地 方僅在於·步驟（2)的95%去乙醯度之幾丁聚聰是以一 80%去乙醯度之幾丁聚醣取代。 14 200902192 表1 製備例 聚乙烯醇（g) 幾丁聚醣（g) 幾丁聚醣/聚乙 (wt% /wt% ) 1 0 A 5 100/0 2 1 A 4 80/20 、、 3 2 ----—- 3 60/40 〜〜 4 3 A— ------ 2 40/60 5 4 A 1 20/80~ - 6 0 B ------ - 5 100/0 製備含有多數銀敕早的葙 <實施例1 > 本實施例的操作步驟如下： (1) 將製備例1製得之含有幾丁聚醣的薄膜裁剪成 邊長為3公分的正方形，並浸泡於i〇ml且濃度 為0.01M的硝酸銀溶液丨小時’形成一螯合$ 多數銀離子的螯合膜。 (2) 以去離子水清洗該螯合膜數次，藉此洗淨過多 的硝酸銀。 (3) 放入一溫度為6〇°C的烘箱中小時。 (4) 放入一溫度為70。〇的烘箱中24小時，以去除殘 留的水分，可得到一經烘乾且螯合有多數銀離 子的螯合膜。 (5) 將該螯合膜在一日光燈下照射4天，即可將該 等銀離子還原成銀粒子，進而得到一含有多數 銀粒子的複合材料。 15 200902192 <實施例2〜6 > 有 中 是 該 的 實施例2至6是以與實施例】相同之步驟製備含 多數銀粒子的複合材料，不同之處在於：該步驟⑴ 所使用的製備例1製得之含有幾丁聚醣的薄膜分別 以製備例2至6製得之含有幾丁聚醣的薄膜取代； 步驟(5)中的日光燈照射4天改為以一波長為245nm 紫外光照射1小時。 复儀奈米鈒齟孑 <實施例7〜12 > 實施例7〜12的操作步驟是將依據實施例丨〜6製得 的s有夕數銀粒子的複合材料置於一溫度為6〇〇。〇的高 溫爐内30分鐘，藉此使幾丁聚醣裂解氣化，進而得到 多數銀粒子。 <應用例1 >抗菌喷劑 應用例1的細作步驟是將依據實施例2製得的含 有多數銀粒子的複合材料溶於一 025wt%稀醋酸溶液中 ’進而製得一抗菌喷劑。 邊_11」董轉換紅外線光譜儀（FTIR 折 以傅利葉轉換紅外線光譜儀（簡稱FTIR，型號： Spectrum One，廠商：perkin Elmer )，在掃描波數介於 4000cm·1至600cm·!下分析實施例1至5製得之含有多 數銀粒子的複合材料，其結果依序如圖丨中的曲線…) 、（b)、（c)、（d)及（e)所示。 以圖1中的曲線（a)為例，可發現136〇cm-i有冷型 16 200902192 幾丁聚醣的NHCOCH3官能基’而在1530 cm-1為NH2The method is such that the composite material obtained by the preparation method as described above is thermally cracked at a temperature ranging from the load to the shoe to separate the nano metal particles. The invention prepares a composite material containing a plurality of nano metal particles, and the aqueous solution containing the chitosan is first formed into a film, thereby eliminating the situation that the molecular chain of the chitosan is entangled in the aqueous solution, so that The amine group on the chitosan molecular chain is dispersed, so that the metal ions chelated thereon can be regularly arranged, and the arrangement of the nano metal particles obtained by the photoreduction method is relatively reversed. It is also relatively regular, and the particle size can be controlled between 5 nm and 14 〇 nm. In addition, a different ratio of water-soluble polymer can be blended in the film, or a different de-acetylation can be used. Sugar, or to control the light intensity and time, so that the particle size is relatively uniform, so the composite material of the invention for preparing most nano metal particles can indeed achieve the object of the present invention, and further can thermally crack the composite material. Most of the nano metal particles on the composite are separated. [Embodiment] 8 200902192 The invention has the following steps for preparing a composite material containing a plurality of bismuth-carbon-free metal particles: (4) providing - a first solution containing a plurality of metal ions' (b) providing - containing a film of chitosan; (c) placing a film containing the dextrozine and the butyl glycan in the step (b) in the first solution of the step (a) to form a smear a chelate film incorporating the metal ions; and (d) applying a light treatment to the chelate amine m ρ 坌 membrane of the step (c), thereby reducing the metal ions of the 3 hai to the nano-gold eve The red 4 I particles are obtained, and the composite material containing the metal particles is obtained. Optionally, the metal ions in the step (4) are precious metal ions such as gold ions, silver ions, and (tetra), and (4) the chitosan-containing film of the step is used to chelate the precious metal ions, thereby forming a Most I half + Μ 古 古 '..., the application price of composite materials belonging to particles r, oh, for antibacterial and sterilization purposes. Optionally, the metal ions in the step a are heavy metal ions such as (tetra) and mercury ions, and then the step (a) is the first step, and the pet can be θ ^ r; the brother/liquid mixture can be a The wastewater of heavy metal ions' is obtained by using the film of the step (b) to form a film of chitosan to sequester the heavy metal ions of the crucible. Preferably, the metal ions in the step (4) are selected from the group consisting of gold ions, silver ions, tin ions, tin ions, surface ions, bells, magnesium ions, mercury. Ions, or a combination of these. Preferably, the first solution of the step (8) is prepared by dissolving a compound containing the 200902192 metal ion in a water solution, such as: silver acetate, sulfate, silver phosphate, silver oxide, Silver fluoride, gold tetrafluoride. In the specific embodiment of the present invention, the metal ions are silver ions and the compound is silver nitrate. Preferably, the chitosan-containing film of the step (b) is obtained by subjecting a second solution containing chitosan to a drying treatment. More preferably, the second solution containing chitosan in the step (b) is prepared by dissolving the chitosan in an acidic solution selected from the group consisting of acetic acid and nitric acid. Hydrochloric acid, acid filled, formic acid, or a combination of this. Preferably, the temperature for the dry treatment of the step (b) is between 6 Torr. 〇 to loot: between. More preferably, the temperature of the drying treatment in the step (b) is between 60 ° C and 70 ° C. Optionally, the second solution of the step (b) further comprises a polymer component comprising at least one polymer soluble in water. Preferably, at least one of the polymer components of the step (b) is soluble in hydroalcohol, polyacryl alcohol, polyacrylic acid, polyurethane, starch, sulfhydryl alginate, gelatin, polyvinyl poly( 2-hydroxyethyl methacrylate). The polymer used in the present invention is selected from the group consisting of polyethylene polymethacrylic acid, polyethylene glycol, xanthan gum, collagen, π ratio slightly calcined, and polyacrylamide. Preferably, the second solution of the step (8) is prepared by dissolving the chitinase and the polymer component in an "acid solution", and the acidic solution is as described above. 10 200902192 The polymer component is used to disperse chitosan, and the applicant has experimentally learned that as the content of the polymer component increases, the particle size of the finally prepared nano metal particles will be smaller, that is, It is said that the particle size of the nano metal particles can be controlled by controlling the blending ratio of the eight or seven knife components of the chitosan group, and that the ten is also the chitosan and the polymer component. Outside Cao Jin, the weight of the chitosan in the second solution of the step (9) is between == and t% to 100% by weight. More preferably, the weight of the chitosan in the second solution of the step (8) is between 20% by weight and 100% by weight based on the total weight of the chitosan and the high molecular component. Most preferably, the weight of the chitosan in the second solution of the step (8) is between 40% by weight and 100% by weight based on the total weight of the chitosan and the polymer component. Optionally, the film containing the chitin domains of the step (b) is formed on the cloth, and the step (4) is to apply the film containing the chitosan to the solution of the step (4). in. Preferably, the chitosan of the step (8) is a chitosan having a deuteration of 70% and 95%. More preferably, the chitosan of the step (9) is chitosan having a degree of deacetylation of between 8〇% and 95%. Preferably, the step (4) further applies a dry treatment to the chelating film to obtain a chelating film which is dried and has a plurality of metal ions. Preferably, the temperature for the dry treatment of the step (4) is between (10) and 1 oo °c. More preferably, the temperature of the slave treatment of the yak good 3 step (4) is 11 200902192 between 60 ° C and 70 ° C. Preferably, the illumination treatment of the step (d) is achieved by irradiating the chelate film with ultraviolet light or by irradiating the chelate film with a fluorescent lamp. However, the chelating film can be directly placed indoors or outdoors in any place where sunlight is irradiated to recover nano metal particles, preferably at a wavelength between 150 nm and 6 〇〇 nm. More preferably, it is illuminated at a wavelength between 2 〇〇 nm and 4 〇〇 nm. In the specific case of this case, ultraviolet light having a wavelength of 245 nm is used. Further, the particle diameter of the prepared nano metal particles can be controlled by changing the light reducing conditions such as the light intensity and the irradiation time. For example, when the chitosan-containing film of the step (b) is composed of 100% by weight of chitosan, the particle size of the nano metal particles reduced by ultraviolet light irradiation for one hour is Between 1011111 and 14011111, the particle size of the nano metal particles reduced after 4 days of irradiation with a fluorescent lamp may be between 1 〇nrn and 3Onm. Preferably, the particle diameter of the nano metal particles of the step (d) is between 5 nm and 140 nm. In a specific example of the present invention, the particle diameter of the nano metal particles is between 10 nm and 30 nm. In another specific example of the present invention, the particle diameter of the nano metal particles is between i. Between 5 〇 nm, in another embodiment of the present invention, the particle diameter of the nano metal particles is between 5 nm and 20 nm. The preparation method as described above can also be further used for preparing an antibacterial spray which is a step in a method of preparing a composite material containing a plurality of nano metal particles as described above (Fantasy 12 200902192 is prepared by performing a step (d,), wherein the composite material containing the majority of the nano metal particles in the step (d) is dissolved in an acidic solution selected from the group consisting of dilute Acetic acid, dilute phosphoric acid, or a combination thereof, preferably 'the concentration of the dilute acetic acid or dilute phosphoric acid is between 0.2 wt% and 2 wt%. Further, the method of preparing the nano metal particles of the present invention is as described above. The composite material prepared by the preparation method is thermally cracked at a temperature of 4 Torr to 800 C to separate the nano metal particles. The present invention will further It is to be understood that the examples are for illustrative purposes only and are not to be construed as limiting the invention. <Chemical> 1. Chitosan: purchased from Chengli Industrial Co., Ltd., The β-type chitosan with a degree of acetamidine of 95% has a molecular weight of about & 10,000, which is represented by chitosan oxime. 2. Chitosan: purchased from Yuli Industrial Co., Ltd. The β-type chitosan with an acetylation degree of 80% has a molecular weight of about 3 million, and the following is represented by chitosan oxime. 3. Acetic Acid (CH3C00H): purchased from Union Chemical ° Silver nitrate solution (AgN03): 本 from the Showa Co., Ltd., the concentration is 〇.〇lln〇i/; i. Preparation of a film containing chitosan 13 200902192 <Preparation Examples 1 to 5> The procedure of Preparation Examples 1 to 5 was as follows: (1) A different amount of polyvinyl alcohol powder as in the following table was taken, and added to a 2%, 70 c aqueous acetic acid solution, and stirred to dissolve into a transparent solution. (7) The transparent solution is cooled to 5 (rc, and then a different amount of 95% deacetylated chitosan powder as shown in the following table is added, and stirred and dissolved to obtain a 5 wt% chitosan/ Polyvinyl alcohol blending liquid, wherein the blending ratio of the chitosan and the decyl vinyl alcohol in each preparation example is as shown in Table 1 below. (3) Pipette 1 〇ml chitosan/polyvinyl alcohol blend into a Petri dish with a glass syringe and let stand for 3 hours. (4) Put in a oven with a temperature of 6 〇. 24 hours. (5) A 70t vacuum oven was placed for 24 hours to remove residual moisture to obtain a film containing chitosan having a thickness of about 0.5 mm. Λ <Preparation Example 6 > Preparation Example 6 The procedure was the same as in Preparation Example 1, except that the 95% deacetylation degree of the step (2) was substituted with a chitosan of 80% deacetylation degree. 14 200902192 Table 1 Preparation Example Polyvinyl Alcohol (g) Chitosan (g) Chitosan/Polyethylene (wt% / wt%) 1 0 A 5 100/0 2 1 A 4 80/20 , 3 2 ------ 3 60/40 ~~ 4 3 A- ------ 2 40/60 5 4 A 1 20/80~ - 6 0 B ------ - 5 100/0 Preparation of a ruthenium containing a majority of silver ruthenium <Example 1 > The procedure of this example was as follows: (1) The film containing chitosan prepared in Preparation Example 1 was cut into a square having a side length of 3 cm. The silver nitrate solution, which was immersed in i〇ml and at a concentration of 0.01 M, was formed to form a chelate film of a majority of silver ions. (2) The chelate film was washed several times with deionized water to wash off excess silver nitrate. (3) Place in an oven at a temperature of 6 ° C for an hour. (4) Put a temperature of 70. In a dry oven for 24 hours to remove residual moisture, a chelated film that has been dried and sequestered with a majority of silver ions is obtained. (5) The chelating film is irradiated for 4 days under a fluorescent lamp to reduce the silver ions to silver particles, thereby obtaining a composite material containing a plurality of silver particles. 15 200902192 <Examples 2 to 6 > In the examples 2 to 6, the composite material containing the majority of silver particles was prepared in the same manner as in the example except that the step (1) was used. The chitosan-containing film prepared in Preparation Example 1 was replaced by the chitosan-containing film prepared in Preparation Examples 2 to 6, respectively; the fluorescent lamp in the step (5) was irradiated for 4 days to have a wavelength of 245 nm. Light was irradiated for 1 hour. Reagent Nanotubes<Examples 7 to 12> The operation steps of Examples 7 to 12 were such that the composite material of the s silver particles prepared according to Examples 丨 to 6 was placed at a temperature of 6 Hey. The chitosan was cleaved and gasified in a high temperature furnace for 30 minutes to obtain a plurality of silver particles. <Application Example 1> Antibacterial Spray The fine procedure of Application Example 1 was that a composite material containing a plurality of silver particles prepared in accordance with Example 2 was dissolved in a 025 wt% dilute acetic acid solution to prepare an antibacterial spray. _11" Dong conversion infrared spectrometer (FTIR is divided into Fourier transform infrared spectrometer (FTIR, model: Spectrum One, manufacturer: perkin Elmer), and the analysis of Example 1 is performed under the scanning wave number between 4000cm·1 and 600cm·! 5 The composite material containing most of the silver particles is obtained, and the results are sequentially shown in the curves of ...), (b), (c), (d) and (e). Taking the curve (a) in Fig. 1 as an example, it can be found that 136 〇cm-i has a cold type of 16 200902192 chitosan NHCOCH3 functional group' and 1530 cm-1 is NH2.
官成基的特性吸收峰；幾丁聚醣在1150 cm·1有C6-OH (一級备基）特性吸收峰及在1〇5〇 cm-1有C3-OH (二 級羥基）特性吸收峰，因此，由FTIR結果可以證實該 等含有多數銀粒子的複合材料的表面確實有胺基（NH2 吕土）存在’且隨著幾丁聚聽的含量變少，nh2的特 性吸收峰亦會變窄變小’由此可知，皿2應為螯合銀離 子之重要官能基。Characteristic absorption peak of Guanchengji; chitosan has C6-OH (primary base) characteristic absorption peak at 1150 cm·1 and C3-OH (secondary hydroxyl group) characteristic absorption peak at 1〇5〇cm-1 Therefore, it can be confirmed from the FTIR results that the surface of the composite material containing most of the silver particles does have the presence of an amine group (NH2 ruthenium), and the characteristic absorption peak of nh2 also changes as the content of chitosan becomes less. It is known that the dish 2 should be an important functional group for chelation of silver ions.
此外還可以看到3200 cnT1至3600 cm·】為N-H 及0 H之寬廣吸收峰，這也說明了 N_H及〇_H應存在 著強弱不同的分子内和分子間氫鍵。 问緩"析~^曼复鏡（HR FE-SEMV>1 、FE SEM觀察實施例i至5及實施例6製得 之含❹數銀粒子的複合材料之表面的銀粒子分佈情 形’並藉此量測古p ， 1 v 。"專銀粒子的粒徑大小，觀察到的粒 子之/刀佈情形依序如圖2 大倍率為5_…H3 —所不。其中，圖2的放 倍，圖3的放大倍率為1〇_倍；圖4 至圖的放大倍率為30000倍。 由圖3量測出的實施例2的銀粒子粒徑介於丨― 至 50nm之間，甘加， 胺某在成膜的一’立子顆粒較大的原因是因為大量的 膜的過程呈現凝集的現象，而導致螯人後的 銀粒子呈現聚集，使銀粒子的顆粒較二上= 烯醇的含量比例掸 仁疋*裝乙 表2所干，㈢T，銀粒子的顆粒會變小，如下 …稀醇的比例增加到…，銀粒 17 200902192 子粒徑可小至5誰至20nm之間’這是因為聚乙烯醇能 分散幾丁聚醣之胺基，減少凝集的現象，使得螯合於 該含有幾丁聚聽的薄膜上的銀離子有良好的分散:，、 也因此還原成銀粒子時的顆粒會比較小。 除了聚乙烯醇的含量比例會影響到銀粒子顆粒大 小外’幾丁聚糖本身的去乙醯度也會影響顆粒大小， 因為去乙醯化程度不同即代表著裸露出的胺基數量不 同，而80%去乙醯度之幾丁中陆田甘^ a > θ 戏j策醣因其所含有的胺基的 量比95%去乙醯度之幾丁平艘步 戍J永醣來仔少，所以能減少幾 丁聚醣之胺基在成膜時的聚佳 务 m lL m 丁 J不本現象，因此利用8〇%去 乙醯度之幾丁聚醣（B)所贺；?呈&人士々土 、W版侍的含有多數銀粒子的複合 材料内的銀粒子粒徑可小至介於5nm至施瓜之間。 此外由圖2里測出的實施例1的銀粒子粒徑可 小至介於10nm至30nm夕pq , a ^ , m之間’但是當光照條件為紫外 光照射1小時時，製借山& 衣瑪出的銀粒子粒徑則是約介於 l〇nm至 140nm，由此 匕了知稭由將光照強度減弱，並以 加長光照時間的方式來推> ro , 進仃逛原時，能調整製得之銀 粒子顆粒的大小及均—性。 18 200902192 表2 實 施 例 幾丁聚 醣種類 幾丁聚醣/ 聚乙稀醇 (wt% /wt% ) 光照 條件 FE- SEM圖 ----—1 銀粒子 粒徑（nm) 1 A 100/0 日光燈 /4天 2 10-30 2 A 80/20 紫外光 /1小時 3 10-50 3 A 60/40 紫外光 /1小時 4 10-50 4 A 40/60 紫外光 /1小時 5 5-20 6 B 100/0 紫外光 /1小時 6 5-20 能量分散光譜儀（EDS)分折In addition, it can be seen that 3200 cnT1 to 3600 cm·] is a broad absorption peak of N-H and 0 H, which also indicates that N_H and 〇_H should have different intramolecular and intermolecular hydrogen bonds.问 ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ Taking the measurement of the ancient p, 1 v. " particle size of the special silver particles, the observed particle / knife cloth situation as shown in Figure 2 large magnification of 5_...H3 - no. Among them, the release of Figure 2 The magnification of Fig. 3 is 1〇_倍; the magnification of Fig. 4 to Fig. 3 is 30000 times. The particle size of the silver particles of Example 2 measured by the amount of Fig. 3 is between 丨― and 50nm, Ganga The reason why the amine is larger in the film formation is because the process of a large number of membranes is agglomerated, and the silver particles after the chelation are concentrated, so that the particles of the silver particles are more than the second. The content ratio of 掸仁疋* is loaded with Table 2, (3) T, the particles of silver particles will become smaller, as follows... The proportion of dilute alcohol is increased to..., silver particle 17 200902192 The particle size can be as small as 5 to 20 nm between ' This is because polyvinyl alcohol can disperse the amine group of chitosan, reduce the phenomenon of agglomeration, and make it chelate in the thin containing The silver ions on the surface have a good dispersion: and, therefore, the particles will be relatively small when reduced to silver particles. In addition to the content of polyvinyl alcohol, the ratio of the particle size of the silver particles will affect the degree of deacetylation of the chitosan itself. It also affects the particle size, because the degree of deacetylation means that the amount of exposed amine groups is different, and 80% of the degree of deacetylation is in the middle of Lutian Gan ^ a > θ The amount of the amine group contained is less than that of the 95% deacetylation degree, and the amount of the amine group is less, so that the amine group of the chitosan can be reduced during the film formation. This phenomenon is not the case, so the use of 8〇% to the degree of chitosan (B) to congratulate; the present and the people of the earth, the W version of the silver particles in the composite material containing most of the silver particles can be The particle size of the silver particles of Example 1 as measured by Figure 2 can be as small as between 10 nm and 30 nm between pq and a ^ , m 'but when the light conditions are When the ultraviolet light is irradiated for 1 hour, the particle size of the silver particles produced by the mountain and the mountain is about 1 nm to 140 nm, thereby knowing the light from the light. The strength is weakened, and the light is extended by the method of lengthening the light time. When the original is browsed, the size and uniformity of the obtained silver particle particles can be adjusted. 18 200902192 Table 2 Examples Chitin type Glycan/polyethylene glycol (wt% / wt%) Illumination conditions FE-SEM image-----1 Silver particle size (nm) 1 A 100/0 Fluorescent lamp / 4 days 2 10-30 2 A 80/ 20 UV/1 hour 3 10-50 3 A 60/40 UV/1 hour 4 10-50 4 A 40/60 UV/1 hour 5 5-20 6 B 100/0 UV/1 hour 6 5 -20 Energy Dispersive Spectrometer (EDS)
以EDS(型號為INCA400EDS)分析實施例i得 到之含有多數銀粒子的複合材料的一部份區域，其 EDS所分析的能譜圖，如圖6所示，經與軟體内的資 料庫比對後，發現確實有銀存在 丁聚醣確實有螯合銀離子之能力 推測出螯合有該等金屬離子的螯 ’因此，可以證實幾 。而申請人以此為例 I膜的結構應如下所 示： 19 200902192A portion of the composite material containing the majority of silver particles obtained in Example i was analyzed by EDS (Model INCA400EDS), and the energy spectrum analyzed by EDS, as shown in Fig. 6, was compared with the database in the soft body. After that, it was found that the presence of silver does have the ability to chelate silver ions, and the ability to chelate the chelate of these metal ions is speculated. Therefore, several can be confirmed. The applicant's structure as an example I should be as follows: 19 200902192
f ch2-ch4-I n 〇Hf ch2-ch4-I n 〇H
H Η Η2Νι Η H w ch2qh ^ 本發 方法利用 理，確實 南的奈米 材料進一 明方法因 幾丁聚醣 具有螯合 米金屬粒 等奈米金 高，可以 複合材料 時’其抗 供一種可 或奈米孔 有幾丁聚 溶液中， 奈米金屬 nh2 CHj -CH~^· 明製備含有多數奈米金屬粒子之複合材料的 含有幾丁聚醣的薄膜，並配合適當的光照處 可以製得一含有多數排列規則且大小一致性 金屬粒子的複合材料，同 步藉由熱裂解製得多數奈 為幾丁聚醣已經先被製成 懸浮液中的幾丁聚醣糾結 金屬離子的功能。此外， 子的複合材料，因為已經 屬粒子因分散性佳、排列 提供較大且均勻的反應表 的某一區域，因此在例如 囷效果相對也會比較好。 以直接將現有醫療用敷材 洞結構的無機或有機材料 醣的溶液中，再浸於—含_ 並透過光照還原法，進而 粒的複合材料的方法。％ 時也可將上述複合 米金屬粒子，本發 膜，因而不會有如 的情形，但是卻仍 本發明含有多數奈 是成膜且其中的該 整齊又大小一致性 面積，不會侷限於 醫療上的實際應用 再者，本發明亦提 、不織布、具微米 等基材先浸在一含 有多數金屬離子的 得到一螯合有多數 此之外，利用添加 20 200902192 不同量的水溶性高分子或改變幾丁聚醣的去乙醯化程 度，可以藉由使幾丁聚醣的胺基分散性變好或是裸露 出的胺基數量變多，進而控制所需要的金屬粒子顆粒 大小。 表 τ'上所述，依照本發明方法確實可以製備出一含 有分散性佳、排列整齊又大小一致性高的多數奈米金 屬粒子的複合材料，並具有製程安全簡單、低污染且 成本低廉的優點，而且製得的奈米金屬粒子又可廣泛 應用於醫療或導電用途’極具有商業應用價值，故本 發明製備含有多數奈米金屬粒子之複合材料及奈米金 屬粒子的方法確實能達到本發明的目的。 惟以上所述者，僅為本發明之較佳實施例而已， 當不能以此限定本發明實施之範圍，即大凡依本發明 申請專利範圍及發明說明t J^容所作之簡I#等效變 化與修飾，皆應仍屬本發明專利涵蓋之範圍内。 【圖式簡單說明】 圖1是一透射率對波數圖，其中曲線（a) 、（b)、 (c)、（d)及⑷分別顯示以FTIR_ATR在掃描波數介於 4000cm至600Cm 1下分析實施例ι至$製得之含有多 數銀粒子的複合材料的結果； 圖2疋一 SEM圖，顯示實施例1製得之含有多數 銀粒子的複α材料之表面，其倍率為$刪〇倍； 圖3疋SEM圖，顯示實施例2製得之含有多數 銀粒子的複合材料之表面，其倍率為1_〇倍； 21 200902192 圖4 一 SEM圖，顯示實施例3製得之含有多數銀 粒子的複合材料之表面，其倍率為30000倍； 圖5 — SEM圖，顯示實施例4製得之含有多數銀 粒子的複合材料之表面，其倍率為30000倍； 圖6 — SEM圖，顯示實施例6製得之含有多數銀 粒子的複合材料之表面，其倍率為30000倍；及 圖7是一能譜圖，說明實施例1中步驟（4)得到之 經烘乾且螯合有多數銀離子的螯合膜中的元素。 【主要元件符號說明】無 22H Η Η2Νι Η H w ch2qh ^ The method of the present invention utilizes the fact that the nano-materials of the south are in a clear way because the chitosan has a high nano-gold content such as chelated rice metal particles, and can be used as a composite material. Or a nano-pore solution, a nano-metal nh2 CHj -CH~^········································· A composite material containing a plurality of regularly arranged and uniform-sized metal particles is synchronously produced by thermal cracking to obtain a function of a plurality of chitosan which has been first formed into a chitosan entangled metal ion in a suspension. In addition, the composite material of the sub-composite is relatively good because, for example, the granules are relatively good in dispersibility and provide a large and uniform reaction table. A method of directly immersing a solution of an inorganic or organic material sugar of a conventional medical dressing hole structure in a composite material containing _ and passing through a light reduction method and further granules. In the case of %, the above-mentioned composite rice metal particles can also be used in the present invention, but the present invention does not have the case, but the present invention contains a majority of the film which is formed into a film and the uniformity and size of the uniform area therein is not limited to medical treatment. In practical application, the present invention also proposes that the non-woven fabric, the substrate with micron and the like are first immersed in a metal ion containing a plurality of chelating materials, and the addition of 20 200902192 different amounts of water-soluble polymer or change The degree of deacetylation of chitosan can be controlled by increasing the amine group dispersion of chitosan or increasing the number of exposed amine groups, thereby controlling the particle size of the desired metal particles. According to the method of the present invention, a composite material containing a plurality of nano metal particles having good dispersibility, neat arrangement and high dimensional consistency can be prepared according to the method of the present invention, and has a safe and simple process, low pollution and low cost. The advantages, and the prepared nano metal particles can be widely used in medical or conductive applications, which have great commercial application value. Therefore, the method for preparing a composite material containing most nano metal particles and nano metal particles can achieve the present invention. The purpose of the invention. However, the above is only the preferred embodiment of the present invention, and the scope of the present invention cannot be limited thereto, that is, the equivalent of the patent application scope and the invention description of the present invention is equivalent to the simple I# Changes and modifications are still within the scope of the invention. BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a graph of transmittance versus wavenumber, wherein curves (a), (b), (c), (d), and (4) are respectively displayed with FTIR_ATR at a scanning wave number between 4000 cm and 600 cm. The results of the analysis of Examples 1 to 0 of a composite material containing a plurality of silver particles were obtained. Fig. 2 is an SEM image showing the surface of a complex α material containing a plurality of silver particles prepared in Example 1, and the magnification was $ Figure 3疋SEM image showing the surface of the composite material containing the majority of silver particles prepared in Example 2, the magnification of which is 1_〇 times; 21 200902192 Figure 4 SEM image showing the preparation of Example 3 The surface of the composite material of most silver particles has a magnification of 30,000 times; FIG. 5 is an SEM image showing the surface of the composite material containing the majority of silver particles prepared in Example 4, and the magnification is 30,000 times; FIG. 6 - SEM image, The surface of the composite material containing the majority of silver particles prepared in Example 6 is shown to have a magnification of 30,000 times; and FIG. 7 is an energy spectrum showing that the step (4) in Example 1 is dried and sequestered. The element in the chelate film of most silver ions. [Main component symbol description] None 22