201008872 六、發明說明： 【發明所屬之技術領域】 本發明係關於使用可氧化還原之奈米粒子和被覆該奈 米粒子之碳材料所構成之奈米複合材料的水漿、及其製造 方法。 【先前技術】 粉末狀之碳材料被使用於電化學蓄電裝置中之正極及 負極電極、以防止帶電爲目的之導電性塗料、作爲著色材 料之水性塗料等多種用途。於國際公開第2007/0446 1 4號 公報（專利文獻1)中，揭示由可氧化還原之奈米粒子、與 被覆該奈米粒子之碳材料所構成的奈米複合材料。但是， 粉末狀之碳材料表面一般爲拒水性，對於水的分散困難。 於是’期望碳材料於水中安定且均勻分散的水漿及其製造 方法。 於 Genki Nakamura 等人「Green Tea Solution Individually201008872 VI. Description of the Invention: [Technical Field] The present invention relates to a water slurry using a nanocomposite composed of a redoxable nanoparticle and a carbon material coated with the nanoparticle, and a method for producing the same. [Prior Art] The powdery carbon material is used in various applications such as a positive electrode and a negative electrode in an electrochemical storage device, a conductive paint for preventing charging, and a water-based paint as a coloring material. Japanese Patent Publication No. 2007/0446 (Patent Document 1) discloses a nanocomposite comprising a redox-reducible nanoparticle and a carbon material coated with the nanoparticle. However, the surface of the powdery carbon material is generally water-repellent, and it is difficult to disperse water. Thus, a water slurry in which a carbon material is desirably and uniformly dispersed in water and a method for producing the same are desired. At Genki Nakamura et al. "Green Tea Solution Individually
Solubilizes S ingle-walled Carbon Nanotubes」’ChemistrySolubilizes S ingle-walled Carbon Nanotubes”’Chemistry
Letters Vol. 36，Νο·9 (2007) p_1140-1141(非專利文獻 l) 中，揭示爲了將代表之碳材料的奈米碳管於水中分散，乃 將奈米碳管添加至綠茶水溶液後，僅以超音波照射，使奈 米碳管均勻分散於水中的方法。 先前技術文獻 專利文獻 -5- 201008872 專利文獻1 :國際公開第2007/044014號公報 非專利文獻 非專利文獻 1 : Genki Nakamura 等人「Green Tea Solution Individually Solubilizes Single-walled Carbon Nanotubes 」，Chemistry Letters Vol. 36，No.9 (2007) p.1140-1141 【發明內容】 (發明所欲解決之問題） 但是，奈米複合材料爲形成製法上強固的凝集體，僅 將茶成分等之添加，難於水中以平均二級粒徑Ιμιη以下分 散。 本發明爲用以解決上述問題而完成者，其目的爲提供 可氧化還原之奈米粒子（以下，亦單稱爲「奈米粒子」）、 與被覆該奈米粒子之碳材料所構成的奈米複合材料爲以平 均二級粒徑1 μιη以下分散的水漿，以及，可藉由廉價且簡 便的方法製造該水漿的方法。 (解決問題之手段） 本發明之特徵爲在含有茶成分之水溶液中，使可氧化 還原之奈米粒子與被覆上述奈米粒子之碳材料所構成的奈 米複合材料分散而成的水漿中，分散之奈米複合材料的平 均二級粒徑爲1 μιη以下。 於本發明之水漿中，上述碳材料以形成層爲佳。此時 ’上述碳材料形成之層數爲2〜1 000’其總厚度爲1〜 201008872 200nm，且奈米粒子之粒徑爲0.5〜400nm爲更佳。 本發明之水漿以奈米複合材料，於氮環境氣體下，由 室溫，以升溫速度°C/分鐘升溫，到達600。(：時之重量 減少率爲3重量％以下爲佳。 本發明之水槳中的奈米複合材料，以依序包含下列（1) 及（2)步驟之製造方法而取得爲佳。 (1) 在可氧化還原之奈米粒子存在下，使碳材料前驅物 聚合，在上述奈米粒子表面形成碳材料中間體的步驟， (2) 將上述碳材料中間體碳化，形成被覆上述奈米粒子 的碳材料，製造奈米複合材料的步驟。 本發明亦爲製造上述本發明水漿之方法，提供關於將 含有可氧化還原之奈米粒子與被覆該奈米粒子之碳材料所 構成之奈米複合材料的原料漿粉碎，並且將粉碎之原料漿 與含有茶成分之水溶液混合製造水漿之方法。 (發明之效果） 若根據本發明，使用可氧化還原之奈米粒子、與被覆 該奈米粒子之碳材料所構成之奈米複合材料的水漿，可提 供平均二級粒徑Ιμιη以下分散的水漿。又，該水漿可藉由 廉價且簡便之方法進行製造之方法。 【實施方式】 本發明之水漿其特徵爲在茶成分之存在下，奈米複合 粒子爲以平均二級粒徑Ιμη!以下，較佳爲0.02〜μιη於 -7- 201008872 水中分散。如此，實現奈米複合粒子爲以平均二級粒徑 l/xm以下分散的水漿’達成應用於電極材料或導電材料時 之導電性提高’形成塗膜時之充塡性和密黏性，硬度提高 等之效果。此處，所謂於水漿中分散之奈米複合材料的「 平均二級粒徑」，係意指奈米複合材料於水中實際分散的 粒徑，於凝集之情形，表示其凝集粒徑。此類奈米複合材 料之平均二級粒徑可使用雷射繞射散亂法算出，具體而言 ，使用雷射繞射-散亂式粒度分佈測定裝置，例如， Microtrack HRA(Ritz & Noserap 公司製）、SALD 系列（島 _ 津製作所製）、LS系列（Beckman Colter公司製）等，將本 發明之水漿添加至水中，稀釋並調整至指定濃度後測定， 求出粒度分佈曲線，並以相當50重量％粒徑（D5e)型式算 出。 本發明所用之奈米複合材料，具有可氧化還原的奈米 粒子、和奈米粒子之一部分或全部以袋狀被覆的碳材料， 即0.5 nm〜800nm左右，其典型形狀可列舉粒狀。此處， 奈米複合材料中所謂奈米粒子之「可氧化還原」，係意指 ® 構成奈米粒子之金屬原子可授受電子。奈米粒子爲如此可 氧化還原下’具有可促進碳材料前驅物之聚合及/或碳材 料中間體之形成及碳化的優點。 本發明中的奈米複合材料具有下列（A)要件爲佳，更 且’具有下列（B)、（C)及（D)要件爲更佳。 (A) 碳材料爲形成層、 (B) 碳材料形成之層數爲2〜1〇〇〇、較佳爲2〜1〇〇、 -8 · 201008872 (C) 碳材料形成層之總厚度爲1〜200nm、較佳爲1〜 20nm、 (D) 奈米粒徑爲0.5〜400nm、較佳爲0.5〜200nm。 此處，碳材料較佳爲類似石墨之層狀，即多層狀。此 層爲沿著奈米粒子表面，彎曲或折彎亦可。 又，奈米複合材料中之奈米粒徑爲未達〇.5nm之情形 中，於後述奈米粒子之製造步驟中，難以抑制奈米粒子彼 此間的凝集。又，超過400nm時，亦包含碳材料層的奈米 複合材料之粒徑變得肥大，對於所謂電極材料或導電性塗 .料之用途，有無法取得適當效果之虞。奈米粒子之粒徑更 佳爲0.5〜50nm之範圍內。此處，本發明中的奈米粒子不 限於包含約球狀之等軸，即縱橫比爲約1的粒子，而亦包 含棒狀、圓筒狀、角柱狀等具有長徑與短徑者。奈米粒子 爲具有長徑與短徑時，至少短徑爲進入上述範圍內爲佳。 本發明中之奈米粒子以包含約球狀之等軸粒子爲佳。 於奈米複合材料中，其形狀、和碳材料形成層時之層 數、碳層之總厚度、奈米粒子之粒徑可根據穿透型電子顯 微鏡（TEM)測定。另外，於奈米複合材料中，內包奈米粒 子且於周圍形成之碳材料形狀、粒徑爲依賴奈米粒子形狀 、粒徑的部分大。 本發明此類之奈米複合材料，可適當使用依序包含下 列（1)、（2)步驟之製造方法所得者。 (1)在可氧化還原之奈米粒子存在下，使碳材料前驅物 聚合，在上述奈米粒子表面形成碳材料中間體的步驟， -9- 201008872 (2)將上述碳材料中間體碳化，形成被覆上述奈米粒子 的碳材料，製造奈米複合材料的步驟。 首先，於步驟（1)中，可氧化還原之奈米粒子爲如下處 理製造。即，使用1個或數個奈米粒子前驅物與1個或數 個分散劑，使奈米粒子前驅物與分散劑反應或結合’形成 前驅物複合體。一般而言，將奈米粒子前驅物與分散劑於 適當溶劑或分散介質中溶解（將此時所得者稱爲「複合體 溶液」）、或、分散（將此時所得者稱爲「複合體懸浮液J ) ，使得奈米粒子前驅物與分散劑結合形成此前驅物複合體 〇 奈米粒子前驅物，若可促進後述碳材料前驅物之聚合 及/或碳材料中間體之碳化者，則無特別限定，具體而言 ，構成元素除了鋰、鈉、鉀等之鹼金屬元素、鈣、鎂等之 鹼土類金屬元素、鈦、鉻等之第4族元素、釩、鈮等之第 5族元素、銘、銀、鎢等之第6族元素、銅、銀、金等之 第11族元素、鋅、鎘等之第12族元素、鋁、鎵、銦等之 第13族元素、矽、鍺、錫、鉛等之第14族元素以外，可 列舉錳、鐵、鈷、鎳、鈀、鈾等之過渡金屬元素。奈米粒 子前驅物可列舉此等元素所構成的金屬單體、含有2個以 上此等元素的合金，含有1個以上此等元素的金屬化合物 、或、其混合物。奈米粒子前驅物，由可輕易變化價數的 理由而言，以含有由锰、鐵、鈷及鎳所組成群中選出1種 以上之元素爲佳，且由可更加促進碳材料前驅物體之聚合 及/或碳材料中間體之碳化的理由而言，以含有鐵爲更佳 -10- 201008872 前驅物複合體爲含有1個或數個分散劑。此分散劑係 由促進具有目的之安定性、大小、均勻性之奈米粒子的生 成者中選取。所謂分散劑係爲各種有機分子、高分子、低 聚物等。此分散劑爲於適當之溶劑或分散介質中溶解或分 散供使用。 將奈米粒子前驅物及含有分散劑之前驅物複合體溶解 或分散所用的溶劑或分散介質，可使用公知的各種溶劑或 分散介質。此類溶劑或分散介質較佳可列舉水、甲醇、乙 醇、正丙醇、異丙醇、乙腈、丙酮、四氫呋喃、乙二醇、 二甲基曱醯胺、二甲基亞《、二氯甲烷等，又，亦可將其 混合使用。 於上述溶劑或分散介質中溶解或分散的前驅物複合體 ，認爲係由溶劑分子或分散介質分子所圍住之奈米粒子前 驅物與分散劑所得的複合體。於複合體溶液或複合體懸浮 液中生成前驅物複合體後，將溶劑或分散介質經由乾燥等 除去，則可取得已乾燥的前驅物複合體。又，此已乾燥的 前驅物複合體在加入適當溶劑或分散介質下，亦可恢復成 溶液或懸浮液。 如此使奈米粒子前驅物與分散劑於溶劑或分散介質中 溶解或分散，調製複合體溶液或複合體懸浮液時，在複合 體溶液或複合體懸浮液中，可控制分散劑與奈米粒子前驅 物的莫耳比。 又，如上述處理調製複合體溶液或複合體懸浮液時， -11 - 201008872 分散劑可促進非常小且均勻粒徑之奈米粒子的形成° 一般 而言，在分散劑存在下奈米粒子前驅物爲以1 以下之大 小形成。較佳爲500nm以下，更佳爲50nm以下。 於複合體溶液或複合體懸浮液中，亦可含有用以促進 奈米粒子形成的添加物。添加物例如可加入無機酸和鹼化 合物。無機酸可列舉例如，鹽酸、硝酸、硫酸、磷酸等’ 無機鹼化合物可列舉氫氧化鈉、氫氧化鉀、氫氧化鈣、氫 氧化銨等。 又，爲了將pH調整至8〜13、較佳爲10〜11之範圍 內，亦可在複合體溶液或複合體懸浮液中添加鹼性物質（ 例如，氨水溶液）。將複合體溶液或複合體懸浮液調整至 上述範圍內之高pH値，因可使奈米粒子前驅物微細分離 ，因此複合體溶液或複合體懸浮液的pH對奈米粒子的粒 徑造成影響。 又，將用以促進奈米粒子形成的固體物質加至複合體 溶液或複合體懸浮液亦可。例如，於形成奈米粒子時可加 入離子交換樹脂作爲固體物質。固體物質可經由簡單操作 由最終的複合體溶液或複合體懸浮液中除去。 典型上，將上述複合體溶液或複合體懸浮液混合〇.5 小時〜14日，則取得奈米粒子。又，混合溫度爲0〜200 °C左右。混合溫度係對於奈米粒子的粒徑造成影響的重要 因子。 於使用鐵作爲奈米粒子前驅物之情形中，奈米粒子前 驅物在典型上可列舉氯化鐵、硝酸鐵、硫酸鐵等之鐵化合 -12- 201008872 物。奈米粒子前驅物藉由與分散劑反應或結合’則變成奈 米粒子。此等化合物大部分情況溶解於水系之溶劑。藉由 使用金屬鹽之奈米粒子的形成，則生成副生成物。典型的 副生成物，於使用金屬調製奈米粒子時出現氫氣。典型的 實施態樣爲以混合步驟使奈米粒子活化’更且使用氫更加 進行還原。 奈米粒子以形成安定且活性之奈米粒子的懸浮液型式 爲佳。藉由奈米粒子的安定性，抑制奈米粒子彼此間的凝 集。即使一部分或全部的奈米粒子沈降，亦可經由混合而 輕易地再懸浮化。 如上述處理所得之奈米粒子，可擔任步驟（1)中作爲促 進碳材料前驅物聚合及/或碳材料中間體形成之觸媒的作 用。 步驟（1)中所用之碳材料前驅物，以可分散奈米粒子者 爲佳。使奈米粒子分散，在該奈米粒子存在下，使碳材料 前驅物聚合，則可在奈米粒子表面形成碳材料中間體。作 爲碳材料前驅物之合適的有機材料，可列舉分子中具有J 個或數個芳香族環’且具有用以聚合化之官能基的苯和萘 衍生物。用以聚合化之官能基可例示COOH、C = 0、OH、 C = c、S03、NH2、SOH、N = c = 0 等。 較佳之碳材料前驅物可列舉間苯二酣、酣樹脂、三$ 氰胺-甲醯胺膠、聚糠醇、聚丙烯腈、砂糖、石油瀝青等 〇 奈米粒子爲以其表面聚合碳材料前驅物般，與碳材料 -13- 201008872 前驅物混合。奈米粒子爲觸媒活性之情形中，在該奈米粒 子附近可擔任開始及/或促進碳材料前驅物聚合的職務。 碳材料前驅物相對於奈米粒子之份量，以碳材料前驅 物爲均勻形成最大量碳材料中間體般設定。奈米粒子之份 量亦依據所用之碳材料前驅物的種類。碳材料前驅物與奈 米粒子的莫耳比，較佳爲0.1: 1〜1〇〇: 1，更佳爲1: 1 〜3 0 ·· 1。此莫耳比、奈米粒子之種類、粒徑對於所得碳 材料的厚度等造成影響。 奈米粒子及碳材料前驅物之混合物，在奈米粒子表面 ® 充分形成碳材料中間體爲止’充分熟化。形成碳材料中間 體所必要之時間’係依據溫度、奈米粒子之種類、奈米粒 子之濃度、溶液之pH、所用之碳材料前驅物的種類。另 外’爲了調整pH而加入氨，加速聚合的速度、增加碳材 料前驅物彼此間的交聯量，且有時可有效聚合。 可經由熱而聚合的碳材料前驅物，通常，溫度愈上升 則愈進行聚合。使碳材料前驅物聚合時的溫度，較佳爲〇 〜200。。，更佳爲25〜12(TC。 ® 具體而言’使用間苯二酚一甲醛膠（使用鐵粒子時， 4浮液pH爲1〜14之情形）作爲碳材料前驅物時，其最適 的聚合條件爲〇〜90。(：，熟化時間爲！〜72小時。 步驟（2)中’將步驟（1)所得之碳材料中間體碳化形成 碳材料’取得奈米複合材料。通常以煅燒進行碳化。典型 上锻燒爲以500〜2500 °C、較佳爲1〇〇〇〜2500 之溫度 。煅燒時，碳材料中間體中的氧原子、氮原子被放出，引 -14- 201008872 起碳原子的再排列，形成碳材料。如此處理所形成的碳材 料，較佳爲類似石墨的層狀（多層狀），其層數可根據碳材 料中間體的種類、厚度、煅燒溫度而控制。又，奈米複合 材料中之碳材料厚度（層厚度）亦可經由調整碳材料前驅物 之聚合及/或碳材料中間體之碳化進行度而加以控制。 根據上述方法所得之奈米複合材料，於水中以漿型式 懸浮時的平均二級粒徑爲3〜ΙΟΟμιη。又，槳中之奈米複 合材料的含量，相對於水1 〇 〇重量份以1重量份以上未達 5 〇重量份。用以分散奈米複合材料之溶劑爲使用水，視需 要’亦可加入乙醇、甲醇、丙酮、醋酸乙酯等之水溶性溶 劑。此時之水溶性溶劑的添加量，相對於水1 0 0重量份以 0.1〜20重量份之範圍內爲佳。 又，根據上述方法所得之奈米複合材料，BET比表面 積（根據JIS-Z-8 8 3 0所規定之方法之氮吸黏法測定）通常爲 80〜400m2/g之範圍內，較佳爲1〇〇〜2〇〇m2/g之範圍內。 奈米複合材料之BET比表面積未達80m2/g之情形中，顯 示奈米複合材料之初級粒子彼此間燒結，有難以經由後述 粉碎而分散之虞。另一方面，奈米複合材料之BET比表面 積爲超過400m2/g之情形中，經由進行後述粉碎所得之水 漿黏度有顯著變高的傾向。 奈米複合材料中之奈米粒子的含量並無特別限制，通 常換算成金屬原子爲1000〜200000ppm之範圍內。 本發明中之奈米複合材料，於氮環境氣體下，由室溫 ’以升溫速度1 0 °C /分鐘升溫，到達6 0 0 °C時之重量減少 -15- 201008872 率爲3重量％以下爲佳，以2重量％以下爲更佳。如後述 比較例4所示般’上述重量減少率爲超過3重量％之情形 中’即使未添加茶成分亦分散。但是，上述重量減少率爲 3重量％以下之情形中缺乏分散性，經由茶成分的添加使 分散性顯者提筒’且本發明可特別合適應用。 本發明亦提供關於由上述平均二級粒徑爲3〜100μιη 且奈米複合材料於水中分散狀態的原料漿，取得奈米複合 材料爲以平均二級粒徑1 μιη以下分散狀態存在之本發明水 漿之水漿的製造方法。本發明之水漿的製造方法，其特徵 © 爲將含有可氧化還原之奈米粒子與被覆該奈米粒子之碳材 料所構成之奈米複合材料的原料漿粉碎，並且將粉碎之原 料漿與含有茶成分之水溶液混合。於本說明書中，所謂「 原料漿」，係指用以製造本發明水漿之水漿，含有奈米複 合材料，但不含茶成分的水漿。 懸浮奈米複合材料之原料漿的粉碎，可使用球磨、高 速迴轉粉碎機、介質攪拌磨等之粉碎裝置進行。粉碎所用 之介質可使用氧化鋁、二氧化锆等之公知介質。 將上述原料漿以粉碎裝置予以粉碎的時間，並無特別 限制，較佳爲〇. 1〜5小時。粉碎時間未達0.1小時’則有 難以加以用於減弱奈米複合材料彼此間強凝集之充分的粉 碎能量之虞。另一方面，即使粉碎時間比5小時更長’亦 無法取得配合處理時間之效果。 本發明之水漿之製造方法中’在粉碎後之原料黎中’ 混合含有茶成分的水溶液。此處’本發明中所謂「茶成分 -16- 201008872 」，係指烏龍朱、綠茶、紅茶等之茶葉及/或莖，以指定 溫度與水和含水乙醇、乙醇、含水甲醇、甲醇、丙酮、醋 酸乙酯等之水溶性溶劑接觸所萃取的萃取物。萃取茶成分 所用之溶劑亦可使用由上述選出二種以上之溶劑。茶成分 之萃取量被溶劑與茶葉及/或茶莖的配合比所影響，通常 ，相對於溶劑100重量份，茶葉及/或茶莖爲0 01〜5重量 份’萃取至茶成分之萃取量達到平衡爲止爲佳。 如此卒取所得之茶成分中，主要含有村松敬一郎編 著「茶之科學」ρ· 85〜93所記載之化合物，例如兒茶酸類 (兒茶酸、掊兒茶酸、表兒茶酸、表掊兒茶酸、兒茶酸掊 酸酯、表兒朱酸掊酸酯、掊兒茶酸掊酸酯' 表掊兒茶酸掊 酸酯）和丹寧類等之多酚類。 含有茶成分之水溶液的混合量，相對於粉碎後之原料 漿1〇〇重量份以1〜200重量份之範圍內爲佳，以5〜ι〇〇 重量份之範圍內爲更佳。含有茶成分之水溶液的混合量， 相對於粉碎後之原料漿100重量份未達1重量份之情形中 ，因爲無法供給使奈米複合材料分散至所欲粒徑之充分的 茶成分，故在水中之分散粒徑有變大之傾向，又，於超過 2〇〇重量份之情形中，有無法取得配合添加量之效果的傾 向。 根據本發明之製造方法將含有奈米複合材料之原料漿 粉碎後，添加含有茶成分之水溶液’則可製造於含有茶成 分之水溶液中，奈米複合材料爲以平均二級粒徑1 . 0 Pm以 下分散之狀態存在的水漿。相對地’即使於含有粉碎前之 -17- 201008872 奈米複合材料的原料獎中添加茶成分，並將其粉碎，亦無 法取得奈米複合材料爲以平均二級粒徑Ι.Ομηι以下分散之 狀態存在的水漿。 關於本發明之水漿的用途並無特別限定，可適當應用 於與先前公知之含有碳黑之水漿同樣之用途，將該水漿塗 佈至基板，或與樹脂和無機粉末、其他水漿複合化，則可 應用於鋰蓄電池用、非水系電容器用及燃料電池用等之電 極材料和導電材料、導電塗料、硬塗材料、水性塗料、注 入空氣輪胎等之橡膠製品製造用的濕式母煉膠等之廣泛用 途0 實施例 以下，列舉實施例及比較例更加詳細說明本發明，但 本發明不被限定於此。 <實施例1 > 於BET比表面積117 m2/g、平均二級粒徑16 μιη、Fe 含量8440ppm、氮環境氣體下，由室溫，以升溫速度丨0°c /分鐘升溫，將到達600°C時之重量減少率爲0.8重量％之 奈米複合材料粉末30重量份加至純水970重量份中，攪 拌取得原料漿。將此原料漿100重量份與直徑0.1 mm之氧 化鉻珠粒150毫升裝入濕式介質磨（砂硏磨器，imex公司 製（內容積：4〇0毫升）），並以迴轉速度2000rpm進行60 分鐘粉碎處理。粉碎後，以開孔75μηι之篩將氧化鍩珠粒 -18- 201008872 與原料漿予以篩別。 將市售的乾燥茶葉（莖茶，有限公司脇製茶場製）3克 於850μπι之SUS製篩上展開，注入75°C之純水1公升， 萃取茶成分（萃取時間：3分鐘）。其後，以開孔42 μηι之 SUS製篩除去固形成分，調製含有茶成分的水溶液。另外 ，此水溶液的液色爲L値·· 9 5 · 8、a値：-0.9、b値：5 . 1 5 〇 將上述原料漿、與含有茶成分之水溶液以重量比1: 1 混合，並以300 W之超音波發生裝置進行5分鐘超音波處 理。所得水漿中之奈米複合材料的平均二級粒徑爲 0.5 0 μιη 〇 另外，上述之平均二級粒徑係指使用雷射散亂式粒度 分佈計（Microtrack HRA，Ritz & Noserap 公司製），於水中 添加水漿，於稀釋且調整至指定濃度後測定，求出粒度分 佈曲線，並以相當50重量％粒徑（D5Q)型式算出之値。又 ^ ，上述之BET比表面積係指根據JIS-Z-8 830所規定之方 9 法，以氮吸黏法算出之値。又，含有上述茶成分之水溶液 的液色（L値、a値、b値），係指於玻璃元件中放入該水溶 液’使用測色色差計（ZE-2000，日本電色工業股份有限公 司製）測定2次，算出其値之算術平均値所得之値。 上述之重量減少率爲使用熱重量差示熱同時測定裝置 (TG/DTA 3 00，精工電子製），氮流量200ml/分鐘，將奈米 複合材料粉末8.0毫克，作爲參考之α-Α203 1 0毫克分別 裝入鉑元件，並以無上蓋之狀態由室溫以丨〇艺/分鐘之速 -19- 201008872 度進行加熱至8001爲止，測定TG曲線’根據由室溫到 達600 °C時爲止的重量減少量算出。 <比較例1 > 除了未添加含有茶成分的水溶液以外’進行與實施例 1同樣之操作，調製含有奈米複合材料的水漿。水漿與純 水以重量比1 : 1混合，並於300W之超音波發生裝置中 進行5分鐘超音波處理。所得水漿中之奈米複合材料的平 均二級粒徑（同實施例1處理測定）爲6.8 μιη。 <比較例2> 將實施例1所用之奈米複合材料粉末30重量份，於 含有實施例1調製之茶成分的水溶液970重量份中混合後 ，以實施例1同樣之方法粉碎’取得含有奈米複合材料的 水漿。水漿與純水以重量比1 : 1混合，並於3 0 0 W之超 音波發生裝置中進行5分鐘超音波處理。所得水漿中之奈 米複合材料的平均二級粒徑（同實施例1處理測定）爲 6.2 μτη ° 〈比較例3 > 將實施例1所用之奈米複合材料粉末30重量份加入 純水970重量份中’於攪拌所得之水獎中，將含有實施例 1同樣茶成分之水溶液以重量比1 : 1混合，並於3〇〇%之 超曰波發生裝置中進丫了 5分鐘超音波處理。所得水浆中之 -20- 201008872 奈米複合材料的平均二級粒徑爲14μιη。 結果示於表1。 [表1] 粉碎之有無 茶成分添加時& 1 實施例1 有 粉碎後 0 50 比較例1 有 — 添加無 6 8 比較例2 有 混合時 6 2 比較例3 yfrrr. Μ 混合時 14 <比較例4 > 除了使用BET比表面積106m2/g、平均二級粒徑 16μηι、Fe含量7444ppm，氮環境氣體下以升溫速度1〇<t/ 分鐘升溫時之到達600°C時之重量減少率爲3_7重量％的 奈米複合材料粉末以外，以實施例1同樣之條件進行粉碎 ，取得不含有茶成分的水漿。 以300W之超音波發生裝置進行5分鐘超音波處理。 〇 所得水漿中之奈米複合材料的平均二級粒徑爲0.4 7 μιη。 本回所揭示之實施形態及實施例全部爲例示，不應認 爲係爲限制的。本發明之範圍並非爲以上述之說明，而爲 根據申請專利範圍所示，意圖包含與申請專利範圍均等之 意義及範圍內全部之變更。In Letters Vol. 36, Ν · 9 (2007) p_1140-1141 (Non-Patent Document 1), it is disclosed that in order to disperse a carbon nanotube of a representative carbon material in water, a carbon nanotube is added to a green tea aqueous solution. A method of uniformly dispersing a carbon nanotube in water by irradiating only with ultrasonic waves. PRIOR ART DOCUMENT Patent Document - 5 - 201008872 Patent Document 1: International Publication No. 2007/044014 Non-Patent Document Non-Patent Document 1: Genki Nakamura et al. "Green Tea Solution Individually Solubilizes Single-walled Carbon Nanotubes", Chemistry Letters Vol. 36, No. 9 (2007) p. 1140-1141 [Problem to be solved by the invention] However, the nano composite material is a solid aggregate formed by the method, and only the tea component or the like is added, which is difficult to be in the water. Disperse below the average secondary particle size Ιμηη. The present invention has been made to solve the above problems, and an object thereof is to provide a nanoparticle composed of a redox-reducible nanoparticle (hereinafter, simply referred to as "nanoparticle") and a carbon material coated with the nanoparticle. The rice composite material is a water slurry dispersed at an average secondary particle diameter of 1 μηη or less, and a method in which the water slurry can be produced by an inexpensive and simple method. (Means for Solving the Problem) The present invention is characterized in that in the aqueous solution containing the tea component, the nanocomposite composed of the redoxable nanoparticle and the carbon material coated with the nanoparticle is dispersed in a slurry. The average secondary particle diameter of the dispersed nano composite is 1 μηη or less. In the aqueous slurry of the present invention, the above carbon material is preferably formed as a layer. At this time, the number of layers formed of the above carbon material is 2 to 1 000', the total thickness thereof is 1 to 201008872 200 nm, and the particle diameter of the nanoparticles is preferably 0.5 to 400 nm. The water slurry of the present invention is heated at a temperature rise rate of C/min by a nanocomposite material under a nitrogen atmosphere to reach 600. (The weight reduction rate at the time of 3% is preferably 3% by weight or less. The nano composite material in the water jet of the present invention is preferably obtained by sequentially including the production methods of the following steps (1) and (2). a step of polymerizing a carbon material precursor in the presence of redoxable nanoparticles to form a carbon material intermediate on the surface of the nanoparticle, and (2) carbonizing the carbon material intermediate to form the coated nanoparticle The carbon material is a step of producing a nano composite material. The present invention is also a method for producing the above water slurry of the present invention, and provides a nanometer comprising a carbon material containing redoxable nanoparticles and a carbon material coated with the nano particles. A raw material slurry of a composite material is pulverized, and a method of producing a water slurry by mixing the pulverized raw material slurry with an aqueous solution containing a tea component. (Effect of the Invention) According to the present invention, redox nanoparticles can be used and the nanoparticle can be coated. The water slurry of the nano composite material composed of the carbon material of the particles can provide a water slurry dispersed below the average secondary particle size 。μηη. Moreover, the water slurry can be carried out by an inexpensive and simple method. [Method] The aqueous slurry of the present invention is characterized in that in the presence of the tea component, the nanocomposite particles have an average secondary particle diameter Ιμη! or less, preferably 0.02 to μηη in -7-201008872 water. Dispersion. In this way, the nano-composite particles are obtained by using a water slurry dispersed with an average secondary particle diameter of l/xm or less to achieve an increase in conductivity when applied to an electrode material or a conductive material. The effect of improving the hardness and hardness. Here, the "average secondary particle diameter" of the nano composite material dispersed in the aqueous slurry means the particle size of the nano composite material actually dispersed in water, in the case of agglomeration. , indicating the agglomerated particle size. The average secondary particle size of such a nanocomposite material can be calculated using a laser diffraction scattering method, specifically, a laser diffraction-scattering particle size distribution measuring device, for example, Microtrack HRA (manufactured by Ritz & Noserap Co., Ltd.), SALD series (made by Shimadzu Corporation), LS series (manufactured by Beckman Colter Co., Ltd.), etc., the water slurry of the present invention is added to water, diluted and adjusted to a specified concentration, and then measured. Calculate the particle size distribution curve and calculate it with a particle size of 50% by weight (D5e). The nanocomposite used in the present invention has redox-reducible nanoparticles and a part or all of the nanoparticles in a bag shape. The coated carbon material, that is, about 0.5 nm to 800 nm, may be exemplified by a granular shape. Here, the "oxidizable reduction" of the so-called nanoparticle in the nanocomposite means that the metal atom constituting the nanoparticle is The electrons can be imparted. The nano particles are such that they can redefine and have the advantage of promoting the formation and carbonization of the polymerization of the carbon material precursor and/or the carbon material intermediate. The nano composite material of the present invention has the following (A) The requirements are better, and the 'has the following (B), (C) and (D) requirements is better. (A) The carbon material is a forming layer, and (B) the carbon material is formed into a layer of 2 to 1 〇〇〇, preferably 2 to 1 〇〇, -8 · 201008872 (C) The total thickness of the carbon material forming layer is 1 to 200 nm, preferably 1 to 20 nm, and (D) a nanoparticle diameter of 0.5 to 400 nm, preferably 0.5 to 200 nm. Here, the carbon material is preferably a layer similar to graphite, that is, a multilayer. This layer may be curved or bent along the surface of the nanoparticle. Further, in the case where the nanoparticle diameter in the nanocomposite is less than 5 nm, it is difficult to suppress the aggregation of the nanoparticles with each other in the production step of the nanoparticles described later. Further, when the thickness exceeds 400 nm, the particle size of the nanocomposite material containing the carbon material layer becomes large, and the use of the so-called electrode material or the conductive coating material may not achieve an appropriate effect. The particle diameter of the nanoparticles is preferably in the range of 0.5 to 50 nm. Here, the nanoparticles of the present invention are not limited to those having an equiaxed shape of about spherical shape, i.e., an aspect ratio of about 1, and also include a long diameter and a short diameter, such as a rod shape, a cylindrical shape, and a prismatic shape. When the nanoparticles have a long diameter and a short diameter, it is preferred that at least the short diameter is within the above range. The nanoparticle of the present invention preferably comprises an equiaxed particle of about spherical shape. In the nanocomposite, the shape, the number of layers when the carbon material is formed, the total thickness of the carbon layer, and the particle diameter of the nanoparticles can be measured by a transmission electron microscope (TEM). Further, in the nanocomposite material, the shape of the carbon material which is surrounded by the nanoparticles and which is formed around the nanoparticle is large in the shape of the nanoparticle-dependent particle size. The nano composite material of the present invention can be suitably obtained by a production method comprising the following steps (1) and (2). (1) a step of polymerizing a carbon material precursor in the presence of redoxable nanoparticles to form a carbon material intermediate on the surface of the above-mentioned nanoparticle, -9-201008872 (2) carbonizing the carbon material intermediate, A step of forming a carbon composite material by coating the carbon material of the above nano particles to produce a nano composite material. First, in the step (1), the redox-reducible nanoparticles are produced by the following treatment. That is, the nanoparticle precursor is reacted with or combined with the dispersant using one or several nanoparticle precursors and one or more dispersing agents to form a precursor complex. In general, the nanoparticle precursor and the dispersing agent are dissolved in a suitable solvent or dispersion medium (the resultant is referred to as a "complex solution"), or dispersed (the resultant at this time is referred to as a "complex" Suspension J), which combines a nanoparticle precursor with a dispersant to form a precursor precursor composite nanoparticle precursor, and if it promotes polymerization of a carbon material precursor and/or carbonization of a carbon material intermediate, In particular, the constituent elements include an alkali metal element such as lithium, sodium or potassium, an alkaline earth metal element such as calcium or magnesium, a group 4 element such as titanium or chromium, and a fifth group such as vanadium and niobium. Group 6, element of element, imprint, silver, tungsten, etc., group 11 element of copper, silver, gold, etc., group 12 element of zinc, cadmium, etc., group 13 element of aluminum, gallium, indium, etc. Examples of the Group 14 element such as ruthenium, tin, and lead include transition metal elements such as manganese, iron, cobalt, nickel, palladium, and uranium. The precursor of the nanoparticle particles may be a metal monomer composed of such elements. An alloy of two or more of these elements, containing more than one such element The metal compound of the element, or a mixture thereof, preferably contains one or more elements selected from the group consisting of manganese, iron, cobalt, and nickel, for the reason that the valence number can be easily changed. Further, in order to further promote the polymerization of the carbon material precursor object and/or the carbonization of the carbon material intermediate, it is more preferable to contain iron as a -10-201008872 precursor complex containing one or several dispersing agents. The dispersant is selected from those who promote the formation of nano particles having the desired stability, size, and uniformity. The dispersant is various organic molecules, polymers, oligomers, etc. The dispersant is a suitable solvent. Or dissolved or dispersed for use in a dispersion medium. A known solvent or dispersion medium may be used for the solvent or dispersion medium used for dissolving or dispersing the nanoparticle precursor and the precursor composition containing the dispersant. Such solvent or dispersion Preferred examples of the medium include water, methanol, ethanol, n-propanol, isopropanol, acetonitrile, acetone, tetrahydrofuran, ethylene glycol, dimethyl decylamine, dimethyl amide, and methylene chloride. Further, it may be used in combination. The precursor complex dissolved or dispersed in the above solvent or dispersion medium is considered to be obtained by a nanoparticle precursor and a dispersing agent surrounded by solvent molecules or dispersion medium molecules. After the precursor complex is formed in the composite solution or the composite suspension, the solvent or the dispersion medium is removed by drying or the like to obtain a dried precursor composite. Further, the dried precursor compound is composited. The solution may be recovered into a solution or a suspension by adding a suitable solvent or a dispersion medium. When the nanoparticle precursor and the dispersing agent are dissolved or dispersed in a solvent or a dispersion medium to prepare a complex solution or a composite suspension, In the complex solution or composite suspension, the molar ratio of the dispersant to the nanoparticle precursor can be controlled. Further, when the complex solution or the composite suspension is prepared as described above, the dispersant can be promoted by -11 - 201008872 Formation of very small and uniform particle size nanoparticles In general, the nanoparticle precursor is formed to have a size of 1 or less in the presence of a dispersant. It is preferably 500 nm or less, more preferably 50 nm or less. Additives for promoting the formation of nanoparticles may also be contained in the composite solution or the composite suspension. As the additive, for example, a mineral acid and a base compound can be added. Examples of the inorganic acid include hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid, etc. The inorganic base compound may, for example, be sodium hydroxide, potassium hydroxide, calcium hydroxide or ammonium hydroxide. Further, in order to adjust the pH to a range of 8 to 13, preferably 10 to 11, a basic substance (for example, an aqueous ammonia solution) may be added to the composite solution or the composite suspension. Adjusting the complex solution or the composite suspension to a high pH in the above range, the pH of the composite solution or the composite suspension is affected by the particle size of the nanoparticle precursor because the nanoparticle precursor is finely separated. . Further, a solid substance for promoting the formation of nanoparticles may be added to the composite solution or the composite suspension. For example, an ion exchange resin may be added as a solid substance in forming the nanoparticles. The solid material can be removed from the final composite solution or complex suspension via a simple operation. Typically, the above composite solution or composite suspension is mixed for about 5 hours to 14 days to obtain nanoparticle. Further, the mixing temperature is about 0 to 200 °C. The mixing temperature is an important factor affecting the particle size of the nanoparticles. In the case where iron is used as the precursor of the nanoparticle, the nanoparticle precursor is typically exemplified by iron compound -12-201008872 of iron chloride, iron nitrate, iron sulfate or the like. The nanoparticle precursor becomes a nanoparticle by reacting or bonding with the dispersant. Most of these compounds are dissolved in the solvent of the aqueous system. By forming a nanoparticle of a metal salt, a by-product is produced. A typical by-product produces hydrogen when using metal-modulated nanoparticles. A typical embodiment is to activate the nanoparticles in a mixing step and to reduce them more with hydrogen. The nanoparticles are preferably in the form of a suspension which forms stable and active nanoparticles. The aggregation of the nanoparticles is inhibited by the stability of the nanoparticles. Even if some or all of the nanoparticles are sedimented, they can be easily resuspended by mixing. The nanoparticle obtained by the above treatment can serve as a catalyst for promoting the formation of a carbon material precursor polymerization and/or a carbon material intermediate in the step (1). The carbon material precursor used in the step (1) is preferably a dispersible nanoparticle. The carbon material intermediate is formed on the surface of the nanoparticle by dispersing the nanoparticle and polymerizing the carbon material precursor in the presence of the nanoparticle. As a suitable organic material for the carbon material precursor, benzene and a naphthalene derivative having J or a plurality of aromatic rings in the molecule and having a functional group for polymerization can be cited. The functional group used for polymerization can be exemplified by COOH, C = 0, OH, C = c, S03, NH2, SOH, N = c = 0, and the like. Preferred carbon material precursors include m-benzoquinone, anthracene resin, tri-cyanamide-formamide gel, polynonanol, polyacrylonitrile, granulated sugar, petroleum pitch, etc., and the surface polymerized carbon material precursor Like, mixed with carbon material-13- 201008872 precursor. In the case where the nanoparticle is catalytically active, it can serve as a starting and/or promoting polymerization of the carbon material precursor in the vicinity of the nanoparticle. The amount of the carbon material precursor relative to the amount of the nanoparticle is set such that the carbon material precursor uniformly forms the largest amount of the carbon material intermediate. The amount of nanoparticle is also dependent on the type of carbonaceous material precursor used. The molar ratio of the carbon material precursor to the nanoparticles is preferably 0.1:1 to 1 〇〇: 1, more preferably 1:1 to 3 0 ··1. The type of the molar ratio, the type of the nanoparticle, and the particle diameter affect the thickness of the obtained carbon material. The mixture of nanoparticle and carbon material precursor is fully cured until the surface of the nanoparticle ® is sufficiently formed into a carbon material intermediate. The time necessary to form the carbon material intermediate depends on the temperature, the type of the nanoparticle, the concentration of the nanoparticle, the pH of the solution, and the type of the carbon material precursor used. Further, ammonia is added to adjust the pH, the rate of polymerization is accelerated, the amount of crosslinking of the carbon material precursors is increased, and polymerization is sometimes effective. Carbon material precursors which can be polymerized by heat, generally, the higher the temperature, the more the polymerization proceeds. The temperature at which the carbon material precursor is polymerized is preferably 〇 〜200. . More preferably, it is 25~12 (TC. ® specifically - the use of resorcinol-formaldehyde gel (when iron particles are used, 4 float pH is 1 to 14) as the precursor of carbon material, the most suitable The polymerization conditions are 〇~90. (:, the aging time is ～72 hours. In step (2), the carbon material intermediate obtained by the step (1) is carbonized to form a carbon material to obtain a nano composite material, usually by calcination. Carbonization. Typically, calcination is carried out at a temperature of 500 to 2500 ° C, preferably 1 to 2500. When calcined, oxygen atoms and nitrogen atoms in the carbon material intermediate are released, and carbon is introduced from -14 to 201008872. The atoms are rearranged to form a carbon material. The carbon material thus formed is preferably a graphite-like layer (multilayer), and the number of layers can be controlled according to the type, thickness, and calcination temperature of the carbon material intermediate. Moreover, the thickness (layer thickness) of the carbon material in the nano composite material can also be controlled by adjusting the degree of carbonization of the carbon material precursor and/or the carbon material intermediate. The nano composite material obtained by the above method, Slurry in water The average secondary particle diameter of the film is 3 to ΙΟΟμιη. Further, the content of the nanocomposite in the paddle is less than 5 parts by weight per part by weight of the water, and is used to disperse the nanocomposite. The solvent of the material is water, and if necessary, a water-soluble solvent such as ethanol, methanol, acetone, ethyl acetate or the like may be added. The amount of the water-soluble solvent added at this time is 0.1 to 20 parts by weight relative to 100 parts by weight of water. Further, in the range of parts by weight, the BET specific surface area (measured by the nitrogen adsorption method according to the method specified in JIS-Z-8 803) is usually 80 to 400 m 2 /. In the range of g, preferably in the range of 1 〇〇 2 〇〇 m 2 /g. In the case where the BET specific surface area of the nano composite material is less than 80 m 2 /g, it is shown that the primary particles of the nano composite material are sintered to each other. On the other hand, in the case where the BET specific surface area of the nano composite material is more than 400 m 2 /g, the viscosity of the water slurry obtained by the pulverization described later tends to be remarkably high. Nanoparticles in composite materials The amount is not particularly limited, and is usually converted into a metal atom in the range of 1000 to 200,000 ppm. The nanocomposite of the present invention is heated at room temperature by a temperature rise rate of 10 ° C / min under a nitrogen atmosphere. The weight loss at 60 ° C is -15 - 201008872, preferably 3% by weight or less, more preferably 2% by weight or less. As shown in Comparative Example 4 described later, the weight reduction rate is more than 3% by weight. In the case, 'the tea component is dispersed even if it is not added. However, in the case where the weight reduction rate is 3% by weight or less, the dispersibility is lacking, and the dispersibility is remarkable by the addition of the tea component', and the present invention can be suitably applied. The present invention also provides a raw material slurry in which the average secondary particle diameter is 3 to 100 μm and the nano composite material is dispersed in water, and the nano composite material is obtained by the present invention in a dispersed state having an average secondary particle diameter of 1 μm or less. A method for producing a slurry of water slurry. The method for producing a water slurry according to the present invention is characterized in that a raw material slurry containing a nanocomposite comprising a redox-reducible nanoparticle and a carbon material coated with the nanoparticle is pulverized, and the pulverized raw material slurry is The aqueous solution containing the tea component is mixed. In the present specification, the term "raw material slurry" means a water slurry for producing the water slurry of the present invention, which contains a nanocomposite material but does not contain a tea component. The pulverization of the raw material slurry of the suspended nano composite material can be carried out by using a pulverizing apparatus such as a ball mill, a high-speed rotary pulverizer or a medium agitating mill. As the medium used for the pulverization, a known medium such as alumina or zirconia can be used. The time for pulverizing the above-mentioned raw material slurry by the pulverizing means is not particularly limited, and is preferably 1 to 5 hours. If the pulverization time is less than 0.1 hour, it is difficult to apply it to the sufficient pulverization energy for weakening the agglomeration of the nanocomposites with each other. On the other hand, even if the pulverization time is longer than 5 hours, the effect of the processing time cannot be obtained. In the method for producing a water slurry of the present invention, an aqueous solution containing a tea component is mixed in the raw material of the pulverized material. Here, the term "tea component-16-201008872" in the present invention refers to tea leaves and/or stems of oolongzhu, green tea, black tea, etc., at a specified temperature with water and aqueous ethanol, ethanol, aqueous methanol, methanol, acetone. A water-soluble solvent such as ethyl acetate is contacted with the extracted extract. For the solvent used for extracting the tea component, two or more solvents selected from the above may be used. The extraction amount of the tea component is affected by the mixing ratio of the solvent and the tea leaf and/or the tea stem. Usually, the tea and/or tea stem is 0 01 to 5 parts by weight relative to 100 parts by weight of the solvent. It is better to reach equilibrium. Among the tea ingredients obtained from such a stroke, there are mainly the compounds described in "Science of Tea" ρ· 85~93, such as catechins (catechins, catechins, epicatechins, and peony). Polyphenols such as catechin, catechin phthalate, quercetin phthalate, catechin phthalate, and tannins. The amount of the aqueous solution containing the tea component is preferably in the range of 1 to 200 parts by weight based on 1 part by weight of the raw material slurry after the pulverization, and more preferably in the range of 5 to 10 parts by weight. When the amount of the aqueous solution containing the tea component is less than 1 part by weight based on 100 parts by weight of the raw material slurry after the pulverization, since the nanocomposite is not supplied with a sufficient tea component to disperse the desired particle size, The dispersed particle diameter in water tends to be large, and in the case of more than 2 parts by weight, the effect of blending the amount of addition is not obtained. According to the manufacturing method of the present invention, the raw material slurry containing the nano composite material is pulverized, and the aqueous solution containing the tea component is added to be produced in the aqueous solution containing the tea component, and the nano composite material has an average secondary particle diameter of 1.0. A water slurry in a state in which Pm is dispersed. In contrast, even if the tea component is added to the raw material prize of the -17-201008872 nanocomposite before the pulverization, and the pulverization is carried out, the nanocomposite cannot be obtained by dispersing the average secondary particle size Ι.Ομηι. The water slurry in the state. The use of the aqueous slurry of the present invention is not particularly limited, and can be suitably applied to the same use as the previously known water-containing slurry containing carbon black, and the aqueous slurry is applied to a substrate, or with a resin, an inorganic powder, and other water slurry. When it is compounded, it can be applied to electrode materials for lithium batteries, non-aqueous capacitors and fuel cells, and wet-type mothers for the manufacture of rubber products such as conductive materials, conductive coatings, hard coating materials, water-based paints, and air-injected tires. A wide range of applications such as rubber mixing. EXAMPLES Hereinafter, the present invention will be described in more detail by way of examples and comparative examples, but the invention is not limited thereto. <Example 1 > When the BET specific surface area is 117 m2/g, the average secondary particle diameter is 16 μm, the Fe content is 8,440 ppm, and the temperature is raised by room temperature at a temperature increase rate of °0 °c /min, 30 parts by weight of a nanocomposite powder having a weight reduction ratio of 0.8% by weight at 600 ° C was added to 970 parts by weight of pure water, and the raw material slurry was obtained by stirring. 100 parts by weight of this raw material slurry and 150 ml of chrome oxide beads having a diameter of 0.1 mm were placed in a wet medium mill (sand honing machine, manufactured by Imex Co., Ltd. (internal volume: 4 〇 0 ml)), and subjected to a rotation speed of 2000 rpm. 60 minutes crushing treatment. After pulverization, the cerium oxide beads -18-201008872 were sieved with the raw material slurry through a sieve of 75 μm. 3 g of commercially available dried tea leaves (stem tea, manufactured by Kyowa Co., Ltd.) was spread on a SUS sieve of 850 μm, and 1 liter of pure water at 75 ° C was poured to extract tea components (extraction time: 3 minutes). Thereafter, the solid component was removed by a SUS sieve having an opening of 42 μm to prepare an aqueous solution containing a tea component. Further, the liquid color of the aqueous solution is L値·· 9 5 ·8, a値:-0.9, b値:5 . 15 5 , and the raw material slurry and the aqueous solution containing the tea component are mixed at a weight ratio of 1:1. Ultrasonic processing was performed for 5 minutes with a 300 W ultrasonic generator. The average secondary particle diameter of the nanocomposite in the obtained aqueous slurry is 0.50 μm. In addition, the above average secondary particle diameter refers to a laser-scattered particle size distribution meter (Microtrack HRA, manufactured by Ritz & Noserap). A water slurry was added to the water, and the mixture was diluted and adjusted to a predetermined concentration, and then measured, and the particle size distribution curve was determined, and the enthalpy was calculated in a 50% by weight particle diameter (D5Q) pattern. Further, the above-mentioned BET specific surface area refers to the enthalpy calculated by the nitrogen adsorption method according to the method specified in JIS-Z-8 830. Further, the liquid color (L値, a値, b値) of the aqueous solution containing the above tea component means that the aqueous solution is placed in a glass element. [Use of a colorimetric color difference meter (ZE-2000, Nippon Denshoku Industrial Co., Ltd.) The system was measured twice, and the 算术 obtained by the arithmetic mean of 値 was calculated. The weight reduction rate described above was measured by using a thermogravimetric differential heat measuring device (TG/DTA 3 00, manufactured by Seiko Instruments Inc.), a nitrogen flow rate of 200 ml/min, and a nanocomposite powder of 8.0 mg as a reference α-Α203 1 0 The milligrams were respectively charged into the platinum element, and were heated from room temperature to the temperature of 800-1 at the speed of -19/minutes -19-201008872 without the top cover, and the TG curve was measured according to the time from room temperature to 600 °C. The amount of weight loss is calculated. <Comparative Example 1 > A water slurry containing a nanocomposite was prepared in the same manner as in Example 1 except that the aqueous solution containing the tea component was not added. The water slurry was mixed with pure water at a weight ratio of 1:1, and subjected to ultrasonic treatment for 5 minutes in a 300 W ultrasonic generating device. The average secondary particle diameter of the nanocomposite in the obtained aqueous slurry (measured in the same manner as in Example 1) was 6.8 μηη. <Comparative Example 2> 30 parts by weight of the nanocomposite powder used in Example 1 was mixed in 970 parts by weight of an aqueous solution containing the tea component prepared in Example 1, and then pulverized in the same manner as in Example 1 to obtain a content. A slurry of nanocomposites. The water slurry was mixed with pure water at a weight ratio of 1:1, and subjected to ultrasonic treatment for 5 minutes in a 300 W ultrasonic generating device. The average secondary particle diameter of the nano composite material in the obtained aqueous slurry (measured in the same manner as in Example 1) was 6.2 μτη ° <Comparative Example 3 > 30 parts by weight of the nanocomposite powder used in Example 1 was added to pure water. In 970 parts by weight of the water prize obtained by stirring, the aqueous solution containing the same tea component of Example 1 was mixed at a weight ratio of 1:1, and was subjected to a 5 〇〇% super chopping device for 5 minutes. Sound processing. The average secondary particle size of the -20-201008872 nanocomposite in the obtained water slurry was 14 μm. The results are shown in Table 1. [Table 1] When the presence or absence of the pulverization of the tea component was added & 1 Example 1 After pulverization 0 50 Comparative Example 1 Having - Adding no 6 8 Comparative Example 2 When mixing 6 2 Comparative Example 3 yfrrr. Μ When mixing 14 < Comparative Example 4 > In addition to the use of a BET specific surface area of 106 m 2 /g, an average secondary particle size of 16 μηι, and an Fe content of 7444 ppm, the weight was reduced at a temperature rise rate of 1 〇 < t / minute when the temperature was reached to 600 ° C under a nitrogen atmosphere. The mixture was pulverized under the same conditions as in Example 1 except that the ratio of 3 to 7 wt% of the nanocomposite powder was obtained, and a water slurry containing no tea component was obtained. Ultrasonic processing was performed for 5 minutes with a 300 W ultrasonic generating device.纳米 The average secondary particle size of the nanocomposite in the obtained water slurry is 0.47 μηη. The embodiments and examples disclosed herein are illustrative and are not to be considered as limiting. The scope of the present invention is defined by the scope of the claims and the scope of the claims