TW201229161A

TW201229161A - One-pack type coating composition, photocatalyst, coating and method for producing coating

Info

Publication number: TW201229161A
Application number: TW100127857A
Authority: TW
Inventors: Hirohito Nagata; Ren-Hua Jin; Pei-Xin Zhu; Jian-Jun Yuan
Original assignee: Dainippon Ink & Chemicals; Kawamura Inst Chem Res
Priority date: 2010-08-06
Filing date: 2011-08-05
Publication date: 2012-07-16
Also published as: WO2012017846A1; JP5087184B2; JPWO2012017846A1

Abstract

Provided are powder having a sufficient photocatalytic function even under visible light and a one-pack type coating composition having thereof capable of directly coating on a substrate. The powder, comprising a complex formed by baking and fixing particles of titania or tungsten trioxide having a nanometer-order particle size on a nanometer-order structure comprising the silica as the main constituent component, have a higher photocatalytic function than single particles of titania or tungsten trioxide used as a main raw material. A one-pack type coating composition is formed by mixing those powders and a resin having a polysiloxane skeleton. The particles of titania or tungsten trioxide can be exposed from the surface of a coating by coating those coating compositions on various substrates, drying it and then irradiating it a predetermined light. The coating obtained by this method can express a photocatalytic function under visible light and its surface becomes super-hydrophilic simultaneously.

Description

201229161 六、發明說明：【發明所屬之技術領域】本發明係有關於一種1液型塗料組成物，使用它之光觸媒粉末’和由該等得到之光觸媒塗膜、超親水性塗膜及該等的製造方法。該丨液型塗料組成物係含有將氧化欽、氧化鎢固定在二氧化矽奈米結構體而成的粉體及具有聚矽氡烷骨架的樹脂。【先前技術】近年來，氧化鈦等的光觸媒，因為能夠將污染和有害物質等自發分解而無害化，在產業上係非常地受到注目。其應用領域係擴展至住宅、車輛、醫療、土地處理等’且佔有構築循環型社會之不可缺少的技術之位置。通常，光觸媒本身係粉末，為了在現實空間使用，藉由與黏合劑樹脂混合之塗料化、進而塗膜化係必要的◦塗膜化之後’為了顯現塗膜的觸媒活性，必須成為光觸媒活性點（例如氧化鈦粒子）被分布、固定在塗布表面之狀態’而且’其光觸媒必須保護塗膜連續層（黏合劑）及被塗布的基材。特別是將以有機系黏合劑為主的光觸媒塗膜設作目標之情況，該問題係無法避免。亦即，光觸媒塗膜在防止基材表面的污染之同時若無法保護基材其應用係4乎無法期待。因此，關於光觸媒塗膜，係進行研讨各式各樣的辦法。例如，有想出一種方法，其係在基材表面製作底塗膜之後’在其上面形成含有光觸媒的上塗膜（例如參照專利文獻1〜4)。專利文獻1係使用烷氧基矽烷及紫外線吸 201229161 收劑等作為底㈣塗液而將其塗布在基材後乾燥，其上面塗布包含氧化鈦等的光觸媒粉末及：氧化石夕溶膠液之塗液而使其形成光觸媒塗膜。依照該手法，藉由‘ 基材具有耐候性且將光觸媒固定在上塗層，能“ 止〉ϋ予超親水性等。專利文獻2係提供_種方法其係將含有烧氧基石夕炫類及在側鍵具有脂、進而按照必要之多官能異氛酸醋樹脂成分之= 明塑膠基材用m塗液，將其塗布在基材表面成： ' 之後’在其上面塗布含有氧化鈦粉末之光觸媒組係藉二在=二；：；案揭示-種光觸媒塗膜，其糾 |外線下亦不會劣化且具有強耐候性之含氣，i脂的聚#氧烧溶膠液作為底塗組成物而塗布乾燥之後直在其上面塗布光觸媒組成物來謀求長壽命化。而且，利文獻4亦針對光觸媒塗布劑有引起基材表面產匕的可能性之基材的底塗法進行研討。具體上，係揭不-種方法’其係使㈣氧鈦酸水溶用組成物而進行霧塗布，且在其上面塗布氧化鈦先為^用 :想出不使用底塗膜而將光觸媒組成物直接塗布在 ::面：例如藉由將光觸媒活性較低而紫外線吸收能氧==石型氧化欽及光觸媒活性較高的銳欽礦型 /、3有聚丙烯酸酯 '聚矽氧烷、膠體二氧化矽面合劑混合’且將其組成物直接塗布在基材表伊传二：觸媒塗膜(例如參照專利文獻5)。該方法的目 =日強结石型氧化鈦的紫外線吸收底塗層之功能。、丁无則的 201229161 實際上，光觸媒塗料的情況，作為光觸媒的功能之氧化鈦等’無法露出表面時，其功能會低落。因此此研討設法使氧化鈦的露出頂部之光觸媒塗膜之梦造亦 (例如參照專利文獻6)。專利文獻6係記載藉由將的聚石夕氧_塗料等塗布在基材表面且乾^而使塗膜表面呈多孔吳狀，隨後在該多孔質膜的上面塗布含有光媒粉末及聚合物黏合劑之組成物時’因為聚合物點合：係溶液狀態而滲透至多孔質的孔穴，使得光觸媒固體容易殘留在其表面’能夠盡可能使較多的光觸媒：塗膜表面露出。又，相較於螢光燈，長壽命h肖Μ力較少的咖照明係呈現急遽地普及’推測在不久的將來，咖照明會佔有室内用照明的大部分。因此’為了在室内環：中有效地使用光觸媒，開發對應LED燈的發光波長之士八可見光應答型的光觸媒係有必要的。該LED照明係完全不含有紫外線，全部的發光波長係可見光線’使用通常的氧化鈥係無法顯現光觸媒功能 :又’即便現狀的可見光應答型氧化鈦光觸媒，在㈣光源下亦只能夠顯示微弱的光觸媒活性。近年來’不具有可見光應答能力之氧化鈦有了變化 ’原本具有可見光吸收能力且具有光觸媒功能之氧化鎢光觸媒係受到注目。但是，> 氧化鶴之能帶隙_㈣較低的情況，從價電子帶被激發至導電帶之電子係容易返回，為了顯現觸媒功能’設計能夠將該電子「庫存或捕捉（pool or trap)」之結構係必要的。有研究一種在氧 201229161 化鶴負載過渡金屬之方法（例如參照專利文獻7) 該：載過渡金屬的氧化鎢光觸媒，其光觸媒活性 ^前的可見光應答型氧化鈦之3倍左右，怎麼也是能夠滿足在室内空間的LEI)照明用途之性能。上述氧化鶴光觸媒的製造過程，係藉由將高溫炮到的氧化鶴粒子粉碎且通過過遽器而得到氧化鎮子之後，在其微粒子負載過渡金屬者，未達到結的程度且其製造過程可以是無效率的。如上述，雖然在使用可見光應答型的光觸媒它之光觸媒塗膜及其製造進行各式各樣的研討，' -手法之結果，均是花費許多工夫且實際上係麻在該狀態下，即便該等塗膜的光觸媒功能係充分用性亦不適合。實際上，針對在室内照明下使用媒塗膜，係只有預測有效性者，目前尚未發現在有效的光觸媒塗膜。為了以沒有底塗之非2次塗 k光觸媒塗膜，只有重新思考設計思想。這是因合劑設計與光觸媒設計同時考慮係有必要的。 [先前技術文獻] [專利文獻] [專利文獻1]特開2004_3 1 5722號公報 [專利文獻2]特開2〇〇8_〇45〇52號公報 [專利文獻3]特開2〇〇8·212821號公報 [專利文獻4]特開2008-073588號公報 [專利文獻5]特開2009-221362號公報 [專利文獻6]特開2004-148143號公報 [專利文獻7]特開2009-226299號公報 '但是，係只有無法說而且，燒而得的微粒構設計和使用但是任須的。，在實的光觸實用面布來製為將黏 201229161 【發明内容】 [發明所欲解決之^ 考慮實用上的的直接塗布。因此刖的方式而設計。光觸媒塗膜本身均膜中的光觸媒之活樹脂本身。綜合地考慮上要奈米至微米等級光觸媒的功能之活固定之凸部係不可樹脂本身係必須具固疋亦是必要的。因此，本發明丁亦具有光觸媒功直接塗布之塗料組到之塗膜表面，係媒的活性部位係被位與塗料組成物中得到成為具有光觸〇 [解決課題之手段] 為了解決前述結果’發現藉由使果題] 光觸媒塗膜時，被要求必 1 ’有必要將光觸媒塗膜的在此’作為前提條件，係不可使劣化基材劣化，而性部位（active site)係不可述時，光觸媒塗膜的表面的凹凸結構’且其凸部係性部位為最佳。但是，光以由黏合劑樹脂形成。而有充分的对候性，且將光欲解決之課題，係提供一能之粉體、及含有它之i 成物’在將該組成物塗布自發性地形成凹凸結構之固定在凸部的最表面，而的黏合劑樹脂係不直接鍵媒功能之塗膜、及其簡便課題，本發明者等重複地用將氧化鈦或氧化鶴的奈須是1液塑結構脫離先任何方式’ 且光觸媒塗傷害黏合劑結構係有必固定有作為觸媒部位被且，黏合劑觸媒緊固地種在可見光液型而能夠且乾燥而得同時，光觸且該活性部結，而能夠的製造方法專心研討的米粒子燒結 201229161 在以奈米纖維作為基氧化矽太半& & 土負之八肩1设雜形狀的高比表面積二乳化矽不'水結構體末狀光觸媒、或氧夕，氧化鈦複合型的粉聚石夕氧燒骨架之聚上=3型的粉末狀光觸媒、與具有哿人物 Λ 。物鏈鍵結而成之（曱基）丙烯酸酯系聚合物的樹脂混合认甘# L 成之主枓組成物，塗布在任意材質的基材上且乾燥使，、更而成之塗膜，係在太陽光及 ^且‘，、、、下顯示非常高的光觸媒功能及基於該結構之超親水性功能，而完成了本發明。 —本心月係提供-種1液型塗料組成物，及使用、匕，到之光觸媒塗膜、超親水十生塗膜及該等的製造方 1 &型塗料组成物之特徵在於：含有將氧化欽⑷）厂氧化石夕奈米結構體（a 2)而成之粉體（A 1)及/或將氧化鶴（a3)固&在二氧化石夕奈米結構體（&2)而成之粉體 (A2)，及具有聚矽氧烷骨架之樹脂（b)。而且，本發明係提供一種光觸媒、及該等之簡便的製造方法。該光觸媒係包含將氧化鈦（al)或氧化鎢（a3) 疋在氧化石夕奈米結構體（a 2)而成的複合體之粉體狀的光觸媒，其特徵在於：前述二氧化矽奈米結構體02) 係以粗度或厚度為1 0〜1 〇〇nm且縱橫比為2以上的二氧化石夕奈米纖維或二氧化矽奈米帶作為基本單元而在1 # m〜20 的範圍聚集而成者，而且，在該複合體中之氧化鈦（al)或氧化鎢（a3)的含有率為10〜8〇質量％。 [發明之效果] 通常’作為光觸媒使用之氧化鈦結晶粉末，其折射率高而使光觸媒反應必要的大部分光線反射掉，致使來 201229161 用。本發明的氧化鈦/二氧化觸媒’係與先前完全不同，形狀的二氧化矽奈米結構體化矽複合型之光觸媒，光線 ’而且亦容易被二氧化矽奈會照射被固定在二氧化矽奈光觸媒活性部位的氧化鈦光觸媒活性提升。又，在被二氧化矽奈米結構體之間係米等級的界面亦與使氧化鈦大有關聯。化鶴的粒子燒結而固定在二成夠在非晶的二氧化矽與結等級的界面，該氧化鎢係本應合型的光觸媒功能之可能電子庫（electron pool)效果，激·發電子捕捉而發揮高量子之氧化鎢/二氧化矽複合型的氧化矽奈米結構體亦容易引子關入觸媒活性部位周邊之自光源的光線無法有效地活矽奈米結構體的複合體之光係氧化鈦的奈米粒子與複雜複合而成。在該氧化鈦/二氧係不僅是直接被氧化鈦吸收米結構體散射，而其散射光米結構體之氧化欽。其結果之光吸收概率增大，結果，燒結之氧化鈦的奈米粒子與形成奈米等級的界面，該奈的光觸媒活性部位之功能增又，同樣地，藉由將氧氧化矽奈米結構體的表面，晶性的氧化鎢之間形成奈米來具有能夠顯現作為可見光性°該奈米界面係具有一種藉由將因照射光線所產生的產率效果。又’在如此構成光觸媒，具有複雜形狀的二起光散射，而能夠達成將光功能。乳化矽奈米結構體係具有許捕捉空氣。又，在二氧切之非晶結構係有 4基’其係經f有效率地吸附水分子 '而且，一—切奈米結構體表面係能夠在觸媒活性部位周邊有 -10- 201229161 效地擴散.吸附挤氧化鶴複合型的光觸媒二貝的有機物。.因此，二氧化石夕/ 明光線下，其功处：、即便在不含有紫外線之LED照解之觸媒。”月"* '、此夠作為有夕文率地將有機化合物分於製功能的特定結構之粉體使用構體的結構之凹=複雜形狀的二氧切奈米結矽夺乎蛀播駚Α 、，且破植入黏合劑,樹脂之二氧化米結構體部分传以部而露出頂部之二氧化石夕奈膜狀態亦容易產生光：方式形成膜。因此’即便塗米結構體部分之’被固定在露出頂部的奈觸媒的ΙΪ1辨冑媒活性部位’其功能係能夠與該光二 =粉末同樣的狀態。這是因為與將氧化鈦等的 q i接鍵結於黏合劑之先前的光觸媒塗膜在根十工1糸不同者。用_:且，因為本發明的光觸媒塗膜係在膜整體具有利化矽不米結構體之凹凸性，在光觸媒產生功能時，骐整體係容易成為w B 干座生力此時膜係能夠藉由將塗料：物作二，發明的光觸媒塗燥之簡便的牛驟“ 塗布且使其乾能夠作A冗/ —得到。因此，本發明的光觸媒塗膜係用。：’、°因應室内、室外之高效率的光觸媒塗膜而使或形L /本發明的1液型塗料組成物係不管基材的材質木材、厂’均能夠適應於玻璃、塑膠、金屬、陶器、係作聿：等：二广因為本發明的1液型塗料組成物菜性專之病便性’專巧業者當然不用說，即便是並豕庭亦能夠塗布在必要的位置來製造光觸媒塗膜。亦 -11 - 201229161 即，本發明係即便不含有紫外線的照明光線下，亦能夠作為具有防止污染、自我清洗（self cleaning)、空氣淨化、殺In、抗病毒專作用之光觸媒塗膜而舒適地使用在產業現場、醫療現場、學校、養老院、家庭等廣闊範圍的建築設施。【實施方式】 L用以實施發明之形態] 光觸媒塗膜已具有接近20年的歷史了，特別是作為屋外（紫外線）用途，光觸媒塗膜係顯示防止污染及利用超親水性之自我清洗效果，而高層大廈和大型建築係少有施行使用氧化鈦粉體之光觸媒塗膜。但是，考慮屋内用途或獨戶住宅等之情況，只有在塗膜的結構㈣氧化鈦結晶粉末狀態的光觸媒’光觸媒的活路係無法擴展。 :’已知能夠吸收可見光而分解有機物之氧化鎢 tr射可見光能量的狀態，在電子與電洞係產生電； :故，難以說是具有安定的光觸媒功能，即便：：：；化，仍然無法成為長期有效的光觸媒塗膜。U 為了開拓光觸媒塗膜，係、首先配設計光觸媒。因此，本發明係想出…；構柴而高數倍的功能。其氧化鈦^晶粉末本身在二氧化…結構體而成之二粒子燒結複合型的光觸媒係容易產:：、·，。構的光觸媒。此種活性部位的光利 ^入效果，在使光觸媒 W之同時，在氧化欽或氧化鶴 -12- 奈米結構體而使其形成奈不僅疋單純的活性部位，構’其整體產生協調而能以氧化鈦或氧化鎢作為有精Φ的結構設計’能夠期、從被分離的電子之氧還鍵的直接氧化、及水的氧 ’光觸媒係不僅是由氧化，而且必須構築滿足下列以將光線擴散、或關入之媒活性部位周邊捕捉空氣縮」功能；在觸媒活性部質有機物之「立足點」功性化之奈米界面結構等。型光觸媒使用於形成塗膜黏合劑樹脂，藉由在表面之凹凸’能夠容易地使光。這是因為同等於使光觸能夠使在塗膜表面的光觸塗膜的開拓係強烈地被要一體化之化學結構要素及有機聚合物含有無機成分本發明係以滿足上述的要設計作為基礎而提案揭示下，詳細地說明本發明。 201229161 的奈米粒子、與二氧化石夕面’以提升光觸媒功能。通常，所謂觸媒，係设計其活性部位的周邊結現作為觸媒之功能者。在分之光觸媒’亦是藉由其荷分離狀態的長時間維持產生活性氧、正孔之C-H 生成自由基羥基等。亦即氧化鎢的活性部位所構成要素之結構：在其周邊用光子濃縮」功能；在觸氧及水分之「氧、水的濃邊有效率地擴散、集聚基及促進觸媒活性部位的活將上述本發明的複合光觸媒本身係不是被埋入利用二氧化矽奈米結構體活性部位的部分露出頂部黏合劑浮出空中的狀態，能最大限地顯現。光觸媒合劑樹脂t要有與光觸媒候性。這是因為在通常的態之混合樹脂係必要的。光觸媒設計及黏合劑樹脂光觸媒塗膜的新概念。以未界藉由夠顯效成待電原來化之欽和各種所謂中的位周能；時，形成觸媒媒從媒功求黏強耐的狀求之一種 -13- 201229161 [氧化鈦（al)] 作為本發明所使用的氧化鈦（a i)，係沒有特別限定 ’銳鈦礦、金紅石或銳鈦礦/金紅石混晶的任一結晶相均可’又’亦可以是在該氧化鈦的結晶中摻雜金屬離子或氮原子等而成之氧化鈦。又’為了效率良好地將氧化鈦（a丨）固定在後述的二氧化石夕奈米結構體（a2)上，以使用i 0〜100ηπι之微粒子狀的氧化鈦粉末為佳。 [二氧化矽奈米結構體（a2)] 在本發明所使用的二氧化矽奈米結構體（a2)，係將具有直鏈狀聚乙亞胺骨架之聚合物在水系介質中形成之結晶性締合體作為鑄模’且使用二氧化矽前驅物亦即烷氧基石夕烧的溶膠凝膠反應而製造者。具體上，已經由本發明者在特開2005-264421號、特開2005-336440號、特開2006-63097號、特開2006-306711號、特開 2007-5 1056號、特開2009-24124號所提供之任何二氧化石夕奈米結構體亦能夠使用作為本發明的二氧化矽奈米結構體（a2)。該等二氧化矽奈米結構體（a2)係與二氧化矽凝膠等通吊的巨尺寸二氧化石夕不同，其特徵在於：以奈米等級的基本單元作為構成單元，且其係以三維空間集合而成者。又，在該等的專利文獻所提供之二氧化矽奈米構體之中，亦包含金屬離子或金屬奈米粒子的情況，但是因為該等係不會阻礙光觸媒功能者（依照金屬種，亦有增強光觸媒功能之效果），能夠適合直接使用作為在本發明所使用之二氧化矽奈米結構體（&2)。 -14- 201229161 作為製造方法’例如使具有直鏈狀聚乙亞胺骨架之聚合物懸浮在水中’且使其於80°C附近的溫度溶解。確 s忍聚合物洛解之後’進行靜置冷卻至室溫（2 $〜3 〇 )。在 30分鐘左右的靜置冷卻，藉由具有直鏈狀聚乙亞胺骨架之聚合物的整體結構或共存的其他物質（金屬離子或酸性化合物等）’能夠得到以奈米纖維、奈米帶、奈米奈米纖維等的結構作為基本單元之聚集體（亦即沈澱物）。在此’藉由使其混合含有20 wt%左右之四院氧基矽烧（包含縮合物）等的二氧化石夕源之乙醇溶液，能夠使二氧化石夕在含有具有聚乙亞胺骨架之聚合物的各種結構之基本單元上均勻地析出’同時該基本單元之間係形成締合體，能夠得到在内部具有聚合物鏈之二氧化矽奈米結構體。又’在使具有上述直鏈狀聚乙亞胺骨架之聚合物於 8 0 C加溫溶解時’藉由使其混合聚乙二醇等其他的聚合物’亦能夠得到以不同形狀作為基本單元之沈澱物，且亦能夠使用藉由同樣的手法使二氧化矽在該沈澱物中之聚乙亞胺上析出而得到之複雜形狀的二氧化矽奈米結構體。又’作為使具有上述直鏈狀聚乙亞胺骨架之聚合物溶解在水中之方法，不只是利用加溫之溶解，利用添加酸之溶解亦可以。該手法係溶解後添加鹼性化合物，藉由調整至pH為8左右，能夠使有直鏈狀聚乙亞胺骨架之聚合物的奈米結晶體析出，且藉由在其與前述同樣地混合一氧化石夕源時’能夠得到複雜形狀的二氧化矽奈米結構體。 •15- 201229161 使用該等方法徵在於：以奈米笼于1之二氧化矽奈米結構體，其特聚集而成為微米尺寸。！乍為基本結構，且該等係产A ^化矽奈米結構體〇2)，具體上可舉出以粗度為10〜100nm，較佳$ Μ 、肢上了舉出以粗佳是s 、佳疋20〜80nm ;縱橫比係2以上，較單元者以及上的厂纖維狀結構體(以下，奈米纖維)作為基本 = 厚度為1〇〜一較佳是一為佳 Ά亥厚度設作縱橫比時，其值為2以上，較佳 :上的帶狀結構體（以下，奈米帶）作為基本單元者。沾作為構成早兀且聚集而成之聚集體 j (使用ΤΕΜ景> 像觀察時之最長的部分），係通常為 A坩〜20" m ,較佳是3〜l5// m。又，在使用上述方法所調製之二氧化矽奈米結構體 ^卩存在有使用作為鑄模之具有直鏈狀的聚乙亞胺月架之t合物，係能夠藉由將該結構體於4 〇〇〜9 〇〇煅燒而除去。此時，因為整體形狀係在煅燒前後沒有變化，所以能夠得到以二氧化矽作為主要構成成分之二氧化石夕奈求結構體。而且’所謂以二氧化矽作為主要構成成 /刀’係指雖然亦有因煅燒溫度、氣體環境等致使聚合物石反化而成之成分殘留，在未故意併用第三成分之情況，係顯示不含有二氧化矽以外之成分者。在本發明，前述含有聚合物鏈的二氧化矽奈米結構體（複合體），藉由煅燒而除去該聚合物鏈而成之二氧化矽奈米結構體亦適合使用。 •16- 201229161 [包含將氧化鈦（al)固定在二氧化矽奈米結構體（a2)而成的複合體之粉體（A1)] 前述在二氧化矽奈米結構體（a2)固定氧化鈦（ai)，係月b夠藉由吸附」及繼續進行的「煅燒」而能夠容易且再現性良好地實施。具體上，係首先藉由將二氧化矽奈米結構體(a2)的粉末與氧化鈦)的粉末在水系介質中懸浮而進行分散·混合及物理性吸^此時係以使用超音波處理和攪拌器等進行攪拌、分散為佳。、常由於—氧化石夕的表面係存在有多數的OH基而極性強’又’氧化鈦表面亦基於同樣的理由而極性高。因此’在進行攪拌、分散處理之後，藉由離心分離等來除去上部澄清水溶液且進行乾職理，㈣使氧化欽 (al)的粉末物理吸附在二氧化石夕奈米結構體(a2)的表面。就氧化鈦⑷)的粉末與二氧化矽奈米結構體(a2)的使用比例而言，你幺,、，，Λ、 ’’’、（al)/(a2)所表示的質量比係以 10/95:80/20為佳，…〇〜卿的範圍為更佳。 e Kt#u 1 m =氧化$奈米結構體 :之：系介質的量係沒有特別限定，相對於氧化欽⑷) 與一氧化石夕奈米結構體(a2)的合計質量 10〜30倍的範圍時為適合。貝里作為月j述的水系介質，係除了水單獨以外亦可以是…親水性有機溶劑之混合溶劑，例如可舉出乙醇、2 -丙醇、丙_等。 =系介質中混合氧化鈦⑷）與二氧切奈米結構 ()夺’為了使吸附更確實’亦可併用驗性聚合物。 -17- 201229161 作為此時能夠使用的鹼性聚合物，例如可舉出聚乙亞胺、聚烯丙胺、聚乙烯胺、聚離胺酸等的聚胺類。氧化鈦（al)與二氧化矽奈米結構體（a2)的混合之吸附步驟的詳細方法係沒有特別限制，例如以一定比例混合之後’藉由將其在室溫（20〜30°C )攪拌1〜24小時，能夠充分地物理吸附。藉由將氧化鈦（a 1)的粉末吸附在上述所得到之二氧化矽奈米結構體（a2)而成之結構體進行加熱煅燒，能夠传到包含氧化鈦（al)固定在二氧化矽奈米結構體而成的複合體之粉體（A 1)。所使用的二氧化矽奈米結構體（a2)係已經除去内部的聚合物鏈者之情況，加熱煅燒溫度係以35〇〜9〇〇。〇的溫度範圍時為佳，使用聚合物鏈係存在於内部之二氧化矽奈米結構體（a2)之情況，為了同時進行除去聚合物鏈之目的，係以400。(：以上的溫度進行煅燒。且以程式控制溫度煅燒時間係通常2〜8小時即可上升為佳。例如以1小時使其從室温上升後，以30分鐘其上升至赋之後，使其在該溫度保 3小時等階段性的煅燒為佳。溫度上升程式會對所得到之包含氧化鈦燒結固定後的二氧化矽奈米結構體之粉體（A1)的光觸媒活性造成影響，但以依照所固定之氧化鈦（al)的種類而每次調整其程式而佳。例如將摻雜有碳或氮之氧化鈦燒結固定時，為了使摻雜後的結構維持，以將在溫度上升時之最高溫度設定為50(TC以下為佳，以450t以下為更佳。又，2 -18- 201229161 固定之氧化鈦結晶係已經是銳鈦礦與金紅石的二結晶之混晶狀態的情況’以將在锻燒之最高溫度設為6 〇〇以下為佳。又’以在空氣環境下進行加熱般燒過程為佳，亦可在惰性氣體，例如氮氣環境下進行。般燒後的氧化鈦（a 1)之含有率係基本上係取決於被吸附的氧化鈦（al)之量，能夠在10〜80質量％的範圍調製在包含使用上述製法所得到之將氧化鈦（a丨）固定而成的二氧化矽奈米結構體之粉體（A1)，氧化鈦（al)的結晶與二氧化矽奈米結構體（a2)係形成何種接合界面係不清楚，但是就不進行煅燒處理時係未觀察到觸媒活性提升而吕’且就即便不具有二氧化碎凝膠等的複雜形狀之二氧化石夕系亦觀察到觸媒活性係某種程度提升而言推則在氧錢（al)與二氧化石夕奈米結構體（a2)的接合界面係果二"I::關入1果及在奈米界面之有機物質的濃縮效 “、活性部位附近將光分解之有機物質濃縮）。猎則述手法所得到之將氧化欽矽奈米結構體而占认、—a 疋在一乳化苒體(a2)而成的铍合體之粉顯現作為光觸媒之# ^ 7诉罝接此夠化鈦⑹：=二相較於氧化欽單獨的觸媒，氧 (A"係提高=1=構體⑷:的複合狀態之粉體位重量觸# θ 歹在乙醛的分解反應，以單位置里觸媒量比較時卞媒所含有的氧化❹I 1的複合狀態之光觸月〜乳化鈦係少很多，佳异同重量的氧化鈦之系統倍增。、/ ’係比使用 -19- 201229161 又，在此所得到的粉體（A1)係使用各式各樣的光源陽光n水銀燈、齒素燈、黑光、勞光燈等而顯示高觸媒活性。 [包含將氧化鶴(a3)固定在二氧切奈米結構體(a2)而成的複合體之粉體（A2)] 先别，製造氧化鎢的粉末係使用鎢酸鹽，且體上，係使鶴酸鹽類成為各種溶液，且將使其乾燥而得到的前驅物進行锻燒之方〉去。因為該前驅物係不具有特定的周期結構’藉由煅燒而粒子產生成長且形成大的大塊㈣㈨體。將大塊體的氧化鎢粉末固定在二氧化矽奈米結構體 (a2)的表面係困難的。本發明係研討控制往此種大塊體成長之方法發現了以下步驟作為將氧化鎢（a3)的粒子固定在二氧化矽奈米結構體（a 2)之方法。第一方法係在前述二氧化矽奈米結構體（a2)(可以是在内存在有聚合物’亦可以是藉由煅燒除去而以二氧夕作為主要構成成分者）的分散液，混合鶴酸鹽（a 3，）來使鎢S义鹽(a3’)吸附在二氧化矽奈米結構體(&2)中之後將其在9〇(TC以下進行煅燒來將氧化鎢（&3)粒子固定在 —氧化矽奈米結構體（a2)者。將使一氧化石夕奈米結構體（a2)分散在介質而成之分政液與氧化鎢（a3)的來源（亦即鎢酸鹽（a3，））在介質中混 :時，與混合前述氧化鈦（a 1)時同樣地，係在二氧化矽不米結構體(a2)的表面，該鎢酸鹽(a3，)被吸附且被濃縮。成為該狀態之後進行煅燒時，在表面被吸附之鎢酸鹽 -20- 201229161 U3’）係成為氧化鎢（a3)，子的成長係受到抑制而成為==該位置’所以粒作為在此能夠使用之—/尺寸的乳化鶴⑷）。為氧化鈦者即可，沒有特“卿’)，係藉由锻燒而成鶴酸納、㈣等定，例如可舉出鶴酸録、锻燒亦能夠除去相對離子^原枓容易取得性、藉由。銳點，以使用偏鎢酸銨為佳通常，由於二氡化石々沾主. α. % ^ , ，表面係存在有多數的OH基而極性強。因此，將使二査土叩而忐之八埤y 沐米結構體（a2)分散在介質 f t ^ ^ ^ v J)的起源（亦即鎢酸鹽（a3，））在負甲進丁搜掉、分散虛卜邦，、双、生卜、々、崦理之後，藉由離心分離等除去 ,.,w 祀知4理時’能夠得到鎢酸鹽 (a3 )吸附在二氧化;g夕奈米 .下、、Ό構體U2)表面上之粉體。作為鶴酸鹽（a 3，）盥-氧/ )---礼化矽奈米結構體（a2)的使用比例，係以般燒後的童#雜俊的氧化鎢（a3)與烺燒後的二氡化矽奈米結構體（a 2)之比例，亦g卩，、，， ’比例亦即以（a3)/(a2)表示之質量比係成為10/95〜80/20的方式使用失办飞便用為佳，以30/60〜50/50的範圍為更佳。將鶴S义鹽⑷）與二氧化秒奈米結構體㈤）混合時所使用之介質的量係沒有特別限定，相對於鶴酸鹽(a3, )與二氧化矽奈米結構體㈣的合計之質量，以質量比計在10〜30倍的範圍時為適合。作為前述介質’係除了水單獨以外，亦可以是與各種親水性有機溶劑之满人、、六兔丨为例；，令則您此Q /谷劑，例如可舉出乙醇、2_丙醇、丙酮等。 21 - 201229161 在介質中混合鎢酸鹽（a3，）與二氧化矽奈米結構體 U2)時，為了使吸附更確實’亦可併用聚胺。亦即，亦可以疋在一氧化矽奈米結構體（a2)的分散液混合聚胺且使其吸附之後，混合鎢酸鹽（a3，）之方法。作為前述聚胺，例如可舉出聚乙亞胺、聚烯丙胺、聚乙烯胺、聚離胺酸類，可單獨亦可併用2種以上。鎢酸鹽（a3 ’）與二氧化矽奈米結構體（a2)的混合之吸附步驟的詳細方法係沒有特別限制，例如以一定比例混合之後，藉由將其在室溫（20〜3(rc)攪拌丨〜24小時，能夠充分地物理吸附。 [锻燒步驟] 精由將上述所得到之在二氧化矽奈米結構體（&2)吸附有鎢酸鹽（a3，）之粉體加熱煅燒，能夠將氧化鎢（a3)的粒子固定在二氧化矽奈米結構體（a2)。使用已經除去内部的聚合物鏈之二氧化矽奈米結構 ()之清况，加熱般燒溫度係3 5 0〜9 0 0 °C的溫度範圍時即可’使用聚合物鏈係存在於内部之二氧化矽奈米結構體（a2)之情況、併用聚胺之情況等，為了同時進行除去忒等有機物之目的，係以6〇(η:以上的溫度進行煅燒為佳又，超過900°C的溫度時，二氧化矽會開始熔融，氣化石夕奈米結構體（a2)的該結構有崩潰之可能性.，又因為氧化鎢（a3)亦有產生粒子成長之可能性，般燒溫度的上限為900°C。锻燒時間係通常2〜8小時即可，且以程式控制溫度上升為佳。例如以1小時使其從室溫上升至3〇〇。(：，隨 •22- 201229161 後，以30分鐘其上升至5〇〇t之後，使其在該溫度保持 3小時等階段性的煅燒為佳。又，以在空氣環境下進行加熱煅燒過程為佳，亦可在惰性氣體，例如氮氣環境下進行。煅燒後的氧化鎢（a3)之含有率係基本上係取決於被吸附的鎢酸鹽(a3，)之量，能夠在1〇〜8〇質量％的範圍調製。 [氧化鎢（a3)的粒子之製造方法、及使用其之粉體之製造方法] 首先，調整氧化鎢（a3)的粒子，藉由使其物理吸附在二氧化矽奈米結構體（a2)之後進行煅燒，亦進行能夠將氧化鎢（a3)的粒子固定在二氧化矽奈来結構體（a2)。亦即，使具有直鏈狀聚乙亞胺骨架之聚合物在水系介質中進行締合，進而混合鎢酸鹽（a3，）的水溶液而得到聚合物與鎢酸或鎢酸鹽（a3，）締合而成之析出物，將其加熱煅燒時能夠得到氧化鶴（a3)的粒子，將其使用與前述同樣 1方法使其吸附在二氧化矽奈米結構體（a2)且將其煅燒時’能夠得到本發明的粉體（A2)。得到前述具有直鏈狀聚乙亞胺骨架之聚合物的締合體之方法，係與得到前述二氧化矽奈米結構體㈣之方法同樣。得到聚合物的締合體之後，代替二氧化矽源，在水系介質下混合氧化鎢的來源(亦即鎢酸鹽⑷，))時，能夠得到該聚合物與鎢酸鹽(a 3，)或鎢酸複合化而成之沈澱物。 -23- 201229161 此時，作為聚合物與鎢酸鹽（a3，）之使用比例’在該聚合物中之乙亞胺單元與鎢酸鹽（a3，）的莫耳比係 95/5〜20/80的範園’就兩者的複合化能夠確實地進行而言，乃是較佳。又，聚合物與鎢酸鹽（a3 ’）之混合係在水系介質中進行，作為此時的濃度’係聚合物的濃度在0.01〜1〇.〇質量 %的範圍為佳。作為水系介質，係除了水單獨以外，醇類等親水性溶劑與水的混合溶劑亦佳，但是必須是聚合物的缔合體不溶解或不容易溶解。而且，得到具有直鏈狀聚乙亞胺骨架之聚合物的締合體時，亦可藉由添加金屬離子、或添加有機酸等來控制締合體的形態。具有直鏈狀聚乙亞胺骨架之聚合物與鎢酸鹽（a3，）或鎢酸的複合化係迅速地進行，以在室溫（2〇〜30°C )進行授摔1〜2 4小時左右的範圍為適合。如此進行而得到的複合物係沈澱物。將其離析之後 ’藉由加熱煅燒而能夠得到氧化鎢（a3)的奈米粒子（具有奈米等級的平均粒徑之粒子）。加熱煅燒溫度係以 500〜800°c為佳。煅燒時間係通常2〜8小時即可，且以程式控制溫度上升為佳。例如以小時使其從室溫上升至 3〇〇°C ’隨後’以30分鐘其上升至50(rc之後，使其在該溫度保持3小時等階段性的煅燒為佳。又，加熱煅燒過程係以在空氣環境下進行為佳，亦可在惰性氣體，例如氮氣環境下進行，來使聚合物殘留。 -24- 201229161 相較於只有藉由單純乾燥使鎢酸鹽（a3，）析出且藉由锻燒s周整而成者，使用上述方法所得到之氧化鎢（a3)的奈米粒子係表面積較大，又，例如即便不含有紫外線的 LED照明光線亦會顯現光觸媒活性。推測這是由於聚合物的自組織化效果，氧化鎢的成長受到控制之緣故。藉由將如此進行而得到的氧化鎢（a3)的奈米粒子與前述同樣地固定在二氧化矽奈米結構體（a2)，其光觸媒作用係進一步被活性化。 ' 藉由上述所得到的氧化鎢（a3)奈米粒子固定在二氧化矽奈米結構體（a2)之粉體（A2)的製造方法，係基本上與刚述同樣。亦即，在水性介質中混合藉由前述手法所尸到之氧化鎢（a3)的奈米粒子與二氧化矽奈米結構體，來使一氧化矽奈米結構體（a2)吸附氧化鎢（a3)的奈米；立子且藉由離心分離等除去上部澄清液而進行乾燥處孝後，將其煅燒。之二氧化矽奈米結構體（a2)與氧化鎢（a3)的奈米板之使用比例係沒有特別限定，前者/後者所表示之質^子為95/10〜20/80的範圍時，因為吸附會迅速地里比是較佳。丁乃將前述二氧化石夕奈米結構體（a2)與氧化鶴（米粒子混合時所使用的水系介質之量係沒有特別阳、奈相對於固體含量的合計質量，以1〇〜3〇倍量為適合、定，又’作為前述介質，係可以是水單獨、或水性介質與水的混合溶劑，此時，與前述同樣地，親夠藉由併用聚胺而促進行吸附。亦 25- 201229161 作為前述_ _ & 工^ 一乳化矽奈米結構體（a2)與氧化鎢（a3)粒子的混合方法仫力 ^ ^ 你 >又有特別限定，將該等以一定比例混合之後’错由蔣甘+ —、认再在至溫（20〜30。〇攪拌1〜24小時係充分的0 [煅燒步驟] 错由將卜；+，α π t > 迷所仔到之在二氧化矽奈米結構體（a2)吸附有氧化鶏太，的奈朱粒子之粉體加熱煅燒，能夠將氧化鎢（a3)的如2 m a '子固疋在二氧化矽奈米結構體（a2)·。使用 p έτ 、’’丄除去内部的聚合物鏈之二氧化石夕奈米結構體（a 2)之愔、、w ^ 即u 凡’加熱煅燒溫度係350〜900°C的溫度範圍時 °使用聚合物鏈係存在於内部之二氧化矽奈米結構體（a 2)之愔、本、。θ也’為了同時進行除去聚合物鏈之目的，係 6〇0 C以上的溫度進行煅燒為佳。又，超過900°C的溫度時，二备儿yv —乳化矽會開始熔融，二氧化矽奈米結構體（a2) 的該結構有崩潰之可能性，又，因為氧化鶴（a3)亦有產粒子成長之可能性’煅燒溫度的上限為9 0 0 °C。瓜燒時間係通常2〜8小時即可，且以程式控制溫度升為佳。例如以1小時使其從室溫上升至300°C，隨後以30分鐘其上升至5〇(rCi後使其在該溫度保持3 小時等階段性的煅燒為佳。又以在空氣環境下進行加熱煅燒過程為佳，亦可在惰性氣體’例如氮氣環境下進行。瓜燒後的氧化鎢（a3)之含有率係基本上係取決於被及附的氧化鎢（a3)之量，能夠在1〇〜8〇質量％的範圍調製 -26- 201229161 在本發明之包含固定有氧化鎢（a3)的二氧化矽奈米結構體（a2)之粉體（A2)，氧化鎢（a3)的粒子與二氧化矽奈米結構體（a 2)係形成何種接合界面係不清楚，但是就不進行煅燒處理時係未觀察到觸媒活性提升而言，推測在氧化鎢（a3)與二氧化矽奈米結構體（a2)的接合界面，係顯現高激發電子的庫存（pool)效果、光線關入效果及有機物質的濃縮效果。 [光觸媒功能] 使用前述方法所得到之粉體（A1)或粉體（A2)係單獨在有機物質的分解反應為有效的，所使用的光源係太陽光、螢光燈等任一者均可。特別是將氧化鎢複合化而成之粉體（A 2 )，係即便在不含有近紫外線（只有含有可見光 )的光線之LED照明光線下亦具有應答性，在提高其活性方面，相較於先前的光觸媒，其應用範圍係較廣闊。在本發明，作為測量粉體〔A丨）或粉體（A2)的活性之手法，係能夠藉由將該粉體在封入有一定濃度的揮發性有機化合物（VOC)氣體之玻璃製反應容器中靜置且對反應器照射可見光/LED光線，而從揮發性有機化合物氣體進行氧化分解所產生之伴隨著光照射時間而變化的二氧化碳濃度來估計。使用前述方法測定光觸媒的活性時，所使用的揮發性有機化合物的濃度為50〜5〇〇ppm即可’具有觸媒作用的粉體的使用量，係相對於反應器的體積，以在 5〜100mg/5 00mL的範圍為適合。 -27- 201229161 作為前述揮發性有機化合夠使用低分早右嫉心入係，又有特別限定，能機化合物，例如有撫“。：且低分子化合物以外的有的表面時，萨由°光=素、聚合物等能夠黏附在光觸媒測定有機色能夠進行分解反應，例如藉由丄素的發色程度亦能夠測定光觸媒的活性。光照射時間係依昭所使用構而異，…、所使用的有機物質的濃度或其結 Λ 1小打〜1天的範圍為佳。源單Ξ H:氧化鶴複合化而成之粉體(Α2)係在led光昭丄‘、、、^下，即便其光量係非常低的狀態（例如室㈤ =量r°:ix左右)，亦能夠充分地具有心= 二:光；，月的粉體(ai)、(a2)係在包含紫外線例如氣燈'水銀燈、㈣燈、榮 =源下均具有作為光觸媒之功能。以，本發觸媒，即便不县古& 的光、光、而是在太陽光或各種光源照明被反射·散射之壯能之功能。心的至内光線，亦具有作為光觸媒 [具有聚矽氧烷骨架之樹脂（Β)] 在：發:月之塗料用組成物作為點合劑所使用的樹曰’糸/、要疋具有聚石夕氧院骨架之樹脂（Β)即可，以在白含（甲基）丙烯酸S旨系單體之聚合物的-部分單體殘基的側鏈’鍵結具有聚石夕氧烧骨架之聚合物而成之樹脂為佳。作為具有此種結構之樹脂(B)，可舉出DIC股份公司製的CERANATE系列的製品。χ，亦可依照特開平 10-365Μ號公報、特開藤_328354號公報及國則0剛67.742所揭示的方法進行合成。 -28- 201229161 例如能夠使用將三烷氧基烷基（苯基）矽烷的水解性矽化合物、或含有前述含有三烷氧基烷基（苯基）矽烷的加水分解性矽化合物與二烷氧基二烷基矽烷類、四烷氧基矽烷類之加水分解矽化合物之混合物水解縮合，隨後使所得到之具有鍵結於矽原子的羥基及/或水解性基之聚矽氧烷與同時具有水解性矽烷基及酸基之（曱基）丙烯酸酿系共聚物縮合反應之後，使錢性化合物進行部分 t和或完全中和而得到之樹脂分散或溶解於水而得到之水性樹脂的分散液或溶液。或是能夠使用使前述的聚矽氧烷、與同時具有水解性矽烷基及酸基及其他的官能基之（曱基）丙烯酸酯系共聚物進行縮合反應之後，使用鹼性化合物進行部分中2 或完全中和而得到之樹脂分散或溶解於水而得到之水性樹脂的分散液或溶液。更單純地說，上述水性樹脂（B)的合成法，特別是其特徵在於：在（甲基）丙烯酸酯系共聚物中的一部分單體殘基的側鏈含有三烷氧基石夕烷的官能基，然後，藉由將該共聚物之賴的三院氧基残官能基與貌氧基^烧類混合且使其進行水解的縮合反應，而在（甲基）丙稀酸醋系共聚物的側鏈鍵結聚石夕氧院。作為其具體例’能夠採用下述的反應。在反應容器添加470g異丙醇，且在氮氣的通氣下升溫至80°C。隨後於同溫度將1〇〇g苯乙烯、3〇〇§甲基丙稀酸"旨、334g甲基丙烯酸正丁，、U6g丙烯酸正二旨、3〇g 3-甲基丙烯醯氧基丙基三甲氧基石夕烷、、丙稀酸 -29- 201229161 及50g第二丁基過氧化-己酸2_乙酯與45〇g異丙醇混合且以4小時滴下至前面在反應容器所準備之47〇g異丙醇中。滴下結束之後，藉由亦在同溫度攪拌丨6小時，來得到不揮發成分為53.5%且數量平均分子量為1〇〇〇〇〇c以上之同時具有羧基及三甲氧基矽烷基之共聚物。將上述1 480g共聚物、354g苯基三甲氧基矽烷及 365g異丙醇的混合物升溫至_。隨後於同溫度以5 分鐘滴下2_9g酸式磷酸異丙酿（is〇pr〇pyl acU phosphate)及96g離子交換水之混合物，且在同溫度進行攪拌4小時而生成含有聚矽氧烷結構的樹脂。隨後，於同溫度以30分鐘滴下54g三乙胺及1Q5()g離子交換水。隨後藉由減壓蒸餾除去溶劑（亦即異丙醇），而得到不揮發成分為42.3%之水性的樹脂（B^如此進行而得到的之樹脂（Β)係塗布後只有在室溫乾燥亦能夠硬化。又，與 f氧基石夕烷化合物混合之後’藉由塗布且乾燥亦能夠使如此在室溫乾燥硬化而得到之塗膜係顯示強耐候怡 :例如使用太陽光耐候試驗機即便曝露到達2,〇〇〇小時 :inf:膜不劣化且不產生裂縫而且能夠將表面光澤性維用作上。由此得知上述水性的樹脂（Β)係能夠適合使用作為光觸媒的黏合劑樹脂。脂(二作為在本發明所使用之具有聚矽氧烷骨架之掏臂妙盡卜U疋活性能量線硬化性的樹脂。作為此時之的耐久'll架的含有率’因為能夠得到可形成具有優良之硬化膜之紫外線硬化性樹脂，以1〇〜95質量 -30- 201229161 以30〜75質量％ %的範圍為佳，以30〜95質量％為較佳為更佳。如此的樹脂（B)係能夠使用各種方法來製造，其中使用下述（1)〜（3)所表示之方法製造為佳。 (1)預先調製含有矽烷醇基及/或水解性矽烷基之聚口物片段’且混合該聚合物片段、與同時兼具有矽烷醇基及/或水解性錢基和聚合性雙鍵之錢化合物，行水解縮合反應之方法。人（2)=先調製含有矽烷醇基及/或水解性矽烷基之聚合物片段。又’將同時兼具有矽烷醇基及/或水解性矽烷 :H &雙鍵之⑦烧化合物進行水解縮合反應而預先周衣忒矽氧烷。然後’混合聚合物片段與聚矽氧烷而進行水解縮合反應之方法。 (3)混β削述聚合物片段、同時兼具有矽烷醇基及/ 或水解性⑦;^基和聚合性雙鍵之⑦烧化合物、與聚石夕氧烷而進行水解縮合反應之方法。在引述（1) (3)所表示之樹脂（Β)的製造步驟之水解縮合反應’係能夠使用各種方法使反應進行，在前述製造步驟’因為較簡便，以供給水及觸媒使其進行反應之方法為佳，而且刖述所s胃水解反應，係指前述水解性基的一部分因水等的影響而被水解且形成經基，隨後在該經基之間或疋忒羥基與水解性基之間進行之縮合反應。作為前述含有矽烷醇基及/或水解性矽烷基之聚合物片段，能夠使用》有矽烷醇基及/或水解性矽烷基 -31 - 201229161 之丙稀酸聚合物、含有矽烷醇基及/或水解性矽烧基之氣烯煙flk合物、含有石夕烧醇基及/或水解性石夕院基之乙締酿系聚合物、含有矽烷醇基及/或水解性矽烷基之芳香族乙烯基聚合物和含有矽烷醇基及/或水解性矽烷基之聚稀 fe XK合物等之含有矽烧醇基及/或水解性矽院基之乙稀基聚合物、含有矽烷醇基及/或水解性矽烷基之聚胺甲酸 S旨聚合物、含有石夕烷醇基及/或水解性矽烷基之聚酯聚合物、含有矽烷醇基及/或水解性矽烷基之之聚醚聚合物等。特別是以使用含有矽烷醇基及/或水解性矽烷基之乙稀基聚合物和含有矽烷醇基及/或水解性矽烷基之聚胺甲酸酯聚合物為佳，以使用含有矽烷醇基及/或水解性矽烷基之丙烯酸聚合物為更佳。作為前述含有矽烧醇基及/或水解性矽院基之聚合物片段係使用丙烯酸聚合物時，該丙烯酸樹脂係例如能夠藉由將含有矽烷醇基及/或水解性矽烷基之乙烯基系單體與按照必要之其他的乙烯基系單體進行聚合來得到。作為前述含有矽烷醇基及/或水解性矽烷基之乙稀基系單體’例如可舉出乙烯基三曱氧基矽烷、乙稀基三乙氧基石夕烷、乙烯基甲基二甲氧基矽烷、乙烯基三（2_甲氧基乙氧基）矽烷、乙烯基三乙醯氧基矽烷、乙烯基三氯矽烷、2-三曱氧基矽烷基乙基乙烯醚、3_(曱基）丙烯醯氧基丙基三曱氧基矽烷、3_(甲基）丙烯醯氧基丙基三乙氧基矽烷、3-(甲基）丙烯醯氧基丙基曱基二甲氧基矽“、3_( 甲基）丙烯醯氧基丙基三氯矽烷等。其中，因為容易進行水解反應，且容易除去反應後的副產物，以乙烯基三曱氧基矽烷'3-(甲基）丙烯醯氧基丙基三甲氧基矽烷為佳。 -32- 201229161 钕…、义要之其他的乙烯基系單體丙烯酸系單體。且體上，彳了舉出 /田苴、八姐上例如可舉出（甲基）丙烯酸甲❿ 、（甲基)丙晞酸乙醋、（甲基)丙燁酸正丙醋 '(甲基)丙：酸=、(甲基)丙稀酸異丁婚、(甲基)丙稀酸第三丁離、（甲基）丙烯酸2-乙基己酯、（甲基）丙烯酸月桂醋等且有石厌原子數為卜22的烷基之（甲基）丙烯酸烷醋類4甲基丙烯酸节醋、(甲基)丙稀酸2_笨基乙醋等的(甲基)丙稀土酸芳烧醋K甲基）丙稀酸環己酿、（甲基）丙稀酸異茨醋等的（甲基）丙烯酸環烷醋類；（甲基）丙烯酸2_甲氧基乙醋、 (甲基）丙烯酸4-曱氧基丁酯等的（曱基）丙烯酸〇院氧基烷酯類；#乙烯、對第三丁基苯乙烯…甲基苯乙烯、乙烯基甲苯等的芳香族乙烯基單體類；乙酸乙酯、丙酸乙烯酯、三甲基乙酸乙烯酯、苯甲酸乙烯酯等的羧酸乙烯酯類；巴豆酸曱酯、巴豆酸乙酯等巴豆酸的烷酯類；順丁烯二酸二曱酯、順丁烯二酸二正丁酯、反丁烯二酸一甲S曰、伊康酸二甲酯等不飽和二元酸的二烧酯類；乙稀、丙烯等的（2-烯烴類；偏二氟乙烯、四氟乙烯、六氟丙烯氣二乱乙稀荨的氟締fe類；乙基乙稀鍵、正丁基乙烯醚等的烧基乙烯醚類；環戊基乙烯醚、環己基乙烯趟等的環烷基乙烯醚類；ν,ν-二甲基（曱基）丙烯醯胺、Ν-(曱基）丙烯醯基嗎福林、Ν-(曱基）丙烯醯基吡咯啶、 Ν-乙烯基吡咯啶酮等含有3級醯胺基的單體類等。使用乙烯基聚合物作.為前述聚合物片段時，該乙烯基聚合物係例如能夠使用塊狀自由基聚合法、溶液自由基聚合法、非水分散自由基聚合法等的各種聚合法使其 -33- 201229161 聚合來製造。使樹腊（B)溶解於有機溶劑而作為紫外線硬化性樹脂組成物時，係以在有機溶劑使前述乙烯基單體進行自由基聚合而作為乙稀基聚合物為佳。作為前述有機溶劑，例如能夠將正己烷、正庚烷、正辛院、環己烷、環戊烷等的脂肪族系或脂環族系的烴類；曱苯、二曱苯、乙苯等的芳香族烴類；甲醇、乙醇、正丁醇、乙二醇一曱基醚、丙二醇一曱基醚等的醇類，乙酸乙酯、乙酸正丁酯、乙酸正戊酯、乙二醇一甲基謎乙酸醋、丙二醇一曱基醚乙酸酯等的酯類；丙酮、曱基乙基酮、甲基異丁基酮、甲基正戊基酮、環己酮等的酮類’二伸乙甘醇二甲基醚、二伸乙甘醇二丁基醚等的聚伸烧基二醇二烷基醚類；1，2-二甲氧基乙院、四氫吱喃、二院等的醚類；N_曱基吡咯啶酮、二曱基甲醯胺、二曱基乙醯胺或碳酸伸乙酯單獨使用或併用2種以上而使用。又，使用自由基聚合法使前述乙婦基單體聚合時，能夠按照必要使用聚合起始劑。作為如此的聚合起始劑，例如能夠使用2,2，-偶氮雙（異丁腈）、2,2，_偶氮雙（2,4· 二曱基戊腈）、2,2，-偶氮雙（2-曱基丁腈）等的偶氮化合物類；過氧化三甲基乙酸第三丁酯、過氧化笨甲酸第三丁酯、第三丁基過氧基-己酸2_乙酯、過氧化笨甲酸第三丁酯、異丙苯過氧化氫、過氧化碳酸二異丙酯等的過氧化物類等。作為前 500〜200,000 述聚合物片段’係以數量平均分子量為的聚合物片段為佳，以數量平均分子量為 -34- 201229161 700〜100, 〇〇〇的聚合物片段為更佳。以數量平均分子量為 1，000〜5〇,〇〇〇的聚合物片段為特佳。藉由使用具有如此範圍内的數量平均分子量之聚合物片段能夠防止製造樹舳（B)時之增黏和凝膠化，而且能夠得到可得到耐久性優良的塗膜之紫外線硬化性樹脂組成物。藉由使用具有聚合性雙鍵基的聚合物片段作為構成在本發明使用的樹脂（B)之聚合物片段，能夠使其形成更具有耐久性之硬化塗膜。具有聚合性雙鍵的聚合物片段 ’係例如能夠藉由使用具有m基之聚合物片段，在此添加同時具有聚合性雙鍵及環氧基之化合物、例如甲基丙烯酸環氧丙酯並使其反應來得到。作為在前述（1)所使用之同時具有矽烷醇基及/或水解性矽烷基和聚合性雙鍵之矽烷化合物，例如可舉出乙烯基二甲氧基矽烷、乙烯基三甲氧基矽&、乙烯基甲基二甲氧基錢、乙稀基三（2-甲氧基乙氧基μ夕烧、乙稀基二乙醯氧基矽烷、乙烯基三氣矽烷、2·三甲氧基矽烷基乙烯醚3-(甲基）丙烯醯氧基丙基三曱氧基矽烷、3_( 甲土）丙烯酿氧基丙基二乙氧基石夕烧、曱基）丙稀酸氧基丙基甲基二甲氧基石夕烧、3·(甲基)丙稀醢氧矽烷等。作為前述同時具有矽烷醇基及/或水解性矽烷基和聚合，雙鍵之錢化合物，因為水解縮合反應能夠容易也進仃一又，能夠容易地除去反應後的副產⑯，以使用烯基-甲氧基石夕虎、3·(甲基）丙稀酿氧基丙基三甲氧基 -35- 201229161 則述方法（l)所使用的矽烷化合物係按照必要併用同時兼具有矽烷醇基及/或水解性矽烷基和聚雙鍵之矽烷化合物以外之其他的矽烷化合物。作為其他的矽烷化合物，例如可舉出甲基三甲矽烷、甲基二乙氧基矽烷、甲基三正丁氧基矽烷、三甲氧基矽烷、正丙基三甲氧基.矽烷、異丁基三甲矽烷、環己基三甲氧基矽烷、苯基三甲氧基矽烷、二乙氧基矽烷等各種的有機三烷氧基矽烷類；二甲甲氧基矽烷、二甲基二乙氧基矽烷、二甲基二正丁石夕烧、二乙基二甲氧基矽烷、二苯基二甲氧基矽烷基锿己基二甲氧基矽烷或甲基苯基二甲氧基矽烷等的一有機二烷氧基矽烷類；甲基三氣矽烷、乙基三烷、苯基三氯矽烷、乙烯基三氣矽烷、二甲基二氣、一乙基二氣矽烷或二苯基二氯矽烷等的氣矽烷類作為前述其他矽烷化合物，因為水解縮合反應今易地進打，又，能夠容易地除去反應後的副產物有機三烧氧基妙烷或二有機二烷氧基矽烷為佳。又’作為前述其他的矽烷化合物，亦能夠併用氧基石夕院、四乙氧基矽烷或四正丙氧基矽烷等的4 烧氧基石夕院化合物或該4官能烷氧基矽烷化合物的 :解縮合物。併用前述4官能烷氧基矽烷化合物或刀水解縮合物時’係以相對於構成前述聚矽氧烷片〜、矽原子’具有該4官能烷氧基矽烷化合物的矽原不超過20莫耳％的範圍之方式併用為佳。、亦可合性氧基乙基氧基苯基基二氧基、甲各種氣矽矽烷〇能夠，以四甲官能部分其部段之子為 -36- 201229161 此種树脂（B)係存在許多源自聚矽氧烷骨架的矽烷醇（Si-OH)基。該官能基係在與二氧化矽粉末混合時，能夠與二氧化矽表面的矽烷醇基進行脫水縮合。該性質係本發明在光觸媒塗膜設計之重要的結構因素。 [含有粉體（A1)及/或粉體（A2)及樹脂^)之}液型塗料組成物] 本發明的1液型塗料組成物係藉由在介質中混合粉體（A 1)及/或粉體（a 2)與具有聚碎氧烧骨架之樹脂（b )而能夠容易地調製；該粉體（A丨）係包含將氧化鈦（a丨）的奈米粒子固定在前述二氧化矽奈米結構體（a2)而成的複合體，而§亥粉體（A2)係包含將氧化鎢（a3)的奈米粒子固定在前述二氧化石夕奈米結構體（a 2)而成的複合體。調製塗料組成物時，首先係以在介質中將粉體（A j) 及/或粉體（A2)混合且將該混合物使用均質混合機等高剪切力的分散裝置授拌’來調製光觸媒粉體的分散液為佳。隨後，將在此所得到的分散液與樹脂（B)的分散液或溶液混合且藉由於室溫（2 〇〜3 0 °C:)搜拌1〜3小時，能夠得到均勻分散的塗料組成物。調製上述塗料組成物時，能夠混合在合成樹脂（B) 時和調整其分散液或溶液時所使用的溶劑等。作為塗料組成物中的粉體（A 1)及/或粉體（a 2 )、及樹脂（B)的合計之固體含量含有率（不揮發成分），在 1 0〜8 0 wt%的範圍時係能夠適合使用，以配合使用條件、目的而適當地調製為佳。 -37- 201229161 又作為塗料組成物中不揮發成分的粉體（A1)及/或粕體（A2)及树知（B)之組合比例，粉體（A1)與粉體（A2) 的合計與前述樹脂（B)之使用比例係以[(AD + MWWB) 表示的質量㈡10/90〜_〇的範圍為佳，為了使光觸媒活性部位的塗膜表面之密度提升，卩將其質量比在 3 5/65〜65/35的範圍調整為更佳。 +本發明的塗料組成物亦能夠混合顏料、染料而成為 2塗枓。顏料或染料的使用量能夠配合顏色的濃淡而调製，以樹脂（B)的50質量％以下為佳。前述所得到之1液型塗料組成物係長時間靜置i天 =時，組成物中的光觸媒之粉體有沈降之傾向，但是時安定分散狀態…：能夠再次維持數小，即##總# °亥，·且成物係室溫保存半年以上時沒有凝膠化之㈣產生沈降’但是組成物整體係完全沒有凝膠化，即便長期保存之後 [光觸媒塗膜的製造] b ° ^ ° 用。的任：1液型塗料組成物塗布在任意形狀的任思基材，稭由使其在季節線，能約得到呈有非常古…兄，皿度下乾燥且照射光媒塗膜。/、有非“的先觸媒能力及财候性之光觸上述的塗料組成物在基材 ’能夠配合用途而適當地塗布。作特別限定用棒塗布、旋轉塗布、刷子、噴’、' 、’忐夠採刷等的方法。、霧、、祠版印刷、凹版印藉由使用上述光觸媒塗膜塗膜的膜厚度，係以在i…0仃塗布而形成之光觸媒 3〇am的範圍為適合。 -38- 201229161 夠在：/述光觸媒塗膜進行塗布之塗膜硬化，能此所境溫度（5〜饥）〜2(^的範圍進行硬化。在已…：％境溫度的硬化’實際上係只有使其乾燥而越高==Γ24:時為適合。加熱硬化時，溫度寺間越短，以數分鐘至數小時的範圍為佳。人物。：ΐ明的塗料組成物中’亦能夠混合各種矽烷化 :為矽烷化合物’例如可舉出甲基三甲氧基矽烷二二乙氧基石夕烧、乙基三甲氧基石夕院、乙基三乙氧 :丙：：正丙基三甲氧基石夕烧'正丙基三乙氧基石夕烧、 :甲i:甲々氧基石夕烷、異丙基三乙氧基石夕烷、3-氣丙烷 :氡基矽烷、3_氯丙基三乙氧基矽烷、乙烯基三甲氧烷乙烯ί三乙氧基矽烷、3-環氧丙氧基丙基三曱 -矽燒*、3-環氧丙氧基丙基三乙氧基石夕院、3胺丙基 ::氧基石夕烧、3-胺丙基三乙氧基石夕烧、3_氫硫基丙基二:基钱、3·氫硫基三乙氣基碎烧、3,3,3_三氣丙基一 1基矽烷、3,3,3·三氟丙基三乙氧基矽烷、3_曱基丙烯醯氧基丙基三甲氧基矽烷、3_甲基丙烯醯氧基丙基三乙，基矽烷、苯基三曱氧基矽烷、苯基三乙氧基矽二、對風甲基苯基三甲氧基矽烷'對氣甲基苯基三乙氧基矽烷、二甲基二甲氧基矽烷、二甲基二乙氧基矽烷、二乙基二甲氧基矽烷、二乙基二乙氧基石夕烷等。又，在上述的塗料組成物添加光聚合起始劑且藉由照射UV ’亦能夠使其硬化。特別是在樹脂（B)中使用具有聚合性雙鍵者之情況，以進行活性能量線硬化為佳。此時’亦可以在空氣環境下或惰性氣體，例如氣氣環境下進行塗布的硬化過程。 -39- 201229161 將前述組成物塗布在基材且剛使I 表面，雖然具有凹凸結構，但是因為| 活性部位（氧化鈦和氧化鎢的奈米粒子係黏附有黏合劑樹脂亦即樹脂（B)，此用光觸媒聋膜之功能。為了使其具有作肩月必須對硬化後的塗膜照射光線，隹位所黏附的樹脂因光照射而產生分解。法係不限定於特別的光源，藉由將塗冲室外、室内的自然光環境下即充分。相陽光下的曝露狀態時，照射1小時以』功能係能夠有效果地顯現。室内自然夫天以後時，塗膜的光觸媒功能係能夠有使塗膜的光觸媒顯現時，在作業上源時，亦能夠適合使用黑光、螢光燈、燈等。雖然使用該等光源的光照射時間的強度’強度較強的高壓水銀燈、氙燈 1小時以上係充分的’強度較低的黑光射5〜24小時的範圍為適合。 [光觸媒塗膜] ^ - 'Μ 到之无糸光觸媒活性部位在表面露出頂 :二氧化矽奈米結構體係被植入〇 :、有章魚頭(光觸媒活性部位) 在塗膜的連續層伸展之結構。因二氧切奈米結構體㈣的Sl_〇 r硬化之後的塗m r出頂部的光觸媒存在之部位）部分態係不具有作為 f光觸媒塗膜之工力 -在光觸媒活性部作為光照射之方後的塗膜放置在別是在室外的太 -時塗膜的光觸媒 >時’數小時或I 效果地顯現若有需要特定光高壓水銀燈、氣係依存於光源燈等的情況，照射、螢光燈時，照膜，其基本結構支撐其露出頂部的連續層。這宛面露出而足部係於章魚的足部之基係與黏合劑樹 -40- 201229161 脂亦即樹脂(B)中& s201229161 VI. Description of the Invention: [Technical Field] The present invention relates to a one-liquid type coating composition, a photocatalyst powder thereof using the same, a photocatalyst coating film obtained therefrom, a super-hydrophilic coating film, and the like Manufacturing method. The sputum type coating composition contains a powder obtained by fixing oxidized osmium or tungsten oxide to a cerium oxide nanostructure, and a resin having a polydecane skeleton. [Prior Art] In recent years, photocatalysts such as titanium oxide have been decomposed by pollution and harmful substances, and have been intensively degraded in the industry. Its application area extends to residential, vehicle, medical, land processing, etc. and it is an indispensable technology for building a recycling society. In general, the photocatalyst itself is a powder, and it is required to be photocatalytic activity in order to exhibit the catalyst activity of the coating film after being coated with a binder resin and further coated with a coating film for use in a real space. The dots (for example, titanium oxide particles) are distributed and fixed on the coated surface 'and the photocatalyst must protect the continuous layer of the coating film (adhesive) and the substrate to be coated. In particular, when a photocatalyst coating film mainly composed of an organic binder is set as a target, this problem cannot be avoided. That is, the photocatalyst coating film can not be expected to protect the substrate while preventing contamination on the surface of the substrate. Therefore, regarding the photocatalyst coating film, various methods are studied. For example, a method has been devised in which an undercoat film containing a photocatalyst is formed on the surface of the substrate after the undercoat film is formed (for example, refer to Patent Documents 1 to 4). Patent Document 1 uses alkoxy decane, ultraviolet light absorption 201229161, and the like as a base (four) coating liquid, and applies it to a substrate, and then dries it, and applies a photocatalyst powder containing titanium oxide or the like and a coating of an oxidized stone sol solution. The liquid is allowed to form a photocatalyst coating film. According to this method, by the fact that the substrate has weather resistance and the photocatalyst is fixed to the overcoat layer, it is possible to "stop" super-hydrophilicity, etc. Patent Document 2 provides a method for containing an alkoxy group. And the side key has a fat, and then according to the necessary polyfunctional sulphuric acid vinegar resin component = the plastic substrate is coated with m coating liquid on the surface of the substrate: 'after' coated with titanium oxide powder thereon The photocatalyst group is based on the second in the second;:; reveals a photocatalyst coating film, which is not degraded under the outer line and has a strong weather resistance gas, i grease poly-oxygen sol-gel solution as a primer After coating and drying the composition, the photocatalyst composition is applied directly thereon to achieve a long life. Further, the literature 4 also investigates a primer coating method of a substrate in which the photocatalyst coating agent may cause the surface of the substrate to be produced. Specifically, it is a method in which a (four) oxytitanate aqueous solution is used for mist coating, and a titanium oxide is coated thereon to use: a photocatalyst composition is proposed without using a primer film. Directly coated on:: face: for example It is made up of a photocatalyst with low activity and ultraviolet absorption energy oxygen == stone type oxidation and photocatalyst activity is higher, /3 polyacrylate 'polyoxane, colloidal cerium oxide surface agent mixed' and will The composition is directly applied to a substrate, i.e., a catalyst coating film (for example, refer to Patent Document 5). The method is intended to function as a UV-absorbing primer layer of a strong-strength stone-type titanium oxide. 201229161 In fact, in the case of photocatalyst coatings, titanium oxide, etc., which functions as a photocatalyst, cannot be exposed when the surface is not exposed. Therefore, this study seeks to make the photocatalyst coating of the top of titanium oxide exposed (see, for example, a patent). Document 6) Patent Document 6 discloses that the surface of the coating film is formed in a porous form by applying a poly-stone coating or the like onto the surface of the substrate, and then coating the surface of the porous film with a light medium. When the composition of the powder and the polymer binder is 'infiltrated into the porous cavity due to the polymer bonding: the photocatalyst solid tends to remain on the surface thereof', it is possible to make more light as much as possible. Catalyst: The surface of the coating film is exposed. Moreover, compared with the fluorescent lamp, the coffee lighting system with a long life and less energy is rapidly becoming popular. It is speculated that in the near future, coffee lighting will occupy most of the indoor lighting. Therefore, in order to effectively use the photocatalyst in the indoor ring: it is necessary to develop a photocatalytic system that is equivalent to the visible light response type of the LED lamp. The LED illumination system does not contain ultraviolet light at all, and all the emission wavelengths are visible light. 'The use of the usual yttrium oxide system does not reveal the photocatalytic function: 'Also, even the current visible light-responsive titanium oxide photocatalyst can only display weak photocatalytic activity under the (four) light source. In recent years, 'the titanium oxide without visible light response ability has The change of 'tungsten oxide photocatalyst with visible light absorbing ability and photocatalytic function is noticed. However, when the band gap _(4) of the oxidized crane is low, the electrons that are excited from the valence band to the conductive band are easy to return. In order to show the catalyst function, 'design can structure the electronic "pool or trap" necessary. There is a method for loading a transition metal in a crane in oxygen 201229161 (for example, refer to Patent Document 7). The tungsten oxide photocatalyst carrying a transition metal is about three times as large as the visible light-responsive titanium oxide before photocatalytic activity. Performance in LEI) lighting applications in indoor spaces. The manufacturing process of the above-mentioned oxidized crane photocatalyst is obtained by pulverizing the oxidized crane particles obtained by the high temperature and passing through the damper to obtain the oxidized town. After the granules are loaded with the transition metal, the degree of the knot is not reached and the manufacturing process may be Inefficient. As described above, although various kinds of studies have been carried out on the photocatalyst coating film using the visible light responsive photocatalyst and the manufacture thereof, it takes a lot of effort and actually hemp in this state, even if it is It is also not suitable for the photocatalytic function of the coating film to be sufficient. In fact, for the use of the vehicle coating film under indoor lighting, it is only predictive of effectiveness, and no effective photocatalyst coating film has been found yet. In order to coat the photocatalyst with a non-primary coating, there is only a rethinking of the design idea. This is because it is necessary to consider both the mixture design and the photocatalyst design. [PRIOR ART DOCUMENT] [Patent Document 1] Japanese Laid-Open Patent Publication No. JP-A No. Hei. No. Hei. [Patent Document 5] Japanese Laid-Open Patent Publication No. JP-A No. Hei. No. Hei. No. Hei. No. Hei. No. Bulletin 'But it is only impossible to say, and the structure and use of the fired particles are not required. In the actual light touch, the practical surface is made to be sticky. 201229161 [Summary of the Invention] [The invention is intended to solve the problem of practical direct coating. Therefore, it is designed in a way that is embarrassing. The photocatalyst coating film itself is the photocatalyst in the film. The resin itself. Considering the function of the photocatalyst from nanometer to micron level, the fixed convex part is not necessary. It is also necessary that the resin itself must be solid. Therefore, the present invention also has a coating layer directly coated with a photocatalytic work to the surface of the coating film, and the active site of the medium is obtained by having a light touch with the coating composition [a means to solve the problem] in order to solve the aforementioned result' It has been found that when the photocatalyst is coated with a photocatalyst, it is required that the photocatalyst coating film is required to be used as a precondition, and the deteriorated substrate cannot be deteriorated, and the active site cannot be described. The uneven structure of the surface of the photocatalyst coating film is excellent in the convex portion. However, light is formed by a binder resin. However, there is a sufficient pair of properties, and the subject to be solved by light is to provide a powder of a kind, and a composition containing the same, in which the composition is coated with a concave-convex structure and fixed at the convex portion. The most surface-based adhesive resin is a coating film which does not have a direct bond function, and a simple subject thereof, and the present inventors have repeatedly used the titanium oxide or the oxidized crane to form a liquid-structure which is separated from any of the first modes and photocatalyst. The coating-in-the-moisture-adhesive structure is a method of manufacturing a method that is capable of being fixed as a catalyst site, and is capable of being adhered to a visible light liquid type, and which is capable of drying and having a light contact with the active portion. Concentrated research on the sintering of rice particles 201229161 In the nanofibers based on nanofibers &&&&&& The powdered photocatalyst of the type of the titanium oxide composite type powder poly-stone-oxygen-fired skeleton is a type 3 powder, and has a 哿 character. The resin of the (fluorenyl) acrylate-based polymer which is bonded by the chain is mixed with the main composition of the material, coated on a substrate of any material, dried, and further coated. The present invention has been accomplished by displaying a very high photocatalytic function under the sunlight and the ',,, and under, and the super-hydrophilic function based on the structure. - The present invention provides a liquid coating composition, a photocatalytic coating film, a super-hydrophilic ten-coating film, and the above-mentioned manufacturing 1 & type coating composition. A powder (A 1) formed by oxidizing the oxidized chin (4) plant oxidized granules (a 2) and/or solidified & oxidized crane (a3) in a cerium dioxide structure (& 2) A powder (A2) and a resin (b) having a polyoxyalkylene skeleton. Moreover, the present invention provides a photocatalyst, and such a simple manufacturing method. The photocatalyst comprises a powdery photocatalyst comprising a composite of titanium oxide (al) or tungsten oxide (a3) in a oxidized cerium nanostructure (a 2), characterized in that the cerium oxide The rice structure 02) is a core unit having a thickness or a thickness of 10 0 to 1 〇〇 nm and an aspect ratio of 2 or more as a basic unit at 1 #m to 20 The content of the titanium oxide (al) or tungsten oxide (a3) in the composite is 10 to 8 mass%. [Effects of the Invention] Generally, the titanium oxide crystal powder used as a photocatalyst has a high refractive index and reflects most of the light necessary for the photocatalytic reaction, resulting in 201229161. The titanium oxide/dioxide catalyst of the present invention is completely different from the prior art, and the shape of the ruthenium oxide nanostructure is a composite photocatalyst, and the light is also easily irradiated by the ruthenium dioxide to be fixed in the dioxide. The photocatalytic activity of titanium oxide in the active site of the photocatalyst is improved. Further, the interface at the level of the titanium dioxide structure between the cerium oxide nanostructures is also strongly correlated with the titanium oxide. The particles of the crane are sintered and fixed at an interface between the amorphous ceria and the junction level. The tungsten oxide is the possible electron pool effect of the photocatalyst function, and the electron capture The high-quantum tungsten oxide/cerium oxide composite type yttrium oxide nanostructure is also easy to introduce the light from the light source around the active site of the catalyst, and the light structure of the composite of the nanostructure cannot be effectively activated. Nanoparticles of titanium oxide are complexly compounded. The titanium oxide/diox system is not only directly scattered by the titanium oxide absorption structure, but also oxidized by the light crystal structure. As a result, the light absorption probability increases, and as a result, the interface between the nanoparticle of the sintered titanium oxide and the nanoscale-forming layer increases the function of the photocatalytic active site of the naphthalene, and similarly, by oxidizing the nanostructure of oxygen On the surface of the body, crystalline tungsten is formed between the tungsten oxide to have a visible light. The nano interface has a yield effect by irradiation of light. Further, in the case of constituting a photocatalyst, two light scatterings having a complicated shape can achieve the function of light. The emulsified 矽 nanostructures have the ability to capture air. Further, in the amorphous structure of the dioxo, there are 4 groups which are capable of adsorbing water molecules efficiently by f. Moreover, the surface of the 1-Chenami structure can be around the active site of the catalyst. Diffusion. Adsorption of oxidized crane composite photocatalyst dibe organic matter. . Therefore, under the SiO2/Bright light, its work is: even in the absence of ultraviolet light, the LED illuminates the catalyst. "Month" "*', this is enough to be used as an organic compound to divide the organic compound into a specific structure of the structure of the powder using the structure of the concave structure = complex shape of the dioxinene crunch駚Α , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , The function of the ΙΪ1 胄胄活性活性活性被奈奈奈奈奈奈奈奈奈奈奈奈 ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' 奈奈奈The photocatalyst coating film is different in the root coating. _: and, because the photocatalyst coating film of the present invention has the concavity and convexity of the enamel structure in the whole film, when the photocatalyst generates a function, the enamel system is It is easy to become the power of w B. At this time, the film system can be obtained by coating the coating material with a simple coating of the photocatalyst of the invention and drying it. Therefore, the photocatalyst coating film of the present invention is used. : ', ° in response to indoor and outdoor high-efficiency photocatalyst coating film or L / the first liquid type coating composition of the present invention, regardless of the material of the substrate wood, the factory can be adapted to glass, plastic, metal, Pottery, 聿聿: Etc.: 广广 Because the one-liquid type coating composition of the present invention is a disease-specific disease, it is of course not necessary to say that even the 豕庭 can be coated in a necessary position to manufacture a photocatalyst. Coating film. -11 - 201229161 That is, the present invention can be comfortably used as a photocatalyst coating film having anti-pollution, self-cleaning, air purification, killing, and anti-virus effects even under illumination light containing no ultraviolet rays. Use a wide range of building facilities such as industrial sites, medical sites, schools, nursing homes, and homes. [Embodiment] L is a form for carrying out the invention. The photocatalyst coating film has a history of nearly 20 years, and particularly, it is used as an outdoor (ultraviolet) coating, and the photocatalyst coating film exhibits a self-cleaning effect of preventing contamination and utilizing superhydrophilicity. Photovoltaic coatings using titanium oxide powder are rarely used in high-rise buildings and large-scale buildings. However, considering the use of indoors or single-family houses, only the structure of the coating film (4) The photocatalyst of the photocatalyst in the state of titanium oxide crystal powder cannot be expanded. : 'It is known that it can absorb visible light and decompose organic matter. The state of tungsten oxide is visible light energy, and electricity is generated in electrons and holes. Therefore, it is difficult to say that it has a stable photocatalytic function. Even if it is ::: Become a long-term effective photocatalyst coating film. U In order to develop a photocatalyst coating film, the photocatalyst is first designed. Therefore, the present invention contemplates the function of building a firewood several times higher. The titanium oxide crystal powder itself is oxidized by a two-particle structure of a oxidized ... structure. The composite photocatalyst system is easy to produce: :, ·,. Photocatalyst. The photo-sensing effect of the active site is such that the photocatalyst W is simultaneously oxidized or the oxidized crane-12-nano structure to form a neat, not only a simple active site, but also a coordinated It is possible to design titanium oxide or tungsten oxide as a structure with fine Φ. The direct oxidation of the oxygen bond from the separated electrons and the oxygen photocatalyst of water are not only oxidized, but must be constructed to satisfy the following Light diffuses, or traps the air around the active part of the medium to capture the air shrinkage function; the nano-interface structure of the "foothold" function of the active organic matter in the catalyst. The photocatalyst is used to form a coating film adhesive resin, and light can be easily made by the unevenness on the surface. This is because the chemical structural elements and the organic polymer containing inorganic components which are strongly integrated with the development of the photo-contact coating film on the surface of the coating film are the same as the above-mentioned design. The present invention will be described in detail with the disclosure of the proposals. The nanoparticles of 201229161 and the surface of the dioxide dioxide enhance the photocatalytic function. Generally, the so-called catalyst is designed to function as a catalyst for the peripheral development of its active site. In the photocatalyst ', the active oxygen, the C-H of the positive hole, and the radical hydroxyl group are generated by maintaining the separation state for a long period of time. That is, the structure of the active sites of the tungsten oxide: the function of concentrating with photons around it; the efficient diffusion of oxygen and water in the oxygen and water, and the active sites of the catalyst The composite photocatalyst of the present invention is not embedded in the active portion of the cerium oxide nanostructure, and the top adhesive is exposed to the air, and can be exhibited to the utmost. The photocatalyst mixture resin t and the photocatalyst are required to be present. This is because the mixed resin in the normal state is necessary. Photocatalyst design and the new concept of the adhesive resin photocatalyst coating film. The unconstrained by the sufficient effect to become the original and the various so-called middle weeks In the case of the titanium oxide (ai) used as the present invention, the titanium oxide (ai) is not particularly limited. Any crystal phase of the ore, rutile or anatase/rutile mixed crystal may be 'again' or may be doped with metal ions or nitrogen atoms in the crystal of the titanium oxide. In order to efficiently fix the titanium oxide (a 丨) to the later-described SiO2 structure (a2), it is preferable to use a titanium oxide powder in the form of fine particles of i 0 to 100 ηπ. [Ceria nanostructure (a2)] The ceria nanostructure (a2) used in the present invention is a crystal formed by a polymer having a linear polyethylenimine skeleton in an aqueous medium. The conjugated body is produced as a mold and is produced by a sol-gel reaction using a cerium oxide precursor, that is, an alkoxy cerium. In particular, the inventors of the present invention have disclosed in Japanese Patent Laid-Open No. 2005-264421, No. 2005-336440 Any of the dioxide celestial structures provided by JP-A-2006-63097, JP-A-2006-306711, JP-A-2007-5056, and JP-A-2009-24124 can also be used as the dioxide of the present invention.矽 nanostructure (a2). The ruthenium dioxide nanostructure (a2) is different from the giant sized silica dioxide which is suspended by a cerium oxide gel or the like, and is characterized by a basic level of nanometer. Unit as a constituent unit, and it is a collection of three-dimensional space Further, in the cerium oxide nanostructures provided in the above-mentioned patent documents, metal ions or metal nanoparticles are also included, but since these systems do not hinder the photocatalytic function (in accordance with the metal species) It also has the effect of enhancing the photocatalytic function), and can be suitably used as the cerium oxide nanostructure (&2) used in the present invention. -14- 201229161 As a manufacturing method, for example, it has a linear polyethylene The polymer of the imine skeleton is suspended in water 'and dissolved at a temperature around 80 ° C. After the polymer is dissolved, it is allowed to stand to cool to room temperature (2 $ to 3 〇). After standing cooling for about 30 minutes, nanofibers and nanobelts can be obtained by the overall structure of a polymer having a linear polyethylenimine skeleton or other substances coexisting (metal ions or acidic compounds, etc.) The structure of the nano-nanofiber or the like serves as an aggregate (i.e., a precipitate) of the basic unit. Here, by mixing an ethanol solution containing about 20% by weight of a tetrakidoxy group (containing a condensate), such as a condensate, it is possible to make the silica dioxide contain a polyethyleneimine skeleton. The basic unit of various structures of the polymer is uniformly precipitated 'and an association body is formed between the basic units, and a cerium oxide nanostructure having a polymer chain therein can be obtained. Further, 'when the polymer having the linear polyethylenimine skeleton is dissolved at 80 C, the other polymer can be obtained as a basic unit by mixing other polymers such as polyethylene glycol. As the precipitate, a complex shape of a cerium oxide nanostructure obtained by depositing cerium oxide on the polyethyleneimine in the precipitate by the same method can also be used. Further, as a method of dissolving a polymer having the linear polyethylenimine skeleton in water, it may be dissolved not only by heating but also by addition of an acid. In this method, a basic compound is added after being dissolved, and by adjusting to a pH of about 8, a nanocrystal of a polymer having a linear polyethyleneimine skeleton can be precipitated, and the mixture is mixed in the same manner as described above. When the oxidized oxide source is used, it is possible to obtain a complex shape of the cerium oxide nanostructure. • 15-201229161 The use of these methods is characterized by the fact that a nanocapsule is placed in a nano-sized structure of 1 cerium oxide, which is specifically aggregated to have a micron size. !乍 is a basic structure, and these systems produce A ^ 矽矽 nanostructures 〇 2), specifically, the thickness is 10 to 100 nm, preferably $ 、, and the limbs are exemplified to be coarse s , 疋 20~80nm; aspect ratio is more than 2, compared with the unit and the upper fibrous structure (below, nanofiber) as the basic = thickness is 1〇~1 is preferably a thickness When the aspect ratio is 2 or more, it is preferable that the upper band structure (hereinafter, a nanobelt) is a basic unit. As a group of aggregates that make up early and gather together, j (using the longest part), it is usually A坩~20" m, preferably 3~l5//m. Further, in the cerium oxide nanostructures prepared by the above method, there is a t compound having a linear polyimine moon frame as a mold, which can be obtained by using the structure in 4 〇〇~9 〇〇 calcined and removed. At this time, since the overall shape does not change before and after the calcination, a structure of the ruthenium dioxide having the ruthenium dioxide as a main component can be obtained. In addition, the term "cerium dioxide is used as the main component of the knives" means that the components of the polymer stone are regenerated by the calcination temperature and the gas atmosphere, and the third component is not intentionally used. Does not contain components other than cerium oxide. In the present invention, the cerium oxide nanostructure (composite) containing the polymer chain and the cerium oxide nanostructure obtained by removing the polymer chain by calcination are also suitably used. • 16-201229161 [Powder (A1) containing a composite in which titanium oxide (al) is fixed to the cerium oxide nanostructure (a2)] The above-mentioned fixed oxidation of the cerium oxide nanostructure (a2) Titanium (ai) can be easily and reproducibly performed by "adsorption" and "calcination" which are continued by the adsorption. Specifically, first, by dispersing, mixing, and physically absorbing the powder of the powder of the cerium oxide nanostructure (a2) and the titanium oxide in an aqueous medium, ultrasonic treatment and It is preferred to stir and disperse the stirrer or the like. It is often because the surface of the oxidized stone has a large number of OH groups and the polarity is strong. The surface of the titanium oxide is also highly polar for the same reason. Therefore, 'after stirring and dispersing, the upper clear aqueous solution is removed by centrifugation or the like, and the dry work is carried out. (4) The powder of the oxidized alk (al) is physically adsorbed on the SiO2 structure (a2). surface. In terms of the ratio of the powder of titanium oxide (4)) to the size of the cerium oxide nanostructure (a2), the mass ratio expressed by 幺,,,, ', '', (al)/(a2) is 10/95: 80/20 is better, ... 〇 ~ Qing's range is better. e Kt#u 1 m = Oxidation of the nanostructure: The amount of the medium is not particularly limited, and is 10 to 30 times the total mass of the oxidized chin (4) and the oxidized oxalite structure (a2). The range is appropriate. Berry is a mixed solvent of a hydrophilic organic solvent, and may be, for example, ethanol, 2-propanol or propylene. = The titanium oxide (4) is mixed with the dioxetane structure in the medium, and the polymer is used in order to make the adsorption more reliable. -17- 201229161 The basic polymer which can be used at this time is, for example, a polyamine such as polyethyleneimine, polyallylamine, polyvinylamine or polylysine. The detailed method of the adsorption step of mixing the titanium oxide (al) with the ceria nanostructure (a2) is not particularly limited, for example, after mixing in a certain ratio 'by leaving it at room temperature (20 to 30 ° C) Stirring for 1 to 24 hours allows sufficient physical adsorption. By heating and calcining a structure in which the powder of titanium oxide (a1) is adsorbed on the above-mentioned ceria nanostructure (a2), it is possible to pass the titanium oxide (al) to the cerium oxide. A powder of a composite of nanostructures (A 1). The cerium oxide nanostructure (a2) used is one in which the internal polymer chain has been removed, and the heating calcination temperature is 35 Torr to 9 Torr. The temperature range of ruthenium is preferably a case where a polymer chain is present in the internal ruthenium oxide nanostructure (a2), and 400 is used for the purpose of simultaneously removing the polymer chain. (The calcination is carried out at the above temperature. The calcination time is usually controlled by a program for 2 to 8 hours. For example, after raising the temperature from room temperature for 1 hour, it is raised to the end after 30 minutes, so that it is It is preferable to carry out the staged calcination at a temperature of 3 hours, etc. The temperature rise program affects the photocatalytic activity of the obtained powder (A1) containing the cerium oxide nanostructure after sintering and fixation of titanium oxide, but in accordance with It is preferable to adjust the type of titanium oxide (al) to be fixed each time. For example, when titanium oxide doped with carbon or nitrogen is sintered and fixed, in order to maintain the structure after doping, it is necessary to increase the temperature. The maximum temperature is set to 50 (below TC, preferably 450t or less. Also, 2-18-201229161 fixed titanium oxide crystal system is already in the mixed crystal state of anatase and rutile. It is preferable to set the maximum temperature of the calcination to 6 〇〇 or less. It is preferable to carry out the heating-like process in an air atmosphere, or to carry out an inert gas such as a nitrogen atmosphere. a 1) The rate is basically dependent on the amount of titanium oxide (al) to be adsorbed, and can be prepared in a range of 10 to 80% by mass in the oxidation containing titanium oxide (a丨) obtained by the above-mentioned production method. What kind of joint interface is formed between the crystal of the nanostructure (A1), the crystal of titanium oxide (al) and the structure of the tantalum dioxide nanostructure (a2), but it is not observed when the calcination treatment is not performed. When the activity of the catalyst is increased, and even if it does not have a complex shape such as a oxidized crushed gel, it is observed that the catalyst activity is improved to some extent in the oxygen (al) The joint interface of the smectite smectite structure (a2) is the second "I:: the effect of the concentration of the organic matter at the nano interface and the concentration of the organic matter in the vicinity of the active site. The hunting method described in the method of oxidizing the 矽矽矽矽结构占占占 — 疋疋疋疋疋疋疋疋疋疋疋疋疋疋疋疋疋疋疋疋疋疋疋疋疋粉 ^ ^ ^ ^ 粉 ^ 粉 ^ 粉粉粉粉粉粉粉Titanium (6): = two phases compared to oxidation alone, the catalyst, oxygen (A " improved =1=Construction (4): The powder position weight of the composite state is # θ 歹 In the decomposition reaction of acetaldehyde, the composite state of cerium oxide I 1 contained in the cerium is compared with the amount of catalyst in a single position. ~ The emulsified titanium system is much less, and the system of titanium oxide with the same weight is multiplied. / / 'System use -19- 201229161 Moreover, the powder (A1) obtained here uses a variety of light source sunlight n mercury lamp A high-catalyst activity is exhibited by a dentate lamp, a black light, a work light lamp, etc. [A powder comprising a composite body in which an oxidized crane (a3) is fixed to a dioxetane structure (a2)" (A2)] First, a tungsten oxide is used as the powder for producing tungsten oxide, and the precursor is made into a variety of solutions, and the precursor obtained by drying it is subjected to calcination. Since the precursor system does not have a specific periodic structure, particles are grown by calcination and a large bulk (four) (nine) body is formed. It is difficult to fix the bulk tungsten oxide powder on the surface of the ceria nanostructure (a2). The present invention has been devised to control the growth of such a bulk. The following procedure has been found as a method of fixing particles of tungsten oxide (a3) to the cerium oxide nanostructure (a 2). The first method is a dispersion of the above-mentioned cerium oxide nanostructure (a2) (which may be a polymer present or may be removed by calcination and having dioxin as a main component). The acid salt (a 3) is used to adsorb the tungsten S salt (a3') in the cerium oxide nanostructure (&2) and then calcined at 9 Torr (TC below to oxidize tungsten (& 3) The particles are fixed in the yttrium oxide nanostructure (a2). The source of the oxidized stone and the tungsten oxide (a3) is obtained by dispersing the oxidized yttrium nanostructure (a2) in a medium (ie, When the tungstate (a3,)) is mixed in the medium, it is on the surface of the cerium oxide structure (a2) in the same manner as in the case of mixing the titanium oxide (a1), and the tungstate (a3, It is adsorbed and concentrated. When it is calcined in this state, the tungstate-20-201229161 U3') adsorbed on the surface becomes tungsten oxide (a3), and the growth of the sub-system is suppressed and becomes == this position 'So the granules are emulsified cranes (4) which can be used here-/size). It is a titanium oxide, and there is no special "Qing". It is determined by calcination of sodium sulphate, (4), etc., for example, it can be removed from the acid, and the calcination can also remove the relative ions. With the sharp point, it is better to use ammonium metatungstate, because the two fossils are stained with the main. α. % ^ , , the surface system has a large number of OH groups and is highly polar. Therefore, the origin of the second 查埤沐沐沐沐分散分散 ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( After dropping, dispersing the virtual state, double, raw, sputum, and sputum, remove by centrifugation, etc. , w 祀 know 4 Timing' can get the tungstate (a3) adsorption in the dioxide; g sin na. The powder on the surface of the lower, Ό U U2). As the use ratio of the sulphate (a 3,) 盥-oxygen/)--- 礼化矽 nanostructure (a2), it is a kind of tungsten oxide (a3) and simmered in the child The ratio of the latter bismuth nanostructure (a 2) is also g卩,,,,, and the ratio of the mass ratio expressed by (a3)/(a2) is 10/95 to 80/20. It is better to use the lost fly, preferably in the range of 30/60 to 50/50. The amount of the medium used when mixing the crane S salt (4)) and the second-oxide nanostructure (5) is not particularly limited, and is based on the total of the sulphate (a3, ) and the cerium oxide nanostructure (4). The mass is suitable in the range of 10 to 30 times by mass ratio. As the medium, in addition to the water alone, it may be an example of a person with a variety of hydrophilic organic solvents, and a six-way rabbit; for example, the Q/treat agent may, for example, be ethanol or 2-propanol. , acetone, etc. 21 - 201229161 When the tungstate (a3,) and the cerium oxide nanostructure U2) are mixed in a medium, a polyamine may be used in combination in order to make the adsorption more reliable. Namely, it is also possible to mix the tungstate (a3,) after mixing the polyamine in the dispersion of the cerium oxide nanostructure (a2) and adsorbing it. Examples of the polyamine include polyethyleneimine, polyallylamine, polyvinylamine, and polylysine. These may be used alone or in combination of two or more. The detailed method of the adsorption step of mixing the tungstate (a3 ') with the ceria nanostructure (a2) is not particularly limited, for example, after mixing at a certain ratio, by using it at room temperature (20 to 3 ( Rc) Stirring 丨~24 hours, sufficient physical adsorption. [Sintering step] Fine powder obtained by adsorbing the tungstate (a3,) in the cerium oxide nanostructure (&2) obtained above The body is heated and calcined, and the particles of the tungsten oxide (a3) can be fixed to the cerium oxide nanostructure (a2). The cerium oxide nanostructure () which has been removed from the internal polymer chain is heated and burned. When the temperature is in the temperature range of 3 5 0 to 90 ° C, the case where the polymer chain is present in the inside of the ceria nanostructure (a2) and the case of using the polyamine can be used simultaneously. For the purpose of removing organic matter such as hydrazine, it is preferable to carry out calcination at a temperature of 〇: η: or higher, and when the temperature exceeds 900 ° C, cerium oxide starts to melt, and the gasified smectite structure (a2) The structure has the possibility of collapse. Moreover, since tungsten oxide (a3) also has the possibility of particle growth, the upper limit of the normal firing temperature is 900 °C. The calcination time is usually 2 to 8 hours, and it is preferable to control the temperature rise by a program. For example, it is raised from room temperature to 3 Torr in 1 hour. (:, after •22-201229161, after 30 minutes of rising to 5〇〇t, it is better to keep it at this temperature for 3 hours, etc. Further, the heating and calcination process is carried out in an air environment. Preferably, it can also be carried out under an inert gas such as a nitrogen atmosphere. The content of the tungsten oxide (a3) after calcination depends substantially on the amount of the adsorbed tungstate (a3,), and can be in the range of 1 〇 8 The range of the mass % is adjusted. [Method for Producing Particles of Tungsten Oxide (a3), and Method for Producing Powder Using the Same] First, the particles of the tungsten oxide (a3) are adjusted to be physically adsorbed to the ceria After the nanostructure (a2) is fired, the particles of the tungsten oxide (a3) can be fixed to the cerium oxide nanostructure (a2). That is, the polymerization of the linear polyethyleneimine skeleton is performed. The object is combined in an aqueous medium, and an aqueous solution of the tungstate (a3,) is further mixed to obtain a precipitate obtained by associating a polymer with tungstic acid or a tungstate (a3,), and heating and calcining can be obtained. The particles of the oxidized crane (a3) are used in the same manner as described above. (1) The powder (A2) of the present invention can be obtained by adsorbing it in the ceria nanostructure (a2) and calcining it. The association of the above-mentioned polymer having a linear polyethylenimine skeleton is obtained. The method is the same as the method of obtaining the above-mentioned cerium oxide nanostructure (IV). After obtaining the association of the polymer, instead of the cerium oxide source, the source of the tungsten oxide (ie, the tungstate (4) is mixed under the aqueous medium, When)), a precipitate obtained by combining the polymer with tungstate (a 3,) or tungstic acid can be obtained. -23- 201229161 At this time, as the ratio of the use of the polymer to the tungstate (a3,) 'the molar ratio of the ethylimine unit to the tungstate (a3,) in the polymer is 95/5 to 20 The /80's Fanyuan' is better in terms of the fact that the combination of the two can be carried out reliably. Further, the mixture of the polymer and the tungstate (a3') is carried out in an aqueous medium, and the concentration of the polymer at this time is 0. 01~1〇. The range of 〇 mass % is better. The aqueous medium is preferably a mixed solvent of a hydrophilic solvent such as an alcohol and water, in addition to water alone, but it is necessary that the aggregate of the polymer does not dissolve or is not easily dissolved. Further, when an association of a polymer having a linear polyethylenimine skeleton is obtained, the form of the aggregate can be controlled by adding a metal ion or adding an organic acid or the like. The composite of a polymer having a linear polyethylenimine skeleton with tungstate (a3,) or tungstic acid is rapidly carried out to carry out a drop at room temperature (2 〇 to 30 ° C) 1 to 2 4 The range around the hour is suitable. The composite obtained in this manner is a precipitate. After the separation, the nanoparticles of tungsten oxide (a3) (particles having an average particle diameter of a nanometer order) can be obtained by heating and calcination. The heating calcination temperature is preferably 500 to 800 ° C. The calcination time is usually 2 to 8 hours, and the temperature rise is preferably controlled by a program. For example, it is preferable to raise it from room temperature to 3 ° C in 'hours' and then increase it to 50 in 30 minutes (after rc, it is preferable to keep it at this temperature for 3 hours, etc.), and the calcination process is heated. It is preferably carried out in an air atmosphere or in an inert gas such as nitrogen to leave the polymer. -24- 201229161 The tungstate (a3,) is precipitated by simple drying only The surface of the tungsten oxide (a3) obtained by the above method has a large surface area by the calcination s. Further, for example, even if the LED illumination light does not contain ultraviolet rays, photocatalytic activity is exhibited. The growth of the tungsten oxide is controlled by the self-organization effect of the polymer. The nanoparticle of the tungsten oxide (a3) obtained in this manner is fixed to the cerium oxide nanostructure in the same manner as described above ( A2) The photocatalytic action is further activated. The method for producing the powder (A2) of the ceria nanostructure (a2) by the tungsten oxide (a3) nanoparticle obtained as described above Basically with The same applies to the adsorption of the niobium oxide nanostructure (a2) by mixing the nanoparticle of tungsten oxide (a3) and the niobium dioxide nanostructure which are formed by the aforementioned method in an aqueous medium. A tungsten oxide (a3) nanoparticle; The ratio of the use of the rice plate is not particularly limited. When the former/the latter indicates that the mass is in the range of 95/10 to 20/80, the adsorption is rapid and the ratio is preferably better. The amount of the aqueous medium used in the mixing of the nanostructures (a2) and the oxidized cranes (the amount of the aqueous medium used in the mixing of the rice particles is not particularly high, and the total mass of the naphthalene relative to the solid content is suitably adjusted to be 1 〇 to 3 〇. 'As the medium, it may be water alone or a mixed solvent of an aqueous medium and water. In this case, as in the above, it is sufficient to promote adsorption by using a polyamine in combination. Also 25-201229161 as the aforementioned _ _ & An emulsified 矽 nanostructure (a2) and oxidation (a3) Mixing method of particles ^ ^ You> There are special restrictions, after mixing them in a certain ratio, 'wrong by Jiang Gan + —, recognize again to the temperature (20~30. 〇 stirring 1~24 Hour is sufficient 0 [calcination step] wrong by +;,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,, Calcination, it is possible to solidify the tungsten oxide (a3) such as 2 ma ' in the cerium oxide nanostructure (a2). Use p έτ, ''丄 to remove the internal polymer chain of SiO2结构愔、、、结构结构结构结构结构结构结构结构结构结构结构结构结构结构结构结构结构结构结构结构结构结构结构结构结构结构结构加热加热加热加热加热加热加热加热加热加热加热加热加热加热加热加热加热加热加热After, this, and. θ is also preferably calcined at a temperature of 6 〇 0 C or more for the purpose of simultaneously removing the polymer chain. Moreover, when the temperature exceeds 900 °C, the yv-emulsified enamel will start to melt, and the structure of the cerium oxide nanostructure (a2) may collapse, and because the oxidized crane (a3) also has The possibility of particle growth 'The upper limit of the calcination temperature is 900 ° C. The melon burning time is usually 2 to 8 hours, and it is better to control the temperature by the program. For example, it is raised from room temperature to 300 ° C in 1 hour, and then it is raised to 5 Torr in 30 minutes (rCi is preferably maintained at this temperature for 3 hours, etc., and is preferably carried out in an air atmosphere. The heating and calcining process is preferably carried out under an inert gas such as a nitrogen atmosphere. The content of tungsten oxide (a3) after melon burning is basically determined by the amount of tungsten oxide (a3) to be attached thereto. Range modulation of 1 〇 to 8 〇 mass% -26- 201229161 Powder (A2) containing tungsten oxide (a3) fixed with tungsten oxide (a3), tungsten oxide (a3) What kind of bonding interface is formed between the particles and the cerium oxide nanostructure (a 2), but it is not clear that the catalyst activity is not observed when the calcination treatment is performed, and it is presumed that tungsten oxide (a3) and two are The bonding interface of the cerium oxide nanostructure (a2) exhibits a pool effect of high excitation electrons, a light-in effect, and a concentration effect of an organic substance. [Photocatalyst function] The powder obtained by the above method (A1) ) or powder (A2) is a separate decomposition of organic matter It should be effective, and the light source to be used may be any of sunlight, fluorescent lamps, etc. In particular, the powder (A 2 ) obtained by combining tungsten oxide does not contain near ultraviolet rays (only contains The light of visible light is also responsive under the illumination of LED light, and its application range is wider than that of the previous photocatalyst in improving its activity. In the present invention, as a powder (A丨) or a powder ( The activity of A2) can be volatilized by allowing the powder to stand in a glass reaction vessel sealed with a certain concentration of volatile organic compound (VOC) gas and irradiating the reactor with visible light/LED light. The organic compound gas is estimated by the oxidative decomposition of the carbon dioxide concentration which changes with the light irradiation time. When the activity of the photocatalyst is measured by the above method, the concentration of the volatile organic compound used is 50 to 5 〇〇 ppm, and the amount of the powder having the catalytic action is relative to the volume of the reactor. A range of ~100mg/5 00mL is suitable. -27- 201229161 As the aforementioned volatile organic compound, it is possible to use a low-sorting early-right heart-in-heart system, and there is a special limitation, and an organic compound, for example, has a surface other than a low-molecular compound. Light, element, polymer, etc. can adhere to the photocatalyst to measure the organic color, and the photocatalyst activity can be measured, for example, by the color development of the halogen. The light irradiation time varies depending on the structure used by the Zhaozhao. The concentration of the organic substance used or its crucible is preferably in the range of 1 hour to 1 day. The source is ΞH: The powder of the oxidized crane is compounded (Α2) in the led light, ',, ^, Even if the light quantity is very low (for example, chamber (five) = quantity r°: ix or so), it can fully have heart = two: light; the moon's powder (ai), (a2) is containing ultraviolet rays such as gas. The lamp 'mercury lamp, (four) lamp, and rong=source all have the function as a photocatalyst. Therefore, the present catalyst, even if it is not the light and light of the county, is reflected and scattered in the sunlight or various light sources. The function of the strong energy. The inner light of the heart also has the light as Catalyst [Resin (poly) with a polyoxane skeleton]: A tree that is used as a point-in-time agent for a coating composition for a month: a resin with a polymetallic skeleton. It is preferable that a resin having a polyoxo-oxygen skeleton polymer bonded to a side chain of a part of a monomer residue of a polymer containing a (meth)acrylic acid S-based monomer is preferred. The resin (B) having such a structure is a product of the CERANATE series manufactured by DIC Co., Ltd., and it can also be published in accordance with Japanese Patent Publication No. Hei 10-365 No., JP-A-328354, and 67. The method disclosed in 742 was synthesized. -28- 201229161 For example, a hydrolyzable hydrazine compound containing a trialkoxyalkyl (phenyl) decane or a hydrolyzable hydrazine compound containing a dialkoxyalkyl (phenyl) decane described above and a dialkoxy group can be used. Hydrolytically condensing a mixture of hydrodecomposition hydrazine compounds of a dialkyl decane or a tetraalkoxy decane, and then having the obtained polyoxy siloxane having a hydroxyl group and/or a hydrolyzable group bonded to a ruthenium atom A dispersion of an aqueous resin obtained by subjecting a hydrolyzable decyl group and an acid group (mercapto) acrylic acid-based copolymer to a condensation reaction after partially or completely neutralizing the volatile compound to obtain a resin obtained by dispersing or dissolving the resin in water. Or solution. Alternatively, after the condensation reaction of the above polysiloxane, a (fluorenyl) acrylate copolymer having a hydrolyzable decyl group and an acid group, and other functional groups, a basic compound can be used for the partial 2 Or a dispersion or solution of an aqueous resin obtained by completely neutralizing the resin obtained by dispersing or dissolving the resin. More specifically, the synthesis method of the above aqueous resin (B) is characterized in that the side chain of a part of the monomer residue in the (meth) acrylate-based copolymer contains a functional group of a trialkoxy oxalate. a (meth)acrylic acid vinegar copolymer by a condensation reaction in which the copolymer of the tri-yard oxy group and the oxy group are mixed and hydrolyzed. The side chain is bonded to the polystone. As a specific example, the following reaction can be employed. 470 g of isopropanol was added to the reaction vessel, and the temperature was raised to 80 ° C under a nitrogen atmosphere. Then at the same temperature, 1 〇〇g styrene, 3 〇〇 methacrylic acid ", 334g n-butyl methacrylate, U6g acrylic acid, 3〇g 3-methyl propylene methoxy propylene Trimethoxy-oxanthene, acrylic acid -29-201229161 and 50g of 2-butylperoxy-hexanoic acid 2-ethyl ester mixed with 45〇g isopropanol and dripped to the front in the reaction vessel for 4 hours 47 〇 g of isopropanol. After the completion of the dropwise addition, the non-volatile content was obtained by stirring the crucible for 6 hours at the same temperature. A copolymer having 5% and a number average molecular weight of 1 〇〇〇〇〇c or more and having a carboxyl group and a trimethoxydecyl group. A mixture of the above 1480 g copolymer, 354 g of phenyltrimethoxynonane and 365 g of isopropyl alcohol was heated to _. Then, a mixture of 2_9 g of isopropyl phosphamate (is〇pr〇pyl acU phosphate) and 96 g of ion-exchanged water was dropped at the same temperature for 5 minutes, and stirred at the same temperature for 4 hours to form a resin containing a polyoxyalkylene structure. . Subsequently, 54 g of triethylamine and 1Q5 () g of ion-exchanged water were added dropwise at the same temperature for 30 minutes. Subsequently, the solvent (i.e., isopropanol) was removed by distillation under reduced pressure to give a nonvolatile content of 42. 3% of the water-based resin (B) is obtained by drying the resin (Β) after drying, and can be hardened only by drying at room temperature. Further, after being mixed with the f-oxyxanthene compound, it can be coated and dried. The coating film obtained by drying and hardening at room temperature exhibits strong weather resistance: for example, using a solar weathering tester, even if the exposure reaches 2, 〇〇〇 hours: inf: the film does not deteriorate and cracks are not generated and the surface glossiness can be obtained. It is understood that the above-mentioned aqueous resin (Β) can be suitably used as a binder resin as a photocatalyst. The lipid (two is used as a polyxanthene skeleton used in the present invention.疋Reactive energy ray-curable resin. As a result of the durability of the durable 'll-frame at this time', it is possible to obtain an ultraviolet curable resin which can form an excellent cured film, from 1 〇 to 95 mass -30 to 201229161 to 30 The range of ～75 mass% is preferably 30% by mass to 95% by mass. Such a resin (B) can be produced by various methods using the following (1) to (3). Method of manufacturing (1) pre-modulating a segment of a polymer containing a stanol group and/or a hydrolyzable decyl group and mixing the polymer segment, and having both a stanol group and/or a hydrolyzable ketone group and a polymerizable double A compound of a bond, a method of hydrolyzing a condensation reaction. Human (2) = first preparing a polymer segment containing a stanol group and/or a hydrolyzable decyl group. Further, it will have both a stanol group and/or a hydrolyzability.矽 : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : A polymer fragment, a 7-sintering compound having both a stanol group and/or a hydrolyzable group and a polymerizable double bond, and a method of performing a hydrolysis condensation reaction with polyoxetane. Reference (1) ( 3) The hydrolysis condensation reaction in the production step of the resin (Β) can be carried out by various methods, and it is preferable to carry out the reaction by supplying water and a catalyst because the production step is simple. And repeat the s stomach hydrolysis reaction It means that a part of the hydrolyzable group is hydrolyzed by the influence of water or the like to form a radical, and then a condensation reaction between the radicals or between a hydroxyl group and a hydrolyzable group is carried out. / or a polymer fragment of a hydrolyzable alkylene group, which can be used as an acrylic acid polymer having a decyl alcohol group and/or a hydrolyzable decyl group -31 - 201229161, a gas containing a stanol group and/or a hydrolyzable sulphur group. An olefinic flk compound, an ethylene-based polymer containing a sulphuric acid alcohol group and/or a hydrolyzable stone base, an aromatic vinyl polymer containing a stanol group and/or a hydrolyzable decyl group, and a decane containing decane An alcohol-based and/or hydrolyzable alkylene group-containing polyvalent fe XK compound or the like which contains a thiol alcohol group and/or a hydrolyzable oxime-based ethylene-based polymer, a stanol-containing group and/or a hydrolyzable decyl group. A polyamic acid S-based polymer, a polyester polymer containing a linalool group and/or a hydrolyzable decyl group, a polyether polymer containing a stanol group and/or a hydrolyzable decyl group, and the like. In particular, it is preferred to use a vinyl polymer containing a stanol group and/or a hydrolyzable alkylene group and a polyurethane polymer having a stanol group and/or a hydrolyzable decyl group to use a stanol group. And/or a hydrolyzable alkylene group acrylic polymer is more preferred. When an acrylic polymer is used as the polymer segment containing the oxime alcohol group and/or the hydrolyzable oxime group, the acrylic resin can be, for example, a vinyl group containing a stanol group and/or a hydrolyzable decyl group. The monomer is obtained by polymerization with other vinyl monomers as necessary. Examples of the vinyl group-based monomer having a stanol group and/or a hydrolyzable decyl group include vinyl trimethoxy decane, ethylene triethoxy oxane, and vinyl methyl dimethyl oxide. Base decane, vinyl tris(2-methoxyethoxy) decane, vinyl triethoxy decane, vinyl trichloro decane, 2-trimethoxy fluorenyl alkyl ethyl vinyl ether, 3 _ fluorenyl ) acryloxypropyltrimethoxy decane, 3-(meth) propylene methoxy propyl triethoxy decane, 3-(methyl) propylene oxypropyl decyl dimethoxy fluorene" , 3-((methyl) propylene methoxy propyl trichloro decane, etc. Among them, since the hydrolysis reaction is easy to carry out, and the by-product after the reaction is easily removed, vinyl trimethoxy decane '3-(meth) propylene It is preferably methoxypropyltrimethoxydecane. -32- 201229161 钕..., other vinyl-based monomeric acrylic monomers, and physically, for example, 苴田,八姐上, for example Examples include methyl (meth)acrylate, ethyl (meth)propionate, and (methyl)propionic acid n-propyl vinegar '(methyl)propene: acid =, (methyl) ) Isobutyl acrylate, third derivative of (meth)acrylic acid, 2-ethylhexyl (meth)acrylate, laurel vinegar of (meth)acrylic acid, etc. Alkyl (meth)acrylic acid alkyl vinegar 4 methacrylic acid vinegar, (methyl) acrylic acid 2 - styrene vinegar, etc. (methyl) propylene rare earth aryl sulphuric acid K methyl) acrylic acid (meth)acrylic naphthenic acid such as cyclohexanyl, (meth)acrylic acid isobutyl vinegar; (meth)acrylic acid 2-methoxyacetic acid, 4-methoxylated (meth)acrylic acid Ethyl oxyalkyl esters of (mercapto) acrylates such as esters; aromatic vinyl monomers such as ethylene, p-tert-butyl styrene, methyl styrene, vinyl toluene, etc.; ethyl acetate, C a vinyl carboxylate such as vinyl acetate, trimethyl vinyl acetate or vinyl benzoate; an alkyl ester of crotonic acid such as crotonate or ethyl crotonate; dinonyl maleate, cis Di-n-butyl esters of di-n-butyl succinate, succinic acid monomethyl sulfonium, dimethyl dimethyl sulphate, etc.; non-saturated dibasic acids such as ethylene, propylene, etc. (2-olefins; Difluoroethylene, Fluorinated feta of tetrafluoroethylene, hexafluoropropylene gas, diamethylene ethene, ethyl vinyl ether, n-butyl vinyl ether, etc.; cyclopentyl vinyl ether, cyclohexyl vinyl hydrazine, etc. Cycloalkyl vinyl ethers; ν, ν-dimethyl(fluorenyl) acrylamide, fluorenyl-(fluorenyl) propylene hydrazino, hydrazine-(fluorenyl) propylene decyl pyrrolidine, hydrazine-ethylene A monomer containing a tertiary amide group such as a pyrrolidone or the like. In the case of the above polymer segment, the vinyl polymer can be produced by, for example, polymerizing -33-201229161 by various polymerization methods such as a bulk radical polymerization method, a solution radical polymerization method, or a non-aqueous dispersion radical polymerization method. . When the wax (B) is dissolved in an organic solvent to form an ultraviolet curable resin composition, it is preferred that the vinyl monomer is subjected to radical polymerization in an organic solvent to obtain an ethylene-based polymer. The organic solvent may, for example, be an aliphatic or alicyclic hydrocarbon such as n-hexane, n-heptane, hexane, cyclohexane or cyclopentane; anthracene, diphenyl or ethylbenzene; Aromatic hydrocarbons; alcohols such as methanol, ethanol, n-butanol, ethylene glycol monodecyl ether, propylene glycol monodecyl ether, ethyl acetate, n-butyl acetate, n-amyl acetate, ethylene glycol Esters such as methyl mycoacetate, propylene glycol monodecyl ether acetate; ketones such as acetone, mercaptoethyl ketone, methyl isobutyl ketone, methyl n-amyl ketone, cyclohexanone, etc. a poly(alkylene glycol dialkyl ether) such as ethylene glycol dimethyl ether or diethylene glycol dibutyl ether; 1,2-dimethoxyethane, tetrahydrofuran, second hospital The ethers such as N-decylpyrrolidone, dimethylmercaptoamine, dimercaptoacetamide or ethyl acetate are used singly or in combination of two or more. Further, when the above-mentioned ethylenic monomer is polymerized by a radical polymerization method, a polymerization initiator can be used as necessary. As such a polymerization initiator, for example, 2,2,-azobis(isobutyronitrile), 2,2,-azobis(2,4·dimercaptophthalonitrile), 2,2,- can be used. Azo compounds such as azobis(2-amidylbutyronitrile); tert-butyl peroxytriacetate, tert-butyl peroxybenzoate, and tert-butylperoxy-hexanoic acid 2_ Ethyl ester, peroxide such as tert-butyl benzoate, cumene hydroperoxide or diisopropyl peroxycarbonate. As the first 500 to 200,000 polymer fragments, the polymer fragments having a number average molecular weight are preferred, and the number average molecular weight is -34 to 201229161 700 to 100, and the polymer fragment of ruthenium is more preferable. With a number average molecular weight of 1,000 to 5 Å, a polymer segment of ruthenium is particularly preferred. By using a polymer fragment having a number average molecular weight within such a range, it is possible to prevent sticking and gelation in the production of tree shrew (B), and to obtain an ultraviolet curable resin composition which can obtain a coating film excellent in durability. . By using a polymer segment having a polymerizable double bond group as a polymer segment constituting the resin (B) used in the present invention, it is possible to form a more durable cured coating film. The polymer fragment having a polymerizable double bond can be, for example, a compound having a polymerizable double bond and an epoxy group, such as glycidyl methacrylate, by using a polymer segment having an m group. The reaction is obtained. Examples of the decane compound having a decyl alcohol group and/or a hydrolyzable decyl group and a polymerizable double bond used in the above (1) include vinyl dimethoxy decane, vinyl trimethoxy sulfonium & , vinyl methyl dimethoxy money, ethylene tris(2-methoxyethoxy oxime, ethylene diethoxy decane, vinyl trioxane, 2 · trimethoxy decane 3-vinyl(meth)acryloxypropyltrimethoxy decane, 3_(methane) propylene oxypropyldiethoxy sulphur, sulfhydryl oxypropylpropyl A dimethyloxy group, a tris(methyl) acrylonitrile, or the like. As the above-mentioned money compound having a decyl alcohol group and/or a hydrolyzable decyl group and a polymerization, double bond, since the hydrolysis condensation reaction can be easily carried out, the by-product 16 after the reaction can be easily removed to use an alkenyl group. - methoxy sylvestre, 3 · (meth) propylene oxypropyl trimethoxy - 35 - 201229161 The decane compound used in the method (1) is used as necessary and has both a stanol group and / or a decane compound other than a hydrolyzable decyl group and a poly double bond decane compound. Examples of other decane compounds include methyltrimethyl decane, methyl diethoxy decane, methyl tri-n-butoxy decane, trimethoxy decane, and n-propyltrimethoxy. Various organic trialkoxy decanes such as decane, isobutyl trimethyl decane, cyclohexyl trimethoxy decane, phenyl trimethoxy decane, diethoxy decane; dimethyl methoxy decane, dimethyl di Oxydecane, dimethyl di-n-butoxide, diethyl dimethoxy decane, diphenyl dimethoxy decyl decyl dimethoxy decane or methyl phenyl dimethoxy decane Mono-alkoxy decane; methyl trioxane, ethyl trioxane, phenyl trichloro decane, vinyl trioxane, dimethyl di gas, monoethyl dioxane or diphenyl As the other decane compound such as chlorodecane, since the hydrolytic condensation reaction is easily carried out, the by-product by-product, the organic trisodium oxyalkylene or the diorganodialkoxy decane can be easily removed. good. Further, as the other decane compound, a 4-oxo-oxan compound or a tetra-functional alkoxy decane compound such as oxylybene, tetraethoxy decane or tetra-n-propoxy decane may be used in combination: Condensate. When the above-mentioned tetrafunctional alkoxydecane compound or a knife is used to hydrolyze the condensate, the amount of the oxime having the tetrafunctional alkoxy decane compound relative to the constituting the polyfluorene oxide sheet 〜矽 atom is not more than 20 mol%. The scope of the scope is better. Further, it is also possible to synthesize oxyethyloxyphenyldioxy, a variety of gas alkane oxime, and the tetramethyl functional moiety has a segment of -36-201229161. There are many sources of such a resin (B). a stanol (Si-OH) group derived from a polyoxyalkylene skeleton. The functional group can be dehydrated and condensed with the stanol group on the surface of the ceria when mixed with the ceria powder. This property is an important structural factor in the design of the photocatalyst coating film of the present invention. [Liquid type coating composition containing powder (A1) and/or powder (A2) and resin)] The one-liquid type coating composition of the present invention is obtained by mixing a powder (A 1) in a medium and / or the powder (a 2) and the resin (b) having a polyoxygen skeleton can be easily prepared; the powder (A) comprises fixing titanium nanoparticles (a) to the foregoing two a composite of the cerium oxide nanostructure (a2), and the shoal powder (A2) comprises a nanoparticle of tungsten oxide (a3) fixed to the aforementioned SiO2 structure (a 2) a composite body. When preparing the coating composition, the photocatalyst is first prepared by mixing the powder (A j) and/or the powder (A2) in a medium and mixing the mixture with a high shear dispersing device such as a homomixer. The dispersion of the powder is preferred. Subsequently, the dispersion obtained here is mixed with a dispersion or solution of the resin (B) and mixed by room temperature (2 〇 to 30 ° C:) for 1 to 3 hours to obtain a uniformly dispersed coating composition. Things. When the above coating composition is prepared, a solvent or the like used in the case of synthesizing the resin (B) and adjusting the dispersion or solution thereof can be mixed. The solid content content (nonvolatile content) of the powder (A 1) and/or the powder (a 2 ) and the resin (B) in the coating composition is in the range of 10 to 80% by weight. The time can be suitably used, and it is preferable to appropriately modulate it according to the use conditions and purpose. -37- 201229161 The total ratio of powder (A1) and powder (A2) to the ratio of the powder (A1) and/or the steroid (A2) and the tree (B) which are non-volatile components in the coating composition. The ratio of the use of the resin (B) to the above-mentioned resin (B) is preferably in the range of (2) 10/90 to 〇, and in order to increase the density of the surface of the photocatalyst active portion, the mass ratio is increased. The range of 3 5/65 to 65/35 is adjusted to be better. + The coating composition of the present invention can also be mixed with a pigment or a dye to form a coating. The amount of the pigment or the dye to be used can be adjusted in accordance with the color shade, and it is preferably 50% by mass or less of the resin (B). When the one-liquid type coating composition obtained as described above is left to stand for one day for a long time, the powder of the photocatalyst in the composition tends to settle, but the dispersion state is stable...: It is possible to maintain the number again, that is, ##总# °H, · and the system is not gelled when stored at room temperature for more than half a year. (4) Settling is formed, but the composition is completely gel-free, even after long-term storage [manufacturing of photocatalyst coating] b ° ^ ° . Any one: The liquid coating composition is applied to the Rensi substrate of any shape, and the straw is made to have a very ancient appearance in the season line, and the film is dried under the dish and irradiated with the film. /, there is a non-"first-catalyst ability and financial light to touch the above-mentioned coating composition in the substrate" can be appropriately applied in accordance with the application. Specially limited to bar coating, spin coating, brush, spray ', ' Method of 'scraping enough to brush, etc.., fog, stencil printing, gravure printing The film thickness of the coating film by using the above photocatalyst coating film is a range of photocatalyst 3 〇am formed by coating at i...0 仃It is suitable for: -38- 201229161 Enough in: / The photocatalyst coating film is applied to harden the coating film, can be hardened at this temperature (5 ~ hunger) ~ 2 (^ range. In the already ...:% ambient temperature hardening 'In fact, it is only made to dry and higher == Γ24: It is suitable. When heating and hardening, the shorter the temperature temple is, the range is from several minutes to several hours. Character:: The coating composition of ΐ明'Also can be mixed with various decaneization: a decane compound', for example, methyltrimethoxydecane didiethoxy sulphur, ethyltrimethoxy sylvestre, ethyltriethoxy: propyl:: n-propyl Trimethoxy-stone-burning 'n-propyltriethoxy-stone burning, :i: Methoxy alkane, isopropyl triethoxy oxane, 3-aeropropane: mercapto decane, 3-chloropropyl triethoxy decane, vinyl trimethoxy ethane ethylene triethoxy decane, 3-glycidoxypropyltris-germanium*, 3-glycidoxypropyltriethoxyxanthine, 3-aminopropyl::oxycarbazide, 3-aminopropyltriethyl Oxygen sulphur, 3_Hhenylthiopropyl 2: hydroxy, 3 thiol triethyl ketone, 3,3,3_trimethyl propyl-1-yl decane, 3,3,3· Trifluoropropyltriethoxydecane, 3-mercaptopropenyloxypropyltrimethoxydecane, 3-methylpropenyloxypropyltriethyl, decyl, phenyltrimethoxy decane, benzene Triethoxy bismuth, p-methyl phenyl trimethoxy decane 'p-methyl phenyl triethoxy decane, dimethyl dimethoxy decane, dimethyl diethoxy decane, two Ethyl dimethoxy decane, diethyl diethoxy oxane, etc. Further, a photopolymerization initiator may be added to the above coating composition and cured by irradiation of UV ', especially in a resin ( In the case of using a polymerizable double bond in B), The active energy ray hardening is preferred. At this time, the hardening process of the coating can also be carried out under an air atmosphere or an inert gas such as an air atmosphere. -39- 201229161 The foregoing composition is coated on the substrate and the surface of the I is just Although it has a concavo-convex structure, since the active site (the titanium oxide of titanium oxide and tungsten oxide adheres to the binder resin, that is, the resin (B), the photocatalyst is used as a film. In order to make it have a shoulder-shoulder The hardened coating film is irradiated with light, and the resin adhered by the niobium is decomposed by light irradiation. The method is not limited to a special light source, and is sufficiently exposed to the outdoor light in the outdoor or indoor environment. In the state, the function is illuminated for 1 hour. When the photocatalytic function of the coating film can be used to make the photocatalyst of the coating film appear after the natural day, it is also possible to use black light, a fluorescent lamp, a lamp, etc. when working. A high-pressure mercury lamp or a xenon lamp having a strong intensity of light irradiation time using these light sources is suitable for a period of 5 hours to 24 hours in which a sufficiently low intensity black light is used for 5 hours or more. [Photocatalyst coating film] ^ - 'Μ The photocatalyst active site is exposed on the surface: the cerium oxide nanostructure is implanted 〇: There is an octopus head (photocatalyst active site) stretching in the continuous layer of the coating film structure. The portion of the photocatalyst where the mr is applied to the top portion of the dioxonella structure (4) after the S1_〇r hardening is not present as a working force of the photocatalyst coating film - as the light irradiation portion in the photocatalyst active portion When the film is placed in the photocatalyst of the coating film which is not in the outdoor time, it is displayed for a few hours or I. If there is a need for a specific light high-pressure mercury lamp, the gas system depends on the light source lamp, etc. In the case of a light, the film, its basic structure supports its continuous layer that exposes the top. This is the base and adhesive tree that is exposed to the foot of the octopus. -40- 201229161 Fat is also the resin (B) & s

Si-〇_Si鍵，4 a &此基進行脫水縮合而形成相§於章备屈都的—好，，係與黏合劑層点'、、、虱化矽奈米結構體（U) ，其特徵在趴工Μ。因此’在本發明的光觸媒塗獏鍵結。於：全部的構成成分（光觸媒及樹脂）係化學 2〜50" m的範、基材密著性 5〜2 0 /z m為佳月的光觸媒塗膜的厚度係能夠< 圍调製。A 了提升光觸媒塗膜的觸媒活,f 、塗膜耐候性等，u將塗膜的厚度調製肩又’亦能夠使本發明的光觸媒塗膜為著色狀態。著係以顏料或染料被埋入塗膜的黏合劑樹佳。該狀態時，因為色素成分不會與露出頂部的光觸： :I·生。P位接觸而呈分離之狀態，不會因光觸媒(氧化鈦和氧化鎢）而產生分解。本發明的光觸媒塗膜之表面係包含凹凸結構，其露出頂部的凸部係親水性無機成分的Ti〇2/si〇2、w〇3/Si〇 ’其係擴展至膜表面全面。因此，其特徵在於：表面係對水容易濕潤、即便水滴落下亦會濕潤擴展至膜表面且保持水接觸角為5 °以下的狀態。亦即，顯示超親水性。本發明之顯示超親水性的光觸媒塗膜係能夠有效地將揮發性有機化合物（VOC)分解成為二氧化碳。揮發性有機化合物係在室外或室内自然光被分解，又，即便榮光燈、LED的照明用燈下亦會被分解。使用特定光源時，高壓水銀燈、氙燈、鹵素燈、黑光照射下，揮發性有機化合物（有害氣體）能夠有效地分解。 -41 - 201229161 [實施例] 以下，藉由實施例及參考例而更具體地說明本發明 ’但是本發明係不被該等限定u未特別地預先告知 ’ 「％」係表示「質量％」。 [氧化鈦及水性樹脂] 在本貫施例作為氧化鈦(al)，係使用日本股份公司製P25[以下，稱為氧化鈦⑷」）]。作為水性之具有聚矽氧烷骨架樹脂（B)，係使用DIC股份公司製 CERANATE WSA_1070(以下，稱為樹脂（b i)。 [掃描型電子顯微鏡] 掃描型電子顯微鏡係使用KEYENCE製的VE_98〇〇。 [UV-vis反射光譜] UV-vis反射光瑨係使用〇cean〇ptics製的分光器、DH-2000燈。 [X射線繞射法（XRD)l 將試料載置在測定用保持器且將其安裝在Rigaku股份公司製廣角X射線繞射裝置「Rint_ultma」，而且以 Cu/Κα線、40kV/30mA、掃描速度丄〇。/分鐘、掃描範圍 20〜40°的條件進行。 [使用透射型電子顯微鏡之結構觀察] 透射型電子顯微鏡係使用J.EOL製的TEM2200FS，且以電壓20〇keV的條件進行。 [使用BET法之比表面積測定] 比表面積測定係使用SHIMADZU製的TriStar且使用BET法進行。又，孔徑分布係從孔體積分率對孔徑的繪圖進行估計。 -42- 201229161 [藉由榮光x射線光譜測定氧化鈦/氧化鎢含量] 營光X射線測定係使用Rigaku股份公司製的ZSX 而在真空條件下進行。 [光觸媒活性評價] 光觸媒活性係從在氣相反應之乙醛的氧化分解反應之一氧化碳產生量的時間變化進行評價。乙醛氣體係在模擬太％光黑光照射下為使用500ppm、瑩光燈照射下為使用200ppm而進行。粉體狀的光觸媒係使用〇 ^，光觸媒塗膜係使用10cm2的大小者，且以封入5〇〇mL的玻璃製反應器之狀態進行照射光線。光量係模擬太陽光 (SOLAX SET-140F)為使用約 10,0001x、黑光（Panas〇nic 製FL10BL-B)為使用約uoou、螢光燈（Panas〇nic製 FL-10D)為使用約6000 lx而進行。LED照明係使用東芝股份公司製E-CORE LEL-BR9N-F型，在約20,0Ό01χ照射下進行。又，二氧化碳產生量係使用四氫吱σ南製的管路將 INNOVA 公司的光音響 Multi-Gas Monitors 13 12.型連接至光反應器而調查。關於塗膜表面的光觸媒防污功能性，係藉由通常光觸媒塗膜防污評價經常被使用之亞曱基藍色素（東京化成製）的脫色反應速度試驗來評價。所使用的亞曱基藍試驗液的濃度為30ppm ’在光觸媒塗膜上滴下一滴且自然乾燥後在螢光燈照射下進行評價。螢光燈的光量係使用約6,0 0 0 1 X而進行。關於光觸媒塗膜的超親水性功能評價，係藉由在塗膜形成後’進行照射黑光1 2小時來將黏附在凸部光觸媒 -43- 201229161 活性部位的樹脂成分除去之後，在暗處靜置約2星期，隨後觀察伴隨著螢光燈（光暈約6,〇〇〇丨χ)照射時間之水接觸角的降低來進行。合成例1[二氧化矽奈米結構體（a2-l)及（a2-2)的製造] 依照在專利文獻（特開2005-264421號公報、特開 2005-336440號公報、特開2〇〇6_〇63〇97號公報、特開 2007-05 1 056號公報特開平號公報）所揭示之方法來製造二氧化石夕奈米結構體。〈線狀聚乙亞胺（PK5)的合成> 使5 g市售的聚乙基嘮唑啉（數量平均分子量為 ’(^，(^(^平均聚合度為^⑽^八^^仏公司製^容解於 2〇ml之5M的鹽酸水溶液。使用油浴將該溶液加熱至 C且在。亥/皿度搜拌1 〇小時’在反應液添加$ 〇爪l丙酮來使聚合物完全沈澱，而且將其過濾且使用甲醇洗淨3 -人’1來付到白色的聚乙亞胺的粉末。將所得到的粉末使用H-NMR (重水）進行鑑定時，能夠確認源自聚乙基噚 $啉的側鏈乙基之尖峰i 2ppm(CH3)& 2 3ppm(CHj係完全消失。亦即，顯示聚乙基嘮唑啉係完全被水解且變換成為聚乙亞胺。將該粉末溶料5mL的蒸潑水且㈣拌、邊在該溶、八滴下1 5 %的氨水。將該混合液放置一晚之後，將沈殿的氣末過渡且使用冷水洗淨該粉末3次。將洗淨後的粉末在乾燥器於室溫（25。〇乾燥，來得到線狀的聚乙亞胺（ρ5κ) 。產量為4.5g(含有社曰士、 # ^ ^ 3令、、° Β曰水）。藉由聚乙基噚唑啉的水解所 :到的聚乙亞胺係只有側鏈進行反應，而主鏈係沒有變化因此Ρ5Κ的聚合度係與水解前的5，綱同樣。 -44- 201229161 <二氧化矽奈米結構體的合成> 在蒸餾水中混合一定量的P5K，將其加熱至9〇°C來得到透明溶液之後’調製成為整體為3 %的水溶液。將該水溶液自然冷卻至室溫（2 5 °C )，來得到雪白之p 5 K的締合體之分散液。邊授拌邊在10 OmL該締合體分散液中，添加70mL的TMOS(四甲氧基矽烷）的乙醇溶液（體積濃度為50%) ’且在室溫繼續撥拌1小時。藉由過遽析出的沈澱物，將其使用乙醇洗淨3次之後，於4〇t加熱下進行乾燥來得到1 5g粉體。將所得到之粉體的SEM照片顯示在第1圖。粉體係將奈米纖維設作基本單元，確認了其係成為束狀的結構。將其設作二氧化矽奈米結構體 (a2-1)。從在此所得到之二氧化矽奈米結構體（a2-1)的熱重量損失分析（SII. Nano Technology Inc 公司製的 TG/DTA6300)，確認聚合物含量為7wt%。又，進行比表面積測定（Micrometries公司製Flow Sorb II 2300)之結果，為 1 12m2/g。 <藉由加熱煅燒之二氧化矽奈米結構體（a2-2)的製造> 藉由將前述所得到之聚合物與二氧化矽的複合體亦即二氧化矽奈米結構體（a2-l) ’於600°C煅燒1小時，來得到已除去聚合物成分之二氧化矽奈米結構體。將煅燒後之二氧化矽奈米結構體的SEM照片顯示在第2圖。所得到的二氧化矽奈米結構體係即便在煅燒處理亦未觀察到形狀的變化等，確認了係包含二氧化矽之奈米纖維的締合體。又，進行比表面積測定之結果，為3 1 5m2/g。將上述所得到的粉末設作二氧化矽奈米結構體（a2-2)。 f -45 - 201229161 合成例2[二氧化矽奈米結構體（a2-3)及（a2-4)的製造] 與合成例1的 <直鏈狀聚乙亞胺的合成 >之前段同樣地進行聚乙基嘮唑啉的水解’來得到直鏈狀聚乙亞胺的鹽酸鹽。將5g該鹽酸鹽溶解於90mL的蒸館水，邊攪拌邊在該溶液混合29.5mL之i.4m〇l/L的氨水溶液。藉由將該混合液攪拌12小時之後，再次將i2.5mL之i.4mol/L 的氨水溶液每隔1 0小時分成5次滴下，隨後進行檀拌1 小時來得到白色的沈澱物。使用離心分離將析出的沈澱物洗淨3次。將洗淨後所得到的粉末分散在1 2〇mL的蒸德水中。在該分散液中’添加15mL的矽酸甲酯（MS51) ’且於室溫下（2 0〜2 5 C )授拌4小時《藉由將反應溶液使用離心分離處理，且使用甲醇洗淨析出的固體含量之後 ’於室溫乾燥來得到包含聚乙亞胺與二氧化矽之複合體。產量：9.7g。第3圖係顯示所得到的複合體的SEM照片。能夠確認係具有奈米層片（n a η 〇 s h e e t)的結構之聚集體。從XRD能夠觀察到源自直鍵狀聚乙亞胺的結晶體之尖峰。將其設作二氧化矽奈米結構體（a2_3)。 <藉由加熱煅燒之二氧化矽奈米結構體（a2-4)的製造> 將0_5g在前述步驟所得到之奈米層片狀的二氧化石夕奈米結構體（a 2 - 3)添加至氧化紹掛禍，且在電爐内將其锻燒。爐内溫度係以1小時上升至8 0 0。(：且在該溫度保持2 小時。將其自然冷卻且除去聚合物成分，來得到粉末。在此所得到之粉末的比表面積係3 1 9.0m2/g。第4圖係顯示SEM觀察之影像照片。奈米層片係重疊且結構係8〇〇 °C煅燒後亦沒有變化。將該奈米層片的聚集體亦即粉末設作二氧化矽奈米結構體（a2-4)。 -46- 201229161 合成例3[二氧化矽奈米結構體（&2_5)及（32_6)的製造] <聚乙亞鹽酸鹽水溶液的調製、結晶化、複合奈米纖維的合成> 與合成例1的<直鏈狀聚乙亞胺的合成>的前段同樣地進行聚乙基唑啉的水解，來得到直鏈狀聚乙亞胺的鹽酸鹽。將5g該鹽酸鹽溶解於6〇mL的蒸餾水且邊攪拌、邊在該溶液滴下10mL之5m〇1/L的氫氧化鈉溶液。該混合液的pH係9.0。將該混合液攪拌4小時之後，將析出的締合體離心分離且進行洗淨3次。將洗淨後的粉末分散至50〇mL的蒸餾水中。在此時點之分散液的值為在，、刀月欠液中添加5 ·mL的矽酸甲酯（MS 5 1)，且於室溫下（20〜25。〇授拌i小時。藉由將反應液使用離心分離處理，且將析出的固體含量使用水洗淨之後，在室二乾燥，來得到包含聚乙亞胺與二氧化石夕之複合體。匕.10.8g。$ 5圖係顯示所得到的複合體的隨照片夠確認係纖維係、圓盤狀地聚集而成之結構。從刪 ^規察到源自直鏈狀聚乙亞胺的結晶體之#峰。將其没作一氧化矽奈米結構體（a2_5)。 <奈米管狀的二氧化石々太伞纟士槐触, 礼化矽奈未結構體（a2-6)的製造〉 lOmL的甲二t述所付到的二氧化妙奈米結構體(a2_5)在 lOmL的曱醇中浸潰 ^ 0 « , 夺後匕濾且在室溫使固體含量二二二部的直鏈狀聚乙亞胺係溶解且被將其包 :心；Π内表面吸附，能夠得到纖維的編失广二氧切奈米結構體㈣。將 m㊉奈米結構體（心）使用於表面分析測 -47- 201229161 疋BET表面積係286m2/g。骆甘裝顯干扁笛 < 將其專溫線及孔分布各自頁不在第6及7圖。從孔徑分你巷 a_ 布的、、、°果，在孔徑為3.5nm 位置’顯現尖銳的尖峰。該斗％峰值係正好反映管内徑尺寸。從孔徑為2nm開始增大，. 降柄。、-β 在4nm以下經過尖峰值而降低适疋強烈地暗示該纖 « ^ 戮、、隹狀的二氧化矽中，係形成規則的中空結構、亦即管道。〜产又，攸TEM觀察，能夠確 ⑽祖度為12ηηι以下之筆吉μ 甘# 丄韋直延伸的纖維係緊密地重疊，其係形成層片，而且纖維的中、 .β 幻中〜。Ρ係顯現透明（第8圖）。亦即，中心部係空洞且其网杬為3〜4nm。從熱分析，重篁扣失為25.3wt%。 <藉由二氧化矽奈米結構體（a2 結構體（a2-7)的製造> -6)的煅燒之二氧化矽奈米將〇.5g在前述步驟所得到之奈米管狀的複合體亦即二乳切奈米結構體⑽6)添加至氧化㈣堝，且在電爐内將其锻燒。爐内溫；^W + 盈Μ，凰度係以1小時上升至80(TC且在該溫度保持2小時。將1自炒、人” ^竹具自然冷邯且除去聚合物成分，來得到粉末。在此所得到之粉末的比表面積係418m2/g。該粉末的等溫線及孔徑分布係各自顯示在第9 & 1〇圖。從孔徑為 2nm降低’從3nm附近增大且尖峰值後再降低。這正好反映官内徑尺寸。又，第丨丨圖係顯示tem觀察之影像照片。奈米纖維的重疊結構係8〇〇t煅燒後亦沒有變化。在孔徑分布之中空尺寸（4 2nm)係與在TEM觀察的内徑（4nm)大約一致。將該奈米管狀的粉末設作二氧化矽奈米結構體（a2-7)。 -48- 201229161 [氧化鎢的粒子之製造] 合成例4<使用直鏈狀聚乙亞製造〉錢鶴U3])的粒子之使〇.43g前述合成例}所得到之粉末懸浮在100m!的蒸餾水，且於8〇它 ' 私的其溶解。確認聚合物溶解之後，於室溫（2Q〜饥=來使置冷卻30分鐘，來得到以奈米纖維( )進仃靜亞胺的沈澱物。在所得到之沈澱物的水：散二之聚乙Si-〇_Si bond, 4 a & This base undergoes dehydration condensation to form a phase-like bond, which is good, and the binder layer layer ',,, and bismuth telluride nanostructure (U) , its characteristics are in the work. Therefore, the photocatalyst of the present invention is bonded. In all the constituents (photocatalyst and resin) are chemical 2~50" m, substrate adhesion 5~2 0 /z m is good. The thickness of the photocatalyst coating film can be adjusted. A. The catalyst activity of the photocatalyst coating film is improved, f, the weather resistance of the coating film, etc., and the thickness of the coating film is adjusted to the shoulder. The photocatalyst coating film of the present invention can also be colored. It is good to use a binder in which a pigment or a dye is embedded in a coating film. In this state, because the pigment component does not touch the light at the top: :I·sheng. The P site is in a separated state and is not decomposed by the photocatalyst (titanium oxide and tungsten oxide). The surface of the photocatalyst coating film of the present invention contains a concavo-convex structure in which the top portion of the convex portion is a hydrophilic inorganic component of Ti〇2/si〇2, w〇3/Si〇' which extends to the entire surface of the film. Therefore, it is characterized in that the surface is easily wetted by water, and even if the water drops, it spreads to the surface of the film and maintains a water contact angle of 5 ° or less. That is, it shows super hydrophilicity. The photocatalytic coating film exhibiting superhydrophilicity of the present invention can effectively decompose volatile organic compounds (VOC) into carbon dioxide. Volatile organic compounds are naturally decomposed outside or indoors, and even under the illumination of glory lamps and LEDs. When a specific light source is used, volatile organic compounds (harmful gases) can be effectively decomposed under high-pressure mercury lamps, xenon lamps, halogen lamps, and black light. -41 - 201229161 [Embodiment] Hereinafter, the present invention will be described more specifically by way of examples and reference examples. However, the present invention is not limited by the above, and the "%" indicates "% by mass". . [Titanium oxide and water-based resin] In the present embodiment, as the titanium oxide (al), P25 (hereinafter referred to as "titanium oxide (4)")) manufactured by Nippon Co., Ltd. was used. As a water-based polysiloxane catalyst (B), CERANATE WSA_1070 (hereinafter referred to as resin (bi)) is used. [Scanning Electron Microscope] The scanning electron microscope uses VE_98 manufactured by KEYENCE. [UV-vis reflection spectrum] The UV-vis reflection beam system uses a spectroscope manufactured by 〇cean〇ptics and a DH-2000 lamp. [X-ray diffraction method (XRD) l The sample is placed on the measurement holder and This was mounted on a wide-angle X-ray diffraction device "Rint_ultma" manufactured by Rigaku Co., Ltd., and was carried out under conditions of Cu/Κα line, 40 kV/30 mA, scanning speed 丄〇·/min, and scanning range of 20 to 40°. Observation of the structure of the electron microscope] The transmission electron microscope was performed using TEM2200FS manufactured by J.EOL under the conditions of a voltage of 20 〇 keV. [Measurement of specific surface area by BET method] The specific surface area was measured using TriStar manufactured by SHIMADZU. The BET method is performed. Further, the pore size distribution estimates the pore size from the pore volume fraction. -42- 201229161 [Measurement of titanium oxide/tungsten oxide content by glory x-ray spectroscopy] Campography X-ray measurement system uses Ri ZSX manufactured by Gaku Co., Ltd. was carried out under vacuum conditions. [Photocatalyst Activity Evaluation] Photocatalyst activity was evaluated from the time change of the amount of oxidized carbon produced by the oxidative decomposition reaction of acetaldehyde in the gas phase reaction. The acetaldehyde gas system was simulated too. % light black light irradiation is performed using 500 ppm, and irradiation with a fluorescent lamp is 200 ppm. The powder photocatalyst is 〇^, and the photocatalyst coating film is 10 cm2, and it is made of glass of 5 〇〇mL. The state of the reactor is irradiated with light. The amount of light is simulated sunlight (SOLAX SET-140F) is about 10,0001x, black light (FL10BL-B by Panas〇nic) is used for about uoou, fluorescent lamp (FL by Panas〇nic) -10D) was carried out for about 6000 lx. The LED lighting was carried out using Toshiba Co., Ltd. E-CORE LEL-BR9N-F type, and it was irradiated at about 20,0Ό01χ. In addition, the amount of carbon dioxide produced was tetrahydroanthracene. The system was investigated by connecting INNOVA's Optical Acoustic Multi-Gas Monitors 13 12. to the photoreactor. The photocatalyst antifouling function on the surface of the coating is evaluated by the usual photocatalyst coating. It is evaluated by the decolorization reaction rate test of the used fluorenyl blue pigment (manufactured by Tokyo Chemical Industry Co., Ltd.). The concentration of the sulfhydryl blue test solution used is 30 ppm. 'A drop is dropped on the photocatalyst coating film and naturally dried. Evaluation was carried out under lamp irradiation. The amount of light of the fluorescent lamp is performed using about 6,0 0 0 1 X. The super-hydrophilic function evaluation of the photocatalyst coating film was carried out in the dark after removing the resin component adhering to the active portion of the convex photocatalyst-43-201229161 by irradiating the black light for 12 hours after the formation of the coating film. About 2 weeks, it was followed by observation of a decrease in the contact angle of water accompanying the irradiation time of the fluorescent lamp (halo about 6, 〇〇〇丨χ). Synthesis Example 1 [Production of cerium oxide nanostructures (a2-l) and (a2-2)] [Patent Document No. 2005-264421, JP-A-2005-336440, JP-A-2002 A cerium oxide structure is produced by the method disclosed in Japanese Laid-Open Patent Publication No. Hei. No. 2007-05 No. 056-A. <Synthesis of linear polyethylenimine (PK5)> 5 g of commercially available polyethyloxazoline (number average molecular weight is '(^,(^(^ average degree of polymerization is ^(10)^八^^仏) The company made a solution of 2M ml of 5M hydrochloric acid in water. The solution was heated to C using an oil bath and mixed at 1 hr for 1 hr. The powder was completely precipitated, and it was filtered and washed with methanol to wash the white polyethylenimine powder. When the obtained powder was identified by H-NMR (heavy water), it was confirmed that it was derived from poly The peak of the side chain ethyl group of ethyl hydrazine porphyrin i 2 ppm (CH3) & 2 3 ppm (CHj system completely disappeared. That is, it was shown that the polyethyl oxazoline system was completely hydrolyzed and converted into polyethyleneimine. The powder solution was sprayed with 5 mL of steamed water and (4) mixed, and 15% of ammonia water was dissolved in the solution. After the mixture was allowed to stand overnight, the air was transferred to the end of the chamber and the powder was washed three times with cold water. The washed powder was dried in a desiccator at room temperature (25 ° , to obtain linear polyethylenimine (ρ5κ). The yield was 4.5 g (containing a gentleman, # ^ ^ 3令,, °Β曰水). By the hydrolysis of polyethyloxazoline: the polyethyleneimine system has only the side chain reaction, but the main chain system does not change, so the polymerization degree of Ρ5Κ -4 - 201229161 <Synthesis of cerium oxide nanostructures> A certain amount of P5K was mixed in distilled water and heated to 9 ° C to obtain a transparent solution. The aqueous solution was 3% in total. The aqueous solution was naturally cooled to room temperature (25 ° C) to obtain a dispersion of the white complex of p 5 K. The mixture was mixed in 10 mL of the dispersion of the association. Add 70 mL of TMOS (tetramethoxydecane) in ethanol (50% by volume)' and continue to mix for 1 hour at room temperature. Wash the precipitate by using sputum and wash it 3 times with ethanol. Thereafter, the mixture was dried under heating at 4 Torr to obtain 15 g of a powder. The SEM photograph of the obtained powder is shown in Fig. 1. The powder system was set as a basic unit, and it was confirmed that the ray was bundled. The structure is set as a cerium oxide nanostructure (a2-1). From the dioxin obtained here The thermal weight loss analysis of the 矽 nanostructure (a2-1) (SII. TG/DTA6300, manufactured by Nano Technology Inc.) was confirmed to have a polymer content of 7 wt%. Further, the specific surface area was measured (Flow Sorb II manufactured by Micrometries Co., Ltd.). The result of 2300) is 1 12 m 2 /g. <Production of the calcined cerium oxide nanostructure (a2-2) by heating> by the composite of the above-obtained polymer and cerium oxide That is, the cerium oxide nanostructure (a2-l)' was calcined at 600 ° C for 1 hour to obtain a cerium oxide nanostructure having a polymer component removed. A SEM photograph of the calcined cerium oxide nanostructure is shown in Fig. 2. In the obtained cerium oxide nanostructure system, no change in shape was observed even after the calcination treatment, and an association of nanofibers containing cerium oxide was confirmed. Further, as a result of measuring the specific surface area, it was 3 1 5 m 2 /g. The powder obtained above was used as a cerium oxide nanostructure (a2-2). f -45 - 201229161 Synthesis Example 2 [Production of cerium oxide nanostructures (a2-3) and (a2-4)] Synthesis of <linear polyethylenimine of Synthesis Example 1 > The hydrolysis of polyethyloxazoline was carried out in the same manner to obtain a hydrochloride of a linear polyethylenimine. 5 g of this hydrochloride was dissolved in 90 mL of steamed water, and 29.5 mL of an aqueous solution of i.4 m〇l/L was mixed in the solution while stirring. After the mixture was stirred for 12 hours, i2.5 mL of an aqueous solution of i.4 mol/L of ammonia was again dropped into 5 times every 10 hours, followed by sandalwood mixing for 1 hour to obtain a white precipitate. The precipitated precipitate was washed 3 times using centrifugation. The powder obtained after washing was dispersed in 12 mL of distilled water. Add '15 mL of methyl decanoate (MS51)' to the dispersion and mix for 4 hours at room temperature (20 to 2 5 C) by washing the reaction solution using centrifugation and washing with methanol. The precipitated solid content is then dried at room temperature to obtain a composite comprising polyethyleneimine and cerium oxide. Yield: 9.7 g. Fig. 3 is a SEM photograph showing the obtained composite. It is possible to confirm an aggregate having a structure of a nano layer (n a η 〇 s h e e t). From the XRD, a sharp peak derived from a crystal of a direct-bonded polyethyleneimine can be observed. This was designated as a cerium oxide nanostructure (a2_3). <Production of the calcined cerium oxide nanostructure (a2-4) by heating> 0-5 g of the nanocrystalline sheet-shaped cerium oxide yttrium structure obtained in the above step (a 2 - 3) ) It is added to the oxidation slag and burned in an electric furnace. The furnace temperature rose to 800 in 1 hour. (: and kept at this temperature for 2 hours. The powder was naturally cooled and the polymer component was removed to obtain a powder. The specific surface area of the powder obtained herein was 3 1 9.0 m 2 /g. Fig. 4 shows an image of SEM observation. Photographs: The nanolayer sheets overlap and the structure is unchanged after calcination at 8 ° C. The aggregate of the nano layer sheets, that is, the powder, is used as the cerium oxide nanostructure (a2-4). 46-201229161 Synthesis Example 3 [Production of cerium oxide nanostructures (& 2_5) and (32_6)] <Preparation and crystallization of polyethyl amide aqueous solution, synthesis of composite nanofibers> The hydrolysis of the polyethyloxazoline was carried out in the same manner as in the synthesis of <linear polyethylenimine of Synthesis Example 1 in the same manner to obtain a linear polyethylenimine hydrochloride. 5 g of the hydrochloride was obtained. After dissolving in 6 mL of distilled water and stirring, 10 mL of a 5 m 〇 1 /L sodium hydroxide solution was added dropwise to the solution. The pH of the mixed solution was 9.0. After the mixture was stirred for 4 hours, the precipitate was precipitated. The mixture was centrifuged and washed three times. The washed powder was dispersed in 50 mL of distilled water. The value of the dispersion is 5 mL of methyl decanoate (MS 5 1) added to the yoke solution, and it is mixed at room temperature (20 to 25 Torr for 1 hour. By using the reaction solution) The mixture was centrifuged, and the precipitated solid content was washed with water, and then dried in a chamber to obtain a complex comprising polyethyleneimine and sulphur dioxide. 1.10.8 g. $5 shows the obtained The structure of the composite was confirmed to be a structure in which the fiber system or the disk was aggregated. The #峰 of the crystal derived from the linear polyethylenimine was observed from the ruthenium. Rice structure (a2_5). <Nano-tubular dioxide, 々太伞纟士槐, manufacture of 礼化矽奈未结构(a2-6)〉1OmL The nucleus structure (a2_5) is impregnated in 10 mL of sterols ^ 0 « , and the linear polyethylenimine series having a solid content of 22 parts is dissolved and packaged at room temperature. :Heart; adsorption on the inner surface of the crucible, the fiber can be obtained by the loss of the dioxane structure (4). The m ten nanostructure (heart) is used for surface analysis-47-2012291 61 疋 BET surface area is 286m2 / g. Luo Gan installed the dry flat flute < The temperature line and the hole distribution of each page are not in Figures 6 and 7. From the aperture, you divide the a_ cloth, ,, ° fruit, in The hole diameter is 3.5nm. The position shows a sharp peak. The peak value of the bucket reflects the inner diameter of the tube. It increases from the hole diameter of 2nm. The shank decreases. -β decreases below 4nm and the peak value is strong. In the fiber « ^ 戮, 隹-shaped cerium oxide, a regular hollow structure, that is, a pipe is formed. ~ Production, 攸 TEM observation, can be sure (10) the ancestor is 12ηηι below the pen ji y Gan # 丄 Wei straight stretched fiber system closely overlaps, it is formed into layers, and the fiber of the middle, .β illusion ~. The tethered system appears transparent (Fig. 8). That is, the center portion is hollow and its mesh is 3 to 4 nm. From the thermal analysis, the weight loss was 25.3 wt%. <The calcined cerium oxide nanoparticle by the cerium oxide nanostructure (manufacturing of the a2 structure (a2-7)> -6) 〇. 5g of the nano tubular composite obtained in the aforementioned step The body, i.e., the di- cleavage nanostructure (10) 6), is added to the oxidized (tetra) oxime and calcined in an electric furnace. The temperature inside the furnace; ^W + surplus, the phoenix rises to 80 (TC at 1 hour and keeps at this temperature for 2 hours. 1 self-frying, human" bamboo is naturally cooled and the polymer component is removed. The powder obtained herein has a specific surface area of 418 m 2 /g. The isotherms and pore size distributions of the powders are each shown in the 9th & 1 。 diagram. The decrease from the pore size of 2 nm 'increased from the vicinity of 3 nm and the peak After the value is lowered, this reflects the size of the official inner diameter. In addition, the second image shows the image of the tem observation. The overlapping structure of the nanofibers is not changed after 8 〇〇t calcination. (4 2 nm) is approximately the same as the inner diameter (4 nm) observed by TEM. The nano-tubular powder is used as the cerium oxide nanostructure (a2-7). -48- 201229161 [Particles of tungsten oxide Manufacture] Synthesis Example 4 <Production using Linear Polyethylene> Particles of Qianhe U3]) The powder obtained by the above-mentioned Synthesis Example} was suspended in 100 m of distilled water, and it was private. It is dissolved. After confirming that the polymer is dissolved, it is allowed to cool for 30 minutes at room temperature (2Q~Hungry= In the nanofiber () into the Ding static imine precipitate in water of the resulting precipitate: two of polyethylene dispersion

㈤偏鶴酸館水溶液(曰本無機化學工業股份公= NV. 50%水溶液）且攪拌工小時。 I 。將已乾燥的粉末在空二=〇C使其乾燥12小時轧％士兄7使用電爐以30分鐘從室溫加熱至3〇〇°d3〇〇t/1小時保持後，進而以3〇分鐘升溫至_C且在該溫度保持3()分鐘後，自然冷卻。使用SEM調查在此所得到粉末的表面，確認係'⑽… 下之氧化鶴的粒子(第12圖）。使用咖調查結晶構造時’能夠確認係具有高結晶度之氧化鶴(第㈣）。而且使用UV-…射光譜測定吸光度光譜，確認係在約 52〇nm為止的可見光區域具有大的吸收（第“圖卜又，使用BET法之比表面積測定係9化·、。將在此所得到之氧化鶴的粒子設作（a 3 · 1 )。合成例5<藉由乾燥法之氧化鎢粒子的製造〉 +將l〇ml偏鶴酸録水溶液在5〇nU%狀燒瓶中使用旋轉蒸發器除去蒸餾水，將所得到的析出物使用真空乾燥機於1 20 C使其乾燥1 2小時。#已乾燥的粉末在空氣環 -49- 201229161 境下使用電爐以3〇分鐘從室溫加熱至300°C，且300°C /1小時保持後’進而以3〇分鐘升溫至6〇〇°c，在該溫度保持3 0分鐘後’自然冷卻。藉由該煅燒程式來得到氧化鎢的粉末。SEM觀查在此所得到粉末的表面時，確認係巨尺寸等級的大塊（第15圖）。又，使用BET法之比表面積測定係3.2m-2/g。將在此所得到之氧化鎢的粒子設作 (α-1)。合成例6<具有聚矽氧烷骨架之樹脂（Β_2)的合成> 依照專利文獻（國際公開 W02010/067742)所揭示之方法’來合成具有聚;5夕氧炫骨架之樹脂。在具備攪拌器、溫度計、滴液漏斗、冷卻器及氮氣導入口之反應容器，添加191g苯基三曱氧基矽烷（PTMS) 且升溫至1 2 0 °C。隨後，將包含1 6 9 g曱基丙烯酸甲酯 (MMA)、llg 3-曱基丙烯醯氧丙基三曱氧基矽烷（MPTS) 、18g第三丁基過氧化己酸2-乙酯（TBPEH)之混合物，以4小時滴下至前述反應容器中。隨後，於同溫度攪拌 1 6小時來調製具有三曱氧基矽烷基之乙烯基聚合物。隨後，將前述反應容器的溫度調整為80 °C，且將 131g甲基三甲氧基矽烷（MTMS)、226g 3-丙烯醯氧基丙基三甲氧基矽烷（APTS)、116g二甲基二曱氧基矽烷 (DMDMS)添加至前述反應容器中。隨後藉由將6.3g堺化學股份公司製的磷酸異丙酯與97g脫離子水之混合物以 5分鐘滴下’且於同溫度攪拌2小時使其水解縮合反應，來得到反應生成物。將反應生成物使用MR分析時’前述具有乙烯基聚合物之三曱氧基矽烷基係大約 -50- 201229161 1 00%水解。隨後，藉由將前這反應生成物在10〜300mmHg 的減壓下，以40〜6(TC的條件；左餾ο , 士来件療顧2小時，除去所生成的甲醇及水，來得到6 〇〇 g包么不插 8匕。不揮發成分為99.4%的聚矽氧烷片段及乙烯基聚合物片段之樹脂(β·2卜實施例Κ二氧化石夕奈米結構體與氧化鈦的複合型光觸媒亦即粉體（Α1-1)的合成> -使10.5g上述所知到之在内邹含有直鏈狀聚乙亞胺之二氧化矽奈米結構體⑻])及Ο,氧化鈦⑷”的粉末懸浮在3〇ml的蒸館水中，進行照射超音川、時之後，使用離心分離器μ -级、太# ~ 窃陈去上部澄清蒸餾水，且使用直空乾燥機將固體含量於12(rc下乾燥2小時。將已乾燥的粉末在空氣環境下使用電爐以3〇分鐘從室溫加熱至3〇〇 C，於30CTC保持i小時後，進而以3〇分鐘升溫至_ C且在該溫度保持30分鐘後，自然冷卻。藉由該煅燒程式來得到氧化鈦⑷])與二氧化石夕奈米結構體（以）複合而成之粉體（AH)。在第16圖顯示所得到之粉體（Μ) 的雇照片。能夠確認氧化欽（a1])的奈来粒子係鍵結接合在二氧化矽奈米纖維上且形成有突起部分。(5) Aqueous solution of the shale plant (Sakamoto Inorganic Chemical Industry Co., Ltd. = NV. 50% aqueous solution) and stirred for hours. I. The dried powder was dried in air = 〇 C for 12 hours. The steel was heated from room temperature to 3 〇〇 ° d 3 〇〇 t / 1 hour using an electric furnace for 30 minutes, and then 3 minutes. The temperature was raised to _C and maintained at this temperature for 3 () minutes, and then naturally cooled. The surface of the powder obtained here was examined by SEM, and the particles of the oxidized crane under '(10)... were confirmed (Fig. 12). When using a coffee to investigate a crystal structure, it is possible to confirm an oxidized crane (fourth) having high crystallinity. Further, the absorbance spectrum was measured by UV-... emission spectroscopy, and it was confirmed that the absorption region had a large absorption in the visible light region of about 52 〇 nm (the same applies to the specific surface area measurement system using the BET method). The particles of the obtained oxidized crane were set as (a 3 · 1 ). Synthesis Example 5 <Production of Tungsten Oxide Particles by Drying Method> + Using l〇ml of a solution of hexanoic acid in a 5 〇 nU% flask The distilled water was removed by an evaporator, and the obtained precipitate was dried at 1200 C for 12 hours using a vacuum dryer. # Dried powder was heated from room temperature in an air oven at -49-201229161 using an electric furnace for 3 minutes. After cooling to 300 ° C and 300 ° C / 1 hour, 'further increase to 6 ° C for 3 minutes, and then cool for 30 minutes after this temperature. Naturally cooled by the calcination program. Powder. When the surface of the powder obtained was observed by SEM, it was confirmed that it was a large size (Fig. 15). Further, the specific surface area measured by the BET method was 3.2 m-2/g. The particles of the tungsten oxide were set as (α-1). Synthesis Example 6 <With polyoxetane bone Synthesis of resin (Β_2) according to the method disclosed in the patent document (International Publication No. WO2010/067742) to synthesize a resin having a poly-5-oxygen skeleton. It is equipped with a stirrer, a thermometer, a dropping funnel, and cooling. And a reaction vessel for the nitrogen inlet, adding 191 g of phenyltrimethoxydecane (PTMS) and raising the temperature to 120 ° C. Subsequently, it will contain 169 g of methyl methacrylate (MMA), llg 3- a mixture of mercaptopropenyl methoxypropyltrimethoxy decane (MPTS) and 18 g of tert-butylperoxyhexanoic acid 2-ethyl ester (TBPEH) was dropped into the aforementioned reaction vessel over 4 hours. Subsequently, at the same temperature The vinyl polymer having a trimethoxydecylalkyl group was prepared by stirring for 16 hours. Subsequently, the temperature of the aforementioned reaction vessel was adjusted to 80 ° C, and 131 g of methyltrimethoxydecane (MTMS) and 226 g of 3-propene were added. Methoxypropyltrimethoxydecane (APTS), 116 g of dimethyldimethoxyoxydecane (DMDMS) was added to the above reaction vessel, followed by 6.3 g of isopropyl phosphate and 97 g of Sigma Chemical Co., Ltd. The mixture of deionized water is dripped in 5 minutes' and stirred at the same temperature 2 When the reaction product is hydrolyzed and condensed, the reaction product is obtained. When the reaction product is analyzed by MR, the above-mentioned trimethoxyoxyalkylalkyl group having a vinyl polymer is hydrolyzed by about -50 to 1,229,161,100% by 00%. The former reaction product was decompressed under a reduced pressure of 10 to 300 mmHg at 40 to 6 (TC conditions; left-distilled ο, 士来件 for 2 hours, and the generated methanol and water were removed to obtain 6 〇〇g. Pack does not insert 8 匕. a non-volatile component of 99.4% of a polyoxyalkylene fragment and a resin of a vinyl polymer segment (β·2) Example 复合 a composite photocatalyst of a cerium dioxide structure and a titanium oxide, that is, a powder (Α1- Synthesis of 1)> - 10.5 g of the above-mentioned known cerium oxide nanostructure (8)]) containing a linear polyethyleneimine and cerium, titanium oxide (4)" powder suspended in 3 〇 In the steaming water of ml, irradiate the super-sonic, and then use the centrifugal separator μ-class, too #~ to clarify the upper clarified distilled water, and use a straight-air dryer to dry the solid content at 12 (rc for 2 hours) The dried powder was heated from room temperature to 3 ° C in an air atmosphere using an electric furnace for 3 minutes, maintained at 30 CTC for 1 hour, and then heated to _ C for 3 minutes and maintained at this temperature for 30 minutes. Natural cooling. The powder (AH) obtained by combining titanium oxide (4)]) with a cerium oxide nanostructure (by) is obtained by the calcination procedure. The obtained powder is shown in Fig. 16. Photograph of the employment. It is possible to confirm that the Neilay particle system of the oxidized chin (a1) is bonded to the cerium oxide nanofiber. The protrusion is formed on the dimension.

實施例2<1液型塗料組成物的調製：介質水Z 使1.5g實施例i所得到粉體（八丨“）懸浮在蒸餾水且使用混合型分散機FILM]:x(pRIMIX製4〇_4〇型）以40m/s的旋轉速度使其分散3〇秒。將粉體（A_i)及具有水性的聚矽氧烷骨架之樹脂（B_n以固體:量質量/比 (A1-1)/(B-1)成為表i所記載的比例之方式思合，且進行照射超音波1小時來得到丨液型塗料組成物。 -51 - 201229161 [表i] 組成物 No. Til T12 T13 T14 T15 T16 A1-1/B-1 (質量比） 10/90 20/80 35/65 50/50 65/35 80/20 不揮發成分 (wt%) 37 33 30 27 24 22 實施例3<1液型塗料組成物的調製：介質異丙醇> 在實施例2，除了使介質為異丙醇以外，與實施例2 同樣地進行來調製表2所表示之1液型塗料組成物。 [表2] 組成物 No. T21 T22 T23 T24 T25 T26 Al-l/B-1 (質量比） 10/90 20/80 3.5/65 50/50 65/35 80/20 不揮發成分 (wt%) 37 33 30 27 24 22 比較例 < 氧化鈦與水性樹脂的混合物之調整：介質水> 除了將氧化鈦（a 1 -1)直接使用以外，與實施例2同樣地進行且使其分散於蒸餾水之後，以氧化鈦（al-Ι)與樹脂 (B-1)的固體含量質量比（al-l)/(B-l)為表3所記載的比例之方式混合，且進行照射超音波1小時來得到比較用的水性塗料組成物。 [表3] 組成物 No. T31 T32 T33 T34 T35 T36 al-1/B-l (質量比） 10/90 20/80 35/(55 50/50 65/35 80/20 不揮發成分 (wt%) 37 33 30 27 24 22 -52- 201229161 實施例4<藉由將1液塑塗料組成物塗形成光觸媒塗膜> 將實施例2所得到之No . T 1 4的使用塗膜器（YOSHIMITU製）且以速度器塗布在玻璃基材上。將所製造之塗置乾燥一晚後，照射黑光5小時來得該光觸媒塗膜的SEM膜觀察影像顯开確認源自二氧化矽奈米結構體形狀的展至膜整體之影像。在表面層出現的表面’可觀察到白色顯像的粒狀物。部狀態的氧化鈦（al-Ι)的奈米粒子。比較例2 作為比較，使用在比較例1所得到 T34而同樣地進行且使用棒塗布器製置乾燥一晚。使用SEM觀察將該氧化之塗膜之結果，係與實施例4不同，複雜形狀者而是形成平滑的塗膜（第1 化鈦的粒子係埋沒在黏合劑層之狀態所得到的塗膜係完全未觀察到裂紋，膜係可觀察到明確的裂紋。從該等不例4的塗膜，在粉體（Α1-1)中的二氧強力地與樹脂（Β)中的聚矽氧烷鍵結，使塗膜強度提升。 <塗膜評價1 :埘磨耗性試驗1 > 進行實施例4及比較例2所得到布在玻璃基材上來 1液型塗料組成物 10、RDS16棒塗布膜於室溫（25°C )靜到光觸媒塗膜。將 :在第17圖。能夠表面凹凸結構係擴二氧化矽奈米纖維該粒狀物係露出頂的塗料組成物No. 造塗膜，在室溫靜鈦的粒子直接使用係完全無法確認為 8圖）。能夠確認氧。又，在實施例 4 但是比較例2的塗同，係暗示在實施化矽奈米結構體係且形成網狀結構而之塗膜的耐磨耗性 -53- 201229161 試驗。將使用曰本製紙CRECIA股份公司製的紙製擦拭布（KIMWIPES)且使用手操作研磨次之結果顯示在第 1 9圖。實施例4的塗膜係即便進行研磨亦完全未觀察到剝離等的現象，但是比較例2的塗膜能夠確認明確的剝離。這強烈地暗示二氧化矽奈米結構體係與黏合劑強力地鍵結而使塗膜的物理強度提升。 <塗膜評價2 :耐磨耗性試驗2> 進行實施例4及比較例2所得到之塗膜的耐磨耗性 β式驗。作為磨耗材質，係設想通常家庭等所使用的用途，針對海綿（DUSKIN股份公司製廚房用海綿抗菌型Ν、材料.酯系胺曱酸酯發泡體/聚酯不織布）的重複磨擦試驗進行評價。試驗機係使用HEid〇n公司製、往復磨耗試驗機TYPE30S，施加10g的負荷而進行5,〇〇〇次研磨，來評價研磨前後的光觸媒活性變化。實施例4所得到的塗膜係從研磨前後的光觸媒活性’能夠確認即便進行Example 2 <1 Preparation of Liquid Coating Composition: Medium Water Z 1.5 g of the powder obtained in Example i (eight 丨") was suspended in distilled water and a mixed disperser FILM was used: x (pRIMIX manufactured 4 〇 _ 4〇) Disperse for 3 sec. at a rotation speed of 40 m/s. Powder (A_i) and resin with aqueous polyoxyalkylene skeleton (B_n as solid: mass/ratio (A1-1)/ (B-1) The method of the ratio shown in Table i is considered, and the sputum-type paint composition is obtained by irradiating the ultrasonic wave for 1 hour. -51 - 201229161 [Table i] Composition No. Til T12 T13 T14 T15 T16 A1-1/B-1 (mass ratio) 10/90 20/80 35/65 50/50 65/35 80/20 nonvolatile content (wt%) 37 33 30 27 24 22 Example 3 <1 liquid type Preparation of Coating Composition: Medium Isopropyl Alcohol> In the same manner as in Example 2 except that the medium was isopropyl alcohol, the one-liquid type coating composition shown in Table 2 was prepared. Composition No. T21 T22 T23 T24 T25 T26 Al-l/B-1 (mass ratio) 10/90 20/80 3.5/65 50/50 65/35 80/20 Non-volatile content (wt%) 37 33 30 27 24 22 Comparative Example < Titanium Oxide and Waterborne Resin Adjustment of mixture: medium water > In the same manner as in Example 2 except that titanium oxide (a 1-1) was used as it is, it was dispersed in distilled water, and titanium oxide (al- Ι) and resin (B- 1) The solid content mass ratio (al-1)/(Bl) was mixed as shown in Table 3, and ultrasonic waves were irradiated for 1 hour to obtain a comparative aqueous coating composition. [Table 3] Composition No. T31 T32 T33 T34 T35 T36 al-1/Bl (mass ratio) 10/90 20/80 35/(55 50/50 65/35 80/20 Non-volatile content (wt%) 37 33 30 27 24 22 - 52-201229161 Example 4 <Application of a liquid-liquid coating composition to form a photocatalyst coating film> The No. T1 4 obtained by using the coating machine (manufactured by YOSHIM) and coated with a speeder On the glass substrate, after the coating was dried for one night, black light was irradiated for 5 hours to obtain an SEM film image of the photocatalyst coating film, and the image derived from the shape of the cerium oxide nanostructure was observed to the entire film. A white-visible granule is observed on the surface appearing on the surface layer. Nanoparticles of titanium oxide (al-Ι) in a partial state. Comparative Example 2 As a comparison, T34 obtained in Comparative Example 1 was used in the same manner, and drying was carried out overnight using a bar coater. The result of observing the oxidized coating film by SEM was different from that of Example 4, and a smooth coating film was formed instead of the complicated shape (the coating system obtained by burying the particles of the first titanium in the adhesive layer) No crack was observed at all, and a clear crack was observed in the film system. From the coating film of the above-mentioned Example 4, the dioxane in the powder (Α1-1) strongly and the polyoxyalkylene in the resin (Β) Bonding, the coating film strength was improved. <Coating film evaluation 1: 埘Abrasion test 1 > The coatings obtained in Example 4 and Comparative Example 2 were coated on a glass substrate to coat the liquid coating composition 10 and the RDS 16 rod. The film is allowed to stand at room temperature (25 ° C) to the photocatalyst coating film. In Fig. 17, the surface uneven structure is capable of expanding the cerium oxide nanofiber, and the granule is exposed to the top of the coating composition No. At the room temperature, the direct use of the particles of titanium is completely unrecognizable as 8 (Fig. 8). Can confirm oxygen. Further, in the fourth embodiment, the application of the comparative example 2 is directed to the abrasion resistance of the coating film which is formed into a reticulated nanostructure and which forms a network structure - 53 - 201229161 test. The result of using the paper wiping cloth (KIMWIPES) manufactured by EC本纸纸 CRECIA Co., Ltd. and using the hand-operated grinding step is shown in Fig. 19. In the coating film of Example 4, no peeling or the like was observed even when it was polished, but the coating film of Comparative Example 2 was able to confirm the clear peeling. This strongly suggests that the cerium oxide nanostructures are strongly bonded to the binder to increase the physical strength of the coating film. <Coating film evaluation 2: abrasion resistance test 2> The abrasion resistance of the coating film obtained in Example 4 and Comparative Example 2 was examined. As a wear material, it is assumed that the use of a sponge (DUSKIN Co., Ltd. kitchen sponge antibacterial type, material, ester type amine phthalate foam / polyester non-woven fabric) is evaluated. . The test machine was subjected to a reciprocating abrasion tester TYPE 30S manufactured by HEID〇n Co., Ltd., and subjected to a load of 10 g, and subjected to 5 times of grinding to evaluate the change in photocatalytic activity before and after the polishing. The coating film obtained in Example 4 can be confirmed from the photocatalytic activity before and after polishing.

的塗膜。Coating film.

圖）。實施例4的塗膜中之氧化鈦离、以及樹脂（B-1)直接坡螭基板而得到（第2 i 的含有率，係儘管相較 -54- 201229161 於比較例2的塗膜為較少的氧化鈦量，但是顯示非常高的乙醛分解速度。從實施例4的塗膜中之實際的氧化鈦含量為比較例2的塗膜中含有的氧化鈦之35”％換算時 ’氧化鈦的觸媒活性係提升約6倍。 k膜坪彳貝.4 .在模擬太陽光照射下之光觸媒活性〉在模擬太1%光照射下評價塗膜之光觸媒活性，該塗膜係將實施例4及比較例2所得到的塗膜、以及樹脂 (B-1)直接與實施例4同樣地進行且塗布在玻璃基板而得到（第22圖）。實施例4的塗膜係與黑光照射下同樣，即便在模擬太陽光照射下亦顯示高觸媒活性。此情形係暗示本發明的塗膜係能夠應用在實際空間之外牆塗布。 <塗膜評價5 :在螢光燈照射下之光觸媒活性> 在通常豕庭被廣泛地使用之白色螢光燈照射下評價塗瞑之光觸媒活性，該塗膜係將實施例4及比較例2所得到的塗膜、以及樹脂（B—i)直接與實施例4同樣地進行且塗布在玻璃基板而得到（第23圖）。與上述的評價結果同樣地，實施例4的塗膜係即便在螢光燈照射下亦顯示非常高的光觸媒活性。此情形係強烈地暗示本發明的塗膜係不僅是外牆用塗布，而且在室内空間亦具有高的實用性。 <塗膜評價6 :在螢光燈照射下之超親水性能> 在瑩光燈照射下評價實施例4所得到之塗膜的超親水性能力。對室溫乾燥後的塗膜進行照射黑光丨2小時，來使氧化鈦面露出。此時點係成為接觸角為5。以下的超覩水性表面。使該塗在暗處靜置2星期之後，再次測定 -55- 201229161 接觸角時為約28° 。對接觸角28。狀態的塗膜進行照射螢光燈。能夠確認伴隨著照射時間的經過，接觸角係降低（第2 4圖）。藉由照射螢光燈9小時而再次回復至完全的超親水塗膜。將該塗在暗處靜置8小時之後，確認再次測定接觸角時係保持超親水狀態。上述的結果係強烈地暗示實施例4的塗膜係在室内空間係顯示發揮非常高的超親水性功能，此情形係強烈地暗示具有非常高的實用性（例如洛室壁用、便器用等）。 <塗膜評價7 :評價在螢光燈照射下之使用曱基藍色素之防污功能> 藉由使用通常作為光觸媒防污功能的評價試藥使用之曱基藍色素的脫色速度來評價實施例4所得到的塗骐之防污功能。首先，對室溫乾燥後的塗膜進行照射黑光 12小時，來使氧化鈦面露出。隨後，滴下一滴甲基藍水溶液且室溫乾燥之後，進行評價在螢光燈照射下之脫色速度。能夠確認伴隨著螢光燈照射時間的經過’曱基藍色素的脫色係逐漸進展的情形（第25圖）。能夠確認藉由 ,.、、射5小時曱基藍色素係完全脫色。這顯示本發明的塗膜係在”、'射螢光燈下不僅有害氣體分解性能，而且兼具非㊉雨的光防污功能，此情形係強烈地暗示在室内空間具有高實用性能。實施例5及比較例3 除了使用組成物中的樹脂固體含量的存在比率高的組成物Νο· τ 12以外’係與實施例4同樣地進行而在坡璃基板上製造塗膜(第26圖）。藉由與第17圖比較，能 -56- 201229161 夠確認由於樹脂的存在比率高’樹脂係掩埋氧化鈦（ai i) 與二氧化矽奈米結構體（a2-i)複合而成之粉體（八丨-”所構成的空間。但是，塗膜的表面係具有凹凸，能夠確認在最表面存在有粉體（A1-1)。作為比較，使用在比較例\ 所得到的組成物No. T32且同樣地製造塗膜（第27圖）。由於樹脂的存在比率高，同樣地製造塗膜（第2 7圖）。由於樹脂的存在比率高，雖然能夠抑制產生裂紋，但是氡化鈦（al-Ι)係埋沒至樹脂中，能夠確認觸媒係無法存在於塗膜表面。 <塗膜評價8 :模擬太陽光照射下之光觸媒活性> 在模擬太陽光照射下評價塗膜之光觸媒活性，該塗膜係將實施例5及比較例3所得到的塗膜、以及樹脂 (B -1)直接與實施例3同樣地進行且塗布在玻璃基板而得到（第28圖）。即便樹脂固體含量增加的情況，換算平均實際氧化鈦單位量時，能夠確認顯示6倍以上的光觸媒活性。這顯示藉由將氧化鈦^^^與二氧化矽奈米結構體 (a2-l)中的二氧化矽奈米纖維複合化，能夠使氧化鈦 (al-Ι)露出塗膜表面。實施例6<藉由在玻璃基材上塗布1液型塗料組成物之形成光觸媒塗膜：介質異丙醇> 除了使用在實施例3所得到的組成物No. T24以外 ’係與實施例4同樣地進行而在玻璃基材上製造塗膜。將所製造的塗膜在室溫約靜置乾燥1晚之後，照射黑光 5小時來得到光觸媒塗膜。將該光觸媒塗膜的S EM膜觀察影像顯示在第29圖。與在實施例4所得到之塗膜同樣 -57- 201229161 地’其表面係凹凸’能夠確認在最表面所觀測到的二氧化矽奈米纖維表面上之露出頂部狀態的氧化鈦（a丨_丨）的奈米粒子。 <塗膜评價9 :模擬太陽光照射下之光觸媒活性> 在模擬太陽光照射下評價塗膜之光觸媒活性，該塗膜係將實施例6及比較例2所得到的塗膜、以及樹脂 (B-1)直接與實施例4同樣地進行且塗布在玻璃基板而得到（第30圖）。即便將分散溶劑從蒸餾水變更成為異丙醇之隋况，亦能夠確認平均氧化鈦單位量的光觸媒活性為 6倍以上。這暗示本發明的塗料組成物係即便在介質使用醇類’亦能夠製造良好的光觸媒塗膜。實鈀例7「在地磚板上所製造之具有超親水性能的光觸媒塗膜> 將只施例2所彳于到之No. T 14的塗料組成物使用市 =的刷子塗布在通常使用的陶瓷器製的地碑上，且在室酿=仃乾燥硬化1晚。對硬化後的塗膜照射光線之前， =水接觸角時，為108.3。（第31圖：cl)。將其曝露外的太陽光下1小時之後，再次測定接觸角時為5 、下（第3 1圖.c2)。認為因為曝露前之光觸媒活性部位的表面係被樹脂覆蓋，由疏水性成分形成表面之緣故 ::妾觸角係變高。藉由在太陽光下曝露，覆蓋光觸媒觸：位之樹脂成分係被分解’其表面層係變化成為光性部位露出頂部’而成為具有凹凸的塗膜表面係二:成為超親水性膜。將塗膜直接曝露在屋外三個月期 ::。’塗膜表面係沒有損傷或損害，且水接觸角係保持以下的超親水性狀態（第3 1圖：c 3)。 -58- 201229161 實施例8<在各式各樣的基材上形成之光觸媒塗膜及光觸媒活性> 使用實施例2所得到之N〇. T14的塗料組成物而在除了玻璃基材以外之各式各樣的基材上製造塗膜，來進行評價光觸媒活性。所使用的基材係木材（檜木）、氣乙烯板、聚對酞酸乙二酯（ΡΕΤ)、壓克力板、聚碳酸酯（pc) 、聚笨乙稀板（PS)、不鑛鋼板、鋁板、内牆用地磚、屋外用地磚、浴室用地磚、天然石 '布（棉）。而且，關於氣乙稀板、聚對酿酸乙二酯薄膜、壓克力板、聚碳酸酯板、聚苯乙烯板、不鏽鋼板、鋁板，係在塗布前進行電. ，灸處理（春曰電機股份公司製 PLASMA SHOWER P S - 6 0 1 S)數秒鐘’來將表面處理成為親水狀態。在各自的基板塗布N 〇 . T 1 4的塗料組成物之後，進行照射黑光 1 2小時’來使氧化鈦面露出。照射黑光後的各光觸媒塗膜係全部的基材為顯示5。以下的超親水性功能（參照表 4〜5)。即便在模擬太陽光照射下之乙醯氣體的光分解反應’係與玻璃基材上的塗膜同樣，顯示非常高的光觸媒活性（第3 2.圖）。這顯示藉由使用本發明的i液型塗料組成物’能夠簡便地在各種基材上形成光觸媒塗膜，且強烈地暗示在現實空間係具有非常高的實用性。 [表4] 基材名木材氣乙烯板 PET 壓克力板 PC PS 不鏽鋼板鋁板塗布後光照射前接觸角η 104.3 102.2 104.3 104.8 101.9 101.2 102.2 106.1 塗布後光照射後接觸角π 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 -59- 201229161 [表5] 基材名内牆用地磚屋外用地磚浴室用地碑天然石布塗布後光照射前接觸角(。） 101.5 107.3 101.7 103.4 89.3 塗布後光照射後接觸角(°) 0.0 0.0 0.0 0.0 0.0 實施例9<製造使用在室溫靜置3個月後的組成物之塗膜> 將在實施例2所得到之組成物Ν〇 · T 1 4且在2 5 °C ~3 0 °C的室溫下靜置3個月後。雖然靜置3個月後的組成物係固體含量沈降，但是藉由手動攪拌能夠再分散。使用經再分散後的組成物且與實施例4同樣地進行在玻璃基材上製造塗膜。於室溫進行乾燥丨天之後，進行照射黑光12小時，確認接觸角為〇.〇，確認能夠使氧化鈦的奈米粒子露出。〈塗膜評價1 0 :在照射模擬太陽光下之光觸媒活性> 在照射模擬太陽光下，評價在實施例4及實施例9 所得到之塗膜的光觸媒活性（第3 3圖）。即便將調整後的 1液型塗料組成物於室溫靜置3個月之後，確認所得到之塗膜的光觸媒活性為良好，相較於調整後立刻塗布者亦不遜色之光觸媒塗膜。實施例10<氧化鎢（a3-1)固定在二氧化矽奈米結構體 (a2-2)> 將合成例1所得到的二氧化矽奈米結構體〇2-2)與合成例4所得到的氧化鎢（a3-1 )，以該等的使用比例為表 6所記載之值的方式使用，使該混合物的合計為1.5 g懸浮在3Οτηΐ蒸餾水且進行照射超音波1小時之後，靜置1 -60- 201229161 晚。使用離心分離器除去蒸顧水，且使用真空乾燥機進一步乾燥》將所得到的粉末在空氣環境下使用電爐以π 分鐘從室溫加熱至30(TC，30(TC/1小時保持後進而以 3〇分鐘升溫至40(TC且在該溫度保持3〇分鐘後，自缺冷卻。藉由該煅燒程式，來將氧化鎢（a3_1}的粒子燒結定在二氧化矽奈米結構體（a2_2)上而成。將所得到的粉末之氧化鶴的含有率顯示在表6。 [表6] 試料No. T41 T42 T43 T44 T45 T46 (a3-l)/(d-2)質量比 1/9 2/8 3.5/6.5 5/5 6.5/3.5 8/2 氧化鎢含有率(〇/0) 9.7 21.2 32.4 50.6 67.2 84.3 使用TEM進行觀察試料No. T43的表面之結果，能夠確認氧化鎢的粒子係被固定在二氧化矽奈米纖維上（第34圖）。實施例1 1 <氧化鎢（a3-1)固定在二氧化矽奈米結構體 (a2-4)> 除了使用在合成例2所得到之二氧化石夕奈米結構體 (a2_4)代替合成例丨所得到的結構體（a2-2)作為所使用的二氧化石夕奈米結構體以外，與實施例1 〇同樣地進行，來進行氧化鎢（a3 -1)之藉由燒結而固定在二氧化矽奈米結構體。將氧化鎢（a3-l)與二氧化矽奈米結構體（a2-4)的使用比例、及所得到的固體中之氧化鎢含有率顯示在表7 [表7] 試料No. T51 T52 T53 T54 T55 T56 (a3-l)/(a2-4)質量比 1/9 2/8 3.5/6.5 5/5 6.5/3.5 8/2 氧化鎢含有率(％) 10.4 23.7 31.9 55.1 64.9 83.3 -61 - 201229161 使用TEM進行觀察試料ν〇· T53的表面之結果，能夠確認氧化鎢的粒子係被固定在二氧化矽奈米層片上（第35圖）。實施例12<氧化鎢（a3_i)固定在二氧化矽奈米結構體 (a2-7)> 除了使用在合成例3所得到之二氧化矽奈米結構體 (a2-7)代替合成例丨所得到的结構體（a2_2)作為所使用的二氡化矽奈米結構體以外，與實施例丨〇同樣地進行來進行氧化鎢（a3-l)之藉由燒結而固定在二氧化矽奈米結構體。將氧化鎢（a3-l)與二氧化矽奈米結構體（32 7)的使用比例、及所得到的固體中之氧化鎢含有率顯示在表8。 [表8] 試料No. T51 T52 T53 T54 T55 T56 (a3-l)/(a2-4)質量比 1/9 2/8 3.5/6.5 5/5 6.5/3 5 8/2 jzT 氧化鎢含有率(％) 10.4 23.7 31.9 55.1 649" --------1 使用TEM進行觀察試料no. T63的表面之έ士婁Ab . ，。禾，能句確涊氧化鎢的粒子係被固定在二氧化矽奈米管上 36圖）。（弟實施例13<氧化鎢（以—”藉由吸附及煅燒化石夕奈米結㈣㈤在二氧除了使用在合成例丨所得到的聚合物與二氣化矽複合體亦即二氧化矽奈米結構體（a2-l)代替在合成的所付到的結構體（a2_2)以外，與實施例丨〇同樣地進行，1 來進仃氧化鎢（a3-l)之藉由吸附及燒結而固定在二一矽奈米結構體（同時除去聚合物）。將氧化鎢（a3M)、物及一氧化矽的複合體亦即二氧化矽奈米結構體（U ^ •62· 201229161 表9 [表9] 的使用比例、及所得到的固體中之氧化鎢含有率顯示在 (a3-l)/(a2-l)質量比 ^氧化鎢含有率(％)Figure). The titanium oxide in the coating film of Example 4 and the resin (B-1) were directly obtained by sloping the substrate (the content of the second i is compared with the coating film of Comparative Example 2 in comparison with -54 to 201229161). The amount of titanium oxide is small, but shows a very high rate of decomposition of acetaldehyde. The actual titanium oxide content in the coating film of Example 4 is 35% by weight of the titanium oxide contained in the coating film of Comparative Example 2 The catalytic activity of titanium is increased by about 6 times. k-film 彳 mussels. 4. Photocatalytic activity under simulated sunlight irradiation> The photocatalytic activity of the coating film is evaluated under simulated 1% light irradiation, and the coating system will be implemented. The coating film obtained in Example 4 and Comparative Example 2 and the resin (B-1) were directly applied to a glass substrate in the same manner as in Example 4 (Fig. 22). The coating film of Example 4 and black light irradiation were obtained. Similarly, high catalyst activity is exhibited even under simulated sunlight. This suggests that the coating film of the present invention can be applied to the outer wall coating in real space. <Coat Film Evaluation 5: Under Fluorescent Lamp Irradiation Photocatalyst activity> White fluorescent light that is widely used in the court The photocatalytic activity of the enamel coating was evaluated under irradiation, and the coating film obtained in Example 4 and Comparative Example 2 and the resin (B-i) were directly applied to the glass substrate in the same manner as in Example 4, and were obtained by coating on a glass substrate ( Fig. 23) In the same manner as the above evaluation results, the coating film of Example 4 showed a very high photocatalytic activity even under irradiation with a fluorescent lamp. This case strongly suggests that the coating film of the present invention is not only external The wall is coated and has high practicality in the indoor space. <Coating film evaluation 6: Super hydrophilic property under irradiation of a fluorescent lamp> Evaluation of the coating film obtained in Example 4 under irradiation of a fluorescent lamp Ultra-hydrophilic ability: The coating film after drying at room temperature was irradiated with black light for 2 hours to expose the surface of the titanium oxide. At this time, the point became a super-hydrophobic surface with a contact angle of 5. or less. After the second week, the contact angle was approximately 28° when the contact angle was measured again. The contact film was irradiated with a fluorescent lamp at the contact angle of 28. The contact angle was reduced with the passage of the irradiation time (2nd) 4)). By photo The fluorescent lamp was returned to the completely super-hydrophilic coating film again for 9 hours. After the coating was allowed to stand in the dark for 8 hours, it was confirmed that the contact angle was maintained at the super-hydrophilic state. The above results strongly suggest that Example 4 The coating film exhibits a very high super-hydrophilic function in the indoor space system, and this situation strongly suggests that it has a very high practicality (for example, for room walls, toilets, etc.) <Coating film evaluation 7: Evaluation The antifouling function using ruthenium blue pigment under irradiation with a fluorescent lamp> The enamel obtained in Example 4 was evaluated by using the decoloring speed of thiol blue pigment which is generally used as an evaluation agent for photocatalyst antifouling function. Antifouling function: First, the coating film after drying at room temperature was irradiated with black light for 12 hours to expose the surface of the titanium oxide. Subsequently, after dropping a drop of the methyl blue water solution and drying at room temperature, the decolorization speed under irradiation with a fluorescent lamp was evaluated. It was confirmed that the decolorization system of the thiol blue pigment gradually progressed along with the irradiation time of the fluorescent lamp (Fig. 25). It was confirmed that the ruthenium-based blue pigment system was completely decolored by the injection of . This shows that the coating film of the present invention is not only harmful gas decomposition performance under the "," fluorescent lamp, but also has a non-rainy light antifouling function, which strongly implies a high practical performance in the indoor space. Example 5 and Comparative Example 3 A coating film was produced on a glass substrate in the same manner as in Example 4 except that the composition 高ο· τ 12 having a high ratio of the resin solid content in the composition was used (Fig. 26). By comparing with Fig. 17, it is possible to confirm the powder of the resin-based buried titanium oxide (ai i) and the cerium oxide nanostructure (a2-i) due to the high ratio of the resin. The surface of the coating film has a concavity and convexity, and it can be confirmed that the powder (A1-1) is present on the outermost surface. For comparison, the composition No. obtained in the comparative example is used. T32 and a coating film are produced in the same manner (Fig. 27). The coating film is produced in the same manner because of the high ratio of the resin (Fig. 27). Since the existence ratio of the resin is high, cracking can be suppressed, but titanium oxide can be suppressed. (al-Ι) is buried in the resin It was confirmed that the catalyst system could not exist on the surface of the coating film. <Coating film evaluation 8: Photocatalytic activity under simulated sunlight irradiation> The photocatalytic activity of the coating film was evaluated under simulated sunlight irradiation, and the coating film was applied in Example 5. The coating film obtained in Comparative Example 3 and the resin (B-1) were directly obtained in the same manner as in Example 3 and applied to a glass substrate (Fig. 28). Even if the resin solid content was increased, the average actual oxidation was converted. In the case of a titanium unit amount, it was confirmed that the photocatalytic activity was 6 times or more. This shows that by combining the titanium oxide with the cerium oxide nanofiber in the cerium oxide nanostructure (a2-l), Titanium oxide (al-Ι) was exposed on the surface of the coating film. Example 6 < Formation of Photocatalyst Coating Film by Coating a Liquid Coating Material on a Glass Substrate: Medium Isopropyl Alcohol> Except for Use in Example 3 The obtained composition No. T24 was produced in the same manner as in Example 4 to produce a coating film on a glass substrate. The produced coating film was left to dry at room temperature for about 1 night, and then black light was irradiated for 5 hours to obtain a coating film. Photocatalyst coating film The S EM film observation image of the coating film is shown in Fig. 29. The same as the coating film obtained in Example 4, -57-201229161, the surface roughness is able to confirm the cerium oxide nanocrystal observed on the outermost surface. Nanoparticles of titanium oxide (a丨_丨) in the top state on the surface of the fiber. <Coating film evaluation 9: Photocatalytic activity under simulated sunlight irradiation> Photocatalyst for evaluating coating film under simulated sunlight irradiation In the coating film, the coating film obtained in Example 6 and Comparative Example 2 and the resin (B-1) were directly obtained in the same manner as in Example 4 and applied to a glass substrate (Fig. 30). When the dispersion solvent was changed from distilled water to isopropyl alcohol, it was confirmed that the photocatalytic activity per unit amount of the average titanium oxide was 6 times or more. This suggests that the coating composition of the present invention can produce a good photocatalytic coating film even when an alcohol is used in the medium. Example palladium 7 "Photocatalyst coating film having super-hydrophilic property produced on floor tile" > Only the coating composition of No. T 14 to which Example 2 is applied is coated with a brush of the city = commonly used. On the earthenware made of ceramics, it is dried and hardened for 1 night in the chamber. Before the light is applied to the hardened coating film, the water contact angle is 108.3. (Fig. 31: cl). After one hour under sunlight, the contact angle was measured again at 5 and below (Fig. 31.c2). It is considered that the surface of the active portion of the photocatalyst before exposure is covered with a resin, and the surface is formed by a hydrophobic component: The 妾妾系。。。。。。。藉藉藉藉藉藉藉藉藉藉藉藉藉藉藉藉藉藉藉藉藉藉藉藉藉藉藉藉藉藉藉藉藉藉藉藉藉藉藉藉藉藉藉It becomes a super-hydrophilic film. The film is directly exposed to the outside of the house for three months:: 'The surface of the film is not damaged or damaged, and the water contact angle maintains the following super-hydrophilic state (Fig. 3: c 3 -58- 201229161 Example 8<in a wide variety of Photocatalyst coating film and photocatalytic activity formed on the material> Using the coating composition of N〇. T14 obtained in Example 2, a coating film was produced on various substrates other than the glass substrate, and evaluated. Photocatalyst activity. The substrate used is wood (eucalyptus), gas vinyl sheet, polyethylene terephthalate (ΡΕΤ), acrylic sheet, polycarbonate (pc), polystyrene board (PS), Non-mineral steel plate, aluminum plate, interior wall floor tile, exterior floor tile, bathroom floor tile, natural stone 'cloth (cotton). Moreover, about ethylene slab, poly-ethylene glycol film, acrylic plate, polycarbonate Ester plate, polystyrene plate, stainless steel plate, aluminum plate, before the coating, electricity, moxibustion treatment (PLASMA SHOWER PS - 6 0 1 S made by Chunyu Electric Co., Ltd.) for a few seconds to surface treatment into a hydrophilic state. After the coating composition of N 〇. T 1 4 was applied to each of the substrates, the black light was irradiated for 12 hours to expose the surface of the titanium oxide. The substrate of each of the photocatalyst coating films after the black light was irradiated was displayed 5. Super hydrophilic function (refer to Table 4~5) Even when the photodegradation reaction of the acetamethylene gas under the irradiation of the simulated sunlight is the same as the coating film on the glass substrate, it exhibits a very high photocatalytic activity (Fig. 3). This shows that by using the present invention i The liquid type coating composition' can easily form a photocatalyst coating film on various substrates, and strongly suggests that it has a very high practicality in a real space system. [Table 4] Substrate name Wood gas vinyl sheet PET Acrylic sheet Contact angle of light before coating of PC PS stainless steel plate aluminum plate 104.3 102.2 104.3 104.8 101.9 101.2 102.2 106.1 Contact angle after light irradiation after coating π 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 -59- 201229161 [Table 5] The use of floor tiles for external use of floor tiles in the bathroom with a natural stone cloth coated with light before the contact angle (. 101.5 107.3 101.7 103.4 89.3 Contact angle after light irradiation (°) 0.0 0.0 0.0 0.0 0.0 Example 9 <Production of coating film using composition after standing at room temperature for 3 months> The obtained composition Ν〇· T 1 4 was allowed to stand at room temperature of 25 ° C to 30 ° C for 3 months. Although the composition after standing for 3 months was solid content sedimentation, it was redispersed by manual stirring. A coating film was formed on the glass substrate in the same manner as in Example 4, using the re-dispersed composition. After drying at room temperature for a few days, black light was irradiated for 12 hours, and it was confirmed that the contact angle was 〇.〇, and it was confirmed that the titanium nanoparticles of titanium oxide can be exposed. <Coating film evaluation 10: Photocatalyst activity under irradiation of simulated sunlight> The photocatalytic activity of the coating films obtained in Example 4 and Example 9 was evaluated under irradiation of simulated sunlight (Fig. 3). Even after the adjusted one-liquid type coating composition was allowed to stand at room temperature for three months, it was confirmed that the photocatalytic activity of the obtained coating film was good, and that the photocatalyst coating film which was not inferior to the coating immediately after the adjustment was obtained. Example 10 <Tungsten Oxide (a3-1) fixed to cerium oxide nanostructure (a2-2)> The cerium oxide nanostructure 〇2-2) obtained in Synthesis Example 1 and Synthesis Example 4 The obtained tungsten oxide (a3-1) was used in such a manner that the ratios of use were as shown in Table 6, and the total of the mixture was 1.5 g suspended in 3 Οηηΐ distilled water and irradiated for 1 hour, and then static. Set 1 -60- 201229161 night. The water was removed by using a centrifugal separator, and further dried using a vacuum dryer. The obtained powder was heated from room temperature to 30 in an air atmosphere using an electric furnace for π minutes (TC/30 (TC/1 hour hold and then After heating to 40 (TC for 3 minutes and maintaining at this temperature for 3 minutes, there is no cooling. By this calcination procedure, the tungsten oxide (a3_1} particles are sintered in the cerium oxide nanostructure (a2_2). The content of the oxidized crane of the obtained powder is shown in Table 6. [Table 6] Sample No. T41 T42 T43 T44 T45 T46 (a3-l)/(d-2) Mass ratio 1/9 2 /8 3.5/6.5 5/5 6.5/3.5 8/2 Tungsten oxide content (〇/0) 9.7 21.2 32.4 50.6 67.2 84.3 Using TEM to observe the surface of sample No. T43, it was confirmed that the particle system of tungsten oxide was confirmed. It was fixed on cerium oxide nanofiber (Fig. 34). Example 1 1 <Tungsten oxide (a3-1) was fixed in cerium oxide nanostructure (a2-4)> The obtained SiO2 sulphate structure (a2_4) is used instead of the structure (a2-2) obtained in the synthesis example as the used sulphur dioxide In the same manner as in Example 1 except for the rice structure, tungsten oxide (a3 -1) was fixed by sintering to a cerium oxide nanostructure. The tungsten oxide (a3-l) and cerium oxide were used. The ratio of use of the nanostructure (a2-4) and the content of tungsten oxide in the obtained solid are shown in Table 7 [Table 7] Sample No. T51 T52 T53 T54 T55 T56 (a3-l)/(a2- 4) Mass ratio 1/9 2/8 3.5/6.5 5/5 6.5/3.5 8/2 Tungsten oxide content (%) 10.4 23.7 31.9 55.1 64.9 83.3 -61 - 201229161 Using TEM to observe the surface of the sample ν〇·T53 As a result, it was confirmed that the particles of the tungsten oxide were fixed on the cerium oxide nano layer (Fig. 35). Example 12 <Tungsten oxide (a3_i) was fixed to the cerium oxide nanostructure (a2-7)&gt In addition to the structure (a2_2) obtained by using the ruthenium oxide nanostructure (a2-7) obtained in Synthesis Example 3 instead of the synthesis example a, as the used ruthenium bismuth nanostructure, In the same manner, the tungsten oxide (a3-l) is fixed in the cerium oxide nanostructure by sintering. The tungsten oxide (a3-l) and the dioxin are formed. The ratio of use of the nanostructure (32 7) and the content of tungsten oxide in the obtained solid are shown in Table 8. [Table 8] Sample No. T51 T52 T53 T54 T55 T56 (a3-l)/(a2 -4) Mass ratio 1/9 2/8 3.5/6.5 5/5 6.5/3 5 8/2 jzT Tungsten oxide content (%) 10.4 23.7 31.9 55.1 649" --------1 Using TEM Observe the sample no. T63 on the surface of the gentleman 娄 Ab . Wo, the particle system of the tungsten oxide can be fixed on the ruthenium dioxide nanotubes (Fig. 26). (Third Embodiment 13 <Tungsten Oxide (by -" by adsorption and calcination of the fossil yttrium knot (4) (5) In addition to the use of the polymer obtained in the synthesis example and the bismuth ruthenium complex, ie, ruthenium dioxide The rice structure (a2-l) was carried out in the same manner as in Example 以外 except for the structure (a2_2) to be synthesized, and the adsorption of tungsten oxide (a3-l) by adsorption and sintering was carried out. It is fixed in a two-nanometer nanostructure (while removing the polymer). The composite of tungsten oxide (a3M), a substance and cerium oxide is also known as a cerium oxide nanostructure (U ^ • 62· 201229161 Table 9 [ The ratio of use of Table 9] and the content of tungsten oxide in the obtained solid are shown in (a3-1)/(a2-l) mass ratio ^tungsten oxide content (%)

- —丨使用TEM進行觀察試料N〇 T73的表面之結果，試料No. 能夠確認氧化鎢的粒子係被固定在二氧化矽奈米纖第37圖）。（實施例14<使用鎢酸鹽且固定在二氧化矽奈米結 (a2-7)> ^ 秤量〇.2g在合成例3所得到的二氧化矽奈米結構體 (a2-7)。又’使用蒸餾水將偏鎢酸銨水溶液調整為”，將調整後的5%水溶液稱為(a3M”將該等以質量比二 10中所記載的比例混合，而且添加蒸餾水來將整體積調製10m1。將其攪# 1小時，從所得到的懸浮液除去蒸餾水，而且使用真空乾燥器而於12(rc乾燥12小時。將已乾燥的粉末在空ϋ援札衣丨兄下使用電爐以3 0分鐘從室溫加熱至 300°C，於 /1 I n士，化300 C /1小時保持後，進而以3〇分鐘升溫至600°C且在兮，、田洚仅杜 ^ 仕皿度保持30分鐘後，自然冷卻。藉由該煅燒程式，來將氦仆雜"，， +时氧化鎢的粒子燒結而固定在二氧化矽奈米結構體（a2-7) & λ·、 & 1 7)上而成。將所得到固體之氧化鎢的含有率顯示在表10。 [表 10] 試料No. T81 T82 T83 T84 T85 T86 -l)/(a2-7)質量比氧化鎢含有率(％) 0.2/0.5 '*-----J 0.2/1.0 0.2/1.7 0.2/2.7 0.2/4.0 0.2/5.4 20.2 31.7 40.9 63.7 81.1 -63- 201229161 使用TEM進行觀察試料n〇.T83的表面，能夠氧化鎢的粒子係以奈米尺寸被固定在二氧化矽奈米 (第38圖）。又，使用X射線繞射測定而調查試料N〇的結晶構造，確認係氧化鎢的結晶構造（第39圖）。使用擴散反射光譜而測定試料No. T83的吸光度光確認在約至520nm之可見光區域具有源自氧化鎢的區域（第40圖）。實施例1 5<使用直鏈狀聚乙亞胺之氧化鎢奈米粒子在二氧化石夕奈米結構體（a2-7)> 使〇_7g合成例3所得到的二氧化矽奈米結 (a2-7)分散在l〇mL蒸餾水中之後，添加合成例1所之直鏈狀聚乙亞胺（PEI)的粉末，且於80°c攪拌1小使聚合物溶解《隨後’於室溫進行靜置冷卻3 〇分鐘此’以二氧化矽奈米結構體（a2-7)與煅燒後的氧化鎢量比為7 0 / 3 0的方式添加0 · 6 m L偏鶴酸鍵水溶液，室溫下攪拌1小時。使用離心分離機除去上部澄清館水之後，使用真空乾燥器於1 201：乾燥1 2小時而粉末。又’ PEI的使用量係以乙亞胺單元對偏鎢酸莫耳比為表1 1中所記載的比例之方式進行秤量而儀將所得到的粉末在空氣環境下使用電爐以30 從室溫加熱至30(TC，於30(TC/；l小時保持後，進 30分鐘升溫至600°C且在該溫度保持30分鐘後，自卻。藉由該煅燒程式，在除去直鏈狀聚乙亞胺之同氧化鎢的粒子係被煅燒而固定在二氧化矽奈米結 (a2-7)上。將該結果顯示在表1 1。確認管中 .T83 又，譜，吸收固定構體得到時來。在的質且於的蒸得到銨的 L用。分鐘而以然冷時，構體 -64 - 201229161 [表 11] 試料No. T91 T92 T93 T94 T95 T96 PEI/偏鶴酸錄莫耳比 0.1/0.1 0.5/0.1 1.0/0.1 2.0/0.1 5.0/0.1 10.0/0.1 氧化鎢含有率(％) 23.2 25.5 32.1 30.4 31.9 32.2 使用TEM進行觀察試料No. T93的表面，能夠確認氧化鶴的粒子係以奈米尺寸被固定在二氧化石夕奈米管上 (第41圖）。又，使用X射線繞射測定而調查試料N〇. T93 的結晶構造.，確認係氧化鎢的結晶構造（第42圖）。又，使用擴散反射光譜而測定試料No. T93的吸光度光譜，確認在約至520nm之可見光區域具有源自氧化鎢的吸收區域（第43圖）。貫施例1 6 <使用聚合物與二氧化矽的複合體亦即二氧化石夕奈米結構體（a2-6)之氧化鎢粒子的固定> 使〇.2g在合成例3所得到之聚合物與二氧化矽的複合物亦即奈米管狀的二氧化矽奈米結構體（a2_6)分散於 10ml蒸館水中之後，將已調整為5%之偏鎢酸銨水溶液 (a3 ’ -1)以質量比為表} 2所記載的比例秤量且混合後，在室溫下搜拌1小時，將所得到的懸浮液的上部澄清液使用離心分離器除去，且重複進行使用蒸餾水洗淨之作業 3次。將所得到的沈澱物使用真空乾燥‘器於1 2〇。〇乾燥ι 2 小時，來得到粉末。將所得到的粉末在空氣環境下使用電爐以30分鐘從室溫加熱至3〇〇〇c，於3〇〇(Jc/1小時保持後，進而以30分鐘升溫至6〇(rc且在該溫度保持3〇分鐘後，自然冷卻。藉由該煅燒程式，二氧化矽奈米結構體（a2-6)中的聚合物成分消失，且氧化鎢奈米粒子係被 -65- 201229161 燒結固定在二氧化矽奈米結構體（a2-7)上。將其結果顯示在表12。 [表 12] 試料No. Τ101 Τ102 Τ103 Τ104 Τ105 Τ106 (Χ·3)/(Α'-1)質量比 0.2/0.5 0.2/1.0 0.2/1.7 0.2/2.7 0.2/4.0 10.0/0.1 氧化鎢含有率 13.2 21.9 27.6 33.1 35.9 36.6 使用TEM進行觀察試料No. T103的表面，能夠確認氧化鎢的粒子係以奈米尺寸被固定在二氧化矽奈米管上（第44圖）。又，使用X射線繞射測定而調查試料N〇. T 1 〇3的結晶構造，確認係氧化鎢的結晶構造（第45圖）。又，使用擴散反射光譜而測定試料No. T73的吸光度光譜’確認在約至520nm之可見光區域具有源自氧化鎢的吸收區域（第4 6圖）。比較例3<氧化鎢434)固定在二氧化矽凝膠> 除了使用市售的二氧化矽凝膠（Merck : Silica gel 60 ’以下稱為B ’）作為二氧化矽材料以外’使用與實施例 1 〇同樣的手法燒結氧化鎢（a3_〗）。將結果顯示在表丨3 ^ [表 13] 試料No. Till T112 T113 T114 T115 ~ T116 (A-1)/(B5)質量比 1/9 2/8 3.5/6.5 5/5 6.5/3.5 •8/2 氧化鎢含有率(％)~ 11.3 21.4 32.8 49.9 61.9 84.1 比較例4<銅二價鹽負載三氧化鎢可見光應答型光觸媒〉為了評價在LED照射下的光觸媒活性，進行調製銅二價鹽負載三氧·化鎢可見光應答型光觸媒（特開 2009-226299號公報的追蹤實驗）作為比較例。，藉由將氧化鎢粉末(平均粒徑為25、高純度化學化學研究所股份公司）通過過渡器而除去粒徑為i⑽以 -66 - 201229161 上的粒子’且進行於65(TC煅燒3小時之前處理，來得到三氧化鎢。隨後使該三氧化鎢微粒子以在蒸餾水中為 1 0質置％的方式懸浮，隨後在此，以0.1質量％ (c u (11) V S. WO3)的量添加CuCh . 21〇(和光純藥工業股份公司製） ’邊擾拌邊加工至9(TC且保持1小時。隨後，使用吸引過渡將所得到的懸浮液過濾分開之後，使用蒸餾水洗淨殘渣，進而藉由在u (TC加熱乾燥而得到負載銅二價鹽之二氧化鶴微粒子作為比較用試樣。評價1 <氧化鎢（a3 -1)的光觸媒活性評價> 使用氧化鎢的奈米粒子（a3 _ 1)及氧化鎢的粒子（α -1)而進行乙駿的氧化分解實驗，來評價作為光觸媒之觸媒活！·生其中该氧化鎢的奈米粒子（a 3 _ 1)係使用在合成例 4所得到的直鏈狀聚乙亞胺；而該氧化鎢的粒子（〇 “）係在合成例5所得到。將結果顯示在第47圖。相較於氧化鎢的奈米粒子（a3 _丨），氧化鎢的粒子（^ _丨）係顯示只有 3分之1左右的觸媒活性。推定這是因為藉由使用直鏈狀聚乙亞胺而製造氧化鎢的粒子，能夠形成具有高比表面積之奈米尺寸的粒子。評價2 <將氧化鎢的粒子固定之二氧化矽奈米結構體的光觸媒活性評價1 > 使用貫施例10的試料No. T43、實施例1 1的試料- 丨 The result of observing the surface of the sample N〇 T73 by TEM, the sample No. was able to confirm that the particle system of the tungsten oxide was fixed to the cerium oxide nanofiber (Fig. 37). (Example 14 < Use of tungstate and fixed to cerium oxide nano-junction (a2-7)> ^ Measured 2. 2 g of the cerium oxide nanostructure (a2-7) obtained in Synthesis Example 3. Further, 'the aqueous solution of ammonium metatungstate was adjusted to "with distilled water", and the adjusted 5% aqueous solution was referred to as (a3M), and the mixture was mixed at a mass ratio of two, and distilled water was added to prepare a whole volume of 10 m1. The mixture was stirred for 1 hour, distilled water was removed from the obtained suspension, and dried using a vacuum drier at 12 (rc for 12 hours. The dried powder was used in an electric furnace under the air 札札札以以 3 3 The temperature is heated from room temperature to 300 ° C, and after maintaining at 300 ° C for 1 hour, the temperature is raised to 600 ° C for 3 minutes, and the temperature is maintained at 兮, 洚, 杜After 30 minutes, it is naturally cooled. By this calcination procedure, the particles of the cerium oxide <,, +-time tungsten oxide are sintered and fixed in the cerium oxide nanostructure (a2-7) & λ·, & 1 7) The content of the tungsten oxide of the obtained solid is shown in Table 10. [Table 10] Sample No. T81 T82 T83 T84 T85 T86 -l) / (a2-7) mass ratio tungsten oxide content (%) 0.2/0.5 '*-----J 0.2/1.0 0.2/1.7 0.2/2.7 0.2/4.0 0.2/5.4 20.2 31.7 40.9 63.7 81.1 -63- 201229161 Using TEM to observe the surface of the sample n〇.T83, the particles capable of oxidizing tungsten are fixed to the cerium oxide nanometer in a nanometer size (Fig. 38). Further, X-ray diffraction measurement is used. The crystal structure of the sample N〇 was examined, and the crystal structure of the tungsten oxide was confirmed (Fig. 39). The absorbance of the sample No. T83 was measured by the diffusion reflection spectrum to confirm that the region derived from tungsten oxide was present in the visible light region of about 520 nm ( Fig. 40) Example 1 5 <Tungsten Oxide Nanoparticles Using Linear Polyimine in the Sebium Oxide Structure (a2-7)> 〇7g Synthesis Example 3 After the cerium oxide nano-junction (a2-7) was dispersed in 1 mL of distilled water, the powder of the linear polyethylenimine (PEI) of Synthesis Example 1 was added, and the mixture was stirred at 80 ° C for 1 hour to obtain a polymer. Dissolve "Subsequently" to allow for standing cooling at room temperature for 3 minutes. The ratio of the amount of tungsten dioxide structure (a2-7) to the amount of tungsten oxide after calcination is 70. In a manner of /3 0, an aqueous solution of 0·6 m L of hexanoic acid was added, and the mixture was stirred at room temperature for 1 hour. After removing the upper clarified water using a centrifugal separator, the powder was dried using a vacuum dryer at 1 201: for 12 hours. Further, the amount of PEI used was measured by the ratio of the ethylenimine unit to the molar ratio of metatungstic acid to the ratio shown in Table 11. The obtained powder was placed in an air atmosphere using an electric furnace at room temperature of 30 from room temperature. Heat to 30 (TC, after 30 (TC /; l hours of holding, after 30 minutes of warming to 600 ° C and after this temperature is maintained for 30 minutes, since then. By this calcination procedure, the particle system of the same tungsten oxide which removes the linear polyethyleneimine is calcined and fixed on the ceria nanostructure (a2-7). The results are shown in Table 11. Confirm that the tube .T83 is again in the tube, and the absorption of the fixed structure is obtained. The quality of the product is obtained by steaming ammonium. In the minute and then cold, the body-64 - 201229161 [Table 11] Sample No. T91 T92 T93 T94 T95 T96 PEI/Herbic acid recorded Mohr ratio 0.1/0.1 0.5/0.1 1.0/0.1 2.0/0.1 5.0/0.1 10.0/0.1 Tungsten oxide content (%) 23.2 25.5 32.1 30.4 31.9 32.2 Using TEM to observe the surface of the sample No. T93, it was confirmed that the particle size of the oxidized crane was fixed on the SiO2 tube in a nanometer size ( Figure 41). In addition, the crystal structure of the sample N〇.T93 was examined by X-ray diffraction measurement, and the crystal structure of the tungsten oxide was confirmed (Fig. 42). Further, the absorbance spectrum of the sample No. T93 was measured by using a diffuse reflection spectrum, and it was confirmed that an absorption region derived from tungsten oxide was present in a visible light region of about 520 nm (Fig. 43). Example 1 6 <Fixed tungsten oxide particles of a composite of a polymer and cerium oxide, i.e., a silica magnetite structure (a2-6)> 〇.2g obtained in Synthesis Example 3 After the polymer and the cerium oxide complex, that is, the nano-tubular cerium oxide nanostructure (a2_6), is dispersed in 10 ml of steaming water, the aqueous solution of ammonium metatungstate adjusted to 5% (a3 ' - 1) After the mass ratio is weighed and mixed in the ratio shown in Table 2, the mixture is mixed at room temperature for 1 hour, and the supernatant liquid of the obtained suspension is removed by a centrifugal separator, and washed repeatedly with distilled water. The work is 3 times. The resulting precipitate was vacuum dried using a 12 Torr apparatus. Dry ι for 2 hours to obtain a powder. The obtained powder was heated from room temperature to 3 〇〇〇c in an air atmosphere using an electric furnace for 30 minutes, and after 3 minutes of Jc/1 hour retention, the temperature was further increased to 6 Torr in 30 minutes (rc and After the temperature was maintained for 3 minutes, it was naturally cooled. By the calcination procedure, the polymer component in the cerium oxide nanostructure (a2-6) disappeared, and the tungsten oxide nanoparticle was sintered at -65-201229161. The ruthenium oxide nanostructure (a2-7) was shown in Table 12. [Table 12] Sample No. Τ101 Τ102 Τ103 Τ104 Τ105 Τ106 (Χ·3)/(Α'-1) mass ratio 0.2 /0.5 0.2/1.0 0.2/1.7 0.2/2.7 0.2/4.0 10.0/0.1 Tungsten oxide content rate 13.2 21.9 27.6 33.1 35.9 36.6 Using TEM to observe the surface of the sample No. T103, it was confirmed that the particle size of the tungsten oxide was It was fixed on a ruthenium dioxide nanotube (Fig. 44). Further, the crystal structure of the sample N〇.T 1 〇3 was examined by X-ray diffraction measurement, and the crystal structure of the tungsten oxide was confirmed (Fig. 45). Further, the absorbance spectrum of the sample No. T73 was measured using a diffusion reflection spectrum to confirm that it was visible at about 520 nm. The light region has an absorption region derived from tungsten oxide (Fig. 46). Comparative Example 3 <Tungsten oxide 434) Fixed to cerium oxide gel> In addition to using a commercially available cerium oxide gel (Merck: Silica gel 60) 'hereinafter referred to as B') In the same manner as in Example 1 except for the cerium oxide material, tungsten oxide (a3_) was sintered by the same method as in Example 1. The results are shown in Table 3 ^ [Table 13] Sample No. Till T112 T113 T114 T115 ~ T116 (A-1) / (B5) mass ratio 1/9 2/8 3.5/6.5 5/5 6.5/3.5 • 8/2 Tungsten oxide content (%) ~ 11.3 21.4 32.8 49.9 61.9 84.1 Comparative example 4&lt Copper divalent salt-supported tungsten trioxide visible light-responsive photocatalyst 〉 In order to evaluate the photocatalytic activity under LED irradiation, a photocatalyst for modulating copper divalent salt-supported trioxane-tungsten visible light-responsive photocatalyst is disclosed (JP-A-2009-226299) Experiment) As a comparative example, a particle having a particle diameter of i(10) of -66 - 201229161 was removed by passing a tungsten oxide powder (having an average particle diameter of 25 and a high purity chemical chemical research institute) through a transition device. 65 (TC calcined 3 hours before treatment to get trioxane Tungsten. The tungsten trioxide fine particles were then suspended in a manner of 10% in distilled water, and then CuCh was added in an amount of 0.1% by mass (cu (11) V S. WO3). Wako Pure Chemical Industries Co., Ltd.) 'Breaking the edge to 9 (TC and keeping it for 1 hour). Subsequently, the obtained suspension was separated by filtration using a suction transition, and the residue was washed with distilled water, and the oxidized crane fine particles of the copper-loaded divalent salt were obtained as a comparative sample by heat drying in UC (TC). <Evaluation of Photocatalytic Activity of Tungsten Oxide (a3 -1)> The oxidative decomposition test of junjun was carried out using tungsten nanoparticles (a3 _ 1) and tungsten oxide particles (α -1) to evaluate the photocatalyst as photocatalyst. The catalyst is produced by the nanoparticle (a 3 _ 1) in which the tungsten oxide is produced, and the linear polyethylenimine obtained in Synthesis Example 4 is used; and the tungsten oxide particles (〇") are The results obtained in Synthesis Example 5. The results are shown in Fig. 47. Compared with the tungsten nanoparticles (a3 _ 丨), the tungsten oxide particles (^ _ 丨) show only about one-third of the catalyst activity. It is presumed that this is because the particles of tungsten oxide are produced by using linear polyethylenimine, and particles having a nano surface having a high specific surface area can be formed. Evaluation 2 < Photocatalyst activity evaluation of rice structure 1 > The sample No. T43 of Example 10 and the sample of Example 1 1 were used.

No. T53、實施例12的試料ν〇· T63而進行光觸媒活性評價。作為比較，使用比較例3的試料N〇 T1 13及在比 -67- 201229161 較例4所得到之銅二價鹽負载三氧化嫣。將結果顯示在第48圖。在此，LED燈的光量係設定為2〇〇〇〇ΐχ。在本發明的全部試料，能夠確認非常高的乙醛光分解活性。特別是進行燒結固定在二氧化石夕奈米管之試料ν〇了63 的觸媒活性高，照射光線20分鐘後乙醛的分解反應有大致結束之傾向。試料No. Τ63係特別3= 尔荷别疋初期活優良，相較於比較例4的觸媒，單位時間照射光線1〇分鐘之二氧化碳氣體產生量為，約40倍。No_ T63係氧化鎢的構成量為約35%，能夠確認觸媒的功能係效率良好。比較例3 所得到的試料N〇. TU3’ _然發揮超過比較例4的觸媒若干之觸媒活性，但是相較於本發明的光觸媒時，係活性較低。評價3 <锻燒前後的光觸媒活性之比較> 一在實施例12，進行比較試料No. T63之煅燒前後的光觸媒活性。將結果顯示在第49圖。確認藉由煅燒處理 :進仃燒結固定氧化鎢，觸媒活性提升。由此，能夠推 =在氧化鎢的奈米粒子與二氧化矽奈米結構體的界面係參與光觸媒功能。評價4 <將氧化鎢的粒子固定之二氧化矽奈米結構體的光觸媒活性評價2> 、進行在實施例丨3所得到之試料Ν〇 Τ7丨的光觸媒活性ό平價。你炎示在卞為比較，係使用比較例4的光觸媒。將結果顯 50圖。相較於比較用觸媒，試料No. Τ71之單仿時間光，昭身 +彳Λ & 、、射1 〇刀知之二氧化碳氣體產生量為約28倍。 -68- 201229161 評價5 <將氧化鎢的粒子固定之二氧化矽奈米結構體的光觸媒活性評價3 > 進行在實施例14所得到之試料No. T83的光觸媒活 ί生#彳貝。作為比較，係使用比較例4的光觸媒。將結果顯不在第5 1圖。相較於比較用觸媒，試料No. Τ83之單位時間光照射1 0分鐘之二氧化碳氣體產生量為約30倍〇評價6 <將氧化鶴的粒子固定之二氧化矽奈米結構體的光觸媒活性評價進订在實施例1 5所得到之試料Ν〇· T93的光觸媒活 I"生。平饧。作為比較，係使用比較例4的光觸媒。將結果顯示在镇矛/圖。相較於比較用觸媒，試料No. T93之單位時間光照射1 〇分鐘之二氧化碳氣體產生量為約28倍〇評價7 <將氧化鶴的粒子固定之二氧化矽奈米結構體的光觸媒活性評價5 > 進行在實施例1 6所得到之試料Ν ο · T 1 0 3的光觸媒 ’舌性評價。作為比較，係使用比較例4的光觸媒。將結果顯示在第53圖。相較於比較用觸媒，試料No. T103 之單位時間光照射1 〇分鐘之二氧化碳氣體產生量為約 29倍。No. T53 and the sample ν〇·T63 of Example 12 were evaluated for photocatalytic activity. For comparison, the sample N〇 T1 13 of Comparative Example 3 and the copper divalent salt supported by Comparative Example 4 of -67-201229161 were used to carry the antimony trioxide. The result is shown in Figure 48. Here, the amount of light of the LED lamp is set to 2 〇〇〇〇ΐχ. In all of the samples of the present invention, very high acetaldehyde photodegradation activity was confirmed. In particular, the catalyst which was sintered and fixed in the cerium oxide nanotubes had a high catalytic activity of 63, and after 20 minutes of irradiation with light, the decomposition reaction of acetaldehyde tends to be largely ended. The sample No. Τ63 was particularly excellent in the initial stage of 3: erhobe, and the amount of carbon dioxide gas generated by irradiating light per unit time per unit time was about 40 times as compared with the catalyst of Comparative Example 4. The composition amount of No. T63-based tungsten oxide was about 35%, and it was confirmed that the function of the catalyst was excellent. The sample N〇.TU3' obtained in Comparative Example 3 exhibited a certain amount of catalyst activity exceeding that of the catalyst of Comparative Example 4, but was less active than the photocatalyst of the present invention. Evaluation 3 <Comparison of photocatalytic activity before and after calcination> First, in Example 12, photocatalytic activity before and after calcination of Comparative Sample No. T63 was performed. The result is shown in Fig. 49. It was confirmed that the catalyst activity was improved by the calcination treatment: the tungsten oxide was fixed by sintering. Thereby, it is possible to participate in the photocatalytic function in the interface between the nanoparticle of tungsten oxide and the cerium oxide nanostructure. Evaluation 4 < Photocatalytic activity evaluation 2 of the cerium oxide nanostructure in which the particles of tungsten oxide were fixed] The photocatalytic activity ό ό of the sample Ν〇丨 7 obtained in Example 丨 3 was carried out. The photocatalyst of Comparative Example 4 was used for comparison. The result is shown in Figure 50. Compared with the comparative catalyst, the sample No. Τ71 is a single-time light, and the amount of carbon dioxide gas generated by the 彳Λ 彳Λ 彳Λ amp 、。知知。。。。。。。。。。。。。。。二氧化碳二氧化碳二氧化碳二氧化碳二氧化碳二氧化碳-68-201229161 Evaluation 5 <Photocatalyst activity evaluation of the ceria nanostructure in which the particles of tungsten oxide were fixed 3 > The photocatalyst activity of the sample No. T83 obtained in Example 14 was carried out. For comparison, the photocatalyst of Comparative Example 4 was used. The results are not shown in Figure 51. Compared with the comparative catalyst, the amount of carbon dioxide gas generated by the light per unit time of the sample No. Τ83 was about 30 times. Evaluation 6 < Photocatalyst of the cerium oxide nanostructure in which the particles of the oxidized crane were fixed The activity evaluation was carried out in the photocatalyst activity I" of the sample Ν〇·T93 obtained in Example 15. Flat. For comparison, the photocatalyst of Comparative Example 4 was used. Display the results in the town spear/map. Compared with the comparative catalyst, the amount of carbon dioxide gas generated by the sample No. T93 per unit time of light irradiation for about 1 minute is about 28 times. Evaluation 7 < Photocatalyst of the cerium oxide nanostructure in which the particles of the oxidized crane are fixed Activity Evaluation 5 > The photocatalyst 'tongue evaluation' of the sample Ν ο · T 1 0 3 obtained in Example 16. For comparison, the photocatalyst of Comparative Example 4 was used. The result is shown in Fig. 53. Compared with the comparative catalyst, the amount of carbon dioxide gas generated by the sample No. T103 per unit time of light irradiation for about 1 minute was about 29 times.

S -69- 201229161 評價8 〈將氧化鎢的粒子固定之二氧化矽奈米結構體在5〇〇〇ΐχ 照射下之光觸媒活性評價> 使用在貫施例1 〇所得到之試料Ν〇 Τ43，使LED照射的光量為較弱之5 〇〇〇 i χ，在該條件下，進行乙醛的光分解。作為比較，係使用比較例4的光觸媒。將結果顯不在第54圖。試料Νο. Τ43係從照射初期顯示顯著的觸媒活H，相較於比較用觸媒，在照射光線6 〇分鐘時點之二氧化碳氣體產生量為約1 2倍。評價9 <將氧化鎢的粒子固定之二氧化矽奈米結構體在55〇u 照射下之觸媒活性評價> 在評價8 ’除了使照射光量為5〇〇〇χ以外，與評價8 同樣地進行而且進行評價。將結果顯示在第55圖。儘管照射如此程度微弱的光量，本發明的試料Ν〇 Τ43係隨著 <’、、射時間而一氧化碳產生量係顯著地地增大，且在照射光線60分鐘後’二氧化碳產生量係上升至ι65ρρπ^ 為了比較而使用的觸媒之情況，低光量照射時，係即便照射1 80分鐘亦無法確認產生明確的二氧化碳。實施例1 7<1液型塗料組成物的調製：介質2_丙醇> 使〇.375g實施例1所得到的粉體（Α1-1)與1.125g實施例12所得到的試料n〇.T63[25/75(質量比）]懸浮在 3 0mL 2 -丙醇（和光純藥工業製、有機合成用）且使用混合型分散機FILMIX(PRIMIX製40-40型）以4〇m/s的旋轉速度使其分散3 0秒。藉由使用該高速混合機而進行分散 -70- 201229161 處理，旎夠使粉體（八1-1)與N〇 T63以奈米等級均句地分散。將合成例6所得到之樹脂（B_2)使用2_丙醇以樹脂固體含量為55%的方式稀釋而使用。以粉體（Αΐ ι)及試料 No.T63的合計質量與黏合劑樹脂（B)的固體含量質量比[(A1) + (A2)]/(B-1)成為表}所記載的比例之方式混合 .且進行照射超音波丨小時來得到丨液型塗料組成物。S -69-201229161 Evaluation 8 <Evaluation of photocatalytic activity of cerium oxide nanostructures in which tungsten oxide particles are fixed under 5 & irradiation> Using the sample obtained in Example 1 Ν〇Τ43 The amount of light irradiated by the LED is 5 〇〇〇i χ, and under this condition, photodecomposition of acetaldehyde is performed. For comparison, the photocatalyst of Comparative Example 4 was used. The results are not shown in Figure 54. The sample Νο. Τ43 showed a remarkable catalytic activity H from the initial stage of irradiation, and the amount of carbon dioxide gas generated at the point of 6 minutes of irradiation with light was about 12 times as compared with the comparative catalyst. Evaluation 9 < Evaluation of Catalytic Activity of Cerium Oxide Nanostructures in Which Titanium Oxide Particles Are Fixed Under 55〇u Irradiation> In Evaluation 8' except that the amount of irradiation light was 5〇〇〇χ, and evaluation 8 The same was carried out and evaluated. The result is shown in Figure 55. In spite of such a weak amount of light, the sample 本43 of the present invention significantly increased the amount of carbon monoxide generated with the time of '', and the amount of carbon dioxide generated after the irradiation of the light for 60 minutes. Ι65ρρπ^ In the case of a catalyst to be used for comparison, it is impossible to confirm that a clear carbon dioxide is generated even when irradiated for a low light amount for a low light amount. Example 1 7<1 Liquid type coating composition preparation: medium 2_propanol> 375 g of the powder obtained in Example 1 (Α1-1) and 1.125 g of the sample obtained in Example 12 were prepared. .T63 [25/75 (mass ratio)] suspended in 30 mL of 2-propanol (manufactured by Wako Pure Chemical Industries, Ltd. for organic synthesis) and using a hybrid disperser FILMIX (Model 40-40 manufactured by PRIMIX) at 4 μm/ The rotational speed of s is allowed to disperse for 30 seconds. Dispersion -70 - 201229161 was carried out by using the high-speed mixer, and the powder (eight 1-1) and the N 〇 T63 were uniformly dispersed in a nanometer scale. The resin (B_2) obtained in Synthesis Example 6 was diluted with 2% propanol so that the resin solid content was 55%. The ratio of the total mass of the powder (Αΐ ι) and the sample No. T63 to the solid content of the binder resin (B) [(A1) + (A2)] / (B-1) is in the ratio shown in Table} The method was mixed and irradiated with ultrasonic waves for a few hours to obtain a sputum-type paint composition.

實施例1 8<藉由將1液型塗料組成物塗布在玻璃基材上來形成光觸媒塗膜> 將實施例17所得到之No. ‘T124的1液型塗料組成物使用塗膜盗（YOSHIMITU製）且以速度l〇、RDS16棒塗布益塗布在玻璃基材上。將所製造之塗膜於室溫（25。〇）靜置乾燥一晚，來得到光觸媒塗膜。將該光觸媒塗膜的膜觀察影像顯示在第56圖。能夠確認源自二氧化矽奈米結構體形狀的表面凹凸結構係擴展至膜整體之影像。實施例1 9<二氧化矽奈米結構體與氧化鈦之複合型光觸媒亦即粉體（A1-1)與樹脂（B_2)的混合物之調整：介質2_ 丙醇> 除了只有使用粉體（A 1 -1)以外，與實施例1 7同樣地進行而使其分散於2 -丙醇之後，粉體（A 1 -1)與樹脂（b - 2) 係以固體含量質量比（A1)/(B)成為表15所記載的比例之方式混合’且進行照射超音波1小時來得到1液型塗料 -71 - 201229161 組成物，其中該樹脂（B-2)係使用2丙醇而以樹脂固體含量為55 %的方式稀釋而成。 [表 15] 組成物No. T131 T132 T133 T134 T135 ^T136 A1/B (質量比） 10/90 20/80 35/65 50/50 65/35 80/20 — 不揮發成分 (wt%) 37 33 30 27 24 22 實施例20<藉由將只含有粉體（八卜丨）之塗料組成物塗布在玻璃基材上來形成光觸媒塗膜> 除了使用實施例19所得到之No. T 134的塗料組成物以外’與貫施例1 8同樣地進行而使用棒塗布器塗布在玻璃基材上。將該光觸媒塗膜的SEM膜觀察影像顯示在第57圖實施例2 1 <二氧化矽奈米結構體與氧化鎢之複合型光觸媒亦即粉體（A2)與樹脂（B_2)的混合物之調整：介質2_ 丙醇> 除了只有使用在實施例1 2所得到之試料n 〇. T 6 3以外’與實施例1 7同樣地進行而使其分散於2_丙醇之後， s式料N 〇. T 6 3與樹脂（B _ 2)係以固體含量質量比（a 2) / ( B ) 成為表1 6所記載的比例之方式混合，且進行照射超音波 1小時來得到1液型塗料組成物， [表 16] 組成物No. T141 T142 T143 T144 T145 T146 A2/B (質量比） 10/90 20/80 35/65 50/50 65/35 80/20 不_發成分 (wt%) 37 33 30 27 24 22 -72- 201229161 實施例22<藉由將只含有粉體（A2)之塗料組成物塗布在玻璃基材上來形成光觸媒塗膜；> 除了使用實施例21所得到之n 〇. τ 1 4 4的塗料組成物以外，與實施例1 8同樣地進行而使用棒塗布器塗布在玻璃基材上。將该光觸媒塗膜的SEM膜觀察影像顯示在第58圖 <塗膜评‘ 11.在太陽光曝露下之光觸媒塗膜Ν〇τΐ4 的超親水性能評價> 將在實施例1 8所得到的塗膜、在實施例2 〇所得到的塗膜、在實施例22所得到的塗膜曝露在太陽光，且評價曝露日數的經過引起水接觸角的變化（第5 9圖）。從全部的塗膜，能夠確認伴隨著曝露日數的經過，水接觸角係明確地降低。太陽光曝露3〇天後，係全部的塗膜均成為接觸角為5 °以下的超親水性塗膜。只含有二氧化矽奈米結構體與氧化鎢進行複合化而成的粉體（A2)之塗膜，雖然觀察到超親水化，但是相較於使用粉體（A丨）者，為了超親水化必須長期間的太陽光曝露。只有使用含有氧化欽之複合型粉體（A1)時，薄膜會在短的太陽光曝露時間產生超親水化。推測這是因為將氧化鈦粒子與二氧化石夕奈米結構體複合化而成之粉末（A丨）係藉由太陽光曝露’在塗膜中會發揮高光觸媒活性且將被覆形成有表面凹凸結構的二氧化矽奈米結構體之黏合劑樹脂分解，在較短的太陽光曝露日數，氧化鈦的奈米粒子會露出頂部之緣故°又’雖然使用粉體（A1)與粉體（A2)混合之塗膜亦比只有使用粉體（A1)的塗膜差，但是相較.於只使用粉 -73- 201229161 體（A2)的塗胺^，Ab私^ & 。能夠推、>卜°確認在較短的曝露期間會超親水化 ⑷)係在太陽光照射:Λ 勾分散之粉體僅曰才ψν興會發择非常尚的光觸媒活性，不疋在如體(Μ)周邊所存在的樹體（Α2)周邊所在力沾此向且耶將在如的觸媒… 成分分解，而使在粉體(Α2)中的觸炼活性部位亦g $ -卩氧化鎢粒子面露出塗膜表面上之緣的複八：二係暗不糟由將二氧化矽奈米結構體與氧化鈦 ==即粉體⑷)與二氧化梅結構體與氧化鶴可見光應答性之氧化鶴光膜，能夠使具有高 .‘，先觸媒活性面在短期間的光照射下有效率地露出。 <塗膜評價12 : LED照明照射下之光觸媒活性〉在塗膜評價1卜曝露於太陽光至能夠確認超親水化之後，進行評價纟LED照明照射下之光觸媒活性（在實施例18所得到的塗膜：22天期間、在實施例20所得到的塗膜：10天期間、在實施例22所得到的塗膜：3〇天期間各自曝露在太陽光之後進行評價）。從在實施例i 8 所得到的塗膜及在實施例22所得到的塗膜，能夠確認藉由LED照明照射，乙醛係明確地分解（第6〇圖卜另一方面，使用只有以氧化鈦作為活性部位的粉體（A1)之塗膜（在實施例20所得到的塗膜）係在LED照明照射下不顯示光觸媒活性。在實施例丨8所得到的塗膜及在實施例22 所得到的塗膜’係藉由將氧化鎢作為活性部位的粉體 (A2)有效率地起作用，而發揮同程度之高應答能力。此情形係暗示藉由將粉體（A丨）及粉體（A2)混而來製造 -74- 201229161 塗膜，粉體（A2)中的觸媒活性部位亦即氧化鎢面係明確地露出塗膜表面上，而對作為在LED照明照射下具有高活性的光觸媒塗膜產生功能，且意味著混合粉體（A 1)係能夠使粉體（A2)的氧化鎢活性面藉由由短期間的照射光線而露出。從前述的結果，強烈地暗示在本發明的光觸媒塗膜，特別是使用氧化鎢者，係即便在實際空間之室内LED照明照射下亦具有非實用性。【圖式簡單說明】第1圖係合成例1所得到之二氧化矽奈米結構體 (a2-l)的 SEM 照片。第2圖係合成例1所得到之二氧化矽奈米結構體 (a2-2)的 SEM 照片。第3圖係合成例2所得到之二氧化矽奈米結構體 (a2-3)的 SEM 照片。第4圖係合成例2所得到之二氧化矽奈米結構體 (a2-4)的 SEM 照片。第5圖係合成例3所得到之二氧化矽奈米結構體 (a2-5)的 SEM 照片。第6圖係合成例3所得到之二氧化矽奈米結構體 (a2-6)的氮氣吸附（下）-脫附（上）之等溫線。第7圖係·合成例3所得到之二氧化矽奈米結構體 (a2-6)的孔體積分布曲線。第8圖係合成例 3所得到之二氧化矽奈米結構體 (a2-6)的 TEM 照片。 -75- 201229161 到之二氧化矽奈米結構體 )之等溫線。到之二氧化矽奈米結構體第9圖係合成例3所得 (a2-7)的氮氣吸附（下）_脫附（」-第10圖係合成例3所得 (a2-7)的孔體積分布曲線。之二氧化矽奈米結構體第11圖係合成例3所得到 (a2-7)的 TEM 照片。 1 2圖係合成例 4所得到之氧化鎢（a3-l)的SEM照片第13圖係合成例4所得到之氧化鶴（a3-l)的X射線繞射圖表。第14圖係合成例4所得到之氡化鎢（a3__ UV vis 擴散反射光譜。第15圖係合成例5所得到之氧化鶴（α-l)的SEM照第1 6圖係貫施例i所得到之粉體（a卜丨）的τεμ照片。第17圖係實施例4所得到的塗膜的SEM照片。. 第1 8圖係比較例2所得到的塗膜的SEM照片。第19圖係實施例4所得到的塗膜（CA1)與比較例2 所得到的塗膜（CB1)之研磨前後(1〇次）的照片（研磨後的照片係各自為CA2、CB2)。第20圖係將實施例4所得到的塗膜使用海綿研磨 5,00〇次時之研磨前塗膜（□)、研磨後塗膜（△)之利用乙醛分解之二氧化碳濃度增加量對光照射時間的繪圖（照射條件：黑光、光量1，0 0 0 1 X)。 -76- 201229161 第2 1圖係將實施例4所得到的塗膜（□)、比較例2 所得到的塗膜（△)、只有使用樹脂而得到的塗膜（〇）之利用乙醛分解之二氧化碳濃度增加量對光照射時間的繪圖（照射條件：黑光、光量LOOOix)。第22圖係將實施例4所得到的塗膜（□)'比較例2 所得到的塗膜（△)、只有使用樹脂（B_i)而得到的塗骐（〇）之利用乙醛分解之二氧化碳濃度增加量對光照射時間的繪圖（照射條件：模擬太陽光、光量1〇,〇〇〇ΐχ)。第23圖係將實施例4所得到的塗膜（□)、比較例2 所得到的塗膜（△)、只有使用樹脂（Β_υ而得到的塗膜（〇）之利用乙醛分解之二氧化碳濃度增加量對光照射時間的繪圖（照射條件：螢光燈.、光量6,〇〇〇1χ)。第24圖係顯示實施例4所得到的塗膜之伴隨著照射發光燈的時間經過之接觸角的變化之圖表。第2 5圖係使用實施例4所得到的塗膜時之亞曱基藍色素的光脫色反應的照片（照射條件：螢光燈、光量 6,0001χ) 〇第26圖係實施例5所得到的塗膜的SEM照片。第27圖係比較例3所得到的塗膜的SEM照片。第2 8圖係將實施例5所得到的塗膜（□)、比較例3 所得到的塗膜（△)、只有使用樹脂（Β_丨）而得到的塗膜（〇）之利用乙醛分解之二氧化碳濃度增加量對光照射時間的繪圖（照射條件：模擬太陽光、光量l〇,〇〇〇lx)。第29圖係實施例6所得到的塗膜的SEM照片。 -77- 201229161 第30圖係將實施例6所得到的塗膜（□)、比較例2 所得到的塗膜（A )、只有使用樹脂（Β-1)而得到的塗膜（〇）之利用乙醛分解之二氧化碳濃度增加量對光照射時間的繪圖（照射條件：模擬太陽光、光量l〇,〇〇〇lx)。第3 1圖係將實施例7所得到的塗膜之在屋外曝露三個月後的接觸角。（c 1 :塗布後曝露前、c2 :塗布後曝露 1小時後、c 3 :塗布後曝露三個月後、d 1 :無塗布且曝露前、d2 :無塗布且曝露三個月後）第3 2圖係在實施例8所得到的各式各樣的基板上所製造的塗膜之利用乙醛分解之二氧化碳濃度增加量對光照射時間的繪圖（照射條件：黑光、光量1,000 lx)。玻璃、木材（□)、氣乙烯板（△)、聚對酜酸乙二酯（〇）、壓克力板（◊)、聚碳酸酯板（X )、聚苯乙烯板（+ )、不鏽鋼板（*)、鋁板（_ )、内牆用地磚（（▲)、屋外用地磚（ Φ)、浴室用地碑（♦)、天然石…布（一）。第33圖係在實施例4(口）、實施例9(Λ )所得到的塗膜之利用乙醛分解之二氧化碳濃度增加量對光照射時間的繪圖（照射條件：模擬太陽光、光量1 〇，〇〇〇 1 X )。第34圖係在實施例1 0所得到的試料No. Τ43的ΤΕΜ 照片。第35圖係在實施例11所得到的試料No. T53的TEM 照片。第36圖係在實施例12所得到的試料No. T63的TEM 照片。第37圖係在實施例13所得到的試料No. T73的TEM 照片。 -78- 201229161 第38圖係在實施例14所得到的試料No. Τ83的ΤΕΜ 照片。第39圖係在實施例14所得到的試料No. Τ83的X 射線繞射圖表。第40圖係在實施例14所得到的試料No. T83的 UV-vis擴散反射光譜。第41圖係在實施例1 5所得到的試料No. T93的TEM 照片。第42圖係在實施例15所得到的試料No. T93的X 射線繞射圖表。第43圖係在實施例15所得到的試料No. T93的 UV-vis擴散反射光譜。第4 4圖係在實施例1 6所得到的試料Ν ο · T 1 0 3的 TEM照片。Example 1 8<Photocatalyst coating film was formed by coating a one-liquid type coating composition on a glass substrate> The one-component type coating composition of No. 'T124 obtained in Example 17 was coated with a coating film (YOSHIMITU) And coated with a speed l〇, RDS16 rod coated on a glass substrate. The produced coating film was allowed to stand at room temperature (25 ° C) for one night to obtain a photocatalyst coating film. The film observation image of the photocatalyst coating film is shown in Fig. 56. It was confirmed that the surface uneven structure derived from the shape of the ruthenium oxide nanostructure was extended to the image of the entire film. Example 1 9<Complex photocatalyst of cerium oxide nanostructure and titanium oxide, that is, adjustment of a mixture of powder (A1-1) and resin (B_2): medium 2_propanol> except that only powder was used ( In the same manner as in Example 1 7 except that A 1 -1) was dispersed in 2-propanol, the powder (A 1-1) and the resin (b-2) were solid-content-mass ratio (A1). / (B) was mixed as in the ratio shown in Table 15 and irradiated with ultrasonic for 1 hour to obtain a one-component paint-71 - 201229161 composition in which the resin (B-2) was treated with 2 propanol The resin was diluted in a solid content of 55%. [Table 15] Composition No. T131 T132 T133 T134 T135 ^T136 A1/B (mass ratio) 10/90 20/80 35/65 50/50 65/35 80/20 — Nonvolatile matter (wt%) 37 33 30 27 24 22 Example 20 <Formation of Photocatalyst Coating Film by Coating a Coating Composition Containing Only Powder (Bei Bu) on a Glass Substrate> In addition to the coating of No. T 134 obtained in Example 19 The composition was applied in the same manner as in Example 18 except that the composition was applied to a glass substrate using a bar coater. The SEM film observation image of the photocatalyst coating film is shown in the mixture of the phosphoric acid nanostructure and the tungsten oxide composite photocatalyst, that is, the mixture of the powder (A2) and the resin (B_2). Adjustment: medium 2_propanol> In addition to the sample n 〇. T 6 3 obtained in Example 12, the same procedure as in Example 1 7 was carried out to disperse it in 2-propanol. N 〇. T 6 3 and the resin (B _ 2) are mixed in such a manner that the solid content mass ratio (a 2) / ( B ) is in the ratio shown in Table 16, and the ultrasonic wave is irradiated for 1 hour to obtain one liquid. Type coating composition, [Table 16] Composition No. T141 T142 T143 T144 T145 T146 A2/B (mass ratio) 10/90 20/80 35/65 50/50 65/35 80/20 No _ hair composition (wt %) 37 33 30 27 24 22 -72- 201229161 Example 22 < A photocatalyst coating film was formed by coating a coating composition containing only the powder (A2) on a glass substrate; > In the same manner as in Example 18 except that the coating composition of τ 1 4 4 was applied, the coating was applied to a glass substrate using a bar coater. The SEM film observation image of the photocatalyst coating film is shown in Fig. 58 <Paint film evaluation' 11. Evaluation of superhydrophilic performance of photocatalyst coating film Ν〇τΐ4 under sunlight exposure> The coating film obtained in Example 2, the coating film obtained in Example 22, and the coating film obtained in Example 22 were exposed to sunlight, and the change in the contact angle was evaluated to cause a change in the water contact angle (Fig. 5). From the entire coating film, it was confirmed that the water contact angle was clearly lowered with the passage of the number of exposure days. After exposure to sunlight for 3 days, all the coating films were super-hydrophilic coatings with a contact angle of 5 ° or less. The coating film of the powder (A2) which is obtained by combining only the ruthenium oxide nanostructure and the tungsten oxide is superhydrophilic, but is super-hydrophilic compared to the powder (A丨). The sunlight must be exposed for a long period of time. Only when a composite powder (A1) containing oxidized chin is used, the film is superhydrophilic in a short exposure time of sunlight. It is presumed that this is because the powder (A丨) obtained by combining the titanium oxide particles and the SiO2 sulphate structure exhibits high photocatalytic activity in the coating film by sunlight exposure, and is coated with surface unevenness. The binder resin of the structure of the cerium oxide nanostructure is decomposed, and in the short days of exposure to sunlight, the nanoparticles of titanium oxide will be exposed to the top of the surface, while using powder (A1) and powder ( A2) The mixed coating film is also inferior to the coating film using only the powder (A1), but compared to the only coating of the powder -73-201229161 (A2), Ab private ^ & It is possible to push, > to confirm that it will be super-hydrophilic during a short exposure period. (4)) It is exposed to sunlight: Λ The powder dispersed in the hook is only used to select a very photocatalytic activity. The surrounding body (Α2) around the body (Α2) is in the same direction and the yeah will be decomposed in the catalyst... The active part in the powder (Α2) is also g $ -卩The surface of the tungsten oxide particles is exposed on the surface of the coating film. The second layer is not affected by the cerium oxide nanostructure and the titanium oxide == powder (4)) and the oxidized plum structure and the visible light of the oxidized crane. The oxidized light film can be made to have a high density, and the first catalyst active surface is efficiently exposed under light irradiation for a short period of time. <Coating film evaluation 12: Photocatalyst activity under irradiation of LED illumination> Evaluation of coating film 1 After exposure to sunlight to confirm superhydrophilization, photocatalytic activity under evaluation of LED illumination was evaluated (obtained in Example 18) The coating film was evaluated during the period of 22 days, the coating film obtained in Example 20: 10 days, and the coating film obtained in Example 22: each exposed to sunlight after 3 days. From the coating film obtained in Example i8 and the coating film obtained in Example 22, it was confirmed that the acetaldehyde was decomposed by LED illumination, and the acetaldehyde was decomposed. The coating film of the powder (A1) having titanium as the active site (the coating film obtained in Example 20) showed no photocatalytic activity under the illumination of the LED illumination. The coating film obtained in Example 8 and Example 22 The obtained coating film 'effectively functions by using the tungsten oxide as the active material powder (A2), and exhibits the same high degree of responsiveness. This case implies that the powder (A 丨) and Powder (A2) is mixed to produce -74- 201229161 Coating film, the active site of the catalyst in the powder (A2), that is, the tungsten oxide surface is clearly exposed on the surface of the coating film, and has the effect of being illuminated under LED illumination. The highly active photocatalyst coating film functions, and means that the mixed powder (A 1 ) can expose the tungsten oxide active surface of the powder (A2) by irradiation light for a short period of time. From the foregoing results, strongly Implying in the photocatalyst coating film of the present invention, particularly using oxidation Tungsten is not practical even in indoor LED lighting in real space. [Simplified illustration] Fig. 1 is a SEM of the cerium oxide nanostructure (a2-l) obtained in Synthesis Example 1. Fig. 2 is a SEM photograph of the cerium oxide nanostructure (a2-2) obtained in Synthesis Example 1. Fig. 3 is a cerium oxide nanostructure obtained in Synthesis Example 2 (a2-3) SEM photograph. Fig. 4 is a SEM photograph of the cerium oxide nanostructure (a2-4) obtained in Synthesis Example 2. Fig. 5 is a cerium oxide nanostructure obtained in Synthesis Example 3 (a2- 5) SEM photograph. Fig. 6 is an isotherm of nitrogen adsorption (lower)-desorption (top) of the cerium oxide nanostructure (a2-6) obtained in Synthesis Example 3. Fig. 7 The pore volume distribution curve of the cerium oxide nanostructure (a2-6) obtained in Synthesis Example 3. Fig. 8 is a TEM photograph of the cerium oxide nanostructure (a2-6) obtained in Synthesis Example 3. -75- 201229161 The isotherm of the cerium oxide nanostructure). Fig. 9 shows the pore volume of (a2-7) obtained in Synthesis Example 3 (a2-7) by nitrogen adsorption (bottom)_desorption ("-Fig. 10). Distribution curve. The ruthenium dioxide nanostructures Figure 11 is a TEM photograph of (a2-7) obtained in Synthesis Example 3. 1 2 SEM photograph of the tungsten oxide (a3-l) obtained in Synthesis Example 4 13 is an X-ray diffraction chart of the oxidized crane (a3-1) obtained in Synthesis Example 4. Fig. 14 is a tungsten oxide obtained by Synthesis Example 4 (a3__UV vis diffusion reflection spectrum. Fig. 15 is a synthesis example) The SEM photograph of the obtained oxidized crane (α-l) is the τεμ photograph of the powder (a) obtained in Example i. Fig. 17 is a coating film obtained in Example 4. SEM photograph: Fig. 18 is a SEM photograph of the coating film obtained in Comparative Example 2. Fig. 19 is a polishing of the coating film (CA1) obtained in Example 4 and the coating film (CB1) obtained in Comparative Example 2. Photographs before and after (1 time) (photographs after polishing are CA2 and CB2). Fig. 20 is a pre-polishing coating film when the coating film obtained in Example 4 was ground by a sponge at 5,00 times. ), after painting (△) A plot of the amount of increase in carbon dioxide concentration by decomposition of acetaldehyde versus light irradiation time (irradiation conditions: black light, light quantity 1, 0 0 0 1 X) -76- 201229161 Figure 2 is obtained in Example 4. The coating film (□), the coating film (Δ) obtained in Comparative Example 2, and the coating film obtained by using the resin (〇), the amount of increase in the concentration of carbon dioxide by decomposition of acetaldehyde, and the irradiation time (lighting conditions: The black film and the light amount LOOOix). Fig. 22 is a coating film (?) obtained in the coating film (?) obtained in Example 4, and a coating film (?) obtained by using only the resin (B_i). The drawing of the light irradiation time by the amount of increase in the concentration of carbon dioxide decomposed by acetaldehyde (irradiation conditions: simulated sunlight, amount of light, 〇〇〇ΐχ). Fig. 23 shows the coating film (□) obtained in Example 4, Comparative Example 2 The coating film (Δ) obtained by using only the resin (Β υ υ 之之之之之之二氧化碳二氧化碳的的的的的的 ( ( ( ( ( ( ( ( ( ( ( ( ( ( Light quantity 6, 〇〇〇1χ). Figure 24 shows The graph of the change in the contact angle of the coating film obtained in Example 4 with time when the illuminating lamp was irradiated. Fig. 25 is a photodecolorization reaction of the fluorenyl blue pigment when the coating film obtained in Example 4 was used. Photograph (irradiation condition: fluorescent lamp, light amount: 60001 χ) Fig. 26 is a SEM photograph of the coating film obtained in Example 5. Fig. 27 is a SEM photograph of the coating film obtained in Comparative Example 3. 8 shows the coating film (□) obtained in Example 5, the coating film (Δ) obtained in Comparative Example 3, and the coating film (〇) obtained by using only the resin (Β_丨), which was decomposed by acetaldehyde. The drawing of the increase in the concentration of carbon dioxide on the light irradiation time (irradiation conditions: simulated sunlight, amount of light l〇, 〇〇〇lx). Fig. 29 is a SEM photograph of the coating film obtained in Example 6. -77-201229161 Figure 30 shows the coating film (□) obtained in Example 6, the coating film (A) obtained in Comparative Example 2, and the coating film (〇) obtained only using the resin (Β-1). A plot of the amount of increase in carbon dioxide concentration by decomposition of acetaldehyde versus light irradiation time (irradiation conditions: simulated sunlight, amount of light l〇, 〇〇〇lx). Fig. 3 is a graph showing the contact angle of the coating film obtained in Example 7 after exposure to the outside for three months. (c 1 : before exposure after coating, c2 : after exposure for 1 hour after coating, c 3 : after exposure for three months after coating, d 1 : no coating and before exposure, d2 : no coating and three months after exposure) 3 2 is a plot of the amount of increase in carbon dioxide concentration by acetaldehyde decomposition of the coating film produced on each of the substrates obtained in Example 8 (lighting conditions: black light, light amount: 1,000 lx). Glass, wood (□), gas vinyl sheet (△), polyethylene terephthalate (〇), acrylic sheet (◊), polycarbonate sheet (X), polystyrene sheet (+), stainless steel Plate (*), aluminum plate (_), interior wall tiles ((▲), exterior tiles (Φ), bathroom monuments (♦), natural stone... cloth (1). Figure 33 is in Example 4 (mouth) (Painting conditions: simulated sunlight, amount of light 1 〇, 〇〇〇 1 X ). The figure is a ΤΕΜ photograph of sample No. Τ43 obtained in Example 10. Fig. 35 is a TEM photograph of sample No. T53 obtained in Example 11. Fig. 36 is a sample No. obtained in Example 12. TEM photograph of T63. Fig. 37 is a TEM photograph of sample No. T73 obtained in Example 13. -78-201229161 Fig. 38 is a photograph of the sample No. Τ83 obtained in Example 14. The X-ray diffraction chart of the sample No. Τ83 obtained in Example 14 is shown in Fig. 40. The sample No. T83 obtained in Example 14 is shown in Fig. 40. UV-vis diffuse reflectance spectrum. Fig. 41 is a TEM photograph of sample No. T93 obtained in Example 15. Fig. 42 is an X-ray diffraction chart of sample No. T93 obtained in Example 15. Fig. 43 is a UV-vis diffuse reflection spectrum of Sample No. T93 obtained in Example 15. Fig. 4 is a TEM photograph of the sample ο ο · T 1 0 3 obtained in Example 16.

第45圖係在實施例16所得到的試料No. T103的X 射線繞射圖表。第4 6圖係在實施例1 5所得到的試料Ν 〇. T 1 0 3的 U V - v i s擴散反射光譜。第47圖係顯示評價1的結果之圖表。（a3-l) : □、（ α -1) : △Fig. 45 is an X-ray diffraction chart of sample No. T103 obtained in Example 16. Fig. 4 is a U V - v i s diffuse reflection spectrum of the sample Ν T T 1 0 3 obtained in Example 15. Figure 47 is a graph showing the results of Evaluation 1. (a3-l) : □, ( α -1) : △

第48圖係顯示評價2的結果之圖表。實施例10 : □、實施例11 : △、實施例12 :〇、比較例3 : ◊、比較例4 : X 第49圖係顯示評價3的結果之圖表。實施例13煅燒後：□、實施例13煅燒前混合物：△、比較例4 :〇 -79- 201229161 第5 0圖係顯示評價4的結果之圖表。實施例1 3 : □、比較例4 : △ 第5 1圖係顯示評價5的結果之圖表。實施例14 : =1、比較例4 : △ 第52圖係顯示評價6的結果之圖表。實施例1 5 : =1、比較例4 : △ 第5 3圖係顯示評價7的結果之圖表。實施例1 6 : =1、比較例4 : △ 第54圖係顯示評價8的結果之圖表。實施例10 : =]、比較例4 : △ 第5 5圖係顯示評價9的結果之圖表。實施例10 : =!、比較例4 : △ 第56圖係實施例1 8所得到的塗膜的SEM照片。第57圖係實施例20所得到的塗膜的SEM照片。第58圖係實施例22所得到的塗膜的SEM照片。Figure 48 is a graph showing the results of Evaluation 2. Example 10: □, Example 11: △, Example 12: 〇, Comparative Example 3: ◊, Comparative Example 4: X Figure 49 shows a graph showing the results of Evaluation 3. Example 13 After calcination: □, Example 13 Pre-calcination mixture: Δ, Comparative Example 4: 〇 -79- 201229161 Figure 5 shows a graph showing the results of Evaluation 4. Example 1 3 : □, Comparative Example 4: Δ Figure 51 shows a graph showing the results of Evaluation 5. Example 14: =1, Comparative Example 4: Δ Figure 52 shows a graph showing the results of Evaluation 6. Example 1 5: =1, Comparative Example 4: Δ Figure 5 3 shows a graph showing the results of Evaluation 7. Example 1 6 : =1, Comparative Example 4: Δ Figure 54 shows a graph showing the results of Evaluation 8. Example 10: =], Comparative Example 4: Δ Figure 5 is a graph showing the results of Evaluation 9. Example 10: =!, Comparative Example 4: Δ Figure 56 is a SEM photograph of the coating film obtained in Example 18. Fig. 57 is a SEM photograph of the coating film obtained in Example 20. Fig. 58 is a SEM photograph of the coating film obtained in Example 22.

第5 9圖係顯示塗膜評價1 1的結果之圖表。實施例 18 : □、實施例20 : △'實施例22 ·· X 第60圖係顯示塗膜評價1 2的結果之圖表。實施例 1 8 : □、實施例20 : △、實施例22 : X 【主要元件符號說明】私〇 *、、、 -80-Fig. 5 is a graph showing the results of the coating film evaluation 1 1 . Example 18: □, Example 20: Δ'Example 22 ·· X Fig. 60 is a graph showing the results of coating film evaluation 1 2 . Example 1 8 : □, Example 20: △, Example 22: X [Description of main component symbols] Private 〇 *, ,, -80-

Claims

201229161 VII. Patent Application Range: 1. A one-component coating composition characterized in that it contains a powder (A1) obtained by fixing titanium oxide (a1) to a cerium oxide nanostructure U2) and / or a powder (A2) obtained by fixing tungsten oxide (a3) to the cerium oxide nanostructure (a2); and a resin (B) having a polyoxyalkylene skeleton. 2. The liquid coating composition according to the ninth aspect of the invention, wherein the cerium oxide (al) or the tungsten oxide (a3) has a particle size ranging from ι 〇 to 1 〇〇 ηηη. 3. The liquid coating composition according to claim 1 or 2, wherein the cerium oxide nanostructure (a2) is a fibrous material having a thickness or a thickness of 10 to 100 nm and an aspect ratio of 2 or more. Or a ribbon-shaped cerium oxide as a main component structure. 4. The liquid coating composition according to any one of claims 1 to 3, wherein the powder (A1) or the powder (A2) is agglomerated by the aforementioned cerium oxide nanostructure U2) The particle size of the powder (A1) or (A2) is in the range of 1 to m 20 /Z m . 5. The composition of the i-liquid type coating composition according to any one of claims 1-4 to 4, wherein the content of the titanium oxide in the powder (A) is -8 Å by mass. %. 6. The composition of the liquid-liquid type coating according to any one of the items of the first aspect of the invention, wherein the content of the oxidized crane (9) in the powder (A2) is 1 〇 to 8 〇 mass% on a mass basis. 7. The liquid coating composition of any one of the U 6th patent application scope, wherein the resin (B) having a polyoxyalkylene skeleton is used in the (• 81 - 201229161 fluorenyl) acrylate series The side chain of the polymer of the body is composed of a polymer having a polysulfide skeleton. The liquid coating composition according to any one of claims 1 to 7, wherein the total of the powder (A1) and the powder (A2) is the same as that of the resin ( The ratio of use of B) is in the range of 10/90 to 80/20 by the mass ratio expressed by [(A1) + (A2)] / (B)" 9. For the patent scopes 1 to 5, 7, A β 1 night type coating composition according to any one of the items 8, wherein the powder (A 1) is produced by the following steps: (1-1) a polymer having a linear polyethylenimine skeleton a step of associating in an aqueous medium; (1 - 2) by adding an alkoxy decane in the presence of an aqueous medium in the association of the polymer to which the step (丨_丨) is added to obtain the aforementioned = a step of complexing the association of the substance with cerium oxide; (1-3) removing the composite obtained in the step (1_2) or calcining the composite to remove the polymer in the composite a step of adsorbing the powder of titanium oxide (a1) in a dispersion of oxygen dioxide = nanostructures U2) and a powder of titanium oxide (al) in an aqueous "quality"; and (14) step (1) _3) The retort or the yttrium oxide nanostructure (a2) of the obtained adsorbed titanium oxide (a1) powder is fixed at 600~9001: in order to fix the titanium oxide (a1) in the second Step of ruthenium oxide nanostructure (a2). 10. A liquid-type coating composition according to claim 9 of the patent application, wherein titanium oxide (a 1) and diterpene # rA + , gas fossil The ratio of the use of the sago nanostructure (a2) is in the range of 10/95 to 80/20, which is represented by (al)/(a2), and the range of 10/95 to 80/20. Patent No. 1 to 4, 6, 7, and 8 of your type of coating composition, wherein the powder (A2) is made of ^1 liquid: the polymer is in water (2-1) a step of associating a medium having a linear polyethylenimine skeleton; (2-2) by an association of the polymer in the presence of an aqueous medium, 9 a step of complexing a compound with cerium oxide; W, cerium poly(2-3), the dispersion of the composite obtained in the step (2-2) is calcined to polymerize the composite Material removed The dispersion of the oxidized cermetite nanostructure (a2) is mixed with the sulphate (5), and is: 'to adsorb the tungstate (a3,) in the composite or the samarium oxide structure (a2). And (2-4) calcining the tungsten oxide (a3) particles by calcining the tungstate composite or the cerium oxide nanostructure U2 obtained in the step (2_3) at 900 ° C or lower The step in the ruthenium oxide nanostructure (5)). 1 2 · If the coating composition of the first type of the patent application is produced, the manufacturer: 1 to 4, 6, 7, 8 of the liquid of any one of the items (A 2 ) is subjected to the following steps ( 3-1) a step of associating a polymer having a linear polyethylenimine skeleton in an aqueous medium; (3-2) a polymer obtained in the step (3-1) in the presence of an aqueous medium a combination of alkoxysilane to obtain a complex of the polymer and bismuth hydride; -83-201229161 (3-3) a dispersion of the composite obtained in the step (3-2), ^ The dispersion of the cerium oxide nanostructure (a2) obtained by calcining the s-up composite to remove the polymer in the composite is mixed with a polyamine to form a cerium oxide nanostructure (a2) a step of adsorbing the polyamine on the surface layer, (3-4) a dispersion of the polyamine-adsorbed complex or the ceria nanostructure (a2) obtained in the step (3-3), and the tungstic acid Salt (U,) is a combination of the steps of adsorbing the sulphate (a3 ') in the complex or the cerium oxide nanostructure (a2); and " (3 -5) The compound or the cerium oxide nanostructure (a2) having the tungstate (a3,) obtained in the step (3 - 4) is calcined at 9 ° C or lower to form the tungsten oxide (a3) particles. The step of immobilizing on the ruthenium oxide nanostructure. For example, in the scope of patent application No. 1 to 4, 6, 7, and 8. (1), the liquid composition of the liquid material (A2) is produced by the following cattle: 4-1) a step of associating a polymeric medium having a linear polyethylenimine skeleton; (4-2) by a step in the presence of an aqueous medium, in the step a combination of alkoxy decane to obtain a complex of a precursor and a cerium oxide; Κ (4-3) to associate a polymer t having a linear polyethylenimine skeleton in an aqueous medium Further, an aqueous solution of tungstate (a3') is mixed to obtain a precipitate obtained by associating a compound with tungstic acid or tungstate (a3,), and * ^ ^ 兮 is heated to obtain an emulsified crane (a Step 3) particles; -84 - 201229161 (4_4) The powder of tungsten oxide (a3) obtained in the step (4-3) and the polymer obtained in the step (4-2) a composite of ruthenium or a ruthenium dioxide nanostructure (a2) obtained by calcining the composite to remove the polymer in the composite in an aqueous medium a step of adsorbing particles of tungsten oxide (a3) by the cerium oxide nanostructure (a2); and (4-5) a composite of particles of the oxidized crane (10) obtained by the step (4·4) or The cerium oxide nanostructure (a2) is a step of fixing particles of 9 〇〇 (>c or less to oxidize tungsten oxide U3) to the cerium oxide nanostructure (a2). A liquid coating composition of any one of the first to the eleventh, wherein the tungsten oxide (a 3) or the sputum knee/., , & ^ citrate (a3,) and cerium oxide nano The ratio of the use of the structure (a 2 ) is 0.4. The mass ratio expressed by (a3)/(a2) is in the range of 10/95 to 80/20. 1 5 · Photocatalyst, which is a packaged preparation μ, a photocatalyst in which a particle of emulsified titanium (a1) or tungsten oxide (a3) is fixed to a composite of a cerium oxide cerium (a half) and a mouth structure (a2), which is characterized by: η 1ΛΛ not...,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,, ,and ... in the range of 1....the vanity is the oxidation record (al) or 10 to 80% by mass in the composite. The content of the oxide crane (a3) is 16. The manufacturing method of a coating film (1) mixed powder The body (A1) is characterized by comprising the steps of: and/or powder (A2), and a resin having a polyfluorene-85-201229161 sintered skeleton (B) to prepare a coating composition; the powder (A) 1) The titanium oxide (a 1) is fixed to the cerium oxide nanostructure (a2), and the powder (A2) is a tungsten oxide (a3) fixed to the cerium oxide nanostructure (a2) (II) a step of coating the coating composition obtained in the above step (1) on a substrate and hardening it; and (ΠΙ) photo-decomposing the light applied to the coating film obtained in the step of escaping The step of coating the organic component of the surface layer of the film: a photocatalyst coating film according to the patent application of the invention, which is obtained by the method of the first aspect.

: Use as patent application van 86 -