201200355 六、發明說明： [相關申請案】 本申請案，係主張於20 10年3月25 國特許出願2010-070198號的優先權， 的說明書作爲本申請案之揭示內容的一 【發明所屬之技術領域】 本發明係關於一種特別適合於建築 裝材等用途，且具備耐候性、光觸媒分 種覆膜性能佳之光觸媒層之光觸媒塗裝 【先前技術】 氧化鈦等之光觸媒，近年來係應用 等用途。其可應用藉由光觸媒的光能所 種有害物質分解，或是使塗佈有光觸媒 而容易以水將附著於表面之髒污沖洗去 欲得此般光觸媒塗裝體時，係在成 光觸媒之間，進行黏著、及/或以藉由 表面的劣化者爲目的而設置中間層。可 觸媒之此般光觸媒塗裝體的技術，爲人 底層之基材與光觸媒之間，設置聚矽氧 間層之技術（例如參照專利文獻1 ( 97/00 1 34號手冊））。 此外，爲人所知者亦有在中間層中 曰提出申請之曰本 並援引此等申請案 部分。 物等之外裝材、內 解性、耐光性及各 體。 在建築物的外裝材 激發之活性，將種 之基材表面親水化 除。 爲基底層之基材與 光觸媒來抑制基材 得到塗佈有此般光 所知者有在成爲基 烷改質樹脂等的中 曰本國際公開第 ，應用珠粒作爲塡 C： -5- 201200355 充材之技術（例如參照專利文獻2 (日本特開2009-1 368 1 1 號公報））。 [先前技術文獻] [專利文獻] [專利文獻1]日本國際公開第97/00 1 34號手冊 [專利文獻2]日本特開2009-1 368 1 1號公報 爲了提高光觸媒活性，以往是藉由增加光觸媒層中所 含的光觸媒量來進行，但此時可能產生基材因光觸媒而導 致劣化等缺失之疑慮，故仍存在侷限性。 【發明內容】 本發明者們此次係發現到，藉由在以接觸於光觸媒層 的下方之方式所設置之中間層中添加特定珠粒，可提升光 觸媒活性，其結果可降低光觸媒層中的光觸媒量，而有效 地防止基材的劣化。如此，本發明係依據該發現而創作出 〇 因此，本發明之目的在於提供一種可降低光觸媒層中 所含之光觸媒量，並且光觸媒分解功能佳之光觸媒塗裝體 〇 亦即’本發明之光觸媒塗裝體，爲至少具備：基材、 含有光觸媒粒子而成之光觸媒層、以及位於前述基材與前 述光觸媒層之間並以接觸於前述光觸媒層的下方之方式所 設置之中間層而成之光觸媒塗裝體，其特徵爲： 前述中間層至少含有：選自由樹脂珠粒、中空玻璃珠 -6 - 201200355 粒、及中空陶瓷珠粒所組成之群組的至少一種珠粒，以及 聚矽氧烷改質樹脂而成；該珠粒係在前述中間層與前述光 觸媒層之界面上，形成由該形狀所起因之凸部而成。 此外，本發明係關於一種用以形成上述光觸媒塗裝體 之塗層組成物，該塗層組成物爲用以形成光觸媒塗裝體的 中間層之塗層組成物，該光觸媒塗裝體至少具備：基材、 含有光觸媒粒子而成之光觸媒層、以及位於前述基材與前 述光觸媒層之間並以接觸於前述光觸媒層的下方之方式所 設置之前述中間層而成，其特徵爲： 含有：選自由樹脂珠粒、中空玻璃珠粒、及中空陶瓷 珠粒所組成之群組的至少一種珠粒：聚矽氧烷改質樹脂： 以及溶劑而成，且前述珠粒的表觀密度被設爲較聚矽氧烷 改質樹脂及溶劑更小。 此外，本發明係關於上述光觸媒塗裝體的製造方法， 該方法係包含：將至少含有選自由樹脂珠粒、中空玻璃珠 粒、及中空陶瓷珠粒所組成之群組的至少一種珠粒與聚矽 氧烷改質樹脂與溶劑而成之塗層液，應用在基材表面，然 後進行乾燥來形成中間層之步驟；以及將含有光觸媒粒子201200355 VI. Description of the invention: [Related application] This application claims priority to the priority of the Japanese Patent Application No. 2010-070198, filed on March 30, 2010, which is incorporated herein by reference. BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photocatalyst coating of a photocatalyst layer which is particularly suitable for use in construction materials and has weather resistance and photocatalyst separation film properties. [Prior Art] Photocatalysts such as titanium oxide, etc. use. It can be applied to photocatalyst coating by applying photocatalytic light energy to decompose harmful substances or by coating a photocatalyst and easily rinsing the dirt adhering to the surface with water. The intermediate layer is provided for the purpose of adhesion, and/or for the purpose of deterioration of the surface. The technique of a photocatalyst-coated body which is a catalyst is a technique in which a polyelectrolyte layer is provided between a substrate of a human underlayer and a photocatalyst (for example, refer to Patent Document 1 (Handbook No. 97/00 1 34)). In addition, those who are known are also transcripts of applications in the middle tier and quote the parts of these applications. Materials such as materials, internal solution, light resistance and various materials. The surface of the substrate is hydrophilized by the activity of the exterior material of the building. In the substrate of the base layer and the photocatalyst, it is known that the base material is coated with the light. In the case of the base-based modified resin, Nippon International Publication Co., Ltd. is applied as a 塡C: -5- 201200355 The technique of filling the material (for example, refer to Patent Document 2 (JP-A-2009-1 368 1 1)). [PRIOR ART DOCUMENT] [Patent Document 1] Japanese Patent Publication No. 97/00 1 34 [Patent Document 2] JP-A-2009-1 368 1 1 discloses that in order to improve photocatalytic activity, it has been conventionally Although the amount of photocatalyst contained in the photocatalyst layer is increased, there is a concern that the substrate may be degraded due to deterioration of the photocatalyst, and thus there are still limitations. SUMMARY OF THE INVENTION The present inventors have discovered that by adding a specific bead to an intermediate layer provided in contact with the photocatalyst layer, photocatalytic activity can be enhanced, and as a result, the photocatalyst layer can be lowered. The amount of photocatalyst is effective to prevent deterioration of the substrate. Thus, the present invention has been created in accordance with the findings. Therefore, it is an object of the present invention to provide a photocatalyst coating body which can reduce the amount of photocatalyst contained in the photocatalyst layer and which has a good photocatalytic decomposition function, that is, the photocatalyst coating of the present invention. The package is provided with at least a substrate, a photocatalyst layer containing photocatalyst particles, and a photocatalyst disposed between the substrate and the photocatalyst layer and in contact with the lower layer of the photocatalyst layer. A coated body, characterized in that: the intermediate layer contains at least: at least one bead selected from the group consisting of resin beads, hollow glass beads-6 - 201200355 particles, and hollow ceramic beads, and polyoxyalkylene oxide The modified resin is obtained by forming a convex portion formed by the shape on the interface between the intermediate layer and the photocatalyst layer. Furthermore, the present invention relates to a coating composition for forming the photocatalyst coating body, the coating composition being a coating composition for forming an intermediate layer of a photocatalyst coating body, the photocatalyst coating body having at least a substrate, a photocatalyst layer containing photocatalyst particles, and the intermediate layer disposed between the substrate and the photocatalyst layer and contacting the photocatalyst layer, and characterized in that: Selecting at least one bead of a group consisting of resin beads, hollow glass beads, and hollow ceramic beads: a polyoxyalkylene modified resin: and a solvent, and the apparent density of the aforementioned beads is set It is smaller than the polyoxyalkylene modified resin and solvent. Furthermore, the present invention relates to a method of producing the photocatalyst coated body, comprising: at least one bead comprising at least one selected from the group consisting of resin beads, hollow glass beads, and hollow ceramic beads; a coating solution of a polyoxyalkylene-modified resin and a solvent, which is applied to a surface of a substrate and then dried to form an intermediate layer; and a photocatalyst-containing particle
I 而成之光觸媒塗層液應用在該中間層來形成光觸媒層之步 驟。 根據本發明之光觸媒塗裝體，能夠提供一種可降低光 觸媒層中所含之光觸媒量，並且光觸媒分解功能佳之光觸 媒塗裝體。 201200355 【實施方式】 光觸媒塗裝體 本發明之光觸媒塗裝體，爲至少具備：基材、含有光 觸媒粒子而成之光觸媒層、以及位於前述基材與前述光觸 媒層之間並以接觸於前述光觸媒層的下方之方式所設置之 中間層而成之光觸媒塗裝體，前述中間層至少含有：選自 由樹脂珠粒、中空玻璃珠粒、及中空陶瓷珠粒所組成之群 組的至少一種珠粒，以及聚矽氧烷改質樹脂而成；該珠粒 係在前述中間層與前述光觸媒層之界面上，形成由該形狀 所起因之凸部而成。 藉由本發明之光觸媒塗裝體，可提供一種降低光觸媒 層中所含之光觸媒量，並且光觸媒分解功能佳之光觸媒塗 裝體，該理由雖未明，但可考量如下。於本發明之光觸媒 塗裝體之中間層與光觸媒層之界面上，形成由該形狀所起 因之凸部，其結果可在位於中間層上之光觸媒層形成適度 的凹凸。該適度的凹凸增大光觸媒層表面的表面積，因而 提升光觸媒分解功能。然而，此僅止於假設，本發明並不 限定於此。 本發明中，珠粒係在中間層與光觸媒層之界面上形成 由該形狀所起因之凸部。在此，所謂由珠粒形狀所起因之 凸部，是指在中間層與光觸媒層之界面上，起因於珠粒的 至少一部分相對地突出存在所形成之部分。本發明中，珠 粒可從中間層暴露出或不暴露出。此外，亦可在中間層與 光觸媒層之界面上存在有由珠粒以外者所起因之凹凸。本 -8- 201200355 發明的一項形態中，珠粒爲樹脂製時，珠粒不從界面暴露 出，以改質聚矽氧烷覆蓋珠粒且該改質聚矽氧烷接觸於光 觸媒層之形態，就耐候性之觀點來看爲較佳。本發明中， 可爲實質沿著珠粒形狀之形狀的凸部，或是稍微和緩地反 映珠粒形狀之凸部。 此外，本發明之光觸媒塗裝體，因情況的不同，亦可 期待藉由中間層與光觸媒層之界面的凹凸而提高中間層與 光觸媒層之密著性的效果，就此點亦爲有利。 中間層 本發明之中間層，係至少含有：選自由樹脂珠粒、中 空玻璃珠粒、及中空陶瓷珠粒所組成之群組的至少一種珠 粒，以及聚矽氧烷改質樹脂而成》 本發明中，珠粒爲選自由樹脂珠粒、中空玻璃珠粒、 及中空陶瓷珠粒所組成之群組的至少一種珠粒，較佳爲樹 脂珠粒。構成珠粒之樹脂的例子，可列舉出丙烯酸樹脂、 環氧樹脂、聚醯胺樹脂、聚胺基甲酸酯樹脂、不飽和聚酯 樹脂、乙烯酯樹脂、酚樹脂、聚矽氧烷樹脂、丙烯酸聚矽 氧烷樹脂、氟樹脂、酮樹脂、聚乙烯樹脂、聚丙烯樹脂、 超短油型醇酸樹脂、短油型醇酸樹脂、中油型醇酸樹脂、 長油型醇酸樹脂、超長油型醇酸樹脂、三聚氰胺樹脂、胺 基醇酸共縮合樹脂、脲樹脂、氯乙烯樹脂、乙酸乙烯酯樹 脂、聚乙烯醇、聚乙烯縮醛等。 根據本發明之較佳形態，珠粒的粒徑被設爲較光觸媒 -9 - 201200355 塗裝體之光觸媒層的膜厚更大。此外，根據本發明之其他 較佳形態，珠粒的粒徑被設爲較光觸媒塗裝體之中間層的 膜厚更小。根據本發明之較佳形態，中間層的膜厚較佳爲 Ιμιη以上ΙΟΟμιη以下，下限尤佳爲3μηι，更佳爲ΙΟμιη，此 外，上限較佳爲50μπι。因此，珠粒的粒徑可考量上述情況 來適當地決定，具體而言，較佳爲0.3〜30μιη的範圍，尤佳 爲1〜30μιη，最佳爲3~30μηιβ 珠粒的添加量，相對於中間層的固形份重量，較佳爲 1〜50%，尤佳爲3〜30%，最佳爲5〜20%。藉由位於上述範圍 ，可提升光觸媒分解功能，並有效地防止對基材所造成的 不良影II。 本發明中，藉由將中間層的膜厚、珠粒的粒徑及其添 加量預先設定在上述範圍，可有效率地在中間層與光觸媒 層之界面上形成由該形狀所起因之凸部。 再者，根據本發明之一項較佳形態，用以形成後述中 間層之塗層組成物中，珠粒的表觀密度被設爲較珠粒以外 之該組成物的成分，尤其至少較聚矽氧烷改質樹脂及溶劑 更小。藉此，形成中間層時，珠粒可在該組成物中往上方 浮起，使珠粒集中在中間層之與光觸媒層之界面附近，而 有效率地形成由該形狀所起因之凸部。除了調整中間層的 膜厚、珠粒的粒徑及其添加Λ之外，藉由應用表觀密度小 的珠粒，可視爲能夠有效率地在中間層與光觸媒層之界面 上形成由該形狀所起因之凸部。 本發明之光觸媒塗裝體的中間層，至少由上述珠粒與 -10- 201200355 聚矽氧烷改質樹脂所構成。聚矽氧烷改質樹脂基本上具有 作爲中間層的基質之功能，該具體例，可適當地應用樹脂 中含有聚矽氧烷之聚矽氧烷改質丙烯酸樹脂、聚矽氧烷改 質環氧樹脂、聚矽氧烷改質胺基甲酸酯樹脂、聚矽氧烷改 質聚酯等。 根據本發明之一項較佳形態，本發明之光觸媒塗裝體 的中間層，可將含有上述珠粒之聚矽氧烷改質樹脂的水分 散體用作爲用以形成中間層之塗層組成物，並應用在基材 ’較佳爲塗佈在基材後使其硬化而形成。此般水性分散體 ’例如可列舉出含有約50~200nm的矽氧烷之樹脂系膠態分 散液、硬化性聚矽氧烷改質樹脂乳化液等。 樹脂系膠態分散液，可列舉出由下列複合樹脂所構成 之水分散體等，該複合樹脂係使具有矽烷基之丙烯酸、胺 基甲酸酯等之聚合物鏈段，與具有鍵結於矽原子之羥基之 分枝聚矽氧烷鏈段形成複合化而成。 根據本發明之其他較佳形態，中間層的聚矽氧烷改質 樹脂基質，可將硬化性聚矽氧烷改質樹脂乳化液塗佈在基 材後硬化形成。在此，硬化反應可適當地應用水解及縮合 反應、光聚合反應等。當硬化反應爲水解及縮合反應時， 可適當地應用具有烷氧基作爲官能基，且可藉由水解及縮 合反應生成矽氧烷鍵之硬化性聚矽氧烷乳化液。 硬化性聚矽氧烷乳化液中，除了產生上述硬化反應之 官能基之外，係存在有乳化聚合之有機交聯部。有機交聯 部’可適當地應用乙烯基與乙烯基聚合而成之乙烯交聯部 -11 - 201200355 般之藉由自由基聚合所生成之交聯部。只要是藉由自由基 聚合所生成之交聯部，則不限定於烴基，可適當地應用各 種改質基的組合。 此外，硬化性聚矽氧烷乳化液中，除了產生上述硬化 反應之官能基、有機交聯部之外，亦可存在有鍵結於矽原 子之有機基。在此，有機基可列舉出烷基、苯基、環烷基 等之烴基，以及該氫的一部分由改質基所取代之有機基。 在此，改質基可列舉出胺基、羧基、毓基、丙烯酸基、環 氧基等。 用作爲上述乳化液的乳化劑之界面活性劑，可應用以 往所知之非離子系、陽離子系、陰離子系的各種界面活性 劑，以及含有可自由基聚合之官能基之反應性乳化劑。再 者，可應用之具體例，可列舉出聚氧乙烯烷醚、聚氧乙烯 烷基苯醚、聚氧乙烯羧酸酯、山梨醇酐酯、聚氧乙烯山梨 醇酐酯等之非離子系界面活性劑：氯化烷基三甲基銨、氯 化烷基苄銨等之陽離子系界面活性劑；烷基或烷基烯丙基 硫酸鹽、烷基或烷基烯丙基磺酸鹽、二烷磺酸基琥珀酸鹽 等之陰離子系界面活性劑；胺基酸型、三甲甘胺酸型等之 雙性離子型界面活性劑；日本特開平8-2 7347號公報中所 記載之分子中含有磺酸鹽、聚氧乙烯鏈、四級銨鹽等之含 有親水性基之可自由基聚合的（甲基）丙烯酸酯、含有苯 乙烯、馬來酸酯化合物等衍生物之各種反應性界面活性劑 〇 此等界面活性劑可使用1種或2種以上。界面活性劑， -12- 201200355 較佳係使用乳化液中之樹脂固形份的〇. 5 ~ 1 5重量％，特佳 爲使用1〜10重量％。 根據本發明之一項較佳形態，構成聚矽氧烷改質樹脂 基質之聚矽氧烷改質樹脂中的矽氧烷（Si-o)含量，相對 於前述聚矽氧烷改質樹脂的固形份，較佳爲〇.4質量％以上 3 3質量％以下，尤佳爲1 2質量％以上3 3質量％以下。藉此可 充分地抑制在中間層相對於紫外線之耐候性、光觸媒所造 成之侵蝕，並且可有效地抑制龜裂的產生。在此，聚矽氧 烷改質樹脂中的矽原子含量，可藉由依據X射線光電子分 光儀（XPS )所進行之化學分析來測定。 根據本發明之較佳形態，可於中間層更含有紫外線吸 收劑，藉此可提升中間層的耐候性。紫外線吸收劑相對於 中間層之添加量，較佳爲0.001~10質量％，尤佳爲0.01~5 質量％。紫外線吸收劑的例子，可列舉出二苯基酮系、苯 並三唑系、三氮雜苯系紫外線吸收劑等，尤其在三氮雜苯 系紫外線吸收劑中，羥苯基三氮雜苯在3 8 Onm以下的波長 之吸收特性佳，且化學性質安定，故較佳。 羥苯基三氮雜苯化合物，爲羥苯基三氮雜苯及/或具 有由下列一般式表示之基本骨架之羥苯基三氮雜苯的衍生 物，可適當地應用市售的三氮雜苯系紫外線吸收劑。The photocatalyst coating liquid formed by I is applied to the intermediate layer to form a photocatalyst layer. According to the photocatalyst-coated body of the present invention, it is possible to provide a photocatalyst-coated body which can reduce the amount of photocatalyst contained in the photocatalyst layer and which has a good photocatalytic decomposition function. 201200355 [Embodiment] Photocatalyst-coated body The photocatalyst-coated body of the present invention includes at least a substrate, a photocatalyst layer containing photocatalyst particles, and a photocatalyst between the substrate and the photocatalyst layer. a photocatalyst coated body formed by an intermediate layer provided in a lower layer of the layer, the intermediate layer comprising at least one bead selected from the group consisting of resin beads, hollow glass beads, and hollow ceramic beads And a polyoxyalkylene-modified resin; the beads are formed on the interface between the intermediate layer and the photocatalyst layer to form a convex portion caused by the shape. According to the photocatalyst coating body of the present invention, it is possible to provide a photocatalyst coating body which reduces the amount of photocatalyst contained in the photocatalyst layer and which has a good photocatalytic decomposition function. Although this reason is not known, it can be considered as follows. At the interface between the intermediate layer of the photocatalyst-coated body of the present invention and the photocatalyst layer, a convex portion due to the shape is formed, and as a result, a moderate unevenness can be formed in the photocatalyst layer on the intermediate layer. This moderate unevenness increases the surface area of the surface of the photocatalyst layer, thereby enhancing the photocatalytic decomposition function. However, this is merely an assumption, and the present invention is not limited thereto. In the present invention, the beads form a convex portion due to the shape at the interface between the intermediate layer and the photocatalyst layer. Here, the convex portion caused by the shape of the bead means a portion formed by the at least a part of the bead which is relatively protruded at the interface between the intermediate layer and the photocatalyst layer. In the present invention, the beads may or may not be exposed from the intermediate layer. Further, irregularities caused by beads other than beads may be present at the interface between the intermediate layer and the photocatalyst layer. In one aspect of the invention, when the beads are made of a resin, the beads are not exposed from the interface, the beads are covered with the modified polyoxyalkylene oxide, and the modified polyoxyalkylene is contacted with the photocatalyst layer. The form is preferable from the viewpoint of weather resistance. In the present invention, it may be a convex portion substantially in the shape of a bead shape, or a convex portion having a bead shape slightly and gently reflected. Further, in the photocatalyst-coated body of the present invention, the effect of improving the adhesion between the intermediate layer and the photocatalyst layer by the unevenness of the interface between the intermediate layer and the photocatalyst layer may be expected depending on the case, and this is also advantageous. Intermediate layer The intermediate layer of the present invention comprises at least: at least one bead selected from the group consisting of resin beads, hollow glass beads, and hollow ceramic beads, and a polyoxyalkylene modified resin. In the present invention, the beads are at least one type of beads selected from the group consisting of resin beads, hollow glass beads, and hollow ceramic beads, preferably resin beads. Examples of the resin constituting the beads include an acrylic resin, an epoxy resin, a polyamide resin, a polyurethane resin, an unsaturated polyester resin, a vinyl ester resin, a phenol resin, a polyoxyalkylene resin, and the like. Acrylic polyoxyalkylene resin, fluororesin, ketone resin, polyethylene resin, polypropylene resin, ultrashort oil type alkyd resin, short oil type alkyd resin, medium oil type alkyd resin, long oil type alkyd resin, super Long oil type alkyd resin, melamine resin, amino alkyd co-condensation resin, urea resin, vinyl chloride resin, vinyl acetate resin, polyvinyl alcohol, polyvinyl acetal, and the like. According to a preferred embodiment of the present invention, the particle size of the beads is set to be larger than the film thickness of the photocatalyst layer of the photocatalyst -9 - 201200355 coated body. Further, according to another preferred embodiment of the present invention, the particle diameter of the beads is set to be smaller than the film thickness of the intermediate layer of the photocatalyst-coated body. According to a preferred embodiment of the present invention, the film thickness of the intermediate layer is preferably Ιμηη or more and ΙΟΟμιη or less, and the lower limit is preferably 3 μm, more preferably ΙΟμηη, and the upper limit is preferably 50 μm. Therefore, the particle size of the beads can be appropriately determined in consideration of the above, and specifically, it is preferably in the range of 0.3 to 30 μm, particularly preferably 1 to 30 μm, and most preferably 3 to 30 μηπβ. The solid content of the intermediate layer is preferably from 1 to 50%, particularly preferably from 3 to 30%, most preferably from 5 to 20%. By being in the above range, the photocatalytic decomposition function can be improved, and the adverse effect on the substrate can be effectively prevented. In the present invention, by setting the film thickness of the intermediate layer, the particle diameter of the beads, and the addition amount thereof in advance in the above range, the convex portion caused by the shape can be efficiently formed at the interface between the intermediate layer and the photocatalyst layer. . Further, according to a preferred embodiment of the present invention, in the coating composition for forming the intermediate layer described later, the apparent density of the beads is set to be a component of the composition other than the beads, especially at least The decane-modified resin and solvent are smaller. Thereby, when the intermediate layer is formed, the beads can float upward in the composition, and the beads are concentrated in the vicinity of the interface between the intermediate layer and the photocatalyst layer, and the convex portion caused by the shape is efficiently formed. In addition to adjusting the film thickness of the intermediate layer, the particle size of the beads, and the addition of ruthenium, by applying beads having a small apparent density, it can be considered that the shape can be efficiently formed at the interface between the intermediate layer and the photocatalyst layer. The convex part of the cause. The intermediate layer of the photocatalyst-coated body of the present invention comprises at least the above beads and -10-201200355 polyoxyalkylene modified resin. The polyoxyalkylene-modified resin basically has a function as a matrix of the intermediate layer. In this specific example, a polyoxyalkylene-modified acrylic resin or a polyoxyalkylene-modified ring containing polyoxyalkylene in the resin can be suitably used. Oxygen resin, polyoxyalkylene modified urethane resin, polyoxyalkylene modified polyester, and the like. According to a preferred embodiment of the present invention, in the intermediate layer of the photocatalyst-coated body of the present invention, an aqueous dispersion of the polyoxyalkylene-modified resin containing the above-mentioned beads can be used as a coating layer for forming an intermediate layer. And applied to the substrate 'preferably formed by coating the substrate to harden it. The above-mentioned aqueous dispersion ′ is, for example, a resin-based colloidal dispersion containing a deuterated oxygen of about 50 to 200 nm, a curable polydecane-modified resin emulsion, and the like. The resin-based colloidal dispersion may, for example, be an aqueous dispersion composed of the following composite resin, which has a polymer segment such as an alkylene group-containing acrylic acid or a urethane, and has a bond with The branched polyoxyalkylene segment of the hydroxyl group of the ruthenium atom is formed into a composite. According to another preferred embodiment of the present invention, the polysiloxane-modified resin matrix of the intermediate layer can be formed by applying a curable polyoxyalkylene-modified resin emulsion to a substrate and then hardening. Here, the hydrolysis reaction can be suitably applied to hydrolysis, condensation reaction, photopolymerization reaction or the like. When the hardening reaction is a hydrolysis reaction or a condensation reaction, a curable polyoxyalkylene emulsion having an alkoxy group as a functional group and capable of forming a siloxane chain by hydrolysis and condensation reaction can be suitably used. In the curable polyoxyalkylene emulsion, in addition to the functional group which causes the above-mentioned hardening reaction, there is an organic crosslinking portion which is emulsion-polymerized. The organic cross-linking portion can be suitably used as a cross-linking portion formed by radical polymerization of a vinyl cross-linking portion of a vinyl group and a vinyl group -11 - 201200355. The cross-linking portion formed by radical polymerization is not limited to a hydrocarbon group, and a combination of various modifying groups can be suitably applied. Further, in the curable polyoxyalkylene emulsion, in addition to the functional group or the organic crosslinking portion which causes the above-mentioned curing reaction, an organic group bonded to the indole atom may be present. Here, the organic group may, for example, be a hydrocarbon group such as an alkyl group, a phenyl group or a cycloalkyl group, or an organic group in which a part of the hydrogen is replaced by a modifying group. Here, examples of the modifying group include an amine group, a carboxyl group, a decyl group, an acrylic group, and an epoxy group. As the surfactant of the emulsifier of the above emulsion, various nonionic, cationic or anionic surfactants and reactive emulsifiers containing a radical polymerizable functional group can be used. Further, specific examples of the applicable examples include nonionic systems such as polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, polyoxyethylene carboxylate, sorbitan ester, and polyoxyethylene sorbitan ester. Surfactant: a cationic surfactant such as alkyltrimethylammonium chloride or alkylbenzylammonium chloride; alkyl or alkylallyl sulfate, alkyl or alkylallylsulfonate, An anionic surfactant such as a dialkylsulfonic acid succinate; an amphoteric surfactant such as an amino acid or a trimethylglycine; and a molecule described in JP-A-8-2737 The radically polymerizable (meth) acrylate containing a hydrophilic group such as a sulfonate, a polyoxyethylene chain or a quaternary ammonium salt, and various reactivityes of a derivative containing a styrene or a maleate compound Surfactant 〇 One or two or more kinds of these surfactants can be used. The surfactant, -12-201200355 is preferably used in an amount of 5% to 15% by weight of the resin solid content in the emulsion, and particularly preferably 1 to 10% by weight. According to a preferred embodiment of the present invention, the content of siloxane (Si-o) in the polyoxyalkylene-modified resin constituting the polyoxyalkylene-modified resin matrix is relative to that of the aforementioned polyoxyalkylene-modified resin. The solid content is preferably 44% by mass or more and 3% by mass or less, and particularly preferably 12% by mass or more and 3% by mass or less. Thereby, the weathering resistance of the intermediate layer with respect to ultraviolet rays and the photocatalyst can be sufficiently suppressed, and the occurrence of cracks can be effectively suppressed. Here, the content of germanium atoms in the polyoxane-modified resin can be measured by chemical analysis by X-ray photoelectron spectroscopy (XPS). According to a preferred embodiment of the present invention, the ultraviolet absorbing agent can be further contained in the intermediate layer, whereby the weather resistance of the intermediate layer can be improved. The amount of the ultraviolet absorber added to the intermediate layer is preferably 0.001 to 10% by mass, particularly preferably 0.01 to 5% by mass. Examples of the ultraviolet absorber include a diphenylketone type, a benzotriazole type, and a triazabenzene type ultraviolet absorber, and among them, in particular, a triazabenzene type ultraviolet absorber, hydroxyphenyl triazabenzene It is preferred because it has a good absorption characteristic at a wavelength of 3 8 Onm or less and is chemically stable. The hydroxyphenyltriazabenzene compound is a hydroxyphenyltriazabenzene and/or a derivative of hydroxyphenyltriazabenzene having a basic skeleton represented by the following general formula, and a commercially available trinitrogen can be suitably used. A benzene-based UV absorber.
-13- 201200355 根據本發明之較佳形態，可於中間層更含有受阻胺系 及/或受阻酚系等之光安定劑。藉由與上述紫外線吸收劑 之相互作用，本發明之光觸媒塗裝體之耐候性、耐光性的 提升可令人期待。尤其當使用羥苯基三氮雜苯化合物作爲 紫外線吸收劑時，可選擇受阻胺系作爲光安定劑。藉由羥 苯基三氮雜苯化合物，可得到未達380nm的短波長之紫外 線吸收性能安定之優點。光安定劑相對於中間層之添加量 ，較佳爲0 · 0 0 1〜1 0質量％，尤佳爲0 · 0 1 ~ 5質量％。 受阻胺系光安定劑的具體例，可列舉出雙（2,2,6,6-四甲基-4 -哌啶基）琥珀酸酯、雙（2，2,6,6 -四甲基-4 -哌啶 基）癸二酸酯、雙（1，2,2,6,6-五甲基-4-哌啶基）2-(3,5-二-三級丁基-4-羥苄基）-2-丙二酸丁酯、l-[2-[3-(3,5-二-三級丁基-4-羥苯基）丙炔氧基]乙基]-4-[3- ( 3,5-二-三 級丁基-4-羥苯基）丙炔氧基]-2,2,6,6 -四甲基哌啶、雙（ 1，2,2,6,6-五甲基-4-哌啶基）癸二酸酯與甲基·丨，2,2,6,6-五 甲基-4-哌啶基-癸二酸酯之混合物（Ciba Japan股份有限公 司製、商品名稱：TINU VIN-292 )、雙（1 -辛氧-2，2，6,6-四甲基-4 -哌啶基）癸二酸酯、TINUVIN-123 (商品名稱、 0：沁玨13?311股份有限公司製）、1'11^1；¥11^-111?〇1^(商品名 稱、Ciba Japan股份有限公司製）、TINUVIN 292 (商品 名稱、Ciba Japan股份有限公司製）、以及丨，2,2,6,6-五甲 基-4-哌啶基甲基丙烯酸酯、1,2,2,6,6-五甲基-4-哌啶基甲 基丙烯酸酯、2,2,6,6 -四甲基-4 -哌啶基甲基丙烯酸酯、 -14- 201200355 2,2,6,6-四甲基-4-哌啶基甲基丙烯酸酯、1，2,2,6,6-五甲基-4-亞胺哌啶基甲基丙烯酸酯、2,2,6,6-四甲基-4-亞胺哌啶 基甲基丙烯酸酯、4-氰基-2,2,6,6-四甲基-4-哌啶基甲基丙 烯酸酯、4_氰基-1,2,2,6,6-五甲基-4-哌啶基甲基丙烯酸酯 等之聚合性的受阻胺系紫外線吸收劑或此等之（共）聚合 物。此外，受阻酚系光安定劑的具體例，可列舉出雙（ 3,5-三級丁基）-4-羥甲苯、TINUVIN-144 (商品名稱、 Cib a Japan股份有限公司製）等。 本發明之光觸媒塗裝體的中間層，可含有擴展顏料、 著色顏料、防藻劑、黏性調整劑等作爲任意成分。 擴展顏料，例如可列舉出氧化鈦晶鬚、碳酸鈣晶鬚、 硼酸鋁晶鬚、鈦酸鉀晶鬚、雲母、滑石等。 著色顏料，例如可列舉出氧化鈦白、氧化鋅白氧化鐵 、碳黑、尖晶石綠、紅色氧化鐵、烏敏酸鈷、群青等之無 機著色顏料，或酞菁系、苯并咪唑酮系、異吲哚啉酮系、 偶氮系、蒽醌系、喹啉黃系、蒽吡啶系、喹吖啶酮系、甲 本胺系、皮恵嗣系、菲系等之有機著色顏料。 防藻劑可適當地應用與中間層的樹脂成分相溶性良好 之有機防霉劑’例如可列舉出有機氮硫系化合物、吡啶硫 酮系化合物、有機碘化合物、三氮雜苯系化合物、異噻唑 啉系化合物、咪唑系化合物、吡啶系化合物、腈系化合物 、硫胺甲酸酯系化合物、噻唑系化合物、二硫化物系化合 物等。 黏性調整劑，例如可列舉出有機皂土系、超微粉二氧 -15- 201200355 化矽系、表面處理碳酸鈣系、醯胺蠟系、加氫蓖麻油 、苯亞甲基葡萄糖醇系、各種金屬皂類、氧化聚乙烯 聚合植物油系、硫酸酯系陰離子活性劑、聚醚/酯型 活性劑、聚羧酸的胺鹽、鎂鋁矽酸鹽系、三仙膠系、 豆膠系、聚丙烯酸鈉系、丙烯酸-丙烯酸酯共聚物等 增黏系）、聚乙烯醇系、聚環氧乙烷系、經胺基甲酸 質之聚醚系等。 中間層，可藉由將至少由珠粒及聚矽氧烷改質樹 構成之上述組成物應用在，較佳爲塗佈在基材上而製 。中間層的應用方法，可應用刷毛塗佈、滾動塗佈、 塗佈、輥塗佈、流動塗佈、浸泡塗佈、淋流塗佈、網 刷等之一般所廣泛進行的方法來應用該組成物。將組 應用在基材後，在常溫下乾燥或是因應必要進行加熱 而形成中間層。藉由乾燥，可維持將在組成物中往上 起之珠粒集中在與光觸媒層之界面之中間層的表面附 狀態，而有效率地形成由該形狀所起因之凸部。 用以形成中間層之塗層組成物的溶劑，只要是可 地使上述構成成分分散之溶劑，則均可使用，可爲7 或有機溶劑。此外，該組成物的固形份濃度並無特別 ，就塗佈容易度來看，較佳爲10~60質量％，尤佳爲1 質量％。用以形成中間層之塗層組成物的成分分析， 樹脂成分，可藉由紅外線分光分析來進行。 用以形成中間層之塗層組成物中，除了上述之外 含有顏料分散劑、消泡劑、抗氧化劑等之塗料用添加 蠟系 系、 界面 瓜耳 (鹼 酯改 脂所 造出 噴霧 版印 成物 乾燥 方浮 近之 適當 [C及/ 限定 5~50 關於 ，可 劑、 -16- 201200355 一般塗料中所含之其他成分。又，亦可含有二氧化矽微粒 子等消光劑。 光觸媒層 本發明之光觸媒層，爲含有中間層上所設置之光觸媒 粒子之層。 光觸媒粒子，可列舉出銳鈦礦型氧化鈦、金紅石型氧 化鈦、板鈦礦型氧化鈦、氧化錫、氧化鋅、鈦酸緦、氧化 鎢、氧化铈般之金屬氧化物的粒子。 根據本發明之較佳形態，光觸媒粒子較佳係具有1 〇nm 以上且未達lOOnm的平均粒徑，尤佳爲l〇nm以上60nm以下 。該平均粒徑，是藉由掃描型電子顯微鏡來測定進入於2〇 萬倍的視野之任意1 〇〇個粒子的長度，並作爲個數平均値 而算出。 粒子的形狀最佳爲真球狀，大致爲圓形或橢圓形者亦 佳，此時的粒子長度可大致算爲（（長徑+短徑）/2)。位於 此範圍內時，可有效率地發揮耐候性、光觸媒分解性、及 期望的各種覆膜特性（透明性、塗膜強度等）。 根據本發明之較佳形態，爲了顯現出更高的光觸媒能 ，可將選自由釩、鐵、鈷、鎳、鈀、鋅、釕、铑、銅、銀 、鉑及金所組成之群組的至少一種金屬及/或由該金屬所 構成之金屬化合物，添加於光觸媒層或應用在用以形成光 觸媒層之中間層上的光觸媒塗層液。該添加，可藉由將前 述金屬或金屬化合物混合於塗層液並使其溶解或分散之方 -17- 201200355 法、或將前述金屬或金屬化合物撐持於光觸媒層 粒子之方法等之任意方法來進行。 根據本發明之較佳形態，前述光觸媒層中所 觸媒粒子，係設爲超過1質量％且未達20質量％， 過1質量％且未達5質量％。藉由使光觸媒粒子的 此範圍，可有效地發揮光觸媒的分解功能，並可 得到不易產生基材及中間層的劣化之效果》 本發明之較佳形態中，係使前述光觸媒層具 。藉此，增加光觸媒粒子與被分解物之接觸機會 優異的光觸媒分解功能。 本發明之光觸媒塗裝體的光觸媒層，爲了確 ’較佳係實質上不含水解性聚矽氧烷的縮聚合物 完全不含。在此所謂水解性聚矽氧烷，爲具有烷 機矽氧烷及/或其部分水解物之總稱。水解性聚 縮聚合物之含量，以二氧化矽換算相對於光觸媒 機氧化物粒子及水解性聚矽氧烷的縮聚合物之爸 質量份，較佳爲0質量份以上且未達10質量份，j 量份以下’最佳爲0質量份。水解性聚矽氧烷， 以2〜4官能矽烷作爲單體單位之聚矽氧烷化合物 適當地應用乙基矽酸鹽、甲基矽酸鹽、含烷基的 、含苯基的聚矽氧烷等。 本發明之光觸媒塗裝體的光觸媒層，爲了確 ’較佳係實質上不含有機金屬化合物之水解物的 ’尤佳爲完全不含。在此所謂有機金屬化合物， 或光觸媒 含有之光 尤佳爲超 含量位於 有效率地 有通氣性 ，而發揮 保通氣性 ，尤佳爲 氧基之有 砂氧烷的 粒子、無 Γ計量100 :：佳爲5質 較常使用 ，例如可 聚矽氧烷 保通氣性 縮聚合物 爲含有鈦 -18- 201200355 '锆'鋁等金屬元素之金屬烷氧化物、金屬有機錯合物等 。有機金屬化合物之水解物的縮聚合物之含量，以金屬氧 化物換算相對於光觸媒粒子、無機氧化物粒子及水解性聚 矽氧烷之合計量100質量份，較佳爲0質量份以上且未達10 質量份，尤佳爲5質量份以下，最佳爲0質量份。 本發明之光觸媒層中，係至少含有選自由水解性聚矽 氧烷的縮聚合物、有機金屬化合物的水解物所組成之群組 的至少一種作爲任意成分。任意成分的含量，相對於光觸 媒粒子與無機氧化物粒子與此等任意成分的氧化物換算量 之合計量100質量份，較佳爲0質量份以上且未達10質量份 ，尤佳爲5質量份以下，最佳爲〇質量份。 根據本發明之較佳形態，前述光觸媒層，除了光觸媒 粒子以外，可含有無機氧化物粒子。該無機氧化物粒子係 具有黏合劑成分之功能，可對光觸媒層賦予充分的通氣性 ’增加光觸媒粒子與被分解物之接觸機會，而得到發揮優 異的光觸媒分解功能之優點。 無機氧化物粒子只要是可與光觸媒粒子一同形成層之 無機氧化物的粒子即可，並無特別限定，此般無機氧化物 粒子的例子，可列舉出二氧化矽 '氧化鋁、氧化锆、氧化 铈、三氧化二釔、氧化錫、氧化鐵、氧化錳、氧化鎳、氧 化鈷、氧化給等之單一氧化物的粒子；及鈦酸鋇、矽酸鈣 、硼酸鋁、鈦酸鉀等之複合氧化物的粒子，尤佳爲二氧化 矽粒子。此等無機氧化物粒子，較佳爲以水作爲分散劑之 水性膠體；或是以膠態狀分散於乙醇、異丙醇、或以二醇 -19- 201200355 等之親水性溶劑之有機溶膠形態，特佳爲膠態二氧化矽。 根據本發明之一項較佳形態，上述無機氧化物粒子係 具有超過5nm且爲20nm以下，較佳爲10nm以上20nm以下的 平均粒徑。該平均粒徑，是藉由掃描型電子顯微鏡來測定 進入於20萬倍的視野之任意1〇〇個粒子的長度，並作爲個 數平均値而算出。粒子的形狀最佳爲真球狀，大致爲圓形 或橢圓形者亦佳，此時的粒子長度可大致算爲（（長徑+ 短徑）/2 )。位於此範圍內時，可有效率地發揮耐候性、光 觸媒分解性、及期望的各種覆膜特性（透明性、塗膜強度 等），尤其不僅可得到透明且密著性良好之光觸媒層，並 可得到相對於滑動磨耗更爲堅固之膜。 根據本發明之一項較佳形態，光觸媒層，相對於前述 光觸媒粒子、前述無機氧化物粒子、及前述任意成分的氧 化物換算量之合計量100質量份，係含有超過1質量份且未 達20質量份的光觸媒粒子，及超過70質量份且未達99質量 份的無機氧化物粒子，以及0質量份以上且未達1 0質量份 之作爲任意成分之選自由水解性聚矽氧烷的縮聚合物、與 有機金屬化合物之水解物的縮聚合物之群組的至少一種而 構成。尤佳爲，前述光觸媒層，相對於前述光觸媒粒子、 前述無機氧化物粒子、及前述任意成分的氧化物換算量之 合計量100質量份，係含有超過1質量份且未達5質量份的 光觸媒粒子，及超過85質量份且未達99質量份的無機氧化 物粒子，以及0質量份以上且未達1 0質量份之作爲任意成 分之選自由水解性聚矽氧烷的縮聚合物、與有機金屬化合 -20- 201200355 物之水解物的縮聚合物之群組的至少一種而構成。藉由構 成此般光觸媒層，可增加光觸媒粒子與被分解物之接觸機 會，有效地發揮優異的光觸媒分解功能，並且可將基材及 中間層的耐候性，提升至可承受在熱帶中長期使用之程度 。再者，亦可抑制由光觸媒所造成之基材及中間層的劣化 0 根據本發明之一項較佳形態，本發明之光觸媒塗裝體 的光觸媒層，實質上構成爲透明。 根據本發明之一項形態，光觸媒層的膜厚較佳爲 Ο.ίμηι以上5.0μιη以下，尤佳爲0.5μηι以上3·0μηι以下，最佳 爲Ι.Ομιη以上2.0μιη以下。藉由設爲此範圍內，可在膜厚方 向上增加含有比率較無機氧化物粒子更低之光觸媒粒子， 而能夠提升光觸媒分解性。再者，亦可得到透明性佳之特 性。 本發明之光觸媒塗'裝體，可藉由將含有光觸媒粒子與 溶劑之光觸媒塗層液應用在，較佳爲塗佈在具有以上述方 法所形成之中間層之基材上而製造出。光觸媒層的應用方 法，可應用刷毛塗佈、滾動塗佈、噴霧塗佈、輥塗佈、流 動塗佈、浸泡塗佈、淋流塗佈、網版印刷等之一般所廣泛 進行的方法來應用前述液劑。將塗層液應用在基材後，可 在常溫下乾燥或是因應必要進行加熱乾燥。 添加於上述光觸媒塗層液的光觸媒，可在溶膠形態下 添加，該溶膠的溶劑，可使用能夠適當地使上述構成成分 分散之溶劑，可爲水及/或有機溶劑，特佳爲水。 -21 - 201200355 此外，上述光觸媒塗層液的溶劑，可使用能夠適當地 使上述構成成分分散之溶劑，可爲水及/或有機溶劑。此 外，光觸媒塗層液的固形份濃度並無特別限定，就塗佈容 易度來看，較佳爲卜10質量％。此外，光觸媒塗層組成物 中之構成成分的成分分析，可藉由超過濾將塗層液分離爲 粒子成分及濾液，並分別藉由紅外線分光分析、凝膠滲透 層析、螢光X射線分光分析等來分析各成分，並藉由解析 光譜來進行評估。 上述光觸媒塗層液可含有作爲任意成分之界面活性劑 。界面活性劑，相對於光觸媒塗層液可含有0質量份以上 且未達10質量份，較佳爲0質量份以上且未達8質量份，尤 佳爲0質量份以上且未達6質量份。添加界面活性劑的效果 之一爲對基材的平坦性，用以獲得該效果之下限値約爲 0.1質量份。此外，界面活性劑對於用以改善光觸媒塗層 液的潤濕性爲有效成分，但對於塗佈後所形成之光觸媒層 ，已成爲不再有益於達到本發明之光觸媒塗裝體的效果之 不可避免的雜質。因此，界面活性劑，可因應光觸媒塗層 液所要求之潤濕性而在上述含量範圍內使用，但只要無潤 濕性上的問題，則亦可實質上或完全不含有。界面活性劑 的種類，可考量光觸媒及無機氧化物粒子的分散安定性、 塗佈在中間層上時的潤濕性來適當地選擇，較佳爲非離子 性界面活性劑，尤佳爲醚型非離子性界面活性劑、酯型非 離子性界面活性劑、聚伸烷二醇非離子性界面活性劑、氟 系非離子性界面活性劑、矽系非離子性界面活性劑。 -22- 201200355 基材 本發明之光觸媒塗裝體的基材，只要是可於其上方形 成中間層之材料即可，不論是無機材料或有機材料的各種 材料均可，該形狀亦無限定。就材料的觀點來看，基材的 較佳例子，可列舉出金屬、陶瓷、玻璃、塑膠、橡膠、石 、水泥、混凝土、纖維、布帛、木、紙、此等之組合、此 等之層合體、以及此等之表面上具有至少1層覆膜者。就 用途的觀點來看，基材的較佳例子，可列舉出建材、建物 外裝及內裝、窗框、窗玻璃、結構構件、乘載物的外裝及 塗裝 '機械裝置或物品的外裝、防塵蓋及塗裝、交通標誌 、各種顯示裝置、廣告塔、道路用隔音牆、橋樑、導軌的 外裝及塗裝、隧道內裝及塗裝、礙子、太陽能電池蓋、太 陽熱能溫水器集熱蓋、塑膠膜溫室、車輛用照明燈的蓋體 、室外用照明器具、台座、浴室材料、廚房板材、流理台 、微波爐、通風扇、空調、過濾器、便斗、浴槽及貼著於 上述物品表面之薄膜、薄片、密封片等。 [實施例] 根據下列例子來更具體地說明本發明，但本發明並不 限定於此等例子。 <塗裝體試樣的製作> 以下列方式來製作實施例及比較例。 -23- 201200355 例1 首先製備白色琺瑯塗裝基材作爲基材。 接著以下列方式形成中間層。亦即，於矽氧烷含量相 對於聚矽氧烷改質樹脂的固形份爲30質量％之聚矽氧烷改 質丙烯酸樹脂乳化液（固形份濃度：40% ) 1 00重量份中， 加入著色顔料漿液（金紅石型氧化鈦、固形份濃度：65% )43重量份、丙烯酸樹脂珠粒（平均粒徑：18μ：η) 16重量 份、離子交換水55重量份、黏性調整劑4重量份，並混合 於作爲溶劑之水，而得中間層塗層液。將此塗層液滾動塗 佈在上述基材，在室溫（23 °C)下乾燥24小時後，形成膜 厚40μπι的中間層。 以下列方式形成光觸媒層。亦即，將銳鈦礦型氧化鈦 水分散體（平均粒徑：約50nm、分散劑：二乙胺）與水分 散型膠態二氧化矽（平均粒徑：約1 1 nm、鹼性）混合而得 光觸媒塗層液。光觸媒塗層液中之光觸媒及無機氧化物的 合計固形份濃度設爲5.5質量％。將所得之光觸媒塗層液噴 霧塗佈在預先加熱之上述中間塗料塗裝體上，在常溫（23 °C )下乾燥24小時。所得之光觸媒層中的氧化鈦爲10質量 份，二氧化矽爲90質量份。此外，光觸媒層的膜厚爲 0.5 μηι。 例2〜1 0 將丙烯酸樹脂珠粒構成爲後述表中所記載之平均粒徑 -24- 201200355 ’並藉由調整中間層塗層液的量以將中間層構成爲後述表 中所記載之膜厚，除此之外，其他與實施任"相同而得光 觸媒塗裝體。例8及例9中，係添加中空無機玻璃珠粒（平 均粒徑：30*16μπ〇 8重量份來取代丙烯酸樹脂珠粒。例 10中，未添加丙烯酸樹脂珠粒。 光觸媒分解能的評估 對所得之光觸媒塗裝體’依循：TISR1703_2「光觸媒材 料的自我清淨性能試驗方法-第2部：濕式分解性能」的試 驗法，來評估甲烯藍分解能。所得之分解活性指數如下列 表所示。 [表1] 1 2 3 4 5 6 7 8 9 10 (比較例） 中間層的膜厚—） 40 50 16.5 40 30 40 90 40 40 40 珠粒粒徑（μ nr〇 18 46 6 6 46 110 110 30 16 厚度/粒徑 0.45 0.92 0.36 0.15 1.53 2.75 1.22 0.75 0.4 - 甲烯藍分解能 14.8 13.75 14.5 15.05 13.8 13.8 14 14.1 14.5 13.3 -25-Further, according to a preferred embodiment of the present invention, a light stabilizer such as a hindered amine system and/or a hindered phenol system may be further contained in the intermediate layer. The improvement in weather resistance and light resistance of the photocatalyst-coated body of the present invention can be expected by interaction with the above ultraviolet absorber. Particularly when a hydroxyphenyltriazabenzene compound is used as the ultraviolet absorber, a hindered amine system can be selected as the light stabilizer. By virtue of the hydroxyphenyltriazabenzene compound, the advantage of the ultraviolet absorption property stability of a short wavelength of less than 380 nm can be obtained. The amount of the light stabilizer to be added to the intermediate layer is preferably from 0. 0 0 1 to 10% by mass, particularly preferably from 0. 0 1 to 5 mass%. Specific examples of the hindered amine light stabilizers include bis(2,2,6,6-tetramethyl-4-piperidyl)succinate and bis(2,2,6,6-tetramethyl). -4 -piperidinyl) sebacate, bis(1,2,2,6,6-pentamethyl-4-piperidinyl)2-(3,5-di-tertiary butyl-4- Butyl hydroxybenzyl)-2-propanedioate, 1-[2-[3-(3,5-di-tri-tert-butyl-4-hydroxyphenyl)propynyloxy]ethyl]-4- [3-(3,5-di-tri-butyl-4-hydroxyphenyl)propynyloxy]-2,2,6,6-tetramethylpiperidine, bis( 1,2,2,6 ,6-pentamethyl-4-piperidinyl) sebacate and a mixture of methyl hydrazine, 2,2,6,6-pentamethyl-4-piperidinyl-sebacate (Ciba Japan) Co., Ltd., trade name: TINU VIN-292), bis(1-octooxy-2,2,6,6-tetramethyl-4-piperidinyl) sebacate, TINUVIN-123 (trade name) , 0: 沁玨13?311 Co., Ltd.), 1'11^1; ¥11^-111?〇1^ (trade name, manufactured by Ciba Japan Co., Ltd.), TINUVIN 292 (trade name, Ciba Japan shares) Co., Ltd.), and bismuth, 2,2,6,6-pentamethyl-4-piperidyl methacrylate, 1,2,2,6,6-pentamethyl-4-piperidinyl Base Acid ester, 2,2,6,6-tetramethyl-4-piperidyl methacrylate, -14- 201200355 2,2,6,6-tetramethyl-4-piperidyl methacrylate 1,2,2,6,6-pentamethyl-4-imine piperidinyl methacrylate, 2,2,6,6-tetramethyl-4-imidopiperidinyl methacrylate 4-cyano-2,2,6,6-tetramethyl-4-piperidyl methacrylate, 4-cyano-1,2,2,6,6-pentamethyl-4-piperidin A polymerizable hindered amine-based ultraviolet absorber such as pyridine methacrylate or a (co)polymer thereof. In addition, specific examples of the hindered phenol-based photostabilizer include bis(3,5-tributyl)-4-hydroxytoluene, TINUVIN-144 (trade name, manufactured by Cib a Japan Co., Ltd.), and the like. The intermediate layer of the photocatalyst-coated body of the present invention may contain an extender pigment, a coloring pigment, an algicide, a viscosity modifier, or the like as an optional component. Examples of the extendable pigment include titanium oxide whiskers, calcium carbonate whiskers, aluminum borate whiskers, potassium titanate whiskers, mica, and talc. Examples of the coloring pigment include inorganic coloring pigments such as titanium oxide white, zinc oxide white iron oxide, carbon black, spinel green, red iron oxide, cobalt urate, and ultramarine, or phthalocyanine or benzimidazolone. An organic coloring pigment such as an isoindolinone, an azo, an anthraquinone, a quinoline yellow, an anthracene pyridine, a quinacridone, a methylamine, a quercetin or a phenanthrene. As the anti-algae agent, an organic antifungal agent having a good compatibility with the resin component of the intermediate layer can be suitably used, and examples thereof include an organic nitrogen-sulfur compound, a pyrithione compound, an organic iodine compound, and a triazabenzene compound. A thiazoline-based compound, an imidazole-based compound, a pyridine-based compound, a nitrile-based compound, a thiourethane-based compound, a thiazole-based compound, a disulfide-based compound, or the like. Examples of the viscosity modifier include an organic bentonite system, an ultrafine powder, a dioxane-15-201200355 chemical system, a surface-treated calcium carbonate system, a guanamine wax system, a hydrogenated castor oil, and a benzylidene glucose alcohol system. Various metal soaps, oxidized polyethylene polymerized vegetable oils, sulfate-based anionic active agents, polyether/ester-type active agents, amine salts of polycarboxylic acids, magnesium aluminum citrates, Sanxian gums, bean gums, A polyacrylate system such as a sodium polyacrylate type or an acrylic acid acrylate copolymer, a polyvinyl alcohol type, a polyethylene oxide type, or a urethane type polyether type. The intermediate layer can be produced by applying the above-mentioned composition composed of at least a bead and a polyoxyalkylene-modified tree, preferably coated on a substrate. The application method of the intermediate layer can be applied to a general application method such as brush coating, roll coating, coating, roll coating, flow coating, dip coating, leaching coating, net brush, etc. to apply the composition. Things. After the group is applied to the substrate, it is dried at room temperature or heated as necessary to form an intermediate layer. By drying, the surface of the intermediate layer which is the upper side of the interface with the photocatalyst layer is maintained by the beads which are raised in the composition, and the convex portion caused by the shape is efficiently formed. The solvent for forming the coating composition of the intermediate layer may be any solvent as long as it can disperse the above constituent components, and may be 7 or an organic solvent. Further, the solid content concentration of the composition is not particularly large, and from the viewpoint of ease of coating, it is preferably from 10 to 60% by mass, particularly preferably from 1% by mass. The component analysis of the coating composition for forming the intermediate layer, and the resin component, can be carried out by infrared spectroscopic analysis. The coating composition for forming the intermediate layer, in addition to the above, contains a pigment dispersant, an antifoaming agent, an antioxidant, and the like, and an additive wax system, and an interface guar (alkali ester modified to produce a spray printing) Appropriate drying of the product is appropriate [C and / / 5 ~ 50 about, can be used, -16- 201200355 other components contained in the general coating. Also, it can also contain matting agents such as cerium oxide microparticles. Photocatalyst layer The photocatalyst layer of the invention is a layer containing photocatalyst particles provided on the intermediate layer. Examples of the photocatalyst particles include anatase titanium oxide, rutile titanium oxide, brookite titanium oxide, tin oxide, zinc oxide, and the like. According to a preferred embodiment of the present invention, the photocatalyst particles preferably have an average particle diameter of 1 〇 nm or more and less than 100 nm, and more preferably l 〇 nm. The above-mentioned 60 nm or less. The average particle diameter is measured by a scanning electron microscope to measure the length of any one of the particles entering the field of view of 20,000 times, and is calculated as a number average 値. The shape is preferably a true spherical shape, and is preferably a circular or elliptical shape. The particle length at this time can be roughly calculated as ((long diameter + short diameter)/2). When it is within this range, it can be efficiently It exhibits weather resistance, photocatalytic decomposition property, and various desired film properties (transparency, film strength, etc.). According to a preferred embodiment of the present invention, in order to exhibit higher photocatalytic energy, it may be selected from vanadium, iron, At least one metal of a group consisting of cobalt, nickel, palladium, zinc, ruthenium, iridium, copper, silver, platinum, and gold, and/or a metal compound composed of the metal, added to the photocatalyst layer or used to form a photocatalyst coating liquid on the intermediate layer of the photocatalyst layer. The addition may be carried out by mixing the above metal or metal compound in a coating liquid and dissolving or dispersing it, or by using the aforementioned metal or metal compound. According to a preferred embodiment of the present invention, the catalyst particles in the photocatalyst layer are more than 1% by mass and less than 20% by mass, and more than 1% by mass. Not up to 5 quality By setting this range of the photocatalyst particles, the decomposition function of the photocatalyst can be effectively exhibited, and the effect of deterioration of the substrate and the intermediate layer can be obtained. In a preferred embodiment of the present invention, the photocatalyst layer is provided. Thereby, the photocatalytic decomposition function which is excellent in the chance of contact between the photocatalyst particles and the substance to be decomposed is increased. The photocatalyst layer of the photocatalyst-coated body of the present invention does not have a polymer which is substantially free of hydrolyzable polyoxyalkylene. The hydrolyzable polyoxyalkylene is a general term for a hydrolyzed alkane and/or a partially hydrolyzed product thereof. The content of the hydrolyzable polycondensate is measured in terms of cerium oxide relative to the photocatalyst oxide particles. And the mass fraction of the polymer of the hydrolyzable polyoxyalkylene is preferably 0 parts by mass or more and less than 10 parts by mass, and the amount of the mass of the polymer is less than 0 parts by mass. Hydrolyzable polyoxyalkylene, polyoxonane compound having 2 to 4 functional decane as a monomer unit, ethyl citrate, methyl phthalate, alkyl group-containing, phenyl group-containing polyoxyl Alkane, etc. The photocatalyst layer of the photocatalyst-coated body of the present invention is preferably completely excluded in order to ensure that the hydrolyzate substantially free of the organometallic compound is contained. Here, the organic metal compound or the photocatalyst contains light, which is preferably a super-content, which is effective in aeration, and which exhibits aeration resistance, and is particularly preferably an oxy-containing sulphate particle, innocent measurement 100: It is more commonly used. For example, the polyoxyalkylene aeration-reducing polymer is a metal alkoxide or a metal-organic complex containing a metal element such as titanium-18-201200355 'zirconium aluminum. The content of the condensed polymer of the hydrolyzate of the organometallic compound is preferably 0 parts by mass or more based on 100 parts by mass of the total amount of the photocatalyst particles, the inorganic oxide particles, and the hydrolyzable polyoxyalkylene. Up to 10 parts by mass, particularly preferably 5 parts by mass or less, and most preferably 0 parts by mass. The photocatalyst layer of the present invention contains at least one selected from the group consisting of a polycondensate of a hydrolyzable polyoxyalkylene and a hydrolyzate of an organometallic compound as an optional component. The content of the optional component is preferably 0 parts by mass or less and less than 10 parts by mass, more preferably 5 parts by mass, based on 100 parts by mass of the total amount of the photocatalyst particles and the inorganic oxide particles and the oxides of the optional components. Below the weight, the best is 〇 by mass. According to a preferred embodiment of the present invention, the photocatalyst layer may contain inorganic oxide particles in addition to the photocatalyst particles. The inorganic oxide particles have a function as a binder component, and can impart sufficient air permeability to the photocatalyst layer. </ RTI> The chance of contact between the photocatalyst particles and the substance to be decomposed is increased, and an excellent photocatalytic decomposition function is obtained. The inorganic oxide particles are not particularly limited as long as they are inorganic oxide particles which can form a layer together with the photocatalyst particles. Examples of the inorganic oxide particles include cerium oxide, aluminum oxide, zirconium oxide, and oxidation. a composite of a single oxide of antimony, antimony trioxide, tin oxide, iron oxide, manganese oxide, nickel oxide, cobalt oxide, oxidation, etc.; and a combination of barium titanate, calcium citrate, aluminum borate, potassium titanate, and the like The particles of the oxide are particularly preferably cerium oxide particles. These inorganic oxide particles are preferably an aqueous colloid which uses water as a dispersing agent; or an organosol which is colloidally dispersed in ethanol, isopropanol or a hydrophilic solvent such as diol-19-201200355; , especially good for colloidal cerium oxide. According to a preferred embodiment of the present invention, the inorganic oxide particles have an average particle diameter of more than 5 nm and not more than 20 nm, preferably from 10 nm to 20 nm. The average particle diameter is calculated by scanning electron microscopy to measure the length of any one of the particles entering the field of view of 200,000 times, and is calculated as the number average 値. The shape of the particles is preferably a true spherical shape, and is preferably a circular or elliptical shape. The particle length at this time can be roughly calculated as ((long diameter + short diameter)/2). When it is in this range, weather resistance, photocatalytic decomposition property, and desired various film properties (transparency, film strength, etc.) can be exhibited efficiently, and in particular, not only a photocatalyst layer which is transparent and excellent in adhesion can be obtained, and A film that is stronger than sliding wear can be obtained. According to a preferred embodiment of the present invention, the photocatalyst layer contains more than 1 part by mass and not more than 100 parts by mass of the total amount of the oxide of the photocatalyst particles, the inorganic oxide particles, and the optional component. 20 parts by mass of the photocatalyst particles, and more than 70 parts by mass and less than 99 parts by mass of the inorganic oxide particles, and 0 parts by mass or more and less than 10 parts by mass of the optional component selected from the group consisting of hydrolyzable polysiloxanes It is composed of at least one of a group of a condensed polymer and a condensed polymer of a hydrolyzate of an organometallic compound. In particular, the photocatalyst layer contains more than 1 part by mass and less than 5 parts by mass of the photocatalyst in an amount of 100 parts by mass based on the total amount of the photocatalyst particles, the inorganic oxide particles, and the oxides of the optional components. The particles, and more than 85 parts by mass and less than 99 parts by mass of the inorganic oxide particles, and 0 parts by mass or more and less than 10 parts by mass of the condensed polymer selected from the hydrolyzable polyoxyalkylene as an optional component, and The organometallic compound -20-201200355 is composed of at least one of a group of condensed polymers of a hydrolyzate of a substance. By forming such a photocatalyst layer, the contact chance between the photocatalyst particles and the decomposed material can be increased, the photocatalytic decomposition function can be effectively exhibited, and the weather resistance of the substrate and the intermediate layer can be improved to withstand long-term use in the tropics. The extent of it. Further, deterioration of the substrate and the intermediate layer by the photocatalyst can be suppressed. 0 According to a preferred embodiment of the present invention, the photocatalyst layer of the photocatalyst-coated body of the present invention is substantially transparent. According to an aspect of the present invention, the film thickness of the photocatalyst layer is preferably Ο.ίμηι or more and 5.0 μm or less, more preferably 0.5 μηι or more and 3·0 μηι or less, and most preferably Ι.Ομηη or more and 2.0 μηη or less. By setting it as such a range, the photocatalyst particles having a lower ratio than the inorganic oxide particles can be added in the film thickness direction, and the photocatalytic decomposability can be improved. Furthermore, the transparency is also good. The photocatalyst coating of the present invention can be produced by applying a photocatalyst coating liquid containing photocatalyst particles and a solvent, preferably to a substrate having an intermediate layer formed by the above method. The application method of the photocatalyst layer can be applied by generally widely used methods such as brush coating, roll coating, spray coating, roll coating, flow coating, dip coating, trickle coating, screen printing, and the like. The aforementioned liquid agent. After applying the coating liquid to the substrate, it can be dried at room temperature or dried as necessary. The photocatalyst to be added to the photocatalyst coating liquid may be added in the form of a sol. The solvent of the sol may be a solvent which can appropriately disperse the above constituent components, and may be water and/or an organic solvent, and particularly preferably water. Further, the solvent of the photocatalyst coating liquid may be a solvent which can appropriately disperse the above constituent components, and may be water and/or an organic solvent. Further, the solid content concentration of the photocatalyst coating liquid is not particularly limited, and is preferably 10% by mass in terms of coating ease. In addition, component analysis of the constituent components in the photocatalyst coating composition can be separated into particle components and filtrate by ultrafiltration, and separately subjected to infrared spectroscopic analysis, gel permeation chromatography, and fluorescent X-ray spectrometry. Analysis and the like are performed to analyze each component and evaluated by analyzing the spectrum. The photocatalyst coating liquid may contain a surfactant as an optional component. The surfactant may be contained in an amount of 0 parts by mass or more and less than 10 parts by mass, preferably 0 parts by mass or more and less than 8 parts by mass, particularly preferably 0 parts by mass or more and less than 6 parts by mass based on the photocatalyst coating liquid. . One of the effects of adding a surfactant is the flatness to the substrate, and the lower limit 以获得 to obtain the effect is about 0.1 part by mass. In addition, the surfactant is an effective component for improving the wettability of the photocatalyst coating liquid, but it is not beneficial for the photocatalyst layer formed after coating to achieve the effect of the photocatalyst coating body of the present invention. Avoid impurities. Therefore, the surfactant may be used within the above content range in accordance with the wettability required for the photocatalyst coating liquid, but may be substantially or completely excluded as long as there is no problem in wettability. The type of the surfactant can be appropriately selected in consideration of the dispersion stability of the photocatalyst and the inorganic oxide particles and the wettability when applied to the intermediate layer, and is preferably a nonionic surfactant, particularly preferably an ether type. A nonionic surfactant, an ester type nonionic surfactant, a polyalkylene glycol nonionic surfactant, a fluorine-based nonionic surfactant, and a lanthanide nonionic surfactant. -22-201200355 Substrate The substrate of the photocatalyst-coated body of the present invention is not particularly limited as long as it is a material which can be squared on the intermediate layer, and can be any material of an inorganic material or an organic material. From the viewpoint of materials, preferred examples of the substrate include metal, ceramic, glass, plastic, rubber, stone, cement, concrete, fiber, cloth, wood, paper, combinations of these, and the like. Fitted, and at least one layer of film on the surface of the body. From the viewpoint of the use, preferred examples of the substrate include building materials, exterior and interior construction, window frames, window glass, structural members, exterior mounting of the carrier, and painting of mechanical devices or articles. Exterior, dust cover and painting, traffic signs, various display devices, advertising towers, soundproof walls for roads, exterior and painting of bridges, guide rails, tunnel interiors and paintings, insults, solar battery covers, solar thermal energy Heater collector cover, plastic film greenhouse, cover for vehicle lighting, outdoor lighting, pedestal, bathroom material, kitchen board, flow table, microwave oven, ventilation fan, air conditioner, filter, toilet, bath And a film, a sheet, a sealing sheet, or the like attached to the surface of the above article. [Examples] The present invention will be specifically described based on the following examples, but the present invention is not limited thereto. <Preparation of coated body sample> Examples and comparative examples were produced in the following manner. -23- 201200355 Example 1 A white enamel coated substrate was first prepared as a substrate. The intermediate layer is then formed in the following manner. That is, in the polyoxyalkylene modified acrylic resin emulsion (solid content concentration: 40%) in a solid content of 30% by mass based on the solid content of the polyoxyalkylene-modified resin, 100 parts by weight, Coloring pigment slurry (rutile-type titanium oxide, solid content concentration: 65%) 43 parts by weight, acrylic resin beads (average particle diameter: 18 μ: η) 16 parts by weight, ion-exchanged water 55 parts by weight, viscosity adjuster 4 Parts by weight and mixed with water as a solvent to obtain an intermediate layer coating liquid. This coating liquid was roll-coated on the above substrate, and dried at room temperature (23 ° C) for 24 hours to form an intermediate layer having a film thickness of 40 μm. The photocatalyst layer was formed in the following manner. That is, an anatase-type titanium oxide aqueous dispersion (average particle diameter: about 50 nm, dispersant: diethylamine) and water-dispersed colloidal ceria (average particle diameter: about 11 nm, alkaline) The photocatalyst coating liquid is mixed. The total solid content of the photocatalyst and the inorganic oxide in the photocatalyst coating liquid was 5.5% by mass. The obtained photocatalyst coating liquid was sprayed onto the above-mentioned intermediate coating body which was previously heated, and dried at normal temperature (23 ° C) for 24 hours. The titanium oxide in the obtained photocatalyst layer was 10 parts by mass, and the cerium oxide was 90 parts by mass. Further, the photocatalyst layer has a film thickness of 0.5 μm. Example 2 to 10 The acrylic resin beads were formed into the average particle diameter of the following Table - 201200355 ' and the amount of the intermediate layer coating liquid was adjusted to form the intermediate layer as the film described in the following table. Thick, in addition to the other, the same as the implementation of the "photocatalyst coating body. In Examples 8 and 9, hollow inorganic glass beads (average particle diameter: 30*16 μπ〇8 parts by weight in place of acrylic resin beads were added. In Example 10, acrylic resin beads were not added. Evaluation of photocatalytic decomposition energy was obtained. The photocatalyst coating body is evaluated according to the test method of TISR1703_2 "Test method for self-cleaning performance of photocatalyst materials - Part 2: Wet decomposition performance". The decomposition activity index obtained is shown in the following table. Table 1] 1 2 3 4 5 6 7 8 9 10 (Comparative Example) Film thickness of the intermediate layer -) 40 50 16.5 40 30 40 90 40 40 40 Bead size (μ nr〇18 46 6 6 46 110 110 30 16 Thickness / particle size 0.45 0.92 0.36 0.15 1.53 2.75 1.22 0.75 0.4 - Dimethyl blue decomposition energy 14.8 13.75 14.5 15.05 13.8 13.8 14 14.1 14.5 13.3 -25-