201231533 六、發明說明： 【發明所屬之技術領域】 本發明關於具有有害氣體分解性、降雨·水 淨性、水洗容易性、VOC (揮發性有機化合救 organic compounds))分解性、抗菌性、防霉性 性等的光觸媒機能之光觸媒塗裝體。再者，本發 由在構成外裝、內裝等的構件上形成塗佈層，而 害氣體分解性、降雨·水洗的自潔淨性、水洗 VOC分解性、抗菌性、防霉性、抗病毒性等之光 的光觸媒塗佈液。 【先前技術】 氧化鈦等的光觸媒係近年來利用於建築物的 構造物、交通工具及構成彼等的構件、複合材等 作爲在室外的利用，藉由在基材表面上擔持 而賦予基材利用光能量分解NOx、SOx等有害物 。又，於光照射時成爲親水性的層表面，係藉由 掉所附著的污垢，即具有所謂的自潔淨機能。 另外，作爲室內的利用’藉由在基材表面擔 ’而賦予基材利用光能量分解VOC等有害物質 或賦予抗菌機能、防霉機能、抗病毒機能。 當爲建築物的建造物、構造物、交通工具及 的構件、複合材等時’爲了生活空間所利用’賦 觸媒機能的基材之表面，多爲持有式樣設計性者 洗的自潔 1 (volatile 、抗病毒 明關於藉 能賦予有 容易性、 觸媒機能 建造物、 〇 光觸媒， 質之機能 降雨而沖 持光觸媒 之機能， 構成彼等 有上述光 -5- 201231533 因此，以往有提案在光觸媒層中添加著色顏料，而使 同時具有式樣設計性（專利文獻1 ;特開2004-051644號 公報）。 另一方面，於建築物的建造物、構造物、交通工具及 構成彼等的構件、複合材中，作爲基材的如樹脂板、壁紙 、塗裝板、薄膜積層板、化妝板等，多爲含有有機物的表 面之基.材，於彼等基材中，多數的情況爲賦有式樣設計性 的著色。當於彼等基材上形成光觸媒層時，要求發揮光觸 媒機能，同時基材不易被紫外線或光觸媒的分解活性所劣 化，即基材所具有的式樣設計係可長期間維持。 作爲解決上述問題的1個方法，有提案在基材與光觸 媒層之間，形成不含有光觸媒的中間層之技術（專利文獻 2;特開平7-171408號公報）。然而，於此方法中，由於 工時增加而成本變高。因此，要求不形成中間層而能同時 發揮光觸媒機能與基材因紫外線或光觸媒的分解活性所致 的劣化之抑制機能的技術。 作爲在如此的基材上直接一次塗佈以發揮光觸媒機能 之光觸媒塗佈組成物，例如已知由含有經矽烷改性的光觸 媒粒子、鍵結於矽原子的烷氧基及/或羥基之含量爲7〜 2 0mmol/g的膠態矽石、鍵結於矽原子的烷氧基及/或羥基 的含量爲1〜20mmol/g的聚合物乳液粒子所成之水系有機 •無機複合組成物（專利文獻3;特開2008-222887號公 報）。 [先前技術文獻] -6 - 201231533 [專利文獻] [專利文獻1]特開20〇4_05 1 644號公報 [專利文獻2]特開平7- 1 7 1 408號公報 [專利文獻3]特開2008-2228 87號公報 【發明內容】 [發明所欲解決的問題] 本發明者們此番發現藉由含有經具有全氟基的物質所 被覆或改性處理的矽石粒子、光觸媒性金屬氧化物粒子與 樹脂乳液之塗佈液而形成之光觸媒層，與直接使用未處理 的矽石粒子所形成的光觸媒層比較下，係具有顯著改善的 光觸媒機能，本發明係以該知識爲基礎。 因此，本發明之目的在於提供光觸媒機能優異，可長 期抑制其外觀變化的光觸媒塗裝體，及其之形成用的光觸 媒塗佈液。 [解決問題的手段] 而且，本發明的光觸媒塗裝體係在基材表面具備有光 觸媒層的光觸媒塗裝體，前述光觸媒層具備光觸媒性金屬 氧化物粒子、矽石粒子與樹脂乳液的乾燥物，前述矽石粒 子係被具有全氟基的物質所被覆或改性處理。 又，本發明的光觸媒塗佈液具備光觸媒性金屬氧化物 粒子、矽石粒子、樹脂乳液與溶劑，前述矽石粒子係被具 有全氟基的物質所被覆或改性處理。 201231533 本發明的光觸媒塗裝體係光觸媒機能優異。再者，依 照本發明的較佳態樣’可抑制基材被光觸媒所侵蝕或紫外 線降解，當光觸媒層爲透明時，可活用基材的式樣設計， 當光觸媒層中含有著色顏料時，基材隱蔽性優異，可藉由 光觸媒層賦予式樣設計。 【實施方式】 [實施發明的形態] 光觸媒塗裝體 本發明的光觸媒塗裝體係在基材表面上具備有光觸媒 層的光觸媒塗裝體，前述光觸媒層係含有光觸媒性金屬氧 化物粒子、矽石粒子與樹脂乳液的乾燥物所成，前述矽石 粒子係被具有全氟基的物質所被覆或改性處理。藉由使用 經具有全氟基的物質所被覆或改性處理之矽石粒子，與直 接添加矽石粒子的情況比較下，意外地可顯著地增加光觸 媒活性。而且，可長期抑制塗裝體的外觀變化》 再者’本發明所言的光觸媒層，就是指適用於在基材 表面上形成含有光觸媒粒子的塗佈液之部分。光觸媒粒子 若存在於該部分’則可爲任何形態。即，可完全成爲膜狀 ，也可部分成爲膜狀。又，亦可在基材表面上以島狀離散 地存在。 依照本發明的較佳形態，具有全氟基的物質係具有全 氟基的矽烷及/或具有全氟基的聚矽氧。此等物質由於具 有與矽石粒子共通的矽氧烷鍵，藉由偶合處理等，可容易 -8- 201231533 進行此等物質所致的矽石表面之被覆、改性。 依照本發明的較佳形態，前述光觸媒層的膜厚係超過 3μιη且未達3μπΐ。由於超過3μιη，光觸媒層所致的紫外線 之遮蔽性高，可降低紫外線對基材的影響。結果，可有效 地抑制紫外線所致的基材之劣化。又，於光觸媒層中含有 著色顏料時，充分得到基材的隱蔽性，可藉由光觸媒層對 基材賦予式樣設計。又，由於未達3 mm，可維持作爲塗膜 的基本性狀，以適當的熟化時間可形成塗膜。 依照本發明的較佳形態，光觸媒層係透明。由於光觸 媒層係透明，可直接利用基材所具有的式樣設計。此處， 「透明j程度係在波長550nm中的光觸媒層的直線透過率 爲5 0 %以上，較佳爲7 0 %以上，更佳爲確保8 0 %以上。 依照本發明的較佳形態，樹脂乳液的乾燥物之含量， 相對於樹脂乳液、光觸媒性金屬氧化物粒子及矽石粒子的 固體成分之合計質量而言爲5〇%以上，較佳爲70%以上， 最佳爲85 %以上。藉由成爲如此的含量，容易確保光觸媒 層的透明性。 依照本發明的一個較佳形態，光觸媒層可更含有著色 顏料。由於光觸媒層被著色顏料所著色，而得到基材的隱 蔽性，而且可藉由光觸媒層對基材賦予式樣設計。 依照本發明的較佳形態’樹脂乳液係聚矽氧乳液及/ 或氟樹脂乳液。藉由此等乳液的利用，即使在室外的嚴苛 條件下使用時，也發揮優異的光觸媒分解機能，而且可長 期抑制基材的外觀變化。 -9 - 201231533 依照本發明的較佳形態，樹脂乳液的平均粒徑係比光 觸媒性金屬氧化物粒子及前述矽石粒子的平均粒徑還大。 藉此，光觸媒性金屬氧化物粒子係移動至光觸媒層表面方 向，光觸媒對基材的影響變小而較佳。 依照本發明的較佳形態，作爲光觸媒性金屬氧化物粒 子，可合適地利用銳鈦礦型氧化鈦、金紅石型氧化鈦、板 鈦礦型氧化鈦等之氧化鈦，如氧化錫、氧化鋅、鈦酸緦、 氧化鎢、氧化铈之金屬氧化物的粒子，複合有複數種的此 等粒子之粒子，於此等粒子中複合或摻雜有銅、鈾、鐵、 鈀、銀、金、氧化亞銅、氧化銅等的粒子，此等粒子的表 面經矽烷或聚矽氧或水解性金屬鹽所被覆或改性處理的粒 子等。 依照本發明的較佳形態，光觸媒性金屬氧化物粒子較 佳爲具有l〇nm以上且未達lOOnm的平均粒徑，更佳爲 10nm以上60ηιη以下。再者，此平均粒徑係藉由掃描型電 子顯微鏡測定20萬倍的視野內之任意1 〇〇個粒子的長度 所算出的個數平均値。 粒子的形狀最佳爲真球，但亦可爲略圓形或橢圓形， 該情況的粒子長度係作爲（（長徑+短徑）/2 )大略算出。若 爲此範圍內，則高效率地發揮耐候性、有害氣體分解性， 同時透明性、塗膜強度等變良好。201231533 VI. Description of the Invention: [Technical Fields of the Invention] The present invention relates to decomposing harmful gases, rainfall, water repellency, ease of washing, VOC (organic compounds), antibacterial properties, and anti-bacterial properties. Photocatalyst coating body for photocatalytic function such as mildew. In addition, in the present invention, a coating layer is formed on a member constituting an exterior or an interior, and the gas decomposability, self-cleaning property of rain/water washing, water-washing VOC decomposition property, antibacterial property, mold resistance, and disease resistance are formed. Photocatalyst coating liquid for light such as toxicity. [Prior Art] In recent years, photocatalysts such as titanium oxide have been used in buildings, vehicles, and components and composite materials constituting them, for use outdoors, and are provided on the surface of the substrate. The material utilizes light energy to decompose harmful substances such as NOx and SOx. Further, the surface of the layer which becomes hydrophilic at the time of light irradiation has a so-called self-cleaning function by dropping the adhered dirt. In addition, as a use in the interior of the substrate, the base material is imparted with light energy to decompose harmful substances such as VOC or impart antibacterial function, anti-mold function, and anti-viral function. When it is a building, a structure, a vehicle, a member, a composite material, etc., the surface of the substrate that is used for the living space is often self-cleaning. 1 (Volatile, anti-viral, and the function of the photocatalyst, which is easy to use, the function of the catalyst, the photocatalyst, and the function of the rain, which constitutes the above-mentioned light-5-201231533 Adding a coloring pigment to a photocatalyst layer, and having a design of the pattern at the same time (Patent Document 1; JP-A-2004-051644). On the other hand, in buildings, structures, vehicles, and structures of buildings Among the members and composite materials, such as resin sheets, wallpapers, coated sheets, film laminates, and cosmetic boards, which are substrates, are mostly base materials of surfaces containing organic substances, and in many cases, Designed with a design color. When forming a photocatalyst layer on these substrates, it is required to play the photocatalytic function, and the substrate is not easily degraded by the decomposition activity of ultraviolet light or photocatalyst. The pattern design of the substrate can be maintained for a long period of time. As one method for solving the above problems, there is a proposal to form an intermediate layer containing no photocatalyst between the substrate and the photocatalyst layer (Patent Document 2; Japanese Patent Publication No. 7-71408. However, in this method, the cost is increased due to an increase in the number of working hours. Therefore, it is required to simultaneously exhibit the decomposition activity of the photocatalytic function and the substrate due to ultraviolet rays or photocatalyst without forming an intermediate layer. A technique for suppressing the function of deterioration. As a photocatalyst coating composition which is directly applied to such a substrate to exhibit a photocatalytic function, for example, an alkoxy group containing a decane-modified photocatalyst particle and bonded to a ruthenium atom is known. A water system of a colloidal vermiculite having a base and/or a hydroxyl group content of 7 to 20 mmol/g, an alkoxy group bonded to a halogen atom, and/or a polymer emulsion particle having a hydroxyl group content of 1 to 20 mmol/g. Organic/inorganic composite composition (Patent Document 3; JP-A-2008-222887). [Prior Art Document] -6 - 201231533 [Patent Document] [Patent Document 1] JP-A-20〇4_05 1 644 [Problem to be Solved by the Invention] The present inventors have found that the inclusion by the present invention has been discovered by the inventors of the present invention. The photocatalyst layer formed by the coating of the vermiculite particles, the photocatalytic metal oxide particles and the coating liquid of the resin emulsion coated or modified by the perfluoro group is compared with the photocatalyst layer formed by directly using the untreated vermiculite particles. The present invention is based on this knowledge. Therefore, the object of the present invention is to provide a photocatalyst coating body which is excellent in photocatalytic performance and can suppress its appearance change for a long period of time, and a photocatalyst for forming the same. Coating solution. [Means for Solving the Problem] The photocatalyst coating system of the present invention includes a photocatalyst coating body having a photocatalyst layer on the surface of the substrate, and the photocatalyst layer is provided with photocatalytic metal oxide particles, dried particles of vermiculite particles and resin emulsion, The vermiculite particles are coated or modified with a substance having a perfluoro group. Further, the photocatalyst coating liquid of the present invention comprises photocatalytic metal oxide particles, vermiculite particles, a resin emulsion and a solvent, and the vermiculite particles are coated or modified with a substance having a perfluoro group. 201231533 The photocatalyst coating system of the present invention is excellent in photocatalytic performance. Furthermore, in accordance with a preferred embodiment of the present invention, the substrate can be inhibited from being eroded by the photocatalyst or degraded by the ultraviolet light. When the photocatalyst layer is transparent, the substrate can be used in a pattern design. When the photocatalyst layer contains a coloring pigment, the substrate is used. Excellent concealment, can be given to the design by photocatalyst layer. [Embodiment] The present invention provides a photocatalyst coating system comprising a photocatalyst coating body having a photocatalyst layer on a surface of a substrate, wherein the photocatalyst layer contains photocatalytic metal oxide particles and vermiculite The particles are formed by drying a resin emulsion, and the vermiculite particles are coated or modified with a substance having a perfluoro group. By using vermiculite particles coated or modified with a substance having a perfluoro group, the photocatalytic activity is unexpectedly significantly increased as compared with the case of directly adding vermiculite particles. Further, the change in the appearance of the coated body can be suppressed for a long period of time. Further, the photocatalyst layer as used in the present invention means a portion suitable for forming a coating liquid containing photocatalyst particles on the surface of the substrate. The photocatalyst particles may be in any form if they are present in the portion. That is, it may be completely film-formed or partially formed into a film shape. Further, it may be present in an island shape discretely on the surface of the substrate. According to a preferred embodiment of the present invention, the substance having a perfluoro group has a perfluoro group of decane and/or a polyfluorene group having a perfluoro group. These materials can be coated and modified by the surface of the vermiculite caused by these materials by the coupling treatment or the like, because of the coupling of the oxime bonds which are common to the vermiculite particles. According to a preferred embodiment of the present invention, the photocatalyst layer has a film thickness of more than 3 μm and less than 3 μπ. Since it exceeds 3 μm, the ultraviolet ray shielding property by the photocatalyst layer is high, and the influence of ultraviolet rays on the substrate can be reduced. As a result, deterioration of the substrate by ultraviolet rays can be effectively suppressed. Further, when the coloring pigment is contained in the photocatalyst layer, the concealing property of the substrate is sufficiently obtained, and the substrate can be given a pattern design by the photocatalyst layer. Further, since it is less than 3 mm, the basic properties of the coating film can be maintained, and a coating film can be formed with an appropriate aging time. According to a preferred embodiment of the invention, the photocatalyst layer is transparent. Since the photocatalyst layer is transparent, the design of the substrate can be directly utilized. Here, "the degree of transparency j is such that the linear transmittance of the photocatalyst layer at a wavelength of 550 nm is 50% or more, preferably 70% or more, more preferably 80% or more. According to a preferred embodiment of the present invention, The content of the dried product of the resin emulsion is 5% or more, preferably 70% or more, and most preferably 85% or more based on the total mass of the resin emulsion, the photocatalytic metal oxide particles, and the solid content of the vermiculite particles. By making such a content, it is easy to ensure the transparency of the photocatalyst layer. According to a preferred embodiment of the present invention, the photocatalyst layer may further contain a coloring pigment. Since the photocatalyst layer is colored by the coloring pigment, the substrate is concealed. Further, the substrate can be given a pattern design by a photocatalyst layer. According to a preferred embodiment of the present invention, a resin emulsion is a polyoxyxide emulsion and/or a fluororesin emulsion, whereby the use of such an emulsion allows harsh conditions even outdoors. When used underneath, it also exhibits excellent photocatalytic decomposition function, and can suppress the change in appearance of the substrate for a long period of time. -9 - 201231533 According to a preferred embodiment of the present invention, the average particle size of the resin emulsion The diameter is larger than the average particle diameter of the photocatalytic metal oxide particles and the vermiculite particles. Thereby, the photocatalytic metal oxide particles move to the surface direction of the photocatalyst layer, and the influence of the photocatalyst on the substrate is small, which is preferable. According to a preferred embodiment of the present invention, as the photocatalytic metal oxide particles, titanium oxide such as anatase type titanium oxide, rutile type titanium oxide or brookite type titanium oxide such as tin oxide or zinc oxide can be suitably used. a particle of a metal oxide of barium titanate, tungsten oxide or cerium oxide, which is compounded with a plurality of particles of such particles, wherein the particles are compounded or doped with copper, uranium, iron, palladium, silver, gold, Particles such as cuprous oxide or copper oxide, particles whose surface is coated or modified with decane or polyoxo or a hydrolyzable metal salt, etc. According to a preferred embodiment of the present invention, photocatalytic metal oxide particles It is preferably an average particle diameter of 10 nm or more and less than 100 nm, more preferably 10 nm or more and 60 ηηη or less. Further, the average particle diameter is measured by a scanning electron microscope in a field of view of 200,000 times. The number of particles calculated by the length of any one of the particles is 値. The shape of the particle is preferably a true sphere, but it may be a slightly circular or elliptical shape. In this case, the particle length is used as ((long diameter + short) In the range of this, the weather resistance and the decomposability of harmful gases are exhibited efficiently, and the transparency and the coating film strength are improved.
又，依照本發明的較佳形態，光觸媒性金屬氧化物粒 子較佳爲具有3 nm以上且未達3 Onm的平均雛晶直徑，更 佳爲5nm以上20nm以下。再者，此平均粒徑係由粉末X -10- 201231533 射線繞射法所得之X射線輪廓的3強線之積分寬度，藉由 謝樂（Scherrer)式算出。 依照本發明的較佳形態，光觸媒性金屬氧化物粒子的 含量，以乾燥質量（固體成分質量）計，相對於前述樹脂 乳液、前述光觸媒性金屬氧化物粒子及前述矽石粒子的合 計質量而言，係超過〇. 1質量％且未達1 5質量％，更佳爲 超過0.5質量％且未達5質量％。 依照本發明的較佳形態，矽石粒子較佳爲具有超過 5nm且100nm以下之平均粒徑，更佳爲超過10nm且50nm 以下之平均粒徑。再者，此平均粒徑係藉由掃描型電子顯 微鏡測定20萬倍的視野內之任意100個粒子的長度所算 出的個數平均値。粒子的形狀最佳爲真球，但亦可爲略圓 形或橢圓形，該情況的粒子長度係作爲（（長徑+短徑）/2 ) 大略算出。藉由使用如此的矽石粒子，由於一邊提高塗膜 強度，一邊提高光觸媒分解活性而有利。 作爲將矽石粒子被覆或改性處理之具有全氟基的物質 ，例如可合適地利用具有鍵結至矽石粒子用的官能基及全 氟基之物質。具體地，可合適地利用具有全氟基的水解性 矽烷、具有全氟基的水解性聚矽氧、具有全氟基的含乙烯 基之氟樹脂、具有全氟基的含乙烯基之烴樹脂 '具有全氟 基的含（甲基）丙烯酸官能基之氟樹脂、具有全氟基的含 丙烯酸官能基之烴樹脂、具有全氟基的含環氧官能基之氟 樹脂、具有全氟基的含環氧官能基之烴樹脂、具有全氟基 的含矽烷基之氟樹脂、具有全氟基的含矽烷基之烴樹脂、 -11 - 201231533 彼等物質經改性基取代之物質、彼等物質的嵌段共聚物等 。用於被覆或改性處理的物質之量，相對於矽石量而言， 較佳爲0.1〜20質量％，更佳爲1〜10質量％。 作爲具有全氟基的水解性矽烷，例如可舉出3,3,3 -三 氟丙基三甲氧基矽烷、3，3,3-三氟丙基三乙氧基矽烷等的 .單烷氧基矽烷類等。又，此等係可單獨使用。還有，可爲 2種以上或混合其它水解性矽烷使用。 作爲本發明中所用之具有全氟基的水解性聚矽氧，可 合適地利用含有上述矽烷單體單位之水解.縮合部位的聚 砂氧。 作爲本發明中所用的樹脂乳液，例如可利用氟樹脂、 聚矽氧、丙烯酸酯聚矽氧、醋酸乙烯酯、醋酸乙烯酯丙烯 酸酯、丙烯酸酯胺基甲酸酯、丙烯酸酯、環氧樹脂、氯乙 烯醋酸乙烯酯、偏二氯乙烯、SBR乳膠等的乳液。 作爲氟樹脂乳液’例如可合適地利用聚四氟乙烯、聚 偏二氟乙稀、聚氟乙烯、聚氯三氟乙烯、四氟乙烯-六氟 丙烯共聚物、乙烯-四氟乙烯共聚物、乙烯_氯三氟乙烯共 聚物、四氟乙嫌-全氟烷基乙烯醚共聚物、全氟環聚合物 、乙烯醚-氟烯烴共聚物、乙烯酯-氟烯烴共聚物、四氟乙 烯-乙烯醚共聚物、氯三氟乙烯_乙烯醚共聚物、四氟乙烯 胺基甲酸酯交聯體、四氟乙烯環氧交聯體、四氟乙烯丙烯 酸父聯體、四氟乙烯三聚氰胺交聯體等之含氟基的聚合物 之乳液。 又’作爲聚砂氧的乳液，可合適地利用甲基三甲氧基 -12- 201231533 矽烷、甲基三乙氧基矽烷、甲基三氯矽烷、甲基三溴矽烷 、甲基三異丙氧基矽烷、甲基三第三丁氧基矽烷、乙基三 甲氧基矽烷、乙基三乙氧基矽烷、乙基三氯矽烷、乙基三 溴矽烷、乙基三異丙氧基矽烷、乙基三第三丁氧基矽烷、 正丙基三甲氧基矽烷、正丙基三乙氧基矽烷、正丙基三氯 矽烷、正丙基三溴矽烷、正丙基三異丙氧基矽烷、正丙基 三第三丁氧基矽烷、正己基三甲氧基矽烷、正己基三乙氧 基矽烷、正己基三氯矽烷、正己基三溴矽烷、正己基三異 丙氧基矽烷、正己基三第三丁氧基矽烷、正癸基三甲氧基 矽烷、正癸基三乙氧基矽烷、正癸基三氯矽烷、正癸基三 溴矽烷、正癸基三.異丙氧基矽烷、正癸基三第三丁氧基矽 烷、正辛基三甲氧基矽烷、正辛基三乙氧基矽烷、正辛基 三氯矽烷、正辛基三溴矽烷、正辛基三異丙氧基矽烷、正 辛基三第三丁氧基矽烷、苯基三甲氧基矽烷、苯基三乙氧 基矽烷、苯基三氯矽烷、苯基三溴矽烷'苯基三異丙氧基 矽烷、苯基三第三丁氧基矽烷、二甲基二氯矽烷、二甲基 二溴矽烷、二甲基二甲氧基矽烷、二甲基二乙氧基矽烷、 二苯基二氯矽烷、二苯基二溴矽烷' 二苯基二甲氧基矽烷 、二苯基二乙氧基矽烷、苯基甲基二氯矽烷、苯基甲基二 溴矽烷、苯基甲基二甲氧基矽烷、苯基甲基二乙氧基矽烷 、乙烯基三氯矽烷、乙烯基三溴矽烷、乙烯基三甲氧基矽 烷、乙烯基三乙氧基矽烷、乙烯基三異丙氧基矽烷、乙烯 基三第三丁氧基矽烷、三氟丙基三氯矽烷、三氟丙基三二 溴矽烷、三氟丙基三甲氧基矽烷、三氟丙基三乙氧基矽烷 -13- 201231533 、乙烯基三氯矽烷、三氟丙基三異丙氧基矽烷、三 三第三丁氧基矽烷、γ-環氧丙氧基丙基甲基二甲氧 、γ-環氧丙氧基丙基甲基二乙氧基矽烷、γ-環氧丙 基三甲氧基矽烷、γ-環氧丙氧基丙基三乙氧基矽院 氧丙氧基丙基三異丙氧基砂院、γ-環氧丙氧基丙基 丁氧基矽烷、γ-甲基丙烯醯氧基丙基甲基二甲氧基 γ-甲基丙烯醯氧基丙基甲基二乙氧基矽烷、γ-甲基 氧基丙基三甲氧基矽烷、γ-甲基丙烯醯氧基丙基三 矽烷、γ-甲基丙烯醯氧基丙基三異丙氧基矽烷、γ-烯醯氧基丙基三第三丁氧基矽烷、γ-胺基丙基甲基 基矽烷、胺基丙基甲基二乙氧基矽烷、γ-胺基丙 氧基矽烷、γ-胺基丙基三乙氧基矽烷、γ-胺基丙基 氧基矽烷、胺基甲基丙烯醯氧基丙基三第三丁氧 、γ-甲基巯基丙基甲基二甲氧基矽烷、γ_甲基锍基 基二乙氧基矽烷、γ-甲基毓基丙基三甲氧基矽烷、 锍基丙基三乙氧基矽烷、γ-甲基巯基丙基三異丙氧 、γ-甲基锍基丙基三第三丁氧基矽烷、β· ( 3,4-環 己基）乙基三甲氧基矽烷、β- (3，4-環氧基環己基 三乙氧基砂院之水解、脫水縮聚合物等的乳液。 作爲本發明的塗裝體可含有的著色顏料，無機 易長期抑制外觀變化而較佳。作爲無機顏料，可舉 鈦、辞白、氧化鐵紅、氧化鉻、鈷藍、鐵黑等的金 物系、氧化鋁白、黃色氧化鐵等的金屬氫氧化物系 士藍等的酞花青化合物系、鉻黃、鉻酸鋅、鉬紅等 氟丙基 基矽烷 氧基丙 、γ-環 三第三 矽烷、 丙烯醯 乙氧基 甲基丙 二甲氧 基三甲 三異丙 基政焼 丙基甲 γ-甲基 基矽烷 氧基環 )乙基 顏料容 出氧化 屬氧化 、普魯 的鉻酸 -14- 201231533 鉛系、硫化鋅、朱砂、鎘黃、鎘紅等的硫化物、硒化合物 、重晶石、沈降性硫酸鋇等的硫酸鹽系、重質碳酸鈣、沈 降性碳酸鈣等的碳酸鹽系、含水矽酸鹽、黏土、群青等的 矽酸鹽系、碳黑等的碳系、鋁粉、青銅粉、鋅粉等的金屬 粉系、雲母•氧化鈦系等的珠光顏料系等。 於本發明的塗裝體之情況，在光觸媒層中亦可含有矽 石粒子以外的無機氧化物粒子。無機氧化物粒子只要是能 與光觸媒粒子一起形成層之無機氧化物的粒子，則沒有特 別的限定，可使用各種的無機氧化物之粒子。作爲如此的 無機氧化物粒子之例，可舉出氧化鋁、氧化锆、二氧化铈 、三氧化二釔、氧化錫、氧化鐵、氧化錳、氧化鎳、氧化 鈷、氧化給等的單一氧化物之粒子；及鈦酸鋇、矽酸鈣、 硼酸鋁、鈦酸鉀等的複合氧化物之粒子。 依照本發明的較佳態樣，爲了展現更高的光觸媒能力 ，塗裝體亦可含有由釩、鐵 '鈷、鎳、鈀、鋅、釕、铑、 銅、銀、舶及金所成之群組中選出的至少一種金屬及/或 由該金屬所成的金屬化合物。此等化合物亦可混合在後述 的塗佈液中而存在於光觸媒層，而且藉由使光觸媒粒子擔 持此等化合物，可使存在於光觸媒層中。 本發明的塗裝體之光觸媒層亦可搭配有機防霉劑，作 爲其具體例，可舉出有機氮硫系化合物、吡啶硫酮系化合 物、有機碘系化合物、三哄系化合物、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、有機碘化合物、二硫化物系 -15- 201231533 化合物，可單獨或作爲混合物使用。防霉劑由於一般多兼 具防藻效果，故藉由添加防霉劑，亦可期待抑制霉與藻這 兩者。 本發明的塗裝體之光觸媒層亦可含有紫外線吸收劑。 紫外線吸收劑的含量，只要是不阻礙光觸媒活性及/或親 水性的展現，而爲能提高耐候性的量，則沒有限定，例如 於光觸媒體中爲0.001〜10質量％，較佳爲0.01〜5質量％ 〇 作爲本發明中可利用的紫外線吸收劑，可例示二苯基 酮系、苯并三哩系、三哄系紫外線吸收劑當作較佳者。 特別地’三哄系紫外線吸收劑由於化學安定而較佳。 作爲三畊系紫外線吸收劑，具體地可合適地利用羥基苯基 三哄或其衍生物。 作爲上述二苯基酮系的紫外線吸收劑，具體地可舉出 2,4-二羥基二苯基酮、2-羥基-4-甲氧基二苯基酮、2-羥基-4 -甲氧基二苯基酮-5-磺酸、2-羥基-4-正辛氧基二苯基酮 、2-羥基_4·正十二氧基二苯基酮、2_羥基_4_苄氧基二苯 基酮、雙（5-苯甲醯基-4_羥基·2_甲氧基苯基）甲烷、 2,2’-二羥基-4-甲氧基二苯基酮、2,2，_二羥基_4,4，_二甲氧 基二苯基酮、2,2’，4,4’-四羥基二苯基酮、4_十二氧基-2· 羥基二苯基酮、2 -羥基-4-甲氧基_2，_羧基二苯基酮、2 -羥 基-4-十八氧基二苯基酮、辛苯酮、及2_羥基_4_丙烯醯氧 基二苯基酮、2-羥基_4_甲基丙烯醯氧基二苯基酮、2-羥 基-5-丙烯醯氧基二苯基酮、2-羥基-5-甲基丙烯醯氧基二 -16- 201231533 苯基酮、2-羥基-4-(丙烯醯氧基_乙氧基）二苯基酮、2_ 羥基-4-(甲基丙烯醯氧基-乙氧基）二苯基酮、2羥基_4_ (甲基丙烯醯氧基-一乙氧基）二苯基酮、2-經基-4-(丙 烯醯氧基-三乙氧基）二苯基酮等的聚合性之二苯基酮系 紫外線吸收劑或彼等的（共）聚合物等。 又’作爲上述苯并三唑系的紫外線吸收劑，具體地可 舉出2- (2’-羥基-5’-甲基苯基）苯并三唑、2_ (2, _羥基_ 5第三丁基苯基）苯并三唑、2- (2，-羥基-3，，5，-二第三 丁基苯基）苯并三唑、2- (2-羥基_5_第三辛基苯基）苯并 三唑、2- (2-羥基_3,5-二第三辛基苯基）苯并三唑' 2-[2’-羥基-3’，5’-雙（α，α’-二甲基苄基）苯基]苯并三唑）、 甲基- 3-[3-第三丁基-5-(2Η-苯并三唑-2-基）-4-羥基苯基] 丙酸酯與聚乙二醇（分子量 300)之縮合物（日本Ciba-Geigy(股）製，製品名：TINUVIN-1 130 )、異辛基-3-[3-( 2H-苯并三唑-2-基）-:5-第三丁基-4-羥基苯基]丙酸酯（曰 本 Ciba-Geigy(股）製，製品名：TINUVIN-3 84 ) 、2- ( 3- 十二基-5-甲基-2-羥基苯基）苯并三唑（日本Ciba-Geigy( 股）製，製品名：TINUVIN-571 ) 、2- ( 2’-羥基- 3’-第三丁 基- 5’-甲基苯基）-5-氯苯并三唑、2- (2’-羥基-3’，5’-二第 三戊基苯基）苯并三唑、2-(2’-羥基-4’-辛氧基苯基）苯 并三唑、2 - [ 2 ’ -羥基-3 ’ - ( 3 ”，4 ”，5 ”，6 ” -四氫苯二甲醯亞胺 甲基）-5’-甲基苯基]苯并三唑、2，2 -亞甲基雙[4-( 1，1，3,3-四甲基丁基）-6-(211-苯并三唑-2-基）苯酚]、2-(2H-苯并三唑-2-基）-4,6-雙（1-甲基-1-苯基乙基）苯酚 201231533 (日本 Ciba-Geigy(股）製，製品名：TINUVIN-900 )、及 2- ( 2’-羥基- 5’-甲基丙烯醯氧基乙基苯基）-2H-苯并三唑 (大塚化學（股）製，製品名：RUVA-93 ) 、2· ( 2’-羥基- 5’-甲基丙烯醯氧基乙基-3-第三丁基苯基）-2H-苯并三唑 、2- (2’-羥基- 5’-甲基丙烯醯氧基丙基-3-第三丁基苯基 )-5-氯·2Η-苯并三唑、3-甲基丙烯醯基-2-羥基丙基-3-[3，-(2”-苯并三唑基）-4-羥基、5-第三丁基]苯基丙酸酯（曰 本Ciba-Geigy(股）製，製品名：CGL-104)等的聚合性之 苯并三唑系紫外線吸收劑或彼等的（共）聚合物，以及 TINUVIN-384-2 (製品名，日本 Ciba-Geigy(股）製）， TINUVIN-99-2 (製品名，日本 Ciba-Geigy(股）製）、 TINUVIN-109 (製品名，曰本 Ciba-Geigy(股）製）、 TINUVIN-3 2 8 (製品名，日本 Ciba-Geigy(股）製）、 TINUVIN-92 8 (製品名，日本 Ciba-Geigy(股）製）等。 又，依照本發明的較佳態樣，光觸媒層亦可更含有受 阻胺系及/或受阻酚系等的光安定劑。藉由與上述紫外線 吸收劑的相乘效果，由於本發明的光觸媒層顯示卓越的耐 候性、耐光性而較佳。 特別地，依照本發明的較佳形態，可摻合作爲紫外線 吸收劑的羥基苯基三哄化合物與作爲光安定劑的受阻胺化 合物。藉由此組合，光觸媒層的未達380nm之短波長的紫 外線吸收性能係安定。 於本發明中，光觸媒層中的光安定劑之含量，只要是 不阻礙光觸媒活性及/或親水性的展現，而爲能提高耐候 -18- 201231533 性的量，則沒有限定，例如於光觸媒體中含有0.001〜10 質量％，較佳爲0.01〜5質量％。 作爲受阻胺系光安定劑的具體例，可舉出雙（ 2.2.6.6- 四甲基-4-哌啶基）琥珀酸酯、雙（2,2,6,6-四甲基 哌啶基）癸二酸酯、雙（1，2,2,6,6-五甲基-4-哌啶基）2- (3,5-二第三丁基-4-羥基苄基）-2-丁基丙二酸酯、1-[2-[3- ( 3,5-二第三丁基-4-羥基苯基）丙炔氧基]乙基]-4-[3-(3,5-二第三丁基-4-羥基苯基）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-1，2,2,6,6-五甲基-4-哌啶基-癸二酸酯之混合物（日本 Ciba-Geigy(股）製，製品名：TINUVIN-292 )、雙（卜辛氧 基-2,2,6,6-四甲基-4-哌啶基）癸二酸酯、TINUVIN-123 ( 製品名，日本 Ciba-Geigy(股）製）、TINUVIN-1 1 1FDL ( 製品名，曰本Ciba-Geigy(股）製）、TINUVIN292 (製品名 ’曰本Ciba-Geigy(股）製）、及1，2,2,6,6-五甲基-4-哌啶 基甲基丙烯酸酯、1，2,2,6,6-五甲基-4·哌啶基丙烯酸酯、 2.2.6.6- 四甲基-4-哌啶基甲基丙烯酸酯、2,2,6,6-四·甲基-4-哌啶基丙烯酸酯、1，2,2,6,6-五甲基-4-亞胺基哌啶基甲 基丙烯酸酯、2,2,6,6，-四甲基-4-亞胺基哌啶基甲基丙烯酸 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的聚合性之 受阻胺系紫外線吸收劑或彼等的（共）聚合物。 又，作爲受阻酚系光安定劑的具體例，可舉出雙（ 3,5-第三丁基）：4-羥基甲苯、TINUV IN-144(製品名、日 -19- 201231533 本 Ciba-Geigy(股）製）等。 光觸媒塗佈液 依照本發明的另一態樣，提供光觸媒塗佈液，其適合 於上述的本發明的塗裝體之形成，此塗佈液係含有光觸媒 性金屬氧化物粒子、矽石粒子、樹脂乳液與溶劑所成，前 述矽石粒子係被具有全氟基的物質所被覆或改性處理而成 〇 本發明的塗佈液所含有的光觸媒性金屬氧化物粒子、 矽石粒子與樹脂乳液，除了在構成液體組成物的狀態以外 ，係與上述構成塗裝體的成分實質上相同。又，.作爲彼等 成分以較佳態樣所列舉者，亦可在本發明的塗佈液中同樣 地作爲較佳者添加。 又，塗佈液的組成，只要在乾燥後實現上述組成者即 可。因此，以下的說明係一部分已經說明，但以下爲了其 明確性，不管重複而進行說明。 依照本發明的較佳形態，樹脂乳液的固體成分之含量 ，係相對於樹脂乳液、光觸媒性金屬氧化物粒子及矽石粒 子的固體成分之合計質量而言爲50%以上，較佳爲70%以 上，最佳爲8 5 %以上。 另外，爲了實現含有著色顏料的塗裝體，依照本發明 的較佳形態，本發明的塗佈液可更含有著色顏料。 還有，依照本發明的較佳形態，樹脂乳液係聚矽氧乳 液及/或氟樹脂乳液。 -20- 201231533 依照本發明的較佳形態，於塗佈液中，樹脂乳液的平 均粒徑係比光觸媒性金屬氧化物粒子及前述矽石粒子的平 均粒徑還大。藉此，光觸媒性金屬氧化物粒子係移動至光 觸媒層表面方向，光觸媒對基材的影響變小。 依照本發明的較佳形態，作爲光觸媒性金屬氧化物粒 子’可合適地利用銳鈦礦型氧化鈦、金紅石型氧化鈦、板 鈦礦型氧化鈦等之氧化鈦，如氧化錫、氧化鋅、鈦酸緦、 氧化鎢、氧化鈽之金屬氧化物的粒子，複合有複數種的此 等粒子之粒子，於此等粒子中複合或摻雜有銅、鈾、鐵、 鈀、銀、金、氧化亞銅、氧化銅等的粒子，此等粒子的表 面經矽烷或聚矽氧或水解性金屬鹽所被覆或改性處理的粒 子等。 依照本發明的較佳形態，光觸媒性金屬氧化物粒子較 佳爲具有l〇nm以上且未達l〇〇nm的平均粒徑，更佳爲 l〇nm以上60nm以下。再者，此平均粒徑係藉由掃描型電 子顯微鏡測定20萬倍的視野內之任意1 00個粒子的長度 所算出的個數平均値。 粒子的形狀最佳爲真球，但亦可爲略圓形或橢圓形， 該情況的粒子長度係作爲（（長徑+短徑）/2 )大略算出。若 爲此範圍內，則高效率地發揮耐候性、有害氣體分解性， 同時透明性、塗膜強度等變良好。Further, according to a preferred embodiment of the present invention, the photocatalytic metal oxide particles preferably have an average crystallite diameter of 3 nm or more and less than 3 Onm, more preferably 5 nm or more and 20 nm or less. Further, the average particle diameter is the integral width of the three strong lines of the X-ray profile obtained by the powder X -10- 201231533 ray diffraction method, and is calculated by the Scherrer equation. According to a preferred embodiment of the present invention, the content of the photocatalytic metal oxide particles is based on the total mass of the resin emulsion, the photocatalytic metal oxide particles, and the vermiculite particles in terms of dry mass (solid content). The amount is more than 0.1% by mass and less than 15% by mass, more preferably more than 0.5% by mass and less than 5% by mass. According to a preferred embodiment of the present invention, the vermiculite particles preferably have an average particle diameter of more than 5 nm and 100 nm or less, more preferably an average particle diameter of more than 10 nm and 50 nm or less. Further, the average particle diameter is a number average 値 calculated by measuring the length of any 100 particles in a field of view of 200,000 times by a scanning electron microscope. The shape of the particles is preferably a true sphere, but may be a slightly round or elliptical shape, and the particle length in this case is roughly calculated as ((long diameter + short diameter)/2). By using such vermiculite particles, it is advantageous to increase the photocatalytic decomposition activity while increasing the coating film strength. As the substance having a perfluoro group in which the vermiculite particles are coated or modified, for example, a substance having a functional group bonded to the vermiculite particles and a perfluoro group can be suitably used. Specifically, a hydrolyzable decane having a perfluoro group, a hydrolyzable polyfluorene having a perfluoro group, a vinyl group-containing fluororesin having a perfluoro group, and a vinyl group-containing hydrocarbon resin having a perfluoro group can be suitably used. a fluororesin having a perfluoro group containing a (meth)acrylic functional group, a hydrocarbon resin having a perfluoro group containing an acrylic functional group, an epoxy functional group-containing fluororesin having a perfluoro group, and a perfluoro group An epoxy resin-containing hydrocarbon resin, a perfluoro group-containing fluorenyl group-containing fluororesin, a perfluoro group-containing fluorenyl group-containing hydrocarbon resin, -11 - 201231533, a substance substituted with a modified group, and the like A block copolymer of a substance or the like. The amount of the substance to be coated or modified is preferably from 0.1 to 20% by mass, more preferably from 1 to 10% by mass, based on the amount of the vermiculite. Examples of the hydrolyzable decane having a perfluoro group include a monoalkoxy group such as 3,3,3-trifluoropropyltrimethoxydecane or 3,3,3-trifluoropropyltriethoxydecane. Base decanes and the like. Also, these can be used alone. Further, it may be used in combination of two or more kinds or other hydrolyzable decane. As the hydrolyzable polyfluorene having a perfluoro group used in the present invention, polysilicoxy which contains a hydrolysis and condensation site of the above decane monomer unit can be suitably used. As the resin emulsion used in the present invention, for example, a fluororesin, polyfluorene oxide, acrylate polyoxymethylene, vinyl acetate, vinyl acetate acrylate, acrylate urethane, acrylate, epoxy resin, or the like can be used. An emulsion of vinyl chloride, vinylidene chloride, SBR latex, or the like. As the fluororesin emulsion, for example, polytetrafluoroethylene, polyvinylidene fluoride, polyvinyl fluoride, polychlorotrifluoroethylene, tetrafluoroethylene-hexafluoropropylene copolymer, ethylene-tetrafluoroethylene copolymer, or the like can be suitably used. Ethylene-chlorotrifluoroethylene copolymer, tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer, perfluorocyclopolymer, vinyl ether-fluoroolefin copolymer, vinyl ester-fluoroolefin copolymer, tetrafluoroethylene-ethylene Ether copolymer, chlorotrifluoroethylene-vinyl ether copolymer, tetrafluoroethylene urethane crosslinked body, tetrafluoroethylene epoxy crosslinked body, tetrafluoroethylene acrylate parent complex, tetrafluoroethylene melamine crosslinked body An emulsion of a fluorine-containing polymer. Further, as the emulsion of polysilicic acid, methyltrimethoxy-12-201231533 decane, methyltriethoxydecane, methyltrichlorodecane, methyltribromodecane, methyltriisopropoxide can be suitably used. Base decane, methyl tri-tert-butoxy decane, ethyl trimethoxy decane, ethyl triethoxy decane, ethyl trichloro decane, ethyl tribromodecane, ethyl triisopropoxy decane, B Base three third butoxy decane, n-propyl trimethoxy decane, n-propyl triethoxy decane, n-propyl trichloro decane, n-propyl tribromodecane, n-propyl triisopropoxy decane, N-propyltris-tert-butoxydecane, n-hexyltrimethoxydecane, n-hexyltriethoxydecane, n-hexyltrichlorodecane, n-hexyltribromonane, n-hexyltriisopropoxydecane, n-hexyl Third butoxy decane, n-decyltrimethoxydecane, n-decyltriethoxydecane, n-decyltrichlorodecane, n-decyltribromodecane, n-decyltriisopropoxypropane, positive Mercapto tri-tert-butoxydecane, n-octyltrimethoxydecane, n-octyltriethoxydecane, n-octyl Chlorodecane, n-octyltribromonane, n-octyltriisopropoxydecane, n-octyltris-tert-butoxydecane, phenyltrimethoxydecane,phenyltriethoxydecane,phenyltrichloro Decane, phenyltribromodecane 'phenyltriisopropoxydecane, phenyltris-tert-butoxydecane, dimethyldichlorodecane, dimethyldibromodecane, dimethyldimethoxydecane, Dimethyldiethoxydecane, diphenyldichlorodecane, diphenyldibromodecane 'diphenyldimethoxydecane, diphenyldiethoxydecane, phenylmethyldichlorodecane, benzene Methyl dibromodecane, phenylmethyldimethoxydecane, phenylmethyldiethoxydecane, vinyl trichlorodecane, vinyltribromonane, vinyltrimethoxydecane, vinyl triethyl Oxy decane, vinyl triisopropoxy decane, vinyl tri-tert-butoxy decane, trifluoropropyl trichloro decane, trifluoropropyl tridecabromo decane, trifluoropropyl trimethoxy decane, three Fluoropropyltriethoxydecane-13- 201231533, vinyl trichlorodecane, trifluoropropyl triisopropoxy decane, third three Oxydecane, γ-glycidoxypropylmethyldimethoxy, γ-glycidoxypropylmethyldiethoxydecane, γ-epoxypropyltrimethoxydecane, γ-ring Oxypropoxypropyl triethoxy oxime oxypropyloxypropyl triisopropoxy sand, γ-glycidoxypropyl butoxy decane, γ-methyl propylene methoxy propyl Methyldimethoxy γ-methyl propylene methoxy propyl methyl diethoxy decane, γ-methyloxypropyl trimethoxy decane, γ-methyl propylene methoxy propyl trioxane, γ-Methyl propylene methoxypropyl triisopropoxy decane, γ-olefinoxypropyl tri-tert-butoxy decane, γ-aminopropyl methyl decane, aminopropyl methyl Diethoxydecane, γ-aminopropoxydecane, γ-aminopropyltriethoxydecane, γ-aminopropyloxydecane, Aminomethylpropenyloxypropyl III Butoxy, γ-methylmercaptopropylmethyldimethoxydecane, γ-methylmercaptodiethoxydecane, γ-methylmercaptopropyltrimethoxydecane, mercaptopropyltriethyl Oxydecane, γ-methylmercaptopropyltriisopropyloxy, γ-methyl Hydrolysis and dehydration of propyl tridecyloxydecane, β·(3,4-cyclohexyl)ethyltrimethoxydecane, β-(3,4-epoxycyclohexyltriethoxylate) An emulsion of a polymer or the like. The coloring pigment which can be contained in the coated body of the present invention is preferable because it is easy to suppress the change in appearance for a long period of time. Examples of the inorganic pigment include ruthenium compounds such as titanium, rhodium, iron oxide red, chromium oxide, cobalt blue, and iron black, and metal hydroxide such as alumina white or yellow iron oxide. Fluoropropyl decyloxypropane, γ-cyclotridecane, propylene ethoxyethoxymethylpropadimethoxytrimethyltriisopropyl propyl propyl, chrome yellow, zinc chromate, molybdenum red, etc. A γ-methyl decyloxycyclo) ethyl pigment is oxidized, and ruthenium chromite is a sulphate, a sulphide, a sulphide, a cadmium, a cadmium, etc. a carbonate system such as barite or sedimentary barium sulfate, a carbonate system such as heavy calcium carbonate or sedimentary calcium carbonate, a carbonate system such as aqueous citrate, clay or ultramarine, or a carbon system such as carbon black. Metal powders such as aluminum powder, bronze powder, and zinc powder, and pearlescent pigments such as mica and titanium oxide. In the case of the coated body of the present invention, inorganic oxide particles other than the vermiculite particles may be contained in the photocatalyst layer. The inorganic oxide particles are not particularly limited as long as they are particles of an inorganic oxide capable of forming a layer together with the photocatalyst particles, and various inorganic oxide particles can be used. Examples of such inorganic oxide particles include single oxides of alumina, zirconia, ceria, antimony trioxide, tin oxide, iron oxide, manganese oxide, nickel oxide, cobalt oxide, and oxidation. Particles; and particles of composite oxides such as barium titanate, calcium citrate, aluminum borate, potassium titanate, and the like. According to a preferred embodiment of the present invention, in order to exhibit higher photocatalytic ability, the coated body may also contain vanadium, iron 'cobalt, nickel, palladium, zinc, ruthenium, osmium, copper, silver, and gold. At least one metal selected from the group and/or a metal compound formed from the metal. These compounds may be present in the photocatalyst layer by being mixed in a coating liquid to be described later, and may be present in the photocatalyst layer by allowing the photocatalyst particles to hold these compounds. The photocatalyst layer of the coated body of the present invention may be blended with an organic antifungal agent, and specific examples thereof include an organic nitrogen sulfur compound, a pyrithione compound, an organic iodine compound, a triterpenoid compound, and an isothiazoline. A compound, an imidazole compound, a pyridine compound, a nitrile compound, a thioformate compound, a thiazole compound, an organic iodine compound, and a disulfide system -15-201231533 compound can be used individually or as a mixture. Since the antifungal agent generally has an anti-algae effect, it is also expected to suppress both mold and algae by adding a mold inhibitor. The photocatalyst layer of the coated body of the present invention may also contain an ultraviolet absorber. The content of the ultraviolet absorber is not limited as long as it does not inhibit the activity of the photocatalyst and/or the hydrophilicity, and is not limited, and is, for example, 0.001 to 10% by mass, preferably 0.01%, in the photocontact medium. 5 mass% 〇 As the ultraviolet absorber which can be used in the present invention, a diphenylketone-based, a benzotriazine-based or a triterpenoid-based ultraviolet absorber can be exemplified as preferred. In particular, the triterpenoid ultraviolet absorber is preferred for chemical stability. As the three-till ultraviolet absorber, specifically, hydroxyphenyltriazine or a derivative thereof can be suitably used. Specific examples of the diphenyl ketone-based ultraviolet absorber include 2,4-dihydroxydiphenyl ketone, 2-hydroxy-4-methoxydiphenyl ketone, and 2-hydroxy-4-methoxy Diphenyl ketone-5-sulfonic acid, 2-hydroxy-4-n-octyloxy diphenyl ketone, 2-hydroxy-4·n-dodecyloxydiphenyl ketone, 2-hydroxy-4-yl benzyloxy Diphenyl ketone, bis(5-benzylidenyl-4-hydroxy-2-methoxyphenyl)methane, 2,2'-dihydroxy-4-methoxydiphenyl ketone, 2,2 ,_Dihydroxy-4,4,4-dimethoxydiphenyl ketone, 2,2',4,4'-tetrahydroxydiphenyl ketone, 4-dodecyloxy-2.hydroxydiphenyl ketone , 2-hydroxy-4-methoxy-2,-carboxydiphenyl ketone, 2-hydroxy-4-octadecyldiphenyl ketone, octyl benzophenone, and 2-hydroxy-4-indolyloxyl Diphenylketone, 2-hydroxy-4-methylpropenyloxydiphenyl ketone, 2-hydroxy-5-propenyloxydiphenyl ketone, 2-hydroxy-5-methylpropenyloxy 2 -16- 201231533 Phenyl ketone, 2-hydroxy-4-(acryloxy-ethoxy)diphenyl ketone, 2-hydroxy-4-(methacryloxy-ethoxy)diphenyl ketone , 2-hydroxy_4_(methacryloxy-ethoxy-diphenyl) diphenyl A polymerizable diphenylketone-based ultraviolet absorber such as a ketone or 2-carbyl-4-(propenyloxy-triethoxy)diphenyl ketone or a (co)polymer or the like. Further, as the ultraviolet absorbing agent of the above benzotriazole type, specifically, 2-(2'-hydroxy-5'-methylphenyl)benzotriazole, 2_(2, _hydroxy_ 5 third Butylphenyl)benzotriazole, 2-(2,-hydroxy-3,5,2-di-tert-butylphenyl)benzotriazole, 2-(2-hydroxy-5_t-octyl) Phenyl)benzotriazole, 2-(2-hydroxy-3,5-di-t-th-octylphenyl)benzotriazole '2-[2'-hydroxy-3',5'-bis(α, α'-Dimethylbenzyl)phenyl]benzotriazole), methyl-3-[3-tert-butyl-5-(2Η-benzotriazol-2-yl)-4-hydroxybenzene a condensate of propionate and polyethylene glycol (molecular weight 300) (manufactured by Ciba-Geigy Co., Ltd., product name: TINUVIN-1 130), isooctyl-3-[3-( 2H-benzo) Triazol-2-yl)-:5-t-butyl-4-hydroxyphenyl]propionate (manufactured by Ciba-Geigy Co., Ltd., product name: TINUVIN-3 84 ), 2- ( 3- Dodecyl-5-methyl-2-hydroxyphenyl)benzotriazole (manufactured by Ciba-Geigy Co., Ltd., product name: TINUVIN-571), 2-(2'-hydroxy-3'-third Butyl-5'-methylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3',5'- Di-t-pentylphenyl)benzotriazole, 2-(2'-hydroxy-4'-octyloxyphenyl)benzotriazole, 2 - [ 2 '-hydroxy-3 ' - ( 3 ”, 4",5",6"-tetrahydrobenzidine iminemethyl)-5'-methylphenyl]benzotriazole, 2,2-methylenebis[4-( 1,1, 3,3-tetramethylbutyl)-6-(211-benzotriazol-2-yl)phenol], 2-(2H-benzotriazol-2-yl)-4,6-bis (1 -Methyl-1-phenylethyl)phenol 201231533 (manufactured by Ciba-Geigy Co., Ltd., product name: TINUVIN-900), and 2-( 2'-hydroxy-5'-methacryloxyloxy B Phenyl)-2H-benzotriazole (manufactured by Otsuka Chemical Co., Ltd., product name: RUVA-93), 2·( 2'-hydroxy-5'-methylpropenyloxyethyl-3- Tributylphenyl)-2H-benzotriazole, 2-(2'-hydroxy-5'-methacryloxypropyl-3-tert-butylphenyl)-5-chloro.2Η- Benzotriazole, 3-methylpropenyl-2-hydroxypropyl-3-[3,-(2"-benzotriazolyl)-4-hydroxy, 5-t-butyl]phenylpropene A polymerizable benzotriazole-based ultraviolet absorber such as an acid ester (manufactured by Ciba-Geigy Co., Ltd., product name: CGL-104) Their (co)polymers, as well as TINUVIN-384-2 (product name, manufactured by Ciba-Geigy Co., Ltd., Japan), TINUVIN-99-2 (product name, manufactured by Ciba-Geigy Co., Ltd., Japan), TINUVIN- 109 (product name, Sakamoto Ciba-Geigy Co., Ltd.), TINUVIN-3 2 8 (product name, Japan Ciba-Geigy Co., Ltd.), TINUVIN-92 8 (product name, Japan Ciba-Geigy Co., Ltd.) System) and so on. Further, according to a preferred embodiment of the present invention, the photocatalyst layer may further contain a light stabilizer such as a hindered amine system and/or a hindered phenol system. The photocatalyst layer of the present invention is preferably excellent in weather resistance and light resistance by the synergistic effect with the above ultraviolet absorber. Particularly, according to a preferred embodiment of the present invention, a hydroxyphenyl triguanidine compound which is a combination of an ultraviolet absorber and a hindered amine compound which is a photostabilizer can be blended. By this combination, the ultraviolet absorption performance of the short-wavelength of the photocatalyst layer which is less than 380 nm is stable. In the present invention, the content of the photosensitizer in the photocatalyst layer is not limited as long as it does not inhibit the activity of the photocatalyst and/or the hydrophilicity, and is not limited, for example, in the photo-touch medium. It is contained in an amount of 0.001 to 10% by mass, preferably 0.01 to 5% by mass. Specific examples of the hindered amine light stabilizer include bis(2.2.6.6-tetramethyl-4-piperidyl)succinate and bis(2,2,6,6-tetramethylpiperidinyl). Sebacate, bis(1,2,2,6,6-pentamethyl-4-piperidinyl)2-(3,5-di-t-butyl-4-hydroxybenzyl)-2- Butyl malonate, 1-[2-[3-( 3,5-di-t-butyl-4-hydroxyphenyl)propynyloxy]ethyl]-4-[3-(3,5 -di-t-butyl-4-hydroxyphenyl)propynyloxy]-2,2,6,6-tetramethylpiperidine, bis(1,2,2,6,6-pentamethyl-4 -piperidinyl) sebacate and a mixture of methyl-1,2,2,6,6-pentamethyl-4-piperidinyl-sebacate (made by Ciba-Geigy Co., Ltd., Japan) Name: TINUVIN-292 ), bis(octyloxy-2,2,6,6-tetramethyl-4-piperidinyl) sebacate, TINUVIN-123 (product name, Japan Ciba-Geigy) )), TINUVIN-1 1 1FDL (product name, 曰本 Ciba-Geigy (share) system), TINUVIN292 (product name '曰本 Ciba-Geigy (share) system), and 1,2,2,6,6 -pentamethyl-4-piperidyl methacrylate, 1,2,2,6,6-pentamethyl-4·piperidinyl acrylate, 2.2.6.6-tetramethyl-4-piperidinyl Methyl propyl Acid ester, 2,2,6,6-tetramethyl-4-piperidyl acrylate, 1,2,2,6,6-pentamethyl-4-iminopiperidinyl methacrylate , 2,2,6,6,-tetramethyl-4-iminopiperidinyl methacrylate, 4-cyano-2,2,6,6-tetramethyl-4-piperidinyl Polymeric hindered amine-based ultraviolet absorbers such as acrylate, 4-cyano-1,2,2,6,6-pentamethyl-4-piperidyl methacrylate or the like (total) polymer. Further, specific examples of the hindered phenol-based photostabilizer include bis(3,5-t-butyl): 4-hydroxytoluene, TINUV IN-144 (product name, date -19-201231533, Ciba-Geigy) (share) system, etc. The photocatalyst coating liquid according to another aspect of the present invention provides a photocatalyst coating liquid which is suitable for the formation of the above-described coated body of the present invention, the coating liquid containing photocatalytic metal oxide particles, vermiculite particles, The resin emulsion is formed by a solvent, and the vermiculite particles are coated or modified with a perfluoro group-containing material to form photocatalytic metal oxide particles, vermiculite particles, and resin emulsion contained in the coating liquid of the present invention. It is substantially the same as the component constituting the coated body except for the state in which the liquid composition is formed. Further, as a preferred embodiment of the components, the coating liquid of the present invention may be similarly added as a preferred one. Further, the composition of the coating liquid may be such that the above composition is achieved after drying. Therefore, the following description has been partially described, but the following description will be repeated for the sake of clarity. According to a preferred embodiment of the present invention, the content of the solid content of the resin emulsion is 50% or more, preferably 70%, based on the total mass of the resin emulsion, the photocatalytic metal oxide particles, and the solid content of the vermiculite particles. Above, the best is 85% or more. Further, in order to realize a coated body containing a colored pigment, according to a preferred embodiment of the present invention, the coating liquid of the present invention may further contain a coloring pigment. Further, in accordance with a preferred embodiment of the present invention, the resin emulsion is a polyoxyxide emulsion and/or a fluororesin emulsion. -20- 201231533 According to a preferred embodiment of the present invention, in the coating liquid, the average particle diameter of the resin emulsion is larger than the average particle diameter of the photocatalytic metal oxide particles and the vermiculite particles. Thereby, the photocatalytic metal oxide particles move to the surface direction of the photocatalyst layer, and the influence of the photocatalyst on the substrate becomes small. According to a preferred embodiment of the present invention, titanium oxide such as anatase-type titanium oxide, rutile-type titanium oxide or brookite-type titanium oxide, such as tin oxide or zinc oxide, can be suitably used as the photocatalytic metal oxide particles. a particle of a metal oxide of barium titanate, tungsten oxide or cerium oxide, which is compounded with a plurality of particles of such particles, wherein the particles are compounded or doped with copper, uranium, iron, palladium, silver, gold, Particles such as cuprous oxide or copper oxide, and particles whose surface is coated or modified with decane or polyoxo or a hydrolyzable metal salt. According to a preferred embodiment of the present invention, the photocatalytic metal oxide particles are preferably an average particle diameter of 10 nm or more and less than 10 nm, more preferably 10 nm or more and 60 nm or less. Further, the average particle diameter is a number average 値 calculated by measuring the length of an arbitrary 100 particles in a field of view of 200,000 times by a scanning electron microscope. The shape of the particles is preferably a true sphere, but may be a slightly circular or elliptical shape. In this case, the particle length is roughly calculated as ((long diameter + short diameter)/2). When it is within this range, weather resistance and harmful gas decomposition property are exhibited efficiently, and transparency, film strength, and the like are improved.
又，依照本發明的較佳形態、光觸媒性金屬氧化物粒 子較佳爲具有3nm以上且未達30nm的平均雛晶直徑，更 佳爲5nm以上20nm以下。再者，此平均粒徑係由粉末X -21 - 201231533 射線繞射法所得之X射線輪廓的3強線之積分寬度’藉由 謝樂（Scherrer )式算出。 依照本發明的較佳形態、塗佈液中的光觸媒性金屬氧 化物粒子之含量，以乾燥質量（固體成分質量）計，相對 於前述樹脂乳液、前述光觸媒性金屬氧化物粒子及前述矽 石粒子的合計質量而言，係超過0.1質量％且未達15質量 %，更佳爲超過0.5質量％且未達5質量％。 依照本發明的較佳形態，矽石粒子較佳爲具有超過 5nm且lOOnm以下之平均粒徑，更佳爲超過10nm且50nm 以下之平均粒徑。再者，此平均粒徑係藉由掃描型電子顯 微鏡測定20萬倍的視野內之任意100個粒子的長度.所算 出的個數平均値。粒子的形狀最佳爲真球，但亦可爲略圓 形或橢圓形，該情況的粒子長度係作爲（（長徑+短徑）/2 ) 大略算出。 作爲將矽石粒子被覆或改性處理之具有全氟基的物質 ，例如可合適地利用具有鍵結至矽石粒子用的官能基及全 氟基之物質。具體地，可合適地利用具有全氟基的水解性 矽烷、具有全氟基的水解性聚矽氧、具有全氟基的含乙烯 基之氟樹脂、具有全氟基的含乙烯基之烴樹脂、具有全氟 基的含（甲基）丙烯酸官能基之氟樹脂、具有全氟基的含 丙烯酸官能基之烴樹脂、具有全氟基的含環氧官能基之氟 樹脂、具有全氟基的含環氧官能基之烴樹脂、具有全氟基 的含矽烷基之氟樹脂、具有全氟基的含矽烷基之烴樹脂、 彼等物質經改性基取代之物質、彼等物質的嵌段共聚物等 -22- 201231533 。用於被覆或改性處理的物質之量， 較佳爲0.1〜20質量％，更佳爲1〜1 作爲本發明中所用的樹脂乳液， 聚矽氧'丙烯酸酯聚矽氧'醋酸乙稀 酸酯、丙烯酸酯胺基甲酸酯、丙烯酸 烯醋酸乙烯酯、偏二氯乙烯、SBR乳 於本發明的塗佈液含有著色顏料 期抑制外觀變化而較佳。作爲無機顔 鋅白、氧化鐵紅、氧化鉻、鈷藍、鐵 、氧化鋁白、黃色氧化鐵等的金屬氫 等的酞花青化合物系、鉻黃、鉻酸鋅 、硫化鋅、朱砂、鎘黃、鎘紅等的硫 晶石、沈降性硫酸鋇等的硫酸鹽系、 碳酸鈣等的碳酸鹽系、含水矽酸鹽、 鹽系、碳黑等的碳系、鋁粉、青銅粉 、雲母•氧化鈦系等的珠光顏料系等 本發明的塗佈液亦含有矽石粒子 子。無機氧化物粒子只要是能與光觸 無機氧化物的粒子，則沒有特別的限 機氧化物之粒子。作爲如此的無機氧 出氧化銘、氧化錯、二氧化姉、三氧 化鐵、氧化鍾、氧化鎳、氧化結、氧 之粒子；及鈦酸鋇、矽酸鈣、硼酸鋁 化物之粒子。 相對於矽石量而言， 〇質量％。 例如可利用氟樹脂、 酯、醋酸乙烯酯丙烯 酯、環氧樹脂、氯乙 膠等的乳液。 時，無機顏料容易長 料，可舉出氧化鈦、 黑等的金屬氧化物系 氧化物系、普魯士藍 、鉬紅等的鉻酸鉛系 化物、硒化合物、重 重質碳酸鈣、沈降性 黏土、群青等的矽酸 t 、鋅粉等的金屬粉系 〇 以外的無機氧化物粒 媒粒子一起形成層之 定，可使用各種的無 化物粒子之例，可舉 化二釔、氧化錫、氧 化給等的單一氧化物 、鈦酸鉀等的複合氧 -23- 201231533 依照本發明的較佳態樣，爲了展現更高的光觸媒能力 ，本發明的塗佈液亦可含有由釩、鐵、鈷、鎳、鈀、鋅、 釕、铑、銅、銀、鈾及金所成之群組中選出的至少一種金 屬及/或由該金屬所成的金屬化合物。 作爲本發明的光觸媒塗佈液所用的溶劑，並沒有特別 的限定，可合適地利用水、甲醇、乙醇、丙醇、丁醇等的 醇、水及醇的混合溶劑等。特別地，若使用水當作溶劑， 則由於可在塗膜形成時有效地防止有機物的揮發、蒸發所 伴隨的異臭、環境污染而較佳。 又，光觸媒塗佈液的固體成分濃度係沒有特別的限定 ，但3〜70質量％係塗佈容易而較佳，更佳爲5〜60質量 %，最佳爲1 0〜5 0質量％。再者，光觸媒塗佈液中的構成 成分之分析，係可藉由超濾將塗佈液分離成粒子成分與濾 液，各自用紅外分光分析、凝膠滲透層析術、螢光X射線 分光分析等來分析，將光譜解析而評價。 於本發明的光觸媒塗佈液中，可摻合其它各種添加劑 〇 依照本發明的較佳態樣，光觸媒塗佈液係可含有能溶 於水或與水均勻分散之沸點爲〗〇〇°c以上的被膜形成助劑 。此被膜形成助劑係在大部分的水分氣化後，亦殘留在被 膜中，藉由溶解樹脂乳液界面而促進熔黏，可降低造膜溫 度。具體地，可例示1-丁醇、異丁醇、2-戊醇、3-戊醇、 異戊醇、乳酸甲酯、乳酸乙酯、3-甲基-3-甲氧基丁醇等的 醇類、1，2-丙二醇、1，3-丁二醇、1，4-丁二醇、2,3-丁二醇 • 24- 201231533 、_1，5-戊二醇、2-甲基-2,4-戊二醇、甘油、三經 等的多元醇類、2-丁氧基乙醇、2-苯氧基乙醇、 乙基乙酸酯、2-丁氧基乙基乙酸酯、二乙二醇單 酸酯等的乙二醇衍生物、1-甲氧基-2-丙醇、1-丙醇、1-甲氧基-2-甲基乙基乙酸酯、1-乙氧基 基乙酸酯、二丙二醇、二丙二醇單甲基醚、二丙 基醚、二丙二醇單甲基醚乙酸酯等的丙二醇衍生 氧基丁基乙酸酯等的丁二醇衍生物、環己酮等的 酸丁酯、醋酸異丁酯、γ-丁內酯、碳酸伸丙酯、 二甲酸酯、2，2,4-三甲基-1,3-戊二醇單異丁酸酯 等。特佳爲2-乙氧基乙基乙酸酯、2-丁氧基乙基 二乙二醇單丁基醚乙酸酯、1-乙氧基-2-甲基乙基 二丙二醇單甲基醚乙酸酯等的烷二醇衍生物。 本發明的塗佈液中之上述被膜形成助劑的添 對於聚矽氧樹脂100重量份而言，較佳爲0〜20 特佳爲1〜1 5重量份。 本發明的塗佈液亦可含有界面活性劑當作任 於本發明的較佳態樣中，界面活性劑係以相對於 子1重量份而言添加未達10重量份，更佳爲0. 份左右。 作爲本發明的塗佈液中所可添加的界面活性 可舉出磺酸聚氧乙烯烷基苯基醚銨鹽、磺酸聚氧 苯基醚鈉鹽、脂肪酸鈉皂、脂肪酸鉀皂、二辛基 酸鈉、硫酸烷酯、烷基醚硫酸酯、烷基硫酸酯鈉 甲基丙烷 2-乙氧基 丁基醚乙 乙氧基-2--2-甲基乙 二醇單乙 ，物、3-甲 酮類、醋 二丁基苯 等的酯類 乙酸酯、 乙酸酯、 加量，相 重量份， 意成分。 光觸媒粒 1〜2雷量 劑之例， 乙烯烷基 磺基琥珀 鹽、烷基 -25- 201231533 醚硫酸酯鈉鹽、聚氧乙烯烷基醚硫酸酯、聚氧乙烯烷基酸 硫酸酯鈉鹽、烷基硫酸酯TEA鹽、聚氧乙烯烷基酸硫酸 酯TEA鹽、2·乙基己基烷基硫酸酯鈉鹽、醯基甲基牛磺酸 鈉、月桂醯基甲基牛磺酸鈉、十二基苯磺酸鈉、磺基琥珀 酸月桂基二鈉、聚氧乙烯磺基琥珀酸月桂基二鈉、聚羧酸 、油醯基肌胺酸、醯胺醚硫酸酯、月桂醯基肌胺酸酯、磺 基FA酯鈉鹽等的陰離子性界面活性劑；聚氧乙烯月桂基 醚、聚氧乙烯十三基醚、聚氧乙烯鯨蠟基醚、聚氧乙烯硬 脂基醚、聚氧乙烯油基醚、聚氧乙烯烷基醚、聚氧乙烯烷 基酯、聚氧乙烯烷基苯酚醚、聚氧乙烯壬基苯基醚、聚氧 乙烯辛基苯基醚、聚氧乙烯月桂酸酯 '聚氧乙烯硬脂酸酯 、聚氧乙烯烷基苯基醚、聚氧乙烯油酸酯、山梨糖醇酐烷 酯、聚氧乙烯山梨糖醇酐烷酯、聚醚改性聚矽氧、聚酯改 性聚矽氧、山梨糖醇酐月桂酸酯、山梨糖醇酐硬脂酸酯、 山梨糖醇酐棕櫚酸酯、山梨糖醇酐油酸酯、山梨糖醇酐倍 半油酸酯、聚氧乙烯山梨糖醇酐月桂酸酯、聚氧乙烯山梨 糖醇酐硬脂酸酯、聚氧乙烯山梨糖醇酐棕櫚酸酯、聚氧乙 烯山梨糖醇酐油酸酯 '甘油硬脂酸酯、聚甘油脂肪酸酯' 烷基烷醯基醯胺、月桂酸二乙醇醯胺、油酸二乙醇醯胺、 氧乙烯十二基胺、聚氧乙烯十二基胺 '聚氧乙烯烷基胺、 聚氧乙焴十八基胺、聚氧乙嫌院基丙嫌二胺、聚氧乙燃氧 基丙烯嵌段聚合物、聚氧乙烯硬脂酸酯等的非離子性界面 活性劑；二甲基烷基甜菜鹼、烷基甘胺酸、醯胺甜菜鹼、 咪唑啉等的兩性界面活性劑、十八基二甲基苄基銨氯化物 -26- 201231533 、烷基二甲基苄基銨氯化物、十四基甲基 二油基二甲基銨氯化物、1-羥基乙基-2-烷 、烷基異喹啉鎗溴化物、高分子胺、十八 物、烷基三甲基銨氯化物、十二基三甲基 基三甲基銨氯化物、山荼基三甲基銨氯化 四級鹽、二烷基二甲基銨氯化物、十八基 基胺醋酸鹽、烷基丙烯二胺醋酸鹽、二癸 物等的陽離子性界面活性劑等。 光觸媒塗裝體之製造方法 本發明的光觸媒塗裝體係可藉由將上 塗佈於基材上而製造。.光觸媒層的塗裝方 塗抹、滾筒、噴霧 '輥塗、淋塗、浸塗、 等一般廣泛進行的方法來塗佈前述液劑。 佈液後，可使常溫乾燥，或視需要可加熱 基材 本發明所用的基材係不論無機材料、 材料，而可使用各種的材料，其形狀亦沒 的觀點來看，作爲基材的較佳例，可舉出 璃、塑膠、橡膠、石材、水泥、混凝土、 、紙、彼等的組合、彼等的層合體、在彼 少一層的被膜者。從用途的觀點來看，作 ’可舉出建材、建物外裝及內裝、窗框、 苄基銨氯化物、 基咪唑啉四級鹽 基三甲基銨氯化 銨氯化物、十六 物、烷基咪唑啉 胺醋酸鹽、十四 基一甲基錶氯化 述光觸媒塗佈液 法係可利用刷毛 流塗、網版印刷 於對基材塗佈塗 訖燥。 有機材料、複層 有限定。從材料 金屬、陶瓷、玻 纖維、布帛、木 等的表面具有至 爲基材的較佳例 窗玻璃、構造構 -27- 201231533 件、交通工具的外裝及塗裝、機械裝置或物品的外裝、防 塵蓋及塗裝、交通標識、各種顯示裝置、廣告塔、道路用 遮音壁、鐵路用遮音壁、橋樑、導軌的外裝及塗裝、隧道 內裝及塗裝、絕緣子'太陽電池蓋、太陽熱溫水器集熱蓋 、乙烯樹脂殼、車輛用照明燈的蓋、室外用照明器具、台 、浴室材、廚房面板、流理台'烤爐、通風扇、空調、過 濾器、便器、浴槽及及貼附於上述物品表面用之薄膜、薄 片、密封物等。 [實施例] 用以下之例爲基礎，具體地說明本發明，惟本發明不 受此等例所限定。 實施例1 (矽石粒子之表面被覆處理） 對於矽石粒子（平均粒徑50nm) 100重量份，使全氟 烷基三烷氧基矽烷5重量份反應，以製作經疏水化處理的 矽石粒子。 (光觸媒塗裝體之製作） 調製摻合有銳鈦礦型氧化鈦粒子（平均雛晶直徑 10nm) 1.3質量份、上述經疏水化處理的矽石粒子8.7質 量份、及具有甲基苯基矽烷基的聚矽氧乳液以固體成分計 90質量份之固體成分濃度25質量％之光觸媒水性塗佈液 •28- 201231533 ，在透明的2mm厚之鈉鈣玻璃基材上，以150 °C乾燥5 $ 鐘，而得到光觸媒塗裝體。 (光觸媒塗裝體之評價） 觀察所得之光觸媒塗裝體的光觸媒層之截面，結果_ 厚約7 μπι。 又，光觸媒層的550nm波長之光的透過率爲82%。 對此光觸媒塗裝體，依照JISR1 703 -2「光觸媒材料的 自潔淨性能試驗方法-第2部：濕式分解性能」的試驗$ ，測量光觸媒分解活性。結果，MB活性指數顯示6.5的 良好結果。 實施例2 (矽石粒子之表面被覆處理） 對於矽石粒子（平均粒徑50nm) 100重量份，使全氟 烷基三烷氧基矽烷5重量份反應，以製作經疏水化處理的 矽石粒子。 (光觸媒塗裝體之製作） 調製摻合有銳鈦礦型氧化鈦粒子（平均雛晶直徑 1 〇nm ) 1 .3質量份、上述經疏水化處理的矽石粒子8.7質 量份、及以具有二甲基矽烷基的聚矽氧乳液爲固體成分90 質量之固體成分濃度25質量％的光觸媒水性塗佈液，在透 明的2mm厚之鈉鈣玻璃基材上，以1 50°C乾燥5分鐘，而 -29- 201231533 得到光觸媒塗裝體。 (光觸媒塗裝體之評價） 觀察所得之光觸媒塗裝體的光觸媒層之截面，結果膜 厚約7 μηι。 又，光觸媒層的550nm波長之光的透過率爲84%。 對此光觸媒塗裝體，依照JISR1 703-2「光觸媒材料的 自潔淨性能試驗方法-第2部：濕式分解性能」的試驗法 ，測量光觸媒分解活性。結果，MB活性指數顯示6.4的 良好結果。 比較例1 調製摻合有銳鈦礦型氧化鈦粒子（平均雛晶直徑 10nm) 1.3質量份、矽石粒子（平均粒徑50nm) 8.7質量 份、以甲基苯基聚矽氧乳液爲固體成分90質量份之固體 成分濃度25質量％的光觸媒水性塗佈液，在透明的2mm 厚之鈉鈣玻璃基材上，以150°C乾燥5分鐘，而得到光觸 媒塗裝體。 觀察所得之光觸媒塗裝體的光觸媒層之截面，結果膜 厚約7 μιη。 又，光觸媒層的550nm波長之光的透過率爲83%。 對此光觸媒塗裝體，依照HSR1 703-2「光觸媒材料的 自潔淨性能試驗方法-第2部：濕式分解性能」的試驗法 ，測量光觸媒分解活性。結果，MB活性指數顯示1 .1的 -30- 201231533 低値。 實施例3 (矽石粒子之表面被覆處理） 對於矽石粒子（平均粒徑50nm ) 100重量份’使全氟 烷基三烷氧基矽烷5重量份反應’以製作經疏水化處理的 矽石粒子。 (光觸媒塗裝體之製作） 調製摻合有銳鈦礦型氧化鈦粒子（平均雛晶直徑 1 Onm ) 1 .3質量份、上述經疏水化處理的矽石粒子8.7質 量份、及以具有甲基苯基聚矽氧乳液爲固體成分45質量 、無機顏料45質量份之固體成分濃度40質量％的光觸媒 水性塗佈液，而得到光觸媒塗料。 於經裁切成150mmx65mm的石棉水泥矽酸鈣板（根 據JIS A5418者）上，噴灑塗裝環氧基樹脂系底漆，於室 溫下乾燥24小時。接著，將丙烯酸酯胺基甲酸酯塗料噴 灑塗裝於上述已進行底漆塗裝的石棉水泥矽酸鈣板上，於 室溫下乾燥24小時。再接著，將上述光觸媒塗料以刷毛 塗抹於已進行丙烯酸酯胺基甲酸酯塗裝之石棉水泥矽酸鈣 板上，而得到塗佈物。 (光觸媒塗裝體之評價） 觀察所得之光觸媒塗裝體的光觸媒層之截面，結果膜 -31 - 201231533 厚約40μιη β 對此光觸媒塗裝體，依照JISR 1 703 -2「光觸媒材料的 自潔淨性能試驗方法-第2部：濕式分解性能」的試驗法 ，測量光觸媒分解活性。結果，MB活性指數顯示6.0的 良好結果。 對所得之光觸媒塗裝體，如以下地進行耐候性試驗。 將光觸媒塗裝體投入JIS B7753所規定的日光耐候計（ SUGA試驗機製，S-3 00C)中。經過lOOhr後，取出試驗 片，觀察投入前後的外觀變化。結果在外觀上沒有看到變 化。 實施例4 (銳鈦礦型氧化鈦粒子之表面被覆處理） 對於銳鈦礦型氧化鈦粒子（平均雛晶直徑l〇nm) 100 重量份，使全氟烷基三烷氧基矽烷5重量份反應，以製作 經疏水化處理的氧化鈦粒子。 (矽石粒子之表面被覆處理） 對於矽石粒子（平均粒徑50nm ) 100重量份，使全氟 院基三院氧基砂院5重量份進行反應，以製作經疏水化處 理的矽石粒子。 (光觸媒塗裝體之製作） 調製摻合有上述經疏水化處理的氧化鈦粒子丨.3質量 -32- 201231533 份、上述經疏水化處理的矽石粒子8.7質量份、及具有甲 基苯基矽烷基的聚矽氧乳液以固體成分計90質量份之胃 體成分濃度25質量％的光觸媒水性塗佈液，在透明％ 2mm厚之鈉鈣玻璃基材上，以150t乾燥5分鐘，而得到 光觸媒塗裝體。 (光觸媒塗裝體之評價） 觀察所得之光觸媒塗裝體的光觸媒層之截面，結果_ 厚約7μιη。 又，光觸媒層的550nm波長之光的透過率爲84%。 對此光觸媒塗裝體，依照JISR1703-2「光觸媒材料的 自潔淨性能試驗方法-第2部：濕式分解性能」的試驗法 ，測量光觸媒分解活性。結果，MB活性指數顯示9.3的 良好結果。 實驗例5 (砂石粒子之表面被覆處理） 對於矽石粒子（平均粒徑5Onm) 100重量份’使全氟 垸基三院氧基砂院5重量份反應，以製作經疏水化處理的 砂石粒子。 (光觸媒塗裝體之製作） 調製摻合有銳鈦礦型氧化鈦粒子（平均雛晶直徑 1 Onm) 1.3質量份、上述經疏水化處理的矽石粒子8.7質 -33- 201231533 量份 '及具有甲基苯基矽烷基的聚矽氧乳液以固體成分計 9〇質量份之固體成分濃度25質量％的光觸媒水性塗佈液 ’在石板上有丙烯酸系著色塗裝而成之基材上，以80乞乾 燥30分鐘’而得到光觸媒塗裝體。 對於如此所得之50 x 1 00mm的大小之光觸媒塗裝體， 如以下地進行耐候性試驗。將光觸媒塗裝體投入jIS B7753所規定的日光耐候計（SUGA試驗機製，S-300C) 中。經過lOOhr後，取出試驗片，觀察投入前後的外觀變 化。結果在外觀上沒有看到變化。 實驗例6 (銳鈦礦型氧化鈦粒子之表面被覆處理） 對於銳鈦礦型氧化鈦粒子（平均雛晶直徑10nm) 100 重量份’使全氟烷基三烷氧基矽烷5重量份反應，以製作 經疏水化處理的氧化鈦粒子。 (矽石粒子之表面被覆處理） 對於砂石粒子（平均粒徑50nm) 100重量份，使三垸 氧基矽烷5重量份進行反應，以製作經疏水化處理的矽石 粒子。 (光觸媒塗裝體之製作） 調製摻合有上述經疏水化處理的氧化鈦粒子1 .3質量 份、上述經疏水化處理的矽石粒子8.7質量份、及具有甲 -34- 201231533 基苯基矽烷基的聚矽氧乳液以固體成分計90質量份之固 體成分濃度25質量％的光觸媒水性塗佈液，在透明石板上 有丙烯酸系著色塗裝而成之基材上，以l5〇°C乾燥5分鐘 ，而得到光觸媒塗裝體。 對於如此所得之50 x 1 00mm的大小之光觸媒塗裝體， 如以下地進行耐候性試驗。將光觸媒塗裝體投入JIS B7753中所規定的曰光耐候計（SUGA試驗機製，S-300C )中。經過1 OOhr後，取出試驗片，觀察投入前後的外觀 變化。結果在外觀上沒有看到變化。Further, according to a preferred embodiment of the present invention, the photocatalytic metal oxide particles preferably have an average crystallite diameter of 3 nm or more and less than 30 nm, more preferably 5 nm or more and 20 nm or less. Further, the average particle diameter is calculated by the Scherrer equation from the integral width of the three strong lines of the X-ray profile obtained by the powder X-21-201231533 ray diffraction method. According to a preferred embodiment of the present invention, the content of the photocatalytic metal oxide particles in the coating liquid is based on the dry mass (solid content) relative to the resin emulsion, the photocatalytic metal oxide particles, and the foregoing vermiculite particles. The total mass is more than 0.1% by mass and less than 15% by mass, more preferably more than 0.5% by mass and less than 5% by mass. According to a preferred embodiment of the present invention, the vermiculite particles preferably have an average particle diameter of more than 5 nm and 100 nm or less, more preferably an average particle diameter of more than 10 nm and 50 nm or less. Further, the average particle diameter is measured by a scanning electron microscope to measure the length of any 100 particles in a field of view of 200,000 times. The shape of the particles is preferably a true sphere, but may be a slightly round or elliptical shape, and the particle length in this case is roughly calculated as ((long diameter + short diameter)/2). As the substance having a perfluoro group in which the vermiculite particles are coated or modified, for example, a substance having a functional group bonded to the vermiculite particles and a perfluoro group can be suitably used. Specifically, a hydrolyzable decane having a perfluoro group, a hydrolyzable polyfluorene having a perfluoro group, a vinyl group-containing fluororesin having a perfluoro group, and a vinyl group-containing hydrocarbon resin having a perfluoro group can be suitably used. a perfluoro group-containing (meth)acrylic functional group-containing fluororesin, a perfluoro group-containing acrylic functional group-containing hydrocarbon resin, a perfluoro group-containing epoxy functional group-containing fluororesin, and a perfluoro group A hydrocarbon resin containing an epoxy functional group, a fluoroalkyl group-containing fluororesin having a perfluoro group, a perfluoroalkyl group-containing hydrocarbon resin having a perfluoro group, a substance substituted with a modified group, and a block of the same Copolymers, etc. -22- 201231533. The amount of the substance to be coated or modified is preferably from 0.1 to 20% by mass, more preferably from 1 to 1, as the resin emulsion used in the present invention, polyoxyl' acrylate polyoxyl' acetic acid The ester, acrylate urethane, acryl vinyl acetate, vinylidene chloride, and SBR emulsion are preferably used in the coating liquid of the present invention to contain a coloring pigment to suppress changes in appearance. As a phthalocyanine compound such as inorganic zinc white, iron oxide red, chromium oxide, cobalt blue, iron, alumina white, yellow iron oxide, etc., chrome yellow, zinc chromate, zinc sulfide, cinnabar, cadmium Sulfite such as yellow or cadmium red, sulfate such as sedimentary barium sulfate, carbonate such as calcium carbonate, carbonic acid such as aqueous silicate, salt or carbon black, aluminum powder, bronze powder, mica The coating liquid of the present invention, such as a pearlescent pigment such as a titanium oxide system, also contains vermiculite particles. The inorganic oxide particles do not have any particles of a specific oxide as long as they are particles capable of contacting the inorganic oxide with light. Such particles of inorganic oxygen oxide, oxidation, cerium oxide, iron trioxide, oxidized clock, nickel oxide, oxidized oxide, and oxygen; and particles of barium titanate, calcium silicate, and aluminum borate. 〇% by mass relative to the amount of vermiculite. For example, an emulsion of a fluororesin, an ester, a vinyl acetate acrylate, an epoxy resin, a vinyl chloride or the like can be used. In the case of the inorganic pigment, the inorganic pigment is easily grown, and examples thereof include metal oxide oxides such as titanium oxide and black, lead chromate compounds such as Prussian blue and molybdenum red, selenium compounds, heavy heavy calcium carbonate, and sedimentary clay. A metal powder such as citric acid or the like, such as citric acid or zinc powder, may be formed as a layer together with inorganic oxide particles other than cerium, and examples of various inorganic particles may be used, and diterpene, tin oxide, and oxidation may be used. Complex Oxide of Monooxide, Potassium Titanate, etc. -23-201231533 In accordance with a preferred aspect of the present invention, the coating liquid of the present invention may also contain vanadium, iron, cobalt, in order to exhibit higher photocatalytic ability. At least one metal selected from the group consisting of nickel, palladium, zinc, ruthenium, rhodium, copper, silver, uranium, and gold, and/or a metal compound formed from the metal. The solvent to be used for the photocatalyst coating liquid of the present invention is not particularly limited, and an alcohol such as water, methanol, ethanol, propanol or butanol, a mixed solvent of water and an alcohol, or the like can be suitably used. In particular, when water is used as the solvent, it is preferable to effectively prevent the volatilization of the organic substance, the odor associated with evaporation, and environmental pollution when the coating film is formed. Further, the solid content concentration of the photocatalyst coating liquid is not particularly limited, but it is preferably from 3 to 70% by mass, more preferably from 5 to 60% by mass, most preferably from 10 to 50% by mass. Further, in the analysis of the constituent components in the photocatalyst coating liquid, the coating liquid can be separated into a particle component and a filtrate by ultrafiltration, and each of them is analyzed by infrared spectroscopic analysis, gel permeation chromatography, and fluorescence X-ray spectrometry. Etc. Analysis, the spectrum is analyzed and evaluated. In the photocatalyst coating liquid of the present invention, other various additives may be blended. According to a preferred embodiment of the present invention, the photocatalyst coating liquid may have a boiling point which is soluble in water or uniformly dispersed with water. The above film forming aid. This film forming aid remains in the film after most of the moisture is vaporized, and the melt-adhesiveness is promoted by dissolving the resin emulsion interface, thereby lowering the film forming temperature. Specifically, 1-butanol, isobutanol, 2-pentanol, 3-pentanol, isoamyl alcohol, methyl lactate, ethyl lactate, 3-methyl-3-methoxybutanol, etc. may be exemplified. Alcohols, 1,2-propanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol • 24-201231533, _1,5-pentanediol, 2-methyl- 2,4-pentanediol, glycerin, trihydric polyols, 2-butoxyethanol, 2-phenoxyethanol, ethyl acetate, 2-butoxyethyl acetate, two Ethylene glycol derivative such as ethylene glycol monoester, 1-methoxy-2-propanol, 1-propanol, 1-methoxy-2-methylethyl acetate, 1-ethoxy Butanediol derivatives such as propylene glycol-derived oxybutyl acetate such as benzyl acetate, dipropylene glycol, dipropylene glycol monomethyl ether, dipropyl ether, dipropylene glycol monomethyl ether acetate, and the like Butyl ketone, etc., isobutyl acetate, γ-butyrolactone, propyl carbonate, diformate, 2,2,4-trimethyl-1,3-pentanediol monoisobutyric acid Ester and the like. Particularly preferred is 2-ethoxyethyl acetate, 2-butoxyethyl diethylene glycol monobutyl ether acetate, 1-ethoxy-2-methylethyl dipropylene glycol monomethyl An alkanediol derivative such as an ether acetate. The film-forming auxiliary agent in the coating liquid of the present invention is preferably from 0 to 20, particularly preferably from 1 to 15 parts by weight, per 100 parts by weight of the polyoxymethylene resin. The coating liquid of the present invention may also contain a surfactant as a preferred embodiment of the present invention, and the surfactant is added in an amount of less than 10 parts by weight, more preferably 0% by weight relative to 1 part by weight. About. The interfacial activity which can be added to the coating liquid of the present invention includes sulfonic acid polyoxyethylene alkylphenyl ether ammonium salt, sulfonic acid polyoxyphenyl ether sodium salt, fatty acid sodium soap, fatty acid potassium soap, and dioctane. Sodium sulphate, alkyl sulphate, alkyl ether sulphate, sodium sulphate, sodium methyl propane, 2-ethoxybutyl ether, ethyl ethoxy-2- -2-methyl glycol, monoethyl, An ester acetate such as 3-methanone or acetonate or butyl acetate, an acetate, an added amount, a phase by weight, and an intended component. Example of photocatalyst granule 1~2 sizing agent, vinyl alkyl sulfosuccinium salt, alkyl-25-201231533 ether sulfate sodium salt, polyoxyethylene alkyl ether sulfate, polyoxyethylene alkyl acid sulfate sodium salt , alkyl sulfate TEA salt, polyoxyethylene alkyl acid sulfate TEA salt, sodium 2-ethylhexyl alkyl sulfate, sodium mercaptomethyl taurate, sodium lauryl methyl taurate, Sodium dodecylbenzenesulfonate, disodium lauryl sulfosuccinate, disodium lauryl sulfosuccinate, polycarboxylic acid, oleic acid creatinine, indoleamine sulfate, laurel An anionic surfactant such as an amine ester or a sulfo-FA ester sodium salt; polyoxyethylene lauryl ether, polyoxyethylene tridecyl ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, poly Oxyethylene oleyl ether, polyoxyethylene alkyl ether, polyoxyethylene alkyl ester, polyoxyethylene alkyl phenol ether, polyoxyethylene nonylphenyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene laurel Acid esters 'polyoxyethylene stearate, polyoxyethylene alkyl phenyl ether, polyoxyethylene oleate, sorbitan alkyl ester, poly Ethylene sorbitan alkyl ester, polyether modified polyoxymethylene, polyester modified polyoxyl, sorbitan laurate, sorbitan stearate, sorbitan palmitate, sorbus Sugar anhydride oleate, sorbitan sesquioleate, polyoxyethylene sorbitan laurate, polyoxyethylene sorbitan stearate, polyoxyethylene sorbitan palmitate , polyoxyethylene sorbitan oleate glyceryl stearate, polyglycerol fatty acid ester 'alkyl alkyl decyl decylamine, lauric acid diethanol decylamine, oleic acid diethanol amide, oxyethylene twelve Amine, polyoxyethylene dodecylamine 'polyoxyethylene alkylamine, polyoxyethylene octadecylamine, polyoxyethylene propylene propylene diamine, polyoxyethylene oxypropylene block polymer, a nonionic surfactant such as polyoxyethylene stearate; an amphoteric surfactant such as dimethylalkylbetaine, alkylglycine, guanamine betaine or imidazoline, octadecyl dimethyl Benzyl ammonium chloride -26- 201231533, alkyl dimethyl benzyl ammonium chloride, tetradecyl methyl dioleyl dimethyl ammonium chloride 1-hydroxyethyl-2-alkane, alkylisoquinoline gun bromide, polymeric amine, octadecyl, alkyltrimethylammonium chloride, dodecyltrimethyltrimethylammonium chloride, Cationic surfactants such as behenyltrimethylammonium chloride quaternary salt, dialkyldimethylammonium chloride, octadecylamine acetate, alkyl propylene diamine acetate, diterpene, etc. . Method of Producing Photocatalyst Coating Body The photocatalyst coating system of the present invention can be produced by applying the upper coating to a substrate. . Coating of Photocatalyst Layer The above liquid preparation is applied by a method widely applied, such as painting, roller, and spray, "roll coating, shower coating, dip coating," and the like. After the cloth is liquid, it can be dried at room temperature or, if necessary, the substrate can be heated. The substrate used in the present invention can be used in various materials regardless of the inorganic material or material, and the shape of the substrate is not As a good example, a combination of glass, plastic, rubber, stone, cement, concrete, paper, and others, a laminate thereof, and a film on the other layer may be mentioned. From the point of view of use, it can be cited as building materials, building exterior and interior, window frame, benzyl ammonium chloride, imidazoline tetrabasic salt trimethylammonium chloride chloride, sixteen , alkyl imidazolinium acetate, tetradecyl monomethyl chloride photocatalyst coating liquid system can be applied by brush flow coating, screen printing on the substrate coating and drying. Organic materials and complex layers are limited. From the surface of materials such as metal, ceramics, glass fiber, cloth, wood, etc., there are preferred examples of window glass, structural structure -27-201231533, exterior and painting of vehicles, mechanical devices or articles. Installation, dust cover and painting, traffic signs, various display devices, advertising towers, soundproof walls for roads, soundproof walls for railways, exterior and painting of bridges and guide rails, tunnel interiors and paintings, insulators, solar cell covers, solar heat Heater collector cover, vinyl case, cover for vehicle lighting, outdoor lighting, table, bathroom material, kitchen panel, flow table 'oven, ventilation fan, air conditioner, filter, toilet, bath and And a film, a sheet, a seal, or the like attached to the surface of the above article. [Examples] The present invention will be specifically described on the basis of the following examples, but the present invention is not limited by the examples. Example 1 (surface coating treatment of vermiculite particles) 5 parts by weight of perfluoroalkyltrialkoxydecane was reacted to 100 parts by weight of vermiculite particles (average particle diameter: 50 nm) to prepare hydrophobized vermiculite particle. (Production of photocatalyst-coated body) 1.3 parts by mass of anatase-type titanium oxide particles (average crystallite diameter: 10 nm), 8.7 parts by mass of the above-described hydrophobized vermiculite particles, and methylphenylnonane The base polyfluorene emulsion is dried at 150 ° C on a transparent 2 mm thick soda lime glass substrate by using 90 parts by mass of a solid component concentration of 25% by mass of a photocatalyst aqueous coating liquid, 28-201231533. $ clock, and get the photocatalyst coating body. (Evaluation of Photocatalyst Coating Body) The cross section of the photocatalyst layer of the obtained photocatalyst-coated body was observed, and as a result, the thickness was about 7 μm. Further, the transmittance of light of a wavelength of 550 nm of the photocatalyst layer was 82%. For the photocatalyst coating body, the photocatalytic decomposition activity was measured in accordance with JIS S1 703 -2 "Test Method for Self-cleaning Performance of Photocatalyst Materials - Part 2: Wet Decomposition Performance". As a result, the MB activity index showed a good result of 6.5. Example 2 (surface coating treatment of vermiculite particles) 5 parts by weight of perfluoroalkyltrialkoxydecane was reacted with 100 parts by weight of vermiculite particles (average particle diameter: 50 nm) to prepare hydrophobized vermiculite particle. (Production of photocatalyst-coated body) 1-3 parts by mass of the anatase-type titanium oxide particles (average crystallite diameter of 1 〇nm) and 8.7 parts by mass of the hydrophobized vermiculite particles, and The dimethyl sulfonyl polyoxyxide emulsion is a photocatalyst aqueous coating liquid having a solid content of 90% by mass and having a solid content of 25% by mass. It is dried at 150 ° C for 5 minutes on a transparent 2 mm thick soda lime glass substrate. , and -29- 201231533 obtained photocatalyst coating body. (Evaluation of Photocatalyst Coating Body) The cross section of the photocatalyst layer of the obtained photocatalyst-coated body was observed, and as a result, the film thickness was about 7 μm. Further, the transmittance of light of a wavelength of 550 nm of the photocatalyst layer was 84%. The photocatalyst coating body was measured for photocatalytic decomposition activity in accordance with JIS R1 703-2 "Test method for self-cleaning performance of photocatalyst materials - Part 2: Wet decomposition performance". As a result, the MB activity index showed a good result of 6.4. Comparative Example 1 Modification of anatase-type titanium oxide particles (average crystallite diameter: 10 nm): 1.3 parts by mass, vermiculite particles (average particle diameter: 50 nm), 8.7 parts by mass, and a methylphenyl polyfluorene emulsion as a solid component 90 parts by mass of a photocatalyst aqueous coating liquid having a solid content concentration of 25% by mass was dried on a transparent 2 mm thick soda lime glass substrate at 150 ° C for 5 minutes to obtain a photocatalyst-coated body. The cross section of the photocatalyst layer of the obtained photocatalyst-coated body was observed, and as a result, the film thickness was about 7 μm. Further, the transmittance of light of a wavelength of 550 nm of the photocatalyst layer was 83%. The photocatalyst coating body was measured for photocatalytic decomposition activity in accordance with HSR1 703-2 "Test Method for Self-cleaning Performance of Photocatalyst Materials - Part 2: Wet Decomposition Performance". As a result, the MB activity index showed a low of -30-201231533 of 1.1. Example 3 (Surface coating treatment of vermiculite particles) For vermiculite particles (average particle diameter: 50 nm) 100 parts by weight 'reacting 5 parts by weight of perfluoroalkyltrialkoxydecane' to prepare hydrophobized vermiculite particle. (Production of photocatalyst-coated body) 1-3 parts by mass of the anatase-type titanium oxide particles (average crystallite diameter 1 Onm), 8.7 parts by mass of the above-mentioned hydrophobized vermiculite particles, and The phenyl phenylpolyoxyl emulsion was a photocatalyst aqueous coating liquid obtained by using a photocatalyst aqueous coating liquid having a solid content of 45 masses and an inorganic pigment content of 45 mass% of a solid content of 40% by mass. The epoxy resin primer was spray-coated on a 150 mm x 65 mm asbestos cement calcium silicate board (according to JIS A5418) and dried at room temperature for 24 hours. Next, an acrylate urethane coating was spray-coated on the above-mentioned primer-coated asbestos cement calcium silicate board, and dried at room temperature for 24 hours. Next, the photocatalyst coating was applied to the asbestos cement calcium silicate board which had been subjected to acrylate urethane coating with a bristles to obtain a coated product. (Evaluation of Photocatalyst Coating Body) The cross section of the photocatalyst layer of the obtained photocatalyst coating body was observed, and as a result, the film -31 - 201231533 was about 40 μmη β thick. This photocatalyst coating body was self-cleaning according to JIS R 1 703 -2 "Photocatalyst material. Performance Test Method - Part 2: Wet Decomposition Performance" test method for measuring photocatalytic decomposition activity. As a result, the MB activity index showed a good result of 6.0. The obtained photocatalyst-coated body was subjected to a weather resistance test as follows. The photocatalyst coated body was placed in a solar weathering meter (SUGA test mechanism, S-3 00C) prescribed in JIS B7753. After 100 hours, the test piece was taken out and the appearance change before and after the input was observed. As a result, no change in appearance was observed. Example 4 (Surface coating treatment of anatase-type titanium oxide particles) 5 parts by weight of perfluoroalkyltrialkoxydecane for 100 parts by weight of anatase-type titanium oxide particles (average crystallite diameter l〇nm) The reaction is carried out to prepare hydrophobized titanium oxide particles. (surface coating treatment of vermiculite particles) For 100 parts by weight of vermiculite particles (average particle diameter: 50 nm), 5 parts by weight of a perfluorocarbon-based three-yard oxygen sand court was reacted to prepare hydrophobized vermiculite particles. . (Production of Photocatalyst Coating Body) The above-described hydrophobized titanium oxide particles 丨.3 mass - 32 - 201231533 parts, 8.6 parts by mass of the above hydrophobized vermiculite particles, and methylphenyl group are prepared. The cerium alkyl polyoxyn emulsion was dried on a transparent % 2 mm thick soda lime glass substrate at 150 t for 5 minutes on a transparent % 2 mm thick soda lime glass substrate in an amount of 90 parts by mass based on the solid content of 25% by mass of the photocatalyst aqueous coating liquid. Photocatalyst coating body. (Evaluation of Photocatalyst Coating Body) The cross section of the photocatalyst layer of the obtained photocatalyst-coated body was observed, and as a result, the thickness was about 7 μm. Further, the transmittance of light of a wavelength of 550 nm of the photocatalyst layer was 84%. The photocatalyst coating body was measured for photocatalytic decomposition activity according to the test method of JIS R1703-2 "Test method for self-cleaning properties of photocatalyst materials - Part 2: Wet decomposition performance". As a result, the MB activity index showed a good result of 9.3. Experimental Example 5 (Surface coating treatment of sand and gravel particles) For the vermiculite particles (average particle diameter: 5 Onm) 100 parts by weight, 5 parts by weight of perfluorodecyl-based tri-yard oxide sand yard was reacted to prepare hydrophobized sand. Stone particles. (Production of photocatalyst coated body) Modulation of anatase-type titanium oxide particles (average crystallite diameter 1 Onm) 1.3 parts by mass, the above-mentioned hydrophobized vermiculite particles 8.7 mass-33-201231533 parts ' and The polyfluorene oxide emulsion having a methylphenyl fluorenyl group is a photocatalyst aqueous coating liquid having a solid content of 25% by mass based on the solid content, and is coated on the slate with an acrylic color-coated substrate. The photocatalyst coated body was obtained by drying at 80 Torr for 30 minutes. The photocatalyst coated body of the size of 50 x 100 mm thus obtained was subjected to a weather resistance test as follows. The photocatalyst coating body was placed in a solar weathering meter (SUGA test mechanism, S-300C) prescribed in JIS B7753. After 100 hours, the test piece was taken out and the appearance change before and after the input was observed. As a result, no change was seen in appearance. Experimental Example 6 (surface coating treatment of anatase-type titanium oxide particles) 100 parts by weight of anatase-type titanium oxide particles (average crystallite diameter: 10 nm) was reacted with 5 parts by weight of perfluoroalkyltrialkoxydecane, To prepare hydrophobized titanium oxide particles. (Surface coating treatment of vermiculite particles) To 100 parts by weight of the sandstone particles (average particle diameter: 50 nm), 5 parts by weight of trimethoxy decane was reacted to prepare hydrophobized vermiculite particles. (Production of Photocatalyst Coating Body) 1.3 parts by mass of the hydrophobized titanium oxide particles, 8.7 parts by mass of the hydrophobized vermiculite particles, and a methyl group of -34-201231533 The cerium alkyl polyoxyn emulsion is a photocatalyst aqueous coating liquid having a solid content of 25% by mass based on the solid content, and is coated on a transparent stone plate with an acrylic color-coated substrate at a temperature of 15 ° C. It was dried for 5 minutes to obtain a photocatalyst coated body. The photocatalyst coated body of the size of 50 x 100 mm thus obtained was subjected to a weather resistance test as follows. The photocatalyst coated body was placed in a calender weathering meter (SUGA test mechanism, S-300C) prescribed in JIS B7753. After 100 hrs, the test piece was taken out and the appearance change before and after the input was observed. As a result, no change was seen in appearance.
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