Photocatalyst composition, substance containing photocatalyst, and material functioning as photocatalyst and process for producing the same
Abstract
When a nitrogen oxide (nitrogen monoxide) is contacted with or approaches titanium dioxide functioning as a photocatalyst and compounded with either an amphoteric metal oxide having basic sites (alumina, etc.) or a basic metal oxide (barium oxide, strontium oxide, etc.), the nitrogen monoxide is oxidized into nitrogen dioxide (gas) with •OH which is an active oxygen species generated by the titanium dioxide upon irradiation with light. Since alumina is an amphoteric metal oxide and barium oxide and strontium oxide are basic metal oxides, oxygen atoms of these metal oxides function as basic sites for acidic gases. Consequently, the nitrogen dioxide, which is an acidic gas because of its molecular structure, is attracted by and chemically bonded to these oxygen atoms. Thus, the nitrogen dioxide is held on the metal oxide at positions close to the titanium dioxide, serving as a photocatalyst.

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38 claims: 16 independent, 22 dependent
- 1請求の範囲 1. 光の照射を受けると触媒として機能する光触媒と他の化合物が配合された 光触媒配合物であって、 前記他の化合物は、 前記光触媒が関与する触媒反応に供される被反応物が該触媒反応を受けて化学変 化し該被反応物の構造と前記触媒反応とで規定される最終生成物に変遷する場合、 前記光触媒との共存下で、 前記被反応物から前記最終生成物への変遷程度を高める よう機能する化合物である ことを特徴とする光触媒配合物。
- 2請求項 1記載の光触媒配合配合物であって、 前記他の化合物は、 前記被反応物或いは前記被反応物が前記触媒反応を受けて前記最終生成物に変遷 する以前に生成される中間生成物と化学的に結合する化合物である、 光触媒配合物。
- 3請求項 1又は請求項 2記載の光触媒配合物であって、 前記光触媒は、 照射された光のエネルギにより励起電子と正孔を生成し、 触媒表 面での酸素と水分の存在下で前記励起電子と正孔により活性酸素種を生成する光触 媒である、 光触媒配合物。
- 4請求項 3記載の光触媒配合物であって、 前記他の化合物は、 前記活性酸素種に基づく前記触媒反応に供される前記被反応 物或いは前記中間生成物と化学的に結合する両性金属酸化物、 塩基性金属酸化物又 は酸性金属酸化物の少なくとも一の金属酸化物である、 光触媒配合物。
- 5請求項 4記載の光触媒配合物であって、 前記他の化合物としての前記両性金属酸化物は、 A 1 2 0 3 、 Z nO、 S n〇、 Sn0 2 から選ばれた少なくとも一の金属酸化物であり、 前記塩基性金属酸化物は、 S rO、 B aO、 MgO、 C aO、 Rb 2 0 、 N a 2 0 、 K 2 0 から選ばれた少な くとも一の金属酸化物であり、 前記酸性金属酸化物は、 P 2 0 5 ある、 光触媒配合物。
- 6請求項 2ないし請求項 5いずれか記載の光触媒配合物であって、 前記他の化合物は、 その重量を a、 前記光触媒の重量を bと表した場合、 (a + b) 力 ? 約 0. 0001〜0. 8となるように配合されている、 光触媒配合物。
- 7請求項 2ないし請求項 6のいずれか記載の光触媒配合物であって、 前記光触媒と前記他の化合物とは、 約 0. 005〜0. 5 mの粒径範囲で調整 されて配合されている、 光触媒配合物。
- 8請求項 1ないし請求項 7いずれか記載の光触媒配合物であって、 前記光触媒と前記他の化合物に加え、 水酸基を化学吸着する性質を有する化合物 を第 3の成分として配合して備え、 前記水酸基を前記光触媒および前記第 3の成分としての化合物の表面に化学吸着 して保持し、 該保持された水酸基により親水性を発揮する、 光触媒配合物。
- 9請求項 8記載の光触媒配合物であって、 前記第 3の成分としての化合物は、 前記光触媒が有する湿潤熱と同程度以上の湿 潤熱を有する化合物である、 光触媒配合物。
- 10請求項 9記載の光触媒配合物であつて、 前記第 3の成分としての化合物は、 S i〇 2 , A l 2 〇 3 , Z r0 2 , Ge〇 2 , T h 0 2 , Ζ ηθから選ばれた少なくとも一の金属酸化物である、 光触媒配合物。
- 111 1. 請求項 8ないし請求項 10いずれか記載の光触媒配合物であって、 前記光触媒と前記他の化合物および前記第 3の成分としての化合物に加え、 抗菌 性を発揮する金属を第 4の成分として配合して備え、 前記第 4の成分としての金属は前記光触媒に担持されている、 光触媒配合物。
- 12請求項 1 1記載の光触媒配合物であって、 前記第 4の成分としての金属は、 前記光触媒が放出する自由電子の有する電位以 上の還元電位を有する金属である、 光触媒配合物。
- 13請求項 12記載の光触媒配合物であって、 前記第 4の成分としての金属は、 Ag、 Cu、 P d、 F e、 N i、 C r、 C o、 P t、 Au、 L i、 C a、 Mg、 Aし Z n、 Rh、 Ruから選ばれた少なくとも 一の金属である、 光触媒配合物。
- 14請求項 13記載の光触媒配合物であって、 前記第 4の成分として選ばれた金属の重量を c、 前記光触媒の重量を dと表した 場合、 (:ノ(1カ ? 約0. 00001〜0. 05となるように配合されている、 光触媒 配合物。
- 15光の照射を受けると触媒として機能する光触媒を有する光触媒含有材で めってヽ 請求項 1ないし請求項 7いずれか記載の光触媒配合物が塗料又は釉薬に混合分散 されてなる、 光触媒含有材。
- 16光の照射を受けると触媒として機能する光触媒を有する光触媒含有材で あつ一" 請求項 8ないし請求項 14いずれか記載の光触媒配合物が塗料又は釉薬に混合分 散されてなる、 光触媒含有材。
- 17基材層とその表面に形成された表面層とを有し、 光の照射を受けると光 触媒機能を発揮する材料であって、 前記表面層として、 請求項 1ないし請求項 7いずれか記載の光触媒配合物からなる表面層、 又は請求 項 1 5記載の光触媒含有材からなる表面層を有する、 光触媒機能発揮材。
- 18基材層とその表面に形成された表面層とを有し、 光の照射を受けると光 触媒機能を 揮する材料であって、 前記表面層として、 請求項 8ないし請求項 14いずれか記載の光触媒配合物からなる表面層、 又は請 求項 16記載の光触媒含有材からなる表面層を有する、 光触媒機能発揮材。
- 19請求項 18記載の光触媒機能発揮材料であって、 前記表面層は、 下記の条件 (1) 、 (2) のいずれかを満たす表面性状を有する。 (1) 表面層膜厚:約 0. 01〜約 3. 0 (2) 1%の硝酸銀溶液を表面層に付着させた状態で、 該表面層上における紫外線 強度が 1. 2 mW/ c m 2 で前記表面層に紫外線を 5分間照射した際の紫外線照射 前と紫外線照射後の表面層の色差 A E: 1〜 50
- 202 0 . 基材層とその表面に形成された表面層とを有し、 光の照射を受けると光 触媒機能を発揮する材料であって、 前記表面層は、 請求項 1ないし請求項 1 4いずれか記載の光触媒配合物がバインダを介在させて 前記基材層表面に形成された表面層である、 光触媒機能発揮材。
- 212 1 . 請求項 2 0記載の光触媒機能発揮材であって、 前記バインダは、 前記基材層の基材の変質温度以下の温度で、 重合若しくは溶融 して前記基材層表面に前記光触媒配合物を接着するバインダである、 光触媒機能発 揮材。
- 222 2 . 請求項 2 0又は請求項 2 1いずれか記載の光触媒機能発揮材であって、 前記バインダは、 釉薬又は塗料のいずれかである、 光触媒機能発揮材。
- 232 3 . 基材層とその表面に形成された表面層とを有し、 光の照射を受けると光 触媒機能を発揮する材料であって、 前記表面層は、 光触媒としての T i 0 2 に加え、 A 1 2 0 3 と、 S i 0 2 と、 抗 菌性を発揮する金属を含有する、 光触媒機能発揮材。
- 242 4 . 請求項 1 7ないし請求項 2 3いずれか記載の^!虫媒機能発揮材であって、 前記基材層は、 セラミック、 樹脂、 金属、 ガラス、 陶器、 木材、 珪カル板、 コン クリート板、 セメン ト板、 セメント押出整形板、 石膏ボード若しくはオートクレー プ養生軽量コンクリート板のいずれかの基材からなる、 光触媒機能発揮材。
- 252 5 . 請求項 1 7ないし請求項 2 4いずれか記載の 虫媒機能発揮材であって、 前記表面層は、 熱処理して形成されている、 光触媒機能発揮材。
- 262 6 . 請求項 1 7ないし請求項 2 5いずれか記載の 虫媒機能発揮材であって、 前記表面層の表面には、 抗菌性を発揮する金属又は金属化合物が固着されている、 光触媒機能発揮材。
- 272 7 . 基材層とその表面に形成された表面層とを有し、 光の照射を受けると光 触媒機能を発揮する材料の製造方法であって、 請求項 1ないし請求項 1 4いずれか記載の光触媒配合物又は該光触媒配合物が分 散された光触媒配合物分散ゾルを準備する工程と、 前記光触媒配合物又は前記光触媒配合物分散ゾルを前記基材層表面に層状に配設 する配設工程と、 前記表面層を形成する工程とを有することを特徴とする光触媒機能発揮材の製造 方法。
- 282 8 . 請求項 2 7記載の製造方法であって、 前記配設工程は、 前記光触媒配合物又は前記光触媒配合物分散ゾルを前記基材層表面に層状に配設 する際に、 前記光触媒配合物又は前記光触媒配合物分散ゾルを、 前記基材層表面に 層状に載置、 塗布或いは印刷する工程を有する、 光触媒機能発揮材の製造方法。
- 292 9 . 基材層とその表面に形成された表面層とを有し、 光の照射を受けると光 触媒機能を発揮する材料の製造方法であって、 請求項 1ないし請求項 1 4いずれか記載の光触媒配合物又は該光触媒配合物が分 散された光触媒配合物分散ゾルを準備する工程と、 前記基材層表面にバインダを層状に配設し、 バインダ層を形成する工程と、 前記光触媒配合物又は前記光触媒配合物分散ゾルを前記バインダ層表面に層状に 配設する配設工程と、 前記バインダの性質に応じて熱処理し、 前記表面層を形成する工程とを有するこ とを特徴とする光触媒機能発揮材の製造方法。
- 303 0 . 請求項 2 9記載の製造方法であって、 前記バインダは釉薬であり、 前記表面層を形成するに当たり、 前記釉薬の軟化温 度よりも 3 O t:以上 3 0 0 °C以下の範囲で高く、 且つ、 前記基材層の基材の変質温 度よりも低い温度環境下で熱処理する、 光触媒機能発揮材の製造方法。
- 313 1 . 請求項 2 9記載の製造方法であって、 前記バインダは塗料であり、 前記表面層を形成するに当たり、 前記基材層の基材 の変質温度以下の温度環境下で熱処理する、 光触媒機能発揮材の製造方法。
- 323 2 . 請求項 3 0記載の製造方法であって、 前記表面層を形成するに当たり、 約 1 5 0〜約 1 3 0 0 °Cの温度環境下で熱処理 する、 光触媒機能発揮材の製造方法。
- 333 3 . 請求項 2 7ないし請求項 3 2いずれか記載の製造方法であって、 前記表面層を形成する工程に続いて、 前記形成された表面層の表面に抗菌性を発 揮する金属又は金属化合物が分散された溶液を塗布する工程と、 前記金属又は金属 酸化物を前記表面層の表面に固着させる工程を有する、 光触媒機能発揮材の製造方 法。
- 343 4 . 請求項 2 7ないし請求項 3 2いずれか記載の製造方法であって、 前記配設工程は、 前記光触媒配合物又は前記光触媒配合物分散ゾルを層状に配設した後に、 抗菌性 を発揮する金属又は金属化合物が分散された溶液を塗布する工程を有し、 前記表面層を形成する工程は、 前記表面層の形成と同時に前記金属又は金属酸化物を前記表面層の表面に固着さ せる工程を有する、 光触媒機能発揮材の製造方法。
- 353 5 . 請求項 2 7ないし請求項 3 2いずれか記載の製造方法であって、 前記表面層を形成する工程に続いて、 前記形成された表面層の表面に抗菌性を発 揮する金属のイオンを含む金属塩水溶液を塗布する工程と、 前記表面層に紫外線を 照射して前記金属イオンの光触媒への光還元を利用して前記表面層における光触媒 に前記金属を担持 ·固定する工程を有する、 光触媒機能発揮材の製造方法。
- 363 6 . 光の照射を受けると触媒として機能する光触媒と前記他の化合物と前記 第 3の成分としての化合物と前記第 4の成分としての金属とが配合された請求項 1 1記載の光触媒配合物の製造方法であって、 前記光触媒と前記他の化合物と前記第 3の成分としての化合物のうち、 少なくと も前記光触媒が分散された光触媒分散ゾルを準備する工程と、 抗菌'性を発揮する金属のイオンを含む金属塩水溶液を前記光触媒分散ゾルに混合 し、 前記金属を第 4の成分として前記光触媒に担持する工程とを有することを特徴 とする光触媒配合物の製造方法。
- 373 7 . 光の照射を受けると触媒として機能する光触媒と前記他の化合物と前記 第 3の成分としての化合物と前記第 4の成分としての金属とが配合された請求項 1 1記載の光触媒配合物の製造方法であって、 前記光触媒と前記他の化合物と前記第 3の成分としての化合物のうち、 少なくと も前記光触媒が分散された光触媒分散ゾルを準備する工程と、 抗菌性を発揮する金属のィォンを含む金属塩水溶液を前記光触媒分散ゾルに混合 した後に前記金属の塩と前記光触媒とを共沈させ、 前記金属を第 4の成分として前 記光触媒に担持する工程とを有することを特徴とする光触媒配合物の製造方法。
- 383 8 . 光の照射を受けると触媒として機能する光触媒と前記他の化合物と前記 第 3の成分としての化合物と前記第 4の成分としての金属とが配合された請求項 1 1記載の光触媒配合物の製造方法であって、 前記光触媒と前記他の化合物と前記第 3の成分としての化合物のうち、 少なくと も前記光触媒が分散された光触媒分散ゾルを準備する工程と、 抗菌性を発揮する金属のイオンを含む金属塩水溶液を前記光触媒分散ゾルに混合 した後に紫外線を照射し、 前記金属イオンの光還元を利用して前記金属を第 4の成 分として前記光触媒に担持する工程とを有することを特徴とする光触媒配合物の製 造方法。
Independent claims38
415 paragraphs, as filed
0001Specification A photocatalyst combination thing, a photocatalyst content thing, and manufacturing method of photocatalyst function exertion Lumber material Technical field
0002Photocatalyst combination which contains the present invention and the photocatalyst which functions as receiving irradiation of light as a catalyst Manufacturing method of a thing and the photocatalyst function exertion Materials and photocatalyst combination thing using this photocatalyst combination thing It is related. Background art
0003The former and this kind of photocatalyst and the energy used for a catalyst reaction are nothing with light energies, such as sunlight. Since it is Endurance, that use is being expanded. For example, 2 acid -ized titanium which is a kind of a photocatalyst (T i 0)<sub>2</sub>the titanium dioxide of a Anatase type [ type / especially / crystallized ] -- it glared Light (ultraviolet rays) energy generates an excitation electron and an electron hole -- the generated excitation electron an electron hole -- the bottom of existence of oxygen on the surface of a catalyst and moisture -- O<sub>2</sub>-0 -- the reactive oxygen species of --, - 0 eta ('shows unpaired electron and means being radical species), etc. are generated. And air purification of presenting oxidation reaction by reactive oxygen species with nitrogen oxide in the atmosphere (nuOchi), and making it harmless reaction thing (nitric acid) using the radical character which these reactive oxygen species have Use, disassembly of the bacteria through oxidization of the organic ingredient, what is called an antibacterial use, etc. -- a proposal -- Being done.
0004By the way, at the process in which nitrogen oxide undergos oxidation reaction by reactive oxygen species, it is nitrogen dioxide (nu 0).<sub>2</sub>it is generated as an intermediate product -- these two nitrogen oxide receives oxidization further -- last It is considered as nitric acid-like. And the nitrogen oxide in the atmosphere reduces with generation of this nitric acid. It is carried out and the atmosphere is purified. For this reason, it is active oxygen in order to improve the reduction efficiency of nitrogen oxide. It is indispensable that a seed, nitrogen oxide, or nitrogen dioxide lives together. however, 2 acid Compound where-izing nitrogen was stabilized comparatively chemically (gas) it is -- since -- generated 2 Nitric oxide it secedes from base out of the system of a reaction, and the efficiency of oxidation reaction by reactive oxygen species falls -- consequential -- Deleting It becomes a situation where decrease efficiency also falls. Porous adsorbent like activated carbon is used and it is 2 acid. Power in which aiming at control of secession of-izing nitrogen is also considered<sup>?</sup>It is not necessarily an effect so that it may explain below. Result-like cannot be said.
0005It is this nitrogen dioxide the case where the nitrogen dioxide from which it once seceded in such adsorbent is adsorbed. It may not emit adsorbing in the fine pores of adsorbent. 2 [ for this reason, ] to which it stuck the outside of the system of oxidation reaction by nitric oxide power' reactive oxygen species -- him -- not undergoing oxidation reaction of a lever -- the maximum -- It does not become nitric acid which is a product throughout life. Therefore, finally nitrogen oxide is. It does not change even to nitric acid but reduction efficiency is checked. But coexistence with reactive oxygen species is possible. Field in the system of a reaction, Namely, 2 oxidization by which adsorbent was adsorbed in the field close to a photocatalyst Absorption of a substance [ in / in power s' which nitrogen oxidizes and becomes nitric acid, and the field close to a photocatalyst / adsorbent ] Since it wears and is restricted very much to the field whole [ ] (fine pores are included), It oxidizes even to nitric acid. It can be said that the rate of nitrogen dioxide which is not is high. That is, even if it uses adsorbent, they are two nitrogen oxide. The reduction of nitrogen oxide which let changes of until pass to a stop and nitric acid carrying out adsorption maintenance is that it is enough. It seems that it does not obtain.
0006do in order to solve the present invention and the above-mentioned problem -- that of the catalyst reaction in which a photocatalyst participates Final product of the thing with which attaining much more increase in efficiency or this catalyst reaction is presented to be reacted It aims at aiming at improvement in the reduction efficiency through changes. Opportunity which a photocatalyst achieves It sets it as other purposes to complement ability. The indication of an invention
0007In order [ above-mentioned ] to solve, it is a photocatalyst combination thing of The 1 of the present invention,
0008Photocatalyst distribution which contains the photocatalyst which functions as receiving irradiation of light as a catalyst, and other compounds It is Compound,
0009A compound besides the above,
0010The thing with which the catalyst reaction in which the above-mentioned photocatalyst participates is presented to be reacted undergos the catalyst reaction, and it is a chemical change. It is a front when changing to the final product which carries out and is specified at the structure and the above-mentioned catalyst reaction of this thing to be reacted. Under coexistence with an account photocatalyst, the changes grade from the above-mentioned thing to be reacted to the above-mentioned final product is raised It is a compound which obtains and functions.
0011It is characterized by things. According to the photocatalyst combination thing of The 1 of the present invention which has the above-mentioned composition, it is a final product from a thing to be reacted. Since a changes grade increases, the reduction efficiency of a thing to be reacted can be improved.
0012A mode is taken also in the photocatalyst combination thing of The 1 of the present invention which has the above-mentioned composition. It can do. The 1st mode,
0013A compound besides the above,
0014The above-mentioned thing to be reacted or the above-mentioned anti-[-ed ] Japan Society of Applied Physics power<sup>s</sup>The above-mentioned catalyst reaction is undergone and it is Change to the above-mentioned final product. It is a compound chemically combined with the intermediate product generated before To.
0015Others blended with the thing to be reacted or the intermediate product, and the photocatalyst in the mode of this The 1 It combines with a compound chemically and is held. And this thing to be reacted or intermediate product Other held compounds, Since it is not what takes a porous structure, a photocatalyst involves. They are these things to be reacted or middle generation in the outside of the system of the catalyst reaction to carry out, i.e., the field away from the photocatalyst. A thing is not set, it lets contiguity in the photocatalyst both blended pass -- inside of the system of a catalyst reaction These things to be reacted or an intermediate product is set. And a thing to be reacted or an intermediate product It is [ these things to be reacted or ] inside in the system of a catalyst reaction since combination is chemical. Lycium chinense can do between output certainly. as a result, photocatalyst combination thing of the mode of this The 1 the opportunity and intermediate product in which a catalyst reaction will be presented with a thing to be reacted if it depends -- further -- this catalyst reaction -- For the opportunity held is certainly securable -- a catalyst reaction can be advanced much more efficiently To. And the changes grade to a final product from a thing to be reacted through the improvement in efficiency of a catalyst reaction Since it rises, the reduction efficiency of a thing to be reacted can be improved.
0016The 2nd mode,
0017the above-mentioned photocatalyst and the energy of light with which it was irradiated generate an excitation electron and an electron hole -- the catalyst surface Photocatalyst which generates reactive oxygen species by the above-mentioned excitation electron and an electron hole under existence of oxygen and moisture it is .
0018Inside of the system of the catalyst reaction based on the reactive oxygen species which the photocatalyst generated according to the mode of this The 2 A thing to be reacted or an intermediate product is set, opportunity with which an anti-[-ed / these ] Japan Society of Applied Physics power' catalyst reaction is presented the opportunity for this catalyst reaction to be further presented with an intermediate product is certainly securable -- catalyst reaction It can be made to go on efficiently [ one layer of Ri ]. Therefore, This which improves the reduction efficiency of a thing to be reacted It can do. In this case, as a photocatalyst, it is a titanium dioxide. (T h 0)<sub>2</sub>) -- zinc oxide (Z n O) and vanadium oxide (V)<sub>2</sub>0<sub>5</sub>Tungstic oxide (W0)<sub>3</sub>etc. -- it can illustrate To. these photocatalysts are not caught by the crystallized type which it has -- for example, you A Ze type, a rutile type, or bull Tsukai If it is in the titanium dioxide which has a A type crystallized type, which crystallized type may be used. most -- 2 oxidization Chi you 1Ze type [ from the ease of acquisition, etc. ] tongue power '-- it is desirable. the thing with which the catalyst reaction based on reactive oxygen species is presented to be reacted -- the -- as an intermediate product and a final product -- nitrogen oxide, nitrogen dioxide, nitric acid, and sulfur oxidization A thing, sulfur dioxide, sulfuric acid or sulfurous acid, carbon monoxide, carbon dioxide, a carbonic acid, etc. are illustrated. Things are made. ammonia can also be illustrated as a thing to be reacted -- it becomes nitric oxide, nitrogen dioxide, and nitric acid which were generated from the intermediate product and final product in this case, and ammonia.
0019The 3rd mode,
0020a compound besides the above, and the above-mentioned thing with which the above-mentioned catalyst reaction based on the above-mentioned reactive oxygen species is presented to be reacted or the both sexes metal oxide chemically combined with the above-mentioned intermediate product and a basic metal oxide -- or -- It is at least 1 metal oxide of an acid metal oxide.
0021Inside of the system of the catalyst reaction based on the reactive oxygen species which the photocatalyst generated according to the mode of this The 3 In setting a thing to be reacted or an intermediate product, a thing to be reacted or an intermediate product -- acidity in a certain case, what is called a base point is originated at the atomic arrangement of a basic metal oxide -- specific -- original -- it can form by a child -- certain in a basic metal oxide, a thing to be reacted, or an intermediate product at this base point It can be made to join together chemically. a thing to be reacted or an intermediate product -- base Specific atom which originates what is called Acid point at the atomic arrangement of an acid metal oxide in a certain case it can form -- certainly chemical in an acid metal oxide, a thing to be reacted, or an intermediate product at this Acid point It can be made to join together. furthermore -- if other compounds are used as a both sexes metal oxide -- this -- the specific atom resulting from the atomic arrangement of a both sexes metal oxide -- sex of a thing to be reacted or an intermediate product Since it can be considered as the base point or Acid point which suited quality A thing to be reacted or middle student A product is [ Then, this both sexes metal oxide, a thing to be reacted, or ] inside at basic and acid any. Between output can be combined chemically certainly.
0022In this case, as a both sexes metal oxide, it is alumina. (A 1)<sub>2</sub>0<sub>3</sub>Zinc oxide (Z n O) and tin oxide (S nO, S n0)<sub>2</sub>etc. -- it can illustrate. Basic metal oxidization Nessim (MgO), a calcium oxide (C aO), and rubidium oxide As a thing, they are strontium oxide (S r 0) and barium oxide (B a 0) and an oxidization mug. (Rb)<sub>2</sub>0 ) -- and Sodium Oxide (Na)<sub>2</sub>0 ) -- and Potassium Oxide (K)<sub>2</sub>O etc. -- it can illustrate. As an acid metal oxide, it is phosphorus oxide. (rho)<sub>2</sub>0<sub>5</sub>etc. -- it can illustrate. Forming a base point or Acid point in these metal oxides and a metal oxide are constituted. Metal atom in the difference and the metal oxide surface of electronegativity of a metal atom and an oxygen atom to carry out It originates in the atomic arrangement of an oxygen atom. and the catalyst reaction based on reactive oxygen species -- For -- the thing to be reacted and intermediate product of the To be above are made to correspond -- the above-mentioned basic metal oxide, an acid metal oxide, and a both sexes metal oxide may be chosen suitably. A zinc oxide is a photocatalyst. Since it is and is a both sexes metal oxide, when a zinc oxide is chosen as a photocatalyst, of course, a zinc oxide is not chosen as a both sexes metal oxide.
0023alumina whose titanium dioxide and compound photocatalysts are both sexes metal oxides here, and reaction-ed a thing -- nitrogen oxide (nitric oxide) the case where it carries out is taken for an example -- situation row of advance of a catalyst reaction The situation of combination by alumina is explained. in addition -- in this case -- 2 oxidization Chita nitric oxide oxidizes with the reactive oxygen species which A generated -- an intermediate product -- nitrogen dioxide It becomes. it is typically shown in Drawing 1 -- as -- a photocatalyst -- nitric oxide is contact to a titanium dioxide or -- if it approaches -- this nitric oxide, A titanium dioxide generates in response to irradiation of light. and 0eta (hydroxyl radical) which is Reactive oxygen species Nitrogen dioxide (gas) It oxidizes. To (figure 1 (a)). this nitrogen dioxide is acidity from that molecular structure -- since alumina is both 14^Genus oxide and makes a base point that oxygen atom it has to acidic gas, it can draw near to nitrogen dioxide and this oxygen atom, joins together chemically, and is held at alumina
0024(Drawing 1 (b)). the power which draws nitrogen dioxide near to an oxygen atom is coulomb force -- combination is chemical.
0025The nitrogen dioxide combined with the oxygen atom of alumina and the titanium dioxide which is photocatalysts are approached. At that of Be kept, it is a hydroxyl radical. Oxidation reaction triggered by - 0H (catalyst anti- Response) (figure 1 (b)) in a system. for this reason, opportunity power s' in which nitrogen dioxide oxidizes by this hydroxyl radical and 0 H -- it is secured certainly -- oxidization of nitrogen dioxide advances efficiently. (figure 1 (c)) considered to be joined together 'held by the oxygen atom of the alumina made into the above-mentioned base point with form of nitric acid (final product) with oxidized nitrogen dioxide, nitrate ion, and hydrogen atom in hydroxyl radical' OH.
0026in this case, it will be got blocked if nitrogen dioxide exists from the beginning -- nitrogen dioxide -- a thing to be reacted -- if there is and this nitrogen dioxide oxidize directly with the reactive oxygen species which the titanium dioxide generated. With The nitrogen dioxide chemically combined with alumina as mentioned above is also these reactive oxygen species. It will oxidize. If it puts in another way, in such a case, alumina will reacting be. Thing barrel nitrogen dioxide will be combined chemically.
0027Next, it is sulfur monoxide by the reactive oxygen species which the titanium dioxide generated. (SO) and carbon monoxide
0028(CO) The situation of combination by alumina when power oxidization is carried out is explained. These If an oxide oxidizes, it will become sulfur dioxide, carbon dioxide, and beam acidic gas. as [ show / for this reason, / in Drawing 2 / typically ] -- aluminum which is sulfur dioxide and a both sexes metal oxide it combines with the oxygen atom which is a base point which Na has and adjoins chemically -- alumina -- maintenance -- To be. a figure -- as [ show / in 3 / typically ] -- carbon dioxide, a carbon atom and oxygen atom (figure 3 (a)) Independent oxygen atom which serves as a base point from it being combinable by different bond order as mentioned above or oxygen atom [ (figure 3 (b)) ] which serves as a base point and adjoins -- chemical it joins together -- it is held at alumina. And it further reacts with reactive oxygen species (hydroxyl radical' 0H) which the 2 Oxidizing sulfur yellow combined 'held in this way and a titanium dioxide generated. Sulfuric acid and sulfurous acid (final product) Becoming, carbon dioxide is a carbonic acid. (final product) It becomes. If it is in carbon dioxide, it generates in the case of generation of reactive-oxygen-species barrel hydroxyl radical' 0H. Reaction based on the radical hydrogen atom and reactive oxygen species which are carried out, Methane methano 1 it is thought that it changes to Le -- in this case -- this Methane methano 1 Le -- final product Les and To.
0029The 4th mode,
0030When the weight of a and the above-mentioned photocatalyst is expressed for a compound besides the above, and its weight as b, aZ (a+b) is abbreviation 0.000. It is blended so that it may be set to 1*0.8.
0031Like the mode of this The 4, a (a+b) is abbreviation 0.000. If it is one or more, It is a table at a. Other compounds carried out (a both sexes metal oxide, a basic metal oxide, and an acid metal oxide) A chemical combination of a thing to be reacted or an intermediate product is secured, the efficiency fall of a catalyst reaction is come, and it is It was. Since there is nothing, it is desirable. it is expressed with b if it is (a+b) 0.8 or less a Z Power there is not too little quantity of a photocatalyst to other above-mentioned compounds -- the efficiency of a catalyst reaction -- low -- Since the bottom is not caused, it is desirable.
0032in this case, the quantity of a photocatalyst, and a photocatalyst and the above-mentioned compound which is the other combination thing -- the -- others -- receiving a total amount with the combination thing of the others concerned, when there is a combination thing -- abbreviation 2 0*9 It may be a 5 w t % grade.
0033The 5th mode,
0034the above-mentioned photocatalyst, and a compound besides the above -- about 0.0 0 the particle diameter range of 5* 0 .5 mu m -- adjustment -- Have been combination is carried out.
0035The photocatalyst and other compounds like the mode of this The 5 (a both sexes metal oxide, a basic metal oxidization thing, an acid metal oxide) Particle diameter is abbreviation 0.0. 0 If it is the range of 5* 0 .5 m, Ball Particle diameter adjustment can be easily performed by the existing grinding apparatus, such as Mill, or sol and the gel method, and it is desirable. According to the mode of this The 5, a remarkable difference is not looked at by the particle diameter of a photocatalyst and other compounds. A photocatalyst and other compounds approach by the particles of the almost same size. therefore -- in addition to this -- Make the thing to be reacted or intermediate product chemically combined with the compound approach a photocatalyst. it can do -- efficient-ization through sufficient reservation of the advance opportunity of a catalyst reaction can be attained -- good Up it is by carrying out -- .
0036The 6th mode,
0037it adds to a compound besides the above-mentioned photocatalyst and the above -- compound which has the character which carries out chemical adsorption of the hydroxyl group Blend as the 3rd ingredient and have.
0038carrying out chemical adsorption of the above-mentioned hydroxyl group to the surface of the above-mentioned photocatalyst and the compound as an ingredient of above-mentioned The 3 Keep is carried out -- hydrophilicity is demonstrated with the held hydroxyl group.
0039The hydroxyl group generated through the catalyst reaction of a photocatalyst in the mode of this The 6 and a photocatalyst are bases. Chemical adsorption is carried out to the surface of the compound of the ingredient of The 3, and it is held on it. and the catalyst surface -- Moisture (air Nakamizu steam, rain water, etc.) to kick since the situation used as zero does not occur -- light -- irradiation -- It can be said that between Being done and a hydroxyl group are generated continuously. for this reason -- reaching to an extreme of a hydroxyl group The -- it is held by high density -- since that maintenance is moreover made by combination called chemical adsorption It can be said that the hydroxyl group is held firmly. while [ it ] not being irradiated with light on the other hand -- light the hydroxyl group currently generated by then although the hydroxyl group generation by a catalyst did not break out -- photocatalyst it is firmly held on the surface of the compound of the 3rd ingredient -- a hydroxyl group is removed carelessly There is no To. And if anew irradiated with light, the density of a hydroxyl group will fall by then. Even if it is carrying out, it returns to a high-density holding state promptly. therefore, light of the mode of this The 6 if a catalyst combination thing is fixed to a certain substrate surface -- this substrate surface -- certainly high hydrophilicity it carries out -- it can continue at a long period of time, and can maintain this high hydrophilicity certainly. That is, it becomes the hydrophilic grant material which gives high hydrophilicity to the photocatalyst combination thing of the mode of this The 6, and the substrate surface. Here, the effect which hydrophilicity brings about is explained. hydrophilicity -- an angle of contact with water -- strong -- Seki it supports -- hydrophilic power<sup>?</sup>If high, this angle of contact will become small. the -- on the other hand -- angle-of-contact power -- if small -- the -- Since it hydraulic-power s Becomes difficult to stop at the surface, flow and fall with the dirt adhering to the surface, and this water. It is removed from the surface. Nothing like the city dust containing many Good and oleophilic ingredients or argillite If the hydrophilicity which can present the angle of contact which is less than angles of contact, such as nature dust of a machine, is acquired, these dust can be removed, without demonstrating compatibility. And an angle of contact is Near to the degree of zero. Since hydrophilicity diffuses a rise and water in the shape of a film on the substrate surface and it becomes easy to flow as To, it describes above. Not only city dust but also inorganic dust flows with water from the substrate surface easily, and it falls. This place When heightening Synthesis and the dirt prevention effect, an angle of contact is abbreviation 2. This which is a value near [ in below 0 ° ] zero It is more desirable.
0040Therefore, they are cars, such as the building inside-and-outside wall surface, a car, a train, about the photocatalyst combination thing of the mode of this The 6. It carries out with the high hydrophilicity given in this way when it fixed to both the body surface, and is high Stain. The Prevention effect can be produced. In this case, if rain falls on these surfaces occasionally, it will be hydrophilic high power.<sup>s</sup>Since it is given, surface particulates and pollutants are rain water to each time of the rain. Since it is washed away from the surface, self-consecration of these surfaces is carried out. That is, Flow of water Along with Re, So-called strength soiling due to rain trace, such as particulates, is effectively controlled in the shape of a line. If the photocatalyst combination thing of the mode of this The 6 is fixed to the surfaces, such as glass, a lens or a mirror, it can carry out with high hydrophilicity and can produce the high antifog effect.
0041The 7th mode,
0042The compound as an ingredient of above-mentioned The 3, and heat of wetting which the above-mentioned photocatalyst has and humidity more than comparable It is a compound which has heat.
0043the substance in which a hydroxyl group may exist in heat of wetting and the surface shows the maintenance characteristic of the hydroxyl group of the surface it can regard as an index, so that heat of wetting is high -- the grade of hydroxyl group maintenance -- high -- a hydroxyl group -- dense A degree is high. therefore, the hydroxyl group which the photocatalyst generated according to the mode of this The 7 -- effect it is high-density, and chemical adsorption is carried out [ Result ] to the compound of the 3rd ingredient, and it can hold -- the substrate surface -- high parents It can continue at more certain and a long period of time, and can give water. In this case, it is Special as a photocatalyst. It is Chita Near's desirable heat of wetting, and a you 1Ze type, and isX[ 320*512 ] 10. --<sup>3</sup>Jm--<sup>2</sup>It is a rutile type and is 293*645x10. --<sup>3</sup>J m--<sup>2</sup>It comes out and is 500x10 from a certain thing. --<sup>3</sup>Jm--<sup>2</sup>It is more preferred that it is a compound which has the above heat of wetting.
0044The 8th mode,
0045The compound as an ingredient of above-mentioned The 3 is S iO.<sub>2</sub>, A 1<sub>2</sub>0<sub>3</sub>, Z r 0<sub>2</sub>, G e 0<sub>2</sub>, Th0<sub>2</sub>It is at least 1 metal oxide chosen from Z etatheta.
0046The heat of wetting of Chita Near especially desirable as these metal oxides and a photocatalyst, and A wet more than equivalent Since it has Lubricant, the maintenance density of a hydroxyl group increases more and is preferred. In particular, it is silica. (S i O)<sub>2</sub>Alumina (A 1)<sub>2</sub>0<sub>3</sub>G e 0<sub>2</sub>, Th0<sub>2</sub>Is and its range of heat of wetting which it has The maximum which can be set isX[ 1000 ] 10. --<sup>3</sup>J m1<sup>2</sup>It is more desirable than To overcome.
0047In this case, each compound as the 3rd ingredient (S i 0)<sub>2</sub>, A 1<sub>2</sub>0<sub>3</sub>Z rO<sub>2</sub>, G e 0<sub>2</sub>, Th0<sub>2</sub>Other compounds blended by Z nO and the present invention with the thing aiming at reduction to be reacted, and photocatalyst (A 1)<sub>2</sub>0<sub>3</sub>Z nO, S nO, S n0<sub>2</sub>S rO, B aO, MgO, C aO, R b<sub>2</sub>0 N a<sub>2</sub>0 K<sub>2</sub>0 P<sub>2</sub>0<sub>5</sub>Combination It is taken into consideration and set. Other Conversion which will be blended with a photocatalyst if an example is given and explained It is A 1 as Compound.<sub>2</sub>0<sub>3</sub>When it selects, they are a compound as the 3rd ingredient, and ingredient duplication. It is A 1 in order to avoid.<sub>2</sub>0<sub>3</sub>5i0 of an except<sub>2</sub>, Z r 0<sub>2</sub>, G e 0<sub>2</sub>, Th0<sub>2</sub>Z nO is selected as an ingredient of The 3. And A 1 as other compounds<sub>2</sub>0<sub>3</sub>The Reduced object Other Conversion when a thing to be reacted or its intermediate product is chemically uncombinable It is A 1 as Compound.<sub>2</sub>O<sub>3</sub>Z n 0 of an except, S nO, S n0<sub>2</sub>S rO, B aO, MgO, C aO, Rb<sub>2</sub>O N a<sub>2</sub>0 K<sub>2</sub>O ?<sub>2</sub>0<sub>5</sub>Mosquito selection is carried out and it is A 1 as the 3rd ingredient.<sub>2</sub>0<sub>3</sub>Above including each compound (S i 0)<sub>2</sub>, A 1<sub>2</sub>0<sub>3</sub>, Z r 0<sub>2</sub>, G e 0<sub>2</sub>, T h -
004810
0049O<sub>2</sub>Either of Z nO is selected. Z etatheta It is the same even if it attaches.
0050The 9th mode,
0051it adds to a compound besides the above-mentioned photocatalyst and the above, and the compound as an ingredient of above-mentioned The 3 -- antibacterial properties Blend the metal to demonstrate as an ingredient of The 4, and have it.
0052The metal as an ingredient of above-mentioned The 4 is supported by the above-mentioned photocatalyst.
0053while being irradiated with light in the mode of this The 9, the photocatalyst itself can achieve -- anti- -- light is not irradiated with the bacillus function -- supporting this antibacterial function to a photocatalyst, if it does It can achieve by Metal. For this reason, the antibacterial function which a photocatalyst achieves is complemented. Things are made and synergistic antibacterial properties can be demonstrated with the metal and the photocatalyst which demonstrate antibacterial properties. The 10th mode,
0054More than potential that the free electron which the metal as an ingredient of above-mentioned The 4 and the above-mentioned photocatalyst emit has It is the metal which has reduction potential.
0055reduction potential in which this metal has support of the metal to a photocatalyst in the mode of this The 10 The -- it can carry out easily. in this case, Ag, Cu, P d, F e, N i, C r, C o, P t, Au, L i, C a, and Mg -- it A carried out and was chosen out of Z n, Rh, and R u -- few -- Both -- if it is the metal of 1 since it has the above-mentioned reduction potential, it is desirable -- since Ag, Cu, F d, P t, Au, and reduction potential have a positive value, reduction support breaks out -- easy -- especially -- good -- better Les, And it is c/d power the case where d When table of the weight of c and a photocatalyst is carried out for a metal selected as an ingredient of The 4, and its weight.<sup>s</sup>it is blended so that it may be set to about 0.00001*0.05 things -- power -- it is desirable. namely, the metal of the ingredient of The 4 -- 0.00001 (= cZd) -- the above -- that The, the situation where there is too little metal concerned to completely demonstrate synergistic antibacterial properties not occurring -- 0.05 (= c/d) -- the metal concerned will become superfluous if it is the following -- Touch of a photocatalyst It is desirable for the situation of having a bad influence on an intermediation reaction not occurring.
0056Photocatalyst content material of The 2 of the present invention,
0057it is the photocatalyst content material which has a photocatalyst which functions as receiving irradiation of light as a catalyst -- the photocatalyst combination thing of The 1 of the above-mentioned present invention, or the photocatalyst combination thing of each of that mode -- a paint or Glaze It comes to carry out mixed distribution at medicine.
0058With the photocatalyst content material barrel paint and glaze of The 2 of the present invention which have the above-mentioned composition, it is the present invention. .
00591 One The reduction efficiency of that it is the same as that of the photocatalyst combination thing of The 1 and a thing to be reacted is improved, or, as for Lycium chinense, a thing to be reacted or an intermediate product is made certainly in the system of a catalyst reaction. therefore, this paint -- an application -- it sets on the surface of a Was done thing -- or it sets on the surface of that by which glaze was Glazed(ed) -- thing to be reacted It is efficiently reducible. it sets on these surfaces -- a thing to be reacted -- a catalyst -- anti- -- the opportunity with which Response is presented, and the opportunity for this catalyst reaction to be further presented with an intermediate product -- certain -- reservation it comes -- a catalyst reaction can be advanced much more efficiently.
0060In this case, that it is easy to be the existing thing, the paint and glaze which are the candidates for mixed distribution of a photocatalyst and a compound are Fritz, such as glaze materials, for example, feldspar, and potassium carbonate, if it is in the case of glaze. A etc. and Both The photocatalyst and the compound are distributing in solution. distributed mixture of a photocatalyst and a compound -- the time if it carries out, it may blend with the above-mentioned glaze materials in the process of glaze manufacture -- completed glaze It may blend in advance of the Glazed.
0061In the photocatalyst content material of The 2 of the above-mentioned present invention,
0062the above-mentioned photocatalyst and the energy of light with which it was irradiated generate an excitation electron and an electron hole -- the catalyst surface Photocatalyst which generates reactive oxygen species by the above-mentioned excitation electron and an electron hole under existence of oxygen and moisture It is.
0063A compound besides the above, and the above-mentioned thing with which the above-mentioned catalyst reaction based on the above-mentioned reactive oxygen species is presented to be reacted Or both sexes metal oxide chemically combined with the above-mentioned intermediate product, a basic metal oxide -- or -- it is at least 1 metal oxide of an acid metal oxide -- photocatalyst content material (a paint or glaze) it is -- if -- there are the following advantages.
0064according to this photocatalyst content material, joint and maintenance ensure a thing to be reacted or an intermediate product by a base point or Acid point like the mode which ** intermediation combination thing of The 1 of the present invention described above -- reactive oxygen species As for Lycium chinense, these things to be reacted or an intermediate product is made in the system of the based catalyst reaction. therefore, this photocatalyst content -- material -- it sets on the surface of that to which the paint was applied -- or glaze it sets on the surface of that by which Force application was carried out -- advancing a catalyst reaction much more efficiently it can do -- the reduction efficiency of a thing to be reacted can be improved through this. The of the present invention
0065photocatalyst which has a compound of the ingredient of The 3 like the mode of The 6* The 8 of the photocatalyst combination thing of 1 if it is when a combination thing is used, it sets on these surfaces -- it was based on high hydrophilicity -- high The dirt prevention effect can be produced and it is desirable. Photocatalyst combination thing of The 1 of the present invention -
006612 The 9* The 1 Case where the photocatalyst combination thing which has the metal of the ingredient of The 4 like the mode of 0 is used if it is, it sets on these surfaces -- it is with the metal and the photocatalyst which demonstrate antibacterial properties -- synergistic Antibacterial properties can be demonstrated and it is desirable.
0067If it is in the photocatalyst content material of The 2 of this present invention, especially a paint, it is in existing structure things, such as a guardrail of building construction inside-and-outside walls, such as the existing building, a house, and a bridge, or a road, and a noise-proof wall. It carries out with this paint and can form the coat of photocatalyst content material. therefore, an existing structure thing -- -ed -- The reduction efficiency of a reaction thing is easy for what can also produce the high dirt prevention effect highly. It is changeable.
0068Photocatalyst function exertion material of The 3 of the present invention,
0069it has a base material layer and the surface coat formed in the surface -- if irradiation of light is received -- photocatalyst function It is the material to demonstrate.
0070As the above-mentioned surface coat,
0071The surface consisting of the photocatalyst combination thing of The 1 of the above-mentioned present invention, or the photocatalyst combination thing of each of that mode Photocatalyst function which has a layer or a surface coat which consists of the above-mentioned photocatalyst content material of The 2 of the present invention It is exertion material.
0072the photocatalyst combination thing or photocatalyst content material in which the photocatalyst function exertion material of The 3 of this present invention has the metal as an ingredient of The 4 in addition to the compound as the 3rd ingredient, or the ingredient of this The 3 , -- if it is in some which have a surface coat
0073Above-mentioned surface coat and following condition (1) Voice which has the surface quality with which either of (2) is filled Suppose like.
0074(1) Surface coat film thickness : abbreviation 0.0 1* abbreviation 3 .omicron mu taueta
0075(2) Ultraviolet rays on the surface coat in the state where the silver bath of 1 % was made to adhere to a surface coat Intensity is 1 .2 mW/ c m.<sup>2</sup>Ultraviolet exposure at the time of coming out and irradiating the above-mentioned surface coat with ultraviolet rays for 5 minutes Color difference delta epsilon of the surface coat a front and after an ultraviolet exposure : 1*5 0
0076in the photocatalyst function exertion material of this mode, the compound as an ingredient of The 3 is contained in a surface coat since it becomes things -- the compound of the ingredient of this The 3 -- photocatalyst combination thing of The 1 of the present invention it sets to this surface coat like the The 6* 8th mode -- angle-of-contact power<sup>?</sup>Small intermediary hydrophilicity It can improve and can produce the high dirt prevention effect. and surface coat film thickness -- abbreviation 0.0 1 if it is more than /^m -- film (surface coat) since it is not too thin -- contact of the surface coat itself presenting-as this material-angle power -- it can do certainly and is desirable. that is, contact with a big substrate even if it has an angle, an angle of contact becomes small by the surface coat formed in this substrate -- high Stain The Prevention effect can be produced. Since the adhesion nature of the surface coat to a substrate is maintainable on the other hand if surface coat film thickness is below abbreviation 3 .0 m, it is surface coat exfoliation. (film exfoliation) It can control and is good Up. It is by carrying out and is .. The same may be said of what has the metal as an ingredient of The 4 in addition to the compound as the 3rd ingredient.
0077moreover -- being irradiated with the silver ion in the silver bath adhering to a surface coat, and ultraviolet rays -- excitation state reduction precipitation is carried out by receiving an excitation electron from the photocatalyst which became -- coloration is carried out. For this reason, it is color difference before and after an ultraviolet exposure. deltaepsilon power observation is carried out. Therefore, it is This, so that there is much generation of an excitation electron. Color difference deltaepsilon becomes large. The amount of generation of an excitation electron determines the size of the optical activity of a photocatalyst. Since it is a factor, it is color difference about a photocatalyst activity size. It can evaluate using deltaepsilon.
0078Since reactive oxygen species, such as hydroxyl radical and O H, are generated in the air, the excitation electron of Insecticide is photocatalyst activity power.<sup>5</sup>', so that it is large -- namely, color difference deltaepsilon power<sup>s</sup>They are activities, such as hydroxyl radical' O H, so that it is large. Many oxygen kinds are generated.
0079By the way, the compound of the ingredient of The 3 contained in a surface coat, the excitation electron of a photocatalyst -- generation it has a role holding hydroxyl radical and O H carried out -- quantity of generated hydroxyl radical and O H the hydroxyl group density on the surface of a compound of the 3rd ingredient also increases, so that it is large -- the angle of contact of water -- small -- It becomes and hydrophilicity increases. It is organicity of a surface coat, so that there is much quantity of hydroxyl radical and O H. The amount of disassembly of a compound becomes advantageous to increase and hydrophilicity. therefore, color difference Table in which deltaepsilon shows one or more if it is a surface layer, it has sufficient photocatalyst activity to form high hydroxyl group density -- this up to the grade which can produce the angle of contact of a surface coat to depend, and the dirt prevention effect -- certain -- smallness -- it seems that To can be carried out -- it is desirable. By per one of these, and surface area unit area Quantitative force of a photocatalyst to Nda 1<sup>s</sup>' -- if it increases -- color difference Power in which deltaepsilon becomes large in this case -- substrate Adhesion nature falls and it is thought that exfoliation of a surface coat occurs easily. For this reason, color difference △ E is 5. If it is a surface coat which shows zero or less, it is desirable from a viewpoint of controlling exfoliation of a surface coat. Photocatalyst function exertion material of The 4 of the present invention,
0080it has a base material layer and the surface coat formed in the surface -- if irradiation of light is received -- photocatalyst function It is the material to demonstrate.
0081Previous-words £ surface coat,
0082The photocatalyst combination thing of The 1 of the above-mentioned present invention or the photocatalyst combination thing of each of that mode is a binder. It is the photocatalyst function exertion material which is the surface coat which made intervene and was formed in the above-mentioned base material layer surface. In the 4th photocatalyst function exertion material of this present invention,
0083it is the temperature below the deterioration temperature of the above-mentioned binder and the substrate of a base material layer -- polymerizing or fusing -- basis It is considered as considering it as the binder which pastes up a photocatalyst combination thing on the material layer surface, glaze, or a paint. things -- mosquito<sup>?</sup>It is suitable.
0084Photocatalyst function exertion material of The 5 of the present invention,
0085it has a base material layer and the surface coat formed in the surface -- if irradiation of light is received -- photocatalyst function It is the material to demonstrate.
0086The above-mentioned surface coat and T i 0 as a photocatalyst<sub>2</sub>It is alike, adds and is A 1.<sub>2</sub>0<sub>3</sub>S i 0<sub>2</sub>Antibacterial properties It is the photocatalyst function exertion material containing the metal which demonstrates a sex.
0087With the photocatalyst function exertion material of The 3 of the present invention thru/or The 5 which has the above-mentioned composition, it is formation to a base material layer it sets on the surface of the surface coat carried out -- Deleting of that it is the same as that of the photocatalyst combination thing of The 1 of the present invention, and a thing to be reacted improving decrease efficiency Or -- the inside of the system of a catalyst reaction -- a thing to be reacted or an intermediate product -- certain -- Lycium chinense It can do. therefore, it sets on the surface coat surface of this photocatalyst function exertion material -- a thing to be reacted -- efficiency the opportunity and intermediate product in which it is well reducible and a catalyst reaction is presented with a thing to be reacted -- further -- This the opportunity with which a catalyst reaction is presented is certainly securable -- a catalyst reaction -- more -- much more -- efficient -- advance -- To -- things are made. moreover -- since the metal which demonstrates antibacterial properties to a surface coat is contained -- this table it sets to a surface layer -- synergistic antibacterial properties can be demonstrated with the metal and the photocatalyst which demonstrate antibacterial properties -- good -- better -- There.
0088In The 3 of the above-mentioned present invention, and the 4th photocatalyst function exertion material,
0089the above-mentioned photocatalyst and the energy of light with which it was irradiated generate an excitation electron and an electron hole -- the catalyst surface Photocatalyst which generates reactive oxygen species by the above-mentioned excitation electron and an electron hole under existence of oxygen and moisture It is.
0090A compound besides the above, and the above-mentioned thing with which the above-mentioned catalyst reaction based on the above-mentioned reactive oxygen species is presented to be reacted Or both sexes metal oxide chemically combined with the above-mentioned intermediate product, a basic metal oxide -- or -- it is at least 1 metal oxide of an acid metal oxide -- if it is photocatalyst function exertion material, there are the following advantages.
0091the mode which the photocatalyst combination thing of The 1 of the present invention described above according to this photocatalyst function exertion material -- said -- him -- joint and maintenance ensure a thing to be reacted or an intermediate product by a base point or Acid point -- active acid Lycium chinense comes out of these things to be reacted or an intermediate product in the system of the catalyst reaction based on a matter kind. It cuts. therefore, it sets on the surface coat surface of this photocatalyst function exertion material -- a catalyst reaction -- more -- much more -- it can be made to go on efficiently -- improving the reduction efficiency of a thing to be reacted through this It can do. the mode of The 6* The 8 of the photocatalyst combination thing of The 1 of the present invention -- like -- Formation of The 3 a part -- if it is when the photocatalyst combination thing or photocatalyst content material which has a compound is used, it sets on these surfaces -- the high dirt prevention effect based on high hydrophilicity can be produced -- good -- better -- There. The 9* The 1 of the photocatalyst combination thing of The 1 of the present invention if it is when the photocatalyst combination thing or photocatalyst content material which has the metal of the ingredient of The 4 like the mode of 0 is used, it sets on these surfaces -- it is with the metal and the photocatalyst which demonstrate antibacterial properties -- it is exertion about synergistic antibacterial properties It comes and is desirable.
0092This which takes a mode also in the photocatalyst function exertion material of The 3 of the above-mentioned present invention thru/or The 5 It can do. In the 1st mode, they are the above-mentioned base material layer, ceramics, resin, metal, glass, a china, wood, a Silica Cal board, a concrete slab, a cement plate, and cement. A A extrusion plastic surgery board and gypsum It consists of one substrate of the Vo 1 Do or Wow 1 Tokurepe care-of-health lightweight concrete boards. According to this mode, they are these substrate mosquitoes.<sup>?</sup>the place used, for example, a building, a house, and bridge it sets on building construction inside-and-outside walls, roads, etc., such as a beam, -- a photocatalyst function can be exhibited, environmental pollutants, such as nitrogen oxide, SOx, and carbon dioxide, can be disassembled, and air purification can be attained. furthermore -- if it is when the photocatalyst combination thing which has a compound of the 3rd ingredient is used -- These it sets on a Construction work inside-and-outside wall, a road, etc. -- the high dirt prevention effect based on high hydrophilicity is produced To is made.
0093the 2nd mode -- the above-mentioned surface coat and heat treatment -- for example, it is calcinated and formed. According to this mode, a surface coat can be firmly formed in a base material layer.
0094The metal or metallic compounds which demonstrates antibacterial properties in the surface of the above-mentioned surface coat in the 3rd mode It adheres. While being irradiated with light according to this mode Light touch in a surface coat .
009516 light is not irradiated with the antibacterial function which intermediation can achieve -- if it does, this antibacterial function can be achieved with the metal or the metal oxide on the surface of a surface coat. For this reason, the antibacterial function which a photocatalyst achieves can be complemented. moreover -- adding to a photocatalyst at a surface coat since other compounds of And are contained, it adds to an antibacterial function -- the above-mentioned photocatalyst Attain disassembly of an environmental pollutant, and air purification through the improvement in efficiency of the catalyst reaction which involves. It can do. the mode of The 6* The 8 of the photocatalyst combination thing of The 1 of the present invention -- like -- Formation of The 3 a part -- if it is when the photocatalyst combination thing or photocatalyst content material which has a compound is used, it sets to these surface coats -- the high dirt prevention effect based on high hydrophilicity can be produced It is desirable. The 9* The 1 of the 1st photocatalyst combination thing of the present invention It is Buddy when the photocatalyst combination thing or photocatalyst content material which supports and has the metal of the ingredient of The 4 like the mode of 0 is used. The, They are synergistic antibacterial properties also by the metal of the ingredient of this The 4. Since Vienna can be carried out, the metal or metallic compounds stuck to the surface of a surface coat can be made a very small quantity. If the synergistic antibacterial properties by the metal of the 4th ingredient are high, it is a surface coat of metal or metallic compounds. The adherence to the surface is also omissible.
0096A manufacturing method of the photocatalyst function exertion material of The 6 of the present invention,
0097it has a base material layer and the surface coat formed in the surface -- if irradiation of light is received -- photocatalyst function It is a manufacturing method of the material to demonstrate.
0098The photocatalyst combination thing of The 1 of the above-mentioned present invention, the photocatalyst combination thing of each of that mode, or this Photocatalyst distribution Process for which the photocatalyst combination thing distribution sol by which Compound was distributed is prepared,
0099It is To arrange in layers on the above-mentioned base material layer surface about the above-mentioned photocatalyst combination thing or the above-mentioned photocatalyst combination thing distribution sol. Arrangement process,
0100It has the process of forming the above-mentioned surface coat.
0101In this case, it is a part about a photocatalyst combination thing to solution, such as photocatalyst combination thing distribution sol, water, and alcohol. It is acquirable by making it scatter.
0102From not needing a special process according to the manufacturing method of The 6 of this present invention, From book As the photocatalyst combination thing of The 1 of Ming described, they are a thing to be reacted or middle generation in the system of a catalyst reaction. New photocatalyst machine which causes a catalyst reaction for a thing at high efficiency in a surface coat by Lycium chinense certainly Ability exertion material can be manufactured easily. Under the present circumstances, it is Arrangement if in charge of formation of a surface coat. It responds to the photocatalyst combination thing or photocatalyst combination thing distribution sol which carried out Establishment, and is a proper technique, for example, heat treatment. A drying process can be taken.
0103In the manufacturing method of The 6 of this present invention,
0104The above-mentioned allocation process,
0105It is To arrange in layers on the above-mentioned base material layer surface about the above-mentioned photocatalyst combination thing or the above-mentioned photocatalyst combination thing distribution sol. In the To case the above-mentioned photocatalyst combination thing or the above-mentioned photocatalyst combination thing distribution sol -- the above-mentioned base material layer surface -- layer it has a process laid, applied or printed to A state -- rubbing with the manufacturing method of photocatalyst function exertion material There are The and the following advantages.
0106Table which consists of a photocatalyst combination thing and where thickness is almost uniform according to the manufacturing method of The 6 of this present invention It is To manufacture easily about the new photocatalyst function exertion material which causes a catalyst reaction at high efficiency in a surface layer. To is made. the stratified application of the photocatalyst combination thing on the surface of a base material layer and spray coating etc. -- the proper application technique -- proper printing methods, such as stratified printing and roll printing, -- real -- A line can be carried out.
0107A manufacturing method of the photocatalyst function exertion material of The 7 of the present invention,
0108it has a base material layer and the surface coat formed in the surface -- if irradiation of light is received -- photocatalyst function It is a manufacturing method of the material to demonstrate.
0109The photocatalyst combination thing of The 1 of the above-mentioned present invention, the photocatalyst combination thing of each of that mode, or this Photocatalyst distribution Process for which the photocatalyst combination thing distribution sol by which Compound was distributed is prepared,
0110a binder is allocated in the above-mentioned base material layer surface in layers -- the process of forming a binder layer, and the above-mentioned photocatalyst combination thing or the above-mentioned photocatalyst combination thing distribution sol -- the above-mentioned binder layer surface -- stratified -- Arrangement Allocation process which carries out Establishment,
0111it heat-treats according to the character of the above-mentioned binder -- having the process of forming the above-mentioned surface coat It is considered as the feature.
0112according to the manufacturing method of The 7 of this present invention -- the boundary of a binder layer and a surface coat -- this surface the photocatalyst combination thing in a layer is held in the state where it was buried with the binder layer -- a surface coat -- Vine It can form in the Da layer surface. for this reason, a surface coat is firmly fixable to a binder layer, and it contacts a photocatalyst combination thing in the open air effectively -- things can be carried out. And Light touch of The 1 of the present invention As the intermediation combination thing described, a thing to be reacted or an intermediate product is certainly set in the system of a catalyst reaction. The new photocatalyst function exertion material which causes a catalyst reaction at high efficiency in a surface coat by things is manufactured. It can carry out.
0113in this case, let the above-mentioned binder be glaze -- if it hits forming the above-mentioned surface coat -- above-mentioned Glaze a medicinal apparent initial softening -- 3 more than 0 °C -- 3 0 it is high in the range below 0 °C -- and basis of the above-mentioned base material layer It can heat-treat under temperature environment lower than the deterioration temperature of material. Stoving temperature It is a binder about a degree. (glaze) It is 3 from an apparent initial softening. Glaze by heating since more than 0 °C made it high Softening does not take a long time carelessly but it is desirable. heating temperature -- the apparent initial softening of glaze -- 3 0 since it is not made high more than 0 °C, rapid fusion of glaze is avoided -- fault of a photocatalyst combination thing Surplus is buried and faults, such as generating of a Or concave convex or generating of a pinhole, can be controlled. It hits forming the above-mentioned surface coat, and is about 1. 5 0* abbreviation 1 3 0 It heat-treats under the temperature environment of 0 °C. Carrying out is preferred. if it does in this way, the existing heating device will be used -- high efficiency The new photocatalyst function exertion material which causes a catalyst reaction can be manufactured. and Heat treatment temperature -- abbreviation 1 5 if more than 0 °C is used, it will be made to agree with the heat treatment temperature of existing glaze -- the former and heat Change of processing conditions is not required. heat treatment temperature -- abbreviation 1 3 0 if below 0 °C carries out -- Warmth it is made to agree with the heat treatment temperature at the time of generation of the substrate which requires Reason, for example, a tile, pottery, etc. -- the former Change of a heat treatment condition is not required.
0114let the above-mentioned binder be a paint -- if it hits forming the above-mentioned surface coat -- the above-mentioned base material layer It can heat-treat under the temperature environment below the deterioration temperature of a substrate. It is To like this. Without deteriorating Leave and a substrate, a surface coat can be formed and it is desirable.
0115In The 6 of the above-mentioned present invention, and the 7th manufacturing method,
0116the process of forming the above-mentioned surface coat is followed -- it is exertion about antibacterial properties to the surface of the surface coat formed [ above-mentioned ] The process of applying the solution in which the metal or metallic compounds to carry out was distributed, and the above-mentioned metal or metal acid It shall have a process which sticks a ghost to the surface of the above-mentioned surface coat.
0117setting to a surface coat according to the manufacturing method of the photocatalyst function exertion material of this mode -- the bottom of a bottom of bright place * dark place irrespective of -- being able to demonstrate antibacterial properties and setting to a surface coat -- high efficiency -- a catalyst reaction -- Wake up -- new photocatalyst function exertion material can be manufactured easily. And it is Ming in this way. Photocatalyst function [ character / in which antibacterial properties can be demonstrated irrespective of the bottom of bottom of place , and a dark place ] surface coat formed It can give later Vienna material. In The 6 of the above-mentioned present invention, and the 7th manufacturing method,
0118The above-mentioned allocation process,
0119They are antibacterial properties after allocating the above-mentioned photocatalyst combination thing or the above-mentioned photocatalyst combination thing distribution sol in layers. It has the process of applying the solution in which the metal or metallic compounds to demonstrate was distributed,
0120The process of forming the above-mentioned surface coat,
0121The above-mentioned metal or a metal oxide is stuck to the surface of the above-mentioned surface coat simultaneously with formation of the above-mentioned surface coat. It shall have Step.
0122according to the manufacturing method of the photocatalyst function exertion material of this mode -- irrespective of the bottom of bottom of bright place , and a dark place -- antibacterial properties the character to demonstrate a sex, and the character to cause a catalyst reaction at high efficiency were combined from the beginning -- new are . Photocatalyst function exertion material can be manufactured easily.
0123In The 6 of the above-mentioned present invention, and the 7th manufacturing method,
0124the process of forming the above-mentioned surface coat is followed -- it is exertion about antibacterial properties to the surface of the surface coat formed [ above-mentioned ] Process of applying metal salt solution containing the ion of the metal to carry out, It is Looking about ultraviolet rays to the above-mentioned surface coat. To a photocatalyst [ in / using the optical reduction to the photocatalyst of the above-mentioned metal ion / it puts and / the above-mentioned surface coat ] It shall have the process of supporting and fixing the above-mentioned metal.
0125setting to a surface coat according to the manufacturing method of the photocatalyst function exertion material of this mode -- the bottom of bottom of bright place , and a dark place irrespective of -- being able to demonstrate antibacterial properties and setting to a surface coat -- high efficiency -- a catalyst reaction -- Wake up -- new photocatalyst function exertion material can be manufactured easily. And antibacterial complement Support and fixation of the metal to contribute are done at the photocatalyst in a surface coat using optical reduction. Omission power of the metal concerned<sup>?</sup>occurring -- A -- . Therefore, it is Across to a long period of time about antibacterial complement performance. It is maintainable. Character in which antibacterial properties can be demonstrated in this way irrespective of the bottom of bottom of bright place , and a dark place It can give later the photocatalyst function exertion material surface coat formed. The 9* The 1 of the photocatalyst combination thing of The 1 of the present invention It supports and has the metal of the ingredient of The 4 like the mode of 0. If it is when a photocatalyst combination thing is used, It is synergistic also by the metal of the ingredient of this The 4. Since antibacterial properties can be demonstrated, it passes through the application of metal salt solution, and a subsequent ultraviolet exposure, and it is a table. Metal which the surface layer surface is made to support can be made a very small quantity. gold of the 4th ingredient This which will omit the support to the surface coat surface of this metal if the synergistic antibacterial properties by Genus are high Both -- it can do. A manufacturing method of the photocatalyst combination thing of The 8 of the present invention,
0126Ingredient of a photocatalyst, the compound besides the above which functions as receiving irradiation of light as a catalyst, and above-mentioned The 3 Manufacture of the photocatalyst combination thing which contains the compound to carry out and the metal as an ingredient of above-mentioned The 4 It is a method,
0127Even if small among the above-mentioned photocatalyst, a compound besides the above, and the compounds as an ingredient of above-mentioned The 3 Process for which the photocatalyst distribution sol by which the above-mentioned photocatalyst was distributed is prepared,
0128Method of manufacture of the photocatalyst combination thing which contains the photocatalyst which functions as receiving irradiation of light as a catalyst It is a method,
0129Light touch by which the photocatalyst combination thing of the mode of The 6* The 8 of the photocatalyst combination thing of The 1 of the present invention was distributed Process for which intermediation combination thing distribution sol is prepared,
0130metal salt solution containing metaled Ion which demonstrates antibacterial properties -- the above-mentioned photocatalyst combination thing distribution sol it mixes -- having the process of supporting the above-mentioned metal to the above-mentioned photocatalyst as an ingredient of The 4 It is considered as the feature.
0131A manufacturing method of the photocatalyst combination thing of The 9 of the present invention,
0132Ingredient of a photocatalyst, the compound besides the above which functions as receiving irradiation of light as a catalyst, and above-mentioned The 3 Manufacture of the photocatalyst combination thing which contains the compound to carry out and the metal as an ingredient of above-mentioned The 4 It is a method,
0133Even if small among the above-mentioned photocatalyst, a compound besides the above, and the compounds as an ingredient of above-mentioned The 3 Process for which the photocatalyst distribution sol by which the above-mentioned photocatalyst was distributed is prepared,
0134mixing metal salt solution containing metaled Iron which demonstrates antibacterial properties to the above-mentioned photocatalyst distribution sol the salt of the above-mentioned metal and the above-mentioned photocatalyst combination thing are made to Coprecipitation after It was -- using the above-mentioned metal as the ingredient of The 4 It has a process supported to a And photocatalyst.
0135The 1 of the present invention Manufacturing method of the photocatalyst combination thing of 0,
0136Ingredient of a photocatalyst, the compound besides the above which functions as receiving irradiation of light as a catalyst, and above-mentioned The 3 Manufacture of the photocatalyst combination thing which contains the compound to carry out and the metal as an ingredient of above-mentioned The 4 It is a method,
0137Even if small among the above-mentioned photocatalyst, a compound besides the above, and the compounds as an ingredient of above-mentioned The 3 Process for which the photocatalyst distribution sol by which the above-mentioned photocatalyst was distributed is prepared .
013821 mixing metal salt solution containing the metaled ion which demonstrates antibacterial properties to the above-mentioned photocatalyst distribution sol it irradiates with ultraviolet rays after It was -- using optical reduction of the above-mentioned metal ion -- the above-mentioned metal -- ingredient of The 4 As -- it has a process supported to the above-mentioned photocatalyst
0139These 8 thru/or The 1 according to the manufacturing method of the photocatalyst combination thing of 0 -- these photocatalyst combination things In the surface coat used and formed, antibacterial properties are demonstrated irrespective of the bottom of bottom of bright place , and a dark place. With It is Capacity about the new photocatalyst combination thing which causes a catalyst reaction at high efficiency in this surface coat. It can manufacture to Easy. To and the manufacturing method of The 8 of the present invention and an antibacterial complement They are a hit, photocatalyst distribution sol, and metal salt water for doing support and fixation of the metal to contribute beforehand at a photocatalyst. Since solution is only mixed, simplification of a process can be attained. the present invention The 9 and The 1 in supporting - fixing beforehand the metal contributed to the manufacturing method of 0, and an antibacterial complement at a photocatalyst -- Both -- since Precipitation or optical reduction is used -- omission of the metal from a photocatalyst -- To wake up The Across maintenance of Complex and the antibacterial complement performance can be carried out at a long period of time. The 1 of the present invention it only irradiates with ultraviolet rays on the occasion of support and fixation of the manufacturing method of 0 of, and metal -- medicine etc. Since it does not need at all, simplification of a process can be attained.
0140These 8 thru/or The 1 In the manufacturing method of the photocatalyst combination thing of 0, (Sol (a from [ i.e., ] book) Sol and To by which the photocatalyst combination thing of the mode of The 6* The 8 of the photocatalyst combination thing of The 1 of Ming was distributed To is made.) [ finishing / all of a photocatalyst, other compounds, and the compound as an ingredient of The 3 / distribution / sol / photocatalyst distribution ] The compound of others [ sol / after metal support / photocatalyst distribution ] and the ingredient of The 3 The compound to carry out can also be distributed. Photocatalyst powdered from facilities, such as storage The photocatalyst whose metal as the 4th ingredient has been supported in order to consider it as the combination thing, and other compounds The sol whose compound as an ingredient of The 3 has distributed may be dried.
0141It is also possible to take the present invention and other following modes, and other 1st mode is light. It is a manufacturing method of the combination thing which contains the photocatalyst which functions as receiving irradiation as a catalyst, and is Buddy. The,
0142Particle power of the above-mentioned photocatalyst<sup>s</sup>Process (A) which prepares the sol of The 1 of which 'distribution was done,
0143The above-mentioned thing to be reacted or the above-mentioned thing to be reacted undergos the above-mentioned catalyst reaction, and it is Change to the above-mentioned final product. The particles of a compound besides the above chemically combined with the intermediate product generated before To distribute. Process (B) which prepares the sol of The 2, It has process (C) which mixes the sol of above-mentioned The 1, and the sol of The 2.
0144It is characterized by things.
0145According to the manufacturing method of other modes of this The 1, a solvent can be made to distribute a photocatalyst and other compounds easily by passing through mixture of the 1st and 2nd sol. And only the mixed sol which passed through process (C), and a photocatalyst are power.<sup>?</sup>it condenses, and it exists, or only other compounds condense, and it does not do existence of -- the photocatalyst which forms a photocatalyst combination thing, and other compounds -- Ho (it is a mixed part to ^ 1 [ It becomes the scattered sol. ]) Therefore, it uses as this mixed sol and photocatalyst combination thing distribution sol. The material used suitably for that while it has been liquefied, for example, a paint, the photocatalyst to glaze, and others Combination of a compound becomes easy. Since it is sol-like, The 1 and the amount of * of the 2nd sol Since it is easy, it lets weighing of each sol pass, and it is mixture of a photocatalyst and other compounds easily. A rate can be adjusted. If the solvent in mixed sol is removed by techniques, such as dryness, a photocatalyst and other compounds will be Ho (it becomes the combination thing granular at a solid mixed to ^ 1.).
0146In this case, the solvent of the 1st sol and the sol of The 2 is made into the same thing, or it is what is called familiarity. It is desirable when a good solvent is used.
0147In the manufacturing method of other modes of above The 1,
0148above-mentioned process (A) and the energy of light with which it was irradiated generate an excitation electron and an electron hole -- catalyst the above-mentioned excitation electron and an electron hole generate reactive oxygen species under existence of oxygen in the surface and moisture -- front -- Have the process of adjusting the particles of an account photocatalyst.
0149Above-mentioned process (B), the above-mentioned thing with which the above-mentioned catalyst reaction based on the above-mentioned reactive oxygen species is presented to be reacted Or both sexes metal oxide chemically combined with the above-mentioned intermediate product, a basic metal oxide -- or -- at least 1 metal oxide of an acid metal oxide is prepared as a compound besides the above -- this gold It shall have the process of adjusting the particles of Genus oxide.
0150the photocatalyst and base which cause the catalyst reaction based on reactive oxygen species according to other modes of this The 2 other compounds which combine * hold a thing to be reacted or an intermediate product certainly by a point or Acid point -- almost -- The photocatalyst combination thing mixed uniformly can be obtained easily.
0151In the manufacturing method of other modes of above The 1,
0152Place which expressed the weight of a and the above-mentioned photocatalyst as b for the weight of above-mentioned process (C) and the above-mentioned metal oxide Synthesis and a Z (a+b) are abbreviation 0.0. 0 0 They are the sol of above-mentioned The 1, and The 2 so that it may be set to 1*0.8. It shall have the process of preparing sol.
0153According to other modes of this The 3, it is a metal oxide. (both sexes metal oxide) there is not too little quantity of a basic metal oxide and an acid metal oxide -- metal acid of the above [ the quantity of a photocatalyst ] again Photocatalyst combination which there is not and does not cause the efficiency fall of a catalyst reaction to a ghost A thing can be obtained easily. [ too little ]
0154In the manufacturing method of other modes of above The 1,
0155It is abbreviation 0.0 about above-mentioned process (A) and the above-mentioned photocatalyst. 0 It is Tone to the particles of the particle diameter range of 5*0.5. It has a process which carries out ready,
0156It is abbreviation 0.0 about above-mentioned process (B) and the above-mentioned metal oxide. 0 Particles of the particle diameter range of 5* 0 .5 / m It shall have a process to adjust.
0157According to other modes of this The 4, they are a photocatalyst and a metal oxide. (a both sexes metal oxide, a basic metal oxide, and an acid metal oxide) An existing grinding apparatus or sol ., such as a ball mill By the gel method Particle diameter adjustment can be performed easily and it is desirable. a thing to be reacted or an intermediate product -- Separation from a photocatalyst It comes out to obtain easily the photocatalyst combination thing which there is no Surely and does not cause the efficiency fall of a catalyst reaction. It cuts. furthermore -- according to this mode -- a photocatalyst and metallic compounds -- grain of the almost same size it can be made to be able to approach by a child and a thing to be reacted or an intermediate product can be made to approach a photocatalyst -- catalyst A photocatalyst combination thing with high efficiency of a reaction can be obtained easily. Brief explanation of the drawings
0158Drawing 1 is this titanium dioxide, when oxidizing nitrogen oxide with the titanium dioxide which is a photocatalyst. The situation of advance of the catalyst reaction at the time of blending alumina, and middle of a catalyst reaction Explanatory view showing the situation of combination by alumina of output typically.
0159Drawing 2 is this titanium dioxide, when oxidizing SOx with the titanium dioxide which is a photocatalyst. Connection by Norma of the intermediate product of the catalyst reaction at the time of blending alumina Explanatory view showing the situation of Synthesis typically.
0160Drawing 3 is this titanium dioxide, when oxidizing carbon monoxide with the titanium dioxide which is a photocatalyst. Connection by alumina of the intermediate product of the catalyst reaction at the time of blending alumina Explanatory view showing the situation of Synthesis typically. -
016124 a figure -- Measurement of the reduction effect of the nitrogen oxide by an example tile [ in / in 4 / The 1 example of the present invention ] Schematic structure figure of the test equipment used for the law.
0162Drawing 5 shows the result of the reduction effect of the nitrogen oxide by the example tile in The 1 example. Graph.
0163It was explaining the reduction effect of the ammonia by an example tile [ in / in Drawing 6 / The 1 example ] Because -- a graph .
0164It was explaining the reduction effect of the sulfur dioxide by an example tile [ in / in Drawing 7 / The 1 example ] Because -- a graph .
0165Drawing 8 shows the result of the reduction effect of the nitrogen oxide by the example tile in The 1 example. Graph.
0166Drawing 9 shows the result of the reduction effect of the nitrogen oxide by the example tile in The 1 example. Graph.
0167Drawing 1 0 shows the result of the antibacterial effect which the example tile in The 3 example of the present invention achieves. Graph.
0168Drawing 1 1 is an example tile of The 6 example of a four-ingredient system. (baking type) It sets and supports. It is the weight of Metal c and T i 0<sub>2</sub>c Z d (metal compounding ratio) at the time of expressing Weight as d anti- -- Graph which shows a relation with Fungal power.
0169Drawing 1 2 is an example tile of The 6 example of a four-ingredient system. (paint A type) Gold set and supported It is the weight of Genus c and T i 0<sub>2</sub>c Z d (metal compounding ratio) at the time of expressing Weight as d Antibacterial activity Graph which shows a relation.
0170Drawing 1 3 is an example tile of The 6 example of a four-ingredient system. (baking type) Surface coat which can be set Graph which expresses a relation with an angle of contact at the time of film thickness and Ming.
0171Drawing 1 4 is an example tile of The 6 example of a four-ingredient system. (baking type) Surface coat which can be set Graph showing the relation between film thickness and antibacterial activity.
0172Drawing 1 5 is an example tile of The 6 example of a four-ingredient system. (baking type) Surface coat which can be set Graph showing the relation between film thickness and oil decomposition power.
0173Drawing 1 6 is an example tile of The 6 example of a four-ingredient system. (baking type) Surface coat which can be set Graph showing the relation between film thickness and N 0 oxidization power. Drawing 1 7 is an example tile (baking type) of The 7 example of a three-ingredient system. Surface coat which can be set Graph which expresses a relation with an angle of contact at the time of film thickness and Ming.
0174Drawing 1 8 is an example tile of The 6 example of a four-ingredient system. (paint type) Color difference which can be set deltaepsilon Graph which expresses a relation with an angle of contact at the time of Ming.
0175Drawing 1 9 is an example tile of The 6 example of a four-ingredient system. (paint type) Color difference which can be set epsilon Graph showing a relation with antibacterial activity.
0176Drawing 2 0 is an example tile of The 6 example of a four-ingredient system. (paint type) Color difference which can be set deltaepsilon Graph showing a relation with oil decomposition power.
0177Drawing 2 1 is an example tile of The 6 example of a four-ingredient system. (paint type) Color difference which can be set Graph showing the relation between delta epsilon and NO oxidization power.
0178Drawing 2 2 is an example tile of The 7 example of a three-ingredient system. (paint type) Color difference which can be set deltaepsilon Graph which expresses a relation with an angle of contact at the time of Ming. The best form for inventing
0179Next, an embodiment of the invention is described based on an example.
0180First, preparation of the photocatalyst combination thing to use in the example is explained. as a photocatalyst -- announcer an evening 1 Ze type titanium dioxide is used -- alumina which is a both sexes metal oxide as a metal oxide blended with this photocatalyst, and oxidization A which is basic metal oxides TRON Thium Barium oxide was used. And following it faces preparation of a photocatalyst combination thing, it is Harvest about a process. It was.
0181(1) Particle supply of a photocatalyst and metal oxides
0182The above-mentioned titanium dioxide, alumina, and oxidization A Raw material of TRON Thium and barium oxide It supplies, grinding apparatus, such as a ball mill, grind each -- or sol and the gel method A titanium dioxide, alumina, and oxidization A Minute particles of TRON Thium and barium oxide It obtains. In this case, the particle diameter of each particle is abbreviation 0.0. 0 The particle diameter range of 5* 0 .5 / m Particle size adjustment is performed so that it may become.
0183(2) Preparation of sol
0184next -- it is distribution to solvents, such as water and alcohol, about each combination material adjusted as mentioned above, respectively it carries out -- the sol for every combination material is prepared. In this case, distribution of the distributed material in each sol Quantity (for example, weight solvent capacity of combination material) It specifies.
0185(3) Adjustment of a photocatalyst combination thing
0186Then, prepared titanium dioxide sol (photocatalyst sol) Alumina sol, The metal oxide sol of strontium oxide sol and barium oxide sol is mixed, Titanium dioxide Z Norma mixture sol (T i /A 1 sol) and titanium dioxide Z oxidization A TRON Thium mixture sol (T i/ S r sol) and titanium dioxide Z barium oxide mixture sol (T i ZB a sol) are obtained. in this case, as for the amount of *, in adjustment, the amount of mixtures of photocatalyst sol and the amount of mixtures of metal oxide sol are carried out in each of above-mentioned mixed sol -- changing each amount of weighing -- a photocatalyst and gold The mixed sol which takes the value of combination rate power * versatility of Genus oxide is adjusted. That is, each mixed sol Combination rate (following and this a Z (a+b) are called combination rate determination ratio) power denoted by a /(a+b) in the weight of the metal oxide which can be set when the weight of a and a photocatalyst is expressed as b<sup>s</sup>' -- various -- It is adjusted.
0187A of a particle size adjustment [ be / take the process of above-mentioned (1)*(3), and also / prepared photocatalyst sol ] Particles, such as lumina, are added and it can be made to be able to distribute to also make T i/h 1 sol etc. a particle size -- adjusted photocatalyst particles and particles, such as alumina, -- alternation -- or -- simultaneous -- the above-mentioned solvent -- part making it scatter -- particle power, such as the beginning to photocatalyst particles, and alumina<sup>s</sup>T i ZA 1 dispersed sol etc. It can also carry out.
0188Next, it is One to the photocatalyst function exertion material which exhibits a photocatalyst function using photocatalyst combination thing (T i ZA 1 sol, T i Z S r sol, each mixed sol of T i /B a sol) adjusted as mentioned above. Are and it explains. this example (The 1 example) Then. -- let this photocatalyst function exertion material be a tile -- it manufactured as follows.
0189an unglazed tile is prepared as a substrate -- each above-mentioned mixture of the concentration specified on this tile surface Spray coating of the sol is carried out. If in charge of this spray coating, it is on the tile surface after calcination. The like and its amount of applications from which the film thickness of the photocatalyst mixture which can be set serves as abbreviation 0.8, i.e., Sp, The Leh time is adjusted. Subsequently, temperature in consideration of the degrees of Melting temperature , such as silica blended for fixing of a photocatalyst, a titanium dioxide, and the melting temperature of each of above-mentioned metal oxides (if it is in this Example ) Abbreviation 8 0 At 0 ° C, it is abbreviation 6 about the tile after the spray coating of mixed sol. It is Across in 0 minute. It is carrying out Firing, Substrate (tile) A part for the sol neutrality of the above [ surface ] (a photocatalyst, alumina , etc.) Final photocatalyst function exertion material which has a surface coat to contain (photocatalyst function exertion tile) It carried out. Here, the evaluation is explained. The inside of evaluation and the atmosphere, or indoor toxic substance It carries out and is the existence of reduction A desire rare ing nitrogen oxide, ammonia, and the reduction effect of sulfur dioxide. We decided to give. the outline of the examination is as follows -- first -- nitrogen oxide reduction It attaches and explains. the spray coating of mixed sol -- instead of -- a spin coat and Date Of course, techniques, such as Pukote, can also be taken.
0190(1-1) Evaluation test 1 : Influence of the alumina etc. which are exerted on nitrogen oxide reduction
0191First, it is alumina in order to take contrast with the example article of the present invention, Oxidization A The photocatalyst combination thing which contains only a titanium dioxide excluding TRON Thium and barium oxide at all is used. Photocatalytic function exertion tile (comparative example tile) Photocatalyst function exertion tile of the example (example tile of operation ) was prepared as follows. a comparative example tile and a titanium dioxide carry out spray coating of the photocatalyst sol occupied at a rate of 7. 5 w t % to the tile surface -- the above-mentioned calcination conditions
0192(About 800-degreeCX 60 minutes) It is the calcinated tile. The weight of the titanium dioxide in the tile surface after calcination if this spray coating is faced is abbreviation 3. 3X 10 1.<sup>4</sup>g/ cm<sup>2</sup>
0193(The film thickness of the titanium dioxide in this case is abbreviation 0. 85^m) as [ become ] -- application time etc. It set. They are an example tile, the T i/A 1 following tile, a T i ZS r tile, and T i ZB a evening A ring.
0194T i /A 1 tile and a titanium dioxide -- a comparative example tile -- the same -- rate of 7. 5 w t % as opposed to the photocatalyst sol to occupy -- (a+b) combination rate determination ratio a power<sup>S</sup>'1Z1 it is set to 1 -- as -- T i/A 1 sol to which the combination rate of alumina was adjusted (T i/A 1 sol which the weight ratio of aluminum Na to a titanium dioxide set to 0.1) the same conditions as the above-mentioned comparative example tile -- A It is the tile which was play-applied and was calcinated. T A i ZS r tile, a titanium dioxide, and strontium oxide are spray coating and the calcinated tile on the same conditions as the above-mentioned comparative example tile about the T i/S r sol blended at same combination rate as T i/A 1 tile, and it is Ah. To. T A i ZB a tile is also the same. That is, a comparative example tile and 2 acid on the surface of a tile Since the catalyst function which only-izing titanium has and serves as a standard on comparison and contrast is exhibited, this comparison By comparing an example tile with each of above-mentioned example tiles, it is combination about each metal oxide. the existence of improvement in the catalyst function obtained by having carried out -- power clarification is carried out to that extent. and comparative example it has a surface coat which becomes a tile and the tile surface only from a titanium dioxide -- an example tile, a titanium dioxide, alumina, strontium oxide, or barium oxide -- combination -- It will have a surface coat which consists of a Was done combination thing.
0195It examined as follows about this comparative example tile and each example tile. It compares with an examination. Test device shown in Drawing 4 using the sample piece of 10 c m four quarters of an example tile and each example tile The reduction effect of nitrogen oxide was measured by Place. This test equipment and a sample piece are laid. In the upper stream of glass cell 10 of the letter of sealing, It is from a preparation and this cylinder to NO gas about Bon What 12 which enclosed the nitric oxide gas of constant concentration, It is drawn in with air 1 pump 14, and is humidity regulator 1. The atmosphere by which humidity adjustment was carried out by 5 is mixed by flow control valve 16, This flow control valve 1 It is predetermined concentration from 6 to glass cell 10. (about 0. 95 p pm) NO gas of fixed quantity (1 Liter / m i n) (examination gas) It pours in. moreover -- the lower stream of glass cell 10 -- being concerned -- the concentration side which measures the nitrogen oxide concentration in the gas which passed the cell -- constant vessel (NOx sensor) 1 It has 8. This NOx sensor 18, and NO concentration and nitrogen dioxide concentration in gas (N0)<sub>2</sub>concentration is measured at any time -- measured NO concentration and N0<sub>2</sub>it adds to concentration -- the sum of these both concentration Nitrogen oxide concentration (NOx concentration) As -- it is constituted so that it may output. Examination They are ultraviolet rays to the inside of a device and glass cell 10. (wavelength 300* 400 n m) La with which it irradiates It has Ump 20. In this case, the ultraviolet-rays intensity on lamp 20 and a sample piece is 1.2 mW/cm.<sup>2</sup>Lighting control is carried out so that it may become. and glass of this Trial device it places under the environment where lay a sample piece in cell 10 and it receives irradiation of ultraviolet rays -- comparative example tie Every lapsed time after starting casting of examination gas about Le and each example evening A ring N0<sub>2</sub>It is Plot about concentration and NO X concentration. A was carried out. the result -- a figure -- it is shown in 5. Lamp 20 is an outlet side after starting casting of examination gas. NOx concentration (NO concentration) Power stability The light was switched on after carrying out.
0196it sets to this evaluation test 1 -- if the reaction which oxidizes nitric oxide does not occur -- for example, Ga Generation of the reactive oxygen species by a titanium dioxide [ in / Las cell 10 is occurred under a darkroom and / a surface coat ] Power<sup>s</sup>He is NOx Seng, without examination gas causing what reaction, if a catalyst reaction does not occur that there is nothing. It flows into The 18. Therefore, about the output of NO X sensor 18 in this case, and NO concentration (CNO /o u t), it is the same as that of examination gas concentration (CNOZi n), and is N0.<sub>2</sub>Concentration
0197(CN0<sub>2</sub>Zero and NOx concentration (CNOx/o u t) of /o u t is the same as that of CNOZo u t, i.e., CNOZ i n. carrying out -- power -- it carries out -- the titanium dioxide in a surface coat generated If NO oxidizes by the catalyst reaction based on reactive oxygen species, NO concentration will decrease from CNOZ i n only the part which received the oxidization. N0 generated by NO oxidization<sub>2</sub>If it secedes from if tile surface, it will be the N0 from which it seceded.<sub>2</sub>It is N0 by of.<sub>2</sub>This which concentration increases It becomes. And N0 generated with NO concentration reduction by NO oxidization<sub>2</sub>the of tile surface from -- NO by secession<sub>2</sub>The reduction grade of a relation with the increase in concentration to NOx becomes settled.
0198as [ show / in Drawing 5 / now, ] -- a comparative example tile -- the start of test -- rapid -- NO X concentration it falls -- if abbreviation 5 minutes pass since the start of test -- it or subsequent ones NOx concentration starts to increase -- examination Gas concentration is approached. With this comparative example tile, it is N0 gradually after the start of test.<sub>2</sub>concentration rises -- it was set to abbreviation 0. 18 p pm after 30-minute progress. Increase of this NO X concentration The tendency and NO of Addition<sub>2</sub>The tendency of the rise of concentration has taken the almost same tendency. These Photocatalytic reaction by a titanium dioxide [ in / with the comparative example tile from things / the surface coat ] Power<sup>s</sup>Power N0 in which it goes on, NO oxidizes and NO concentration decreases<sub>2</sub>it follows on the rise of concentration -- the whole Reduction of NOx(es) [-like ] will not progress. Therefore, with a comparative example tile, it is NO.<sub>2</sub>Or It is N0 in order to secede from the A ring surface.<sub>2</sub>The further oxidization in the of tile surface occurs so much. It can be said that there is no Listen. Since the NO X concentration after 30-minute progress was abbreviation 0. 66 p pm, the reduction efficiency of NOx in this comparative example tile was abbreviation 30. 5% (0.95-0.66) (/0. 95).
0199on the other hand, a T iZA l tile, a T i ZS r tile, and a T iZB a tile -- it -- Sudden in that the example tile of Re is the same as a comparative example tile, NOx concentration, and the start of test It fell to Intense and changed at the concentration which increased from the lowered least concentration slightly. That With the example tile of Each, it is N0 from the start of test.<sub>2</sub>Concentration and its rise extent are 3 low. Only small abbreviation 0. 05 p pm was reached also after 0-minute progress. From these things, it is first based on a titanium dioxide [ in / with each example tile / the surface coat ] at The 1. It can be said that a photocatalytic reaction advances, N 0 power' oxidization of is done, and N 0 concentration is decreasing. N0<sub>2</sub>being combined with But alumina, strontium oxide, and barium oxide -- the tile surface comparison secession is not carried out -- this N0 by a titanium dioxide<sub>2</sub>For -- oxidization advances actively -- N0<sub>2</sub>It can be said that concentration does not rise. For this reason, according to each example tile, it can be said that NOx(es) are reducible at very high efficiency. and NOx after 30-minute progress -- dark -- Reduction efficiency of N 0 X in each [ since the degree is abbreviation 0. 45 p pm ] example tile it is abbreviation 52. 6% (0.95-0.45) (/0. 95) -- comparative example evening A ring It was twice mostly. in addition -- having continued the above-mentioned examination about these example tiles -- This the reduction efficiency of Filtration and NO X is maintained with the high value -- thing power clarification was carried out. after 12-hour progress, an examination is ended and flush washing of the example tile surface is carried out -- being contained in the rinse water When Substance was analyzed, existence of nitric acid was checked.
0200As for abnormalities, each example tile is not observed by the concavo-convex grade etc., but the surface state is A. Had been. And J I S -- sliding follow A 6808 and using the plastic eraser When wear trial R^ is tried, even if each example tile finishes about 40 both-way sliding neither degradation nor peeling is looked at by the surface coat -- it also became clear that it excelled in abrasion resistance. This This The photocatalyst combination thing, the calcination paint, and glaze which were manufactured by the technique of mixture of the above-mentioned sol It means being applicable to calcination, printing, a binder, etc. of course. the above Photocatalyst combination which can acquire the reduction efficiency of high nitrogen oxide by a photocatalyst function like A thing and photocatalyst function exertion material can be easily manufactured with the technique of mixture of the above-mentioned sol. When -- it can say.
0201(1-2) Evaluation test 1 : Influence of the alumina etc. which are exerted on ammonia reduction
0202It is the comparative example evening with the same device and technique as the nitrogen oxide described above also about ammonia. The situation of reduction by A ring and T i /A 1 tile and a T i ZS r tile was investigated. this -- , Case, Glass cell Examination gas poured into 10 is ammonia gas of about 4 p pm. It is a concentration side constant vessel of the cell lower stream about ammonia concentration in gas which passed the cell concerned. (gas detecting tube) It measured. And Ann for every lapsed time after starting casting of examination gas about a comparative example tile and example tile (a T iZA l tile, a T i Z S r tile) It is Plot about Monier concentration. A was carried out. the result -- a figure -- it is shown in 6.
0203it is shown in Drawing 6 -- as -- a comparative example tile and an example tile -- the start of test -- ammonia Concentration fell. And the direction of a Across example tile serves as low concentration during the measurement. .
020431 if abbreviation 10 minutes pass since the start of test, it will become the concentration of about 1 law with each tile -- comparative example tie Le -- abbreviation 3. 5 p pm and T i /A 1 tile -- abbreviation 2. 5 p p m and T i /S r tile Then. -- it was abbreviation 2. 6p pm. Therefore, they are the reduction efficiency of ammonia, and a comparative example tile. With abbreviation 12. 5% (4-3.5) (/ 4) and T i /A 1 tile, it is abbreviation 37. 5%.
0205(4-2.5) With Z 4 and a T i /S r tile, it is at abbreviation 35 % (4 -- 2.6) (Z 4). It was. To a titanium dioxide [ in / with the comparative example tile from this / the surface coat ] Photocatalytic reaction advances and ammonia is NO and N0.<sub>2</sub>A chemical change is carried out to etc and it is ammonia. Which example evening of the power reduced to some extent, T i /A 1 tile, and a T iZS r tile If it was in A ring, the reduction efficiency of the ammonia superior to a comparative example tile has been demonstrated. this reason -- it is inferred as follows.
0206ammonia is made to change to other substances -- if it does not reaction (chemical change) power s occur, examination gas flows into a gas detecting tube, without causing what reaction -- the measured ammonia concentration and examination Ga It is the same as that of A. carrying out -- power it carries out -- the reactive oxygen species which the titanium dioxide in a surface coat generated -- basis the part which changed when ammonia changed to other substances in response to the To catalyst reaction -- Ammonier concentration decreases from the concentration in examination gas. Therefore, a comparative example tile and example Tha Ammonia concentration fell [ A ring ] from immediately after the start of test. in this case, ammonia -- Active the nitrogen which constitutes ammonia since the catalyst reaction based on a sex oxygen kind is undergone -- oxidization -- Re, NO, and NO<sub>2</sub>It is generated as Is an intermediate product. and this NO was described above obtaining -- reactive oxygen species -- N0<sub>2</sub>it is alike and oxidizes -- this N0<sub>2</sub>It further oxidizes by Is reactive oxygen species. If it is carried out and a chemical change is carried out to nitric acid, Vanmona will undergo the catalyst reaction based on reactive oxygen species, and it is NO and N0.<sub>2</sub>the grade which boils and carries out a chemical change becomes high -- if the reduction efficiency of ammonia increases -- Inference It guesses.
0207an example tile -- it mentioned already -- as -- N0<sub>2</sub>It is N0 from the tile surface unitedly.<sub>2</sub>secession -- there is no To -- making -- the point which blended alumina and strontium oxide -- a comparative example tile -- different -- It becomes. Therefore, NO generated from ammonia in the comparative example tile<sub>2</sub>the of tile surface from -- in order that secession may occur -- N0<sub>2</sub>It further oxidizes by Is reactive oxygen species and they are chemicals to nitric acid. The changing reaction seldom advances. on the other hand -- an example tile -- ammonia from -- generated NO<sub>2</sub>it is not made to secede from the tile surface -- this N0<sub>2</sub>reactive oxygen species even Ri and also nitric acid are oxidized -- reaction power promotion is carried out. For this reason, it describes above with an example tile. As carried out, in the reduction efficiency of ammonia, superiority or inferiority arose in a rise and the reduction efficiency of ammonia. It thinks.
0208(1-3) Evaluation test 1 : Influence of the alumina etc. which are exerted on sulfur dioxide reduction
0209It is comparative example Tha with the same device and technique as the nitrogen oxide described above also about sulfur dioxide. The situation of reduction by A ring and T iZA 1 tile was investigated. In this case, Glass cell 10 Examination gas to pour in is sulfur dioxide gas of about 10 p pm. The cell concerned was passed. It is a concentration side constant vessel of the cell lower stream about sulfur dioxide concentration in gas. (gas detecting tube) It measured. And it is Flow of examination gas about a comparative example tile and example tile (T i ZA l tile). It is Plot about the sulfur dioxide concentration for every lapsed time after starting a carry out lump. A was carried out. the result a figure -- it is shown in 7.
0210it is shown in Drawing 7 -- as -- a comparative example tile and an example tile -- the start of test -- sulfur dioxide Concentration fell. And it is Power of a Across example tile to a measurement period.<sup>s</sup>' -- it becomes low concentration -- when abbreviation 30 minutes had passed since the start of test, with the comparative example tile, it was abbreviation 2. 7 p pm in abbreviation 7. 7 p pm and T i/A 1 tile. Therefore, reduction efficiency of sulfur dioxide and comparative example Tha At A ring, it is abbreviation 73 % with 23% (10 -- 7.7) (Z10) of abbreviation, and a T i ZA l tile.
0211It was ((10 -- 2.7) / 10). With the comparative example tile from this, it is the table. The photocatalytic reaction by the titanium dioxide in a surface layer advances, and sulfur dioxide is sulfuric acid or Sub. Power T i ZA* which carries out a chemical change to sulfuric acid etc. and by which sulfur dioxide is reduced to some extent Tile (example tile of real Application) If it is, It is exertion about the reduction efficiency of the ammonia superior to a comparative example tile. It came. this reason -- it is inferred as follows.
0212Sulfur dioxide concentration falls [ a comparative example tile and an example tile ], that it is the same as that of the case of nitric oxide and Vanmona, and the reactive oxygen species which the titanium dioxide in a surface coat generated -- Based in response to a Catalyst reaction, sulfur dioxide changes to sulfuric acid or sulfurous acid -- the part which changed -- An It is because Monier concentration decreases from the concentration in examination gas. it can set to this evaluation test the Covered reaction thing explained with Drawing 2 for the sake of the convenience which is Sulfur dioxide and acidic gas -- as -- It joins together chemically and alumina which is a basic metal oxide is adsorbed. For this reason, in the comparative example tile which does not have this alumina, sulfur dioxide is not adsorbed on the tile surface. -
021333 Since it oxidizes with reactive oxygen species and a chemical change is often carried out to sulfuric acid or sulfurous acid, this reaction does not advance gently comparatively. On the other hand, with an example tile, it is sulfur dioxide. Since even sulfuric acid and sulfurous acid are oxidized with reactive oxygen species in the state where it stuck to the Tiru surface, this reaction is promoted. For this reason, it is sulfur dioxide as described above with the example tile. Reduction efficiency is considered that superiority or inferiority arose in a rise and the reduction efficiency of sulfur dioxide.
0214Next, the grade of combination of the alumina etc. which were blended with the photocatalyst and the reduction effect of nitrogen oxide The following two techniques were taken and evaluation about a relation was performed. About this evaluation Alumina was taken for the example and performed.
0215(2) evaluation test 2 : The influence of the alumina combination grade exerted on nitrogen oxide reduction -- the 1 -- in order to take contrast with the example article of the present invention first, The same comparison as the above-mentioned evaluation test 1 An example tile and photocatalyst function exertion tile of an example (example tile) It prepares as follows. It carried out. photocatalyst sol which a comparative example tile and a titanium dioxide occupy at a rate of 7. 5 w t % spray coating is carried out to the tile surface -- the above-mentioned calcination conditions (800 degrees of abbreviation CX 60 minutes) It calcinated. It is a tile. 2 oxidization in the tile surface after calcination if this spray coating is faced Weight PowerX[ 3.3 ] 10 of titanium --<sup>4</sup>gZcm<sup>2</sup>The film thickness of (titanium dioxide set like, the application time used as abbreviation 0. 85;/ m), etc. An example tile and the following T i ZA l tile It is.
0216T i /A 1 tile and a titanium dioxide -- a comparative example tile -- the same -- rate of 7. 5 w t % as opposed to the photocatalyst sol to occupy -- combination rate determination ratio a / (a+b) power 0.0001*0.
0217It is the above-mentioned ratio about T i/A 1 sol to which the combination rate of alumina was adjusted so that it might become the range of 8. They are spray coating and the calcinated tile on the same conditions as the example tile of Comparison. That is, calcination The abbreviationX[ 3.3 ] 1 as a comparative example tile with same weight of the titanium dioxide in the next Tiru surface
02180"<sup>4</sup>g/c m<sup>2</sup>power which is as [ of ] the weight of alumina in the tile surface after calcination -- different -- various T i/A 1 tiles are calcinated -- each T i/A 1 tile -- this evaluation test
0219It was considered as the example tile in 2. Combination rate determination ratio a/(a+b) is 0.01. Alumina in the tile surface after calcination since it is a = b 99 at a case Weight is abbreviationX[ 3.3 ] 10. --<sup>6</sup>gZ cm<sup>2</sup>come out and it is -- combination rate determination ratio a Z (a+b) -- zero.
0220Abbreviation 3. 3 X 10~ since it is a = b when it is 5<sup>4</sup>g/cm<sup>2</sup>It becomes. .
022134 Since Comparative Example Tile Exhibits Catalyst Function Used as Standard even if it is in this Evaluation Trial . Trial 2, The influence of the alumina loadings exerted on improvement in the catalyst function at the time of blending a fixed quantity of photocatalysts by comparing each T i/A 1 Thailand where this comparative example tile differs from alumina loadings is a seal. Ming is carried out.
0222the test equipment same in this evaluation test 2 as evaluation test 1 is used -- predetermined concentration (abbreviation 0. 95 p pm) Start of test which started casting of a fixed quantity of examination gas, and lighting of lamp 20 N 0 after [ a point in time to ] 30-minute progress<sub>2</sub>About concentration and N 0 X concentration, they are a comparative example tile and each example Tai. It measured about Le. And N0 measured with the amount of NO X removal which subtracted measurement N Ox concentration from NO concentration of examination gas about each tile<sub>2</sub>It is Plot about concentration. A was carried out. the -- a result -- a figure -- it is shown in 8. Since a comparative example tile and no alumina are blended, combination rate determination ratio a Z (a+b) is zero.
0223this figure -- it sets to 8 -- comparative example tile (a/(a+b) =0) and graph a Y-axis top -- Plot is carried out -- NO<sub>2</sub>Abbreviation 0. 17 p pm and the amount of NOx removal of concentration were abbreviation 0. 3 p p m. Thus, NO X concentration is Including in the examination gas of that which falls from examination gas. NO without rare Listen<sub>2</sub>Concentration is measured -- as mentioned already, it can set to a surface coat NO from the photocatalytic reaction advance by a titanium dioxide, and the tile surface<sub>2</sub>In order that Withdrawal may occur It is.
0224On the other hand, there are few alumina loadings in T i/A 1 tile by which combination rate determination ratio aZ (a+b) was expressed with X axial seat mark of a graph, and it is combination rate determination ratio a Z. (a+b) power<sup>s</sup>0. It is Thing of 01 and is NO.<sub>2</sub>Concentration is abbreviation 0. 4 p pm, and abbreviation 0. 15 p pm and the amount of NO X removal are Buddy. It was. Alumina loadings are the same as that of a titanium dioxide, and combination rate determination ratio a A (a+b) is N0 with T i /A 1 tile of 0.5.<sub>2</sub>Concentration is abbreviation 0. 14 p pm and the amount of NOx removal. It was abbreviation 0. 43 p pm. And combination rate determination ratio a Z (a+b) is N0 with T i ZA 1 tile of the range of 0.05*0.2.<sub>2</sub>concentration is [ the amount of NOx removal ] abbreviation 0. 44*0. 46 p p m in abbreviation 0. 06*0. 13 p p m -- comparing with comparative example Tiru remarkable -- NO<sub>2</sub>There were many amounts of concentration power * To NOx removal. It is power as a result of combination rate determination ratio a A (a+b's) also approximating T i ZA 1 tile of 0.0001 with the thing of combination rate determination ratio a / (a+b) if 0. 01.<sup>s</sup>Acquired power<sup>s</sup>(N0<sub>2</sub>Concentration = abbreviation 0.1 55 p pm .
022535
0226The amount of NOx removal = it is Plot about abbreviation 0. 36 p pm and this T i/A 1 tile. X axial seat which carries out A Since the mark is close to zero, illustration is omitted.
0227It is like and the thing [ that it is clear from these things ] for which alumina was blended when the range of combination rate determination ratio a/(a+b) was 0.0001*0.5, and is N0.<sub>2</sub>aiming at Withdrawal control it can do -- N 0 [ higher than a comparative example tile ]<sub>2</sub>This which acquires the reduction effect and also the N 0 X reduction effect It can do. In particular, combination rate determination ratio a (a+b) is Ah at the range of 0.05*0.2. The very high NO X reduction effect can be acquired, and it is more desirable than Leave and a comparative example tile. And combination rate determination ratios a Z (a+b) are very few like 0.0001. Blending alumina was also able to acquire the high N 0 X reduction effect.
0228It excelled also in that each T i ZA 1 tile of the surface state which made various values combination rate determination ratio a Z (a+b) is good too, and abrasion resistance.
0229(3) evaluation test 3 : influence 1 of the alumina combination grade exerted on nitrogen oxide reduction -- that 2 -- this evaluation test 3 Total amount of a Insecticide barrel titanium dioxide and alumina (both combination sum) When it presupposed that it is fixed and each loadings of a titanium dioxide and alumina are made into various things in it We decided to investigate the nitrogen oxide reduction effect.
0230First, the comparison same in order to take contrast with the example article of the present invention as the above-mentioned evaluation test 1 An example tile and photocatalyst function exertion tile of an example (example tile) It prepares as follows. It carried out. they are comparative example Tiru and the same evening A ring as the above-mentioned evaluation test 2 -- tile after calcination the weight of the titanium dioxide in the surface -- abbreviation 3. 3X 10"<sup>4</sup>g/c m<sup>2</sup>It comes out. Simple tile using the combination thing which contains only Contains alumina for a photocatalyst entirely (photocatalyst tile which is not demonstrated) The weight of alumina in the tile surface even if it attaches is abbreviationX[ 3.3 ] 10. --<sup>4</sup>g/cm<sup>2</sup>What was carried out was prepared. An example tile and the T i ZA 1 following tile It is.
0231T As opposed to the photocatalyst sol which the total amount of i ZA 1 tile, a titanium dioxide, and alumina occupies at 7. 5 w t% of a rate like a comparative example tile, Combination rate determination ratio a Z (a+b) They are spray coating and the calcinated tile on the same conditions as the above-mentioned comparative example tile about T i ZA 1 sol to which the combination rate of alumina was adjusted so that it might become the range of power 0.05*0.95. That is, the weight of the titanium dioxide in the tile surface after calcination is the increase in the weight of alumina. .
023236 it being Alike and Following -- AbbreviationX[ 3.3 ] 10 --<sup>4</sup>g/cm<sup>2</sup>various T i ZA 1 tiles which decreased in number [ Or ] are calcinated -- each T i/A 1 tile was used as the example tile in this evaluation test 3. Combination .3. 3X 1 of the a+b power above when determination ratio aZ (a+b) is 0.05 comparatively 01<sup>4</sup>gZcm<sup>2</sup>Weight a of alumina in the tile surface after calcination since it is alike and corresponds is abbreviationX[ 1.65 ] 10. -- SgZcm<sup>2</sup>It comes out and weight b of a titanium dioxide is abbreviation 3. 135X 10."<sup>4</sup>g/cm<sup>2</sup>It comes out. case where combination rate determination ratio a (a+b) is 0.95 To -- the -- opposite -- weight a of alumina -- abbreviation 3. 135 X 10"<sup>4</sup>g/c m<sup>2</sup>It comes out and they are 2 oxidization. Weight b of titanium is abbreviation 1.65X10. --<sup>5</sup>gZ cm<sup>2</sup>It comes out. It is in this evaluation test 3. Since a comparative example tile exhibits the catalyst function used as a standard, this comparative example tile and 2 acid comparing each T i/k 1 Thailand where the loadings of-izing titanium and alumina differ -- catalyst machine influence clarification of the loadings of the titanium dioxide and alumina which are exerted on improvement in ability -- it carries out.
0233the test equipment same in this evaluation test 3 as evaluation test 1 is used -- evaluation test 2 -- the same -- N 0<sub>2</sub>It is Plot about concentration and the amount of removal of NO X. A was carried out. the result -- a figure -- it is shown in 9. In addition, Comparison Example tile, Since no alumina is blended Combination rate determination ratio a Z (a+b) It is zero., The above-mentioned tile which does not demonstrate a photocatalyst, A titanium dioxide is blended entirely. Since there is no Listen Combination rate determination ratio a Z (a+b) is 1.,
0234this figure -- it sets to 9 -- comparative example tile (a/(a+b) =0) and graph a Y-axis top -- Plot is carried out -- NO<sub>2</sub>Abbreviation 0. 17 p pm and the amount of NO X removal of concentration were abbreviation 0. 3 p p m. Thus, NO X concentration is Including in the examination gas of that which falls from examination gas. N0 without rare Listen<sub>2</sub>It is to have mentioned already about that Concentration is measured and evaluation test 2. It is a cage. The mere tile of the above which does not demonstrate a photocatalyst and a graph On the X-axis Plot is carried out and it is N0.<sub>2</sub>Naturally concentration and the amount of NO X removal were zero.
0235On the other hand, there are few alumina loadings in T i/A 1 tile by which combination rate determination ratio a/(a+b) was expressed with X axial seat mark of a graph, and it is combination rate determination ratio a. (a+b) power<sup>s</sup>It is a thing of '0. 05 and is N0.<sub>2</sub>Abbreviation 0. 07 p pm and the amount of NO x removal of concentration are abbreviation 0. 46 p pm. It was. Alumina loadings excel titanium dioxide loadings and it is combination rate determination ratio a Z.
0236(a+b) is N0 with T i ZA 1 tile of 0.8.<sub>2</sub>Abbreviation 0. 13 p pm and the amount of N 0 removal of concentration were abbreviation 0. 32 p pm. And combination rate determination ratio a Z (a+b) is NO with T i ZA 1 tile of the range of 0.05*0.65.<sub>2</sub>concentration is [ the amount of NOx removal ] abbreviation 0. 43*0. 52 p pm in abbreviation 0. 07* 0. 09 p pm -- comparing with comparative example Tiru -- remarkable -- N0<sub>2</sub>Concentration is low and there were many amounts of NO X removal. Alumina Arrangement A total amount excels titanium dioxide loadings greatly, and it is combination rate determination ratio aZ. (a+b) power<sup>s</sup>0. With Nine or More T I ZA 1 Tiles, it is Comparative Example Tile and N0 below Equivalent.<sub>2</sub>They were concentration and the amount of NO X removal.
0237The total amount of like, a titanium dioxide [ that it is clear from these things ], and alumina is constant, and they are these. It is aluminum if the range of combination rate determination ratio a Z (a+b) is 0.0001*0.8. It is having blended Na and is N0.<sub>2</sub>Withdrawal control can be aimed at -- N 0 [ higher than a comparative example tile ]<sub>2</sub>The reduction effect and also the N 0 X reduction effect can be acquired. In particular, it is combination rate determination. If ratio aZ (a+b) is a range which is 0.05*0.6, it will reach to an extreme rather than a comparative example tile. The high NO X reduction effect can be acquired and it is desirable. in addition -- the case where it exceeds the case where combination rate determination ratio aZ (a+b) is less than 0.0001, and 0.8 -- a comparative example tile -- said -- Power of acquiring the NO X reduction effect of a grade<sup>s</sup>the case where combination rate determination ratio aZ (a+b) is 0.9 or more especially -- a photocatalyst -- titanium dioxide power -- it is too few and there is crevice [ the particle ] it is enclosed by the To alumina particle and light does not arrive -- it is expected that a photocatalyst function falls
0238'* omicron
0239It excelled also in that each T i ZA 1 tile of the surface state which made various values combination rate determination ratio a Z (a+b) is good too, and abrasion resistance.
0240the titanium dioxide of the Anatase type as a photocatalyst in the The 1 above-mentioned example is used -- this light As the metal oxide blended with a catalyst alumina which is a both sexes metal oxide, and base Of course, it is obtained also in the combination of the photocatalyst and metal oxide of power, the NO X reduction effect mentioned already, and others using strontium oxide and barium oxide which are sex metal oxides. it is . even if it is a titanium dioxide as a photocatalyst -- a crystallized type -- rutile -- or -- Brucky It can also be considered as the titanium dioxide of A. Z nO, V<sub>2</sub>0<sub>5</sub>W0<sub>3</sub>S n0<sub>2</sub>S r T i 0<sub>3</sub>B i<sub>2</sub>0<sub>3</sub>F e<sub>2</sub>O<sub>3</sub>It is NOx reduction even if it uses the photocatalyst of etc. An effect can be produced. Alumina, strontium oxide, and oxidization Bari As the metal oxide replaced with Beam, Zinc oxide and tin oxide (above, both sexes metal oxide), magnesium oxide, a calcium oxide, rubidium oxide, sodium oxide, and oxidization power RIUM (above, basic metal oxide) Even if it uses, the N O x reduction effect can be produced. When making basic gas applicable to reduction, he is oxidization Li besides the above-mentioned both sexes metal oxide. A (acid metal oxide) It can use.
0241Next, the 2nd example is described. At this The 2 example, it is 2 oxidization Chi to the tile surface. It consists of a photocatalyst combination thing which has photocatalysts, such as a tongue, and specific metal oxides, such as alumina. The formation procedure of a surface coat is different. In the example of this The 2 example, a surface coat is formed first. The substrate to carry out is prepared. As this substrate, they are ceramics, resin, metal, glass, and a china. Wood, A Silica Cal board, a concrete slab, and cement A A board and cement A extrusion plastic surgery board, chalk wall or a Wow 1 Tokurepe care-of-health lightweight concrete 1 A board etc. may be used -- if it is a substrate used for building constructions, such as a building, a house and a bridge, and a road noise-proof wall, -- environmental pollution things, such as nitrogen oxide Since quality is reduced on these building construction surfaces and the atmosphere can be purified, it is desirable.
0242Subsequently, a binder layer is formed in this prepared substrate surface. this binder layer -- the -- binder material, like an apparent initial softening is lower than the deterioration temperature of a substrate is selected -- character of a binder It is formed using this binder material by the proper technique of having suited. For example, a substrate is Tha. The glaze layer and seal for performing coloring etc. on the surface, in being A ring and Ho 1 low or pottery Printing layer can be used as it is as a binder layer. Sol, such as T i/A 1 sol in the The 1 example above-mentioned on the surface of the binder layer after binder layer formation It applies or prints, D titanium oxide particles produced from this sol by removing a solvent mixed particles with an alumina particle are sprinkled -- photocatalyst combination Material layer which turns into a surface coat behind It forms. or photocatalyst combination Material layer is formed in the binder layer made separately independently -- this -- A binder layer may be laid in the substrate surface. They are photocatalyst combination Material layer and the back these cases. It may be formed in the binder layer so that it may not secede from a binder layer in the case of calcination. then -- the case where a binder layer is made into the glaze layer which consists of glaze -- binder material (glaze) an apparent initial softening -- 3 more than 0 °C -- 3 0 it is high in the range below 0 °C -- and deterioration of a substrate -- temperature -- Ri is also heat-treated under low temperature environment. passing through this heat-treatment -- binder material
0243(Glaze) Carry out fusion solidification, and a binder layer is firmly fixed to the tile surface, and it is light. A surface coat is formed from catalyst combination Material layer. Under the present circumstances, in a boundary with a binder layer, it is a surface coat. .
024439 particles of the photocatalyst combination thing which can be boiled and set (titanium dioxide particles and alumina particle) it sediments to a binder layer in process of fusion of binder material -- this particle is maintenance in the state where it was buried with the binder layer It is carried out and is firmly fixed to a binder layer. Particles which adjoin in photocatalyst combination Material layer Comrades power<sup>s</sup>A surface coat is a form by joining together by sintering by the intermolecular force between 'particles, or calcination. It is [ in / accomplish and / at this surface coat / that surface ] each of a titanium dioxide and alumina. Particles are exposed. for this reason -- while a surface coat is firmly fixable to a binder layer -- 2 each particle of titanium oxide and alumina is effectively contacted in the open air -- things can be carried out. To obey According to the manufacturing method in The and the The 2 above-mentioned example, a photocatalytic reaction is caused at high efficiency. The building construction material etc. which have a surface coat to obtain can be manufactured easily.
0245in this case, heating temperature -- the apparent initial softening of binder material -- 3 since more than 0 °C made it high, softening of the binder material by heating does not take a long time carelessly, but it is desirable -- Titanium dioxide Since it does not interfere with sedimentation' maintenance of the particles of lumina, it is desirable. heating temperature -- Ba Inge's deterioration temperature -- 3 0 exceeding 0 °C -- high -- since it does not carry out -- rapid Melting of binder material Fusion is avoided -- generating of superfluous sedimentation and the concavo-convex field of the particles of a titanium dioxide or alumina -- or -- Faults, such as generating of a pinhole, can be controlled and it is desirable. Heating temperature and binder material It is 5 from the apparent initial softening of a charge. More than 0 °C is 1. 5 Being [ it / a temperature high in the range below 0 °C ] power<sup>s</sup>good -- better It is.
0246Even if it is the The 2 above-mentioned example, a crystallized type is rutile or bull Tsukai as a photocatalyst. A A titanium dioxide, and Z n O, V<sub>2</sub>0<sub>5</sub>W0<sub>3</sub>S n 0<sub>2</sub>S r T i 0<sub>3</sub>B i<sub>2</sub>O<sub>3</sub>F e<sub>2</sub>0<sub>3</sub>etc may be used. As the metal oxide replaced with To and alumina, If reduction objects are acidic gas, such as N OX, they are a zinc oxide and tin oxide. (above) A both sexes metal oxide, magnesium oxide, a calcium oxide, and rubidium oxide, acid Y sodium and oxidization potassium Um (above, basic metal oxide) it may use -- place which makes basic gas applicable to reduction Phosphorus oxide besides the both sexes metal oxide of the above [ Synthesis ] (acid metal oxide) It may use. Next, other examples are described. They are thing (for example, N O) to be reacted or an intermediate product with the specific compound previous-statement Used as above-mentioned The 1 and the 2nd example, and a photocatalyst. (for example, N 0)<sub>2</sub>
0247it holds in the catalyst system of reaction -- the opportunity and intermediate product with which an anti-[-ed ] Japan Society of Applied Physics power' catalyst reaction is presented securing certainly the opportunity with which this catalyst reaction is presented further -- the reduction effect of toxic substances, such as N O X -
024840 being also adding substances other than the example described below and this specific compound mentioned already, although it is a thing of a To obtain sake, and aiming at further improvement in the N O x reduction effect Or -- new -- The shelf effect is produced.
0249First, the 3rd example is described. this The 3 example and catalyst reaction which was described above it adds to increase in efficiency -- also combining the antibacterial function presented because a photocatalyst generates reactive oxygen species -- Possession It is a thing about Photocatalytic function exertion material. If in charge of the manufacture, it is an effect of a catalyst reaction. Alumina is blended with D titanium oxide by the above-mentioned combination rate determination ratio which can attain rate-ization. ing T i/A l sol, copper (C u), its oxide or silver (A g), and its oxide etc. -- the sol of The 3 which dispersed particles is prepared. Subsequently, it is a tile about T i ZA 1 sol. It applies to the surface, calcinates and forms the layer of this T i ZA 1. this [ then, / on the surface of a tile ] the sol of The 3 is applied to the T i /A 1 layer surface -- methods, such as optical reduction, -- sol ingredient of The 3 It fixes on the surface. this tile is a tile of this The 3 example -- this The 3 example a tile and its surface -- a photocatalyst -- surface coat fixed to the titanium dioxide with alumina it has -- it becomes the tile in which particles, such as C u, adhered to that upper surface further. The 3rd A If the application of Le is faced, the amount of applications is adjusted so that a photocatalyst may be irradiated enough. For example, it is abbreviation 0 .8* 2 .0 g Z c m [ after the weight of C u calcinating ].<sup>2</sup>A of grade is enough. It is. this The 3 example tile and the comparative example tile used by the above-mentioned evaluation test -- just -- The and the following antibacterial evaluations were performed. It decided to give by the existence of a bactericidal effect to the evaluation and coliform bacillus (3110 shares of Escherichia coil w).
0250first, the example tile and comparative example tile of the 3rd example -- both -- the surface -- 7 Toru 0 % Etah Nor it sterilizes by Le -- the after that and Tiru surface -- coliform bacillus fungus liquid 0.1 5 Milli (1* 5 X 1 0)<sup>4</sup>C F U was dropped. putting a glass board on this tile surface -- coliform bacillus -- the tile surface it is made to stick and let this be a sample -- one pair of this sample was prepared about each tile. subsequently -- one sample of the example tile of The 3 example, and a comparative example tile -- a glass board -- connoisseur it carries out and irradiates with a fluorescent light -- the sample of another side was placed under shading environment. And progress of irradiation time Under fluorescent light irradiation (under a bright place) Under a sample and shading (under a dark place) Coliform bacillus in a sample Rate of antibacterial properties which measured the probability of survival and was converted from this probability of survival (coliform bacillus is extinction or multiplication stopped rate) It is Plot to lapsed time. A was carried out. About the result, it is Drawing 1. It is shown in 0. What.
025141 measurement is faced -- wiping the fungus liquid of each sample with sterile absorbent gauze -- physiological saline 10 Milli it collects to Toru -- the probability of survival of the coliform bacillus in this physiological saline is measured -- this can be set in a sample It was considered as the probability of survival.
0252clear from Drawing 10 -- as -- the bottom of fluorescent light irradiation -- the example tile of the 3rd example, and comparison The example tile was able to acquire the antibacterial high effect. under this and fluorescent light irradiation, it can set to a surface coat a titanium dioxide generates reactive oxygen species actively -- these reactive oxygen species -- coliform bacillus -- the -- an owner -- It is considered the body which received the decomposition of the organic ingredient to carry out and stopped extinction or multiplication. deer it carries out -- since generation of reactive oxygen species does not have a comparative example tile under shading -- an antibacterial effect -- Mostly comparatively high [ under shading ] in the example tile of the 3rd example, while there is no It is obtained -- anti- -- The bacillus effect was able to be acquired. particles, such as C u which made it adhere to the surface, exhibit an antibacterial function also under shading It can fold and comes out. therefore, It was which it is under shading according to the example tile of this 3rd example Because -- a photocatalyst -- the antibacterial function in which a titanium dioxide cannot be demonstrated, either can be achieved by particles, such as C u, under shading -- the antibacterial function which a photocatalyst achieves can be complemented Too
0253Even if it is the The 3 above-mentioned example, a crystallized type is rutile or bull Tsukai as a photocatalyst. A A titanium dioxide, and Z nO, V<sub>2</sub>O<sub>5</sub>W0<sub>3</sub>S n0<sub>2</sub>S rT i 0<sub>3</sub>B i<sub>2</sub>O<sub>3</sub>F e<sub>2</sub>0<sub>3</sub>etc may be used -- as the metal oxide replaced with alumina -- a zinc oxide, Acid Y Tin (above, both sexes metal oxide), magnesium oxide, a calcium oxide, and oxidization Levisum, sodium oxide, and potassium oxide (above, basic metal oxide), phosphorus oxide (acid'^Genus oxide) It may use. A thing like metal, such as a substitute, its oxide, silver (Ag) or its oxide, P d and N i, C o, P t, Au, A l, Fe, Z n, C r, Rh, and Ru, which has an antibacterial action also a little with the metal itself is used for Cu. Things are preferred.
0254Next, the 4th and 5th example is described. This The 4 example is the above-mentioned metal oxides, such as a photocatalyst and alumina, like the 1st and The 2 example. (both sexes metal oxide) basic metal acid a ghost and an acid metal oxide are used -- The 3 example of compounds other than this and the above It is a thing of a four-ingredient system which used together metal, such as C u and A g, like. [ these ] The 5th example is light. It is a thing of a three-ingredient system which used compounds other than this together to the above-mentioned metal oxides (a both sexes metal oxide, a basic metal oxide, and acid metal oxide), such as a catalyst and alumina.
0255The free electron which the metal used together in the 4th example and the titanium dioxide which is photocatalysts take out has. 2 oxidization by reduction potential if it is the metal which has the reduction potential more than potential (1 3. 2 V) Support to titanium (reduction support) It can do and is desirable. Being concrete, Ag, Cu, P d, F e, N i, Cr, C o, P It is transition metals, such as t, Au, L i, C a, Mg, A l, Z n, Rh, and R u, among these Ag, Cu, P d, P t, Au, and reduction potential are positive. Since it has a value, it is [ that reduction support especially breaks out easily ] desirable. When using these metal together The technique of supporting the metal concerned to a photocatalyst is explained. The support technique of the metal to a photocatalyst The following techniques are mentioned if it carries out.
0256(1) Simple mixed method: Metal salt solution including the target metal kind is added to photocatalyst sol, and it is Mixed about both. The technique of uniting and supporting by adsorption to the photocatalyst particle surface of a metal ion.
0257(2) coprecipitation method: Precipitant after adding metal salt solution including the target metal kind to photocatalyst sol by addition or heating, metal salt and a photocatalyst are settled simultaneously and Coprecipitation is planned -- metal Io The technique of supporting A to a photocatalyst particle surface.
0258(3) The front [ optical reduction ] supporting method: It irradiates with the ultraviolet energy after adding metal salt solution including the target metal kind to photocatalyst sol, the optical reduction to the photocatalyst particle surface of a metal ion is used, and it is Responsibility. The technique of performing Possession.
0259(4) The after [ optical reduction ] supporting method : irradiate with the ultraviolet energy after applying metal salt solution including the target metal kind on a photocatalyst film, and support using the optical reduction to the photocatalyst film surface of a metal ion. Technique to perform.
0260(5) The vapor-depositing method : support metal particles or metallic compounds with the chemical or physical vapor-depositing method. Technique.
0261(6) in addition : before Granulation(ing) photocatalyst particles using the sol . gel method -- ion of the target metal kind it adds -- the technique of attaining particle-ization of a photocatalyst Z metal ion with a subsequent coprecipitation method etc.
0262The compound used together with a photocatalyst and the above-mentioned metal oxides, such as alumina, and a silica dioxide (silica: S iO)<sub>2</sub>It carried out. It changes to silica and is Z r0.<sub>2</sub>, G e 0<sub>2</sub>T h 0 Oxides, such as 2 and Z nO, can also be used.
0263In this The 4 example, the above-mentioned simple mixed method, the front [ optical reduction ] supporting method, or a coprecipitation method is adopted. The photocatalyst which supported metal with this technique was used.
0264photocatalyst function exertion tile of the 4th example (example tile) Is photocatalyst in the front [ simple mixed method and light reduction ] supporting method or a coprecipitation method whose A g and C u have been supported (titanium dioxide) Light which carried out power distribution catalyst sol is used -- following the process described by evaluation test 1 of the The 1 above-mentioned example this -- Supported [ metal ] photocatalyst sol (photocatalyst Z metal) Other two ingredients (alumina and silica) sol is mixed 'agitated -- spray coating [ of this mixed sol ]' -- pass calcination -- it manufactured. the photocatalyst/metal manufactured by carrying out like this (8 -- evening A ring of a four-ingredient system of 2 or (: 11) Z alumina Z silica is an example tile of The 4 example.) Under the present circumstances, in order to grasp influence of the newly blended metal and silica, it is photocatalyst Z metal. (8 also the two-component system of 2 or (:11) tile)
0265(Reference tile) It manufactured. the example tile of the 5th example -- The 1 example -- the same -- Photocatalyst (titanium dioxide) photocatalyst sol is used -- evaluation trial of the The 1 above-mentioned example Follow the process described by Trial 1. two ingredients of others [ sol / this / photocatalyst ] (alumina and Thilly power) sol -- mixture '-- Stirring is carried out -- spray coating [ of this mixed sol ]' -- pass calcination -- it manufactured. In this way, Tiru of a three-ingredient system of the manufactured photocatalyst Z alumina / silica is The 5 example. It is an example tile. And NO X reduction efficiency was investigated about this The 4, the example tile of the 5th example, the reference tile, the example tile of The 1 example, and the comparative example tile. The Example tile of one example, A comparative example tile is an evaluation test of the 1st example. 1 describes. It is a thing of As expected. The. Combination rate determination ratio of example Tiru of one example a /(a+b) is 1 A 1 1. Combination rate determination ratio of the example tile of The 4 example (S I 0)<sub>2</sub>/ (T i 0<sub>2</sub>+A 1<sub>2</sub>0<sub>3</sub>+ S i 0<sub>2</sub>) -- combination rate determination ratio of 1 A ring 1 it is 1 -- example Tha of the 5th example (A 1)<sub>2</sub>0<sub>3</sub>Z (T i 0<sub>2</sub>+A 1<sub>2</sub>0<sub>3</sub>+ S i 0<sub>2</sub>) -- 1Z1 It is 1. With the reference tile of the two-component system, it is metal and T i 0.<sub>2</sub> 1 of A g combination of Weight ratio (A gZT i 0) It is a reference tile of the two-component system, and is 0.0. 0<sub>2</sub> 1 of C u combination (C uZT i 0) Reference of the two-component system It is a tile and is 0.0.<sub>2</sub>It is.
0266About these tiles, the test equipment shown in Drawing 4 is used, and it is by evaluation test 1 of the 1st example. Like, CNOZo u t, CN0 which were described<sub>2</sub>Zo u t was measured. And this measurement CNOZo u t, CN0 which were carried out<sub>2</sub>After [ the light irradiation from /o u t and known examination gas concentration (CNOZ i n) ] 3 CN in the time (CNO/ i n -- CNOZo u t) of 0 minute passing O o
0267Classification Combination brief sketch Metal support technique (CNO/inch-CNO/out) CN02/out Nox reduction efficiency (%)
0268Comparative example tile Ti02 0 0.1 9 30.5
0269The 1st example tile Tau*theta 2+alpha|2theta3 0.55 0.05 52.6
0270Reference tile (two ingredients) Ti02+Ag simple mixed method 0.46 0.1 7 30.5
0271The before [ reference tile (two ingredients) Ti02+Ag Light origin ] supporting method 0.75 0.27 50.5
0272Reference tile (two ingredients) Ti02+Cu simple mixed method 0.48 0.1 7 32.6 41 >> The front [ reference tile (two ingredients) Ti02+Cu light reduction ] supporting method 0.6 0.22 40
0273Reference tile (two ingredients) Ti02+Cu is 0.5. 0.17 33
02745th example tile (three ingredients) Ti02+aluminum203+Si02 0.53 0.05 50.5
0275It is supporting method 0.62 before 4th example tile (four ingredients) Ti02+aluminum203+Si02+Ag light reduction. 0.1 1 53.7
0276It is supporting method 0.59 before 4th example tile (four ingredients) Ti02+aluminum203+Si02+Cu light reduction. 0.13 48.4
0277<img file="WO9929424A1_D0001.tif" />
0278x 0*N J (CNO/ i n-CNO/o u t) NO is N0.<sub>2</sub>Or N 0<sub>3</sub>Quantity which oxidized to 1
0279(The amount of NO reduction) it is -- it is a value used as the index of the oxidization power of NO. CNO<sub>2</sub>/o u t, NO<sub>2</sub>it is the amount of subgeneration to the outside of a of system -- this CN0<sub>2</sub>Ho with a small value of Zo u t When, N0<sub>2</sub>Do not make it break away out of a system, i.e., N0.<sub>2</sub>Adsorption power of expresses a strong thing. for this reason -- according to [ so that clearly from Table 1 ] the example tile of The 4 example -- the 1st operation an example and N 0 oxidization power more than equivalent can be demonstrated -- high N 0 X reduction efficiency was able to be acquired. the example tile of The 4 example which blended Ag especially -- being big (CNOZ i n-C NO/o u t) -- CNO with it [ high NO oxidization power and ] [ small ]<sub>2</sub>It is powerful N 0 by /o u t.<sub>2</sub>Since it became adsorption power, coexistence of oxidization power and adsorption power was able to be aimed at.
0280If the front [ the light reduction from the result of a reference tile ] supporting method is taken, it will be 2 of a titanium dioxide and metal. This which acquires the 1st example, N 0 oxidization power about equivalent, and N 0 X reduction efficiency even if it is an ingredient system It was able to do. Being [ since The 1 example, N 0 oxidization power about equivalent, and N 0 X reduction efficiency were acquired even if it blended the result of the example tile of the 5th example to silica / no fault by silica combination ] Force if related with NO X reduction.
0281Even if it is above The 4 and the 5th example, a crystallized type is rutile or Wurz as a photocatalyst. Kite's D titanium oxide, and Z nO, V<sub>2</sub>0<sub>5</sub>W0<sub>3</sub>S n0<sub>2</sub>S r T i 0<sub>3</sub>B i<sub>2</sub>O<sub>3</sub>F e<sub>2</sub>0<sub>3</sub>etc may be used. It is if the candidates for reduction are acidic gas, such as NO X, as a metal oxide replaced with alumina, Zinc oxide and tin oxide (above, both sexes metal acid ghost), magnesium oxide, a calcium oxide, rubidium oxide, sodium oxide, and potassium oxide (above, basic metal oxide) it may use -- basic gas -- candidate for reduction the case where it carries out -- phosphorus oxide besides the above-mentioned both sexes metal oxide (acid metal oxide) Use. The -- OK, 83 Well, (: change to 11 -- each of above-mentioned metal is used, or it changes to silica -- each of above-mentioned oxides can also be used.)
0282Next, the 6th and 7th example is described. That it is the same as that of this The 6 example and the The 4 above-mentioned example, and the photocatalyst represented with a titanium dioxide, Both sexes or salt represented with alumina Machine nature or acid metal oxide, It is Description at the metal described in the The 4 examples, such as Cu, Ag, P d, F e, N i, C r, C o, P t, Au, Rh, and R u, and The 4 examples, such as silica. Compound of Other (oxide) It is a thing of a four-ingredient system used together. The 7th example A photocatalyst, both sexes, the base or the acid metal oxide represented with alumina, and compound of others which were described in the The 4 examples, such as silica (oxide) Also that of a three-ingredient system used together It is that. And at this 6th [ the ] and The 7 example, it is resolution of environmental pollutants, such as NO X. The improvement in decomposition power and the prevention from contamination include power were aimed at.
0283That it is the same as that of the 4th example also in the 6th example, and photocatalyst (titanium dioxide) power in the above-mentioned simple mixed method or the front [ optical reduction ] supporting method in which Ag and Cu have been supported<sup>s</sup>The dispersed photocatalyst sol was used. And even if it is on the example tile of the 6th example, it is the 1st example like The 4 example. The process described by evaluation test 1 was followed and manufactured. the sol of that the example tile of The 7 example is the same as that of the 5th example, and ingredient of others [ sol / photocatalyst ] (alumina and silica) -- mixed . churning it carries out -- pass spray coating' calcination of this mixed sol -- it manufactured. In order to grasp the influence of newly blended golden Genus and silica, they are a photocatalyst/metal. (8)<sub>2</sub>Or the two-component system of (11), a photocatalyst Silica It is One to the two-component system and the three-ingredient system of photocatalyst Z metal (Ag or Cu) Z silica. It is a tile even if it is. (reference tile) It manufactured. in this case, substrate of photocatalyst sol (tile) an application is faced -- spray coating -- instead of -- hands, such as a spin coat and a dip coat A method can also be taken. The adherence to the substrate surface of photocatalyst sol is the criticism of the 1st example. Calcination performs like the process described by value examination 1. (baking type) Silico 1 A resin is mixed to photocatalyst sol -- stiffening this silicone resin in low temperature comparatively Method (paint type) It took. And the example tile of this The 6 and The 7 example, the reference tile, and the comparative example tile were evaluated. A comparative example tile is the 1st operation. It is a thing as evaluation test 1 of the example described.
0284Combination rate determination ratio of the example tile of the 6th example (S I0)<sub>2</sub>A (T i 0)<sub>2</sub>+A 1<sub>2</sub>0<sub>3</sub>+ S iO<sub>2</sub>) -- it is 1/10 -- the combination rate determination ratio of example Tiru of the 7th example
0285(A 1<sub>2</sub>0<sub>3</sub>/ (T i 0<sub>2</sub>+ A 1<sub>2</sub>0<sub>3</sub>+ S i 0<sub>2</sub>) -- it is 1Z10. A of photocatalyst Z silica Two-component system (S IO) Combination rate decision of a tile <sub>2</sub>/ (T i 0<sub>2</sub>+ S iO<sub>2</sub>) -- it is 1/5. Photocatalyst Z metal With the reference tile of the two-component system, it is metal and T i 0.<sub>2</sub>It is a reference tile of the Heavy two-component system, and is 0.001 (AgZT i 0). A quantity ratio is A g combination. <sub>2</sub>It is a reference tile of two-component system of Cu combination, and is 0.01 (CuZT i 0).<sub>2</sub>It is. With the reference tile of a three-ingredient system of photocatalyst Z metal Z silica, it is metal and T i 0.<sub>2</sub>Reference tie of the above [ Weight ratio ] -
028647 It is the Same as Le. (0.001 (Ag/T I0))<sub>2</sub>0.01 (C u/T i 0)<sub>2</sub>it is) -- the combination rate determination ratio (S I0)<sub>2</sub>Z (T i 0<sub>2</sub>+S i 0<sub>2</sub>) -- 1 It is 5.
0287First, in order to grasp the influence of the newly blended metal, it is photocatalyst Z metal. (8)<sub>2</sub>Or the reference tile of the two-component system of (:11) is explained. this -- the reference tile of the two-component system -- with baking a Over type -- titanium oxide sol (Ishihara Sangyo S T S -- 11) Various metal salt (Wako Pure Chem reagent best) It blended so that it might become 0. 001* 10 % to the titanium oxide solid content in titanium oxide sol. and a simple mixed method or the front [ optical reduction ] supporting method -- or -- A g or Cu was beforehand supported with the coprecipitation method to the photocatalyst. After mixing metal salt solution of Ag or C u to titanium oxide sol in the front [ optical reduction ] supporting method, it is 1 mWZ c m.<sup>2</sup>purple at Strength it irradiates with outside line for 2 hours -- it was considered as the sol of the photocatalyst in which metal was supported. With a coprecipitation method, it is T iO so.<sub>4</sub>let solution be a starting material -- metal salt solution is added to this solution, and it hydrolyzes into it -- metal It was considered as the sol of the photocatalyst of which power * support was done. then -- it is calcination to the tile surface about these photocatalyst sol next film thickness -- about -- spray coating is carried out so that it may be set to 0. 8 m -- 600*900. C (This 3 Thought tile abbreviation 800degreeC) They are a deed and a reference tile of the two-component system about calcination. (baking tie A) It obtained.
0288By a paint type, it is titanium oxide sol. (Nissan chemicals TA -- 15) Various metal salt (Wako Pure Chem reagent best) It is with 0.001*1% to the titanium oxide solid content in titanium oxide sol. It blended like. And photocatalyst sol in a simple mixed method or the front [ optical reduction ] supporting method whose A g or C u has been supported, silicone resin as a binder -- titanium oxide the solid content ratio of Silico 1 A resin -- 7 : it mixes so that it may be set to 3 -- the Tiru surface -- Spin Coat is carried out -- heating of 150"C -- reference tile of the two-component system (paint type) It obtained.
0289this -- Reference tile of the two-component system (baking type & paint type) about -- chemical substance The following evaluation tests were done to evaluation of decomposition power. To decomposition power, antibacterial activity, and an oil decomposition rate It can evaluate on a The direct target. Coliform bacillus explained in antibacterial activity and the The 3 above-mentioned example here
0290(3110 shares of Escherichia coil w) suppose that the receiving rate of antibacterial properties is used -- photocatalyst (titanium dioxide) The antibacterial activity which the tile which has a photocatalyst layer which consists of simple substances demonstrates was evaluated as 1. an oil decomposition rate -- it set as follows. It is 1 m gZ 100 c m to an examination object.<sup>2</sup>Only vegetable oil it applies -- lmWZcm<sup>2</sup>It irradiated with Of ultraviolet for seven days. and an oil application front and an oil application -- direct The value acquired from expression following it measures the gloss at the back and the end time of irradiation was made into the oil decomposition rate.
0291(I -- the time of the end of irradiation -- Gloss -- (immediately after [ an oil application ] gloss) I
0292Oil decomposition rate (%) = - X 100
0293(I -- front [ an oil application ] gloss 1 (immediately after [ an oil application ] gloss) I -- decomposition of the chemical substance according to a photocatalyst again, it is emitted from the photocatalyst which mainly carried out light excitation -- active Part of the chemical substance by a photocatalyst since it is based on the oxidization operation to the substance by an oxygen kind using-as one index of solution capability-oxidization power of photocatalyst power '-- it is possible. Here, it is nitric oxide as a model reaction. From (NO) to nitrogen dioxide (N0)<sub>2</sub>Translate by oxidization The amount of-izing also performed evaluation of NO oxidization power of various photocatalyst thin films. Using the test equipment shown in Drawing 4, this NO oxidization power measured CN0Z 0 u t, as evaluation test 1 of the 1st example described. And this measured CNOZo u t and known examination gas concentration
0294(CNO/ i n) from -- asking for (CNOZi n-CNO/o u t) for every lapsed time after light irradiation the mol of all the NO(s) which oxidized by the time 1 hour had passed since the light irradiation start -- a number is computed from above (CNOZi n -- CNOZou t) -- this was made into NO oxidization power. However, the conditions in that case and NO gas (examination gas) Casting and 2 Ri The deed and the sample piece were made into the size of 5 c mx 50 c m by Toru/m i n.
0295and the above Reference tile of the two-component system (baking type & paint type) about -- Antibacterial activity, an oil decomposition rate, and NO oxidization power are shown in Table 2. this table -- the antibacterial activity of 2, and oil solution as [ be / from a rate, NO oxidization power, and the above-mentioned explanation / clear ] -- case where a tile is under a bright place It is a thing.
0296Decomposition power evaluation about a baking type reference tile
0297The addition metal kind M/Ti02 (%) metal support method Antibacterial activity Oil decomposition rate (%) NOg Repulsive force / mol hr
0298Additive-free [ 0.000 ] 1.0 30 1.9
0299Cu 0.001 The front [ optical reduction ] supporting method 1.2 40 1.6
03000.010 Front [ Optical Reduction ] Supporting Method 15 50 2.0
03010.100 Front [ Optical Reduction ] Supporting Method 1.5 50 2.0
0302Responsibility before 1.000 light iS origin ; The past 2.0 60 2.4
03031.000 Simple Mixed Method 1.5 50 1.9
030410.000 light jg yuan W supporting method 1.2 30 1.2
03051.000 is 'A 1.6. 50 2.0
0306Ag 0.100 It is support * 2.5 before optical reduction. 50 3.3
03070.100 Simple Mixed Method 1.5 35 1.9
0308Pd 0.100 The front [ optical reduction ] supporting method 2.0 60 2.4
0309Fe 0.100 The front [ optical reduction ] supporting method 1.5 65 2.4 CO
0310(SO paint type decomposition power evaluation which carries out - reference tile This place)
0311An addition metal kind /the Ti02 (%) metal support method Antibacterial activity Oil decomposition rate (%) NO oxidization power / jumol hr
0312Additive-free [ 0.000 ] 1.0 50 0.6
0313Cu 0.001 1.2 50 0.5
03140.010 1.5 70 0.6
03150.100 2.0 90 0.6
03161.000 2.0 90 0.7
03171.000 Simple Mixed Method 1.8 55 0.6
03181.000 is /> 1.9. 60 0.6
0319Ag 0.100 The front [ optical reduction ] supporting method 3.0 80 1.0
03200.100 Simple Mixed Method 2.5 55 0.6
0321.
032250 this Table -- it Sets to Baking Type Reference Tile from 2 -- Cu Addition System -- Optical Reduction C U Adjusted with the Pre-Supporting Method -- T I 0<sub>2</sub>That of which was boiled, and it received and did 1 % support is most excellent in antibacterial activity, an oil decomposition rate, and NO oxidization power. A At g addition system, it is the front [ optical reduction ] supporting method too. Power<sup>?</sup>Antibacterial activity, an oil decomposition rate, and NO oxidization power are most superior to the simple mixed method. It is in front. It is a thing and a ratio additive-free in antibacterial activity, an oil decomposition rate, and NO oxidization power also by addition of the metal of a gap. T i 0 since Comparison is carried out and it is improving<sub>2</sub>Cu boiled and supported, Ag, P d, F e, etc. Metal is T i 0.<sub>2</sub>Contributing-to the improvement in Decomposition power of power<sup>5</sup>' -- I understand. It is C u adjusted with the front [ optical reduction ] supporting method by Cu addition system in the baking type T i 0<sub>2</sub>Be alike and receive.
0323Thing power of which 1* 1 % support was done<sup>s</sup>' -- the highest antibacterial activity is shown. A A g addition system is Cu addition system. Showing [ antibacterial activity with high Ri ] I found out the power.
0324it prints from the above-mentioned result and sets to a type and paint type reference tile -- the metal of Cu, A g, P d, and 6 grades -- 1^0<sub>2</sub>Improving [ decomposition power ]-by it being alike and supporting power 'It understands. That is, the above-mentioned metal is T i 0.<sub>2</sub>It is Connection when it has a function which raises Decomposition power of. Argument can be carried out. To decomposition power, the front [ optical reduction ] supporting method is simple as the support method of a metal kind. Excelling-mixed method power<sup>?</sup>It understands. what the amount of support of the above-mentioned metal is adjusted for T i 0<sub>2</sub>It can be said that Decomposition power of can be changed.
0325this baking type Antibacterial activity at the time of placing reference Tiru of the two-component system under a dark place about -- the investigated place -- a simple mixed method -- C u -- T i 0<sub>2</sub>3 which was alike, and received and carried out 0. 1% support In the Thought tile, antibacterial activity was abbreviation 0.3. It is a simple mixed method and is C u T i 0<sub>2</sub>Also the reference tile of which was boiled, and it received and did 1 % support, antibacterial activity was abbreviation 0.3. It is a simple mixed method and is Ag T i 0<sub>2</sub>Also the reference tile of which was boiled, and it received and did 1 % support, antibacterial activity was abbreviation 0.3. Thus, activity of the photocatalyst is not carried out under a dark place, but they are the antibacterial activity and the supported gold. The genus itself demonstrates. (And a metal additive-free tile, i.e., a photocatalyst, With a thing) They are these reference when it takes into consideration that the antibacterial activity under a dark place is zero mostly. Antibacterial properties which the tile of only the antibacterial activity which the metal itself demonstrates in evening A ring, and a photocatalyst demonstrates Under a bright place, the antibacterial activity exceeding power (table 2 1) can be demonstrated. For example, simple mixture It is a method and Cu T i 0<sub>2</sub>Power in which the antibacterial activity under the bright place of the reference tile of which was boiled, and it received and did 0. 1 % support is 1.5 from Table 2<sup>s</sup>Antibacterial activity (0.3) and the photocatalyst which ', this value, and the Cu itself demonstrate .
032651 It exceeds the sum of tile antibacterial activity [ which accepts it ] (1). This sake (it is 11 Ding1O),<sub>2</sub>It is alike, receives and is To carry. It is To and they are C u and T iO.<sub>2</sub>Acquiring-bigger effect than what was combined with A single power<sup>s</sup>It can be said that it can do.
0327being based on the effect in the above-mentioned reference tile here -- example tile of the 6th and The 7 example about -- it explains. It is Seki to the hydrophilicity which is evaluation criteria new in this The 6 and the 7th example. It evaluated, even if carried out. first, a hydrophilic examination etc. are preceded -- the relation between hydrophilicity and surface contamination -- just -- Explanation is carried out.
0328recent years come -- the dirt of the surface can be prevented by making the surface into hydrophilicity -- knowledge (polymers and the 4th four volumes, the 1 9 9 May, 5 item, and p . 3 0 7) which came to be carried out. hydrophilicity it is convertible by an angle of contact with water -- this angle-of-contact power<sup>s</sup>the water which the wettability over water improved, so that it was small, and contacted the hydrophilic surface -- the contact surface -- a stop -- A -- . and -- such -- water a power' stop -- A -- if -- dirt ingredients, such as city dust contained in rain water etc., -- water -- hydrophilicity it flows and falls from the surface -- the dirt prevention effect increases.
0329for this reason, the graft polymer to which hydrophilicity was given is applied to a building;^wall etc. -- this A Aiming-at [ become dirty from the coat of raft polymer and ]-prevention power<sup>s</sup>Although 'proposal of is done, it is an angle of contact with water. The hydrophilicity converted is abbreviation 3. 0* abbreviation 4 Since it is 0 ° , water is a stop and To comparatively to the surface. Neither To, the dirt prevention effect nor the antifog effect is necessarily enough. moreover -- being represented with argillite an angle of contact with Mineral dust and water -- abbreviation 2 0* abbreviation 5 since it is 0 ° -- the above-mentioned angle of contact -- an owner -- compatibility with the graft polymer to carry out is presented -- it is easy to adhere to the graft polymer surface. It is [ this and ] a graph conjointly. Especially the coat and film of Tolymer are pairs to minerals dust. It was difficult to produce the high dirt prevention effect to carry out.
0330and the city dust which includes an angle of contact for many oleophilic ingredients and minerals dust like argillite etc. -- if it is made smaller than an angle of contact, in the substrate surface, these dust will demonstrate compatibility There is nothing and it can heighten the dirt prevention effect further. And an angle of contact is the degree of zero. Since hydrophilicity diffuses a rise and water in the shape of a film on the substrate surface and it becomes easy to flow so that it approaches, it is a top. Not only the city dust of an account but also inorganic dust flows with water from the substrate surface easily, and it falls. this -- a case -- the dirt prevention effect -- raising -- a top -- Then. -- an angle of contact -- abbreviation 2 It is a value near [ in below 0 ° ] zero. Things are more preferred. Example of the present invention using a photocatalyst (The 6, the 7th example) When it inquires based on such a problem, hydroxyl radical - * H is generated by the catalyst reaction which a photocatalyst presents. The angle of contact with the water which serves as a hydrophilic index as described above from things was investigated. The examination The outline is as follows.
0331The 6 and the example tile of the 7th example which were mentioned already, and the reference tile of two-component system and a three-ingredient system -- about a Comparative example tile, a baking type thing is prepared, respectively -- proper size The sample piece was prepared. And lamp which irradiates with ultraviolet rays the angle of contact of the waterdrop dropped at this sample piece after Tiru manufacture (in 3 2 0* 3 8 0 n m, the light income of the piece of sample of a wavelength is about l mW/ c m)<sup>2</sup>abbreviation 2 After irradiating with Across ultraviolet rays in 4 hours (under a Ming place) sufficient time for the activity by this photocatalyst to stop nearly completely -- Across dark place After neglecting it (under a dark place) about -- it measured. the measurement result -- a table -- it is shown in 3.
0332Hydrophilicity (angle of contact of water) / ° oxidization decomposition power i Specialty fl* Classification Combination brief sketch At the time of Ming At the time of dark Antibacterial activity An oil decomposition rate / % NO oxidization power / imol hr Mohs hardness Comparative example tile tau*02 10 27 1.0 30 1.9 Four Second Example Tile (Three Ingredients) Ti02+Aluminum203+Si02 3 20 1.0 30 1.9 Six Reference Tile (Two Ingredients) Ding I02+Ag10 25'2.5 50 3.3 4 Reference Tile (Two Ingredients) Ti02+Cu 10 27 1.5 50 2.4 Four The 6 example tile (four ingredients) Ti02+aluminum203+Si02+Ag 3 20 2.5 50 3.3 Six The 6 example tile (four ingredients) Ti02+aluminum203+Si02+Cu 6 20 1.5 50 2.4 6 The 6 Example Tile (Four Ingredients) Ti02+Aluminum203+Si02+Pd 3 20 2.8 55 6.0 Six The 6 Example Tile (Four Ingredients) Ti02+Aluminum203+Si02+Fe 3 20 1.5 50 3.0 6 00 -- The 6 Example Tile (Four Ingredients) Ti02+Aluminum203+Si02+Nickel 3 20 2.5 50 3.1 6 The 6 Example Tile (four ingredients) Ti02+aluminum203+Si02+Cr 3 20 1.5 50 2.4 Six The 6 example tile (four ingredients) Ti02+aluminum203+SiO2+Co 3 20 1.5 30 1J 6 The 6 example tile (four ingredients) Ti02+aluminum203+Si02+Pt 3 20 2.8 60 6.0 6 The 6 Example Tile (Four Ingredients) Ti02+Aluminum203+Si02+Au 3 20 1.5 50 2.4 Six The 6 Example Tile (Four Ingredients) Ti02+Aluminum203+Si02+Rh 3 20 1.5 50 2.4 Six The 6 Example Tile (4 Ingredient>Ti02+Aluminum203+Si02+Ru 3 20 1.5 50 2.4 6)
0333.
033454 this Table -- Influence of Metal Combination from Result of 3 was Investigated Reference Tile of Two-component System -- the Same -- 4 Formation Part -- System -- Example Tile (The 6 Example) even if it is -- it is Combination about Metal in Front [, Such as Cu and Ag, ] Carry Out, Antibacterial activity, oil decomposition power, and NO oxidization power can improve, and it can heighten decomposition power. It was. And comparison of only the antibacterial activity and the photocatalyst which the metal in front [, such as Cu and A g, ] itself demonstrates Obtaining the antibacterial activity which exceeds the sum of the antibacterial activity of an example tile or the example tile of a three-ingredient system It was able to do. And the mere tile which does not have the Mohs hardness of a surface coat and a surface coat has. It is equivalent to Mohs hardness and had the practicality as a tile.
0335the angle of contact of the 6th and 7th example and a comparative example tile -- the time of Ming -- regardless of the time of Z dark -- small -- a surface coat since it has become -- T iO<sub>2</sub>S iO both blended<sub>2</sub>Is or A 1<sub>2</sub>0<sub>3</sub>or these both -- letting adsorption of a hydroxyl group pass, as mentioned already -- hydrophilic improvement in the tile surface Contributing became clear. And the metal in front [, such as Cu and A g, ] was blended. By things, it turned out that increase of an angle of contact, i.e., a hydrophilic fall, does not occur. these things from -- functional material which has the functional thin film or such a thin film which makes decomposition power and hydrophilicity compatible TiO of metal, such as Cu which contributes to the improvement in decomposition power, Ag, P d, F e, N i, C r, C o, P t, A u, Rh, and Ru<sub>2</sub>S i 0 which contributes to the support through which it passes, and improvement in hydrophilicity<sub>2</sub>Or A 1<sub>2</sub>0<sub>3</sub>Or T i 0 of these both<sub>2</sub>It can manufacture through the combination through which it passes. It is T i 0 to the example tile of this The 6 and The 7 example, and its surface coat.<sub>2</sub>It is alike, it adds and is A 1.<sub>2</sub>0<sub>3</sub>It is nitrogen oxide etc. as the 1st and 2nd example explained, since it was by Including. Of course, it has the reduction effect of a toxic substance. If N 0 oxidization power of the example tile of The 7 example of a 3 ingredient system which does not contain the above-mentioned metal was on the example tile of power^the 6 [ equivalent to a comparative example tile ], and The 7 example, as the 1st and 2nd example explained, it is intermediate product. (N0)<sub>2</sub>It is carrying out a chemical change even to nitric acid, and is this NO.<sub>2</sub>Also until is To reduce. To. Therefore, according to the example tile of the 6th and 7th example, it is NO and N0.<sub>2</sub>Including it is -- there is no inconsistency in the ability to demonstrate the reduction effect of the whole toxic substance.
0336the improvement effect of the above-mentioned decomposition power -- The 6 of paint Typhoon, and the example tile of the 7th example -- just -- When investigated about whether The is obtained, a result as shown in Table 4 was brought. Therefore, paint According to [ even if it is a type ] the example tile of the 6th and 7th example, it is combination of the metal in front. It can let it pass, antibacterial activity, oil decomposition power, and NO oxidization power can be raised, decomposition power can be heightened, and it is This. It proved. It is Buddy with this paint type of The 6, and the example tile of the 7th example. It is T i 0 like an example tile The and above-mentioned baking type.<sub>2</sub>S i O both blended<sub>2</sub>This which can contribute to the hydrophilic improvement in the tile surface through the hydroxyl group adsorption boiled and depended It is natural. Even if it is this paint type of thing, a surface coat is Pencil hard of 4 H. Since it had a degree, it had the practicality as a tile.
0337Paint type
0338An oxidized part Power
0339Classification Combination brief sketch Antibacterial activity An oil decomposition rate /% NO Change force / mol hr pencil hardness Reference tile (two ingredients) Ti02+Si02 1 50 0.6 4H Second Example Tile (Three Ingredients) Ti02+Al203+Si02 1 50 0.6 4H Reference Tile (Three Ingredients) Ti02+Ag+Si02 2.5 90 1.0 4H Reference Tile (Three Ingredients) Ti02+Cu+Si02 2 90 0 4 -- H The 6 Example Tile (Four Ingredients) Ti02+Aluminum203+Si02+Ag 3 90 1.0 4H The 6 Example Tile (Four Ingredients) Ti02+Al203+Si02+Cu 2 90 0J 4H The 6 Example Tile (Four Ingredients) Ti02+Al203+Si02+Pd 2.8 55 6.0 4H The 6 Example Tile (Four Ingredients) Ti02+Al203+Si02+Fe 1.5 50 3.0 4H The 6 Example Tile (Four Ingredients) Ti02+aluminum203+Si02+nickel 2.5 50 3.1 a 4H The 6 example tile (four ingredients) -- Ti02+aluminum203+Si02+Cr 1 .5 50 2.4 4 -- H The 6 example tile (four ingredients) Ti02+aluminum203+Si02+C o 1.5 30 1 J 4H The 6 example tile (Four ingredients) Ti02+aluminum203+Si02+Pt 2.8 60 6.0 4H 6th Example Tile (Four ingredients) Ti02+aluminum203+Si02+Au 1.5 50 2.4 It is The 6 Example Tile (Four Ingredients) Ti02+Aluminum203+Si02+Rh 1.5 4 H. 50 2.4 It is The 6 Example Tile (Four Ingredients) Ti02+Aluminum203+Si02+Ru 1.5 4 H. 50 2.4 4H
0340Here, it is photocatalyst Z metal Noalmina about the above-mentioned loadings, such as Cu and A g. Thilly The example tile of The 6 example of a four-ingredient system of power is taken and explained to an example. The example tile of operation of the 6th example is a combination rate determination ratio. (S I 0)<sub>2</sub>/ (T i 0<sub>2</sub>+A 1<sub>2</sub>0<sub>3</sub>+S i 0<sub>2</sub>) -- suppose that it is fixed with 1/10 -- metaled weight -- c and T i 0<sub>2</sub>When Weight is expressed as d, it is cZd (metal compounding ratio). What was blended so that it might become a value of power versatility was prepared. And each operation About the example tile, the relation of this metal compounding ratio and antibacterial activity was investigated. burning the result an attachment type and paint type exception -- a figure -- 1 It is shown in 1 and Drawing 12. Antibacterial properties which the example tile of The 7 example of the antibacterial activity in this case and a three-ingredient system of a photocatalyst / alumina Z silica demonstrates Power was expressed as 1.
0341this figure -- 1 as [ show / 1 and Drawing 12 ] -- even if a baking type and a paint type are which metal of Ag, P d, P t, Cu, and C r -- metal combination specific force abbreviation 0.00001 -- with -- When it was a top, the antibacterial activity beyond "value 1" was able to be obtained. In Ag, P d, and P t, a metal compounding ratio is [ the peak of antibacterial activity, and / Cu and O 1" ] about 0.0 at about 0.001. Antibacterial activity became a tendency which decreases a peak and after that by 1. Therefore, as for metal, such as Ag, P d, P t, C u, and C r, the metal compounding ratio is a value of abbreviation 0.00001*0.05. It turned out that it may blend so that it may become. that is, these metal -- 0.00001 -- if it does not break out contribution that there will be too little metal and it will not make it improvement in antibacterial activity at all if blended by the above metal compounding ratio but it is 0.05 or less -- a photocatalyst (T i 0)<sub>2</sub>It is desirable to a saying [ receiving, and metal becoming superfluous and having a bad influence on the catalyst reaction of a photocatalyst ] Power crack. operation of the surface coat which contains Ag, P d, and P t as an ingredient of The 4 the example tile of the surface coat which contains an example tile, Cu, and C r as an ingredient of The 4 -- anti- -- Excelling [ Fungal power ] mosquito understood.
0342To the surface quality of the surface coat formed in the tile surface here using the above-mentioned photocatalyst sol It attaches, Example tile of The 6 example of a four-ingredient system of photocatalyst Z metal / alumina Z silica Example Tiru of The 7 example of a three-ingredient system of a photocatalyst / alumina Z silica is taken for an example, and it is an opinion. Ming is carried out. In this case, the example tile of the 6th and 7th example and a combination rate determination ratio (S IO)<sub>2</sub>
0343/ (T i 0<sub>2</sub>+A 1<sub>2</sub>0<sub>3</sub>+ S i 0<sub>2</sub>) -- suppose that it is fixed with 1Z10 -- one of the surface quality it is -- what has the surface coat it was made to serve as a value of Film thickness force * versatility was prepared. and -- About each example tile, the relation between this surface coat film thickness, and an angle of contact, antibacterial activity, oil decomposition power or N O oxidization power was investigated. the result -- a figure -- 1 3* figure 1 It is shown in 7.
0344Drawing 1 3* figure 1 6, example tile of The 6 example of a four-ingredient system (baking type) One It is. And Drawing 1 Grad to whom 3 expresses a relation with an angle of contact at the time of surface coat film thickness and Ming It is Off, Drawing 1 4 is a graph showing the relation between surface coat film thickness and antibacterial activity, and is Drawing 1. 5 is a table. It is a graph showing the relation between surface layer film thickness and oil decomposition power, and is Drawing 1. 6 is surface coat film thickness and N 0 oxidization. It is a graph showing a relation with power. The antibacterial activity in this case and the antibacterial activity which have a surface coat containing photocatalyst Z alumina Z silica and which carries out tile power exertion were expressed as 1. Drawing 1 7, example tile of The 7 example of three-ingredient system (baking type) Surface coat film which can be set It is a graph which expresses a relation with an angle of contact at the time of thickness and Ming. A g, P d, P t, C u, and Cr shall be contained in the example tile of a four-ingredient system, and a surface coat, respectively -- film thickness -- 0.0 0 It investigated about the thing of 5* 3 m.
0345It is a hydroxyl group as mentioned already in the surface coat in the example tile of a three-ingredient system and a four-ingredient system. S i 0 which contributes to improvement in hydrophilicity through adsorption<sub>2</sub>S i 0 since it was made to contain<sub>2</sub>Function obtained by having made it contain (improvement in hydrophilicity) It asks. it is made sure by the existence of a low angle of contact that the improvement in the hydrophilicity in this case was mentioned already -- an angle of contact -- 2 below 0 ° -- Power<sup>s</sup>It is desirable. this viewpoint to a figure -- 1 3 and Drawing 1 if 7 is considered -- example tile of a baking type three-ingredient system and a four-ingredient system the film thickness of a surface coat -- abbreviation 0.0 more than 1 m -- if there is and 2 the small angle of contact below 0 ° is acquired -- the dirt prevention effect through improvement in hydrophilicity It is obtained and is desirable. Surface coat film thickness is abbreviation 0.0. It is 2 that it is more than 1 mu m. The angle of contact below 0 ° It is obtained, Film (surface coat) Since it is not too thin, it is an angle of contact with a big substrate. Even if had, it is this substrate (tile). Presenting the angle of contact of the formed surface coat itself It is considered the made body.
0346this figure -- 1 3 and Drawing 1 as [ show / in 7 ] -- if surface coat film thickness is more than abbreviation 0 .5 mu m -- angle of contact It becomes as [ a small value ]. A surface coat is denser as one of these and surface coat film thickness become thick. Dense in a substrate and a surface coat, when surface coat film thickness is too thick, since it wears and weight increases per area The fall of arrival nature may be caused and surface coat mosquito exfoliation may be carried out. Therefore, surface coat film thickness, a substrate, and a table Being [ it / below / from a viewpoint of maintenance of adhesion nature with a surface layer / abbreviation 3 m ] power<sup>s</sup>It is desirable. Table -
034759 ultraviolet rays stopping permeating the lower layer of a surface coat at all, and considering it as a photocatalyst, if surface layer film thickness is too thick Since the function of The cannot be exhibited by the whole surface coat, surface coat film thickness is below abbreviation 3 / m. things -- ' -- it can be said that it is desirable.
0348And like and surface coat film Atsunori enclosure defined as mentioned above which are shown in figure 1 6 4* figure 1 (if it is abbreviation 0 .0 1* abbreviation , antibacterial activity, oil decomposition power, and N O oxidization power are raised certainly, To is made, and it is desirable.)
0349Besides the above-mentioned surface coat film thickness, it investigated about the following surface quality.
0350Ultraviolet-rays mosquito<sup>?</sup>If it glares ^* An excitation electron is carried out by Insecticide with a hydroxyl radical. Drawer the phenomenon of occurring by a surface coat by The and this excitation electron is specified -- if a such child is observed, the creation state of this excitation electron, i.e., the creation state of hydroxyl radical and O H, will become clear. S i 0 which does adsorption and maintenance of a hydroxyl group at the example tile of the 6th and The 7 example, and its surface coat<sub>2</sub>Including Hydroxyl radical and O H generated with the photocatalyst since it had are this S iO.<sub>2</sub>Keep at It has. therefore, the quantity of hydroxyl radical * H generated, so that there was much generation of the excitation electron by a photocatalyst increases -- as a result -- S i 0<sub>2</sub>Surface of -- the hydroxyl group density to kick increases -- water It is considered angle-of-contact power ^ and fence intermediary hydrophilicity power quantity Circle. for this reason, a surface coat -- Silver nitrate dissolution If an ultraviolet exposure is performed in the state where liquid was made to adhere, it can set to the silver bath adhering to a surface coat. the electric charge of a silver ion changes with these excitation electricity -- a color reaction occurs -- ultraviolet exposure order Color difference Power observation is carried out. This color difference It is large, so that there are many excitation electrons which participate in a reaction. It becomes an index which it hears and which shows a hydrophilic grade since it becomes. Therefore, we decided to observe color difference △ epsilon as follows.
0351This color difference Silver bath of general 1 % as a reagent which presents a color reaction to measurement of epsilon It used. It reacts to excitation electron (e -) generated with the silver ion contained in this solution, and the photocatalyst, and deposits as silver. It is as an equation and follows. thus, silver by depositing, it discolors the brown in the adhesion surface of a silver bath, or black -- color difference deltaepsilon It is obtained clearly.
0352A g<sup>+</sup>+ e -- ->A g I
0353therefore, the silver bath of 1 % is made to adhere to the surface coat of the example tile of paint type The 6 example (four ingredients) and The 7 example (3 ingredient) -- an ultraviolet exposure is performed in this state -- each Thailand Le -- color difference If deltaepsilon is measured was used. In an ultraviolet-rays and surface coat top, it is 1 .2 mW/c m.<sup>2</sup>it glares so that it may become Strength -- irradiation time was carried out for 5 minutes. And it measured. Color difference The relation between epsilon, and an angle of contact, antibacterial activity, oil decomposition power or N O oxidization power was investigated. the -- a result -- a figure -- 1 8* figure 2 It is shown in 2. Color difference If measurement is faced, it is Remaining on the surface of a tile. It is residual water solution at Kim Taol before wiping, and the amount of silver coloration on the surface of Tiru in this ^ voice and an examination.
0354(Before an ultraviolet exposure) The difference with the amount of silver coloration was searched for. And in measurement of the amount of silver coloration, it is Japan. Color difference meter N D 3 of a discoloration industrial company 0 0 A is used and it is to JIS Z 8729 (1980) and JIS Z 8730 (1980). It was based.
0355Drawing 1 8* figure 2 Example tile of The 6 example of 1 and a four-ingredient system (paint type) about -- It is a thing. and Drawing 1 8 -- color difference the graph which expresses a relation with an angle of contact at the time of Ming -- With and a figure -- 19 -- color difference it is a graph showing a relation with antibacterial activity -- Drawing 2 0 -- surface coat film thickness it is a graph showing a relation with oil decomposition power -- Drawing 2 1 -- color difference Relation between deltaepsilon and N O oxidization power It is a graph to express. It is Including about the antibacterial activity in this case, and photocatalyst Z alumina Z silica. Tile power of having the surface coat which it had<sup>?</sup>The antibacterial activity to demonstrate was expressed as 1. Drawing 2 2 is an example tile of The 7 example of a three-ingredient system. (paint type) Color difference which can be set It is an angle of contact at the time of epsilon and Ming. It is a graph showing a relation. the example tile of a four-ingredient system and a surface coat -- A g -- Including it shall have -- color difference 0*6 It investigated even about the thing used as 0. in this case, color difference The tile of zero, and mere tile which does not generate an excitation electron ( Miya and others of a paint tile which only has a surface coat) it is .
0356Drawing 1 8 and Drawing 2 Color difference from 2 if there is one or more deltaepsilon -- 2 the small angle of contact below 0 ° is acquired -- the dirt prevention effect through improvement in hydrophilicity is acquired, and it is desirable. And color difference deltaepsilon is about 1. With zero or more, an angle of contact serves as as [ a small value ]. The quantity which is a photocatalyst on the other hand can increase. Since it becomes active [ generation of a Excited electron ], it is color difference. Ingredients other than the power which becomes large, and a photocatalyst
0357(A 1<sub>2</sub>0<sub>3</sub>S i 0<sub>2</sub>or quantity of the photocatalyst to the total amount of these and the above-mentioned metal it increases -- the adhesion nature to a substrate falls and exfoliation of a surface coat occurs, so that the amount of photocatalysts increases -- Ease It is considered Go over. for this reason, color difference 5 if it is zero or less -- ingredients other than a photocatalyst there is not too much quantity of the photocatalyst to a total amount -- from a viewpoint of controlling surface coat exfoliation It is desirable. -
035861 And like and color difference defined as mentioned above which are shown in figure 19* figure 21 If it is the range of deltaepsilon (abbreviation 1 * about 50), antibacterial activity, oil decomposition power, and NO oxidization power will be raised certainly. It can do and is desirable.
0359Next, T i 0<sub>2</sub>S 10 which contribute to improvement in Hydrophilicity<sub>2</sub>Or A 1<sub>2</sub>0<sub>3</sub>Other ingredients of etc (golden Genus oxide) Improvement in the super-hydrophilicity function by addition is explained. first, baking Tha Example of the eve (The 8 example) from -- it explains.
0360(1) Supply of the sol of a photocatalyst and a metal oxide;
0361Light catalytic substance Z
0362T i 0<sub>2</sub>Sol: Mean particle size abbreviation 0. 02 m (Ishihara Sangyo S T S -- 1 1) Or average grain Child abundance 0. O l/^m (Taki Chemical A -- 6 L)
0363S n 0<sub>2</sub>Sol: Mean particle size abbreviation 0. 002 m (Taki Chemical)
0364Cheap you―Ze type T i 0 [ harmless in this The 8 example, chemically stable and ]<sub>2</sub>S n0 besides of<sub>2</sub>Crystalline T i 0 which is other light catalytic substances although sol was used<sub>2</sub>S r T i 0<sub>3</sub>Z nO, S i C, G aP, C d S, C d S e, Mo S<sub>3</sub>V<sub>2</sub>0<sub>5</sub>WO 3, S n0<sub>2</sub>B i<sub>2</sub>0<sub>5</sub>F e<sub>2</sub>0<sub>3</sub>It can use as alternative material.
0365Metal oxide ZS i 0<sub>2</sub>Sol: Mean particle size abbreviation 0. 007* abbreviation 0. 009 m (Nissan chemicals SNOWTEX S)
0366A 1<sub>2</sub>O<sub>3</sub>sol: -- mean particle size abbreviation 0.01 111 -- about -- 0. 1//m (Nissan chemicals Alumina sol 200' -- formless) Or mean particle size abbreviation 0. 01* about 0. (Nissan chemicals aluminum Nazor 520 and Be 1 my A)
0367S iO<sub>2</sub>+K<sub>2</sub>O Sol: (Nissan Chemicals SNOWTEX Kappa and S I 02/K20 Molar Ratio 3.3*4.0)
0368S iO<sub>2</sub>+ L iO<sub>2</sub>Sol: (Nissan chemicals lithium Silike 1 A 35 and S i 02ZL i 02 molar ratio 3.5)
0369Z r 0<sub>2</sub>Sol: Mean particle size abbreviation 0. 07 m (Nissan chemicals N Z S -- 30 B)
0370although all the above-mentioned sol used the commercial item -- as a starting material -- metaled Alkoxide -- chloride or a hydrolysis depressant like A tilamin is added -- ethanol and propanol after diluting with alcohol [ like ], it is advance about hydrolysis partially -- or -- perfect -- hydrolysis -
037162 The liquid made to Progress may be used. For example, it is Thet Lae if it is Alkoxide of titanium. Toxy titanium, tetraisopropoxy titanium, and tetra n -- Propoxytitanium and Thet Love Toxy titanium and Thet Rames Toxy titanium etc. can be mentioned. Others Organic metallic compound (chelate and Acethe 1 A) and T i C l<sub>4</sub>T i (S0)<sub>4</sub>)<sub>2</sub>of -- it needs It is also possible to use inorganic metallic compounds as a starting material.
0372(2) Adjustment of hydrophilic grant material;
0373the concentration of solid content of mixture of the sol of the above-mentioned light catalytic substance and a metal oxide is 0.4 % of the weight -- dark -- it dilutes beforehand so that it may become a degree -- the below-mentioned table -- each sol is mixed by the ratio shown in 5 -- enough -- It agitated. The solid content weight ratio after mixture turns into the amount ratio of liquid weight of each used sol.
0374(3) Production of a hydrophilic exertion tile;
0375glazing tile (TOTOAB 06 E 1 1) is prepared as a substrate -- table of this tile Carry out spray coating of the above-mentioned mixed sol of the specified quantity to a field so that that film thickness may be set to abbreviation 0. 5 m. It was. They are 700 degrees (it calcinated in :* 900"C, and calcination time 60 minutes, and manufactured the 8th example tile.) of highest temperature abbreviation at RHK (roller 1 Haas kiln) about this. Power which performed spray coating in this The 8 example tile Coatee It is Florco 1 tee as the Tongue method. Tongue and Spinco 1 Tee Tongue and Di Hopko 1 Tyng and roll coatee Co 1 of Tongue, brush coating, and others Tee The Tongue method is usable. At this The 8 example, it is business about a tile as a substrate. Although it was, in addition to this, metal, ceramics, pottery, glass, plastics, a tree, a stone, cement, concretes or those combination, and the layered product of them are used. Power<sup>s</sup>It is possible. in addition -- supply of the sol of the above [ this The 8 example and the sol to be used ] describes Photocatalyst since it is It was, Both sexes or basic Young represented with alumina The acid metal oxide and compound of others which were described in the The 4 examples, such as silica (oxide) were combined. It is a thing of the two-component system and a three-ingredient system. but the below-mentioned table -- it is shown in 5 like and one ingredient -- two or more sorts of compounds (metal oxide) It may use.
0376(4) Evaluation;
0377The stillness angle of contact of water estimated hydrophilic evaluation. First, examination tile (The 8 example tile and a comparative example tile) Ultraviolet-rays intensity abbreviation 1. 5mWZcm<sup>2</sup>of B LB fluorescent light (product made from Sankyo mind black rye cards, F L 20 B L B) Contact with water after glaring for 24 hours The antenna was measured. Then, 7 2-hour shading preservation (dark place preservation) It carries out and is an angle of contact with water again. It measured. A result is shown in the above-mentioned table. Film strength was evaluated using Mohs hardness. a result -- a table -- it is shown in 5.
0378<img file="WO9929424A1_D0002.tif" />
0379this table -- hydrophilicity-izing by the ultraviolet exposure from No. 2*No. 14 of 5 -- T i 0<sub>2</sub>/
0380(T i 0<sub>2</sub>+S i 0<sub>2</sub>+A 1<sub>2</sub>0<sub>3</sub>the range of *0. 4 -- an angle of contact with water -- 10 degrees or less A fact s it becomes and sufficient hydrophilicity-ization is made -- understand. It is T i 0 after dark place preservation.<sub>2</sub>The amount of of It is A 1 if it is an equivalent amount.<sub>2</sub>0<sub>3</sub>It is hydrophilic power, so that there are many amounts of Addition.<sup>5</sup>' -- A fact currently maintained in the high state<sup>?</sup>It understands. S i 0<sub>2</sub>By adding, it is hardness power by increasing the amount of addition again.<sup>s</sup>Going-up mosquito To understand. From these things to a photocatalyst (T i 0)<sub>2</sub>S i 0<sub>2</sub>And A 1<sub>2</sub>0<sub>3</sub>by adding, the hydrophilicity under light irradiation improves rather than a photocatalyst simple substance -- again -- the bottom of a dark place hydrophilic maintenance power also improves -- improvement in film hardness and precise nature was also checked further. This effect When the sol shown in this example among them is used, the improvement in hydrophilicity is mainly A 1.<sub>2</sub>0<sub>3</sub>it is brought by Addition -- the improvement in film hardness -- S i 0<sub>2</sub>It is brought by Addition. It thinks. No. 1 of Table 4, It is a result about the above-mentioned glazing tile. No. 2, Tile of only a photocatalyst (comparative example tile) about -- it is a result.
0381No. of Table 5 15*No. 18 are S i 0, although the same examination was done.<sub>2</sub>A part of K<sub>2</sub>0 it is alike and replace. This result is S i 0 similarly.<sub>2</sub>K<sub>2</sub>0 A 1<sub>2</sub>0<sub>3</sub>The calcination temperature of improvement in a hydrophilic function and the rise of film hardness is 700 abbreviation * abbreviation 800 by Addition. It is attained in the range of a degree. No. 19 are 3. 10<sub>2</sub>It is A part of L iO<sub>2</sub>It comes out and places and is Conversion. Although it is the obtained examination, as for this, improvement in a hydrophilic function and film hardness is attained similarly.
0382No. 17 and No. 18 are what examined the materials shape of alumina sol, and are Ah. It is Toward of a hydrophilic function further by To using the alumina sol which it is formless and is a feathers-like organization. The top was checked. They are parents rather than being a particle-like, in order for this to raise a hydrophilic function. It is thought that the way power, especially the effect which are organizations with many water machines are high.
0383No. 2 (iT i 0<sub>2</sub>It is alike and is Z r0.<sub>2</sub>It is a result at the time of adding. Future Z rO<sub>2</sub>But it turned out that hydrophilic improvement has an effect.
0384No. 21 and No. 22 are S n0 as a photocatalyst.<sub>2</sub>It is a result of the used examination. S n 0<sub>2</sub>also alone, a hydrophilicity-ized effect is seen -- further -- A 1<sub>2</sub>0<sub>3</sub>It is hydrophilic Toward by adding. The top has been checked. There is no fall of film hardness at this time, and it is S nO.<sub>2</sub>It is considered as the binder of That itself. Also having a function of The was checked.
0385No. 3*: From No. 14 to A 1<sub>2</sub>0<sub>3</sub>The amount power of addition<sup>s</sup>They are angle-of-contact power and a fence, so that it increases. -
038666 it becomes -- hydrophilicity improves. Therefore, A 1<sub>2</sub>0<sub>3</sub>By adjusting the amount of addition, it is a degree of hydrophilicity. A degree can be changed. and a table -- adjusting the amount of support to the photocatalyst of metal, such as the result of 2 to Cu, Ag, P d, and F e, -- T i 0<sub>2</sub>Changing Decomposition power of It is A 1 when it takes that it can do into consideration.<sub>2</sub>0<sub>3</sub>This which performs the amount adjustment of addition, and the amount adjustment of support of the above-mentioned metal The balance of hydrophilic performance and decomposition power (decomposition performance) can be adjusted. As a result, powerful are . The grade which can demonstrate hydrophilicity with a photocatalyst when you need decomposition power, and more than comparable It can be said that this powerful decomposition power needed can be demonstrated, maintaining.
0387Thus, when hydrophilic performance and decomposition performance are made to combine, there are the following advantages. Hydrophilicity Marked improvement in the removal efficiency of adhesion dirt and improvement in removal speed can be aimed at according to two steps of processes of the based dirt removal and the dirt removal based on decomposition performance. In this case, slight dirt left behind after the dirt removal based on hydrophilicity depending on the kind of dirt To the improvement in decomposition power which passed through the amount adjustment of support of the above-mentioned metal although adhesion intensity might sometimes be high Slight dirt with such high adhesion intensity is also removable. furthermore -- such -- Stain since Re is removed, covering the light to a photocatalyst is lost -- it is irradiation to a photocatalyst The light volume carried out can be increased. Therefore, it is a basis to the dirt removal and decomposition performance based on hydrophilicity. To dirt removal can be maintained very efficiently.
0388When it summarizes above, it is S i 0 to a photocatalyst.<sub>2</sub>A 1<sub>2</sub>0<sub>3</sub>Z r 0<sub>2</sub>By adding, it turned out that the bottom angle of contact of light irradiation and the hydrophilic maintenance power after dark place maintenance improve. This effect and power considered to be brought by the hydrophilicity of the substance of these It is Show about the hydrophilicity of a substance. It is considered as Indicators and is heat-of-wetting power.<sup>5</sup>' -- it is mentioned -- T i 0 [ desirable as a photocatalyst ]<sub>2</sub>Wet heat of is you 1. It is a Ze type and isX[ 320*512 ] 10. --<sup>3</sup>J m<sup>2</sup>It is a rutile type and isX[ 293*645 ] 10.<sup>3</sup>J m--<sup>2</sup>It comes out. From this toX[ 500 ] 10 --<sup>3</sup>J m<sup>2</sup>This which is a compound with the above heat of wetting power -- it is desirable -- everything but the three above-mentioned kinds of metal oxides -- germanium 0<sub>2</sub>T h 0<sub>2</sub>Z nO Be lifted. thing in which not only a thing with a crystal structure but these metal oxides are formless it may be -- it turned out that the range of the diameter of a particle is 0.1 or less. S i 0<sub>2</sub>It turned out that film hardness improves by adding. S i 0<sub>2</sub>It is K in a part of amount of Addition.<sub>2</sub>0 Or L I 0<sub>2</sub>Calcination temperature power * Me was also able to raise film hardness by it being alike and carrying out. As a range which can expect the above-mentioned effect especially, it is T i 0.<sub>2</sub>A (all the solid quantities of a hydrophilic grant adjustment agent) -- *0. 5 and S i 0<sub>2</sub>Conditions of / (total amount of solid content of hydrophilic grant adjustment agent) *0. 5 It is a case where it fills.
0389Next, T i 0<sub>2</sub>S i 0 which contributes to improvement in Hydrophilicity<sub>2</sub>Or A 1<sub>2</sub>0<sub>3</sub>other ingredients of etc (golden Genus oxide) The improvement in the super-hydrophilicity function by addition, and improvement in other functions (improvement in film hardness) existence -- paint type example (The 9 example) about -- it explains.
0390(1) Supply of the sol of a photocatalyst and a metal oxide;
0391Light catalytic substance ZT i 0<sub>2</sub>Sol: (Nissan chemicals TA -- 15)
0392Cheap you―Ze type T i 0 [ harmless in this The 9 example, chemically stable and ]<sub>2</sub>S n0 besides of<sub>2</sub>power which uses sol others -- crystalline T iO which is a light catalytic substance<sub>2</sub>S rT iO<sub>3</sub>Z nO, S i C, G a P, C d S, Cd S e, Mo S<sub>3</sub>V<sub>2</sub>0<sub>5</sub>W0<sub>3</sub>S n0<sub>2</sub>B i<sub>2</sub>0<sub>5</sub>F e<sub>2</sub>0<sub>3</sub>It can use as alternative material. Metal oxide ZS i 0<sub>2</sub>Sol: (Japan Synthetic Rubber glass power T 2202)
0393A 1<sub>2</sub>0<sub>3</sub>Sol: Mean particle size abbreviation 0. 01* abbreviation 0. (the Nissan chemicals alumina sol)
0394520 - Bex -Might
0395S iO<sub>2</sub>although Is a commercially available product was used -- silicone (organopolysiloxane) Or Si A fact* using the film forming agent consisting of the precursor of Rico 1 A -- it is possible. T i 0<sub>2</sub>And A 1<sub>2</sub>O<sub>3</sub>as that it is the same as that of the The 8 above-mentioned example although the commercial item was used also about sol, and a starting material -- metaled Alkoxide -- Hydrolysis suppression like chloride or A tilamin pass the process which adding a system agent etc. mentioned already -- it is also possible to prepare these sol.
0396(2) Adjustment of hydrophilic grant material;
0397it dilutes with the ethanol after mixing the above-mentioned materials by a fixed ratio 3 times -- considering it as coating fluid It was. the ingredient ratio of the produced Co 1 Tyng liquid, and the next table -- it is shown in 6. Table 6
0398Ti02 Si02 alphaiota2omicron3
03991 /10 0* 1 /12
04001 /5 0 ~3
04011 /2 0 ~3
04021 0 ~3
04032 0 ~3
04045 0 ~3
0405(3) Production of a hydrophilic exertion tile;
0406it being the same as that of the The 8 above-mentioned example and a glazing tile are prepared as a substrate -- Spinco 1 Tyng method coating -- 1 5 0 times -- 3 it heats for 0 minute -- the coat was hardened. In this The 9 example Spin coatee They are flow coating and a spray coatee as the power which performed Tongue, and a coating method. Tongue and Di The coating method of Hopko 1 Tyng, roll coating, brush coating, and others is usable. moreover -- this The 9 example -- tile others -- metal, ceramics, pottery, glass, plastics, a tree, a stone, and cement using A, concretes or those combination, and the layered product of them as a substrate -- To use is possible. supply of the sol of the above [ this The 9 example and the sol to be used ] stating and a table -- the ingredient shown in 5 -- T i 0<sub>2</sub>S i 0<sub>2</sub>Or A 1<sub>2</sub>0<sub>3</sub>both sexes which come out and are represented with a certain thing to a photocatalyst, and alumina, base, or acidity A metal oxide and compound of others which were described in the The 4 examples, such as silica (oxide) Group It saw. It is a thing of the two-component system and a three-ingredient system.
0407(4) Evaluation;
0408About film hardness, it is a pencil hardness test. (JIS K5400 paint open study) Examination tile (The 9 an example tile and comparative example tile) It carried out. the result -- a table -- it is shown in 7. parents that it is the same as that of the The 8 above-mentioned example about water, and the stillness angle of contact of water -- examination tile (The 9 an example tile and comparative example tile) about -- it measured. the result -- a table -- it is shown in 8. This The ultraviolet-rays intensity of a case is abbreviation 1 .S mWZ c m.<sup>2</sup>Irradiation time is 1. It could be 2 hours.
0409CD<img file="WO9929424A1_D0003.tif" />
0410<img file="WO9929424A1_D0004.tif" />
04118^
0412O t" Facial 61/66 omicronlambda\
0413SO Beam £0/86 df/JO<<I this table -- 7 to S i 0<sub>2</sub>/* i 0<sub>2</sub>A 0.1 or less-But thing and binder (S i 0)<sub>2</sub>sol [ ] -- the fall of being insufficient and film strength is caused -- thing power clarification was carried out. S i 0 from Table 8<sub>2</sub>T i 0<sub>2</sub>In the range of But 1 /5* 2, it is A l.<sub>2</sub>0<sub>3</sub>ZT i 0<sub>2</sub>But 1 1 2*2 -- be -- the effect of the improvement in hydrophilic speed by The and alumina addition is revealed -- thing power clarification was carried out. This effect It is A 1 as the 8th example described.<sub>2</sub>0<sub>3</sub>thinking that it is brought by Hydrophilicity of -- Power to be -- heat of wetting is mentioned as an index which shows the hydrophilicity of a substance -- as a photocatalyst -- good -- better it is -- T i 0<sub>2</sub>Wet heat of is a you 1Ze type and is 3. 2 0*5 1X[ 2 ] 1 0<sup>_3</sup>J m--<sup>2</sup>It is a rutile type and is 2. 9 3*6 4X[ 5 ] 1 0 --<sup>3</sup>J m1<sup>2</sup>It comes out. This to 5 0X[ 0 ] 1 0 --<sup>3</sup>J m1<sup>2</sup>Above Being [ it / a compound with heat of wetting ] power<sup>s</sup>it is desirable -- even if it is this example -- Z r 0<sub>2</sub>G eO<sub>2</sub>T h 0<sub>2</sub>Z nO power s' -- it is mentioned. These metal oxides have a crystal structure. Not only a thing but it may be formless.
0414although the example of the present invention was described above -- the example and embodiment of the above [ the present invention ] -- what it is not limited -- mode which becomes various in the range which does not deviate from the gist of the present invention Of course, it can carry out.
0415For example, particles, such as copper and its oxide, are adhered and Tiru which can fill up an antibacterial function is manufactured. If it hits carrying out, T pass an application on the tile surface and calcination of i /A 1 sol -- beforehand -- light the tile which has a surface coat which consists of a catalyst combination thing is manufactured -- the surface coat of the tile -- anew -- The 3rd sol may be applied and calcinated.
20 sheets
Sheet 1 Sheet 2 Sheet 3 Sheet 4 Sheet 5 Sheet 6 Sheet 7 Sheet 8 Sheet 9 Sheet 10 Sheet 11 Sheet 12 Sheet 13 Sheet 14 Sheet 15 Sheet 16 Sheet 17 Sheet 18 Sheet 19 Sheet 20
Every citation, both ways
| Document | Relation | Office | Category | Cited during |
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Numbers
- Publication
- 99/29424
- Application
- 9803705
Titles2
- English
- PHOTOCATALYST COMPOSITION, SUBSTANCE CONTAINING PHOTOCATALYST, AND MATERIAL FUNCTIONING AS PHOTOCATALYST AND PROCESS FOR PRODUCING THE SAME
- French
- COMPOSITION PHOTOCATALYTIQUE, SUBSTANCE CONTENANT UN PHOTOCATALYSEUR, MATERIAU FONCTIONNANT COMME UN PHOTOCATALYSEUR ET PROCEDE DE FABRICATION CORRESPONDANT
Classification
- CPC, 22
- B01J21/066
- B01J35/39
- B01J35/36
- B01J21/06
- B01J21/063
- B01J23/16
- B01J23/40
- B01J23/70
- B01J37/0217
- B01J37/0244
- B01J35/19
- B01J35/30
- B01J35/70
- B01J35/38
- B01J21/12
- B01J21/10
- B01J23/02
- B01J23/14
- B01J27/16
- B01J23/48
- B01J35/395
- B01J35/45
- IPC, 8
- B01D53 56
- B01D53 86
- B01J21 06
- B01J23 16
- B01J23 40
- B01J23 70
- B01J35 00
- B01J37 02
Designated states92
- Regional, 51
- Ghana
- Gambia
- Kenya
- Lesotho
- Malawi
- Sudan
- Eswatini
- Uganda
- Zimbabwe
- Armenia
- Azerbaijan
- Belarus
- Kyrgyzstan
- Kazakhstan
- Republic of Moldova
- Russian Federation
- Tajikistan
- Turkmenistan
- Austria
- Belgium
- Switzerland
- Cyprus
- Germany
- Denmark
and 27 moreShow fewer
- Spain
- Finland
- France
- United Kingdom
- Greece
- Ireland
- Italy
- Luxembourg
- Monaco
- Netherlands (Kingdom of the)
- Portugal
- Sweden
- Burkina Faso
- Benin
- Central African Republic
- Congo
- Côte d’Ivoire
- Cameroon
- Gabon
- Guinea
- Guinea-Bissau
- Mali
- Mauritania
- Niger
- Senegal
- Chad
- Togo
- National, 41
- Albania
- Australia
- Bosnia and Herzegovina
- Barbados
- Bulgaria
- Brazil
- Canada
- China
- Cuba
- Czechia
- Estonia
- Georgia
- Hungary
- Indonesia
- Israel
- Iceland
- Republic of Korea
- Saint Lucia
- Sri Lanka
- Liberia
- Lithuania
- Latvia
- Madagascar
- North Macedonia
and 17 moreShow fewer
- Mongolia
- Mexico
- Norway
- New Zealand
- Poland
- Romania
- Singapore
- Slovenia
- Slovakia
- Sierra Leone
- Türkiye
- Trinidad and Tobago
- Ukraine
- United States of America
- Uzbekistan
- Viet Nam
- Yugoslavia, later Serbia and Montenegro (until 2006)