TW495384B - Photocatalyst formulation, photocatalyst-containing material, and photocatalytically activatable material and process for producing the same - Google Patents

Abstract

In a formulation comprising titanium dioxide as a photocatalyst and an amphoteric metal oxide (alumina or the like) or a basic metal oxide (barium oxide, strontium oxide or the like) as a material having a base point, when a nitrogen oxide (nitrogen monoxide) comes into contact with or approaches titanium dioxide, upon exposed to light, the carbon monoxide is oxidized to nitrogen dioxide (gas) by OH as an active oxygen species produced by titanium dioxide. As is apparent from the molecular structure, nitrogen dioxide is an acidic gas, alumina as an amphoteric metal oxide, and barium oxide and strontium oxide are a basic metal oxide. The oxygen atom therof serves as a base point to an acid gas. Therefor, nitrogen dioxide is attracted and chemically bonded to the oxygen atom, held on the metal oxide, and kept close to titanium dioxide as the photocatalyst.

Description

495384 A7 B7 五、發明説明（ 經濟部中央標準局員工消費合作社印製 本發明係有關於一種配合有一受到光之照射即可產生 觸媒作用之光觸媒配合物、及用以該光觸媒配合物之光觸 媒功能發揮材料、以及該光觸媒配合物之製造方法。 以往’該種類之光觸媒係因用以於觸媒反應之能源為 太陽光等之光能，而該能源是無止盡，其用途也因此漸漸 擴大°如有下列提案，如為一種光觸媒之二氧化鈦（Ti02) ’尤其是結晶型為鈦礦型二氧化鈦，它經所照射之光（紫 外線）能生成激發電子及空穴，藉該所生成之激發電子及 空穴’在觸媒表面上之氧及水分之存在下，生成〇2·、〇-、· 〇H(•顯示不成對電子，意指自由基物種）等之活性 氧物種。利用該活性氧物種所具有之自由基之性質，藉作 用於經由活性氧物種之氧化反應，使大氣中之氮氧化物 (ΝΟχ)形成無害的反應物（硝酸）之大氣淨化之用途、經有 機成分之氧化之細菌分解、所謂抗菌之用途等。 但氮氧化物接受活性氧物種作用之氧化反應之過程中 ’有二氧化氮（N02)作為中間生成物而生成，該二氧化氮 進而接受氧化，最終變成硝酸。然後，用以該硝酸之生成 ’削減大氣中之氮氧化物，而可淨化大氣。因此為了提高 氮氧化物之削減效率，必須令活性氧物種與氮氧化物，或 二氧化氮共存。但是，因為二氧化氮在化學上是屬於比較 安定之化合物（氣體），所生成之二氧化氮向反應之系外脫 離，作用於活性氧物種之氧化反應之效率降低，結果導致 削減效率也降低。又，用以如活性碳之多孔質吸著劑，意 圖抑制二氧化氮之脫離，正如下列說明，這也未必有效。 本紙張尺度適用中國國家標準（CNS) Μ規格（210Χ297公慶） 請 先 閱 % 背 面 ， 之 注 項 |ψί 訂 線 4 495384 經濟部中央標準局員工消費合作社印製 A7 B7五、發明説明（2 ) 如此之吸著劑，吸著了一旦脫離之二氧化氮時，將該 二氧化氮吸著於吸著劑之細孔中，而不使之放出。因此， 所吸著之二氧化氮置於作用於活性氧物種之氧化作用之體 系外，而不能再接受該氧化作用，而產生不能形成最終生 成物之硝酸的狀況。是故，其氮氧化物最終不能轉化到硝 酸，而阻礙了削減效率。尤其在可與活性氧物種之共存下 反應之體系内之領域，即靠近光觸媒之領域中，吸著於吸 著劑之二氧化氮被氧化而變成硝酸，但靠近光觸媒之領域 係相對於吸著劑中物質之吸著領域全體（含細孔）而言是非 常有限，因此沒有被氧化而轉化成硝酸之二氧化氮的比率 可說極高。即，即使使用了吸著劑，也只能將二氧化氮吸 著並加以保持，透過轉化至硝酸之氮氧化物之削減不能說 是非常充分的。 本發明係用以解決上述問題點而形成，其目的在於謀 求光觸媒作用之觸媒反應更進一步之效率化，或透過作用 於該觸媒反應之被反應物轉化至最終生成物之轉化程度而 提高削減效率。又，另一目的係完成光觸媒之觸媒作用。 用以解決上述問題，本發明之第1種光觸媒配合物， 係以一受到光之照射即可產生觸媒作用之光觸媒與另一化 合物相配合而成者，其特徵在於：該另一化合物係一種， 當作為前述光觸媒所參與之觸媒反應中的被反應物接受觸 媒反應而經化學變化轉化成由該被反應物之構造及前述觸 媒反應所決定之最終生成物時，可與前述光觸媒之共存下 ，提高前述被反應物轉化成前述最終生成物之轉化程度的 (請先閲讀背面之注意事項再本頁)495384 A7 B7 V. Description of the invention (Printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs This invention relates to a photocatalyst complex with a photocatalyst that can be catalyzed by the irradiation of light, and a photocatalyst using the photocatalyst complex Function-generating material and method for manufacturing the photocatalyst complex. In the past, 'the photocatalyst of this type is because the energy used for the reaction of the catalyst is solar energy, such as sunlight, and the energy is endless, and its use is gradually increasing. Enlargement ° If there is the following proposal, such as a photocatalyst titanium dioxide (Ti02) 'especially crystalline titanium dioxide type titanium dioxide, which can generate excited electrons and holes by the light (ultraviolet rays) irradiated, and then use the generated excitation Electrons and holes' in the presence of oxygen and water on the catalyst surface generate reactive oxygen species such as 〇2 ·, 〇-, · 〇H (• show unpaired electrons, meaning radical species), etc. Use this The nature of the free radicals of reactive oxygen species, through the oxidation reaction of reactive oxygen species, makes nitrogen oxides (NOx) in the atmosphere harmless. Application of nitric acid for atmospheric purification, decomposition of bacteria oxidized by organic components, so-called antibacterial applications, etc. However, nitrogen oxide (N02) is used in the oxidation reaction of nitrogen oxides under the action of reactive oxygen species. Intermediate products are generated, and the nitrogen dioxide undergoes oxidation and eventually becomes nitric acid. Then, the production of nitric acid is used to reduce the nitrogen oxides in the atmosphere and purify the atmosphere. Therefore, in order to improve the nitrogen oxide reduction efficiency, Reactive oxygen species must coexist with nitrogen oxides or nitrogen dioxide. However, because nitrogen dioxide is a chemically stable compound (gas), the generated nitrogen dioxide detaches from the reaction system and acts on The efficiency of the oxidation reaction of the active oxygen species is reduced, and as a result, the reduction efficiency is also reduced. In addition, a porous sorbent such as activated carbon is intended to suppress the detachment of nitrogen dioxide, as described below, which may not be effective. Standards are applicable to Chinese National Standards (CNS) M specifications (210 × 297 public holidays) Please read the notes on the back of% first. 4 495384 A7 B7 printed by the Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs 5. Description of the invention (2) Such a sorbent, once absorbing nitrogen dioxide, sorbs the nitrogen dioxide into the sorbent. Fine pores without releasing them. Therefore, the absorbed nitrogen dioxide is placed outside the system that acts on the oxidation of reactive oxygen species, and can no longer accept the oxidation, and produces nitric acid that cannot form the final product. Therefore, its nitrogen oxides cannot be converted to nitric acid eventually, which hinders the reduction of efficiency. Especially in the fields that can react with the coexistence of reactive oxygen species, that is, the areas close to photocatalysts Nitrogen dioxide of the agent is oxidized to become nitric acid, but the area close to the photocatalyst is very limited compared to the entire adsorption area (including pores) of the substance in the adsorbent, so it is not oxidized and converted into nitric acid. The ratio of nitrogen dioxide can be said to be extremely high. That is, even if a sorbent is used, nitrogen dioxide can only be adsorbed and retained, and the reduction of nitrogen oxides by conversion to nitric acid cannot be said to be very sufficient. The present invention is formed to solve the above-mentioned problems, and the purpose thereof is to further improve the efficiency of the catalytic reaction of the photocatalyst, or to improve the conversion degree of the reactant reacting to the final product by the reaction Cut efficiency. Another purpose is to accomplish the catalyst function of photocatalyst. In order to solve the above problems, the first photocatalyst complex of the present invention is a photocatalyst capable of generating a catalyst action upon irradiation with light, and is compounded with another compound, which is characterized in that the other compound is One type, when the reactant in the catalyst reaction in which the photocatalyst participates receives the catalyst reaction and is chemically transformed into the final product determined by the structure of the reactant and the catalyst reaction, the Under the coexistence of photocatalysts, the degree of conversion of the aforementioned reactants into the aforementioned final products is increased (please read the precautions on the back before this page)

訂 線 本紙張尺度適用中國國家標準（CNS ) A4規格（210X 297公釐） 495384 經濟部中央標準局員工消費合作社印製 A7 B7 五、發明説明（3 ) 化合物。 藉具有上述構成之本發明的第1種光觸媒化合物，可 提高從被反應物轉化至最終生成物之轉化程度，因此可提 高被反應物之削減效率。 在具有上述構成之本發明的第1種光觸媒化合物中， 可採取下列態樣。第1態樣為， 前述另一化合物係一種，可與前述被反應物，或者可 與前述被反應物受到前述觸媒反應轉化成前述最終生成物 之前所生成之中間生成物進行化學結合之化合物。 在該第1態樣中，被反應物或中間反應物，與光觸媒 同時配合之另一化合物化學結合而保持。保持該被反應物 或中間生成物之另一化合物並非採用多孔質之構造，因此 不會在光觸媒所參與之觸媒反應之體系内，即與光觸媒分 開之領域上置放該等被反應物或中間生成物。經由與共同 配合之光觸媒之鄰接處，於觸媒反應之系内，放置該等被 反應物或中間生成物。並且該另一化合物與被反應物或中 間生成物之結合為化學結合，因此可確實地將該等被反應 物或中間生成物放置於觸媒反應之系内。是故，藉該第1 態樣之光觸媒配合物，可確保被反應物作用於觸媒反應之 機會，或是進而使中間生成物作用於該觸媒反應之機會， 加以更有效率地進行觸媒反應。又，透過觸媒反應之效率 的改善，可提高被反應物轉化成最終生成物之轉化程度， 而可提高被反應物之削減效率。 第2態樣為， (請先閱讀背面之注意事項 再 本頁) -裝· 訂 線 本紙張尺度適用中國國家標準（CNS ) A4規格（210 X 297公釐） 6 495384 經濟部中央標準局員工消費合作社印製 A7 B7五、發明説明（4 ) 前述光觸媒係一種藉所照射之光能可生成激發電子及 空穴，在觸媒表面上之氧氣及水份存在下，經由前述激發 電子及空穴生成活性氧物種之光觸媒。 依該第2態樣，可在基於光觸媒所生成之活性氧物種 之觸媒反應之系内置放被反應物或中間生成物，確實保持 該等被反應物作用於觸媒反應之機會或進而使中間生成物 作用於該觸媒反應之機會，加以更有效率地進行觸媒反應 。因此，可提高被反應物之削減效率。 此時，作為光觸媒係可舉二氧化鈦（Ti02)或氧化鋅 (ZnO)、氧化釩（V205)、氧化鎢（W03)等為例。該等光觸媒 並不限定於本身具有之結晶型，如銳鈦礦型、金紅石型或 板鈦礦型之結晶型之二氧化鈦，哪一種結晶型皆可。其中 從容易取得等條件來看，以銳鈦礦型之二氧化鈦為佳。又 ，作為作用於基於活性氧物種之觸媒反應之被反應物及該 中間生成物以及最終生成物，各可舉例有：氮氧化物、二 氧化氮以及硝酸；硫氧化物、二氧化硫以及硫酸或亞硫酸 ;一氧化碳、二氧化碳以及碳酸等。又，亦可舉氨作為被 反應物為例，此時之中間生成物及最終生成物則為從氨所 生成之一氧化氮、二氧化氮及頌酸。 第3態樣為， 前述另一化合物係以下列中之至少一種金屬化合物， 即，可與在基於前述活性氧物種而進行之觸媒反應中作為 前述被反應物或前述中間生成物相化學結合的兩性金屬氧 化物、鹼性金屬氧化物或酸性金屬氧化物。 (請先閱讀背面之注意事項再_舄本頁)Alignment This paper size applies to China National Standard (CNS) A4 (210X 297 mm) 495384 Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs A7 B7 V. Description of Invention (3) Compound. With the first photocatalyst compound of the present invention having the above-mentioned constitution, the degree of conversion from the reactant to the final product can be increased, and therefore the reduction efficiency of the reactant can be improved. In the first photocatalyst compound of the present invention having the above constitution, the following aspects can be adopted. In a first aspect, the aforementioned another compound is a compound which can chemically bond with the reactant or an intermediate product formed before the reactant undergoes the catalyst reaction to be converted into the final product. . In this first aspect, the reactant or the intermediate reactant is chemically combined with another compound to be held by the photocatalyst. The other compound that holds the reactant or intermediate product does not adopt a porous structure, so it will not be placed in the system of the catalyst reaction in which the photocatalyst participates, that is, the reactant or Intermediate products. These reactants or intermediate products are placed in the reaction system of the catalyst through the abutment with the photocatalyst which cooperates with each other. In addition, the combination of the other compound and the reactant or the intermediate product is chemically combined, so that the reactant or intermediate product can be reliably placed in the catalyst reaction system. Therefore, by using the photocatalyst complex of the first aspect, the opportunity for the reactant to act on the catalyst reaction can be ensured, or the opportunity for the intermediate product to act on the catalyst reaction can be ensured, and the catalyst can be more efficiently catalyzed. MEDIA REACTION. In addition, by improving the efficiency of the catalyst reaction, the degree of conversion of the reactant into the final product can be increased, and the reduction efficiency of the reactant can be improved. The second aspect is, (Please read the precautions on the back, then this page)-The binding and binding paper size applies to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) 6 495384 Employees of the Central Standards Bureau of the Ministry of Economic Affairs Printed by the consumer cooperative A7 B7 V. Description of the invention (4) The aforementioned photocatalyst is a kind of excited electrons and holes that can be generated by the irradiated light energy. In the presence of oxygen and water on the catalyst surface, the aforementioned excited electrons and air The photocatalyst of active oxygen species is formed in the cave. According to the second aspect, the reactant or intermediate product can be built in the catalyst reaction system based on the reactive oxygen species generated by the photocatalyst, and the opportunity for the reactant to act on the catalyst reaction can be maintained or can be further improved. The intermediate product acts on the opportunity of the catalyst reaction to perform the catalyst reaction more efficiently. Therefore, the reduction efficiency of the reactant can be improved. In this case, examples of the photocatalyst system include titanium dioxide (Ti02), zinc oxide (ZnO), vanadium oxide (V205), and tungsten oxide (W03). These photocatalysts are not limited to the crystalline form itself, such as anatase type, rutile type or brookite type crystalline titanium dioxide, and any crystalline type may be used. Among them, anatase-type titanium dioxide is preferable in terms of easy availability and the like. In addition, as the reactant, the intermediate product, and the final product acting on the catalyst reaction based on the active oxygen species, each may be exemplified by nitrogen oxides, nitrogen dioxide, and nitric acid; sulfur oxides, sulfur dioxide, and sulfuric acid or Sulfurous acid; carbon monoxide, carbon dioxide and carbonic acid. In addition, ammonia can be taken as an example of the reactant. In this case, the intermediate product and the final product are nitrogen oxide, nitrogen dioxide, and oxalic acid produced from ammonia. In a third aspect, the other compound is at least one of the following metal compounds, that is, it can be chemically combined with the reactant or the intermediate product in a catalyst reaction based on the reactive oxygen species. Amphoteric metal oxide, basic metal oxide or acid metal oxide. (Please read the notes on the back before _ 舄 this page)

訂 線- 本紙張尺度適用中國國家標準（CNS ) A4規格（210X 297公釐） 經濟部中央標準局員工消費合作社印製 A7 ~-------— B7____ 五、發明説明（5 ) 依第3態樣，係於基於光觸媒所生成之活性氧物種之 觸媒反應之系内放置被反應物或中間生成物時，該被反應 物或中間生成物為酸性時，以鹼性金屬氧化物之原子配列 起因之特定原子可形成所謂的鹼性自由基，以該鹼性自由 基可確實令驗性金屬乳化物與被反應物，或與中間生成物 相化學結合。又，被反應物或中間生成物為鹼性時，以酸 性金屬氧化物之原子配列起因之特定原子可形成所謂的酸 性自由基，藉該酸性自由基可確實令酸性金屬氧化物與被 反應物或與中間生成物相化學結合。進而，令另一化合物 作為兩性金屬氧化物時，可將起因於該兩性金屬氧化物之 原子配列之特定原子作為適合被反應物或中間生成物性質 之鹼性自由基或是酸性自由基，因此被反應物或中間生成 物即使為鹼性或酸性，亦可確實令兩性金屬氧化物與被反 應物或與中間生成物相化學結合。 此時，作為兩性金屬氧化物可舉氧化鋁（Al2〇3)或氧 化鋅（ZnO)、氧化錫（Sn0、Sn〇2)等為例。又，作為鹼性 金屬氧化物可舉例有：氧化锶（Sr0)或氧化鋇（Ba〇)、氧 化鎮（MgO)、氧化鈣（Ca0)、氧化物（Rb2〇)、氧化鈉（Na2〇) 、氧化鉀（K2〇)等。進而，作為酸性金屬氧化物可舉氧化 礙（Ρ2〇5)為例。在該等金屬氧化物中形成鹼性自由基或酸 性自由基係起因於，構成金屬氧化物之金屬原子與氧原子 的陰電度之差以及金屬氧化物表面之金屬原子及氧原子之 原子配列。然後，令相對於作用於基於活性氧物種之觸媒 反應之上述被反應物及其中間生成物，可適當選擇上述之 本紙張尺度適用中國國家標準（CNS ) Α4規格（210 Χ；297公釐） (請先閲讀背面之注意事項 本頁) .裝· 訂 線Alignment-This paper size applies to China National Standard (CNS) A4 (210X 297 mm) Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs A7 ~ --------- B7____ V. Description of the Invention In a third aspect, when a reactant or an intermediate product is placed in a catalyst reaction system based on an active oxygen species generated by a photocatalyst, when the reactant or intermediate product is acidic, an alkaline metal oxide is used. The specific atoms of the atomic alignment cause the formation of so-called basic radicals, and the basic radicals can surely bond the experimental metal emulsion with the reactant or the intermediate product. In addition, when the reactant or intermediate product is basic, a specific atom caused by the atomic arrangement of the acid metal oxide can form a so-called acidic radical, and the acidic radical can surely make the acid metal oxide and the reactant Or chemically combine with intermediate products. Furthermore, when another compound is used as an amphoteric metal oxide, a specific atom resulting from the atomic arrangement of the amphoteric metal oxide can be used as a basic radical or an acidic radical suitable for the properties of the reactant or intermediate product. Even if the reactant or intermediate product is basic or acidic, the amphoteric metal oxide can be chemically bound to the reactant or the intermediate product. In this case, examples of the amphoteric metal oxide include alumina (Al203), zinc oxide (ZnO), and tin oxide (Sn0, Sn02). Examples of the basic metal oxide include strontium oxide (Sr0) or barium oxide (Ba0), oxidized town (MgO), calcium oxide (Ca0), oxide (Rb2), and sodium oxide (Na2) , Potassium oxide (K2O) and so on. Furthermore, as the acid metal oxide, an oxidation inhibitor (P205) can be mentioned as an example. The formation of basic radicals or acidic radicals in these metal oxides is caused by the difference between the anions of the metal atoms and oxygen atoms constituting the metal oxide and the atomic arrangement of the metal atoms and oxygen atoms on the surface of the metal oxide. . Then, relative to the above-mentioned reactants and their intermediate products acting on the catalytic reaction based on reactive oxygen species, the above paper size can be appropriately selected to apply the Chinese National Standard (CNS) A4 specification (210 X; 297 mm) ) (Please read the caution page on the back first).

發明説明（ 經濟部中央標準局員工消費合作社印製 495384 鹼性金屬氧化物、酸性金屬氧化物、兩性金屬氧化物。又 ，氧化鋅為光觸媒之同時又為兩性金屬氧化物，因此選氧 化鋅作為光觸媒時，當然不會選氧化鋅作為兩性金屬氧化 物。 在此，採用光觸媒為二氧化鈦、化合物為兩性金屬氧 化物之氧化鋁、被反應物為氮氧化物（一氧化氮）為例，說 明觸媒反應之進行情形及經由氧化銘結合之情形。其中， 在這個時候，藉二氧化鈦所生成之活性氧物種將一氧化氮 氧化，而變成中間生成物之二氧化氮。如第i圖所示之模 式’令一氧化氮接觸或靠近光觸媒之二氧化鈦時，該一氧 化亂接焚光之照射，藉二氧化鈦所生成之活性氧物種· 〇H( 氫氧基），氧化成二氧化氮（氣體）（第i(a)圖該二氧化氮 從其分子構造而言為酸性，而氧化鋁為兩性金屬氧化物， 可相對於酸性氣體令該具有之氧原子作為鹼性自由基，因 此一氧化氮被該氧原子吸引進行化學結合，保持於氧化銘 (第1(b)圖）。其中，將二氧化氮吸引且靠近氧原子之力為 庫倫力，結合為化學結合。 結合於氧化鋁之氧原子之二氧化氮，係接近且置留於 光觸媒之二氧化鈦，因此存在於經氫氧基· 〇H所引起之 氧化反應（觸媒反應）之系内。是故，可確實保障該二氧化 氮糟該氫氧基氧化之機會，且使二氧化氮之氧化有效率地 進行之。又，被氧化之二氧化氮形成硝酸離子，與氫氧基 • 0H中之氫原子同時以硝酸形態（最終生成物）結合並保 持於作為前述鹼性自由基之氧化鋁之氧原子（第1(c)圖）。 本紙張尺度適用中國國家標準（CNS ) A4規格（210 X297公釐）Description of the invention (495384 printed by the Consumer Cooperative of the Central Bureau of Standards, Ministry of Economic Affairs, alkaline metal oxides, acid metal oxides, and amphoteric metal oxides. In addition, zinc oxide is a photocatalyst and is also an amphoteric metal oxide, so zinc oxide was selected as the Of course, zinc oxide will not be selected as the amphoteric metal oxide in the photocatalyst. Here, the alumina is used as the photocatalyst is titanium dioxide, the compound is amphoteric metal oxide, and the reactant is nitrogen oxide (nitrogen monoxide). The progress of the media reaction and the combination through oxidation. Among them, at this time, the nitric oxide is oxidized by the reactive oxygen species generated by titanium dioxide to become the nitrogen dioxide of the intermediate product. As shown in Fig. I Mode 'When nitric oxide is in contact with or close to the photocatalyst titanium dioxide, the monoxide is irradiated by the light of the incineration, and the active oxygen species generated by the titanium dioxide, OH (hydrogen), is oxidized to nitrogen dioxide (gas) ( Figure i (a) The nitrogen dioxide is acidic in terms of its molecular structure, while alumina is an amphoteric metal oxide, Because the acidic gas makes the oxygen atom as a basic radical, the nitrogen oxide is attracted by the oxygen atom to be chemically combined and maintained in the oxidized name (Figure 1 (b)). Among them, the nitrogen dioxide is attracted and close to The force of the oxygen atom is the Coulomb force, and the combination is chemical bonding. The nitrogen dioxide bound to the oxygen atom of the alumina is close to and left in the photocatalyst titanium dioxide, so it exists in the oxidation reaction caused by the hydroxyl group · OH (Catalyst reaction) system. Therefore, the opportunity for the oxidation of the nitrogen dioxide and the hydroxyl group can be surely guaranteed, and the oxidation of the nitrogen dioxide can be efficiently performed. Furthermore, the oxidized nitrogen dioxide is formed. The nitrate ion is simultaneously combined with the hydrogen atom in the hydroxyl group • 0H in the form of nitric acid (final product) and is held by the oxygen atom of the alumina as the aforementioned basic radical (Figure 1 (c)). Paper size Applicable to China National Standard (CNS) A4 specification (210 X297 mm)

-9 - 495384 經濟部中央標準局員工消費合作社印製 A7 ——- _______B7 五、利説明（7 ) "—^ ~~^—一 此時，若一開始就存在有二氧化氮時，即，二氧化氮 為被反應物時’該二氧化氮藉二氧化鈦生成之活性氧物^ 直接氧化之_，如上所述，化學結合於氧化紹之二氧化 氣也經由該活性氧物種而氧化。換言之，此時氧化紹與作 為被反應物之二氧化氮進行化學結合。 其次，藉由二氧化鈦生成之活性氧物種氧化轉化成一 氧化硫（SO)及一氧化碳（C0)時，說明藉氧化鋁之結合情形 。該等氧化物一被氧化時，則形成二氧化硫、二氧化碳， 也是形成酸性氣體。因此，如第2圖所示之模式，二氧化 硫係與兩性金屬氧化物之氧化鋁具有之鹼性自由基且相鄰 接之氧原子進行化學結合，而保持於氧化鋁。又，如第3 圖所示之模式，二氧化碳可與碳原子以及氧原子以不同結 合次數相結合，因此如上所述，二氧化碳可與形成鹼性自 由基之單獨氧原子（第3(a)圖），或形成鹼性自由基而相鄰 接之氧原子（第3(b)圖）進行化學結合，而保持於氧化鋁。 又，如此結合並加以保持之二氧化硫進而與二氧化鈦生成 之活性氧物種（氫氧基· 0H)反應，形成硫酸或亞硫酸（最 終生成物），而二氧化碳形成碳酸（最終生成物）。其中， 在二氧化碳上也可能是下列情形，如生成作為活性氧物種 之氫氧基· 0H時，經由基於所生成之自由基的氫原子與 活性氧物種之反應，而轉化成甲烷或甲醇，此時該甲烷或 曱醇也可說是最終生成物。 第4態樣為， 前述另一化合物係可配合成，該重量以a、且前述光 (請先閱讀背面之注意事 項 本頁) ί 1 - - an •裝- 訂 本紙張尺度適用中國國家標準（CNS ) A4規格（210'乂297公釐） 10 495384 A7 B7 五、發明説明（8 ) 觸媒之重量以b表示時，a/(a+b)為0.001〜0.8者。 如該第4態樣，若a/(a+b)為0.0001時，藉以a表示之另 一化合物（兩性金屬化合物、驗性金屬化合物、酸性金屬 化合物），可確保被反應物或中間生成物之化學結合，不 會導致觸媒反應之效率降低，所以理想。又，若a/(a+b)為 0.8以下的話，以b表示之光觸媒之量相對於前述另一化合 物不會太少，因此不會導致觸媒反應降低，所以理想。 此時，光觸媒之量係相對於，光觸媒與除此之外之配 合物之前述化合物以及含有另一配合物時之另一化合物之 總量，為20〜95wt%左右。 第5態樣為， 前述光觸媒及該前述另一化合物係於0.005〜0.5/z m左 右之粒徑範圍内調整而加以配合者。 經濟部中央標準局員工消費合作社印製 (請先閱讀背面之注意事項再本頁) 如第5態樣，光觸媒及另一化合物（兩性金屬氧化物、 鹼性金屬氧化物、酸性金屬氧化物）之粒徑為0.005〜0.5/z m左右之範圍内時，以球磨機等之現有的粉碎裝置或溶膠 •凝膠法，可容易調整粒徑，所以較佳。又，藉該第5態 樣，光觸媒與另一化合物之粒徑沒有顯著的不同，因此光 觸媒與另一化合物可以幾乎相同大小之粒子相接近。是故 ，可令與此另一化合物相化學結合之被反應物或中間生成 物接近於光觸媒，可謀求經充分確保進行觸媒反應之機會 而高度效率化，因此較佳。 第6態樣為， 該光觸媒光合物除前述光觸媒及前述另一化合物之夕卜 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） 11 A7 I五 經濟部中央標準局員工消費合作社印製 ---- ‘_ B7__ 發明説明（9 ) ’並加入而包含有一具有可化學吸著氫氧基之性質的化合 物作為第3成分，而可將前述氫氧基化學吸著並保持於前 述光觸媒及作為前述第3成分之化合物之表面上，俾藉該 保持之氫氧基發揮親水性。 在這第6態樣中，經光觸媒之觸媒反應所生成之氫氧 基’光觸媒不必說，也化學吸著並保持於第3成分之化合 物之表面上。觸媒表面上之水份（空氣中水蒸氣或水等）不 會變成0，因此在光照射之間，氫氧基不斷地生成。因此 ’氫氧基可以高密度保持，且該保持為化學吸著之結合而 進行，故氫氧基可強固地被保持。另外，光不照射時，不 會產生因光觸媒之氫氧基的生成，但到目前為止所生成之 氫氧基強固地保持於光觸媒與第3成分之化合物之表面上 ’因此不會發生因疏忽而使氫氧基消除。並且重新令光照 射’即使在不照射時氫氧基密度降低，也可迅速地回復高 密度之保持狀態。是故，該第6態樣之光觸媒配合物固定 於某一基材表面上，可使該基材表面形成高度親水性，並 可長期且確實地維持該高度親水性。即，該第6態樣之光 觸媒配合物成為一種在基材表面上高度付予親水性之親水 性付予材料。 在此’說明親水性所帶來之效果。親水性與水之接觸 角有極度關係，於親水性高的話，則該接觸角變小。另一 方面，若接觸角小，則該表面上水將難以積留，因此表面 上附著的污垢，可與該水同時流去，而從表面除去。藉此 ，若可得到一種親水性，其親水性係可令含有多量親油性 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） 12 495384 Α7 Β7 五、發明説明（ 10 經濟部中央標準局員工消費合作社印製 成分之都市塵埃及黏土礦物等之無機質塵埃等之接觸角顯 現出變小之接觸角者，則不必發揮親和性即可將該等塵埃 除去。而且，接觸角越接近0度，則親水性越高，水在基 材表面呈膜狀擴散容易流動，因此前述之都市塵埃不必說 ’連無機塵埃也可輕易地從基材表面跟著水一起流掉。此 時，用以提高污垢防止效果時，接觸角在20度以下且接近 〇之值為佳。 藉此’將該第6態樣之光觸媒配合物固定於建築物内 外牆壁表面’以及汽車或電車等車輛車身表面，用以如此 所付予之高親水性，可展現高度防污效果。此時，該等表 面上若有陣雨落下，因付予高度親水性，故每次下雨時， 該表面之灰塵及污濁物質可隨雨水一起從表面洗掉，該等 表面可自己淨化。即，可有效地抑制灰塵順著水流而呈所 謂筋條狀之雨條狀汙垢等。又，將該第6態樣之光觸媒配 合物固定於玻璃及鏡片或鏡子等之表面上，可用以該高度 親水性發揮高度防霧效果。 第7態樣為， 作為則述第3成分之化合物係一種具有與前述光觸媒 所具有之濕潤熱同程度以上之濕潤熱的化合物。 二、、們熱係可用以作為顯示，表面上可能存在有氫氧基 之物質中，保持該表面的氫氧基之保持特性的指標。濕潤 熱愈ν，氫氧基保持之程度愈高，則氫氧基密度也高。是 故，依此第7態樣，將光觸媒產生之氫氧基更加有效地且 南也、度的化學吸著並保持於第3成分之化合物上，可在-9-495384 A7 printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs —— _______B7 V. Explanation of Benefits (7) " — ^ ~~ ^ —At this time, if there is nitrogen dioxide at the beginning, that is, When nitrogen dioxide is the reactant, 'the nitrogen dioxide is directly oxidized by the reactive oxygen species generated by titanium dioxide. As mentioned above, the chemical gas bound to the oxide is also oxidized by the reactive oxygen species. In other words, at this time, the oxide is chemically combined with nitrogen dioxide as a reactant. Secondly, when the reactive oxygen species generated by titanium dioxide are oxidized and converted into sulfur monoxide (SO) and carbon monoxide (C0), the combination of aluminum oxide will be explained. When these oxides are oxidized, they form sulfur dioxide and carbon dioxide, and they also form acid gases. Therefore, as shown in Fig. 2, the sulfur dioxide and the alumina of the amphoteric metal oxide have a basic free radical and adjacent oxygen atoms are chemically bonded with each other, and are held in the alumina. In addition, as shown in Fig. 3, carbon dioxide can be combined with carbon atoms and oxygen atoms at different numbers of times. Therefore, as described above, carbon dioxide can be combined with individual oxygen atoms forming basic radicals (Fig. 3 (a)). ), Or basic oxygen radicals are formed and adjacent oxygen atoms (Figure 3 (b)) are chemically bonded and retained on alumina. In addition, the sulfur dioxide combined and held in this way reacts with an active oxygen species (hydrogen · OH) produced by titanium dioxide to form sulfuric acid or sulfurous acid (the final product), and carbon dioxide forms carbonic acid (the final product). Among them, carbon dioxide may also be the following, for example, when a hydroxyl group, 0H, which is an active oxygen species, is generated, it is converted into methane or methanol via a reaction of a hydrogen atom based on the generated free radical with an active oxygen species. The methane or methanol can also be said to be the final product. The fourth aspect is that the aforementioned another compound can be compounded, the weight is based on a, and the aforementioned light (please read the precautions on the back page first) ί 1--an • Binding-The paper size applies the Chinese national standard (CNS) A4 specification (210 '乂 297 mm) 10 495384 A7 B7 V. Description of the invention (8) When the weight of the catalyst is expressed as b, a / (a + b) is 0.001 ~ 0.8. As in the fourth aspect, if a / (a + b) is 0.0001, another compound (amphoteric metal compound, test metal compound, acidic metal compound) represented by a can ensure the reactant or intermediate product. The chemical combination is ideal because it does not reduce the efficiency of the catalyst reaction. In addition, if a / (a + b) is 0.8 or less, the amount of the photocatalyst represented by b is not too small relative to the other compound described above, so that it does not cause a reduction in the catalyst reaction, which is desirable. At this time, the amount of the photocatalyst is about 20 to 95% by weight with respect to the total amount of the aforementioned compound of the photocatalyst and other complexes and the other compound when containing another complex. In a fifth aspect, the photocatalyst and the another compound are adjusted and blended within a particle size range of about 0.005 to 0.5 / z m. Printed by the Consumer Standards Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs (please read the precautions on the back before this page), as in the fifth aspect, photocatalyst and another compound (amphoteric metal oxide, basic metal oxide, acid metal oxide) When the particle diameter is in the range of about 0.005 to 0.5 / zm, it is preferable to adjust the particle diameter easily by a conventional pulverizing device such as a ball mill or a sol-gel method. Moreover, according to this fifth aspect, the particle size of the photocatalyst is not significantly different from that of the other compound, and therefore, the photocatalyst and the other compound can be made to have particles of almost the same size. This is because it is possible to make the reacted or intermediate product chemically bonded to this other compound close to the photocatalyst, and it is possible to achieve a high degree of efficiency by sufficiently ensuring the opportunity for the catalyst reaction to proceed, so it is preferable. In the sixth aspect, the paper size of the photocatalyst photocompound is in addition to the photocatalyst and the other compound mentioned above. The paper size is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm). Printing ---- '_ B7__ Description of the invention (9)' and added as a third component containing a compound having a property capable of chemically adsorbing hydroxyl groups, and the aforementioned hydroxyl groups can be chemically adsorbed and held at On the surface of the photocatalyst and the compound as the third component, the retained hydroxyl group exerts hydrophilicity. In this sixth aspect, it is needless to say that the hydroxide-based photocatalyst generated by the catalyst reaction of the photocatalyst is chemically adsorbed and held on the surface of the compound of the third component. The moisture (water vapor or water in the air) on the surface of the catalyst does not become zero, so the hydroxyl group is continuously generated between light irradiation. Therefore, the 'hydroxyl group can be held at a high density, and the retention is performed by a combination of chemical adsorption, so that the hydroxyl group can be strongly held. In addition, when the light is not irradiated, the generation of hydroxyl groups due to the photocatalyst will not occur, but the hydroxyl groups generated so far are strongly held on the surface of the photocatalyst and the compound of the third component, so no oversight will occur. The hydroxyl groups are eliminated. In addition, if the density of the hydroxyl group is reduced when the light is not irradiated again, the high-density holding state can be quickly restored. Therefore, the sixth aspect of the photocatalyst complex is fixed on the surface of a certain substrate, so that the surface of the substrate can be highly hydrophilic, and the high hydrophilicity can be reliably maintained for a long period of time. That is, the photocatalyst complex of the sixth aspect becomes a hydrophilic donating material which is highly hydrophilic on the surface of the substrate. Here, the effect of hydrophilicity will be described. Hydrophilicity is extremely related to the contact angle of water. If the hydrophilicity is high, the contact angle becomes small. On the other hand, if the contact angle is small, water on the surface will be difficult to accumulate, so the dirt on the surface can flow away with the water at the same time and be removed from the surface. With this, if a kind of hydrophilicity can be obtained, the hydrophilicity can make the paper containing a large amount of lipophilicity. The paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm). 12 495384 Α7 Β7 V. Description of the invention If the contact angle of inorganic dust, such as urban dust, eg, Egyptian clay minerals, etc., printed by the Bureau of Consumers of the Standards Bureau, the contact angle becomes smaller, the dust can be removed without exerting affinity. The closer the contact angle is, the closer the contact angle is. At 0 degrees, the higher the hydrophilicity, the more the water diffuses in a film form on the surface of the substrate, so the aforementioned urban dust need not say 'even inorganic dust can easily flow away from the surface of the substrate along with water. At this time, use In order to improve the effect of preventing dirt, the contact angle is preferably less than 20 degrees and close to 0. This is used to 'fix the sixth aspect of the photocatalyst complex to the surface of the wall inside and outside the building' and the surface of the vehicle body such as a car or tram With the high hydrophilicity given in this way, a highly antifouling effect can be exhibited. At this time, if a shower falls on these surfaces, due to the high hydrophilicity, Therefore, every time it rains, the dust and dirt on the surface can be washed away from the surface along with the rainwater, and these surfaces can be purified by themselves. That is, the dust can be effectively prevented from flowing along the water flow into a so-called ribbed rain bar shape. Dirt, etc. In addition, the photocatalyst complex of the sixth aspect can be fixed on the surface of glass, lenses, mirrors, etc., and the highly anti-fog effect can be exerted with the high hydrophilicity. The seventh aspect is described as the third aspect. The compound of the component is a compound having a moist heat equal to or higher than the moist heat of the aforementioned photocatalyst. 2. The thermal system can be used as a display. Among the substances that may have a hydroxyl group on the surface, the surface that holds the surface An indicator of the retention characteristics of hydroxyl groups. The more ν the moist heat, the higher the degree of hydroxyl group retention, the higher the density of hydroxyl groups. Therefore, according to this seventh aspect, the hydroxyl groups produced by photocatalysts are more effective. The chemical absorption of Di and Nan Ye and Du is held on the compound of the third component.

(請先閲讀背面之注意事項再本頁)(Please read the notes on the back before this page)

訂 線 13 495384 A7 B7 經濟部中央標準局員工消費合作社印製 五、發明説明（n) 材表面上更加確實且長期性地付予高親水性。此時，作為 光觸媒特佳之二氧化鈦之濕潤熱，其銳鈦礦型為320〜 512xl〇-3Jm_2，而金紅石型為293〜645xlO_3JnT2，因此具有 上述濕潤熱之化合物為佳。 第8態樣為， 作為前述第3成分之化合物為Si02、A1203、Zr02、Ge02 、Th02、ZnO中至少擇一之金屬氧化物。 該等金屬氧化物因具有與作為光觸媒特佳之二氧化鈦 之濕潤熱相等以上之濕潤熱，故可更加提高氫氧基之保持 密度，因此理想。尤其二氧化矽（Si02)、氧化鋁（A1203)、 Ge02、Th02所具有之濕潤熱範圍中的上限係超過1000 xlCT3JnT2，所以理想。 此時，作為第3成分之各化合物（Si02、A1203、Zr02 、Ge02、Th02、ZnO)，係與藉本發明以削減為目的之被 反應物，以及跟光觸媒一起配合之另一化合物（A1203、ZnO 、SnO、Sn02、SrO、BaO、MgO、CaO、Rb20、Na20、K20 、P205)之組合而決定。具體舉例說明，作為與光觸媒共 同配合之另一化合物選擇並決定Al2〇3時，作為第3成分之 化合物係為了避免成分重複，而選定A1203以外的Si02、 Zr02、Ge02、Th02、ZnO作為第3成分。接著，作為另一 化合物之ai2o3不能與削減目的之被反應物或該中間生成 物進行化學結合時，選定Al2〇3以外之ZnO、SnO、Sn02、 SrO、BaO、MgO、CaO、Rb20、Na20、K20、P205作為 另一成分，而作為第3成分則選定包含A1203在内之上述各 (請先閱讀背面之注意事項再本頁) —裝· 、?τ 線· 本紙張尺度適用中國國家標準（CNS ) Α4規格（210X297公釐） 14 495384 A7 B7 五、發明説明（12) 化合物（Si02、Al2〇3、Zr02、Ge02、Th02、ZnO)之任一 種，針對ZnO也是同樣。 第9態樣為， 該光觸媒化合物除前述光觸媒、前述另一化合物及前 述作為第3成分之化合物之外，加入並含有可發揮抗菌性 之金屬作為第4成分，而作為第4成分之金屬係載持於前述 光觸媒。 在該第9態樣中，在光照射間，將光觸媒本身可發揮 之抗菌功能，而藉由光沒照射時將該抗菌功能藉載持於光 觸媒之金屬而展現。因此，可補充光觸媒所發揮之抗菌功 能，用以發揮抗菌性之金屬及光觸媒可發揮雙重抗菌性。 第10態樣為， 作為前述第4成分之金屬係一種具有比前述光觸媒釋 出之自由電子所具有之電位還高之還原電位之金屬。 經濟部中央標準局員工消費合作社印製 在該第10態樣中，可藉該金屬所有之還原電位輕易進 行光觸媒上之金屬載持。此時，若是從Ag、Cu、Pd、Fe 、Ni、Cr、Co、Pt、Au、Li、Ca、Mg、A1、Zn、Rh、Ru 中至少擇一之金屬時，因具有上述之還原電位，所以理想 ，而Ag、Cu、Pd、Pt、Au其還原電位具有正值，容易導 致還原載持，故特佳。又，選作為前述第4成分之金屬， 該重量以c、而光觸媒之重量以d表示時，宜使配合成c/d 為0.00001〜0·05左右者。即，第4成分之金屬為0.00001 (=c/d) 以上時，則不會有因該金屬太少而不能完全發揮雙重抗菌 性之事情發生，若在0.05 (=c/d)以下時，也不會有因該金 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） 15 495384 A7 B7 經濟部中央標準局員工消費合作社印製 五、發明説明（13) 屬過剩而引起光觸媒反應之不良影響，因此理想。 本發明之第2光觸媒含有物為， 一種光觸媒含有物，係含有一受到光之照射即可產生 觸媒作用之光觸媒之光觸媒含有物，係上述本發明之第1 光觸媒配合物或各態樣之光觸媒配合物混合並加以分散於 塗料或釉藥中所形成者。 成為具有上述構成之本發明之第2光觸媒含有物之塗 料以及釉藥，與本發明之第1光觸媒配合物同樣地，可提 高被反應物之削減效率，確實地將被反應物或中間生成物 放置於觸媒反應之系内。藉此，於塗有該塗料者之表面上 ，或是施有釉藥者之表面上，可有效率地削減被反應物。 又，於該等表面中，可確實保有被反應物作用於觸媒反應 之機會，或進而中間生成物作用於該觸媒反應之機會，可 更有效率地進行觸媒反應。 此時，為光觸媒及化合物之混合分散對象之塗料及釉 藥可為現有之物，若是釉藥時，令釉藥原料，例如長石或 碳酸鉀等之透明釉（frit)同時與光觸媒以及化合物分散於 溶液中。又，於光觸媒及化合物之分散混合時，即可在釉 藥製造之過程中與上述釉藥原料共同配合，也可先不施釉 配合於已完成之釉藥上。 於上述本發明之第2光觸媒含有物（塗料或釉藥）中， 前述光觸媒係一種經由照射光能生成激發電子及空穴 ，在觸媒表面上之氧氣及水份存在下，經由前述激發電子 及空穴生成活性氧物種之光觸媒，而 (請先閱讀背面之注意事項再本頁) ^衣· 訂 線 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） 16 495384 A7 經濟部中央標準局員工消費合作社印製 ____B7_五、發明説明（14 ) 前述另一化合物係以下所列者中之至少一種金屬化合 物’即’可與在基於前述活性氧物種而進行之觸媒反應中 作為前述被反應物或前述中間生成物相化學結合之兩性金 屬氧化物、鹼性金屬氧化物或酸性金屬氧化物時，則具有 下列優點。 依該光觸媒含有物，與本發明之第1光觸媒配合物之 上述態樣同樣，以鹼性自由基及酸性自由基確實地將被反 應物或中間生成物結合並加以保持，可在基於活性氧物種 之觸媒反應之系内中放置該等被反應物或中間生成物。藉 此’於塗有成為該光觸媒含有物之塗料物之表面上，或是 施有釉藥物之表面上，可更有效率地進行觸媒反應，經此 ’可提高被反應物之削減效率。又，如本發明之第1光觸 媒配合物之第6〜第8態樣，在使用具有第3成分之化合物 之光觸媒配合物時，於該等表面中，可展現基於高度親水 性之兩度防汙效果，因此理想。進而，如本發明之第1光 觸媒配合物之第9〜第10態樣，在使用具有第4成分之金屬 之光觸媒配合物時，於該等表面中，可用以可發揮抗菌性 之金屬及光觸媒展現雙重抗菌性，因此理想。 又’在該本發明之第2光觸媒含有物，尤其是塗料時 ，在現有之大樓、家居以及橋樑等之建築構造物内外壁或 道路之遵攔、隔音壁等之現有構造物上，施以該塗料，可 形成光觸媒含有物之塗膜。是故，可輕易將現有構造物變 更成可提南被反應物之削減效率，也可展現高度防污效果 之構造物。 (請先閱讀背面之注意事項再本頁)Order 13 495384 A7 B7 Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs. 5. Description of the invention (n) The surface of the material is given more high and long-term hydrophilicity. At this time, the moist heat of titanium dioxide, which is a particularly good photocatalyst, has an anatase type of 320 to 512x10-3Jm_2 and a rutile type of 293 to 645xlO_3JnT2, so a compound having the above-mentioned moist heat is preferred. In an eighth aspect, the compound as the third component is a metal oxide selected from at least one of Si02, A1203, Zr02, Ge02, Th02, and ZnO. Since these metal oxides have a wetting heat equal to or more than that of titanium dioxide, which is a particularly good photocatalyst, it is preferable to further increase the retention density of the hydroxyl group. In particular, the upper limit of the moist heat range of silicon dioxide (Si02), aluminum oxide (A1203), Ge02, and Th02 is more than 1000 × lCT3JnT2, so it is ideal. At this time, each compound (Si02, A1203, Zr02, Ge02, Th02, ZnO) as the third component is another compound (A1203, A1203, and the reactant for the purpose of reduction according to the present invention) and a photocatalyst. ZnO, SnO, Sn02, SrO, BaO, MgO, CaO, Rb20, Na20, K20, P205). Specifically, when Al2O3 is selected and determined as another compound that cooperates with the photocatalyst, the compound that is the third component is selected as Si02, Zr02, Ge02, Th02, and ZnO other than A1203 in order to avoid component duplication. ingredient. Next, when ai2o3, which is another compound, cannot be chemically combined with the reactant or the intermediate product to be reduced, select ZnO, SnO, Sn02, SrO, BaO, MgO, CaO, Rb20, Na20, Al2O3, etc. K20 and P205 are used as another component, and as the third component, the above-mentioned ones including A1203 are selected (please read the precautions on the back before this page) — installation ·, · τ line · This paper size applies Chinese national standards ( CNS) A4 specification (210X297 mm) 14 495384 A7 B7 V. Description of the invention (12) Any of the compounds (Si02, Al2O3, Zr02, Ge02, Th02, ZnO) is the same for ZnO. In a ninth aspect, in addition to the photocatalyst, the other compound, and the compound as the third component, the photocatalyst compound is a metal system containing a metal exhibiting antibacterial properties as the fourth component and a metal component as the fourth component. Supported on the photocatalyst. In this ninth aspect, the photocatalyst itself exhibits an antibacterial function during light irradiation, and the antibacterial function is exhibited by supporting the metal of the photocatalyst when the light is not irradiated. Therefore, the antibacterial function of the photocatalyst can be supplemented, and the metal and the photocatalyst used to exert the antibacterial property can exhibit dual antibacterial properties. In a tenth aspect, the metal as the fourth component is a metal having a reduction potential higher than that of the free electrons released by the photocatalyst. Printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs In this tenth aspect, the metal can be easily carried on the photocatalyst by the reduction potentials possessed by the metal. At this time, if at least one metal is selected from Ag, Cu, Pd, Fe, Ni, Cr, Co, Pt, Au, Li, Ca, Mg, A1, Zn, Rh, and Ru, it has the above-mentioned reduction potential. Therefore, it is ideal, and Ag, Cu, Pd, Pt, and Au have positive reduction potentials, which are likely to cause reduction support, which is particularly preferable. When the metal selected as the fourth component is c, and the weight of the photocatalyst is expressed as d, it is preferable to mix the c / d to 0.00001 to 0.05. That is, when the metal of the fourth component is 0.00001 (= c / d) or more, there will be no occurrence of dual antibacterial properties because the metal is too small. If it is less than 0.05 (= c / d), There will also be no photocatalyst caused by the gold paper size applying Chinese National Standard (CNS) A4 specifications (210X297 mm) 15 495384 A7 B7 Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 5. The invention description (13) is excessive The adverse effect of the reaction is desirable. The second photocatalyst-containing material of the present invention is a photocatalyst-containing material, which is a photocatalyst-containing material that contains a photocatalyst that can produce a catalyst effect when irradiated with light, and is the first photocatalyst complex or various forms of the present invention described above. Photocatalyst complex is formed by mixing and dispersing in paint or glaze. As the coating material and glaze of the second photocatalyst-containing substance of the present invention having the above-mentioned structure, similar to the first photocatalyst complex of the present invention, the reduction efficiency of the reactant can be improved, and the reactant or intermediate product can be reliably removed. Placed in the catalyst reaction system. Thereby, it is possible to efficiently reduce the reactant on the surface coated with the coating material or on the surface coated with the glaze. Furthermore, on these surfaces, the opportunity for the reactant to act on the catalyst reaction can be surely maintained, or the opportunity for the intermediate product to act on the catalyst reaction can be ensured, and the catalyst reaction can be performed more efficiently. At this time, the paint and glaze that are the subject of the mixed dispersion of the photocatalyst and the compound may be the existing ones. In the case of the glaze, the glaze raw material, such as feldspar or potassium carbonate, is transparently dispersed with the photocatalyst and the compound. In solution. In addition, when the photocatalyst and the compound are dispersed and mixed, it can be combined with the above glaze raw materials during the glaze manufacturing process, or it can be blended on the finished glaze without applying glaze first. In the second photocatalyst-containing substance (paint or glaze) of the present invention, the photocatalyst is a kind of excited electrons and holes generated by irradiating light energy, and in the presence of oxygen and water on the catalyst surface, the excited electrons pass through the excited electrons. And photocatalysts that generate active oxygen species and cavities, and (please read the precautions on the back before this page) ^ Clothes · Threading This paper size is applicable to China National Standard (CNS) A4 (210X297 mm) 16 495384 A7 Ministry of Economic Affairs Printed by the Consumer Standards Cooperative of the Central Bureau of Standards ____B7_ V. Description of the Invention (14) The aforementioned another compound is at least one of the metal compounds listed below, that is, can be reacted with a catalyst based on the aforementioned reactive oxygen species When the amphoteric metal oxide, the basic metal oxide, or the acid metal oxide which is chemically bonded to the reacted substance or the intermediate product is used, it has the following advantages. According to this photocatalyst-containing substance, similarly to the above-mentioned aspect of the first photocatalyst complex of the present invention, the reactant or intermediate product is reliably combined and maintained with basic radicals and acidic radicals. The catalyst reaction system of the species places these reactants or intermediate products in it. With this, the catalyst reaction can be performed more efficiently on the surface coated with the coating material that becomes the photocatalyst content, or on the surface with the glaze drug, and the reduction efficiency of the reactant can be improved by this. In addition, as in the sixth to eighth aspects of the first photocatalyst complex of the present invention, when a photocatalyst complex having a compound having a third component is used, a two-degree prevention based on high hydrophilicity can be exhibited on these surfaces. The stain effect is therefore ideal. Furthermore, according to the ninth to tenth aspects of the first photocatalyst complex of the present invention, when a photocatalyst complex of a metal having a fourth component is used, a metal and a photocatalyst that can exhibit antibacterial properties can be used on these surfaces It is ideal because it exhibits dual antibacterial properties. In addition, when the second photocatalyst-containing substance of the present invention, especially paint, is applied to existing structures such as inner and outer walls of existing building structures, homes, bridges, and roads, barriers, and sound insulation walls, etc. This coating material can form a coating film containing a photocatalyst. Therefore, the existing structure can be easily changed into a structure that can reduce the reactant and can also exhibit a highly antifouling effect. (Please read the notes on the back before this page)

、1T 線 本紙張尺度適用中國國家標準（CNS ) Mil格（210X297公釐） -17 - 495384 A7 B7 五、發明説明（15 ) 本發明之第3光觸媒功能發揮材料為， 一種具有基材層及形成於該表面之表面層，且為受光 之照射即可發揮光觸媒功能之材料；而作為前述表面層係 上述本發明之第1光觸媒配合物或其各態樣之光觸媒配合 物形成之表面層，或具有由上述本發明之第2光觸媒含有 物形成之表面層之光觸媒功能發揮材料。 該本發明之第3光觸媒功能發揮材料，係一種具有由 作為第3成分之化合物，或由包含除該第3成分之外且加入 並含有作為第4成分之金屬之光觸媒配合物或光觸媒含有 物所形成之表面層之光觸媒功能發揮材料， 其中該前述表面層係可作成具有滿足下列條件（1)、（2) 中任一條件之表面性狀態之態樣者； (1) 表面層膜厚：約0.01〜3.0/zm; (2) 令1%之硝酸銀溶液附著於表面層之狀態下，該 表面層上之紫外線強度為1.2mW/cm2，在前述表面層上照 射紫外線5分鐘時之紫外線照射前與紫外線照射後之表面 層色差ΔΕ為1〜50。 經濟部中央標準局員工消費合作社印製 在該態樣之光觸媒功能發揮材料中，在表面層上含有 作為第3成分之化合物，藉該第3成分之化合物，如本發明 之第1光觸媒配合物之第6〜第8態樣，在該表面層中，接 觸角變小而親水性提高，因此可展現高度防污效果。又， 若表面層膜厚為0·01 μ m以上時，則膜（表面層）不會太薄 ，因此作為材料可確實地顯現表面層本身之接觸角，因此 理想。即，基材即使具有大的接觸角，藉形成於該基材之 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） 18 經濟部中央標準局員工消費合作社印製 495384 A7 B7____ 五、發明説明（16 ) ""~ " 表面層，可使接觸角變小，而展現出高度防污效果。另一 方面，若表面層膜厚為3·〇以m以下時，因可維持表面層 對基材之密著性，故可抑制表面層剝離（膜剝離），因此 理想。對包含除了作為第3成分之化合物之外且加上作為 第4成分之金屬之光觸媒功能發揮材料也是一樣。 又’附著於表面層之硝酸銀溶液中之銀離子，藉由紫 外線照射而形成激發狀態之光觸媒·，接收激發電子，而還 原並加以析出，而可呈色。因此，可在紫外線照射前後觀 察色差ΔΕ。是故，激發電子之生成愈多，則該色差Δε 就愈大。激發電子之生成量係一決定光觸媒之光活性大小 的因素’因此光觸媒活性大小可用以色差△Ε評價。因為 光觸媒之激發電子在空氣中生成氫氧基· 〇Η等之活性氧 物種，所以隨著光觸媒活性愈大，亦即色差ΔΕ愈大，氫 氧基· 0Η等之活性氧物種之生成愈多。 但是’於表面層所包含之第3成分之化合物，持有保 持藉光觸媒之激發電子所生成之氫氧基· 〇Η之作用，所 生成之氫氧基· 0Η之量愈多，第3成分之化合物表面之氫 氧基密度也愈高，而水之接觸角變小，可提高親水性。又 ’風乳基· 0Η之量愈多，表面層之有機化合物之分解量 增加，而有利於親水性。藉此，若是顯示色差Δ]Ε為1以 上之表面層時，就具有可充分形成高度氫氧基密度之光觸 媒活性，藉此之表面層之接觸角也可作成小至可確實發揮 防污效果之程度，因此理想。另一方面，針對表面積單位 之每單位面積之黏著劑的光觸媒量增加的話，色差δε也 本紙張尺度適用中國國家標準（CNS ) A4規格（210 X29*7公釐） (請先閱讀背面之注意事項再本頁) 裝. 、1Τ 19 經濟部中央標準局員工消費合作社印製 495384 A7 B7 五、發明説明（17 ) 會變大，但在此時，會令對基材之密著性降低，容易引起 表面層之剝離，因此若是表示△ E為50以下之表面層時， 從可抑制表面層之剝離之面來看為佳。 本發明之第4光觸媒功能發揮材料為， 具有基材層及形成於該表面之表面層，且為一種受到 光之照射即可發揮光觸媒功能之材料； 而前述表面層係， 上述本發明之第1光觸媒化合物或其各態樣之光觸媒 配合物經黏著劑形成於前述基材層表面之表面層者。 在這本發明之第4光觸媒功能發揮材料中， 前述黏著劑係宜作為一種，以比前述基材層之基材的 變質溫度以下之溫度聚合或溶化，於前述基材層表面上將 前述光觸媒配合物黏著之黏著劑，以及作為釉藥或塗料。 本發明之第5光觸媒功能發揮材料係， 具有基材層及形成於該表面之表面層，且為一種受到 光之照射即可發揮光觸媒功能之材料， 而前述表面層除作為光觸媒之Ti02之外且加上並包含 有ai2o3、Si02及可發揮抗菌性之金屬。 在具有上述構成之本發明之第3至第5光觸媒功能發揮 材料上，在形成於基材層上之表面層的表面上，與本發明 之第1光觸媒配合物同樣地，可提高被反應物之削減效率 ，以及於觸媒反應之系内可確實放置被反應物或中間生成 物。是故，於該光觸媒功能發揮材料之表面層表面中，可 高效率地削減被反應物之同時，可確實地確保被反應物作 本紙張尺度適用中國國家標準（CNS ) A4規格（210X29?公釐） (請先閲讀背面之注意事項再本頁)1. The paper size of the 1T line is applicable to the Chinese National Standard (CNS) Mil grid (210X297 mm) -17-495384 A7 B7 V. Description of the invention (15) The third photocatalyst function playing material of the present invention is: The surface layer formed on the surface is a material that can exert the photocatalyst function when irradiated by light; and the aforementioned surface layer is the surface layer formed by the first photocatalyst complex of the present invention or the photocatalyst complexes of various forms, Or a photocatalyst function exhibiting material having a surface layer formed of the second photocatalyst-containing substance according to the present invention. The third photocatalyst function exhibiting material of the present invention is a photocatalyst complex or photocatalyst-containing material comprising a compound as a third component or a metal containing a metal as a fourth component in addition to the third component The photocatalyst function exhibiting material of the formed surface layer, wherein the aforementioned surface layer can be made to have a surface state that satisfies any of the following conditions (1), (2); (1) the thickness of the surface layer : About 0.01 ~ 3.0 / zm; (2) When the 1% silver nitrate solution is attached to the surface layer, the ultraviolet intensity on the surface layer is 1.2mW / cm2, and the ultraviolet rays when the ultraviolet rays are irradiated on the surface layer for 5 minutes The color difference ΔE of the surface layer before the irradiation and after the ultraviolet irradiation is 1 to 50. The Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs printed the photocatalyst function display material in this aspect, and the surface layer contains a compound as the third component, and the compound based on the third component is like the first photocatalyst complex of the present invention. In the sixth to eighth aspects, in this surface layer, the contact angle becomes smaller and the hydrophilicity is improved, so that a high antifouling effect can be exhibited. Moreover, if the film thickness of the surface layer is 0.01 μm or more, the film (surface layer) is not too thin, and therefore it is ideal as a material to reliably show the contact angle of the surface layer itself. That is, even if the base material has a large contact angle, the Chinese paper standard (CNS) A4 (210X297 mm) is applied to the paper size formed on the base material. 18 Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 495384 A7 B7____ 5 、 Explanation of invention (16) " " ~ " The surface layer can make the contact angle smaller and show a high antifouling effect. On the other hand, when the film thickness of the surface layer is 3.0 m or less, it is preferable because the adhesion of the surface layer to the substrate can be maintained and the surface layer peeling (film peeling) can be suppressed. The same applies to a photocatalyst-function-producing material containing a compound as a third component and a metal as a fourth component. In addition, the silver ions in the silver nitrate solution attached to the surface layer are irradiated with ultraviolet rays to form an excited photocatalyst ·, receive excited electrons, and reduce and precipitate them to form a color. Therefore, the color difference ΔE can be observed before and after ultraviolet irradiation. Therefore, the more the excited electrons are generated, the larger the color difference Δε is. The amount of excited electrons generated is a factor determining the photoactivity of the photocatalyst '. Therefore, the photocatalytic activity can be evaluated by the color difference ΔE. Because the excited electrons of the photocatalyst generate reactive oxygen species such as hydroxyl groups 〇Η in the air, as the photocatalyst activity increases, that is, the larger the color difference ΔΕ, the more reactive oxygen species such as hydroxyl groups 0 ° are generated. . However, the compound of the third component contained in the surface layer has a role of maintaining the hydroxyl group 〇Η generated by the excited electrons of the photocatalyst, and the more the amount of generated hydroxyl group 0 ，, the more the third component The higher the density of hydroxyl groups on the surface of the compound, the smaller the contact angle of water can improve the hydrophilicity. In addition, the more the amount of wind-milk-based 0Η, the more the amount of decomposition of the organic compounds on the surface layer increases, which is beneficial to hydrophilicity. Therefore, if the surface layer showing a color difference Δ] E of 1 or more has a photocatalytic activity capable of sufficiently forming a high hydroxyl density, the contact angle of the surface layer can also be made small to ensure the antifouling effect. Degree, so ideal. On the other hand, if the photocatalyst amount of the adhesive per unit area of the surface area unit increases, the color difference δε will also apply the Chinese National Standard (CNS) A4 specification (210 X29 * 7 mm) for this paper size (please read the note on the back first) Matters reprinted on this page), 1T 19 Printed by the Consumers' Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs 495384 A7 B7 5. The invention description (17) will become larger, but at this time, the adhesion to the substrate will be reduced. The peeling of the surface layer is likely to occur. Therefore, if the surface layer indicates that ΔE is 50 or less, it is preferable from the viewpoint of suppressing the peeling of the surface layer. The fourth photocatalyst function exhibiting material of the present invention is a material having a base material layer and a surface layer formed on the surface, and is a material that can exhibit the photocatalyst function upon being irradiated with light; and the aforementioned surface layer is the first aspect of the present invention. 1 A photocatalyst compound or a photocatalyst complex of each aspect is formed on a surface layer on the surface of the substrate layer via an adhesive. In the fourth photocatalyst function exhibiting material of the present invention, it is preferable that the adhesive is a kind that polymerizes or melts at a temperature lower than the deterioration temperature of the base material of the base material layer, and applies the photocatalyst on the surface of the base material layer. Adhesive for complex adhesion and as a glaze or coating. The fifth photocatalyst function display material system of the present invention has a base material layer and a surface layer formed on the surface, and is a material that can display the photocatalyst function when exposed to light. The surface layer is in addition to Ti02, which is a photocatalyst. In addition, it contains ai2o3, SiO2, and antibacterial metal. In the third to fifth photocatalyst function exhibiting materials of the present invention having the above-mentioned configuration, the surface of the surface layer formed on the base material layer can improve the reactant in the same manner as the first photocatalyst complex of the present invention. It can reduce the efficiency, and the reactant or intermediate product can be surely placed in the catalyst reaction system. Therefore, in the surface layer surface of the photocatalyst function display material, the reactant can be efficiently reduced, and the reactant can be surely used as the paper standard of China National Standards (CNS) A4 (210X29? %) (Please read the notes on the back before this page)

線- 20 經濟部中央標準局員工消費合作社印製 495384 A7 B7 五、發明説明（18 ) 用於觸媒反應之機會或進而中間生成物作用於該觸媒反應 之機會，而使觸媒反應更加有效率地進行。又，於表面層 上含有可發揮抗菌性之金屬，因此用以可發揮抗菌性之金 屬及光觸媒可展現雙重的抗菌性，故理想。 在上述本發明之第3、第4光觸媒功能發揮材料中， 前述光觸媒係一種經由照射光能生成激發電子及空穴 ，在觸媒表面上之氧氣及水份存在下，經前述激發電子及 空穴可生成活性氧物種之光觸媒，而 前述另一化合物係以下所列者中之至少一種金屬化合 物，即，可與在基於前述活性氧物種而進行之觸媒反應中 作為前述被反應物或前述中間生成物相化學結合的兩性金 屬氧化物、驗性金屬氧化物或酸性金屬氧化物，則具有下 列利點。 藉該光觸媒功能發揮材料時，與本發明之第1光觸媒 配合物之上述態樣同樣地，可以鹼性自由基及酸性自由基 確實地將被反應物或中間生成物結合並加以保持，可在基 於活性氧物種之觸媒反應之系内放置該等被反應物或中間 生成物。藉此，於該光觸媒功能發揮材料之表面層之表面 上，可更有效率地進行觸媒反應，經此，可提高被反應物 之削減效率。又，如本發明之第1光觸媒配合物第6〜第8 態樣，在使用具有第3成分之化合物之光觸媒配令物或光 觸媒含有物時，於該等表面中，可展現基於高度親水性之 高度汙垢防止效果，因此理想。進而，如本發明之第1光 觸媒配合物之第9〜第10態樣，在使用具有第4成分之金屬 本紙張尺度適用中國國家標準（CNS ) A4規格（210X 297公釐） (請先閲讀背面之注意事項再本頁) 訂 21 A7 經濟部中央標準局員工消費合作社印製 -^ _____B7_1、發明説明（19 ) 之光觸媒配合物或光觸媒含有物時，於該等表面中，用以 可發揮抗菌性之金屬及光觸媒可展現雙重抗菌性，因此理 想。 在上述本發明之第3至第5光觸媒功能發揮材料中可採 取下列態樣。在第1態樣中，前述基材層係由陶究、樹月旨 、金屬、玻璃、陶器、木材、珪酸鈣板、混凝土板、水泥 板、水泥擠壓整形板、石膏板或蒸壓養護混凝土中任一種 基材所形成者。經由該態樣，使用了該等基材之場所，如 大樓、房屋以及橋樑等之建築構造物内外壁或道路中發揮 光觸媒功能，分解氮化合物、硫化合物、碳酸氣體等之環 境污染物質，可實現大氣淨化。進而，使用具有第3成分 之化合物之光觸媒配合物時，在該等建築構造物内外壁或 道路等中，可高度展現基於高親水性之防污效果。 在第2態樣時，前述表面層係經熱處理，如燒烤形成 之。藉該態樣，可將表面層強固地形成於基材層上。 在第3態樣中，係於前述表面層之表面上固著有可發 揮抗菌性之金屬或金屬化合物者。藉該態樣，使在光照射 間表面層中之光觸媒可完成之抗菌功能，在光沒照射時， 該抗菌功能可藉由表面層之表面上之金屬或金屬氧化物完 成之。因此，可補充光觸媒所完成之抗菌功能。又，在表 面層中除了光觸媒以外還含有上述另一化合物，因此除了 抗菌功能以外，還可經由上述光觸媒所參與之觸媒反應之 效率提高，實現環境污染物質之分解及大氣淨化。又，如 本發明之第1光觸媒配合物之第6〜第8態樣使用具有第3成 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公羡） (請先閱讀背面之注意事項再 —裝—， 本頁 -訂 -線 22 495384 A7 B7 五、發明説明（2〇 ) 分之化合物之光觸媒配合物或光觸媒含有物時，在該等表 面層中，可高度展現基於高親水性之防污效果，因此理想 。進而，如本發明之第1光觸媒配合物之第9〜第10態樣， 在使用具有載持第4成分之金屬之光觸媒配合物或光觸媒 含有物時，藉該第4成分之金屬也可發揮雙重之抗菌性， 因此可將固著於表面層之表面的金屬或金屬化合物作成極 少量。又，經第4成分之金屬之雙重抗菌性很高時，也可 省略金屬或金屬化合物對表面層之表面的固著。 本發明之光觸媒功能發揮材料之第6製造方法為， 一種製造具有基材層及形成於該表面之表面層，且受 到光之照射即可發揮光觸媒功能之材料的製造方法，其特 徵在於包含有： 一準備程序，係用以準備上述本發明之第1光觸媒配 合物、各態樣之光觸媒配合物或分散有該光觸媒配合物之 光觸媒配合物分散溶膠者； 一配設程序，係將前述光觸媒配合物或前述光觸媒配 合物分散溶膠層狀配設於前述基材層表面上者；及 一形成程序，係形成前述表面層者。 經濟部中央標準局員工消費合作社印製 此時，光觸媒配合物分散溶膠係可從在水、酒精等之 溶液中使光觸媒配合物分散而製成。 藉該本發明之第6之製造方法，因不須特殊程序，如 本發明之第1光觸媒配合物所述，藉可確實地在觸媒反應 之系内放置該等被反應物或中間生成物，故可輕易製造一 以高效率引起觸媒反應之新穎光觸媒功能發揮材料。此時 本紙張尺度適用中國國家標準（CNS ) A4規格（210X 297公釐） 23 經濟部中央標準局員工消費合作社印製 495384 A7 B7 五、發明説明（21 ) ，在形成表面層時，因應所配設之光觸媒配合物或光觸媒 配合物分散溶膠可採取適當手法，如熱處理或乾燥處理。 在該本發明之第6製造方法中， 前述配設程序係作成包含有，將前述光觸媒配合物或 前述光觸媒配合物分散溶膠層狀配設於前述基材層表面上 時，將前述光觸媒配合物或前述光觸媒配合物分散溶膠於 前述基材層表面上進行層狀載置、塗抹或印刷之程序時， 其具有下列優點。 藉該本發明之第6製造方法，在經光觸媒配合物形成 且厚度均勻之表面層中，可輕易製造一以高效率引起觸媒 反應之新穎的光觸媒功能發揮材料。又，對基材層表面之 光觸媒配合物之層狀塗抹係藉喷射式塗抹等之塗抹方式， 而層狀印刷係藉滾壓式印刷等之適當印刷方式實施。 本發明之光觸媒功能發揮材料之第7製造方法， 係一種製造具有基材層及形成於該表面之表面層且為 受到光之照射即可發揮光觸媒功能之材料的方法，其特徵 在於包含有： 一準備程序，係用以準備上述本發明之第1光觸媒配 合物或其各態樣之光觸媒配合物或分散有該光觸媒配合物 之光觸媒配合物分散溶膠者； 一形成程序1，係用以於前述基材層表面上層狀配設 黏著劑，形成黏著層； 一配設程序，係將前述光觸媒配合物或前述光觸媒配 合物分散溶膠層狀配設於前述黏著層表面上者；及 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） (請先閲讀背面之注意事項再本頁) —裝. 太 訂 24 495384 五、發明説明（ 22 經濟部中央標準局員工消費合作社印製 形成：表成：係因應前述黏著劑之性質、一 藉該本發明之第7製造 夕L 方法，係以於黏著層及表面層 兄界上以該表面層中之光觸媒配合物埋設於黏著層之狀 “而加以保持’可將表面層形成於黏著層表面上。此時， I將表面層強固地固定於黏著層之同時，使光觸媒配合物 有效地與外氣相接觸1後，如本發明之^光觸媒配合 物所述#以讀實地在觸媒反應之系内放置該等被反應物 或中間生成物，可輕易在表面層中製造一以高效率引起觸 媒反應之新穎光觸媒功能發揮材料。 ▲此時’前述黏著劑為釉藥，在形成前述表面層時，在 遠比前述釉藥之軟化溫度3(rcj^上且3〇(rc以下之範圍還 兩，且遠比前述基材層之基材的變質溫度還低之溫度環境 下加以熱處理者。因令加熱溫度比黏著劑（釉藥）之軟化溫 度兩出30 C以上，因此藉加熱軟化釉藥時不需長時間，故 理想。又，令加熱溫度超過釉藥之軟化溫度而不高過3〇() °C，因此，可回避釉藥急遽地熔化，抑制光觸媒配合物之 過度埋δ又及凹凸面的產生或針孔之發生等之不良情形。進 而’在形成前述表面層時，可在約^卜^⑼它之溫度環 境下施以熱處理，因此理想。藉此，使用現有之加熱裝置 ’可製造一以高效率引起觸媒反應之新穎的光觸媒功能發 揮材料。然後，將熱處理溫度作成約15(TC以上時，與現 有之釉藥的熱處理溫度一致，不必改變習知之熱處理條件 。又，將熱處理溫度作成約1300°c以下時，與需要熱處理-20 Printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs 495384 A7 B7 V. Description of the invention (18) The opportunity for the catalyst reaction or the opportunity for the intermediate product to act on the catalyst reaction, making the catalyst reaction more Efficiently. In addition, since the surface layer contains a metal capable of exhibiting antibacterial properties, it is preferable to use a metal and photocatalyst which exhibit antibacterial properties to exhibit dual antibacterial properties. In the third and fourth photocatalyst function exhibiting materials of the present invention, the photocatalyst is a kind of excited electrons and holes generated by irradiating light energy. In the presence of oxygen and water on the catalyst surface, the excited electrons and air The hole can generate a photocatalyst of an active oxygen species, and the aforementioned another compound is at least one metal compound listed below, that is, it can be used as the reactant or the aforementioned in a catalyst reaction based on the aforementioned reactive oxygen species. The amphoteric metal oxide, test metal oxide or acid metal oxide chemically bonded with the intermediate product phase has the following advantages. When the photocatalyst function is used to display the material, similar to the above-mentioned aspect of the first photocatalyst complex of the present invention, the basic reactant or the acidic radical can reliably bind and retain the reactant or the intermediate product. These reactants or intermediate products are placed in the catalyst reaction system based on reactive oxygen species. Thereby, the catalyst reaction can be performed more efficiently on the surface of the surface layer of the photocatalyst function exhibiting material, and the reduction efficiency of the reactant can be improved through this. In addition, as in the sixth to eighth aspects of the first photocatalyst complex of the present invention, when a photocatalyst preparation or a photocatalyst-containing material containing a compound having a third component is used, high hydrophilicity can be exhibited on these surfaces. It is highly effective in preventing dirt and is therefore ideal. Furthermore, as in the ninth to tenth aspects of the first photocatalyst complex of the present invention, the Chinese national standard (CNS) A4 specification (210X 297 mm) is applicable to the paper size using a metal with a fourth component (Please read first Note on the back page again) Order 21 A7 Printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs-^ _____B7_1, Invention Description (19) of photocatalyst complexes or photocatalyst inclusions, can be used on these surfaces Antibacterial metals and photocatalysts are ideal because they exhibit dual antibacterial properties. The above-mentioned third to fifth photocatalyst function exhibiting materials can adopt the following aspects. In the first aspect, the base material layer is made of ceramics, tree moon, metal, glass, pottery, wood, calcium acetate board, concrete board, cement board, cement extrusion molding board, gypsum board, or autoclave curing. Formed by any kind of base material in concrete. Through this aspect, places where such substrates are used, such as buildings, houses, bridges, and other internal and external walls of building structures or roads, play a photocatalytic function to decompose environmental pollutants such as nitrogen compounds, sulfur compounds, and carbon dioxide gas. Achieve atmospheric purification. Furthermore, when a photocatalyst complex having a compound having a third component is used, the antifouling effect based on high hydrophilicity can be highly exhibited in the inner and outer walls of such building structures, roads, and the like. In the second aspect, the aforementioned surface layer is formed by heat treatment, such as grilling. With this aspect, the surface layer can be strongly formed on the base material layer. In the third aspect, a metal or a metal compound having antibacterial properties is fixed to the surface of the surface layer. With this aspect, the antibacterial function that can be performed by the photocatalyst in the surface layer between light irradiation can be completed by the metal or metal oxide on the surface of the surface layer when the light is not irradiated. Therefore, it can supplement the antibacterial function performed by the photocatalyst. In addition, the surface layer contains the above-mentioned another compound in addition to the photocatalyst. Therefore, in addition to the antibacterial function, the efficiency of the catalyst reaction in which the photocatalyst participates can be improved to achieve the decomposition of environmental pollutants and the purification of the atmosphere. In addition, if the 6th to 8th aspects of the first photocatalyst complex of the present invention use a paper sheet with a third cost, the Chinese National Standard (CNS) A4 specification (210X297 public envy) is applied (please read the precautions on the back first— Equipment—, This page-order-line 22 495384 A7 B7 V. Description of the invention When the photocatalyst complex or photocatalyst content of the compound (20) is divided, in these surface layers, the protection based on high hydrophilicity can be highly exhibited. The stain effect is ideal. Furthermore, as in the ninth to tenth aspects of the first photocatalyst complex of the present invention, when using a photocatalyst complex or photocatalyst-containing substance having a metal supporting a fourth component, the fourth The metal of the component can also exhibit dual antibacterial properties, so the metal or metal compound fixed on the surface of the surface layer can be made in a very small amount. When the dual antibacterial property of the metal of the fourth component is high, the metal can be omitted. Or the adhesion of the metal compound to the surface of the surface layer. The sixth manufacturing method of the photocatalyst function display material of the present invention is to produce a surface layer having a substrate layer and a surface layer formed on the surface, and subject to A method for manufacturing a material capable of exhibiting a photocatalyst function by irradiation, comprising: a preparation process for preparing the first photocatalyst complex of the present invention, various forms of photocatalyst complexes, or dispersing the photocatalyst complex A photocatalyst complex dispersing a sol; a setting procedure for disposing the aforementioned photocatalyst complex or the photocatalyst complex dispersing sol in a layered manner on the surface of the substrate layer; and a forming procedure for forming the aforementioned surface layer Printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs At this time, the photocatalyst complex dispersing sol can be prepared by dispersing the photocatalyst complex in a solution such as water, alcohol, etc. By the sixth manufacturing method of the present invention Since no special procedure is required, as described in the first photocatalyst complex of the present invention, by placing these reactants or intermediate products in the catalyst reaction system, it is easy to produce New photocatalyst function materials for catalytic reaction. At this time, the paper size is applicable to China National Standard (CNS) A4 (210X 297 mm) 23 Printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs 495384 A7 B7 V. Description of Invention (21) When forming the surface layer, appropriate methods such as heat treatment or Drying process. In the sixth manufacturing method of the present invention, the arrangement procedure includes preparing the photocatalyst complex or the photocatalyst complex-dispersed sol in a layered manner on the surface of the substrate layer. The photocatalyst complex or the aforementioned photocatalyst complex-dispersed sol has the following advantages when it is subjected to a laminar placement, painting or printing process on the surface of the aforementioned substrate layer. According to the sixth manufacturing method of the present invention, a photocatalyst complex is used. In the formed and uniform thickness surface layer, a novel photocatalyst function display material that can cause a catalyst reaction with high efficiency can be easily manufactured. In addition, the laminar application of the photocatalyst complex on the surface of the base material layer is performed by an application method such as spray application, and the laminar printing is performed by an appropriate printing method such as roll printing. The seventh manufacturing method of the photocatalyst function exhibiting material of the present invention is a method for manufacturing a material having a base material layer and a surface layer formed on the surface and capable of exhibiting the photocatalyst function upon exposure to light, and is characterized by comprising: A preparation process for preparing the first photocatalyst complex of the present invention or various forms of the photocatalyst complex or a photocatalyst complex dispersed sol dispersed with the photocatalyst complex; a formation process 1 for the An adhesive layer is arranged on the surface of the substrate layer to form an adhesive layer; a setting procedure is to arrange the photocatalyst complex or the photocatalyst complex dispersed sol in a layer form on the surface of the adhesive layer; and the paper The dimensions are applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) (please read the precautions on the back before this page) — installed. Taiding 24 495384 V. Description of the invention (22 Printed by the Staff Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs Forming: Forming: Based on the properties of the aforementioned adhesive, the seventh manufacturing method of the present invention is applied to the adhesive layer and the surface. In the world, the surface of the photocatalyst complex in the adhesive layer is buried in the adhesive layer "and maintained" to form the surface layer on the surface of the adhesive layer. At this time, while the surface layer is firmly fixed to the adhesive layer, After the photocatalyst complex is effectively brought into contact with the outer gas phase, as described in the photocatalyst complex of the present invention, the reactants or intermediate products are placed in the catalyst reaction system in a realistic manner, and can be easily placed on the surface. In the layer, a novel photocatalyst function display material that causes a catalyst reaction with high efficiency is produced. ▲ At this time, the aforementioned adhesive is a glaze, and when the aforementioned surface layer is formed, the softening temperature of the glaze is much higher than 3 (rcj ^ on). And the range below 30 (rc) is two, and the heat treatment is performed in a temperature environment far lower than the deterioration temperature of the substrate of the aforementioned substrate layer. Because the heating temperature is two times higher than the softening temperature of the adhesive (glaze) Above 30 C, it does not take long to soften the glaze by heating, so it is ideal. In addition, the heating temperature exceeds the softening temperature of the glaze and not higher than 30 () ° C. Therefore, the glaze can be avoided from melting rapidly , Inhibit photocatalyst Excessive buried δ of the complex, the occurrence of uneven surfaces, the occurrence of pinholes, and the like. Furthermore, when forming the aforementioned surface layer, heat treatment can be performed in a temperature environment of about ^ ^ ^ ⑼, so it is ideal. With this, using the existing heating device, a novel photocatalyst function display material that can cause a catalyst reaction with high efficiency can be manufactured. Then, the heat treatment temperature is made about 15 (TC or more, consistent with the heat treatment temperature of the existing glaze, It is not necessary to change the conventional heat treatment conditions. In addition, when the heat treatment temperature is made below 1300 ° c, the heat treatment is required.

(請先閱讀背面之注意. 本頁) .HI I .(Please read the note on the back first. This page) .HI I.

訂 線 本紙張尺度適用中國國家標準（CNS ) M祝格（210X297公釐）Dimensions This paper size is applicable to Chinese National Standard (CNS) M Zhuge (210X297 mm)

25 495384 A7 B7 五、發明説明（23 ) 之基材，如磁磚或陶瓷器等之生成時之熱處理溫度一致， 不必改變習知之熱處理條件。 又，將前述黏著劑為塗料，在形成前述表面層時，可 在前述基材層之基材之改質溫度以下之溫度環境下施以熱 處理。如此，即不須改變基材材質並可形成表面層，因此 理想。 又，上述本發明之第6、第7之製造方法中， 係於形成前述表面層之程序後還包含有： 一塗抹程序，係用以於前述所形成之表面層表面上塗 抹並分散有可發揮抗菌性金屬或金屬化合物之溶液；及一 固著程序，係用以將前述金屬或金屬氧化物可固著於前述 表面層表面者。 藉該態樣之光觸媒功能發揮材料之製造方法，在表面 層中，不限於明處下或暗處下，可發揮抗菌性之同時，可 輕易在表面層中製造一以高效率可引起觸媒反應之新穎的 光觸媒功能發揮材料。而且，可將如此不拘於明處下或暗 處下可發揮抗菌性之性質隨後付予在已完成表面層形成之 光觸媒功能發揮材料上。 經濟部中央標準局員工消費合作社印製 進而，上述本發明之第6、第7製造方法中，可將 前述配設程序作成包含有一塗抹程序，係用以於將前 述光觸媒配合物或前述光觸媒配合物分散凝膠層狀配設後 ，可塗抹一分散有可發揮抗菌性之金屬或金屬化合物之溶 液；而 前述形成前述表面層之程序作成包含有一固著程序， 本紙張尺度適用中國國家標準（CNS ) A4規格（21〇><297公釐） 26 經濟部中央標準局員工消費合作社印製 495384 A7 B7 五、發明説明（24 ) 係用以於形成前述表面層之同時，將前述金屬或金屬氧化 物固著於前述表面層表面上。 藉該態樣之光觸媒功能發揮材料之製造方法，可輕易 製造一起先即兼具不限於明處下或暗處下可發揮抗菌性之 性質，及以高效率可引起觸媒反應之性質的新穎光觸媒功 能發揮材料。 進而，上述本發明之第6、第7製造方法中，可作成 於形成前述表面層之程序後，還包含有： 一塗抹程序，係於前述所形成之表面層之表面上塗抹 含有可發揮抗菌性之金屬的離子之金屬鹽水溶液； 一載置/固定程序，係用以紫外線照射於前述表面層 上，利用前述金屬離子對光觸媒的光還原，可在前述表面 層中之光觸媒上載持/固定者。 藉該態樣之光觸媒功能發揮材料之製造方法，在表面 層中，不限於明處下或暗處下可發揮抗菌性之同時，並可 輕易在表面層中製造一以高效率可引起觸媒反應之新穎的 光觸媒功能發揮材料。並且，可將付予補充抗菌性之金屬 利用光還原載持並固定於表面層中之光觸媒上，因此難以 發生該金屬之脫落。藉此，可長期維持抗菌性之補充作用 。又，可將如此不拘於明處下或暗處下可發揮抗菌性之性 質隨後付予在已完成表面層形成之光觸媒功能發揮材料上 。又，在使用如本發明之第1光觸媒配合物之第9〜第10態 樣具有載持第4成分之金屬的光觸媒配合物時，藉該第4成 分之金屬也可發揮雙重抗菌性，而使金屬鹽水溶液之塗抹 本紙張尺度適用中國國家標準（CNS ) A4祝格（210X297公釐） (請先閱讀背面之注意事項再本頁) —裝_ 太 訂 27 495384 A7 B7 經濟部中央標準局員工消費合作社印製 五、發明説明（25) 以及經塗抹後的紫外線照射載持於表面層之表面上之金屬 作成極少量。又，藉這第4成分之金屬之雙重抗菌性很高 時，也可省略該金屬對表面層表面上之載持。 本發明之光觸媒配合物之第8製造方法， 係一種製造光觸媒配合物者，該光觸媒配合物係由一 受到光之照射即可作為觸媒作用之光觸媒、前述另一化合 物、作為前述第3成分之化合物及作為前述第4成分之金屬 所配合而成；而前述光觸媒配合物之製造方法之特徵在於 包含有： 一準備程序，係用以準備至少分散有前述光觸媒、前 述另一化合物及作為前述第3成分之化合物之中之前述光 觸媒之光觸媒分散溶膠；及 一種配合有一接受光之照射以觸媒作用之光觸媒之光 觸媒配合物之製造方法，其特徵在於包含有： 一準備程序，係用以準備分散有本發明之第1光觸媒 配合物之第6〜第8態樣之光觸媒配合物之光觸媒配合物分 散溶膠；及 一載持程序，係將可發揮抗菌性之金屬的離子之金屬 鹽水溶液混合於前述光觸媒分散溶膠，將前述金屬作為第 4成分，並載持於前述光觸媒。 本發明之光觸媒配合物之第9製造方法， 係一種製造光觸媒配合物者，該光觸媒配合物係由一 受到光之照射即可作為觸媒作用之光觸媒、前述另一化合 物、作為前述第3成分之化合物及作為前述第4成分之金屬 (請先閲讀背面之注意事項再本頁) |裝· 太 、?τ 線 本紙張尺度適用中國國家標準（CNS ) Α4規格（210Χ297公釐） 28 495384 A7 B7 經濟部中央標準局員工消費合作社印製 五、發明説明（26) 所配合而成；前述光觸媒配合物之製造方法之特徵在於包 含有： 一準備程序，係準備至少分散有前述光觸媒、前述另 一化合物及作為前述第3成分之化合物之中之前述光觸媒 之光觸媒分散溶膠；及 一載持程序，係令可發揮抗菌性之金屬離子之金屬鹽 水溶液混合於前述光觸媒分散溶膠之後，令前述金屬的鹽 以及前述光觸媒一起沈澱，將前述金屬作為第4成分載持 於前述光觸媒上。 本發明之光觸媒配合物之第10製造方法， 係一種製造光觸媒配合物者，該光觸媒配合物係由一 受到光之照射即可作為觸媒作用之光觸媒、前述另一化合 物、作為前述第3成分之化合物及作為前述第4成分之金屬 所配合而成；前述光觸媒配合物之製造方法之特徵在於包 含有： 一準備程序，係用以準備至少分散有前述光觸媒、前 述另一化合物及作為前述第3成分之化合物之中之前述光 觸媒之光觸媒分散溶膠；及， 一載持程序，係將含有可發揮抗菌性之金屬離子之金 屬鹽水溶液混合於前述光觸媒分散溶膠之後，照射紫外線 ，利用前述金屬離子之光還原，將前述金屬作為第4成分 並加以載持於前述光觸媒。 藉該等第8〜第10之光觸媒配合物之製造方法，使用 該等光觸媒配合物所形成之表面層中，不拘明處下或暗處 (請先閲讀背面之注意事項 再 本頁) •裝· 訂 -線 本紙張尺度適用中國國家標準（CNS ) A4規格（210X 297公釐） 29 經濟部中央標準局員工消費合作社印製 495384 A7 B7 五、發明説明（27) 下可發揮抗菌性之同時，輕易製造一可於該表面層中以高 效率引起觸媒反應之新穎光觸媒配合物。並且，本發明之 第8製造方法，在係令參與抗菌性之補充的金屬預先載持 固定於光觸媒上時，不過是混合光觸媒分散溶膠及金屬鹽 水溶液，因此可實現程序步驟的簡化。又，本發明之第9 及第10製造方法在係利用共沈或光還原，令參與抗菌性補 充的金屬預先載持固定於光觸媒上，因此使金屬難以從光 觸媒脫落，而可長期維持抗菌性之補充作用。進而，本發 明之第10製造方法，在金屬之載持固定時，不過是照射紫 外線，不需要任何藥品等，因此可實現程序步驟之簡化。 在該等第8〜第10光觸媒配合物之製造方法中，可令 光觸媒分散溶膠作為，光觸媒及另一化合物以及作為第3 成分之化合物全部分散完畢之溶液，即分散有本發明之第 1光觸媒配合物之第6〜第8態樣之光觸媒配合物之溶液。 又，可於金屬載持後之光觸媒分散溶膠中分散另一化合物 及作為第3成分之化合物。進而，從保管上之方便令作成 粉末狀光觸媒配合物放置時，使已分散有已載持作為第4 成分之金屬之光觸媒及另一化合物及作為第3成分之化合 物之溶膠乾燥即可。 本發明亦可採取下列其他之態樣，第1另一態樣係一 種配合有一受到光照射即以觸媒作用之光觸媒之配合物之 製造方法，其特徵在於具備有： 程序（A)，係用以準備分散有前述光觸媒之粒子之第1 溶膠； 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） (請先閲讀背面之注意事項再_舄本頁)25 495384 A7 B7 V. Description of the invention (23) The substrates, such as tiles or ceramics, have the same heat treatment temperature when they are produced. It is not necessary to change the conventional heat treatment conditions. In addition, when the adhesive is a coating material, when the surface layer is formed, heat treatment may be performed in a temperature environment equal to or lower than the modified temperature of the substrate of the substrate layer. In this way, it is desirable to form the surface layer without changing the material of the substrate. In addition, in the manufacturing methods of the sixth and seventh aspects of the present invention, after the procedure of forming the surface layer, the method further includes: an application procedure for applying and dispersing the surface layer formed on the surface of the surface layer. A solution that exerts antibacterial metal or metal compound; and a fixation procedure for fixing the aforementioned metal or metal oxide to the surface of the aforementioned surface layer. By utilizing the photocatalyst function of this aspect, the manufacturing method of the material can be used in the surface layer, not limited to the light or the dark, to exert antibacterial properties, and at the same time, it is easy to manufacture a high-efficiency catalyst that can cause the catalyst in the surface layer. The novel photocatalytic function of the reaction material. In addition, it is possible to impart such antibacterial properties to light-exposed or dark-exposed materials to the photocatalyst function-developing material after the surface layer has been formed. Printed by the Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs Further, in the above-mentioned sixth and seventh manufacturing methods of the present invention, the above-mentioned configuration procedure may be made to include a smearing procedure for combining the aforementioned photocatalyst complex or the aforementioned photocatalyst After the dispersing gel is arranged in a layer, a solution in which a metal or a metal compound capable of exhibiting antibacterial properties is dispersed can be applied; and the aforementioned procedure for forming the aforementioned surface layer includes a fixation procedure, and the paper dimensions are applicable to Chinese national standards ( CNS) A4 specification (21〇 > < 297 mm) 26 Printed by the Employees' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs 495384 A7 B7 V. Description of the invention (24) It is used to form the aforementioned surface layer and the aforementioned metal Or the metal oxide is fixed on the surface of the surface layer. By utilizing the manufacturing method of the photocatalyst function display material in this aspect, it is possible to easily manufacture novel novel materials that have antibacterial properties that are not limited to bright places or dark places, and can cause catalyst reactions with high efficiency. Photocatalyst function material. Furthermore, in the above-mentioned sixth and seventh manufacturing methods of the present invention, after the procedure for forming the aforementioned surface layer, the method further includes: an application procedure, which is applied on the surface of the aforementioned formed surface layer to exhibit antibacterial properties. An aqueous solution of a metal salt of an ion of a stable metal; a placement / fixing procedure, which uses ultraviolet rays to irradiate the aforementioned surface layer, and utilizes the photoreduction of the photocatalyst by the aforementioned metal ion to carry / fix the photocatalyst in the aforementioned surface layer By. By utilizing the photocatalyst function of this aspect, the manufacturing method of the material can be used in the surface layer, not only in the light or in the dark, to exhibit antibacterial properties, but also to easily produce a high-efficiency catalyst that can cause the catalyst in the surface layer. The novel photocatalytic function of the reaction material. In addition, the metal supplemented with antibacterial properties can be supported by photoreduction and fixed on the photocatalyst in the surface layer, so that the metal is hardly detached. In this way, the supplementary effect of antibacterial properties can be maintained for a long time. In addition, the antibacterial properties that can be exhibited in bright or dark places can be subsequently applied to the photocatalyst function exhibiting material on which the surface layer has been formed. In addition, when a photocatalyst complex having a metal carrying a fourth component as in the ninth to tenth aspects of the first photocatalyst complex of the present invention is used, the metal of the fourth component can also exhibit dual antibacterial properties, and Make the application of the metal salt solution suitable for Chinese paper standard (CNS) A4 (210X297 mm) (Please read the precautions on the back before this page) — Pack_ Taiding 27 495384 A7 B7 Central Bureau of Standards, Ministry of Economic Affairs Printed by the Employee Consumption Cooperative. 5. Description of the Invention (25) and the ultraviolet radiation after painting, the metal carried on the surface layer is made in a very small amount. When the dual antibacterial properties of the metal based on the fourth component are high, the support of the metal on the surface of the surface layer may be omitted. The eighth manufacturing method of the photocatalyst complex according to the present invention is a person who manufactures a photocatalyst complex. The photocatalyst complex is a photocatalyst that can act as a catalyst upon exposure to light, the other compound, and the third component. The compound is compounded with the metal as the fourth component; and the method for manufacturing the photocatalyst complex includes: a preparation process for preparing at least the photocatalyst, the other compound, and The photocatalyst-dispersed sol of the aforementioned photocatalyst among the compounds of the third component; and a method for manufacturing a photocatalyst complex compounded with a photocatalyst that receives the irradiation of light to act as a catalyst, characterized in that it includes: a preparation procedure for A photocatalyst complex dispersing sol in which the photocatalyst complexes of the first to the sixth photocatalyst complexes of the present invention are dispersed is prepared; and a supporting procedure is a metal salt aqueous solution that will exhibit antibacterial metal ions. Mixed with the photocatalyst-dispersed sol, with the metal as a fourth component, and supported The aforementioned photocatalyst. The ninth manufacturing method of the photocatalyst complex of the present invention is a person who manufactures a photocatalyst complex. The photocatalyst complex is a photocatalyst that can act as a catalyst upon exposure to light, the other compound, and the third component. Compounds and metals as the fourth component (please read the precautions on the back and then this page) | Package · Too much,? Τ The size of this paper applies the Chinese National Standard (CNS) A4 specification (210 × 297 mm) 28 495384 A7 B7 Printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs. 5. The description of the invention (26); the manufacturing method of the aforementioned photocatalyst complex is characterized by including: a preparation process to prepare to disperse at least the aforementioned photocatalyst, the aforementioned another A compound and the photocatalyst-dispersed sol of the aforementioned photocatalyst among the compounds as the aforementioned third component; and a supporting procedure in which an aqueous solution of a metal salt of a metal ion capable of exhibiting antibacterial properties is mixed with the aforementioned photocatalyst-dispersed sol, and the aforementioned metal is And the photocatalyst are precipitated together, and the metal is supported as the fourth component Photocatalyst on. The tenth manufacturing method of the photocatalyst complex according to the present invention is a person who manufactures a photocatalyst complex. The photocatalyst complex is a photocatalyst that can act as a catalyst upon exposure to light, the other compound, and the third component. The compound is compounded with the metal as the fourth component; the method for manufacturing the photocatalyst complex includes the following steps: a preparation procedure for preparing at least the photocatalyst, the other compound, and the first The photocatalyst-dispersed sol of the aforementioned photocatalyst among the three-component compounds; and, a supporting procedure is to mix an aqueous solution of a metal salt containing metal ions capable of exhibiting antibacterial properties to the photocatalyst-dispersed sol, and then irradiate ultraviolet rays to utilize the aforementioned metal ions The photoreduction is carried out by using the metal as the fourth component and supporting the photocatalyst. According to the manufacturing methods of the 8th to 10th photocatalyst complexes, the surface layer formed by using the photocatalyst complexes is not restricted or hidden (please read the precautions on the back before this page). · Order-line paper size applies to Chinese National Standard (CNS) A4 (210X 297 mm) 29 Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 495384 A7 B7 V. Antibacterial properties can be displayed under (27) It is easy to manufacture a novel photocatalyst complex that can cause a catalyst reaction in the surface layer with high efficiency. In addition, in the eighth manufacturing method of the present invention, when the metal participating in the antibacterial supplement is preliminarily supported and fixed on the photocatalyst, the photocatalyst disperses the sol and the metal salt aqueous solution, so that the procedure can be simplified. In addition, the ninth and tenth manufacturing methods of the present invention use co-precipitation or photoreduction, so that the metal participating in the antibacterial supplement is preliminarily supported and fixed on the photocatalyst, so that it is difficult for the metal to fall off from the photocatalyst, and the antibacterial property can be maintained for a long time. Supplementary role. Furthermore, in the tenth manufacturing method of the present invention, when the metal is fixedly supported, the ultraviolet rays are irradiated, and no medicine or the like is required, so that the procedure steps can be simplified. In the manufacturing methods of the 8th to 10th photocatalyst complexes, the photocatalyst-dispersed sol can be used as a solution in which the photocatalyst and another compound and the compound as the third component are completely dispersed, that is, the first photocatalyst of the present invention is dispersed Solutions of photocatalyst complexes in the sixth to eighth aspects of the complex. In addition, another compound and a compound as a third component can be dispersed in the photocatalyst-dispersed sol after the metal support. Furthermore, when the powdered photocatalyst complex is stored for convenience of storage, the sol having the photocatalyst on which the metal as the fourth component has been dispersed and another compound and the compound as the third component may be dried. The present invention can also take the following other aspects. The first other aspect is a method for manufacturing a complex compounded with a photocatalyst that is irradiated with light and acts as a catalyst, which is characterized by having: a program (A), The first sol used to prepare the particles with the aforementioned photocatalyst dispersed; This paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm) (please read the precautions on the back before _ 舄 this page)

訂 -30 - 495384 A7 B7 經濟部中央標準局員工消費合作社印製 五、發明説明（28) 程序（B)，係用以準備分散有，與前述被反應物或前 述被反應物接受前述觸媒反應轉化至前述最終生成物之前 所生成之中間生成物可化學結合之前述另一化合物之粒子 的第2溶膠；及 程序（C)，係用以混合前述第1溶膠及第2溶膠。 藉該第1另一態樣之製造方法，經由第1及第2溶膠之 混合，可輕易使光觸媒及另一化合物分散於溶媒中。然後 ，經程序（C)之混合溶膠，不會專凝聚光觸媒或只凝聚另 一化合物，而是成為一形成使光觸媒化合物之光觸媒與另 一化合物幾乎平均混合分散之溶膠。藉此，該混合溶膠宜 當作光觸媒配合物分散溶膠，可容易調配用以液體狀態使 用之材料，如用作塗料或釉藥之光觸媒及另一化合物之配 合。進而，因呈溶膠狀，故第1及第2溶膠之秤量簡單，因 此經由每個溶膠之秤量，可輕易調整光觸媒及另一化合物 之混合比率。又，混合溶膠中之溶媒以乾燥方式去除，使 光觸媒及另一化合物成為一均勻混合之呈固態粒狀的配合 物。 此時，使第1溶膠及第2溶膠為同一物品，使用所謂具 有良好相容性之溶媒即佳。 在上述第1另一態樣之製造方法中，係可令 前述（A)程序，係具有一調整前述光觸媒之粒子之程 序，該光觸媒為一種在經由所照射之光能生成激發電子及 空穴，在觸媒表面上之氧氣及水份存在下，經由前述激發 電子及空穴生成活性氧物種之光觸媒，而 (請先閲讀背面之注意事項再本頁)Order -30-495384 A7 B7 Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 5. Description of the invention (28) Procedure (B) is used to prepare the dispersion and accept the aforementioned catalyst with the reactant or the reactant A second sol of particles of the other compound that can be chemically bound to the intermediate product generated before the reaction is converted to the final product; and procedure (C), which is used to mix the first sol and the second sol. According to the manufacturing method of the first other aspect, the photocatalyst and another compound can be easily dispersed in the solvent by mixing the first and second sols. Then, the mixed sol through the procedure (C) does not specifically aggregate the photocatalyst or only another compound, but becomes a sol that forms a photocatalyst compound in which the photocatalyst compound and the other compound are almost evenly dispersed. Therefore, the mixed sol is suitable as a photocatalyst complex dispersing sol, and can be easily blended with a material used in a liquid state, such as a photocatalyst used as a coating or a glaze, and another compound. Furthermore, because it is in the form of a sol, the weighing of the first and second sols is simple. Therefore, the mixing ratio of the photocatalyst and another compound can be easily adjusted by the weighing of each sol. In addition, the solvent in the mixed sol is removed in a dry manner, so that the photocatalyst and the other compound become a uniformly mixed, solid-state granular complex. In this case, it is preferable that the first sol and the second sol are the same article, and a so-called solvent having good compatibility is preferably used. In the above-mentioned first aspect of the manufacturing method, the aforementioned (A) procedure is a procedure having a particle for adjusting the aforementioned photocatalyst, which is a type of excited electrons and holes generated by the irradiated light energy In the presence of oxygen and water on the catalyst surface, the photocatalyst of active oxygen species is generated through the aforementioned excitation of electrons and holes, and (please read the precautions on the back before this page)

訂 線 本紙張尺度適用中國國家標準（CNS ) A4祝格（210X297公釐） 31 495384 經濟部中央標準局員工消費合作社印製 A7 ___ B7 五、發明説明（29 ) 前述（B)程序，係具有一調整下列金屬氧化物之粒子 之程序’使下列者中之至少一種金屬化合物作為前述另一 化合物準備，即，該金屬氧化物為一種可與在基於前述活 性氧物種而進行之觸媒反應中作為前述被反應物或前述中 間生成物相化學結合的兩性金屬氧化物、鹼性金屬氧化物 或酸性金屬氧化物。（第2另一態樣） 依該第2另一態樣，可輕易得到一種令引起基於活性 氧物種之觸媒反應之光觸媒與用以鹼性基或酸性基確實地 使被反應物或中間生成物相結合並保持之另一化合物幾乎 均勻混合之光觸媒化合物。 又，在上述第1另一態樣之製造方法中，係可將 前述（C)程序，係具有一調製前述第”容膠及第2溶膠 之程序，可使前述金屬氧化物之重量以a，而前述光觸媒 之重量以b表示時，使a/(a+b)為0.0001〜〇·8。（第3另一態樣） 依該第3另一態樣，可輕易製得一種光觸媒配合物， 該光觸媒配合物中金屬氧化物（兩性金屬氧化物、驗性金 屬氧化物、酸性金屬氧化物）之量不致於太少，又，光觸 媒之量相對於上述金屬氧化物不會太少，而不會導致降低 觸媒反應之效率。 又’上述第1另一態樣之製造方法中，係可令： 前述（A)程序，係具有一可調整前述光觸媒在〇〇〇5 〜〇.5/zm左右之粒徑範圍中之程序， 前述（B)程序，係具有一可調整前述金屬氧化物在 0.005〜0.5/zm左右之粒徑範圍中之程序。（第4另一態樣） (請先閱讀背面之注意事項再本頁) —裝· 本 訂 -線 本紙張尺度適用中國國家標準（CNS ) A4祝格（210X297公釐） -32 - 495384 經濟部中央標準局員工消費合作社印製 A7 __—___B7_______五、發明説明（3〇 ) 依該第4另一態樣，可輕易用以球磨機等現有粉碎裝 置或溶膠/凝膠法調整光觸媒及金屬氧化物（兩性金屬氧化 物、驗性金屬氧化物、酸性金屬氧化物）之粒徑，因此理 想。又’可輕易製得一種不使被反應物或中間生成物離開 光觸媒且不使觸媒反應之效率降低之光觸媒配合物。進而 ’依該態樣’可令光觸媒與金屬化合物以約略相同大小之 粒子相接近’使被反應物或中間生成物接近於光觸媒，可 輕易得到一高效率的觸媒反應之光觸媒配合物。 圖式簡單說明 第1圖係模式顯示光觸媒之二氧化鈦將氮氧化物氧化 時’該一氧化鈦以及配合有氧化紹時中觸媒反應進行之情 形以及觸媒反應之中間生成物藉氧化鋁之結合情形。 第2圖係模式顯示光觸媒之二氧化鈦將硫氧化物氧化 時’與該二氧化鈦同時配合有氧化鋁時，其中觸媒反應之 中間生成物藉氧化鋁結合時之情形。 第3圖係模式顯示以光觸媒之二氧化鈦將一氧化碳氧 化時與該二氧化鈦同時配合有氧化鋁時，其中觸媒反應之 中間生成物藉氧化鋁之結合情形。 第4圖係用以測定本發明第1實施例之實施例磁磚的氮 氧化物削減效果之測試裝置之概略構成圖。 第5圖係第1實施例之實施例磁磚的氮氧化物削減效果 的結果線圖。 第6圖係第1實施例之實施例磁碑的氨之削減效果的結 果線圖。 (請先閱讀背面之注意事項再本頁) |裝· 訂 -線· 本紙張尺度適用中國國家標準（CNS ) A4規格（21〇'〆297公釐） 33 495384 A7 B7 五、發明説明（31 ) 第7圖係第1實施例之實施例磁磚的二氧化硫之削減效 果之結果線圖。 第8圖係第1實施例之實施例磁磚的氮氧化物之削減效 果之結果線圖。 第9圖係第1實施例之實施例磁磚的氮氧化物之削減效 果之結果線圖。 第10圖係顯示本發明第3實施例之實施例磁磚所發揮 的抗菌效果之結果線圖。 第11圖係4成分系之第6實施例之實施例磁碑（燒烤型） ，將所載持之金屬重量以c、Ti02之重量以d表示時，c/d( 金屬配合比）與抗菌力之關係線圖。 第12圖係4成分系之第6實施例之實施例磁磚（塗料型） ，將所載持之金屬重量以c、1402之重量以d表示時，c/d( 金屬配合比）與抗菌力之關係線圖。 第13圖係4成分系之第6實施例之實施例磁磚（燒烤型） ，其表面層膜厚與明亮時接觸角之關係線圖。 第14圖係4成分系之第6實施例之實施例磁碑（燒烤型） ，其表面層膜厚與抗菌力之關係線圖。 第15圖係4成分系之第6實施例之實施例磁磚（燒烤型） ’其表面層膜厚與油分解力之關係線圖。 第16圖係4成分系之第6實施例之實施例磁磚（燒烤型） ，其表面層膜厚與NO氧化力之關係線圖。 第17圖係3成分系之第7實施例之實施例磁磚（燒烤型) ，其表面層膜厚與明亮時接觸角之關係線圖。 本紙張尺度適用中國國家標準（CNS ) A4祝格（210X297公釐） (請先閱讀背面之注意事項再 —裝—— 本頁) 經濟部中央標準局員工消費合作社印製 34 495384 A7 ____B7__ 五、發明説明（32 ) 第18圖係4成分系之第6實施例之實施例磁碑（塗料型） ’其色差ΔΕ與明亮時接觸角之關係線圖。 第19圖係4成分系之第6實施例之實施例磁磚（塗料型） ，其色差AE與抗菌力之關係線圖。 第2 0圖係4成分系之第6實施例之實施例磁磚（塗料型） ’其色差AE與油分解力之關係線圖。 第21圖係4成分系之第6實施例之實施例磁磚（塗料型） ，其色差ΔΕ與NO氧化力之關係線圖。 第22圖係3成分系之第7實施例之實施例磁磚（塗料型） ’其色差ΔΕ與明亮時接觸角之關係線圖。 圈中元件符號表 (請先閱讀背面之注意事項再本頁) —裝· 訂 經濟部中央標準局員工消費合作社印製 10 玻璃槽 12 氣槪 14 空氣壓縮機 15 濕度調整器 16 流量調整閥 18 NOx感應器 20 燈泡 本紙張尺度適用中國國家標準（CNS ) A4祝格（210X297公釐） 35 經濟部中央標準局員工消費合作社印製 495384 A7 B7 五、發明説明（33) 用以實施發明之最佳形態 首先以實施例說明光觸媒配合物之調配。使用銳鈦礦 型之二氧化鈦作為光觸媒，而作為與該光觸媒共同配合之 金屬氧化物，則是使用兩性金屬氧化物之氧化銘、驗性金 屬氧化物之氧化錄及氧化顧。然後，在光觸媒配合物之調 配時，採取下列程序。 ① 光觸媒以及金屬氧化物之粒子的籌備 準備上述二氧化鈦、氧化紹、氧化鹤及氧化鎖之原料 ，各自以球磨機等之粉碎裝置將該等原料磨碎，或藉溶膠 /凝膠法製得二氧化鈦、氧化鋁、氧化锶及氧化鋇之微小 粒子。此時，各種粒子之粒徑可在0.005〜0.5/zm之粒徑範 圍内進行粒度調整。 ② 溶膠之調配 其次，如上述所調整之各配合材料各自分散於水、酒 精等之溶媒，調製每個配合材料之溶膠。此時，先規定各 溶膠中分散材料之分散量（如配合材料之重量/溶媒容量） 〇 ③ 光觸媒配合物之調整 之後，在已調合完畢之二氧化鈦（光觸媒溶膠）中混合 氧化鋁溶膠、氧化鋰溶膠及氧化鋇溶膠之金屬氧化物溶膠 ，而得到一二氧化鈦/氧化鋁混合溶膠（Ti/Al溶膠）、二氧 化鈦/氧化锶混合溶膠（Ti/Sr溶膠）及二氧化鈦/氧化鋇混合 溶膠（Ti/Ba溶膠）。此時，在調整上述各混合溶膠時，秤量 光觸媒溶膠之混合量及金屬氧化物溶膠之混合量，用以改 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） (請先閱讀背面之注意事項再^k本頁) li衣· 訂 -36 - 495384 經濟部中央標準局員工消費合作社印製 A7 B7五、發明説明（34 ) 變各種秤量，可調整光觸媒及金屬氧化物之配合比採取各 種值之混合溶膠。即，各混合溶膠中之金屬氧化物之重量 以a、光觸媒之重量以b表示時，可以a/(a+b)表示之配合比 率（以下將此a/(a+b)稱為配合比率決定比）調查各種混合量 〇 又，除了採用上述①〜③之程序之外，還可在調合完 畢之光觸媒溶膠中添加並加以分散粒度調整完畢之氧化鋁 等粒子，作成Ti/Al溶膠等。再者，將粒度調整完畢之光 觸媒粒子及氧化鋁等粒子交互或同時分散於上述溶媒，可 作成_一開始就分散有光觸媒粒子及氧化鋁等粒子之Ti/Al 溶膠等。 其次，用以如上述調整之光觸媒配合物（Ti/Al溶膠、 Ti/Sr溶膠、Ti/Ba溶膠之各混合溶膠），說明可發揮光觸媒 作用之光觸媒功能發揮材料。在本實施例（第1實施例）中 ，將該光觸媒功能發揮材料如下製成磁磚。 準備無上釉之磁磚作為基材，在該基材表面上喷射塗 抹所規定濃度之上述各混合溶膠。在該喷射塗抹時，可將 該塗抹量，即，可調整喷射時間，使燒烤後之磁磚表面中 之光觸媒混合物之膜厚為0.85# m左右。接著，為了光觸 媒定著，使用斟酌所配合之二氧化矽等之熔化溫度、二氧 化鈦及上述各金屬氧化物之熔化溫度後所決定之溫度（在 本實施例中約800°C)，將混合溶膠之喷射塗抹後之磁磚燒 烤60分鐘左右形成，藉此燒成一最終光觸媒功能發揮材料 (光觸媒功能發揮磁碑），此材料係具有在基材（磁磚）表面 (請先閲讀背面之注意事項再本頁)The paper size of the guideline is in accordance with the Chinese National Standard (CNS) A4 (210X297 mm) 31 495384 Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs A7 ___ B7 V. Description of the invention (29) The aforementioned (B) procedure has A procedure for adjusting the particles of the following metal oxides' preparing at least one metal compound of the following as the other compound, that is, the metal oxide is a kind which can be reacted in a catalyst reaction based on the aforementioned active oxygen species An amphoteric metal oxide, an alkaline metal oxide, or an acidic metal oxide that is chemically bonded to the reactant or the intermediate product. (Second alternative aspect) According to the second alternative aspect, it is possible to easily obtain a photocatalyst that causes a catalyst reaction based on an active oxygen species and a substrate or an acidic group to surely make the reactant or the intermediate A photocatalyst compound in which another product is combined and held almost uniformly. In addition, in the manufacturing method of the above first aspect, the aforementioned (C) procedure may have a procedure for preparing the aforementioned “capacitor” and the second sol, and the weight of the aforementioned metal oxide may be expressed as a When the weight of the aforementioned photocatalyst is expressed by b, a / (a + b) is 0.0001 to 0.8. (Third aspect) According to the third aspect, a photocatalyst can be easily prepared. The amount of metal oxides (amphoteric metal oxides, test metal oxides, acidic metal oxides) in the photocatalyst complex is not too small, and the amount of photocatalyst is not too small compared to the above metal oxides. It will not reduce the efficiency of the catalyst reaction. Also in the above-mentioned first aspect of the manufacturing method, the above (A) procedure may have an adjustable photocatalyst in the range of 0.0005 to 0.0. The program in a particle size range of about 5 / zm, the aforementioned (B) program has a program that can adjust the aforementioned metal oxide in a particle size range of about 0.005 to 0.5 / zm. (Fourth aspect) (Please read the precautions on the back before this page) —bound · bound-line paper Standards are applicable to Chinese National Standards (CNS) A4 Zhuge (210X297 mm) -32-495384 Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs A7 ______B7_______ V. Description of Invention (3〇) According to the fourth other state In this way, the particle size of photocatalysts and metal oxides (amphoteric metal oxides, test metal oxides, acidic metal oxides) can be easily adjusted with existing pulverizing devices such as ball mills or sol / gel methods, so it is ideal. It is easy to prepare a photocatalyst complex that does not allow the reactant or intermediate product to leave the photocatalyst and does not reduce the efficiency of the catalyst reaction. Furthermore, according to this aspect, the photocatalyst and the metal compound can be approximated by particles of approximately the same size. 'Make the reactant or intermediate product close to the photocatalyst, you can easily obtain a photocatalyst complex with a high-efficiency catalyst reaction. The diagram is briefly explained. Figure 1 shows the photocatalyst when titanium dioxide oxidizes nitrogen oxides. Titanium oxide and the case where the catalyst reaction is carried out when mixed with oxide, and the intermediate product of the catalyst reaction is combined with alumina Figure 2 shows the situation when the photocatalyst titanium dioxide oxidizes sulfur oxides and the titanium oxide is mixed with alumina, and the intermediate product of the catalyst reaction is combined with alumina. Figure 3 shows the mode using photocatalyst. When titanium dioxide is oxidized with carbon monoxide and the titanium dioxide is mixed with alumina, the intermediate product of the catalyst reaction is combined with alumina. Figure 4 is used to determine the tile of the example of the first embodiment of the present invention. FIG. 5 is a schematic configuration diagram of a test device for a nitrogen oxide reduction effect. FIG. 5 is a graph showing a result of the nitrogen oxide reduction effect of the tile of the first embodiment. FIG. 6 is a magnetic monument of the first embodiment. Result line diagram of the effect of reducing ammonia (Please read the precautions on the back before this page) | Binding · Staple-Thread · This paper size applies the Chinese National Standard (CNS) A4 specification (21〇'〆297mm) 33 495384 A7 B7 V. Description of the invention (31) Figure 7 is a result line diagram of the effect of reducing sulfur dioxide of the tile of the first embodiment. Fig. 8 is a graph showing the results of the reduction effect of nitrogen oxides of the tile of the first embodiment. Fig. 9 is a graph showing the results of the reduction effect of the nitrogen oxides of the tile of the first embodiment. Fig. 10 is a graph showing the results of the antibacterial effect exhibited by the tiles of the third embodiment of the present invention. Fig. 11 is an example of the sixth embodiment of the 4-component system magnetic stele (grilled type). When the weight of the metal carried is expressed as c and the weight of Ti02 is expressed as d, c / d (metal mixing ratio) and antibacterial Relationship diagram of force. Fig. 12 is an example of a sixth embodiment of a four-component system tile (paint type). When the weight of the metal carried is expressed as c and the weight of 1402 is expressed as d, c / d (metal mixing ratio) and antibacterial Relationship diagram of force. Fig. 13 is a graph showing the relationship between the film thickness of the surface layer and the contact angle when it is bright, according to the example tile (grilled type) of the sixth embodiment of the four-component system. FIG. 14 is a graph showing the relationship between the surface layer film thickness and the antibacterial power of the magnetic tablet (grilled type) of the sixth example of the four-component system. Fig. 15 is a graph showing the relationship between the film thickness of the surface layer and the oil-decomposing force of the example tile (grilled type) of the sixth example of the four-component system. FIG. 16 is a graph showing the relationship between the film thickness of the surface layer and the NO oxidation power of the example tile (barbecue type) of the sixth example of the four-component system. Fig. 17 is a graph showing the relationship between the film thickness of the surface layer and the contact angle when it is bright, according to the example tile (grilled type) of the seventh embodiment of the three-component system. This paper size applies to the Chinese National Standard (CNS) A4 Zhuge (210X297 mm) (Please read the precautions on the back before loading—this page) Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 34 495384 A7 ____B7__ 5. DESCRIPTION OF THE INVENTION (32) FIG. 18 is a diagram of a magnetic tablet (paint type) according to an example of the sixth embodiment of the four-component system. The relationship between its color difference ΔE and the contact angle when it is bright. Fig. 19 is a graph showing the relationship between the color difference AE and the antibacterial power of the example tile (paint type) of the sixth embodiment of the four-component system. Fig. 20 is a graph showing the relationship between the color difference AE and the oil-decomposing force of an example tile (paint type) of the sixth embodiment of the four-component system. FIG. 21 is a graph showing the relationship between the color difference ΔΕ and the NO oxidation power of the example tile (paint type) of the sixth example of the four-component system. Fig. 22 is a graph showing the relationship between the color difference ΔE and the contact angle when the light is bright, according to the example tile (paint type) of the seventh embodiment of the three-component system. Table of Symbols of Components in the Circle (Please read the precautions on the back first, then this page) — Binding and printing Printed by the Central Consumers' Bureau of the Ministry of Economic Affairs, Consumer Cooperatives 10 Glass troughs 12 Air purifiers 14 Air compressors 15 Humidity regulators 16 Flow regulating valves 18 NOx sensor 20 Bulb This paper size is applicable to Chinese National Standard (CNS) A4 Zhuge (210X297 mm) 35 Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 495384 A7 B7 V. Description of the invention (33) The best form First, the formulation of the photocatalyst complex will be explained with examples. Anatase-type titanium dioxide is used as the photocatalyst, and as the metal oxide cooperating with the photocatalyst, the oxidation inscription of amphoteric metal oxide, the oxidation recording and oxidation of metal oxide are used. Then, in the preparation of the photocatalyst complex, the following procedure is taken. ① Preparation of Photocatalyst and Metal Oxide Particles Prepare the raw materials of the above-mentioned titanium dioxide, oxide oxide, crane crane and oxide lock. Each of these materials is pulverized by a pulverizing device such as a ball mill, or titanium dioxide and oxide are prepared by sol / gel method. Fine particles of aluminum, strontium oxide and barium oxide. At this time, the particle size of various particles can be adjusted within a particle size range of 0.005 to 0.5 / zm. ② Preparation of sol Secondly, each of the compounding materials adjusted as described above is dispersed in a solvent such as water and alcohol to prepare a sol of each compounding material. At this time, first specify the dispersion amount of the dispersing material in each sol (such as the weight of the compound material / solvent capacity). ③ After adjusting the photocatalyst complex, mix the alumina sol and lithium oxide in the titanium dioxide (photocatalyst sol) that has been blended. Metal oxide sol and barium oxide sol to obtain a titanium dioxide / alumina mixed sol (Ti / Al sol), a titanium dioxide / strontium oxide mixed sol (Ti / Sr sol) and a titanium dioxide / barium oxide mixed sol (Ti / Ba Sol). At this time, when adjusting the above mixed sols, measure the mixed amount of the photocatalyst sol and the mixed amount of the metal oxide sol to change the paper size to apply the Chinese National Standard (CNS) A4 specification (210X297 mm) (Please read first Note on the back ^ k this page) li clothes · order -36-495384 printed by the Consumers' Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs A7 B7 V. Description of the invention (34) Various scales can be adjusted, and the combination of photocatalyst and metal oxide can be adjusted Than take a mixed sol of various values. That is, when the weight of the metal oxide in each mixed sol is expressed by a and the weight of the photocatalyst is expressed by b, a mixing ratio expressed by a / (a + b) (hereinafter, this a / (a + b) is referred to as a mixing ratio (Determining ratio) Investigate various mixing amounts. In addition to adopting the procedures of ① ~ ③ above, it is also possible to add and disperse alumina and other particles whose particle size has been adjusted to the prepared photocatalyst sol to prepare Ti / Al sol. In addition, by dispersing the photocatalyst particles and particles of alumina and the like having been adjusted in particle size in the above-mentioned solvent alternately or simultaneously, a Ti / Al sol in which photocatalyst particles and particles of alumina and the like are dispersed at the beginning can be prepared. Next, the photocatalyst complexes (mixed sols of Ti / Al sol, Ti / Sr sol, and Ti / Ba sol) adjusted as described above will be used to describe the photocatalyst function exhibiting materials that can play the role of photocatalyst. In this embodiment (first embodiment), the photocatalyst function display material is made into a tile as follows. An unglazed tile was prepared as a substrate, and each of the above-mentioned mixed sols was spray-coated on the surface of the substrate with a predetermined concentration. In the spray application, the application amount can be adjusted, that is, the spray time can be adjusted so that the film thickness of the photocatalyst mixture on the surface of the tile after grilling is about 0.85 # m. Next, in order to determine the photocatalyst, a temperature determined by considering the melting temperature of the silicon dioxide, etc., and the melting temperature of the titanium dioxide and each of the metal oxides (about 800 ° C in this embodiment) is used to mix the sol. After spraying and painting, the tiles are grilled in about 60 minutes to form a final photocatalyst functioning material (photocatalyst functioning as a magnetic tablet). This material has the surface of the substrate (tile) (please read the note on the back first) (Notes on this page)

訂 線 本紙張尺度適用中國國家標準（CNS ) A4規格（21〇'X297公釐） -37 - 495384 A7 B7 經濟部中央標準局員工消費合作社印製 五、發明説明（35) 上含有上述之溶膠中成分（光觸媒、氧化鋁等）之表面層。 在此，針對該評價說明之。該評價可作為判斷大氣中或室 内有害物質其中希望削減之氮氧化物、氨、二氧化硫之削 減效果的有無。該實驗概要為下列所述，首先，說明氮氧 化物之削減。又，代替混合溶膠之喷射塗抹，當然也可採 用旋轉塗抹、浸潰塗抹等方式。 (1-1)評價實驗1:氧化鋁對氮氧化物削減之影響 首先，為了取得與本發明之實施例品之對比，準備了 如下列樣品：不含氧化鋁、氧化勰及氧化鋇，而只配合有 _ 二氧化鈦之光觸媒配合物之光觸媒功能發揮磁碑（比較例 磁磚），以及實施例之光觸媒功能發揮磁磚（實施例磁磚） 。比較例磁磚係，占有7.5wt%比率的二氧化鈦之光觸媒 溶膠喷射塗抹於磁磚表面上，以上述燒成條件（約800°Cx60 分鐘）燒成之磁碑。在該喷射塗抹時決定塗抹時間等，使 在燒成後之磁磚表面中二氧化鈦的重量為約3.3x10-4g/cm2 (此時之二氧化鈦之膜厚為約0.85/z m)。而實施例磁磚為 以下之Ti/Al磁磚、Ti/Sr磁磚、Ti/Ba磁碑。 Ti/Al磁磚係一種，與比較例磁磚同樣地，將針對占 有二氧化鈦7.5wt%比率之光觸媒溶膠可調整氧化鋁之配 合比率，使配合比率決定比a/(a+b)為1/11之Ti/Al溶膠（針 對二氧化鈦之氧化鋁之重量比為0.1之Ti/Al溶膠），用以上 述比較例磁碑同一條件喷射塗抹並加以燒成之磁磚。Ti/Sr 磁磚則為一種，將二氧化鈦及氧化勰用以與Ti/Al磁磚之 相同配合比率所配合之Ti/Sr溶膠，以上述比較例磁碑同 (請先閱讀背面之注意事項再本頁) 裝· 、?τ -線 本紙張尺度適用中國國家標準（CNS ) Α4規格（210X 297公釐） 38 495384 A7 B7 i____ 經濟部中央標準局員工消費合作社印製 發明説明（36 ) 一條件喷射塗抹並加以燒成之磁磚。而Ti/Ba磁磚也是同 樣作法。即，比較例磁磚只具有磁磚表面之二氧化鈦，在 比較對照上，可發揮作為基準之觸媒功能，因此用以比較 該比較例磁碑及上述各實施例磁磚，可知經各自配合之金 屬氧化物所得到之觸媒功能之提高有無或其程度。在此， 比較例磁碑係一種具有在磁磚表面上只由二氧化鈦形成之 表面層者’而實施例磁磚為一種具有配合二氧化鈦及氧化 紹或氧化錄或者是氧化鋇之配合物所形成之表面層者。 針對該比較例磁碑及各實施例磁磚，進行如下實驗。 在重^用Jb豈命!磁磚及各實施例磁磚1 Ocm &方形 樣本片’以如第4圖所示之實驗裝置，測定氮氧化物之削 減效果。該測試裝置為，可載置樣本片之密閉狀玻璃槽1〇 之上游備有一可密封有一定濃度之一氧化氮氣體之氣瓶12 ’在經該氣瓶12之NO氣體上，以空氣壓縮機14吸引而以 濕度調整器15將已濕度調整之大氣在流量調整閥16加以混 合，從該流量調整閥16將一定濃度（約0.95ppm)且定量（1 升/min)之NO氣體（實驗氣體）流入玻璃槽1〇。又，在玻璃 槽之下游具有一用以測定通過該槽之氣體中氮氧化物濃度 之濃度測定器（NOx感應器）18。該NOx感應器18，係構成 可隨時測定氣體中之NO濃度及二氧化氮濃度（N02濃度）， 除所測定之NO濃度及N02濃度，加入該兩者濃度之和作 為氮氧化物濃度（NOx濃度）輸出。又，實驗裝置係具有一 在玻璃槽10内可照射紫外線（波長300〜400nm)之燈泡20。 此時，燈泡20用以點燈控制，使樣本片上之紫外線強度為 本紙張尺度適用中國國家標準（CNS ) A4規格（21 ο X 297公釐） (請先閱讀背面之注意事項再 —裝II 本頁) -訂 線 39 495384 A7 B7 經濟部中央標準局員工消費合作社印製 五、發明説明（37 ) 1.2mW7cm2。然後，該實驗裝置之玻璃槽1〇中載製置樣本 片’將之放置在受紫外線照射之環境下’針對比較例磁碑 及實施例磁磚，標繪出從開始實驗氣體之流入之每個經過 時間之N〇2濃度及NOx濃度。將其結果示於第5圖。再者 ，從開始流入實驗氣體，等出口處之NOx濃度（N〇濃度）安 定後，燈泡20才點燈。 在該評價實驗1中’若沒引起使一氧化氮氧化之反應 ，如將玻璃槽10放置於暗室，若沒有藉表面層中二氧化鈦 之活性氧物種之生成可使觸媒反應作用時，實驗氣體不會 引起什麼反應而直接流入NOx感應器18。藉此，此時之ΝΟχ 感應器18之輸出係，其NO濃度（CNO/out)與實驗氣體濃度 (CNO/out)相同，NO 濃度（CNO/out)為零、NOx濃度（CNO/out) 為CNO/out、即，與CNO/in相同。但是，藉基於表面層中 二氧化鈦之生成活性氧物種作用之觸媒反應使NO氧化， 而NO濃度係只從CNO/in減少受到氧化之部份。又，經由 NO氧化所生成之N02若從磁磚表面脫離，該脫離n〇2之部 分的N02濃度會增加。然後，藉NO氧化之NO濃度一減少 ，以及藉所生成之N02從磁磚表面脫離之n〇2濃度增加之 關係，決定NOx之削減程度。 如第5圖所示，比較例磁磚在實驗一開始，NOx濃度 就急遽地降低，從測試開始經過5分鐘之後，NOx濃度轉 為增加，漸漸接近於實驗氣體濃度。又，該比較例磁碑在 測試開始後，N02濃度逐漸地上升，經過30分鐘後變成約 0·18ρρπι。該NOx濃度增加之傾向與^[〇2濃度上升之傾向 (請先閲讀背面之注意事項再 —裝I, 本頁The paper size of the booklet is in accordance with the Chinese National Standard (CNS) A4 (21 0'X297 mm) -37-495384 A7 B7 Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 5. The description of the invention (35) contains the sol Surface layer of intermediate components (photocatalyst, alumina, etc.). Here, the evaluation will be described. This evaluation can be used to judge the presence or absence of the reduction effect of nitrogen oxides, ammonia, and sulfur dioxide in the harmful substances in the atmosphere or the room. The outline of this experiment is as follows. First, the reduction of nitrogen oxides will be described. Also, instead of spray coating with a mixed sol, of course, spin coating, dip coating, or the like may be used. (1-1) Evaluation experiment 1: Effect of alumina on nitrogen oxide reduction First, in order to obtain a comparison with the product of the example of the present invention, the following samples were prepared: without alumina, hafnium oxide, and barium oxide, and Only with the photocatalyst function of _ titanium dioxide photocatalyst complex to play the magnetic stele (comparative tile), and the photocatalyst function of the example to play the tile (example tile). In the comparative tile system, a photocatalyst sol of titanium dioxide having a ratio of 7.5% by weight was spray-coated on the surface of the tile and fired under the above firing conditions (about 800 ° Cx60 minutes). At the time of spray application, the application time and the like are determined so that the weight of titanium dioxide on the surface of the tile after firing is about 3.3x10-4 g / cm2 (the film thickness of titanium dioxide at this time is about 0.85 / z m). The example tiles are the following Ti / Al tiles, Ti / Sr tiles, and Ti / Ba steles. A Ti / Al ceramic tile is the same as the ceramic tile of the comparative example. The mixing ratio of alumina can be adjusted for a photocatalyst sol occupying a ratio of 7.5% by weight of titanium dioxide, so that the mixing ratio determining ratio a / (a + b) is 1 / A Ti / Al sol of 11 (a Ti / Al sol with a weight ratio of 0.1 to titanium dioxide) is a tile sprayed and fired under the same conditions as the magnetic monument of the above comparative example. The Ti / Sr ceramic tile is a kind of Ti / Sr sol that uses titanium dioxide and hafnium oxide in the same ratio as the Ti / Al ceramic tile. It is the same as the magnetic stele of the above comparative example. (This page) The size of the paper used for the installation, and ττ-line paper is applicable to the Chinese National Standard (CNS) Α4 specification (210X 297 mm) 38 495384 A7 B7 i____ Description of the invention printed by the Staff Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs (36) Spray painted and fired tiles. The same is true for Ti / Ba tiles. That is, the tile of the comparative example only has titanium dioxide on the surface of the tile, and in comparison and comparison, it can play a catalyst function as a reference. Therefore, it is used to compare the magnetic tablet of the comparative example and the tiles of the above-mentioned embodiments. Whether or not the catalyst function obtained by the metal oxide is improved or not. Here, the comparative example magnetic stele is a type having a surface layer formed of only titanium dioxide on the surface of the tile, and the example magnetic tile is formed by a complex having a combination of titanium dioxide and oxide or oxide or barium oxide. Surface layer. The following experiments were performed on this comparative example magnetic tablet and each example tile. When Jb is used again! Tiles and tiles of each embodiment 1 Ocm & square sample piece 'using an experimental device as shown in Figure 4 to determine the reduction effect of nitrogen oxides. The test device is that a gas cylinder 12 ′ that can seal a nitrogen oxide gas of a certain concentration is provided upstream of a closed glass tank 10 on which sample pieces can be placed, and the NO gas passing through the gas cylinder 12 is compressed by air. The machine 14 is attracted and the humidity-adjusted atmosphere is mixed by a humidity regulator 15 in a flow adjustment valve 16, and from the flow adjustment valve 16, a certain concentration (about 0.95 ppm) and a fixed amount (1 liter / min) of NO gas (experiment Gas) flows into the glass tank 10. Further, downstream of the glass tank, a concentration measuring device (NOx sensor) 18 for measuring the concentration of nitrogen oxides in the gas passing through the tank is provided. The NOx sensor 18 is configured to measure the NO concentration and nitrogen dioxide concentration (N02 concentration) in the gas at any time. In addition to the measured NO concentration and N02 concentration, the sum of the two concentrations is added as the NOx concentration (NOx Density) output. The experimental device includes a bulb 20 which can irradiate ultraviolet rays (wavelength: 300 to 400 nm) in the glass tank 10. At this time, the light bulb 20 is used for lighting control, so that the UV intensity on the sample sheet is based on the Chinese paper standard (CNS) A4 (21 ο X 297 mm) (please read the precautions on the back first—install II (This page)-Order line 39 495384 A7 B7 Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 5. Description of the invention (37) 1.2mW7cm2. Then, a sample piece was placed in the glass tank 10 of the experimental device 'placed in an environment irradiated with ultraviolet rays'. For the comparative example monument and the example tile, each of the inflows from the start of the experimental gas inflow was plotted. NO2 concentration and NOx concentration over time. The results are shown in FIG. 5. Furthermore, from the beginning of the inflow of the experimental gas, after the NOx concentration (NO concentration) at the outlet is stabilized, the bulb 20 is turned on. In this evaluation experiment 1, if the reaction that oxidizes nitric oxide is not caused, for example, if the glass tank 10 is placed in a dark room, if the catalytic reaction is not effected by the generation of reactive oxygen species of titanium dioxide in the surface layer, the test gas It causes no reaction and flows directly into the NOx sensor 18. As a result, the output of the NOx sensor 18 at this time has the same NO concentration (CNO / out) as the test gas concentration (CNO / out), the NO concentration (CNO / out) is zero, and the NOx concentration (CNO / out) It is CNO / out, that is, the same as CNO / in. However, NO is oxidized by a catalyst reaction based on the role of titanium dioxide in the surface layer to generate reactive oxygen species, and the concentration of NO is only reduced from CNO / in to the oxidized portion. In addition, if the N02 generated by NO oxidation is detached from the surface of the tile, the concentration of N02 in the detached portion of N02 will increase. Then, the degree of NOx reduction is determined by the relationship between the decrease in NO concentration of NO oxidation and the increase in the concentration of no2 that is generated when the generated N02 is separated from the tile surface. As shown in Fig. 5, the NOx concentration of the comparative example tile decreased sharply at the beginning of the experiment. After 5 minutes from the start of the test, the NOx concentration increased and gradually approached the test gas concentration. In the comparative example, the N02 concentration gradually increased after the start of the test, and it became about 0 · 18ρρπ after 30 minutes. The tendency of NOx concentration to increase and the tendency of ^ [〇2 concentration to increase (Please read the precautions on the back before-install I, this page

、1T 線 本紙張尺度適用中國國家標準（CNS ) Α4祝格（210X297公釐） 40 495384 Α7 Β7 經濟部中央標準局員工消費合作社印製 五、發明説明L ) 大約相同。從該等狀況可見，在該比較例磁磚時，藉該表 面層之二氧化鈦進行光觸媒反應，使NO氧化，使NO濃度 減少，但伴隨N02濃度之上升，全體而言則形成NOx之削 減不會增進。是故，在該比較例磁磚中’因為N〇2從磁磚 表面脫離，所以N02在磁磚表面上不會再進行氧化。經過 30分鐘後之NOx濃度約〇.66ppm，因此在該比較例磁磚中 之 NOx 之削減效率為 30·5%((0·95-0·66)/0·95)。 相對於此，Ti/Al磁磚、Ti/Sr磁磚、Ti/Ba磁磚之各實 施例磁磚也與比較例磁磚同樣地，NOx濃度也在實驗一開 ___始之同時急速下降，而以比降低後之最低濃度稍微增加之 濃度漸進。又，各個實施例磁磚在從實驗開始之N〇2濃度 其上升程度很低，即使經過30分鐘後也只達到〇.〇5ppm。 從該等狀況來看，在各個實施例磁磚，首先開頭可知，藉 該表面層之二氧化鈦進行光觸媒反應，使NO氧化，因此 NO濃度正在減少。又，N02結合於氧化鋁、氧化錄、氧 化鋇，故難以從磁磚表面脫離，藉該二氧化鈦進而使N02 進而活躍地進行氧化，而使N02濃度不會上升。因此，依 每個實施例磁碑可以極高效率削減NOx。然後，經過30分 鐘後之NOx濃度約〇.45ppm。各實施例磁磚中之NOx之削 減效率約52·6%((0·95-0·45)/0·95)，幾乎是比較例磁碑的2 倍。針對該等實施例磁磚繼續上述實驗時，可知道NOx之 削減效率可維持在高值。又’經過12小時後，結束實驗’ 將實施例磁磚表面用水洗淨，分析含於該洗淨水之物質時 ，可確認硝酸之存在。 n_i 1— * (請先閱讀背面之注意事項再本頁)、 1T line This paper size is applicable to Chinese National Standard (CNS) Α4 Zhuge (210X297mm) 40 495384 Α7 Β7 Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 5. The invention description is about the same. From these conditions, it can be seen that in the comparative example tile, the photocatalytic reaction of the surface layer of titanium dioxide was used to oxidize NO to reduce the concentration of NO. enhance. Therefore, in the tile of this comparative example, 'N02 does not oxidize on the tile surface because No2 is detached from the tile surface. After 30 minutes, the NOx concentration was about 0.66 ppm. Therefore, the NOx reduction efficiency in the tile of this comparative example was 30.5% ((0.95-0.66) /0.95). In contrast, the tiles of the examples of Ti / Al tiles, Ti / Sr tiles, and Ti / Ba tiles are also the same as the tiles of the comparative example. The NOx concentration is also rapid at the beginning of the experiment. It decreases, and it gradually progresses at a concentration slightly increased from the lowest concentration after the decrease. In addition, the increase in the NO2 concentration of the tiles of each example from the beginning of the experiment was very low, and even after 30 minutes, it only reached 0.05 ppm. In view of these situations, in the tiles of the various embodiments, it can be seen at the outset that the titanium dioxide in the surface layer is used for photocatalytic reaction to oxidize NO, so the NO concentration is decreasing. In addition, because N02 is bound to alumina, oxidized oxide, and barium oxide, it is difficult to detach from the surface of the tile, and this titanium dioxide further oxidizes N02, so that the concentration of N02 does not increase. Therefore, the magnetic stele according to each embodiment can reduce NOx extremely efficiently. Then, the NOx concentration was about 0.45 ppm after 30 minutes. The reduction efficiency of NOx in the tiles of each example was about 52.6% ((0.95-0.45) /0.95), which was almost twice that of the comparative example. When the above-mentioned experiments are continued for the tiles of these examples, it is known that the NOx reduction efficiency can be maintained at a high value. "After 12 hours, the experiment was completed." The surface of the example tile was washed with water, and when the substance contained in the washing water was analyzed, the presence of nitric acid was confirmed. n_i 1— * (Please read the precautions on the back before this page)

、1T 本紙張尺度適用中國國家標準（CNS ) A4祝格（210X297公釐） 41 495384 Α7 Β7 經濟部中央標準局員工消費合作社印製 五、發明説明k ) 又，與各實施例磁磚該表面狀態觀察不到凹凸程度等 異常，非常良好。而且，以JIS-A6808之原則嘗試使用橡 皮擦之滑動磨損實驗時，各個實施例磁磚完成40次左右之 往還滑動，也看不到表面層上之惡化或剝落’對抗磨損性 也佳。此事意味著，以上述溶膠之混合之方式製造之光觸 媒配合物適用於燒成塗料或釉藥，當然也包括燒成、印刷 、黏著劑等。又，如上述，可經由上述之溶膠混合之方式 輕易製造一可藉光觸媒功能得到高度氮氧化物之削減效率 之光觸媒配合物或光觸媒功能發揮材料。 _ (1-2)評價實驗2:氧化鋁等對氨削減之影響 針對氨，也以上述氮氧化物同樣之裝置以及進行方式 檢討比較例磁磚Ti/Al磁磚以及Ti/Sr磁碑之削減之情況。 此時，流入玻璃槽10之實驗氣體為大約4PPm之氨氣體。 通過該槽之氣體中之氨濃度以該槽下游之濃度測定器（氣 體檢測管）測定。然後，對比較例磁磚與實施例磁碑（Ti/A1 磁磚、Ti/Sr磁碑）標繪開始流入實驗氣體之每個經過時間 之氨濃度。其結果表示於第6圖。 如第6圖所示，比較例磁碑、實施例磁碑一開始實驗 之同時，氨濃度會降低。然後在測定期間中，實施例磁碑 形成較低之濃度，實驗開始經過約10分鐘，每種磁磚成一 定之濃度，比較例磁磚為3.5PPm左右’ Ti/Ai磁碑約2.5PPm ，而Ti/Sr磁磚約2.6ppm。是故，氨之削減效率在比較例 磁磚為約 12·5%((4-3·5)/4)、Ti/Al磁磚約 37·5%((4-2·5)/4) 、Ti/Sr磁磚約35%((4-2·6)/4)。從此狀況得知，在比較例 (請先閲讀背面之注意事項再本頁) |裝· 訂 線' 本紙張尺度適用中國國家標準（CNS ) Α4規格（210Χ297公釐） 42 495384 A7 __B7_ 五、發明説明（,Λ ) 40 磁磚該表面層中之二氧化敛進行光觸媒反應，氨可化學轉 化成NO、Ν02等，使氨會肖，J減到某種程度，但在Ti/Al磁 磚、Ti/Sr磁碑任一種實施例磁磚，皆可比比較例發揮氨 之削減效率。此理由可從以下所述中推測之。 若不引起使氨轉化成其他之物質之反應（化學反應）時 ，實驗氣體則不會有任何反應，而流入氣體感應器，所測 定之氨濃度與實驗氣體相同。但是.，受到基於表面層中之 二氧化鈦之所生成之活性氧物種之觸媒反應，令氨轉化成 另一物質時，只有轉化之部份使氨濃度從實驗氣體之濃度 減去。因此，比較例磁磚、實施例磁磚都從實驗一開始， 氨濃度就會降低。此時，氨接受基於活性氧物種之觸媒反 應，構成氨之氮受氧化，使NO、N02作為中間生成物生 成。然後，該NO如上述藉活性氧物種氧化變成N02,該N02 藉活性氧物種進而氧化，化學轉化成硝酸，使氨受到基於 活性氧物種之觸媒反應可提高化學轉化成NO、N02之程 度，可提高氨之削減效率。 經濟部中央標準局員工消費合作社印製 實施例磁碑係如已述，已配合有可與N02結合使N02 無法從磁磚表面脫離之氧化铭、氧化銀’此點與比較例磁 磚不同。因此在比較例磁磚，則是由氨生成之no2從磁磚 表面脫離，使no2可藉活性氧物種進而氧化化學變化成硝 酸之反應無法進行。相對於此，在實施例磁磚上，從氨生 成之N02從表面不能脫離，而促進令該N〇2藉活性氧物種 進而氧化成硝酸之反應。因此，實施例磁磚如上述，可使 氨之削減效率提高，令氨之削減效率產生優劣。 本紙張尺度適用中國國家標準（CNS ) A4規格（210X 297公釐） 43 495384 A7 B7 五、發明説明（41 ) (1-3)評價實驗1:氧化鋁等對二氧化硫削減之影響 針對二氧化硫，也與上述氮氧化物同樣裝置以及作業 方式檢討比較例磁磚、Ti/Al磁磚之削減情形。此時，流 入玻璃槽10之實驗氣體為約lOppm之二氧化硫氣體，將通 過該槽之氣體中之二氧化硫濃度以槽下游之濃度檢測器（ 氣體檢測管）測定。再針對比較例磁磚與實施例磁磚（Ti/Al 磁磚），標緣一開始流入實驗氣體之經過時間之二氧化硫 濃度。其結果顯示於第7圖。 如第7圖所示，比較例磁磚與實施例磁磚皆於實驗一 開始，二氧化硫濃度都會降低。然後，隨著測定時間之流 逝，實施例磁磚成為比較低的濃度，從實驗開始經30分鐘 ，在比較例磁磚約7.7ppm，Ti/Al磁磚約2.7ppm。藉此， 二氧化硫之削減效率，比較例磁磚係約23%((10-7.7)/10) ，而Ti/Al磁磚為73%((10-2.7)/10)左右。從此，比較例磁 碑該表面層中之二氧化鈦進行光觸媒反應，而令二氧化硫 化學轉化成硫酸或亞硫酸，使二氧化硫會削減某種程度， 而Ti/Al磁磚（實施例磁磚）可比比較例磁磚發揮優異的氨之 削減效率。該理由可由下列所述推測之。 經濟部中央標準局員工消費合作社印製 比較例磁磚、實施例磁磚皆可使二氧化硫濃度降低係 因，與一氧化氮、氨同樣，接受基於表面層中二氧化鈦之 生成的活性氧物種之觸媒反應，令二氧化硫轉化成硫酸或 亞硫酸，使氨濃度從實驗氣體中之濃度減去該轉化之部份 。在該評價實驗中被反應物之二氧化硫係因屬於酸性氣體 ，如以第2圖所說明，與屬於鹼性金屬氧化物之氧化鋁化 本紙張尺度適用中國國家標準（CNS ) A4祝格（210X297公釐） 44 495384 經濟部中央標準局員工消費合作社印製 A7 B7五、發明説明（42 ) 學結合並加以吸著。因此不含該氧化鋁之比較例磁磚則因 二氧化硫不能吸著在磁磚表面上，而在狀態下無法藉活性 氧物種氧化，而化學轉化成硫酸或亞硫酸，故該反應只能 緩慢地進行。對此，在實施例磁碑係以將二氧化硫吸著於 磁磚表面上之狀態，經由活性氧物種氧化成硫酸或亞硫酸 ，故可促進該反應。因此，實施例磁碑係如上述，可使二 氧化硫之削減效率提高，而產生二氧化硫之削減效率之優 劣比較。 其次，與光觸媒共同配合之氧化鋁等之配合程度與氮 ——氧也翁名惠秦秦果t勝係之評俱，採取不殚 。又。該評價以氧化鋁為例進行。 (2)評價實驗2:氧化鋁配合程度對氮氧化物削減之影 響-其一 首先，為了取得本發明之實施例品之對比，係以上述 評價實驗1同樣之比較例磁磚及實施例之光觸媒功能發揮 磁磚（實施例磁磚）準備如下。比較例磁磚係以占有二氧化 鈦7.5wt%之光觸媒溶膠喷射塗抹於磁磚表面，以上述燒 成條件燒成之磁碑。在喷射塗抹時決定塗抹時間，使燒成 後之磁磚表面中二氧化鈦之重量為約3.3x1 (T4g/cm2(二氧 化鈦之膜厚約0.85 # m)。而實施例磁碑為下列之Ti/Al磁 碑。 Ti/Al磁磚，係對二氧化鈦比率與比較例磁碑同樣地 占有7.5wt%之光觸媒溶膠，將調整氧化鋁之配合比率使 配合比率決定比a/(a+b)為0.0001〜0.8之範圍之Ti/Al溶膠， (請先閱讀背面之注意事項舄本頁) -裝·、 1T This paper size applies Chinese National Standard (CNS) A4 Zhuge (210X297 mm) 41 495384 Α7 Β7 Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 5. Description of the invention k) Also, the surface of the tile with the examples No abnormality such as the degree of unevenness was observed in the state, which was very good. Furthermore, when the sliding abrasion test using a rubber wipe was attempted based on the principle of JIS-A6808, the tiles of each example slipped about 40 times, and no deterioration or peeling on the surface layer was observed. The anti-wear properties were also good. This matter means that the photocatalyst complex produced by mixing the above sols is suitable for firing coatings or glazes, and of course also includes firing, printing, adhesives, and the like. In addition, as described above, a photocatalyst complex or a photocatalyst function display material that can achieve high nitrogen oxide reduction efficiency by the photocatalyst function can be easily manufactured through the above-mentioned sol mixing method. _ (1-2) Evaluation experiment 2: Effect of alumina and other factors on ammonia reduction For ammonia, the same device and method as described above for nitrogen oxides were used to review the comparative examples of Ti / Al tiles and Ti / Sr magnetic monuments. Reductions. At this time, the experimental gas flowing into the glass tank 10 was an ammonia gas of about 4 PPm. The ammonia concentration in the gas passing through the tank is measured by a concentration measuring device (gas detection tube) downstream of the tank. Then, the comparative example tile and the example stele (Ti / A1 tile, Ti / Sr stele) were plotted for the ammonia concentration at each elapsed time when the test gas began to flow. The results are shown in FIG. 6. As shown in Fig. 6, at the same time as the magnetic stele of the comparative example and the magnetic stele of the example, the concentration of ammonia decreases. Then during the measurement period, the example magnetic tablet formed a lower concentration. After the experiment started about 10 minutes, each type of tile became a certain concentration. The comparative example tile was about 3.5PPm, and the Ti / Ai magnetic tablet was about 2.5PPm. The Ti / Sr tile is about 2.6 ppm. Therefore, the reduction efficiency of ammonia in the comparative example tile is about 12.5% ((4-3 · 5) / 4) and the Ti / Al tile is about 37 · 5% ((4-2 · 5) / 4 ), About 35% of Ti / Sr tiles ((4-2 · 6) / 4). From this situation, it is known that in the comparative example (please read the precautions on the back and then this page) | binding and binding line 'This paper size is applicable to the Chinese National Standard (CNS) A4 specification (210 × 297 mm) 42 495384 A7 __B7_ V. Invention It shows that (, Λ) 40 the surface of the ceramic tile is oxidized to perform photocatalytic reaction. Ammonia can be chemically converted into NO, N02, etc., so that ammonia can be reduced to a certain degree, but in Ti / Al tiles, Any of the Ti / Sr magnetic stele tiles of the embodiment can exhibit ammonia reduction efficiency compared to the comparative example. This reason can be inferred from the following. If it does not cause a reaction (chemical reaction) that converts ammonia into other substances, the test gas will not have any reaction, but flows into the gas sensor, and the measured ammonia concentration is the same as the test gas. However, due to the catalyst reaction based on the active oxygen species generated by the titanium dioxide in the surface layer, when ammonia is converted into another substance, only the converted part reduces the ammonia concentration from the concentration of the test gas. Therefore, both the comparative example tile and the example tile decreased the ammonia concentration from the beginning of the experiment. At this time, ammonia receives a catalyst reaction based on reactive oxygen species, and the nitrogen constituting ammonia is oxidized, so that NO and N02 are produced as intermediate products. Then, the NO is oxidized to N02 by the reactive oxygen species as described above, and the N02 is further oxidized by the reactive oxygen species to chemically convert to nitric acid. Subjecting ammonia to a catalyst reaction based on the reactive oxygen species can increase the degree of chemical conversion to NO and N02 Can improve ammonia reduction efficiency. Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs. As described in the example, the magnetic stele system has been combined with an oxide oxide and silver oxide that can be combined with N02 to prevent N02 from detaching from the tile surface. Therefore, in the comparative example tile, the no2 produced by ammonia is detached from the tile surface, so that the reaction of no2 by active oxygen species and then oxidatively chemically changed to nitric acid cannot proceed. In contrast, on the tile of the embodiment, the N02 generated from ammonia cannot be detached from the surface, and the reaction of oxidizing the NO2 to the nitric acid by the active oxygen species is promoted. Therefore, as described above, the tile of the embodiment can improve the efficiency of reducing ammonia and make the efficiency of reducing ammonia good or bad. This paper size applies the Chinese National Standard (CNS) A4 specification (210X 297 mm) 43 495384 A7 B7 V. Description of the invention (41) (1-3) Evaluation experiment 1: the impact of alumina and other factors on the reduction of sulfur dioxide The same device and operation method as the above-mentioned nitrogen oxides were used to review the reduction of the comparative example tiles and Ti / Al tiles. At this time, the experimental gas flowing into the glass tank 10 was about 10 ppm of sulfur dioxide gas, and the concentration of sulfur dioxide in the gas passing through the tank was measured with a concentration detector (gas detection tube) downstream of the tank. For the comparative example tile and the example tile (Ti / Al tile), the concentration of sulfur dioxide in the elapsed time of the beginning of the flow of the test gas into the standard edge. The results are shown in Fig. 7. As shown in Fig. 7, both the comparative example tile and the example tile have a reduced sulfur dioxide concentration at the beginning of the experiment. Then, as the measurement time elapsed, the tile of the example became a relatively low concentration. After 30 minutes from the start of the experiment, the tile of the comparative example was about 7.7 ppm, and the Ti / Al tile was about 2.7 ppm. As a result, the reduction efficiency of sulfur dioxide is about 23% ((10-7.7) / 10) for the tile system of the comparative example, and about 73% ((10-2.7) / 10) for the Ti / Al tile. From then on, in the comparative example, the titanium dioxide in the surface layer of the comparative example undergoes a photocatalytic reaction, so that the sulfur dioxide is chemically converted into sulfuric acid or sulfurous acid, so that the sulfur dioxide will be reduced to a certain extent. The tile exhibits excellent ammonia reduction efficiency. This reason can be speculated as described below. The comparative example tile and the example tile printed by the Employees' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs can reduce the concentration of sulfur dioxide. Like nitric oxide and ammonia, it accepts the touch of reactive oxygen species based on titanium dioxide in the surface layer. Medium reaction, so that sulfur dioxide is converted into sulfuric acid or sulfurous acid, so that the ammonia concentration is subtracted from the concentration in the test gas. In this evaluation experiment, because the sulfur dioxide of the reactant is an acidic gas, as illustrated in Figure 2, the paper is aluminated with alkaline metal oxides. The paper size applies the Chinese National Standard (CNS) A4 Zhuge (210X297 (Mm) 44 495384 A7 B7 printed by the Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs 5. Description of the invention (42) Combined with learning. Therefore, the comparative example tiles that do not contain this alumina can not be adsorbed on the tile surface by sulfur dioxide, and cannot be oxidized by active oxygen species in the state, and are chemically converted into sulfuric acid or sulfurous acid, so the reaction can only be slow get on. In this regard, in the example, the magnetic monument is oxidized into sulfuric acid or sulfurous acid through active oxygen species in a state where sulfur dioxide is adsorbed on the surface of the tile, so the reaction can be promoted. Therefore, the magnetic stele of the embodiment as described above can improve the reduction efficiency of sulfur dioxide and compare the advantages and disadvantages of the reduction efficiency of sulfur dioxide. Secondly, the degree of coordination of alumina and the like that cooperate with the photocatalyst is in line with the evaluation of the nitrogen-oxygen Weng Minghui Qin Qinguo t wins. also. This evaluation was performed using alumina as an example. (2) Evaluation experiment 2: The effect of the degree of alumina blending on the reduction of nitrogen oxides-First, in order to obtain the comparison of the products of the present invention, the same comparative example tiles and examples as in the above evaluation experiment 1 were used. The photocatalyst function display tile (example tile) was prepared as follows. The ceramic tile of the comparative example is a magnetic tablet in which a photocatalyst sol occupying 7.5% by weight of titanium dioxide is spray-coated on the surface of the ceramic tile and fired under the above-mentioned firing conditions. The spraying time is determined during spray coating, so that the weight of titanium dioxide in the surface of the fired tile is about 3.3x1 (T4g / cm2 (the film thickness of titanium dioxide is about 0.85 # m). The example magnetic monument is the following Ti / Al Magnetic monument. The Ti / Al tile has a photocatalyst sol with a titanium dioxide ratio of 7.5% by weight, similar to the magnetic monument of the comparative example. The mixing ratio of alumina will be adjusted so that the determination ratio a / (a + b) is 0.0001 ~ Ti / Al sol in the range of 0.8, (Please read the precautions on the back 舄 this page)

、1T 線 本紙張尺度適用中國國家標準（CNS ) Α4規格（210X 297公釐） 45 495384 A7 B7 五、發明説明（43 ) 以上述比較例磁磚相同條件喷射塗抹以及燒成之磁磚。即 燒成各種，燒成後之磁磚表面之二氧化鈦之重量與比較例 磁磚相同約3.3xl0_4g/cm2，而燒成後之磁碑表面之氧化鋁 之重量不同之Ti/Al磁磚，將每個Ti/Al磁磚當作該評價實 驗2中之實施例磁磚。配合比率決定比a/(a+b)為0.01時， 因a=b/99，故在燒成後之磁磚表面中氧化鋁之重量為 3.3xl0_6g/cm2。而配合比率決定比a/(a+b)為0.5時，因a=b ，則形成約3.3xl(T4g/cm2。在這評價實驗2中，比較例磁 磚也能發揮作為基準之觸媒功能，用以比較該比較例磁磚 與>1-銀|化在呂配合量不同之各個Ti/Al磁磚，可知I化鋁 配合量對提高配合了定量光觸媒時之觸媒功能之影響。 經濟部中央標準局員工消費合作社印製 在該評價實驗2中，用以與評價實驗1相同之實驗裝置 ，針對比較例磁磚及各實施例磁磚，測定以一定濃度（約 0.95ppm)之定量實驗氣體之流入以及燈泡20之點燈時從實 驗開始後經過30分鐘之N02濃度及NOx濃度。然後，針對 各磁磚標繪出從實驗氣體之NO濃度減掉所測定之NOx濃 度之NOx除去量，以及所測定之N02濃度。將結果示於第 8圖。又，比較例磁碑因沒有配合氧化鋁，故其配合比率 決定比a/(a+b)為零。 在第8圖中，比較例磁磚（a/(a+b)=0)標繪在線圖之Y軸 上，其N02濃度約0.17ppm，NOx除去量約0.3ppm。如此 在不含N02且NOx濃度比實驗氣體濃度還低之實驗氣體中 卻可計測到N02之濃度，如已述，係因表面層中之二氧化 鈦之光觸媒反應進行與磁磚表面之N02之脫離的緣故。 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） 46 495384 A7 B7 經濟部中央標準局員工消費合作社印製 五、發明説明（44) 對此’其配合比率決定比a/(a+b)以線圖之X轴座標表 示之Ti/Al磁磚則是，若氧化鋁配合量極少使配合比率決 定比a/(a+b)為0.01者時，N02濃度約〇.15ppm、NOx除去量 為約0.4ppm。又，氧化鋁配合量與二氧化鈦相同之配合 比率決定比a/(a+b)為0.5之Ti/Al磁磚時’則N02濃度約 0· 14ppm、NOx除去量約〇.43ppm。然後’配合比率決定比 a/(a+b)為0.05〜0.2之範圍内之Ti/Al磁碑，則N02濃度約 0.06〜0.13ppm，而NOx除去量為約〇·44〜〇.46ppm，與比較 例相比，其N02濃度非常低，且NOX除去量很多。又，配 合bt牟決定比a/(a+b)為0.0001之Ti/Al磁磚，雖也得到與配 合比率決定比a/(a+b)為〇·〇1者相似之結果（N02濃度=約 0.155ppm、NOx除去量=約〇.36ppm)，但因標繪該Ti/Al磁 磚之X軸座標接近零，故省略其圖示。 從該等結果得知，配合比率決定比a/(a+b)若在0.0001 〜0.5之範圍内，藉以配合氧化鋁，可謀求抑制n〇2之脫離 ，延長遠比比較例磁磚還高之N〇2之削減效果，故可得到 NOx削減效果。尤其，若配合比率決定比a/(a+b)在〇.〇5〜0.2 之範圍内時，可得到遠比比較例磁磚還高之N0x之削減效 果，故佳。然後，也如配合比率決定比a/(a+b)為〇001所 述，即使配合少量氧化鋁也可得到極佳的Ν〇χ削減效果。 又，作成各種配合比率決定比a/(a+b)之值之Ti/Al磁 磚’該等表面狀態良好，且具有優異之抗磨損性。 (3)評價實驗3:氧化鋁配合程度對氮氧化物削減之影 響-其二 (請先閱讀背面之注意事項v •裝-- >寫本瓦) 訂 -線 本紙張尺度適用中國國家標準（CNS ) A4規格（21〇><297公釐） 47 經濟部中央標準局員工消費合作社印製 495384 A7 B7 五、發明説明（45 ) 在該評價實驗3中，將光觸媒之二氧化鈦與氧化鋁之 總量（2者之配合和）為一定，其中將二氧化鈦與氧化鋁作 成各種配合量，檢討氮氧化物之削減效果。 首先，為了取得與本發明之實施例之對比，準備如下 列與上述評價實驗1同樣之比較例磁磚與實施例之光觸媒 功能發揮磁磚（實施例磁磚）。比較例磁碑為上述評價實驗 2同樣之磁磚，燒成後之磁磚表面中之二氧化鈦之重量為 約3.3xl(T4g/cm2，實施例磁磚為下列之Ti/Al磁磚。 該Ti/Al磁磚係一種，相對於其二氧化鈦與氧化鋁之 總I與比農ϋ敬磚同樣地占有7.5wt%比例之光觸媒溶膠 ，配合比率決定比a/(a+b)為0.05〜0.95之範圍内調整氧化 鋁之配合比例Ti/Al溶膠，與上述比較例磁碑同一條件喷 射塗抹並加以燒成之磁磚。即，燒成各種燒成後之磁磚表 面中二氧化鈦之重量係隨著氧化紹之重量增加而從3·3χ l〇-4g/cm2減少之Ti/Al磁磚，將該等Ti/Al磁磚作為這評價 實驗3中之實施例磁磚。配合比率決定比a/(a+b)為0.05時 ，因a+b相當於上述的3.3xl〇-4g/cm2，因此燒成後之磁磚 表面中氧化銘之重量a為約1.65xl0_5g/cm2，而二氧化鈦之 重量b為約3.135xl(T4g/cm2。又，配合比率決定比a/(a+b) 為0.95時，相對地氧化紹之重量a為約3.135xl(T4g/cm2，而 二氧化鈦之重量b為約1.65xl(T5g/cm2。在這評價實驗3中 ，比較例磁磚也可發揮基本觸媒功能，因此用以比較該比 較例磁磚與各種不同之二氧化鈦、氧化鋁之配合量的Ti/Al 磁磚，可知二氧化鈦與氧化鋁之配合量對觸媒功能之改良 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） (請先閱讀背面之注意事項再Uk本頁)、 1T line This paper size applies the Chinese National Standard (CNS) A4 specification (210X 297mm) 45 495384 A7 B7 V. Description of the invention (43) The tiles of the comparative example tiles are spray-painted and fired under the same conditions. That is, firing various Ti / Al tiles with the same weight of titanium dioxide on the surface of the tile after firing as that of the comparative example tile, and the weight of alumina on the surface of the magnetic monument after firing is different. Each Ti / Al tile was used as an example tile in the evaluation experiment 2. When the blending ratio determining ratio a / (a + b) is 0.01, since a = b / 99, the weight of alumina in the surface of the tile after firing is 3.3xl0_6g / cm2. On the other hand, when the ratio a / (a + b) is 0.5, since a = b, about 3.3xl (T4g / cm2) is formed. In this evaluation experiment 2, the comparative example tile can also serve as a benchmark catalyst. Function to compare the tile of this comparative example with each of the Ti-Al tiles with > 1-silver | Printed in the evaluation experiment 2 by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs, the same experimental device as the evaluation experiment 1 is used to measure the comparative example tiles and each example tile at a certain concentration (about 0.95 ppm). Quantitative test gas inflow and N02 concentration and NOx concentration after 30 minutes from the start of the experiment when the light bulb 20 was turned on. Then, for each tile, plot the measured NOx concentration from the NO concentration of the test gas minus the measured NOx concentration. The amount of NOx removed and the measured concentration of N02. The results are shown in Fig. 8. In addition, the comparative example magnetic tablet does not contain alumina, so its blending ratio determination ratio a / (a + b) is zero. In the figure, the comparative example tile (a / (a + b) = 0) is plotted on the Y axis of the line graph, and its N02 concentration The degree of NOx is about 0.17ppm, and the amount of NOx removed is about 0.3ppm. In this way, the concentration of N02 can be measured in the test gas that contains no N02 and the NOx concentration is lower than the test gas concentration. As already mentioned, it is because of the titanium dioxide in the surface layer. The photocatalyst reacts with the detachment of N02 from the surface of the tile. This paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm) 46 495384 A7 B7 Printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs 44) Regarding this, its ratio of determining the ratio a / (a + b) of the Ti / Al tile represented by the X-axis coordinate of the line graph is that if the amount of alumina is very small, the ratio of determining the ratio a / (a + b) When it is 0.01, the concentration of N02 is about 0.15 ppm, and the amount of NOx removal is about 0.4 ppm. In addition, the ratio of alumina and titanium dioxide is the same. The ratio of a / (a + b) is 0.5 Ti / Al magnetic When bricks are used, then the N02 concentration is about 0.14 ppm and the NOx removal amount is about 0.43 ppm. Then, the Ti / Al magnetic monument with the ratio of a / (a + b) in the range of 0.05 to 0.2 is determined by the mixing ratio, and the N02 concentration is about 0.06 to 0.13 ppm, and the amount of NOx removal is about 0.44 to 0.46 ppm, compared with the comparative example, the N02 concentration is not Low, and a large amount of NOX removal. In addition, the Ti / Al ceramic tile with a ratio of 0.0001 determined by bt and a / (a + b) is also obtained, although the ratio determined by the ratio a / (a + b) is 〇 · 〇 The results of 1 are similar (N02 concentration = about 0.155 ppm, NOx removal amount = about 0.36 ppm), but the X-axis coordinate of the Ti / Al tile is plotted near zero, so its illustration is omitted. From these results, it is known that if the ratio of the determination ratio a / (a + b) is in the range of 0.0001 to 0.5, the alumina can be used to suppress the separation of n02 and the extension is far higher than that of the comparative example tile. Since the reduction effect of No 2 is obtained, the NOx reduction effect can be obtained. In particular, if the blending ratio determination ratio a / (a + b) is in the range of 0.05 to 0.2, a reduction effect of N0x, which is much higher than that of the comparative example tile, can be obtained. Then, as described in the blending ratio determining ratio a / (a + b) of 0.001, even when a small amount of alumina is blended, an excellent NOx reduction effect can be obtained. In addition, Ti / Al tiles with various blending ratios that determine the value of a / (a + b) have good surface conditions and excellent abrasion resistance. (3) Evaluation experiment 3: The influence of the degree of alumina mixing on the reduction of nitrogen oxides-the second (please read the precautions on the back v • equipment-> writing tiles) order-line paper size applies Chinese national standards ( CNS) A4 specification (21〇 > < 297 mm) 47 Printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs 495384 A7 B7 V. Description of the invention (45) In this evaluation experiment 3, the photocatalyst titanium dioxide and alumina The total amount (the sum of the two) is constant. Among them, titanium dioxide and alumina are used to make various blending amounts, and the reduction effect of nitrogen oxides is reviewed. First, in order to obtain a comparison with the embodiment of the present invention, the following comparative example tiles and the photocatalytic function exerting tiles of the example (example tiles) are prepared as in the above-mentioned evaluation experiment 1. The magnetic stele of the comparative example is the same ceramic tile of the above-mentioned evaluation experiment 2. The weight of titanium dioxide in the surface of the fired tile is about 3.3 × l (T4g / cm2, and the tile of the example is the following Ti / Al tile. The Ti / Al ceramic tile is a kind of photocatalyst sol that accounts for 7.5% by weight of the total I of titanium dioxide and alumina, as well as that of Bongongjingjing brick, and the mixing ratio determining ratio a / (a + b) is 0.05 ~ 0.95. Within the range, the mixing ratio of alumina Ti / Al sol is adjusted, and the tiles are spray-painted and fired under the same conditions as the magnetic tablets of the above comparative example. That is, the weight of titanium dioxide on the surface of the fired tiles after firing varies with Ti / Al tiles with an increase in the weight of the oxides and a decrease from 3.3 × 10-4 g / cm2 are used as the example tiles in this evaluation experiment 3. The blending ratio determines the ratio a / When (a + b) is 0.05, since a + b is equivalent to the above 3.3xl0-4g / cm2, the weight a of the oxide in the surface of the tile after firing is about 1.65xl0_5g / cm2, and the weight of titanium dioxide b is about 3.135xl (T4g / cm2. When the mixing ratio determination ratio a / (a + b) is 0.95, the relative weight of the oxide a is about 3.135xl (T4g / cm2, and the weight b of titanium dioxide is about 1.65xl (T5g / cm2. In this evaluation experiment 3, the comparative example tile can also play a basic catalyst function, so it is used to compare this comparative example tile with various different titanium dioxide 、 Ti / Al tile with alumina content, it can be seen that the combination of titanium dioxide and alumina improves catalyst function. The paper size is applicable to China National Standard (CNS) A4 specification (210X297 mm) (Please read the back (Notes on this page again)

訂 -48 - 495384 經濟部中央標準局員工消費合作社印製 A7 B7五、發明説明（46 ) 之影響。 在該評價實驗3中，用以與評價實驗1相同的實驗裝置 ，與評價實驗2同樣地標繪N02濃度及NOx之除去量。將 結果示於第9圖。又，比較例磁磚中完全沒有配合氧化鋁 ，故配合比率決定比a/(a+b)為零，而上述不發揮光觸媒作 用之磁磚，則是完全沒有配合二氧化鈦，故配合比率決定 比 a/(a+b)為 1。 在第9圖中，比較例磁磚係（a/(a+b)=0)標在線圖上之Y 軸上，NO〗濃度為0.17ppm，而NOx之除去量為0.3ppm。 如此在不含N02且NOx濃度比實驗氣體濃度還低之實驗氣 體中卻可計測到N02濃度，其緣故係同於評價實驗2所述 。又，上述單純之不發揮光觸媒作用之磁磚係標繪在線圖 上之X軸上，其N02濃度、NOx之除去量當然也是零。 針對於此，配合比率決定比a/(a+b)在線圖之X軸座標 上表示之Ti/Al磁磚，其氧化鋁配合量很少而其配合比率 決定比a/(a+b)為0.05之磁磚則N02濃度為約0.07ppm，而 NOx之除去量為約0.46ppm。又，氧化銘配合量大於二氧 化鈦配合量且配合比率決定比a/(a+b)為0.8之Ti/Al磁磚時 ，則N〇2濃度為約〇.13ppm，而NOx之除去量為約0.32ppm 。然後配合比率決定比a/(a+b)在0.05〜0.65之範圍内之 Ti/Al磁磚時，則N02濃度為約0.07〜0.09ppm，而NOx之除 去量為約0.43〜0.52ppm。與比較例磁磚相比，其N02濃度 為顯著的低，而NOx之除去量很多。又，氧化紹配合量遠 大於二氧化鈦配合量且配合比率決定比a/(a+b)為0.9以上 (請先閲讀背面之注意事_ --裝-- 項本頁) 訂 線- 本紙張尺度適用中國國家標準（CNS ) A4規格（210X 297公釐） 49 495384 經濟部中央標準局員工消費合作社印製 A7 B7五、發明説明（47 ) 之Ti/Al磁磚時，則具有比比較例磁碑同等以下之N02濃度 以及NOx之除去量。 從此清楚可知，二氧化鈦與氧化鋁之總量為一定時， 配合比率決定比a/(a+b)若在0.0001〜0.8之範圍内，經配合 有氧化紹，可意圖抑制N02之脫離，可比比較例磁磚更可 得到N02削減效果進而得到NOx削減效果。尤其，配合比 率決定比a/(a+b)若在0.05〜0.6之範圍内，可得到比比較例 磁磚更高之NOx削減效果，所以理想。又，配合比率決定 比a/(a+b)若低於0.0001時或高於0.8時，亦可得到比比較 例疲磚同等之NOx削減效果。特別是配合比率決定比 a/(a+b)若高於0.9時，可知作為光觸媒之二氧化鈦太少， 使該粒子密密地包圍氧化鋁粒子，導致光無法到達而降低 光觸媒功能。 又，作成各種配合比率決定比a/(a+b)之值之Ti/Al磁 磚，該表面狀態良好，且具有優異之抗磨損性。 在上述第1實施例中，雖用以銳鈦礦型之二氧化鈦作 為光觸媒，而作為與該光觸媒相配合之金屬氧化物則使用 了兩性金屬氧化物之氧化鋁、鹼性金屬氧化物之氧化勰以 及氧化鋇，但已述NOx削減效果當然也可由其他光觸媒與 金屬氧化物之組合得到。例如，作為光觸媒之二氧化鈦也 可使用其結晶型為金紅石或板鈦礦之二氧化鈦。又，使用 ZnO、V205、W03、Sn02、SrTi03、Bi03、Fe203等之光觸 媒，也可發揮NOx削減效果。進而，作為替代氧化鋁、氧 化锶、氧化鋇之金屬氧化物有：氧化鋅、氧化錫（2者為兩 本紙張尺度適用中國國家標準（CNS ) A4規格（210X 公釐） -50 - 495384 A7 ___ B7 五、發明説明（48 ) 性金屬氧化物），氧化錤、氧化辦、氧化修、氧化納、氧 化鉀（以上皆為鹼性金屬氧化物），也可發揮1^〇义削減效果 。又，將鹼性氣體作為削減對象時，除上述之兩性金屬氧 化物之外，可使用氧化磷（酸性金屬氧化物）。 其次，針對第2實施例說明。在該第2實施例中，與在 磁磚表面由具有二氧化鈦等光觸媒及氧化鋁等特定的金屬 氧化物之光觸媒配合物形成之表面層之形成順序不同。在 XI第2實施例之實施例中，首先準備形成表面層之基材。 可作為基材者，若為陶瓷、樹脂、金屬、玻璃、陶器、木 材、莛酸鈣板、混凝土板、水泥板、水泥擠壓整形板、石 膏板或蒸壓養護混凝土板中任一種基材冑可，若為使用於 大樓、居家，以及橋樑道路、隔音壁等建築構造物之基材 ，則可於該等建築構造物表面上將氮氧化物等之環境污染 物質削減，可淨化大氣，故佳。 其次，在這準備的基材表面上形成黏著層。該黏著層 選定其軟化溫度遠比基材之變質溫度還低之黏著劑材料， 以適合黏著劑性質的方法，用以該黏著劑材料而形成之。 例如，基材為磁碑、空心碑或陶瓷器等時，表面上施以彩 色等之釉藥層或印刷層作為黏著層，如此利用形成黏著層 之後，於該黏著層表面上塗抹或印刷上述第丨實施例之 Ti/Al溶膠荨之溶膠，或散布從該溶膠將溶媒去除所得到 之二氧化鈦粒子與氧化鋁粒子之混合粒子，而後形成作為 表面層之光觸媒配合物層。或者是，在另外單獨做的黏著 層上，形成光觸媒配合物層，將該黏著層載放於基材表面 495384 A7 _____Β7_ 五、發明説明（^ ) 49 1 上亦可。此時，光觸媒配合物層在後面燒成時，使不至自 黏著層脫離，而形成黏著層亦可。 接著，係以釉藥形成之釉藥層當作黏著層時，係於遠 比黏著劑材料（釉藥）之軟化溫度還高於3(rc以上、3〇〇〇c 以下之範圍，且遠比基材之變質溫度還低之溫度環境下加 熱處理。經以該加熱處理，黏著劑材料（釉藥）融解固化， 使黏著層可穩固地固定在磁磚表面上之同時，由光觸媒配 合物層形成表面層。此時，在與黏著層之境界上，表面層 上之光觸媒配合物粒子（二氧化鈦粒子、氧化鋁粒子）在黏 著慰貧料一之融化過-程中，沈澱於黏著層，該粒子以埋沒在 黏著層之狀態保持而穩固地固定在黏著層β又，在光觸媒 配合物層中，相鄰接之粒子互相藉粒子間之分子間力或藉 燒成之結合而加以結合，形成表面層，在該表面層，其表 面分別露出二氧化鈦以及氧化紹之粒子。因此，將表面層 穩固地固定於黏著層之同時，可分別將二氧化鈦以及氧化 銘之粒子有效地與大氣相接觸。是故，藉上述第2實施例 之製造方法，可輕易製造以高效率得到光觸媒反應之表面 層之建築構造物材料等。 此時，將加熱溫度作比黏著材料之軟化溫度高3〇〇cw 上，因此不需長時間藉加熱軟化黏著劑材料，故較佳，且 不會影響二氧化鈦或氧化鋁之沈澱及保持，故理想。又， 將加熱溫度作成不會比超過黏著劑之變質溫度3〇〇 t還高 ，因此可避免黏著材料急遽地融化，而可抑制二氧化鈦或 氧化鋁之粒子的過度沈澱及凹凸面的發生，或者針孔的產 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） 觸—~ - -52 - (請先閲讀背面之注意事項再 —裝—— 本頁) 經濟部中央標準局員工消費合作社印製 495384 經濟部中央標準局員工消費合作社印製 A7 B7五、發明説明（5〇 ) 生等之不當，故較佳。又，加熱溫度係遠比黏著材料之軟 化材料高出50°C或低於150°C之範圍内之高溫為佳。 在上述第2實施例中，作為光觸媒也可使用其結晶型 為金紅石或板鈦礦之二氧化鈦，以及ZnO、V205、W03、 Sn02、SrTi03、Bi03、Fe203等。又，作為替代氧化I呂之 金屬氧化物，其削減對象若為NOx等之酸性氣體時，也可 使用氧化鋅、氧化錫（2者為兩性金屬氧化物），氧化鎂、 氧化#5、氧化敛1、氧化納、氧化_(以上皆為驗性金屬氧 化物），若鹼性氣體作為削減對象時，除上述兩性金屬氧 化#r之外，還可使用氧化磷（酸性金屬氧化物）。 其次，針對其他實施例說明。上述第1、第2實施例用 以光觸媒及已述特定化合物，將被反應物（如NO)或中間 生成物（如N02)保持於觸媒反應系内，可確實地保有被反 應物作用於觸媒反應之機會或進而中間生成物作用於該觸 媒反應之機會，而用以得到削減NOx等之有害物質之削減 效果。但下列說明之實施例除已述之特定化合物之外，還 加上其他物質，進而謀求NOx削減效果之提高或者是展現 新的效果。 首先，針對第3實施例說明。第3實施例係除上述之觸 媒反應之效率化之外，還兼具有光觸媒生成活性氧物種所 呈現出抗菌功能之光觸媒功能發揮材料。在其製造上，以 可達到觸媒反應之效率化之上述配合比率決定比，準備氧 化鋁與二氧化鈦共同配合之Ti/Al溶膠，以及分散有銅（Cu) 及其氧化物或銀（Ag)及其氧化物等粒子之第3溶膠。接著 (請先閲讀背面之注意事項再_舄本頁)Rev. -48-495384 Printed by the Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs A7 B7 V. Impact of Invention Statement (46). In this evaluation experiment 3, the same experimental device as that of evaluation experiment 1 was used, and the concentration of N02 and the removal amount of NOx were plotted in the same manner as in evaluation experiment 2. The results are shown in Fig. 9. In addition, the alumina of the comparative example was not blended with alumina at all, so the blending ratio determination ratio a / (a + b) was zero, and the above-mentioned tiles that did not exhibit photocatalyst function were not blended with titanium dioxide at all, so the blending ratio determined the ratio a / (a + b) is 1. In FIG. 9, the comparative example tile system (a / (a + b) = 0) is plotted on the Y-axis on the line diagram, and the concentration of NO is 0.17 ppm, and the removal amount of NOx is 0.3 ppm. In this way, the N02 concentration can be measured in the test gas containing NO2 and the NOx concentration is lower than the test gas concentration, for the same reason as described in Evaluation Experiment 2. In addition, in the above-mentioned simple ceramic tile system which does not exert the photocatalyst function, the N02 concentration and the removal amount of NOx are of course zero on the X axis on the line chart. In view of this, the Ti / Al tile indicated on the X-axis coordinate of the line graph a / (a + b) is determined by the ratio of the mixing ratio. The amount of alumina is small and the ratio of the ratio a / (a + b) is determined. For a tile of 0.05, the N02 concentration is about 0.07 ppm, and the removal amount of NOx is about 0.46 ppm. In addition, when the Ti / Al tile with the oxidizing compound content greater than the titanium dioxide compounding amount and the mixing ratio determining ratio a / (a + b) is 0.8, the NO 2 concentration is about 0.13 ppm and the NOx removal amount is about 0.32ppm. Then, when the mix ratio determines a Ti / Al tile having a ratio (a / (a + b)) in the range of 0.05 to 0.65, the concentration of N02 is about 0.07 to 0.09 ppm, and the removal amount of NOx is about 0.43 to 0.52 ppm. Compared with the comparative example tile, the N02 concentration was significantly lower, and the amount of NOx removed was much larger. In addition, the blending amount of oxide is much larger than the blending amount of titanium dioxide, and the ratio of determination ratio a / (a + b) is 0.9 or more (please read the note on the back first _ --installation-item page) When the Chinese National Standard (CNS) A4 specification (210X 297 mm) is applied 49 495384 A7 B7 printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs 5. The Ti / Al tile of the invention description (47) has a magnetic ratio The concentration of N02 and the amount of NOx removal are equal to or less than the monument. It is clear from this that when the total amount of titanium dioxide and alumina is constant, if the blending ratio determining ratio a / (a + b) is within the range of 0.0001 to 0.8, and with the addition of oxide, it can be intended to inhibit the detachment of N02, which can be compared by comparison. In the example tile, the effect of reducing N02 and the effect of reducing NOx can be obtained. In particular, if the blending ratio determination ratio a / (a + b) is in the range of 0.05 to 0.6, a NOx reduction effect higher than that of the comparative example tile is obtained, which is desirable. When the blending ratio determining ratio a / (a + b) is lower than 0.0001 or higher than 0.8, the same effect as that of the comparative example is obtained, as is the effect of reducing NOx. In particular, if the blending ratio determination ratio a / (a + b) is higher than 0.9, it is found that the titanium dioxide as a photocatalyst is too small, and the particles closely surround the alumina particles, which makes light inaccessible and reduces the photocatalyst function. In addition, Ti / Al tiles having various blending ratios to determine the value of a / (a + b) have good surface conditions and excellent abrasion resistance. In the first embodiment described above, although anatase-type titanium dioxide was used as the photocatalyst, as the metal oxide matched with the photocatalyst, amphoteric metal oxide, alumina, and alkaline metal oxide were used. And barium oxide, but of course the NOx reduction effect can be obtained from a combination of other photocatalysts and metal oxides. For example, as the photocatalyst titanium dioxide, titanium dioxide whose crystal form is rutile or brookite can be used. In addition, the use of photocatalysts such as ZnO, V205, W03, Sn02, SrTi03, Bi03, Fe203, etc. can also exhibit NOx reduction effects. Furthermore, as metal oxides that replace alumina, strontium oxide, and barium oxide: zinc oxide, tin oxide (the two are two paper sizes, applicable to China National Standard (CNS) A4 specification (210X mm) -50-495384 A7 ___ B7 V. Description of the invention (48) Metal oxides), hafnium oxide, oxidation office, oxidation repair, sodium oxide, potassium oxide (all of which are alkaline metal oxides), can also achieve 1 ^ 〇 meaning reduction effect. When an alkaline gas is to be reduced, phosphorus oxide (acidic metal oxide) can be used in addition to the above-mentioned amphoteric metal oxide. Next, the second embodiment will be described. This second embodiment differs from the order in which the surface layer is formed on the surface of a tile by a photocatalyst complex having a photocatalyst such as titanium dioxide and a specific metal oxide such as alumina. In the second embodiment of the XI, first, a substrate for forming a surface layer is prepared. As the substrate, if it is ceramic, resin, metal, glass, pottery, wood, calcium acetate board, concrete board, cement board, cement extruded board, gypsum board or autoclaved cured concrete board Yes, if it is used as a base material for building structures such as buildings, homes, bridges, roads, soundproof walls, etc., environmental pollutants such as nitrogen oxides can be reduced on the surface of these building structures, which can purify the atmosphere, So good. Next, an adhesive layer is formed on the surface of the prepared substrate. The adhesive layer is selected from an adhesive material whose softening temperature is much lower than the deterioration temperature of the substrate, and is formed by using the adhesive material in a method suitable for the properties of the adhesive. For example, when the base material is a magnetic tablet, hollow tablet, or ceramic, the surface is coated with an enamel layer or a printed layer as an adhesive layer. After the adhesive layer is formed, the above is applied or printed on the surface of the adhesive layer. The sol of Ti / Al sol in the first embodiment, or the mixed particles of titanium dioxide particles and alumina particles obtained by removing the solvent from the sol, and then form a photocatalyst complex layer as a surface layer. Alternatively, a photocatalyst complex layer is formed on a separate adhesive layer, and the adhesive layer is placed on the surface of the substrate 495384 A7 _____ Β7_ V. Description of the invention (^) 49 1. At this time, when the photocatalyst complex layer is fired later, the self-adhesive layer may not be detached, and an adhesive layer may be formed. Next, when the glaze layer formed by the glaze is used as the adhesive layer, the softening temperature of the glaze layer is much higher than the range of 3 (rc to 3,000 c), and Heat treatment in a lower temperature environment than the deterioration temperature of the substrate. After this heat treatment, the adhesive material (glaze) is melted and solidified, so that the adhesive layer can be firmly fixed on the tile surface, and the photocatalyst complex is used. The layer forms a surface layer. At this time, on the boundary with the adhesive layer, the photocatalyst complex particles (titanium dioxide particles, alumina particles) on the surface layer are precipitated in the adhesive layer during the melting process of the adhesive material. The particles are held in a state of being buried in the adhesive layer and are firmly fixed in the adhesive layer β. In the photocatalyst complex layer, adjacent particles are combined with each other by intermolecular force between particles or by firing. A surface layer is formed, and the surface of the surface layer respectively exposes titanium dioxide and oxide particles. Therefore, while the surface layer is firmly fixed to the adhesive layer, the titanium dioxide and the oxide The particles are effectively in contact with the atmosphere. Therefore, by the manufacturing method of the second embodiment described above, it is possible to easily manufacture building structure materials and the like that can obtain a photocatalytic reaction surface layer with high efficiency. At this time, the heating temperature is used as the specific adhesive material. The softening temperature is higher than 300cw, so it is not necessary to soften the adhesive material by heating for a long time, so it is better, and it does not affect the precipitation and retention of titanium dioxide or alumina, so it is ideal. Also, the heating temperature is not changed. It is higher than 300t above the deterioration temperature of the adhesive, so it can avoid the rapid melting of the adhesive material, and can prevent the excessive precipitation of titanium dioxide or alumina particles and the occurrence of uneven surfaces, or the production paper size of the pinhole is suitable. China National Standard (CNS) A4 specification (210X297 mm) Touch — ~--52-(Please read the precautions on the back before installing—this page) Printed by the Central Consumers Bureau of the Ministry of Economic Affairs Consumer Cooperatives 495384 Central of the Ministry of Economic Affairs Standard Bureau employee consumer cooperative printed A7 B7 V. Invention description (50) It is better because it is inappropriate, etc. Also, the heating temperature is much softer than the adhesive material It is preferred that the material be at a temperature higher than 50 ° C or lower than 150 ° C. In the above-mentioned second embodiment, as the photocatalyst, titanium dioxide whose crystal form is rutile or brookite, and ZnO, V205 can also be used. , W03, Sn02, SrTi03, Bi03, Fe203, etc. In addition, as a metal oxide instead of oxide I, if the reduction target is an acid gas such as NOx, zinc oxide, tin oxide (the two are amphoteric metals) Oxides), magnesium oxide, oxidation # 5, oxidation convergence 1, sodium oxide, oxidation (all of the above are empirical metal oxides), if alkaline gas is to be reduced, in addition to the above-mentioned amphoteric metal oxidation #r, Phosphorus oxide (acidic metal oxide) can also be used. Secondly, other embodiments will be described. The first and second embodiments described above use photocatalysts and specific compounds as described above, and the reactants (such as NO) or intermediate products ( (Such as N02) is kept in the catalyst reaction system, and the opportunity for the reactant to act on the catalyst reaction or the intermediate product to act on the catalyst reaction can be reliably maintained, and it can be used to obtain NOx and other harmful substances. Cut effect . However, in the examples described below, in addition to the specific compounds already described, other substances are added to further improve the NOx reduction effect or to exhibit new effects. First, the third embodiment will be described. The third embodiment is a photocatalyst function exhibiting material that exhibits an antibacterial function in addition to the efficiency of the catalyst reaction described above, and also has the antibacterial function exhibited by a photocatalyst generating active oxygen species. In the manufacture, the ratio of the above-mentioned mixing ratio that can achieve the efficiency of the catalyst reaction is determined, and a Ti / Al sol in which alumina and titanium dioxide are combined is prepared, and copper (Cu) and its oxide or silver (Ag) are dispersed The third sol of particles such as oxides thereof. Next (Please read the notes on the back before _ 舄 this page)

訂 線_ 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） - 53 - 經濟部中央標準局員工消費合作社印製 495384 A7 __ ____B7_ 五、發明説明（） 51 ； ’將Ti/Al溶膠塗抹於磁磚表面上並加以燒成，形成Ti/A1 層。之後’在磁碑表面之該Ti/Al層之表面上塗抹第3溶膠 ’以光還原等之方法，將第3溶膠成分於表面上固定化。 該磁磚即為第3實施例之磁磚，該第3實施例磁磚係具有該 表面上作為光觸媒之二氧化鈦與氧化鋁共同固著之表面層 ’進而在上面固著有Cu等粒子之磁碑。又，在第3溶膠之 塗抹時，於光觸媒上使充分以光照射調整該塗抹量。如CU 的重量在燒成後約0.8〜2.0//g/cm2左右即足夠。針對該第3 實施例及與上述評價實驗之比較例磁磚，進行下列抗菌性 —評價償為針脅大勝菌有無殺菌-效果而決定之――一 首先，將第3實施例之實施例磁磚與比較例磁磚同時 以70%酒精將表面殺菌，接著，在磁磚表面上滴下大腸菌 菌液0.15亳升（1〜5x1 〇4CFU)。在此磁碑表面上，放置玻璃 板，使大腸菌密著於磁碑表面，以此為樣品，將該樣品對 各種磁磚各準備一對。其次，第3實施例之實施例磁磚與 比較例磁碑之其中一個樣品上透過玻璃板以螢光燈照射， 另一個樣品置於遮光環境下。然後，隨著照射時間之流逝 ，測量螢光燈照射下（明處下）與遮光下（暗處下）之樣品中 大腸菌的生存率，標緣出相對於經過時間之從該生存率所 換算之抗菌率（大腸菌被消滅或停止增殖之比率）。將結果 示於第10圖。又，在測定時，用滅菌紗布將各樣品之菌液 擦去，回收到生理食鹽水1 〇毫升中，測量該生理食鹽水中 大腸菌之生存率，將此作為樣品中之生存率。 從第10圖可知，在螢光燈照射下，第3實施例之實施 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公董) -- (請先閲讀背面之注意事項再_舄本頁) —裝. 本 訂 54 52495384 A7 B7 五、發明説明（ 經濟部中央標準局員工消費合作社印製 例磁碑與比較例磁碑都得到高度抗菌效果。這是因為在螢 光燈照射下，表面層中之二氧化鈦活躍地生成活性氧物種 ，藉該活性氧物種，大腸菌接受其本身之有機成分之分解 而被消滅或停止死亡。但是在遮光下，比較例磁磚因沒有 活性氧物種之生成，幾乎不能獲得抗菌效果，相對於此， 第3實施例之實施例磁磚在遮光下，也可得到較高的抗菌 效果。這是因為固著於表面之Cu等粒子在遮光下也可發 揮抗菌效果。是故，藉這第3實施例之實施例磁碑，因為 遮光的緣故使作為光觸媒之二氧化鈦也不展現抗菌功能， 而在遮光下藉Cu争教子可以達成補充光觸媒所做到的抗 菌功能。 在上述第3實施例中，作為光觸媒也可使用其結晶型 為金紅石或板鈦礦之二氧化鈦，以及Zn〇、v205、W03、 Sn〇2、SrTi〇3、Bi2〇3、Fe^等，作為替代氧化鋁之金屬 氧化物也可使用氧化鋅、氧化錫（2者為兩性金屬氧化物） ,氧化鎂、氧化鈣、氧化铷、氧化鈉、氧化鉀（以上皆為 鹼性金屬氧化物），也可使用氧化磷（酸性金屬氧化物）。 又，替代Cu，如其氧化物，或者是銀（Ag)，或其氧化物 等，以及 Pb、Ni、Co、Pt、An、Al、Fe、Zn、Cr、Rh、 Ru等之金屬，使用金屬本身也具有若干程度之抗菌作用 者為佳。 其次，針對第4、5實施例說明。這第4實施例，與第1 、2同樣地使用光觸媒與氧化鋁等之上述金屬氧化物（兩性 金屬氧化物、驗性金屬氧化物、酸性金屬氧化物），並用 本紙張尺度適用中國國家標準（CNS ) Α4祝格（210Χ297公釐） (請先閲讀背面之注意事項再^:本頁) 裝· 、τ 線 55 經濟部中央標準局員工消費合作社印製 495384 A7 B7 五、發明説明（53 ) 除此之外的化合物，及與第3實施例同樣的Cu、Ag等之金 屬之4成分系者。第5實施例為，除使用光觸媒與氧化鋁等 之上述金屬氧化物（兩性金屬氧化物、驗性金屬氧化物、 酸性金屬氧化物）外，並用除此以外之化合物所形成之3成 分系者。 第4實施例中並用之金屬，若為具有比光觸媒之二氧 化鈦釋放之自由電子所有之電位（-3.2V)還高之還原電位 之金屬，可藉還原電位進行向二氧化鈦之載持，故佳。具 體而言，如 Ag、Cu、Pd、Fe、Ni、Cr、Co、Pt、Au、Li 、Mg、A1、—Rh、Ru等之轉化金屬，其中“Ag、 Cu、Pd、Pt、Au其還原電位為正值，故容易進行還原載 持，所以特佳。在並用該等金屬後說明針對將該金屬載持 於光觸媒之方式。作為對光觸媒之金屬載持方式可列舉如 下。 ① 單純混合法：將含有目的金屬種之金屬鹽水溶液添 加於光觸媒溶膠，將2者混合，藉對金屬離子之光觸媒粒 子表面之吸著，進行載持。 ② 共沈法：將含有目的金屬種之金屬鹽水溶液添加於 光觸媒溶膠後，藉沈澱劑之添加或加熱，使金屬鹽及光觸 媒同時沈澱，使之共沈，將金屬離子載持於光觸媒粒子表 面。 ③ 光還原前載持法：將含有目的金屬種之金屬鹽水溶 液添加於光觸媒溶膠後，以紫外線源照射，利用金屬離子 對光觸媒粒子表面之光還原進行載持。 本紙張尺度適用中國國家標準（CNS ) Α4規格（210 X 297公釐） (請先閱讀背面之注意事項再本頁) 訂 線· 56 495384 A7 B7 五、發明説明（54 ) ④ 光還原後載持法：在光觸媒膜上塗抹含有目的金屬 種之金屬鹽水溶液後，以紫外線源照射，利用金屬離子對 光觸媒粒子表面之光還原進行載持。 ⑤ 蒸鍍法：用以化學或物理蒸鍍法載持金屬粒子或金 屬化合物。 ⑥ 其他：用以溶膠/凝膠法，製造光觸媒粒子之前，添 加目的的金屬種之離子，藉之後之共沈法，俾謀求光觸媒 /金屬離子之粒子化。 又，與光觸媒及氧化鋁等之上述金屬氧化物並用之化 合物為二氧化石夕（给石:Si02)。又，替代二氧化梦也可使用 Zr02、Ge02、Th02、ZnO等氧化物。 在這第4實施例採用上述單純混合法、光還原前載持 法或共沈法，使用了以上列方式載持金屬之光觸媒。 經濟部中央標準局員工消費合作社印製 第4實施例之光觸媒功能發揮磁磚（實施例磁磚），使 用分散有用以單純混合法、光還原前載持法或共沈法將Ag 、Cu載持完畢之光觸媒（二氧化鈦）之光觸媒溶膠，沿襲上 述第1實施例之評價實驗1中所述步驟，將其餘兩成分（氧 化鋁、二氧化矽）混合於該金屬載持完畢之光觸媒溶膠（光 觸媒/金屬）加以攪拌，經該混合溶膠之喷射塗抹、燒成而 製成。而經此製成之光觸媒/金屬（Ag或Cu)/氧化鋁/氧化矽 之4成分系的磁磚為第4實施例之實施例磁碑。此時為了掌 握重新配合之金屬、氧化矽之影響，針對光觸媒/金屬（Ag 或Cu)之2成分系，也製作一磁磚（參考磁磚）。又，第5實 施例磁磚使用了與上述第1實施例中只有光觸媒（二氧化鈦） 本紙張尺度適用中國國家標準（CNS ) A4規格（210X 297公釐） 57 495384 A7 B7 經濟部中央標準局員工消費合作社印製 五、發明説明（55 ) 的光觸媒溶膠，沿襲上述第1實施例之評價實驗1中所述步 驟，將其餘2成分（氧化鋁、二氧化矽）之溶膠混合於該光 觸媒溶膠（光觸媒/金屬）加以攪拌，經該混合溶膠之噴射 塗抹、燒成而製成。而經此製成之光觸媒/氧化鋁/二氧化 矽之3成分系的磁磚為第5實施例之實施例磁磚。然後，針 對這第4、5實施例之實施例磁磚、參考磁磚、第1實施例 磁磚、比較例磁碑，檢討NOx削減‘效率。又，第1實施例 磁磚、比較例磁磚，如同在第1實施例之評價實驗1所述， 第1實施例之實施例磁磚之配合比率決定比a/(a+b)為1/11 。文第4賓^施例^實施例磁磚之配合比率決一定比 (Si02/(Ti02+ Al203+Si02))為1/11。第5實施例之實施例磁 磚之配合比率決定比（Al203/(Ti02+Al203+Si02))為 1/11。2 成分系之參考磁磚中，金屬與Ti02之重量比係，在Ag配 合之2成分系之參考磁磚為0.001(Ag/Ti02)，而Cu配合之2 成分系之參考磁磚為0.01(Cu/TiO2)。 針對該等磁碑，用以如第4圖所示之實驗裝置，如於 第1實施例之評價實驗1所述，測定CNO/out、CN02/out。 然後、從該測定之CNO/out、CN02/out與已知之實驗氣體 濃度（CNO/in)，計算光照射後經30分鐘時之（CNO/in -CNO/out)、CN02/out以及NOx削減效率。將該結果示於表 (請先閲讀背面之注意事項再本頁) —裝· 太 訂 線 本紙張尺度適用中國國家標準（CNS ) A4規格（2丨0><297公釐） 58 495384 A7 B7 五、發明説明（） 56 區 分 配合概要 金屬载持法 (CNO/in —NO/out) CN02/out NOx削減效率 (%) Ti02 〇 0.19 V x w/ 第1貫施例磁確 Ti02+Al203 0.55 0.05 ν/·«/ 參考磁崎 (2成分） Ti02+Ag 單純混合法 0.46 0.17 30.5 (2成分） Ti02+Ag 光還原前載持法 0.75 0.27 50.5 參考磁碑 (2成分） Ti02+Cu 單純混合法 0.48 0.17 32.6 (2成分） Ti02+Cu 光還原前載持法 0.6 0.22 40 參考磁碑 (2成分） Ti02+Cu 共沈法 0.5 0.17 33 第5實施例磁磚 (3成分） Ti02+Al203+ Si02 0.53 0.05 50.5 第4實施例磁碑 (4成分） Ti〇2+Al203+ Si02+Ag 先還原前載持法 0.62 0.11 53J 第4實施例磁碑 (4成分） Ti02+Al203+ Si02+Cu 光還原前栽持法 0.59 0.13 48.4 表1 (請先閲讀背面之注意事項再· —裝-- 本頁)Threading _ This paper size is in accordance with Chinese National Standard (CNS) A4 (210X297 mm)-53-Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 495384 A7 __ ____B7_ V. Description of the invention () 51; The sol is applied on the surface of the tile and fired to form a Ti / A1 layer. After that, the third sol is coated on the surface of the Ti / Al layer on the surface of the magnetic monument with a method such as photoreduction to fix the third sol component on the surface. The tile is the tile of the third embodiment. The tile of the third embodiment has a surface layer where titanium dioxide and alumina are co-fixed on the surface as a photocatalyst, and a magnet having particles such as Cu is fixed on the surface. monument. In the application of the third sol, the amount of the application was adjusted by sufficiently irradiating the photocatalyst with light. It is sufficient if the weight of CU is about 0.8 ~ 2.0 // g / cm2 after firing. For the third embodiment and the comparative example tile with the above-mentioned evaluation experiment, the following antibacterial properties were evaluated—determined by the evaluation of whether or not the sterilization of E. tremella was sterilized—the effect was determined—First, the example of the third embodiment was magnetized. The tile and the comparative example tile were sterilized with 70% alcohol at the same time, and then 0.15 liters (1 to 5 × 104 CFU) of coliform bacteria solution was dropped on the tile surface. A glass plate was placed on the surface of the magnetic monument to allow coliform bacteria to adhere to the surface of the magnetic monument. As a sample, a pair of each sample was prepared for each type of tile. Next, one of the samples of the example tile and the example of the comparative example of the third embodiment is illuminated by a fluorescent lamp through a glass plate, and the other sample is placed in a light-shielded environment. Then, as the irradiation time elapsed, the survival rate of coliforms in the samples under fluorescent light (under the light) and under the light (under the dark) was measured, and the margin was calculated from the survival rate relative to the elapsed time. The antibacterial rate (the rate at which coliforms are destroyed or cease to multiply). The results are shown in Fig. 10. In the measurement, the bacterial solution of each sample was wiped off with a sterile gauze, and recovered in 10 ml of a physiological saline solution. The survival rate of coliforms in the physiological saline solution was measured, and this was taken as the survival rate in the sample. As can be seen from Figure 10, under the illumination of fluorescent light, the implementation of the third embodiment of this paper size is applicable to the Chinese National Standard (CNS) A4 specification (210X297 public director)-(Please read the precautions on the back before _ 舄 本Page) — Equipment. This booklet 54 52495384 A7 B7 V. Description of the invention (The magnetic stele printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs and the magnetic stele printed by Comparative Examples both have a high degree of antibacterial effect. This is because under fluorescent light, Titanium dioxide in the surface layer actively generates reactive oxygen species, and by this reactive oxygen species, coliform bacteria are destroyed or stop dying by accepting the decomposition of its own organic components. However, the comparative example tiles did not generate reactive oxygen species under light shading. It is almost impossible to obtain an antibacterial effect. In contrast, the tile of the third embodiment can also obtain a high antibacterial effect under light shielding. This is because particles such as Cu fixed on the surface can also exhibit under light shielding. The antibacterial effect. Therefore, by taking the magnetic tablet of the example of the third embodiment, titanium dioxide as a photocatalyst does not exhibit antibacterial function because of light shielding. Godson can achieve the antibacterial function supplemented by photocatalyst. In the above third embodiment, as the photocatalyst, titanium dioxide whose crystal type is rutile or brookite, and Zn〇, v205, W03, Sn〇2, can also be used. SrTi〇3, Bi203, Fe ^, etc. As the metal oxide instead of alumina, zinc oxide, tin oxide (the two are amphoteric metal oxides), magnesium oxide, calcium oxide, hafnium oxide, sodium oxide, Potassium oxide (all of the above are basic metal oxides), phosphorus oxide (acidic metal oxide) can also be used. Also, instead of Cu, such as its oxide, or silver (Ag), or its oxide, etc., and Pb, For metals such as Ni, Co, Pt, An, Al, Fe, Zn, Cr, Rh, Ru, etc., it is better to use the metal itself to have a certain degree of antibacterial effect. Second, the fourth and fifth embodiments will be described. This first In the fourth embodiment, the same metal oxides (amphoteric metal oxides, experimental metal oxides, and acid metal oxides) as the photocatalyst and alumina are used in the same way as in the first and second examples, and the Chinese national standard (CNS Α4 210 × 297 mm) (Please read the precautions on the back before ^: this page) Packing ·, τ line 55 Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 495384 A7 B7 V. Description of the invention (53) Compounds other than And the same four-component system of Cu, Ag, and other metals as in the third embodiment. In the fifth embodiment, the above-mentioned metal oxides (amphoteric metal oxides, test metal oxides, etc.) other than the photocatalyst and alumina are used. , Acid metal oxide), and a three-component system formed by using other compounds. If the metal used in the fourth embodiment is a potential possessed by free electrons (-3.2V) than that released by photocatalyst titanium dioxide Metals with a high reduction potential can be supported on titanium dioxide by the reduction potential. Specifically, conversion metals such as Ag, Cu, Pd, Fe, Ni, Cr, Co, Pt, Au, Li, Mg, A1, -Rh, Ru, etc., where "Ag, Cu, Pd, Pt, Au and others The reduction potential is positive, so it is easy to carry out reduction support, so it is particularly good. After using these metals in combination, the method of supporting the metal on the photocatalyst will be explained. As the metal support method of the photocatalyst, the following are listed. ① Simple mixing Method: An aqueous solution of a metal salt containing the target metal species is added to the photocatalyst sol, and the two are mixed, and supported by adsorption on the surface of the photocatalyst particles of the metal ion. ② Co-precipitation method: Metal salt containing the target metal species After the aqueous solution is added to the photocatalyst sol, the metal salt and the photocatalyst are simultaneously precipitated and co-precipitated by adding or heating a precipitant, and the metal ions are supported on the surface of the photocatalyst particles. ③ Supporting method before photoreduction: The target metal is contained This kind of metal salt aqueous solution is added to the photocatalyst sol, and then irradiated with an ultraviolet source, and uses metal ions to support the photoreduction of the surface of the photocatalyst particles. This paper scale is applicable to China Standard (CNS) Α4 size (210 X 297 mm) (Please read the precautions on the back before this page) Threading · 56 495384 A7 B7 V. Description of the invention (54) ④ Support method after photoreduction: in photocatalyst film After applying an aqueous solution of a metal salt containing the target metal species, it is irradiated with an ultraviolet source, and the metal ions are used to support the photoreduction of the surface of the photocatalyst particles. ⑤ Evaporation method: The metal particles or metals are supported by chemical or physical evaporation methods. Compounds. ⑥ Others: The sol / gel method is used to prepare the photocatalyst particles. The target metal ion is added, and the subsequent co-precipitation method is used to obtain the photocatalyst / metal ion particles. In addition, the photocatalyst and alumina are used. The compound used in combination with the above-mentioned metal oxides is stone dioxide (giving stone: Si02). In addition, instead of dreaming of oxides, oxides such as Zr02, Ge02, Th02, and ZnO can be used. In this fourth embodiment, the above-mentioned simple The hybrid method, the pre-reduction support method or the co-precipitation method use the photocatalysts that support the metal as listed above. The 4th embodiment of the light printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs The catalyst functions as a catalyst tile (example tile). The photocatalyst sol that uses the photocatalyst (titanium dioxide) on which Ag and Cu have been supported by a simple mixing method, a pre-reduction support method, or a co-precipitation method is used. The evaluation step of the example 1 is described in step 1. The remaining two components (alumina, silicon dioxide) are mixed in the metal-supported photocatalyst sol (photocatalyst / metal), and the mixed sol is spray-coated, It is made by firing. The photocatalyst / metal (Ag or Cu) / aluminum oxide / silicon oxide 4-component tile made in this way is an example magnetic tablet of the fourth embodiment. In this case, it is necessary to refit For the effect of metal and silicon oxide, a tile is also made for the two-component system of photocatalyst / metal (Ag or Cu) (refer to tile). In addition, the fifth embodiment uses only the photocatalyst (titanium dioxide) in the first embodiment. The paper size is in accordance with the Chinese National Standard (CNS) A4 (210X 297 mm) 57 495384 A7 B7 employees of the Central Standards Bureau of the Ministry of Economic Affairs The photocatalyst sol printed by the Consumer Cooperative 5. The description of the invention (55) follows the steps described in the evaluation experiment 1 of the first embodiment above, and the sol of the remaining 2 components (alumina, silicon dioxide) is mixed with the photocatalyst sol ( The photocatalyst / metal) is stirred, spray-coated and fired by the mixed sol. The photocatalyst / aluminum oxide / silicon dioxide three-component ceramic tile made in this way is the ceramic tile of the fifth embodiment. Next, with regard to the tiles of the fourth and fifth embodiments, the reference tiles, the tiles of the first embodiment, and the comparative example, the efficiency of NOx reduction will be reviewed. In addition, the tile of the first embodiment and the tile of the comparative example are as described in the evaluation experiment 1 of the first embodiment, and the ratio of determination ratio a / (a + b) of the tile of the first embodiment is 1 / 11. In the fourth example of the text, the mixing ratio of the ceramic tile (Si02 / (Ti02 + Al203 + Si02)) must be 1/11. The ratio of the determination ratio of the example tile of the fifth embodiment (Al203 / (Ti02 + Al203 + Si02)) is 1/11. 2 In the reference tile of the composition system, the weight ratio of metal to Ti02 is based on the combination of Ag The reference tile of the two-component system is 0.001 (Ag / Ti02), and the reference tile of the two-component system with Cu is 0.01 (Cu / TiO2). For these magnetic monuments, the experimental apparatus shown in Fig. 4 was used to measure CNO / out and CN02 / out as described in the evaluation experiment 1 of the first embodiment. Then, from the measured CNO / out, CN02 / out and the known experimental gas concentration (CNO / in), calculate the (CNO / in -CNO / out), CN02 / out and NOx reduction at 30 minutes after light irradiation. effectiveness. The results are shown in the table (please read the precautions on the back and then on this page) — installed and over-threaded. The paper size applies the Chinese National Standard (CNS) A4 specification (2 丨 0 > < 297 mm) 58 495384 A7 B7 V. Description of the invention (56) Outline of differentiation and coordination Metal support method (CNO / in —NO / out) CN02 / out NOx reduction efficiency (%) Ti02 〇0.19 V xw / First implementation example Ti02 + Al203 0.55 0.05 ν / · «/ Reference magnetic saki (2 components) Ti02 + Ag simple mixing method 0.46 0.17 30.5 (2 components) Ti02 + Ag support method before photoreduction 0.75 0.27 50.5 Reference magnetic monument (2 components) Ti02 + Cu simple mixing Method 0.48 0.17 32.6 (2 components) Ti02 + Cu Carrying method before photoreduction 0.6 0.22 40 Reference magnetic tablet (2 components) Ti02 + Cu co-precipitation method 0.5 0.17 33 Fifth embodiment tile (3 components) Ti02 + Al203 + Si02 0.53 0.05 50.5 Magnetic monument in the fourth embodiment (4 components) Ti〇2 + Al203 + Si02 + Ag first load reduction method 0.62 0.11 53J Magnetic monument in the fourth embodiment (4 components) Ti02 + Al203 + Si02 + Cu support before light reduction Method 0.59 0.13 48.4 Table 1 (please read the precautions on the back first-installation-this page)

，1T 經濟部中央標準局員工消費合作社印製, 1T Printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs

(CNO/in— CNO/out)係 NO氧化成 Ν〇ΑΝ03-之量（NO 減少量），成為NO之氧化力指標的值。又，cN02/out為向 N〇2之系外之副生成量’而該cN〇2/out之值愈少，表示愈 不能使N〇2向系外脫離，即，表示n〇2之吸著力非常強。 因此，如表1可知，藉第4實施例之實施例磁磚，可展現與 第1實施例同等以上之NO氧化力，得到很高的NOx削減效 率。尤其，配合有Ag之第4實施例之實施例磁磚，因（CNO/in —CNO/out)大，其NO氧化力很高，且因CN02/out小，形 成強力的N02吸著力，故可同時謀求氧化力及吸著力。 又，從參考磁磚之結果而言，採取光還原前載持法， 即使為二氧化鈦及金屬之2成分系，也可獲得與第丨實施例 本紙張尺度適用中國國家標準（CNS )八4規格（21〇χ297公釐） 59 495384(CNO / in—CNO / out) refers to the amount of NO oxidation to NOA03- (NO reduction), which becomes the value of NO's oxidizing power index. In addition, cN02 / out is the amount of by-products generated outside the system of No. 02, and the smaller the value of cN02 / out, the less the ability of No. 2 to escape from the system, that is, the absorption of no. Focus is very strong. Therefore, as shown in Table 1, the tiles of the fourth embodiment can exhibit a NO oxidation power equal to or higher than that of the first embodiment, and a high NOx reduction efficiency can be obtained. In particular, the embodiment tile with the fourth embodiment of Ag, because (CNO / in-CNO / out) is large, its NO oxidation power is high, and because CN02 / out is small, a strong N02 adsorption force is formed, so Both oxidizing power and adsorption power can be sought. In addition, from the results of the reference tile, even if it is a two-component system of titanium dioxide and metal by adopting the pre-reduction support method, it can be obtained in accordance with the Chinese Standard (CNS) 8-4 specification for this paper size. (21 × 297 mm) 59 495384

經濟部中央標準局員工消費合作社印製 同等程度之NO氧化力及Nqx削減效率。進而，從第5實施 例之實施例磁磚之結果而言，合了氧化石夕，也可獲得與 第1實施例同等程度之Ν〇氧化力及Ν〇χ削減效率，因此關 於NOx削減，可知二氧化；g夕配合不會不妥。 在上述第4、5實施例中，作為光觸媒也可使用其結晶 型為金紅石或板鈦礦之二氧化鈦，以及Zn〇、％%、w〇3 、Sn〇2、SrTi〇3、BiA、FeA等。又，作為替代氧化紹 之金屬氧化物，其削減對象若為Ν〇χ等之酸性氣體時，也 可使用氧化鋅、氧化錫（2者為兩性金屬氧化物），氧化鎂 、氧化鍔、氧化撕一、氧化鈉、氧化卸（以上皆為鹼性金屬 氧化物），若鹼性氣體作為削減對象時，除上述兩性金屬 氧化物外也可使用氧化磷（酸性金屬氧化物）^進而，替代 Ag或Cu ,也可使用上述各金屬，替代二氧化矽時，也可 使用上述各氧化物。其次，針對第6、第7實施例說明。這 第6實施例與上述第4實施例相同，為以二氧化鈦為代表之 光觸媒’以氧化紹為代表之兩性或驗性或者是酸性金屬氧 化物，以及 Cu 或 Ag、Pd、Fe、Ni、Cr、Co、Pt、Au、Rh 、Ru等在第4實施例中已述金屬，以及氧化矽等在第4實 施例中已述另一化合物（氧化物）並用之4成分系者。第7實 施例為，光觸媒，及以氧化鋁為代表之兩性或鹼性或者是 酸性金屬氧化物，以及氧化矽等在第4實施例中已述另一 化合物（氧化物）並用之3成分系者。然後，第6、7實施例 係謀求包含NOx等之環境污濁物質之分解能力在内之分解 力之提高以及防污效果。 (請先閲讀背面之注意事項再本頁) i In I— · I'衣· 本 -訂 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） 60 經濟部中央標準局員工消費合作社印製 A7 --------— — B7 五、發明説明（） — --- 58 抑、t施例中’也與和這第4實施例相同，用以上述 皁、:此口法或光還原前載持法，使用了分散有入㈢、a載 持凡畢之光觸媒（二氧化鈦）之光觸媒溶膠。然後，第6實 施例之實施例磁碑’也如第4實施例-般，沿襲上述第巧 ^例之4½實驗”所述步驟製造之。而第7實施例之實施 例磁碑，也如第5實施例，將其餘2成分（氧化紹、二氧化 矽）混σ於光觸媒溶膠並加以攪拌 > 經該混合溶膠之噴射 塗抹、燒成而製造之。又，此時為了掌握重新配合之金屬 一氧化矽之影響，針對光觸媒/金屬（Ag*c幻之2成分系 、光觸媒/氧化石夕之2成分系、光觸媒/金屬（知或叫/二氧 化矽之3成分系，也各製作一磁磚（參考磁碑此時，對 光觸媒溶膠之基材（磁磚）之塗抹時，替代喷射塗抹，也可 採用旋轉塗抹、浸潰塗料之方式。χ，對光觸媒溶膠之 基材表面之固著，如第丨實施例之評價實驗丨所述步驟，藉 燒成進行（燒烤型）、或將硅樹脂混合於光觸媒溶膠，於較 低溫中，使該硅樹脂硬化（塗料型）。又，根據該等第6、7 實施例之實施例磁磚、參考磁磚、比較例磁磚評價。其中 ，比較例磁磚係如在第1實施例之評價實驗丨所述者。 第6貫施例之實施例磁磚之配合比率決定比（gjiQy (Ti〇2+Al2〇3+Si〇2)為1/10，而第7實施例之實施例磁磚之 配合比率決定比（Al203/(Ti024·Al203+Si02))為 1/1〇。光觸 媒/ 一氧化碎之2成分系參考磁碑之配合比率決定比（8丨〇2 /(Ti〇2+Si〇2))為1/5。而光觸媒/金屬之2成分系參考磁磚， 金屬與Ti〇2之重量比，在Ag配合之2成分系參考磁磚為 本紙張尺度適用中國國家標準（CNS ) A4規格（210 X 297公釐） -----^---^---抑衣-- (請先閱讀背面之注意事項再IPr本頁) 訂 線- 61 經濟部中央標準局員工消費合作社印製 495384 A7 B7 五、發明説明（59) 0.001(Ag/Ti02)，Cu配合之2成分系參考磁磚為0.01 (Cu/Ti02)。光觸媒/金屬/二氧化矽之3成分系參考磁磚， 金屬與Ti02之重量比與上述參考磁磚相同（0.001(Ag/Ti02) 0.01(Cu/TiO2))，其配合比率決定比（Si02/(Ti02+Si02))為 1/5 〇 首先，為了掌握重新配合之金屬之影響，針對光觸媒 /金屬（Ag或Cu)之2成分系之參考磁磚說明。這2成分系參 考磁磚，在燒烤型者時，於氧化鈦溶膠（石原產業STS-11) 中，將各種金屬鹽（和光純藥試藥特級）相對於氧化鈦溶膠 中之氧化鈦固態部-呈〇·〇〇1〜10%而配合。然後，以單純混 合法或光還原前載持法或者使以共沈法，先將Ag或Cu載 持於光觸媒。以光還原前載持法時，將Ag或Cu之金屬鹽 水溶液混合於氧化飲溶膠後，以lmW/cm2強度照射紫外線 2小時，作成載持有金屬之光觸媒的溶膠。在共沈法時， 將Ti0S04溶液作為開始原料，在這溶液中加上金屬鹽水 溶液加水分解，作成載持有金屬之光觸媒的溶膠。之後， 將該等光觸媒溶膠喷射塗抹，使磁磚表面燒成後之膜厚為 約0·8/ζ m，以600〜900°C溫度（在參考磁磚時約800°C)進行 燒成，製作2成分系參考磁磚（燒烤型）。 而塗料型則是在氧化鈦溶膠（日產化學TA-15)中，將 各種金屬鹽（和光純藥試藥特級）相對於氧化鈦溶膠中之氧 化鈦固態部呈0.001〜1%而配合。然後，以單純混合法或 光還原前載持法，將Ag或Cu載持完畢之光觸媒溶膠，及 作為黏著劑之硅樹脂，將氧化鈦與硅樹脂之固態部混合成 本紙張尺度適用中國國家標準（CNS ) A4規格（210X 297公釐） (請先閱讀背面之注意事項再^T本頁)Printed by the Consumers' Cooperative of the Central Bureau of Standards of the Ministry of Economics NO oxidation power and Nqx reduction efficiency of the same level. Furthermore, from the results of the example tile of the fifth embodiment, in combination with oxidized stone, NO oxidation power and NO reduction efficiency equivalent to that of the first embodiment can be obtained. It can be known that the oxidation is not wrong. In the above-mentioned fourth and fifth embodiments, as the photocatalyst, titanium dioxide whose crystalline form is rutile or brookite, and Zn0, %%, w03, Sn02, SrTi03, BiA, FeA can also be used. Wait. In addition, as an alternative metal oxide, if the reduction target is an acid gas such as NOx, zinc oxide, tin oxide (the two are amphoteric metal oxides), magnesium oxide, hafnium oxide, and oxidation can also be used. Tear one, sodium oxide, and oxide (all of the above are basic metal oxides). If alkaline gas is used as a reduction target, phosphorus oxides (acidic metal oxides) can be used in addition to the amphoteric metal oxides described above. Ag or Cu may also be used as the above-mentioned metals, and in the case of replacing silicon dioxide, the above-mentioned oxides may also be used. Next, the sixth and seventh embodiments will be described. This sixth embodiment is the same as the fourth embodiment described above. It is a photocatalyst typified by titanium dioxide, an amphoteric or experimental or acidic metal oxide typified by oxide, and Cu or Ag, Pd, Fe, Ni, and Cr. , Co, Pt, Au, Rh, Ru, and the like have been described in the fourth embodiment of the metal, and silicon oxide and the other compound (oxide) have been described in the fourth embodiment in combination with the four-component system. The seventh embodiment is a photocatalyst, and amphoteric or alkaline or acidic metal oxide represented by alumina, and a three-component system in which another compound (oxide) described in the fourth embodiment is used in combination with silicon oxide, etc. By. The sixth and seventh embodiments seek to improve the decomposing power and the antifouling effect including the decomposing ability of environmental fouling substances such as NOx. (Please read the precautions on the back first, and then this page) i In I— · I 'clothing · Book-book size is applicable to China National Standard (CNS) A4 (210X297 mm) 60 Staff Consumer Cooperatives, Central Bureau of Standards, Ministry of Economic Affairs Print A7 ------------ B7 V. Description of the invention ()---- 58 In the embodiment, it is also the same as the fourth embodiment, which is used for the above soap: The photocatalyst sol or the pre-photoreduction support method uses a photocatalyst sol dispersed with a photocatalyst (titanium dioxide) supporting a photocatalyst (titanium dioxide). Then, the magnetic stele of the sixth embodiment is also manufactured in the same manner as in the fourth embodiment, following the steps described in the above-mentioned 4½ experiment of the fourth embodiment. The magnetic stele of the seventh embodiment is also In the fifth embodiment, the remaining two components (alumina and silicon dioxide) are mixed with σ and stirred in a photocatalyst sol. The mixed sol is spray-coated and fired to produce it. At this time, in order to grasp the recombination, The influence of metal silicon oxide is also produced for photocatalysts / metals (Ag * c magic two-component system, photocatalyst / stone oxide two-component system, photocatalyst / metal (known as or three-component system of silicon dioxide) A magnetic tile (refer to the magnetic tablet at this time, instead of spray coating, the method of spin coating and dipping paint can be used when applying the photocatalyst sol substrate (magnetic tile). Χ, the surface of the substrate of the photocatalytic sol Fixation, as described in the evaluation experiment of the example 丨, by firing (grill type), or mixing the silicone resin with the photocatalyst sol, the silicone resin is hardened (paint type) at a lower temperature. In accordance with these 6th, 7th Example tile, reference tile, and comparative example tile evaluation. Among them, the comparative example tile is as described in the evaluation experiment of the first embodiment. The mixing ratio of the example tile of the sixth embodiment The determination ratio (gjiQy (Ti〇2 + Al2〇3 + Si〇2) is 1/10, and the determination ratio of the mixing ratio of the tiles of the seventh embodiment (Al203 / (Ti024 · Al203 + Si02)) is 1 / 1〇. Photocatalyst / Monoxide Fragment 2 component is determined by the reference ratio of the magnetic stele (8 丨 〇2 / (Ti〇2 + Si〇2)) is 1/5. And photocatalyst / metal 2 component system Reference tile, the weight ratio of metal to Ti〇2, the two components in the Ag blend are reference tiles that are based on the Chinese paper standard (CNS) A4 (210 X 297 mm) ----- ^- -^ --- Yiyi-- (Please read the notes on the back before IPr this page) Threading-61 Printed by the Employees' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs 495384 A7 B7 V. Description of the invention (59) 0.001 (Ag / Ti02), Cu 2-component reference tile is 0.01 (Cu / Ti02). Photocatalyst / metal / silicon dioxide 3-component reference tile, the weight ratio of metal to Ti02 is the same as the above reference tile (0 .001 (Ag / Ti02) 0.01 (Cu / TiO2)), and its determining ratio (Si02 / (Ti02 + Si02)) is 1/5 〇 First, in order to grasp the influence of the recombined metal, the photocatalyst / metal ( Ag or Cu) two-component reference tile description. This two-component reference tile, when grilling, in the titanium oxide sol (Ishihara STS-11), various metal salts (Wako Pure Chemical Industries, Ltd. (Medical grade) is 0.001% to 10% with respect to the solid state of titanium oxide in the titanium oxide sol. Then, Ag or Cu is first supported on the photocatalyst by a simple mixing method or a pre-reduction support method or a co-precipitation method. In the photoreduction pre-support method, an Ag or Cu metal salt aqueous solution is mixed with an oxidized drink sol, and then irradiated with ultraviolet rays at an intensity of lmW / cm2 for 2 hours to prepare a sol carrying a metal-containing photocatalyst. In the co-precipitation method, a Ti0S04 solution is used as a starting material, and a metal salt solution is added to this solution to decompose it with water to form a sol containing a photocatalyst containing a metal. Then, the photocatalyst sol is spray-coated so that the film thickness of the tile surface after firing is about 0 · 8 / ζ m, and firing is performed at a temperature of 600 to 900 ° C (about 800 ° C when referring to the tile). , Make a 2-component reference tile (barbecue type). The coating type is a titanium oxide sol (Nissan Chemical TA-15), which mixes various metal salts (Wako Pure Chemical Test Special Grade) with 0.001 to 1% of the titanium oxide solid portion in the titanium oxide sol. Then, using a simple mixing method or a photoreduction preloading method, Ag or Cu supported photocatalyst sol, and a silicone resin as an adhesive, the titanium oxide and the solid portion of the silicone resin are mixed into a paper. The Chinese standard is applicable to the paper size (CNS) A4 size (210X 297mm) (Please read the precautions on the back before ^ T this page)

訂 62 495384 A7 B7 五、發明説明（6〇 ) 7:3，於磁磚表面上旋轉塗抹，經150°C之加熱，製作一2 成分系參考磁碑（塗料型）。 針對這2成分系參考磁磚（燒烤型&塗料型），針對化學 物質之分解力評價，進行下列之評價實驗。分解力可從抗 菌力、油分解率，直接評價。在此，抗菌力用以在上述第 3實施例中說明之大腸菌（Escherichia coil w3110棵）之抗菌 率，將具有由光觸媒（二氧化鈦）單體形成之光觸媒層之磁 磚所發揮之抗菌力當作1，而評價之。油分解率如下定義 之。在實驗體上塗抹沙拉油lmg/100cm2，將lmW/cm2紫 外線照射7天。然後，測定塗油前、塗油後、照射結束時 之光澤，從下列式子所得之值當作油分解率。 | (照射結束時之光澤)一（塗油後光澤）|Order 62 495384 A7 B7 V. Description of the invention (60) 7: 3, spin-coated on the surface of the tile, and heated at 150 ° C to make a 2-component reference magnetic tablet (paint type). For the two-component reference tiles (barbecue type & coating type), the following evaluation experiments were performed to evaluate the decomposition power of chemical substances. Decomposing power can be directly evaluated from antibacterial power and oil decomposition rate. Here, the antibacterial force is used for the antibacterial rate of the coliform bacteria (Escherichia coil w3110) described in the third embodiment, and the antibacterial force exerted by a tile having a photocatalyst layer formed of a photocatalyst (titanium dioxide) monomer is taken as 1, and evaluate it. The oil decomposition rate is defined as follows. The test subject was coated with salad oil 1 mg / 100 cm2, and lmW / cm2 was irradiated with ultraviolet rays for 7 days. Then, the gloss before, after, and at the end of irradiation were measured, and the value obtained from the following formula was taken as the oil decomposition rate. | (Gloss at the end of irradiation) one (gloss after oiling) |

油分解率(％)= -xlOO | (塗油前光澤)一（塗油後光澤）丨 經濟部中央標準局員工消費合作社印製 又，由光觸媒之化學物質之分解，係主要藉由光激發 之光觸媒所放出之活性氧物種對物質之氧化作用，當作經 光觸媒之化學物質之分解能力之一種指標，可利用光觸媒 之氧化力。在此，藉由一氧化氮（NO)氧化至二氧化氮（N02) 之轉化量作為模型反應，進行各種光觸媒薄膜之NO氧化 力之評價。該NO氧化力使用如第4圖所示之實驗裝置，如 第1實施例之評價實驗1所述，測定CNO/out。接著，從這 已測定之CNO/out及已知實驗氣體濃度（CNOAn)，算出每 個光照射後之經過時間之（CNO/in — CNO/out)，從上述 本紙張尺度適用中國國家標準（CNS ) A4規格（21〇X297公釐） 63 495384 A7 B7 五、發明説明（61 ) (CNO/in — CNO/out)算出從光開始照射經過1小時之間所氧 化之全NO的莫耳數，以此當作NO氧化力。但此時條件係 ，NO氣體（實驗氣體）施以2升/min流入，而樣本片為5cm x50cm 〇 將上述2成分系參考磁磚（燒烤型&塗料型）之抗菌力、 油分解率、NO氧化力示於表2。又，表2之抗菌力、油分 解率、NO氧化力係如上說明，可知令磁磚置於明處下所 得者。 (請先閱讀背面之注意事項再本頁)Oil decomposition rate (%) = -xlOO | (gloss before oiling)-(gloss after oiling) 丨 Printed by the Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs The oxidative effect of reactive oxygen species released by the photocatalyst on substances is used as an indicator of the decomposition ability of the chemical substances through the photocatalyst, and the oxidizing power of the photocatalyst can be used. Here, the NO oxidation power of various photocatalyst films was evaluated by using the conversion amount of oxidation of nitric oxide (NO) to nitrogen dioxide (N02) as a model reaction. This NO oxidation power was measured using an experimental apparatus as shown in Fig. 4, and CNO / out was measured as described in Evaluation Experiment 1 of the first embodiment. Then, from the measured CNO / out and the known experimental gas concentration (CNOAn), calculate the elapsed time (CNO / in — CNO / out) after each light irradiation, and apply the Chinese national standard ( CNS) A4 specification (21 × 297 mm) 63 495384 A7 B7 V. Description of the invention (61) (CNO / in — CNO / out) Calculate the number of moles of total NO oxidized within 1 hour from the start of light irradiation This is used as the NO oxidation power. But at this time, the condition is that the NO gas (experimental gas) is applied at 2 liters / min, and the sample piece is 5cm x 50cm. 〇The above two components are the antibacterial power and oil decomposition rate of the reference tile (grilled & paint type) And NO oxidation power are shown in Table 2. In addition, the antibacterial power, oil decomposition rate, and NO oxidation power of Table 2 are as described above. It can be seen that the tile was obtained by placing the tile in a bright place. (Please read the notes on the back before this page)

訂 線 經濟部中央標準局員工消費合作社印製 本紙張尺度適用中國國家標準（CNS ) A4現格（210X297公釐） 64 495384 A7 B7 五、發明説明（^ ) 〇2 有關燒烤型參考磁磚之分解力評價 添加金屬種 M/Ti02 (%) 金屬 載持法 抗菌力 油分解率 (%) NO氧化力 /// mol hr 無添加 0.000 一 1.0 30 1.9 Cu 0.001 光還原前 載持法 1.2 40 1.6 0.010 光還原前 載持法 1.5 50 2.0 0.100 光還原前 載持法 1.5 50 2.0 1.000 光還原前 載持法 2.0 60 2.4 1.000 單純混合 法 1.5 50 1.9 10.000 光還原前 載持法 1.2 30 1.2 1.000 共沈法 1.6 50 2.0 Ag 0.100 ^ 光還原前 載持法 2.5 50 3.3^ 0.100 單純混合 法 1.5 35 1.9 Pd 0.100 光還原前 載持法 2.0 60 2.4 Fe 0.100 光還原前 載持法 1.5 65 2.4 (請先閱讀背面之注意事項再本頁) 經濟部中央標準局員工消費合作社印製 有關塗料型之參考磁磚之分解力評價 添加金屬種 M/Ti02 (%) 金屬載持 法 抗菌力 油分解率 (%) NO氧化力/ a mol hr 無添加 0.000 — 1.0 50 0.6 Cu 0.001 光還原前 載持法 1.2 50 0.5 0.010 光還原前 載持法 1.5 70 0.6 0.100 光還原前 載持法 2.0 90 0.6 1.000 光還原前 載持法 2.0 90 0.7 1.000 單純混合 法 1.8 55 0.6 1.000 共沈法 1.9 60 0.6 Ag 0.100 光還原前 載持法 3.0 80 1.0 0.100 單純混合 法 2.5 55 0.6 表2 本紙張尺度適用中國國家標準（CNS ) Α4規格（210Χ297公釐） -65 - 495384 經濟部中央標準局員工消費合作社印製 A7 B7五、發明説明（63 ) 從表2得知，燒烤型參考磁磚中，在Cu添加系中，藉 光還原前載持法調整Cu相對於Ti02為1%載持者，具有優 異的抗菌力、油分解力、NO氧化力。Ag添加系中，也還 是光還原前載持法遠比單純混合法具有優異的抗菌力、油 分解力、NO氧化力。藉表中任一金屬之添加，在抗菌力 、油分解力、NO氧化力上皆比沒有添加者提高，因此可 知載持於Ti02之Cu、Ag、Pd、Fe等之金屬可付予1402之 分解力提高。燒烤型中，在Cu添加系中，藉光還原前載 持法調整Cu使Ti02載持有0.1〜l%Cu，顯示具有最高之抗 箭力1又，Ag添加^系遠比Cu添加系具亦高抗菌力。------- 由上述結果可知，在燒烤型及塗料型之參考磁碑中， 藉以Cu、Ag、Pd、Fe等金屬載持於Ti02，可提高分解力 。即，上述金屬持有使Ti02之分解力提高之功能。又，針 對分解力，作為金屬種之載持方法，光還原前載持法遠比 單純混合法優異。進而，調整上述金屬之載持量，可變更 Ti02之分解力。 又，檢討該燒烤型之2成分系之參考磁磚放在暗處下 時之抗菌力時，以單純混合法使Ti02載持有0.1%Cu之參 考磁磚，其抗菌力約0.3。又，用以單純混合法使丁丨02載 持有l%Cu之參考磁磚，其抗菌力也約有0·3。進而，用以 單純混合法使Ti02載持有0.1%Ag之參考磁碑，其抗菌力 也約0.3。如此在暗處下，光觸媒不能顯現其活性，其抗 菌力只能靠所載持之金屬本身發揮而已。然後，金屬無添 加之磁磚，即，只有光觸媒之磁磚時，暗處下之抗菌力幾 (請先閲讀背面之注意事項再本頁)Printed by the Central Bureau of Standards, Ministry of Economic Affairs, Employees' Cooperatives. This paper is printed in accordance with Chinese National Standards (CNS) A4 (210X297 mm) 64 495384 A7 B7 V. Description of the invention (^) 〇 2 Evaluation of decomposition force Addition of metal species M / Ti02 (%) Decomposition rate of antimicrobial oil by metal loading method (%) NO oxidation power // mol hr No addition 0.000-1.0 30 1.9 Cu 0.001 Loading method before photoreduction 1.2 40 1.6 0.010 Supported before photoreduction 1.5 50 2.0 0.100 Supported before photoreduction 1.5 50 2.0 1.000 Supported before photoreduction 2.0 60 2.4 1.000 Simple hybrid method 1.5 50 1.9 10.000 Supported before photoreduction 1.2 30 1.2 1.000 Co-precipitation Method 1.6 50 2.0 Ag 0.100 ^ Support method before photoreduction 2.5 50 3.3 ^ 0.100 Simple hybrid method 1.5 35 1.9 Pd 0.100 Support method before photoreduction 2.0 60 2.4 Fe 0.100 Support method before photoreduction 1.5 65 2.4 (Please read first Note on the back page) The evaluation of the decomposing force of the reference type ceramic tile printed by the Consumer Standards Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs. Oil decomposition rate (%) NO oxidation power / a mol hr without adding 0.000 — 1.0 50 0.6 Cu 0.001 Support method before photoreduction 1.2 50 0.5 0.010 Support method before photoreduction 1.5 70 0.6 0.100 Support method before photoreduction 2.0 90 0.6 1.000 Pre-reduction loading method 2.0 90 0.7 1.000 Simple mixing method 1.8 55 0.6 1.000 Co-precipitation method 1.9 60 0.6 Ag 0.100 Pre-reduction loading method 3.0 80 1.0 0.100 Simple mixing method 2.5 55 0.6 Table 2 This paper scale applies to China National Standard (CNS) A4 Specification (210 × 297 mm) -65-495384 Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs A7 B7 V. Description of the Invention (63) It is known from Table 2 that among the barbecue reference tiles, the Cu In the additive system, Cu is adjusted to 1% of the carrier of Ti02 by the support method before light reduction, and has excellent antibacterial power, oil decomposition power, and NO oxidation power. Among Ag-added systems, the pre-photoreduction method has far superior antibacterial, oil-decomposing, and NO-oxidizing power compared to the simple mixing method. By the addition of any metal in the table, the antibacterial power, oil decomposition power, and NO oxidation power are all higher than those without the addition. Therefore, it can be known that Cu, Ag, Pd, Fe and other metals supported on Ti02 can be paid to 1402. Increased resolution. In the barbecue type, in the Cu addition system, the Cu is adjusted to support 0.1 to 1% Cu by using the pre-reduction support method, and Ti02 is shown to have the highest arrow resistance. Also, the Ag addition system is far more than the Cu addition system. Also high antibacterial power. ------- From the above results, it can be seen that in the reference magnetic stele of grill type and paint type, by dissolving Cu, Ag, Pd, Fe and other metals on Ti02, the decomposition force can be improved. That is, the above-mentioned metal has a function of improving the decomposition force of Ti02. In addition, for the decomposition force, as a method for supporting the metal species, the support method before photoreduction is far superior to the simple mixing method. Furthermore, by adjusting the supporting amount of the above metal, the decomposition force of Ti02 can be changed. In addition, when reviewing the antibacterial power of the barbecued 2-component reference tile when placed in a dark place, the reference tile that holds Ti02 with 0.1% Cu by a simple mixing method has an antibacterial force of about 0.3. In addition, by using a simple mixing method, the reference tile containing 1% Cu in Ding 02 has an antibacterial force of about 0.3. Furthermore, by using a simple mixing method to make Ti02 carry a reference magnetic monument containing 0.1% Ag, its antibacterial power is also about 0.3. In the dark, the photocatalyst cannot show its activity, and its antibacterial ability can only be exerted by the metal itself. Then, the metal is not added to the tile, that is, when only the photocatalyst tile is used, the antibacterial power in the dark is less (please read the precautions on the back before this page)

訂 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -66 - 495384 A7 B7 經濟部中央標準局員工消費合作社印製 五、發明説明（64) 乎為零，因此該等參考磁磚可發揮金屬本身展現之抗菌力 以及在明處下可發揮超越只具有光觸媒之磁磚所發揮之抗 菌力的抗菌力。例如用以單純混合法使Ti02載持有0.1%Cu 之參考磁磚之明處下之抗菌力，由表2可知，為1.5。此值 遠超過Cu自己發揮之抗菌力（0.3)與只有光觸媒之磁磚抗 菌力（1)之和。因此，可謂用以Cu載持於Ti02遠比將Cu及 Ti02單獨組合者，能得到較大之結果。 在此，沿襲上述參考磁磚之效果，說明第6、7實施例 之實施例磁碑。在這第6、7實施例，也針對新的評價項目 親木牲作評價。貪先説明親水性及表面污濁之關係^再說 明親水性之實驗等。 到目前已知，將表面作成親水性可使其表面防止污染 (高分子、第44卷、1995年5月號、p307)。其親水性可換 算成與水之接觸角，該接觸角愈小，對水之濕潤性愈可提 高，使接觸於親水性表面的水難以停留在該接觸表面。如 此，若水難以停留的話，包含在雨水等城市塵埃等污垢成 分可跟水一起從該親水性表面流掉，提高防污效果。 因此，而有各種提案關於將付有親水性親水性之接枝 聚合物塗抹在建築物外壁等，謀求在這接枝聚合物之塗膜 上防止污染，但是用以換算成與水之接觸角之親水性約為 30〜40° ，故在表面上水較容易停留而使防污效果及防霧 效果未必充分。又，以黏土礦物代表之無機質塵埃其與水 之接觸角為20〜50°左右，因此與具有上述接觸角之接枝聚 合物產生親和性，容易附著於接枝聚合物表面，隨此接枝 (請先閲讀背面之注意事項再本頁)The paper size of the edition applies to the Chinese National Standard (CNS) A4 specification (210X297 mm) -66-495384 A7 B7 Printed by the Staff Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs 5. The invention description (64) is almost zero, so these reference The brick can exert the antibacterial power exhibited by the metal itself, and in the bright place, it can exert the antibacterial power beyond the antibacterial power exerted by the tiles with only photocatalyst. For example, using a simple mixing method, the antibacterial power of Ti02 loaded with 0.1% Cu reference tiles under the bright spot can be known from Table 2 as 1.5. This value is far more than the sum of the antibacterial power (0.3) exerted by Cu and the antibacterial power (1) of the tile with only photocatalyst. Therefore, it can be said that using Cu to support Ti02 is far more effective than combining Cu and Ti02 alone. Here, following the effects of the reference tile, the magnetic stele of the sixth and seventh embodiments will be described. In the sixth and seventh embodiments, evaluation is also performed on the new evaluation item, Pro-Livestock. The relationship between hydrophilicity and surface fouling will be explained first, and then experiments on hydrophilicity will be explained. Until now, it has been known that making a surface hydrophilic makes it possible to prevent the surface from being contaminated (Polymer, Vol. 44, May 1995, p307). Its hydrophilicity can be converted into a contact angle with water. The smaller the contact angle, the higher the wettability to water, making it difficult for water contacting a hydrophilic surface to stay on the contact surface. In this way, if water is difficult to stay, dirt components such as urban dust such as rainwater can flow out of the hydrophilic surface together with water, thereby improving the antifouling effect. Therefore, various proposals have been made to apply a hydrophilic polymer to the outer wall of a building, etc., in order to prevent contamination on the coating film of the graft polymer, but to convert it into the contact angle with water The hydrophilicity is about 30 ~ 40 °, so the water stays on the surface more easily, so the antifouling effect and antifog effect may not be sufficient. In addition, the inorganic dust represented by clay minerals has a contact angle with water of about 20 to 50 °. Therefore, it has affinity with the graft polymer having the above-mentioned contact angle, and is easy to adhere to the surface of the graft polymer. (Please read the notes on the back before this page)

-訂 本紙張尺度適用中國國家標準（CNS ) A4規格（210X 297公釐） 67 495384 經濟部中央標準局員工消費合作社印製 A7 B7 五、發明説明（^ ) 65 聚合物之塗膜或薄膜，特別是難以高度展現對無機質塵埃 之防污效果。 又，將接觸角作成遠比多含有親油性成分之城市塵埃 及黏土礦物之無機質塵埃等之接觸角還小時，使該等塵埃 不能在基材表面上發揮親和性，更能提高防污效果。並且 ，接觸角愈接近零度、親水性愈高，則水愈能在基材表面 上呈膜狀擴散而流動，不用說上述之城市塵埃連無機質塵 埃也可輕易跟水一起從表面流掉。此時，為以提高防污效 果，令接觸角為20°以下接近零之值為佳。 一將用了光觸媒^本發明實施例（第6、7實施例）二沿襲 如此問題檢討之結果時，藉光觸媒所呈現之觸媒反應生成 氫氧基· ΟΗ，檢討如上述成為親水性之指標的與水之接 觸角。下列為其實驗之概要。 各自針對已述第6、第7實施例之實施例磁磚、2成分 系、3成分系之參考磁磚、及比較例磁磚，準備燒烤型之 磁碑，用以適當大小樣本片備用。然後，針對在磁磚製造 後照射紫外線之燈泡（波長為320〜38Onm下，樣本片之受 光量為lmW/cm2)照射24小時後（明處下），及藉該光觸媒 之活性幾乎完全停止時經充分時間放在暗處後（暗處下）測 定滴在該樣本片之水滴之接觸角。將測定結果示於表3。 本紙張尺度適用中國國家標準（CNS ) A4祝格（210 X 297公釐） (請先閱讀背面之注意事項再本頁) 、言 68 495384 A7 B7 經濟部中央標準局員工消費合作社印製 發明説明Q ) 燒烤型 區分 配合概要 親4 mM c性 觸角)p 氧化分解力 薄膜摩 斯魏 明時 暗時 抗菌 力 油分解率 (%) NOIL化力 //zmolhr 嫌{雜磚 Ti02 10 27 1.0 30 1.9 4 第7實施鄕磚 (3成分） T102+Al203+Si02 3 20 1.0 30 1.9 6 ^^^^2成分） T02+Ag 10 25 2.5 50 3.3 4 封磁4(2成分） TiOffCu 10 27 1.5 50 2.4 4 第6實施沖^磚 (4成分） Ti02+Al203+Si02+Ag 3 20 2.5 50 3.3 6 第6實施例磁碑 (4成分） Ή02+Α12〇3+8ί〇2+Οι 6 20 1.5 50 2.4 6 (4成分） Ήζξ+AipiFacpTd 3 20 2.8- 50 6.0 6 第6實施紳^碑 (4成分） T102+Al203+Si02+Fe 3 20 1.5 50 3.0 6 第6實施例磁碑 (4成分） Ti02+Al203+SA+Ni 3 20 2.5 50 3.1 6 第6實施例^碑 (4成分） Ή02+Α12〇3+8ί〇2+0, 3 20 1.5 50 2.4 6 第6實施ί觸碑 (4成分） Ti02+Al203+Si02~KZb 3 20 1.5 50 1.7 6 第6實施例磁碑 (4成分） Ti02+Al203+Si02+R 3 20 2.8 50 6.0 6 第6實胁m磚 (4成分） T102+Al203+Si02+Au 3 20 1.5 50 2.4 6 第6實施例^磚 (4成分） Ti02+Al203+Si02+Rh 3 20 1.5 50 2.4 6 第6實施例磁磚 (4成分） in〇2+Al203+Si02+Rii 3 20 1.5 50 2.4 6 表3 (請先閱讀背面之注意事項再本頁) |裝- 訂 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） 69 495384 五、發明説明L ) 從這表3之結果來看，與檢討了金屬配合之影響之2成 分系參考磁碑同樣地，4成分系實施例磁磚（第6實施例）用 以配合表中Cii、Ag等之金屬，都可提高抗菌力、油分解 力、NO氧化力’而可提高分解力。並且，可得到一遠超 過表中之Cu、Ag之金屬本身可展現之抗菌力與只有光觸 媒之比較例磁磚，或是與3成分系實施例磁磚之抗菌力之 和之抗菌力。而且，表面層之摩斯硬度係與不具有表面層 之單純磁磚所具有之摩斯硬度同等，具備有作為磁磚之實 用性。 經濟部中央標準局員工消費合作社印製 一&^ 6一、第1施例之接觸角，不論明時或暗時，比 比較例磁磚來得小，因此可知，在表面層與Ti〇2共同配合 之Si〇2或者是Al2〇3或者這兩者如上述經氫氧基之吸著， 可付予磁碑表面之親水性的提高。並且，可知用以配合表 中之Cu、Ag等之金屬，不會使接觸角變大，即，使親水 性降低。從該等結論，分解力及親水性同時具備之功能性 薄膜或具有如此薄膜之功能材料，可經可付予分解力提高 之 Cu、Ag、Pd、Fe、Ni、Cr、Co、Pt、Au、Rh、Ru 等金 屬載持於Ti〇2、以及付予親水性提高之Si〇2或Al2〇3、或 這2者與Ti02配合製造之。 又，該第6、第7實施例之實施例磁磚，在該表面層上 除Ti〇2之外，還含有ΑΙΑ3，因此如第1、第2實施例中之 說明，當然也具有氮氧化物等有害物質之削減效果。又， 不含上述金屬之3成分系之第7實施例之實施例磁磚，其N〇 氧化力與比較例同等，而第6、第7實施例之實施例磁磚如 本纸張又度適) A4規格（⑽—公釐) 495384 A7 B7 五 發明説明 第1、第2實施例中之說明，將中間生成物（N02)化學轉化 成硝酸，因此可連這N02都削減。藉此，根據第6、第7實 施例之實施例磁磚，係不與可發揮含有NO、N02之有害 物質全體之削減效果矛盾。 檢討上述分解力之提高效果對第6、第7實施例之實施 例磁磚是否也可得到，其檢討之結果示於表4。藉此可知 ，即使是塗料型磁碑，藉第6、第7實施例之實施例磁磚， 經表中金屬之配合，抗菌力、油分解力、NO氧化力都可 提高，而可提高分解力。又，藉該塗料型之第6、第7實施 例之實施例磁碑，與上述燒烤型之實施例磁磚同樣，經由 與Ti02共同配合之Si02之氫氧基吸著，可付予提高磁碑表 面之親水性。又，即使是塗料型物品時，其表面層具有4H 之鉛筆硬度，因此具備有作為磁磚之實用性。 塗料型 請 先 閲 讀 背 面 之 注 意 事 項 μ 訂 經濟部中央標準局員工消費合作杜印製 區分 酉略概要 氧化分解力 鉛筆硬度 抗菌力 油分雜/〇 NO 氧^it/7/"xnolhr 封鱗2成分） Ii02+Si02 1 50 0.6 4H 第7實施分崎3成分） Ti02+Al203+Si02 1 50 0.6 4H #4鹤3成分） ]02+Ag+Si02 2.5 90 1.0 4H 辦鐵3成分） Ti024Cu+Si02 2 90 0.7 4H 第6實施分J^|(4成分） Ή02+Α1203+8ί02+Α8 3 90 1.0 4H 第6實施例磁碑(4成分） Έ〇2+Α12〇3+5ί02·+Οι 2 90 0.7 4H 第獅分酬4成分） Ti02+Al203+Si02+Pd 2.8 55 6.0 4H 第6實施命酬4成分） T102+AI203+Si02+Fe 1.5 50 3.0 4H 第6實施命㈣4成分） Ti02+Al203+Si02+Ni 2.5 50 3.1 4H 第6細^K4成分） Ti02+Al203+Si02+Cr 1.5 50 2.4 4H 第6實施_鐵4成分） Ή02+Α1203+8ί02·Ηϋο 1.5 30 1.7 4H 第6實施钟辦K4成分） TO2+Al203+Si02+R 2.8 60 6.0 4H 第6實施例離1(4成分） Ti02+Al203+Si02+Au 1.5 50 2.4 4H 第6攸_碟4成分） Ti02+Al203+Si02+Rh 1.5 50 2.4 4H 第6實施例磁_(4成分） T102+Al203+Si02+Ru 1.5 50 2.4 4H 表4 本紙張尺度適用中國國家標準（CNS ) A4規格（2!〇χ297公釐） 71 在此，針對上述Cu、Ag等之配合量，以光觸媒/金屬/ 氧化紹/氧化矽之4成分系之第6實施例之實施例磁碑為例 說明之。第6實施例之實施例磁磚配合比率決定比（si〇2/ (Ti02+Al203+Si02))以1/10為一定，將金屬之重量為c、Ti02 之重量為d時，準備各種c/d(金屬配合比）值之磁磚。然後 ’根據各實施例磁磚，檢討其金屬配合比與抗菌力之關係 。將結果依燒烤型、塗料型分別示於第11、12圖。又，此 時之抗菌力，將光觸媒/氧化鋁/氧化矽之3成分系之第7實 施例之實施例磁磚可發揮之抗菌力當作1表示。 -------Λ 12 圖可色，Ag、Pd、Pt、Cu、Cr任一種 經濟部中央標準局員工消費合作社印製 金屬，其金屬配合比如果在0.00001以上時，燒烤型、塗 料型都可得到「值1」以上之抗菌力。又，Ag、Pd、Pt金 屬配合比在0·001左右時，形成抗菌力之最大值，Cu、Cr 則在0.01為最大值，之後抗菌力則傾向於減少之方向。是 故，可知Ag、Pd、Pt、Cu、Cr等金屬，其金屬配合比配 合成0.00001〜0.05之值為佳。即，該等金屬若配合成〇·〇〇〇〇 1 以上之金屬配合比時，就不會有金屬太少，完全不能付予 提高抗菌力之事態發生，若在0.05以下時，則不會有金屬 相對於光觸媒（Ti02)顯得過多，而導致光觸媒之觸媒反應 不良影響發生之事態，故理想。又，可知含有Ag、Pd、Pt 作為第4成分之表面層之實施例磁碑之抗菌力高於含有cu 、Cr作為第4成分之表面層之實施例磁碑。 在此，針對用以上述光觸媒溶膠形成於磁磚表面之表 面層之表面性狀態係以光觸媒/金屬/氧化鋁/二氧化石夕之4 本紙張尺度適用中國國家標準（CNS ) A4規格（21〇χ29<7公釐） 495384 、發明説明k 項 成分系第6實施例之實施例磁磚及光觸媒/氧化鋁/二氧化 矽之3成分系第7實施例之實施例磁磚為例說明之。此時， 第6、7實施例之實施例磁碑令配合比率決定比（Si〇2/ (Ti〇2+Al2〇3+Si〇2))設定為1/10 ’準備具有各種表面性狀 態之膜厚之表面層之磁磚。然後，針對各實施例磁磚檢討 該表面層膜厚及接觸角、抗菌力、油分解力或NO氧化力 之關係。將結果示於第13〜17圖。. 訂 第13〜16圖係針對4成分系第6實施例之實施例磁磚（燒 烤型）所得之結果。其中，第13圖係表面層膜厚及明時接 觸爲_之麗^级圖、圖係表面層膜厚及抗菌力之關係線 圖、第15圖係表面層膜厚及油分解力之關係線圖、第16圖 係表面層膜厚及NO氧化力之關係線圖。又，此時之抗菌 力以具有含有光觸媒/氧化鋁/二氧化矽之表面層之磁磚可 發揮之抗菌力為1作代表。第17圖係3成分系第7實施例之 實施例磁磚（燒烤型）中之表面層膜厚及明時接觸角之關係 線圖。又，4成分系之實施例磁磚以在表面層中各含有入呂 、Pd、Pt、Cn、Cr之磁碑為例，針對膜厚〇〇〇5〜3/zn^ 討之。 經 濟 部 中 央 標 準 局 員 工 消 f 合 作 社 印 製 3成分系、4成分系之實施例磁磚，在其表面層中因含 有經已述氫氧基的吸著，可付予親水性之提高，故可謀求 藉含有Si〇2可得到之功能（親水性之提高）。此時之親水性 的提高，如已述，可以有無小接觸角而確定之，在2〇〇以 下之接觸角為佳。從該觀點，檢討第13圖 '第17圖燒烤型 之3成分系、4成分系之實施例磁磚，若表面層之膜厚比〇 本紙張尺度適财關家標準（CNS ) A4規格（ -73 495384 、發明説明 厚時，可得到2〇。以下之小的接觸角，能得到經提高 親水性之防污效果，故佳。表面層膜厚若大於〇〇i#m時 可得到20。以下之接觸角是因，膜（表面層）不會太薄，因 此即使基材具有大的接觸角，也可呈現形成於該基材（磁 磚）之表面層本身之接觸角。 如第13圖、第17圖所示，表面層膜厚若比〇.5/zm以 上時’接觸角則維持在小值。另一方面，表面層膜厚愈厚 ’則令表面層之每單位密接面積之重量增加，因此表面層 如果太厚，則招致基材與表面層之密接性降低，使表面層 剝獻丄係從AM —與表面層ϋ著性維持的觀點而言 ’表面層膜厚低於3em為佳。又，表面層膜厚太厚，紫 外線不能浸透到表面層之下層，則表面層不能以全體發揮 光觸媒之作用，因此從此處也可說表面層膜厚在3am以 下者為佳。 接著，如第14〜16圖所示，若表面層膜厚在上述所定 範圍内（約0.01〜3 #m)，可確實提高抗菌力油分解力以及 NO氧化力，故佳。 經濟部中央標準局員工消費合作社印製 (請先閲讀背面之注意事項再一一^本頁) 除上述表面層膜厚之外，還檢討了下列表面性狀態。 一照射紫外線，則藉光觸媒有激發電子與氫氧基同時 生成。藉此，經由該激發電子，可限定在表面層上可發生 之現象，觀察其態樣，可知該激發電子之生成狀態，即， 氫氧基· OH之生成狀態。第6、第7實施例之實施例磁磚 ，因其表面層含有吸著並加以保持之Si02，故藉光觸媒生 成之氫氧基· OH，可保持於該Si02。是故，藉光觸媒之 74 經濟部中央標準局員工消費合作社印製 495384 A7 ____ B7 _ 五、發明説明（^ ) 激發電子生成愈多，則生成之氫氧基· OH的量愈多，結 果Si〇2之表面上之鼠氧基选度愈面，水之接觸角愈小，則 親水性可提高。因此，以表面層上附著有硝酸銀溶液之狀 癌下，進彳亍紫外線照射時，附著於表面層上之硝酸銀溶液 中的銀離子之電荷經由此激發電能而變化，並有呈色反應 ’在紫外線照射前後，可觀察色差△E。該色差△E係因 作用於反應之激發電子愈多則愈大，可變成一表示親水性 程度之指標。所以如下進行觀察色差AE。 在測定色差ΔΕ時，作為顯現呈色反應之試藥，使用 一羞AH後塵銀溶液。該溶液中所含有之銀離子與藉光 觸媒所生成之激發電子（e—)相反應，以銀析出。反應式如 下所示。如此以銀析出，使硝酸銀溶液之附著表面上變色 成茶色或黑色，可明確得到色差△E。-The size of the paper is in accordance with the Chinese National Standard (CNS) A4 (210X 297 mm) 67 495384 Printed by the Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs A7 B7 V. Description of the invention (^) 65 Polymer coating or film, In particular, it is difficult to exhibit a high antifouling effect on inorganic dust. In addition, the contact angle is much smaller than that of urban dust containing more lipophilic components and inorganic dust of clay minerals, so that the dust cannot exhibit affinity on the surface of the substrate, and the antifouling effect can be improved. Moreover, the closer the contact angle is to zero degrees and the higher the hydrophilicity, the more water can diffuse and flow on the surface of the substrate. Needless to say, the above-mentioned urban dust and inorganic dust can easily flow off the surface together with water. At this time, in order to improve the antifouling effect, it is better to set the contact angle to a value below 20 ° and close to zero. First, photocatalysts will be used. ^ Embodiments of the present invention (sixth and seventh embodiments). When the results of such a review are followed, the reaction of the catalysts presented by the photocatalyst will generate hydroxyl groups. 〇Η, review the above as an indicator of hydrophilicity. Contact angle with water. The following is a summary of the experiments. For the example tiles of the sixth and seventh embodiments, the reference tiles of the two-component system, the reference tiles of the three-component system, and the comparative example tiles, a grill-type magnetic tablet is prepared for use as a sample of a suitable size. Then, after the tile was irradiated with ultraviolet light (at a wavelength of 320 to 38 nm, and the amount of light received by the sample piece was lmW / cm2) after 24 hours (under the light), and when the photocatalyst's activity was almost completely stopped, After being placed in the dark place for a sufficient time (under the dark place), the contact angle of the water droplets dripped on the sample piece is measured. The measurement results are shown in Table 3. This paper size is applicable to the Chinese National Standard (CNS) A4 greetings (210 X 297 mm) (please read the precautions on the back before this page), word 68 495384 A7 B7 printed by the Central Consumers Bureau of the Ministry of Economic Affairs Q) Outline of barbecue-type differentiation and coordination Pro 4 mM c-type antennae) p Oxidative decomposition film Moss Weiming dark antibacterial oil decomposition rate in dark (%) NOIL chemical power // zmolhr Suspect {Miscellaneous brick Ti02 10 27 1.0 30 1.9 4 7Implemented concrete brick (3 components) T102 + Al203 + Si02 3 20 1.0 30 1.9 6 ^^^^ 2 components) T02 + Ag 10 25 2.5 50 3.3 4 Magnetic seal 4 (2 components) TiOffCu 10 27 1.5 50 2.4 4 No. 6Implementing bricks (4 components) Ti02 + Al203 + Si02 + Ag 3 20 2.5 50 3.3 6 Magnetic stele of the sixth embodiment (4 components) Ή02 + Α12〇3 + 8ί〇2 + 〇ι 6 20 1.5 50 2.4 6 ( 4 components) Ήζξ + AipiFacpTd 3 20 2.8- 50 6.0 6 The sixth implementation of the tablet (4 components) T102 + Al203 + Si02 + Fe 3 20 1.5 50 3.0 6 The sixth embodiment of the magnetic tablet (4 components) Ti02 + Al203 + SA + Ni 3 20 2.5 50 3.1 6 6th embodiment ^ stele (4 components) Ή02 + Α12〇3 + 8ί〇2 + 0, 3 20 1.5 50 2.4 6 6th implementation 触 contact monument (4 components) Ti02 + Al203 + Si02 ~ KZb 3 20 1.5 50 1.7 6 Magnetic stele of the sixth embodiment (4 components) Ti02 + Al203 + Si02 + R 3 20 2.8 50 6.0 6 6th solid m brick (4 components) T102 + Al203 + Si02 + Au 3 20 1.5 50 2.4 6 6th Example ^ Brick (4 components) Ti02 + Al203 + Si02 + Rh 3 20 1.5 50 2.4 6 6th Example Tile (4 components) in 〇2 + Al203 + Si02 + Rii 3 20 1.5 50 2.4 6 Table 3 (Please read the notes on the back first, then this page) | Binding-The size of the paper is applicable to the Chinese National Standard (CNS) A4 (210X297 mm) 69 495384 5. Description of the invention L) From this table 3 As a result, similar to the two-component reference magnetic stele that reviewed the effect of metal blending, the four-component example tile (sixth example) used to match the metals in the table such as Cii and Ag can be improved. Antibacterial power, oil decomposing power, and NO oxidation power can increase the decomposing power. In addition, it is possible to obtain an antibacterial force that far exceeds the antibacterial force exhibited by the metals Cu and Ag in the table and the comparative example tile with only the photocatalyst, or the antibacterial force combined with the antibacterial force of the 3-component example tile. In addition, the Morse hardness of the surface layer is the same as that of a simple tile without a surface layer, and has practicality as a tile. Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs & ^ 61. The contact angle of the first example is smaller than that of the comparative example tile in light or dark, so it can be seen that the surface layer and Ti〇2 The combined Si02 or Al203 or both can be absorbed by the hydroxyl group as described above to increase the hydrophilicity of the magnetic tablet surface. In addition, it can be seen that the metals used for blending Cu, Ag, and the like in the table do not increase the contact angle, that is, decrease the hydrophilicity. From these conclusions, functional films or functional materials that have both decomposability and hydrophilicity can pass through Cu, Ag, Pd, Fe, Ni, Cr, Co, Pt, Au that can be decomposed with improved decomposability. Metals such as, Rh, and Ru are supported on Ti02, and Si02 or Al203, which is provided with improved hydrophilicity, or both are manufactured in combination with Ti02. In addition, the tiles of the sixth and seventh embodiments also include AIA3 in addition to Ti02 on the surface layer. Therefore, as described in the first and second embodiments, they also have nitrogen oxidation. Effect of reducing harmful substances such as substances. In addition, the example tile of the seventh example of the three-component system excluding the above metal has the same NO oxidation power as that of the comparative example, and the example tiles of the sixth and seventh examples are as good as this paper. (Applicable) A4 specification (公 —mm) 495384 A7 B7 5. Description of the invention In the first and second embodiments, the intermediate product (N02) is chemically converted into nitric acid, so even this N02 can be reduced. Therefore, the tiles according to the examples of the sixth and seventh embodiments do not contradict the effect of reducing the total harmful substances containing NO and N02. It is examined whether the improvement effect of the above-mentioned dissolving power is also available for the tiles of the sixth and seventh embodiments. The results of the review are shown in Table 4. From this, it can be seen that even if it is a paint-type magnetic tablet, the antibacterial force, oil decomposing force, and NO oxidation force can be improved by the combination of the metals in the table according to the example tiles of the sixth and seventh embodiments, and the decomposition can be improved. force. In addition, according to the magnetic monuments of the sixth and seventh embodiments of the coating type, similar to the magnetic tiles of the grill type, the magnetic field of Si02 combined with Ti02 can be absorbed to increase the magnetic field. The surface of the tablet is hydrophilic. In addition, even in the case of paint-type articles, the surface layer has a pencil hardness of 4H, and therefore has practicality as a tile. Please read the precautions on the back of the coating type μ Ordering the consumer cooperation of the Central Standards Bureau of the Ministry of Economic Affairs Du printed divisions Summary of oxidation and decomposition power Pencil hardness Antibacterial oil miscellaneous / 〇NO oxygen ^ it / 7 / " xnolhr Seal scale 2 Ingredients) Ii02 + Si02 1 50 0.6 4H 3rd component of the seventh implementation) Ti02 + Al203 + Si02 1 50 0.6 4H # 4 Crane 3 ingredients)] 02 + Ag + Si02 2.5 90 1.0 4H Iron 3 ingredients) Ti024Cu + Si02 2 90 0.7 4H 6th implementation J ^ | (4 components) Ή02 + Α1203 + 8ί02 + Α8 3 90 1.0 4H 6th example magnetic tablet (4 components)） 〇2 + Α12〇3 + 5ί02 · + Οι 2 90 0.7 4H 4th part of the lion's remuneration) Ti02 + Al203 + Si02 + Pd 2.8 55 6.0 4H 6th part of the 4th part of life reward) T102 + AI203 + Si02 + Fe 1.5 50 3.0 4H 4th part of the 4th part of life part of Ti02 + Al203 + Si02 + Ni 2.5 50 3.1 4H 6th fine K4 component) Ti02 + Al203 + Si02 + Cr 1.5 50 2.4 4H 6th implementation _iron 4 component) Ή02 + Α1203 + 8ί02 · Ηϋο 1.5 30 1.7 4H 6th implementation clock office K4 Composition) TO2 + Al203 + Si02 + R 2.8 60 6.0 4H 6th Example 1 (4 components) Ti02 + Al203 + Si02 + Au 1.5 50 2.4 4H 6th _ disc 4 component) Ti02 + Al203 + Si02 + Rh 1.5 50 2.4 4H 6th Example Magnetic_ (4 components) T102 + Al203 + Si02 + Ru 1.5 50 2.4 4H Table 4 This paper size applies the Chinese National Standard (CNS) A4 specification (2 × 〇297 mm) 71 Here, for The blending amounts of the above-mentioned Cu, Ag and the like are described by taking the example magnetic tablet of the sixth example of the four-component system of photocatalyst / metal / salt oxide / silicon oxide as an example. In the example of the sixth embodiment, the ratio of determining the mixing ratio of the tiles (si〇2 / (Ti02 + Al203 + Si02)) is constant to 1/10. When the weight of the metal is c and the weight of Ti02 is d, various types of c are prepared. / d (metal mix ratio) value of the tile. Then, according to the tiles of each embodiment, the relationship between the metal mixing ratio and the antibacterial power was reviewed. The results are shown in Figs. 11 and 12 according to the grill type and the paint type, respectively. The antibacterial force at this time is represented by 1 as the antibacterial force exhibited by the tile of the seventh example of the three-component system of photocatalyst / alumina / silica. ------- Λ 12 The picture can be colored, Ag, Pd, Pt, Cu, Cr is any kind of metal printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs. If the metal mix ratio is above 0.00001, grill type, paint Type can get antibacterial power of "value 1" or more. In addition, when the metal, Ag, Pd, and Pt metal compounding ratio is about 0.001, the maximum value of antibacterial power is formed, and the maximum value of Cu and Cr is 0.01, and the antibacterial power tends to decrease afterwards. Therefore, it can be seen that metals such as Ag, Pd, Pt, Cu, and Cr have a metal mixing ratio of 0.00001 to 0.05. That is, if these metals are blended to a metal blending ratio of 0.0000.001 or more, there will not be too little metal, and it will not be possible to increase the antibacterial effect. If it is less than 0.05, it will not It is ideal to have too much metal relative to the photocatalyst (Ti02), which leads to the adverse reaction of the photocatalyst. In addition, it can be seen that the antimony force of the magnetic stele of the example containing the surface layer of Ag, Pd, and Pt as the fourth component is higher than that of the magnetic stele of the example containing the surface layer of cu and Cr as the fourth component. Here, the surface state of the surface layer formed on the surface of the tile with the above photocatalyst sol is based on Photocatalyst / Metal / Alumina / Stone Dioxide. This paper size applies the Chinese National Standard (CNS) A4 specification (21 〇χ29 < 7 mm) 495384, invention description k-item composition example of the sixth embodiment tile and photocatalyst / alumina / silica dioxide 3-component system example of the seventh embodiment . At this time, the ratio of the ratio of the magnetic stele order of the examples of the sixth and seventh examples (Si〇2 / (Ti〇2 + Al2〇3 + Si〇2)) is set to 1/10. The thickness of the surface layer of the tile. Then, the relationship between the film thickness of the surface layer and the contact angle, the antibacterial force, the oil decomposing force, or the NO oxidation force was examined for each example tile. The results are shown in Figs. 13 to 17. Orders 13 to 16 are the results obtained for the tile of the sixth embodiment of the four-component system (fired type). Among them, Fig. 13 shows the film thickness of the surface layer and the contact at bright time is a ^ grade diagram, the diagram of the relationship between the film thickness of the surface layer and the antibacterial force, and the relationship between the film thickness of the surface layer and the oil decomposing force in Fig. 15 The line graph and FIG. 16 are the relationship graphs of the surface layer film thickness and the NO oxidation power. The antibacterial power at this time is represented by the antibacterial power of a tile having a surface layer containing a photocatalyst / alumina / silica dioxide as one. Fig. 17 is a graph showing the relationship between the film thickness of the surface layer and the contact angle at bright time in the example tile (grilled type) of the third embodiment of the three-component system. In the example of the four-component tile, a magnetic tablet containing each of Lu, Pd, Pt, Cn, and Cr in the surface layer is taken as an example, and the thickness of the film is set to 0.05 to 3 / zn ^. The staff of the Central Standards Bureau of the Ministry of Economic Affairs has printed the three-component and four-component example tiles of the cooperative. The surface layer contains the adsorption of the aforementioned hydroxyl groups, which can improve the hydrophilicity. A function (improved hydrophilicity) that can be obtained by containing SiO2 can be sought. The improvement of hydrophilicity at this time can be determined by the presence or absence of a small contact angle, as described above, and a contact angle of less than 2000 is preferred. From this point of view, review the example of the three-component and four-component grilled tiles of Figures 13 and 17, and if the film thickness ratio of the surface layer is 0, this paper size is suitable for financial standards (CNS) A4 specifications ( -73 495384 When the description of the invention is thick, a value of 20 can be obtained. A small contact angle below can obtain an antifouling effect with improved hydrophilicity, which is good. If the thickness of the surface layer is greater than 0〇i # m, 20 can be obtained. The following contact angle is because the film (surface layer) will not be too thin, so even if the substrate has a large contact angle, the contact angle formed on the surface layer of the substrate (tile) can be presented. As shown in Fig. 13 and Fig. 17, if the thickness of the surface layer is more than 0.5 / zm, the 'contact angle is maintained at a small value. On the other hand, the thicker the thickness of the surface layer', the closer the unit of the surface layer is. The weight of the area increases. Therefore, if the surface layer is too thick, the adhesion between the substrate and the surface layer will be lowered, and the surface layer peeling will be from the viewpoint of AM—the surface layer adhesion is maintained. It is better to be less than 3em. Also, the film thickness of the surface layer is too thick, and the ultraviolet rays cannot penetrate the surface layer In the lower layer, the surface layer cannot function as a photocatalyst in its entirety. Therefore, it can be said from this that the surface layer film thickness is less than 3am. Then, as shown in Figures 14 to 16, if the surface layer film thickness is within the above-mentioned range, (Approximately 0.01 ~ 3 #m), it can improve the antibacterial oil decomposing power and NO oxidation power, so it is good. Printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs (please read the precautions on the back first and then ^ this page) ) In addition to the above-mentioned surface layer film thickness, the following surface properties were also reviewed. Upon irradiation with ultraviolet rays, excited electrons and hydroxyl groups are generated simultaneously by the photocatalyst. By this, the excited electrons can be limited to the surface layer. When the phenomenon occurs, the state of generation of the excited electrons, that is, the generation state of the hydroxyl group and OH, can be known. The tiles of the examples of the sixth and seventh embodiments, because the surface layer contains absorbing and applying The Si02 is retained, so the hydroxyl group · OH generated by the photocatalyst can be retained in the Si02. Therefore, the photocatalyst is printed by the Consumer Cooperative of the Central Standard Bureau of the Ministry of Economic Affairs and printed by 495384 A7 ____ B7 _ V. Description of the invention ^) The more the excited electrons are generated, the more the amount of hydroxide and OH are generated. As a result, the more the selectivity of the rat oxy group on the surface of SiO 2 and the smaller the contact angle of water, the higher the hydrophilicity. Therefore, in the case of a cancer in which a silver nitrate solution is attached to the surface layer, when the ultraviolet rays are irradiated, the charge of silver ions in the silver nitrate solution attached to the surface layer changes through this exciting electric energy, and there is a color reaction. Before and after ultraviolet irradiation, the color difference ΔE can be observed. The color difference ΔE is because the more excited electrons acting on the reaction, the larger it can become an index indicating the degree of hydrophilicity. Therefore, observe the color difference AE as follows. When measuring the color difference ΔΕ As a reagent for visualizing a color reaction, a silver solution of AH after dust was used. The silver ions contained in the solution react with the excited electrons (e-) generated by the photocatalyst to precipitate as silver. The reaction formula is shown below. In this way, silver is precipitated, and the surface of the silver nitrate solution adheres to brown or black. The color difference ΔE is clearly obtained.

Ag++e-~>Ag I 藉此’將1%之硝酸銀溶液附著於塗料型之第6實施例 (4成分）及第7實施例（3成分）之實施例磁磚之表面層上，以 該狀態進行紫外線照射，對每磁磚測定色差。紫外線 在表面層上以形成1.2mW/cm2之強度照射，照射時間為5 分鐘。然後，檢討所測定之色差ΔΕ及接觸角、抗菌力、 油分解力或NO氧化力之關係。將結果示於第18〜22圖。又 ，在色差ΔΕ測定時，將磁碑表面的殘留水溶液用手巾擦 拭，算出以該狀態之磁磚表面之銀呈色量及實驗前（紫外 線照射則）之銀呈色量之差。又，在銀呈色量之測定時， 用以日本變色工業社之色差計ND300A，以JISZ8729(1980) 本紙張尺度適财_家兩（c叫A4規格（210X^JJ7 •裝- (請先閎讀背面之注意事項再|^本頁} 、_叮 線---- 75 經濟部中央標準局員工消費合作社印製 495384 五、發明説明（73 以及JISZ8730(1980)為根據。 第18〜21圖係針對4成分系第6實施例之實施例磁磚（塗 料型）所得之結果。其中，第18圖係色差△ e及明時接觸角 之關係線圖、第19圖係色差△ E及抗菌力之關係線圖、第 20圖係色差ΔΕ及NO氧化力之關係線圖。又，此時之抗菌 力以具有含有光觸媒/氧化紹/二氧化梦之表面層之磁碑可 發揮之抗菌力為1代表。第22圖係3成分系之第7實施例之 實施例磁磚（塗料型）中色差ΔΕ及明時接觸角之關係線圖 。又’ 4成分系之實施例磁磚以在表面層中含有Ag之磁碑 為遽1色差△ Ε0〜60檢討之。此時，色差△ Ε為零之 磁磚係不生成激發電子之單純磁磚（只具有由塗料形成之 表面層之磁碑）。 如第18圖、第22圖所示，若色差ΔΕ值為1以上時， 可得到20°以下之小的接觸角，因此可得到經提高親水性 之防污效果，故佳。又，色差ΔΕ值為1〇以上時，接觸角 則維持在小值。另一方面，光觸媒的量增加時，則激發電 子之生成變得活躍，則色差△Ε值會變大，但光觸媒相對 於光觸媒以外之成分（Al2〇3、Si〇2或該等成分與上述金屬） 的總量之量變多時，隨光觸媒量之增加，對基材之密接性 降低，使表面層容易剝離。因此，若色差A E在50以下時 ，則不會有光觸媒之量對光觸媒以外之成分的總量過多， 從抑制表面層剝離的觀點而言為佳。 又，如第19〜21圖所示，色差△ E在上述所定範圍（約卜 約50)内，可確實地提高抗菌力、油分解力以及NO氧化力 (請先閱讀背面之注意事項再頁) 裝 76 495384 經濟部中央標準局員工消費合作社印製 A 7 ___B7五、發明説明Q ) ，故佳。 其次，針對付予Ti02親水性之提高之Si02或藉Al2〇3 等之另一成分（金屬氧化物）添加使超親水性功能之提高說 明。首先，從燒烤型之實施例（第8實施例）說明之。 ①光觸媒以及金屬氧化物之溶膠的籌備： 光觸媒物質/ Ti02溶膠··平均粒徑為〇·〇2以m左右（石原產業STS-11) 或平均粒徑為〇·〇1 V m左右（多木化學A-6L)。 311〇2溶膠：平均粒徑為〇.〇〇2//111左右（多木化學）。 本第8實施例t除了使用無害且化學安定並價格便宜 之銳鈦礦型（Ti02)外，使用了 Sn02溶膠，也可用以另一光 觸媒性物質之結晶性Ti02、SrTi03、ZnO、SiC、GaP、CdS ' CdSe、MoS3、V205、W03、Sn02、Bi205、Fe203 為替 代物質。 . 金屬氧化物/Si02溶膠：平均粒徑為〇·〇〇7〜〇·⑼9// m 左右（日產化學斯若技術S)。 Al2〇3溶膠··平均粒徑為〇·〇1 β m X 0.1以m左右（日產 化學氧化鋁溶膠200無定形）或平均粒徑為〇·〇1 β m〜0·02 # m左右（曰產化學氧化鋁溶膠520勃姆石）。 Si02+K20溶膠：（日產化學斯若技術K*Si02/K20莫耳 比 3.3〜4.0)。 Si02+Li02溶膠··（日產化學鋰硅酸鹽35*si02/Li〇2莫 耳比3.5)。 Zr02溶膠··平均粒徑為0·〇7 # m左右（日產化學NZS- (請先閲讀背面之注意事項再^^本頁) —裝· 訂 線 本紙張尺度適用中國國家標準（CNS ) A4規格（210X 297公釐） 77 495384 A7 B7 經濟部中央標準局員工消費合作社印製 五、發明説明b ) 30B)。 上述溶膠皆使用已販賣品，在金屬之醇鹽中添加鹽酸 或如乙胺之加水分解抑制劑作為起始原料，以乙醇或丙醇 之酒精稀釋後，進行部份加水分解，或也可使用可進行完 全加水分解之液體。例如鈦之醇鹽，可列舉有四乙氧基鈦 、四異丙氧基鈦、四η-丙氧基鈦、四丁氧基鈦、四甲氧基 鈦等。又，另一有機金屬化合物（螯合、醋酸鹽）、TiCl4、 Ti(S04)2等之無機金屬化合物也可以作為起始原料。 ② 親水性付予材料之調整： 前沭糸.觸媒性物質及金屬氧化物之溶膠的混合一開始 就稀釋，使固態成分之濃度為〇.4重量％之濃度，再以後 述表5所示之比率混合各溶膠，再充分地攪拌。混合後之 固態部分重量比成為所使用各溶膠之液體重量比。 ③ 親水性發揮磁磚之製作·· 準備施釉磁磚（TOTO製AB06E11)當作基材，該磁碑 表面用以所定量之上述混合溶膠喷射塗抹，使其膜厚為〇·5 /zm。將此用RHK(輥壓哈斯基輪機）最高溫度約700〜900°C 以燒成時間60分鐘燒成，製造第8實施例磁磚。在這第8實 施例磁磚雖施以喷射塗抹，但塗抹方法也可使用有流動塗 抹、旋轉塗抹、浸潰塗抹、滚壓塗抹、刷毛塗抹、其他塗 抹方法等。又，這第8實施例磁磚雖使用磁磚作為基材’ 但其他也可使用金屬、陶瓷、陶瓷器、玻璃、塑膠、木石 、水泥混凝土或該等組合、及該等積層體。又，這第8實 施例磁碑所使用之溶膠，係以如上述溶膠之籌備中之物， (請先閲讀背面之注意事項舄本頁) 丨裝. -訂 線 本紙張尺度適用中國國家標準（CNS ) Α4規格（210 X 297公釐） 78 495384 A7 B7五、發明説明k ) 因此該磁磚為光觸媒、及以氧化鋁為代表之兩性或鹼性或 者是酸性金屬氧化物、以及氧化矽等在第4實施例中所述 之另一化合物（氧化物）組合之2成分系、3成分系者。不過 ，如後述之表5，也可使用數種以1成分形成之化合物（金 屬氧化物）。 ④評價： 親水性之評價係以水之靜止接觸角評價之。首先，實 驗磁磚（第8實施例磁磚以及比較例磁磚）以紫外線強度約 1.5mW/cm2之BLB螢光燈（三共電氣公司製作黑燈泡 FL2卫BI3)照射24 時後，測定與水之接觸角。隨後，遮 光保存72個小時（暗處保存）後，再測定與水之接觸角。將 其結果示於前述表中。又，用以摩斯硬度評價膜之強度。 其結果示於表5。 經濟部中央標準局員工消費合作社印製 本紙張尺度適用中國國家標準（CNS ) Α4規格（210Χ297公釐） 79 495384 A7 B7 i、發明説明（77) 配合比 測定結果 No 臟酿 Ti02 Sn〇2 Si02 ai2o3 Si02+ κρ so2+ Ii02 Zr02 光· 後 暗處保 极 賴 魏 斯若 氧化鋁 氧化鋁 斯若 趨嫩 NZS- 接觸角 SIS-ll A-6L ms 溶膠 200 溶膠 520 ikm 835 30B 接觸角 1 40 40 6 2 100 10 27 4 3 80 20 0 5 26 6 4 800°C 80 10 10 3 20 6 5 80 0 20 3 18 4 6 900°C 50 50 0 9 24 6 7 50 30 20 8 17 6 8 50 10 40 8 15 4 9 50 0 50 6 15 4 10 20 80 0 19 26 5 11 20 60 20 19 21 5 — 12 20 40 40 18 19 4 13 20 20 60 14 16 3 14 20 0 80 14 15 3 15 100 12 29 4 16 700〇C〜 800°C 50 50 10 21 6 17 40 10 50 7 18 6 18 40 10 50 4 14 6 19 50 50 10 25 6 20 750〇C〜 850〇C 80 20 7 26 4 21 100 16 35 6 22 90 10 11 29 6 表5 (請先閱讀背面之注意事項再本頁) 、τ 線 經濟部中央標準局員工消費合作社印製 本紙張尺度適用中國國家標準（CNS ) A4現格（210X297公釐） 80 經濟部中央標準局員工消費合作社印製 495384 A7 B7 五、發明説明（） 78 從這表5之Νο·2〜No.14可知，在紫外線照射之親水化 上，在TiO2/(TiO2+SiO2+Al2O3)2 0.4之範圍内，則與水之 接觸角形成10度以下，即表示已充分地親水化。又，從暗 處保存後之結果可知，Ti02之量若為同量時，A1203之添 加量愈多，親水性愈可維持在高狀態。又，藉添加Si02 ，又藉以增加該增加量可知，其硬度提高。從這些結果可 知，經由在光觸媒（Ti02)上添加Si02以及Al2〇3，比光觸媒 單體還能提高光照射下之親水性，又在暗處下也能提高親 水性之維持力，進而也確認膜硬度及綿密度之提高。在該 效果中，使里在這實施例中所示之溶膠時，盖親水生之提 高主要係藉由Al2〇3之添加所得到，而膜硬度則是藉由Si02 之添加所致。又，表5之No.l係針對上述施釉磁碑之結果 ，Νο·2為只有光觸媒之磁碑（比較例磁碑）之結果。 表5之No.15〜Νο.18也施以同樣的實驗，其中將一部分 Si〇2替換成Κ20。此結果也同樣地藉由Si02、Κ20、Α12〇3 之添加，其親水性功能之提高及膜硬度之提昇可在燒成溫 度700〜800度左右之範圍内達成。又Νο.19為Si02之一部分 替換成Li02之實驗，從此實驗也可知，同樣地可達到親水 性功能及膜硬度之提高。 Νο·17及No.l8係針對氧化鋁溶膠之原料形狀進行檢討 之樣品，可確認以使用無定形且為羽毛狀組織之氧化鋁溶 膠時，更能提高親水性功能。這是因為提高親水性功能時 ，親水基較多之組織遠比粒子狀者其效果來得高所致。Ag ++ e- ~ > Ag I used this to attach a 1% silver nitrate solution to the surface layer of the tile of the sixth embodiment (four components) and seventh embodiment (three components) of the coating type. UV irradiation was performed in this state, and the color difference was measured for each tile. Ultraviolet light was irradiated on the surface layer at an intensity of 1.2 mW / cm2 for 5 minutes. Then, the relationship between the measured color difference ΔΕ and the contact angle, antibacterial power, oil decomposition power, or NO oxidation power was reviewed. The results are shown in FIGS. 18 to 22. When measuring the color difference ΔΕ, the residual aqueous solution on the surface of the magnetic tablet was wiped with a towel to calculate the difference between the amount of silver coloration on the surface of the tile in this state and the amount of silver coloration before the experiment (for ultraviolet irradiation). In addition, in the measurement of the amount of silver color, the color difference meter ND300A of Japan Color Changing Industry Co., Ltd. was used in accordance with JISZ8729 (1980). This paper is suitable for financial use. Jiajia (c is called A4 specification (210X ^ JJ7 • equipment-(please first闳 Read the notes on the back again | ^ This page}, _ Ding Line ---- 75 Printed by the Consumers' Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs 495384 5. The invention description (73 and JISZ8730 (1980) is based. 18 ~ 21 The graph is the result obtained for the example tile (paint type) of the 6th example of the 4-component system. Among them, the graph of the relationship between the color difference Δe and the contact angle at bright time in Figure 18, and the color difference ΔE in Figure 19 and The antibacterial force relationship diagram, Figure 20 is the relationship between the color difference ΔΕ and the NO oxidation force. In addition, the antibacterial force at this time is the antibacterial that can be exerted by a magnetic tablet with a surface layer containing a photocatalyst / oxide oxide / dream dream The force is 1. The relationship between the color difference ΔE and the contact angle at bright time in the tile (paint type) of the seventh embodiment of the three-component system is shown in Figure 22, and the four-component embodiment of the tile The magnetic stele containing Ag in the surface layer is 遽 1 color difference △ EO0 ~ 60. At this time, the color difference △ E is A zero tile is a simple tile that does not generate excited electrons (only a magnetic tablet with a surface layer made of paint). As shown in Figures 18 and 22, if the color difference ΔE value is 1 or more, 20 can be obtained. A small contact angle below ° is good for antifouling effect with improved hydrophilicity. Also, when the color difference ΔE value is 10 or more, the contact angle is kept small. On the other hand, the amount of photocatalyst increases When the generation of excited electrons becomes active, the color difference ΔE value becomes larger, but the amount of the photocatalyst relative to the total amount of components other than the photocatalyst (Al2 03, Si 0 2 or these components and the above metals) becomes larger As the amount of photocatalyst increases, the adhesion to the substrate decreases and the surface layer is easily peeled. Therefore, if the color difference AE is 50 or less, the amount of photocatalyst will not be too much for the total amount of components other than photocatalyst. From the viewpoint of suppressing the peeling of the surface layer, as shown in Figs. 19 to 21, the color difference ΔE is within the predetermined range (approximately about 50), and the antibacterial force, oil decomposing force, and NO oxidation can be surely improved. Force (Please read the note on the back first Item reprint) Pack 76 495384 Printed by the Consumers Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs A 7 ___B7 V. Invention Description Q), so good. Secondly, for Si02 which is given to improve the hydrophilicity of Ti02 or borrow Al2O3, etc. Addition of a component (metal oxide) to enhance the superhydrophilic function. First, it will be explained from the barbecue type embodiment (eighth embodiment). ① Preparation of photocatalyst and metal oxide sol: Photocatalyst substance / Ti02 sol The average particle diameter is about 0.02 m (Ishihara Industries STS-11) or the average particle diameter is about 0.001 V m (Taki Chemical A-6L). 311〇2 sol: average particle size is about 0.002 / 2/111 (Taki Chemical). In the eighth embodiment, in addition to using anatase (Ti02) which is harmless, chemically stable, and inexpensive, Sn02 sol is used, and crystalline Ti02, SrTi03, ZnO, SiC, and GaP can be used as another photocatalytic substance. , CdS 'CdSe, MoS3, V205, W03, Sn02, Bi205, Fe203 are substitute substances. . Metal oxide / Si02 sol: The average particle diameter is about 0.07 ~ 0.99 // m (Nissan Chemical SRO Technology S). Al2〇3 sol · · The average particle size is about 〇1 β m X 0.1 to m (Nissan Chemical Alumina Sol 200 Amorphous) or the average particle size is about 〇1 β m to 0 · 02 # m ( (Produced chemical alumina sol 520 boehmite). Si02 + K20 sol: (Nissan Chemical SRO technology K * Si02 / K20 mole ratio 3.3 ~ 4.0). Si02 + Li02 sol ... (Nissan Chemical Lithium Silicate 35 * si02 / LiO2 Molar ratio 3.5). Zr02 sol · · Average particle size is about 0 · 〇7 # m (Nissan Chemical NZS- (Please read the precautions on the back before ^^ this page) — Binding and binding This paper size applies Chinese National Standard (CNS) A4 Specifications (210X 297 mm) 77 495384 A7 B7 Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 5. Description of the invention b) 30B). The above sols are all sold products. Hydrochloric acid or hydrolyzation inhibitors such as ethylamine are added to the metal alkoxides as starting materials. After being diluted with ethanol or propanol, they can be partially hydrolyzed. Liquid that can be completely hydrolyzed. Examples of titanium alkoxides include tetraethoxytitanium, tetraisopropoxytitanium, tetraη-propoxytitanium, tetrabutoxytitanium, and tetramethoxytitanium. In addition, inorganic metal compounds such as another organometallic compound (chelate, acetate), TiCl4, Ti (S04) 2, etc. may also be used as starting materials. ② Adjustment of hydrophilicity-imparting materials: Former 沭 糸. The mixing of the catalysing substance and the metal oxide sol is diluted from the beginning so that the concentration of the solid component is 0.4% by weight, which will be described later in Table 5. The sols were mixed at the ratios shown and stirred well. The weight ratio of the solid portion after mixing becomes the liquid weight ratio of each sol used. ③ Production of tiles with hydrophilic properties ... Prepare glazed tiles (AB06E11, manufactured by TOTO) as the base material. The surface of the magnetic monument is spray-coated with the above-mentioned quantitative mixed sol to make the film thickness 0.5 / zm. The RHK (Roller Husky Roller) was used for firing at a maximum temperature of about 700 to 900 ° C for a firing time of 60 minutes to manufacture an eighth embodiment tile. In the eighth embodiment, although the tile is spray-applied, the application method may be flow application, spin application, dip application, roll application, bristle application, or other application methods. In addition, although the tile of the eighth embodiment uses the tile as a substrate ', other metals, ceramics, ceramics, glass, plastic, wood and stone, cement concrete, or combinations thereof, and such laminated bodies may be used. In addition, the sol used in the magnetic stele of the eighth embodiment is the same as the preparation of the above sol, (please read the precautions on the back 舄 this page) 丨 installed. (CNS) A4 specification (210 X 297 mm) 78 495384 A7 B7 V. Description of the invention k) Therefore, the tile is a photocatalyst, and amphoteric or alkaline or acidic metal oxide represented by alumina, and silicon oxide Wait for the two-component system and three-component system of the other compound (oxide) combination described in the fourth embodiment. However, as shown in Table 5 below, several compounds (metal oxides) formed with one component may be used. ④ Evaluation: The evaluation of hydrophilicity was performed by the static contact angle of water. First, the experimental tile (the eighth embodiment tile and the comparative example tile) was irradiated with a BLB fluorescent lamp (black light bulb FL2 and BI3 made by Sankyo Electric Co., Ltd.) with an ultraviolet intensity of about 1.5 mW / cm2 for 24 hours, and then measured water Of contact angle. Then, store it in the dark for 72 hours (save in the dark), and then measure the contact angle with water. The results are shown in the aforementioned table. The strength of the film was evaluated by Morse hardness. The results are shown in Table 5. Printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs. The paper size is applicable to the Chinese National Standard (CNS) A4 specification (210 × 297 mm) 79 495384 A7 B7 i. Description of the invention (77) Mixing ratio measurement result No dirty brewing Ti02 Sn〇2 Si02 ai2o3 Si02 + κρ so2 + Ii02 Zr02 Light · Dark Place Reliance Weiss Ruo Aluminium Oxide Aluminium Oxide Ruoban NZS- Contact Angle SIS-ll A-6L ms Sol 200 Sol 520 ikm 835 30B Contact Angle 1 40 40 6 2 100 10 27 4 3 80 20 0 5 26 6 4 800 ° C 80 10 10 3 20 6 5 80 0 20 3 18 4 6 900 ° C 50 50 0 9 24 6 7 50 30 20 8 17 6 8 50 10 40 8 15 4 9 50 0 50 6 15 4 10 20 80 0 19 26 5 11 20 60 20 19 21 5 — 12 20 40 40 18 19 4 13 20 20 60 14 16 3 14 20 0 80 14 15 3 15 100 12 29 4 16 700 〇C ~ 800 ° C 50 50 10 21 6 17 40 10 50 7 18 6 18 40 10 50 4 14 6 19 50 50 10 25 6 20 750 ° C ~ 850 ° C 80 20 7 26 4 21 100 16 35 6 22 90 10 11 29 6 Table 5 (Please read the notes on the back first, then this page), printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs, the paper is printed in accordance with the Chinese National Standard (CNS) A4 (210X297 mm) ) 80 Printed by the Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs 495384 A7 B7 V. Description of the invention () 78 From No. 2 ~ No. 14 of this Table 5, it can be seen that in the hydrophilization of ultraviolet radiation, TiO2 / (TiO2 + Within the range of SiO2 + Al2O3) 2 0.4, the contact angle with water is less than 10 degrees, which means that it is sufficiently hydrophilized. In addition, from the results after storage in the dark, it can be seen that if the amount of Ti02 is the same, the more A1203 is added, the more hydrophilicity can be maintained in a high state. In addition, by adding Si02 and increasing the increase, it can be seen that the hardness is improved. From these results, it can be seen that by adding Si02 and Al203 to the photocatalyst (Ti02), the hydrophilicity under light irradiation can be improved compared to the photocatalyst alone, and the retention of hydrophilicity can also be improved in the dark. Improved film hardness and cotton density. In this effect, when the sol shown in this example is used, the improvement of the hydrophilicity is mainly obtained by the addition of Al203, and the hardness of the film is caused by the addition of SiO2. In addition, No. 1 in Table 5 is a result of the above-mentioned glazed magnetic stele, and No 2 is a result of a magnetic stele with only photocatalyst (comparative magnetic stele). No. 15 to No. 18 in Table 5 were also subjected to the same experiment, in which a part of SiO2 was replaced with κ20. This result is also achieved by the addition of Si02, K20, and A1203, and the improvement of its hydrophilic function and the increase of film hardness can be achieved within the range of about 700 to 800 degrees of firing temperature. In addition, the experiment in which No. 19 is a part of Si02 replaced with Li02, it can be seen from this experiment that the hydrophilic function and the hardness of the membrane can be improved in the same way. No. 17 and No. 18 are samples that have been reviewed for the shape of the alumina sol. It was confirmed that the use of an alumina sol with an amorphous and feather-like structure can enhance the hydrophilic function. This is because when the hydrophilic function is improved, a tissue with more hydrophilic groups is far more effective than a particle-like one.

No.20係於Ti02上添加Zr02時之結果。從此可知，Zr02 本紙張尺度適用中國國家標準（CNS ) A4規格（210X 297公釐） (請先閱讀背面之注意事項再本頁) 訂 81 495384 A7 B7 五、發明説明（ 79 經濟部中央標準局員工消費合作社印製 也在親水性提高上有效。 Νο·21及Νο·22則為Sn〇2作為光觸媒使用時之實驗結 果^ Sn02單體也可顯現親水性效果，進而添加Al2〇3也可 確認親水性之提高。此時不會導致膜硬度降低，Sn02本 身也確認具有作為黏著劑之功能。 又，從Νο·3〜Νο·14可知，隨八丨2〇3之添加量增加，接 觸角會變小，因此親水性可提高。·是故，經調整八丨2〇3添 加量，可變更親水性之程度《然後，從表2之結果可知， 經調整光觸媒之Cu、Ag、Pd、Fe等金屬載持量，可改善Ti〇2 解力’因此施以A1203添;調整及上述金屬之載 持量的調整，可調整親水性功能及分解力（分解性能）之間 的均衡度其結果，若需強大的分解力時，可令親水性維 持在光觸媒可發揮的程度，並可發揮所需之強大分解力。 如此使之兼具親水性功能及分解性能，即，具有下列 優點。經由基於親水性之去污以及基於分解性能之去污等 兩種階段之步驟，可謀求進一步提高沾污之除去效率，以 及除去速度之提高。此時，根據污染種類，也可能基於親 水性之去污後所殘留之少數污染之付著強度仍高，但藉以 上述金屬之載持量的調整，提高分解力，連這種附著強度 高之少許污染也可除去。進而，因可除去如此之污垢，不 需遮蔽向光觸媒之光，可增加光觸媒之照射量。因此，可 令，於親水性之去污及基於分解性能之去污高度有效率持 續著 以上結論，藉於光觸媒上添加si02、A1203、zrNo. 20 is the result when Zr02 is added to Ti02. It can be known from this that the paper size of Zr02 applies to the Chinese National Standard (CNS) A4 (210X 297 mm) (please read the precautions on the back before this page). Order 81 495384 A7 B7 V. Description of the invention The printing of employee consumer cooperatives is also effective in improving hydrophilicity. Νο · 21 and Νο · 22 are the experimental results when Sn02 is used as a photocatalyst. ^ Sn02 monomer can also show hydrophilic effect, and the addition of Al203 can also be used. It is confirmed that the hydrophilicity is improved. At this time, the hardness of the film will not be reduced, and Sn02 itself is also confirmed to have the function of an adhesive. It is also known from No. 3 to No. 14 that as the amount of addition increases, contact The angle will be smaller, so the hydrophilicity can be improved. · Yes, the degree of hydrophilicity can be changed by adjusting the amount of addition of 8203. Then, from the results in Table 2, it can be seen that the Cu, Ag, and Pd of the photocatalyst are adjusted. The loading capacity of metals such as Fe and Fe can improve the resolution of Ti〇2. Therefore, A1203 is added; the adjustment and adjustment of the loading capacity of the above metals can adjust the balance between the hydrophilic function and the resolution (decomposition performance). As a result, if needed When the strong dissolving power is maintained, the hydrophilicity can be maintained to the extent that the photocatalyst can exhibit and the required strong dissolving power can be exerted. In this way, it has both the hydrophilic function and the decomposing performance, that is, it has the following advantages. Based on the hydrophilicity The two steps of decontamination and decontamination based on decomposition performance can be used to further improve the removal efficiency and speed of removal of contamination. At this time, depending on the type of contamination, it may also be based on hydrophilic decontamination. The strength of the remaining few pollutions is still high, but by adjusting the carrying capacity of the above-mentioned metals, the decomposition force is improved, and even such a small pollution with high adhesion strength can be removed. Furthermore, because such dirt can be removed, it is not necessary Shielding the light to the photocatalyst can increase the exposure of the photocatalyst. Therefore, it is possible to continue the above conclusions in the highly effective decontamination of hydrophilic and decontamination based on the decomposition performance. By adding si02, A1203, zr to the photocatalyst

木紙張尺度適财關家標準（CNS )罐格（ϋ297公慶J (請先閱讀背面之注意事項再 —裝-- 本頁) 訂 線 ! - —1 1 1..... 82 495384 經濟部中央標準局員工消費合作社印製 A7 B7五、發明説明（) 80 可知提高光照射下接觸角及暗處保持後之親水性維持力， 此效果也可藉由該等物質之親水性得之。可舉例有濕潤熱 以作為物質之親水性之指標，宜作為光觸媒之Ti02之濕潤 熱，其銳鈦礦型為320〜512xl(T3Jm·2，金紅石型為293〜 645xl(T3Jm·2,從此可知，具有500xl(T3Jm·2以上濕潤熱之 化合物為佳。除上述3種金屬氧化物之外，另可舉Ge02、 Th02、ZnO為例。該等金屬化合物不只具有結晶構造之物 質，還可為無定形之物質，其粒徑範圍在0.1m以下。又 ，可知經添加Si02可提高膜硬度。藉由Si02之一部分替換 成K20或Li02，即使燒成溫度低，也可提高膜硬度1尤其 ，作為上述可期望之效果的範圍，係於滿足Ti02/(親水性 付予調整劑之全固態形份量）20.5、Si02/(親水性付予調 整劑之全固態形份量）^0.5之條件。 其次，針對塗料型之實施例（第9實施例）說明可付予 Ti〇2之親水性提高之si〇2，或藉ai2o3等另一化合物（金屬 氧化物）之添加，使超親水性功能之提高以及其他功能的 提高（膜硬度提高）之有無。 ①光觸媒以及金屬氧化物之溶膠的籌備： 光觸媒性物質/Ti02溶膠：（曰產化學TA-15)。 又，這第9實施例也是無害且化學安定。又，除了價 格便宜的銳鈦礦型Ti02之外，也使用了 Sn02溶膠，也可使 用其他光觸媒性物質之結晶性Ti02、SrTi03、ZnO、SiC 、GaP、CdS、CdSe、MoS3、V205、W03、Sn02、Bi205 、FeOj，為代替物質。 (請先閲讀背面之注意事項再本頁) •裝· 訂 線 本紙張尺度適用中國國家標準（CNS ) A4規格（21 OX 297公釐） * 83 - 495384 A7 _______B7 五、發明説明（） 81 金屬氧化物/Si〇2溶膠：（日本合成橡膠製格拉司卡 T2202) 〇Wood Paper Standards CNS Canister (ϋ297 公 庆 J (Please read the precautions on the back before you install-this page) Threading!--1 1 1 ..... 82 495384 Economy Printed by the Consumer Standards Cooperative of the Ministry of Standards of the People's Republic of China A7 B7 V. Description of the invention (80) It can be seen that the hydrophilicity retention ability of the contact angle and dark place retention under light irradiation can be improved. This effect can also be obtained by the hydrophilicity of these substances. For example, wetting heat can be used as an indicator of the hydrophilicity of the substance, and it can be used as the moisturizing heat of photocatalyst Ti02. Its anatase type is 320 ~ 512xl (T3Jm · 2, rutile type is 293 ~ 645xl (T3Jm · 2, It can be seen from this that compounds having a wet heat of 500xl (T3Jm · 2 or higher are preferred. In addition to the three metal oxides mentioned above, Ge02, Th02, and ZnO can also be cited as examples. These metal compounds not only have a crystalline structure, but also It can be amorphous, and its particle size range is less than 0.1m. It is also known that the hardness of the film can be improved by adding Si02. By replacing part of Si02 with K20 or Li02, the film hardness can be improved even if the firing temperature is low. In particular, as a range of the above-mentioned expected effects, It satisfies the conditions of Ti02 / (All-solid-state amount of hydrophilicity-imparting modifier) 20.5 and Si02 / (All-solid-state amount of hydrophilicity-imparting modifier) ^ 0.5. Next, a coating-type embodiment (No. 9 Example) Explain that SiO2, which can improve the hydrophilicity of Ti〇2, or the addition of another compound (metal oxide) such as ai2o3, can improve the super hydrophilic function and other functions (improve the film hardness ). ① Preparation of photocatalyst and metal oxide sol: Photocatalyst / Ti02 sol: (say TA-15). This ninth embodiment is also harmless and chemically stable. In addition, it is cheap In addition to the anatase Ti02, Sn02 sol is also used, and crystalline Ti02, SrTi03, ZnO, SiC, GaP, CdS, CdSe, MoS3, V205, W03, Sn02, Bi205, FeOj, and other photocatalytic materials can also be used. Substitute substances. (Please read the precautions on the back, and then this page) • The binding and binding paper size is applicable to the Chinese National Standard (CNS) A4 specification (21 OX 297 mm) * 83-495384 A7 _______B7 V. Description of the invention () 81 metal oxide / Si〇2 sol: (Grasca T2202 made by Japan Synthetic Rubber) 〇

Al2〇3溶膠·平均粒控為〇·〇ι〜002#^左右（日產化學 氧化鋁溶膠520)。 在此，Si〇2雖使用販買品，也可用以形成之塗膜形 成主要成分。又，Ti〇2及Al2〇3溶膠雖使用了販賣品，與 上述第8貫施例相同，可經作為起始原料在金屬之添加鹽 酸或等之加水分解抑制劑等已述之步驟準備該等溶膠。 ②親水性付予材料之調整： _將上述原料以一定比率混合後，用以乙醇稀釋成3倍 ’作成塗抹液。該製成塗抹液之成份比係示於下列表6。 (請先閲讀背面之注意事項再本頁) -裝· 訂Al2O3 sol · The average particle size is about 0.002 ~ 002 # ^ (Nissan Chemical Alumina Sol 520). Here, although SiO2 is a commercially available product, it can also be used as the main component of the formed coating film. In addition, although Ti02 and Al203 sols are sold, they are the same as the eighth embodiment described above, and they can be prepared through the steps described above, such as adding hydrochloric acid or a hydrolytic decomposition inhibitor to metals as starting materials. And so on. ② Adjustment of the hydrophilicity-imparting material: _ After mixing the above raw materials at a certain ratio, diluting it with ethanol three times ′ is used as a coating liquid. The composition ratio of this application liquid is shown in Table 6 below. (Please read the notes on the back before this page)

Ti〇2 si〇2 Al2〇3 1 1/10 0 〜1/12 1 1/5 0〜3 1 1/2 0〜3 1 1 0〜3 1 2 0〜3 1 5 0〜3 表6 線 經濟部中夬標準局員工消費合作社印製 ③親水性發揮磁磚之製作 與上述第8實施例磁碑同樣地準備施轴磁碑作為基材 ’以喷射塗抹法塗抹，再以150eC加熱30分鐘，使塗膜硬 化。在這第9實施例磁磚雖施以喷射塗抹，但塗抹方法也 可使用有流動塗抹、旋轉塗抹、浸潰塗抹、滾壓塗抹、刷 毛塗抹等其他塗抹方法等。又，這第9實施例磁磚除磁磚 本紙張尺度適用中國國家標準（CNS ) M規格（210χ297公釐） -84 - 495384 A7 B7 五、發明説明（。。） 82 外，另可使用金屬、陶瓷、陶瓷器、玻璃、塑膠、木石、 水泥、混凝土或該等組合及該等積層體作為基材。又，這 第8實施例磁磚所使用之溶膠，係以如上述溶膠之籌備中 之物質以及表5中之成分為Ti02、Si02或Al2〇3，因此該磁 磚為光觸媒及以氧化鋁為代表之兩性或鹼性或者是酸性金 屬氧化物以及氧化矽等在第4實施例中所述之另一化合物（ 氧化物）組合之2成分系、3成分系者。 ④評價： 針對其膜硬度，在實驗磁碑（第9實施例及比較例磁磚） 上施以鉛筆硬度實驗（JIS K5400塗料一般實驗）。其結果 示於表7。又，針對親水性與上述第8實施例，同樣地對實 驗磁磚（第9實施例及比較例磁磚）測定水之靜止接觸角。 其結果示於表8。此時之紫外線強度約1.2mW/cm2，照射 時間設為12個小時。 (請先閲讀背面之注意事項再頁) •裝· 經濟部中央標準局員工消費合作社印製 \^/πο2 0 1/24 1/12 1/6 1/4 1/2 1 2 3 1/10 B以下 B以下 B以下 1/5 2H 2H 2H 2H 2H 2H 2H 2H 2H 1/2 4H 4H 4H 4H 4H 4H 4H 4H 4H 1 4H 4H 4H 4H 4H 4H 4H 4H 4H 2 4H 4H 4H 4H 4H 4H 4H 4H 4H 5 4H 4H 4H 4H 4H 4H 4H 4H 4H 表7 本紙張尺度適用中國國家標準（CNS ) A4規格（21 OX297公釐） 85 495384 A7 B7 五、發明説明（83 ) \^°/πο2 SiO，/TiS^\ 0 1/24 1/12 1/4 1/2 1 2 3 1/5 60 70 45 30 0 10 45 75 1/2 60 60 45 40 0 20 45 70 1 60 60 20 0 0 0 20 55 2 70 60 50 50 50 55 60 70 5 80 75 75 75 80 80 80 80 表8 從表7得知，Si02/Ti02在0.1以下時，黏著劑（Si02)不 足時，則會導致膜強度降低《又，從表8可知，Si02/Ti02 在1/5〜2範圍内，若入1203/丁丨02為1/12〜2間，藉氧化鋁之添 加，可發現親水速度提高之效果。此效果，也如第8實施 例中所述，可藉ai2o3之親水性得之，可以顯示物質之親 水性為指標之濕潤熱表示，宜作為光觸媒之Ti02之濕潤熱 為，其中銳鈦礦型為320〜512x1 (T3JnT2，金紅石型為293〜 645xl(T3Jm·2，從此結果可知以具有500xl(T3Jm·2以上之濕 潤熱之化合物為佳。在這實施例可列舉Zr02、Ge02、Th02 、ZnO該等金屬氧化物，不限於具有結晶構造者，無定形 者也可。 經濟部中央標準局員工消費合作社印製 以上，說明了本發明之實施例，在此本發明並不限於 上述實施例或實施態樣，只要不脫離本發明之主旨，都可 以種種態樣實施之。 例如，固著銅或其氧化物等粒子，製造一可補充抗菌 功能之磁磚時，亦可先製造一經向Ti/Al溶膠之磁磚表面 之塗抹並加以燒成，由其光觸媒配合物形成表面層之磁磚 ，再於該磁磚表面層上重新塗抹第3溶膠後加以燒成。 本紙張尺度適用中國國家標準（CNS ) A4祝格（210X 297公釐） 86Ti〇2 si〇2 Al2〇3 1 1/10 0 to 1/12 1 1/5 0 to 3 1 1/2 0 to 3 1 1 0 to 3 1 2 0 to 3 1 5 0 to 3 Table 6 Line Printed by the Consumers' Cooperative of the China Standards Bureau of the Ministry of Economic Affairs. ③ The production of tiles with hydrophilic properties is prepared in the same way as the magnetic tablet of the above-mentioned 8th embodiment. The magnetic tablet is applied as a substrate. To harden the coating. In the ninth embodiment, although the tile is spray-applied, other methods such as flow application, spin application, dip application, roll application, and bristle application can be used. In addition, the paper size of this ninth embodiment of the tile is in accordance with the Chinese National Standard (CNS) M specification (210 x 297 mm) -84-495384 A7 B7 V. Description of the invention (..) 82, metal can also be used , Ceramics, ceramics, glass, plastic, wood and stone, cement, concrete, or combinations thereof and such laminates as the substrate. In addition, the sol used in the tile of the eighth embodiment is based on the preparation of the sol as described above and the composition in Table 5 is Ti02, Si02, or Al203. Therefore, the tile is a photocatalyst and alumina is used. A representative amphoteric or basic or acidic metal oxide, silicon oxide, and other compounds (oxides) described in the fourth embodiment of the two-component system, three-component system. ④ Evaluation: For the hardness of the film, a pencil hardness test (JIS K5400 coating general test) was performed on the experimental magnetic tablet (tile of the ninth example and comparative example). The results are shown in Table 7. For the hydrophilicity, the static contact angle of water was measured on the experimental tiles (the ninth embodiment and the comparative example tiles) in the same manner as in the eighth embodiment. The results are shown in Table 8. The ultraviolet intensity at this time was about 1.2 mW / cm2, and the irradiation time was set to 12 hours. (Please read the precautions on the back first, then the page) • Equipment · Printed by the Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs \ ^ / πο2 0 1/24 1/12 1/6 1/4 1/2 1 2 3 1/10 Below B Below B Below 1/5 2H 2H 2H 2H 2H 2H 2H 2H 2H 1/2 4H 4H 4H 4H 4H 4H 4H 4H 4H 4H 1 4H 4H 4H 4H 4H 4H 4H 4H 4H 2 4H 4H 4H 4H 4H 4H 4H 4H 4H 4H 5 4H 4H 4H 4H 4H 4H 4H 4H 4H 4H Table 7 This paper size applies Chinese National Standard (CNS) A4 specification (21 OX297 mm) 85 495384 A7 B7 V. Description of the invention (83) \ ^ ° / πο2 SiO, / TiS ^ \ 0 1/24 1/12 1/4 1/2 1 2 3 1/5 60 70 45 30 0 10 45 75 1/2 60 60 45 40 0 20 45 70 1 60 60 20 0 0 0 20 55 2 70 60 50 50 50 55 60 70 5 80 75 75 75 80 80 80 80 80 Table 8 It is known from Table 7 that when Si02 / Ti02 is less than 0.1, when the adhesive (Si02) is insufficient, the film strength will decrease. It can be seen from Table 8 that if Si02 / Ti02 is in the range of 1/5 ~ 2, if 1203 / but 丨 02 is 1/12 ~ 2, the effect of increasing the hydrophilic rate can be found by adding alumina. This effect, as described in the eighth embodiment, can be obtained from the hydrophilicity of ai2o3, which can be expressed by the wet heat of the substance as an index, and the wet heat of Ti02, which is suitable as a photocatalyst, is 320 to 512x1 (T3JnT2, rutile type is 293 to 645xl (T3Jm · 2, from this result, it is known that a compound having a moist heat of 500xl (T3Jm · 2 or more) is preferred. In this embodiment, Zr02, Ge02, Th02, Metal oxides such as ZnO are not limited to those with a crystalline structure, but can also be amorphous. Printed by the Staff Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs, the above describes the embodiment of the present invention, and the invention is not limited to the above embodiment. As long as it does not deviate from the gist of the present invention, it can be implemented in various aspects. For example, when fixing copper or its oxide particles to manufacture a tile that can supplement the antibacterial function, the warp warp can also be manufactured first. The surface of the Ti / Al sol tile is painted and fired. The photocatalyst complex is used to form the surface layer of the tile, and the third sol is re-applied on the tile surface layer and fired. Applicable Chinese National Standard (CNS) A4 wish grid (210X 297 mm) 86

Claims (1)

495384 Α8 Βδ C8 D8 申請專利範園 TO 第87121904號專利申請案申請專利範圍修正本 修正日期：91年1月 1 · 一種複合材料，其係在可與水接觸的環境中用於分解 選自空氣中之氮氧化物、氨及二氧化硫所組成之群中 的一者或一者以上的化合物，該複合材料至少包含基 材及表面層，該表面層為親水性且具有自淨化能力， 該表面層包含： 成分⑴一受到光之照射即可產生觸媒作用之光 觸媒； ____ 成分自由 Αία]、ZnO、SrO、BaO、MgO 、CaO、Rb2Q、Na20、K2〇及p2〇5所組成之群中的一 者或一者以上的金屬氧化物；以及 成分（iii)—選自由 Si〇2、Zr02、Th02所組 成之群中的一者或一者以上的金屬氧祀。 如申請專利範圍第1項之複合材料，其該成分（Π) 之金屬氧化物的重量以a表示，該成分⑴芝二光觸媒之重 量以b表示時，a/(a+b)係滿足〇 〇〇1〜〇 8。 如申請專利範圍第1項之複合材料，該其中該成分⑴ 之光觸媒及該成分（ii)之金屬氧化物係具有〇 〇〇5〜〇 5 # m之粒徑範圍内的粒子。 如申請專利範圍第1項之複合材料，其中包含載持於該 成分⑴之光觸媒上，作為成分（iv)之選自於Zn、Ag及 Cu組成之組群的一者或一者以上之可發揮抗菌性的 金屬。 2. 3. 4. 本紙張尺度適用中國國家標準（CNS) A4規格（210 X 297公發） (請先閱讀背面之注意事項再填寫本頁) 87 、申請專利範圍 ^申凊專利範圍第i項之複合材料，其中包含可充分提 阿氧化分解力之量的選自由Ag、Cu、pd、〜、犯、 Cr、Co、Pt、Au&Rh所組成之群中之一者或一者以上 的金屬，以作為成分（iv)。 如申請專利範圍第1項之複合材料，其中包含可充分提 高親水性之量的一者或一者以上選自於u、Ca、Mg 及A1組成之組群中之作為成分的金屬。 如申請專利範圍第4至6項中任一項之複合材料，其中 $該成分（iV)之重量以c表示，該成分⑴之光觸媒的重 時丄c/d^〇e〇〇〇〇1〜〇 〇5 〇 如申請專利範圍第1項之複合材料，其中該表面層係具 有滿足下列條件⑴、(2)巾任_條件之表面性狀態； (1) 表面層膜厚0.01〜3.0/zm ; (2) 令1%之硝酸銀溶液附著於表面層之狀態下 忒表面層上之紫外線強度為i 2mw/cm2，在前述表 面層上照射紫外線5分鐘時之紫外線照射前與紫外線 照射後之表面層色差△^為1〜5〇。 ’ 如申請專利範圍第1項之複合材料，其中在該表面層之 間具有黏著劑。 10.如申請專利範圍第i項之複合材料，其中該黏著劑係在 該基材的變質溫度以下之溫度下聚合或溶化，且於該 基材上固著該表面層。 U·如申請專利範圍第10項之複合材料，其中該黏著劑為 轴藥或塗料。 ’' 6· (請先閲讀背面之注意事項再填寫本頁) 8. 9.495384 Α8 Βδ C8 D8 Patent Application Fan Yuan TO No. 87121904 Patent Application Amendment Scope of Amendment: January 91, 1 · A composite material which is used in an environment that can be in contact with water and decomposed from air A compound of one or more of the group consisting of nitrogen oxides, ammonia and sulfur dioxide, the composite material includes at least a substrate and a surface layer, the surface layer is hydrophilic and has a self-purifying ability, the surface layer Contains: A photocatalyst that can produce a catalyst when it is irradiated by light; ____ Free of ingredients Αία], ZnO, SrO, BaO, MgO, CaO, Rb2Q, Na20, K20, and p205 One or more metal oxides; and component (iii) —a metal oxygen species selected from one or more of the group consisting of Si02, Zr02, and Th02. For example, for a composite material in the scope of application for patent No. 1, the weight of the metal oxide of the component (Π) is expressed by a, and the weight of the photocatalyst of this component is represented by b, a / (a + b) is satisfied. 〇〇1〜〇8. For example, for the composite material of the scope of application for patent No. 1, the photocatalyst of the component ⑴ and the metal oxide of the component (ii) are particles having a particle size within the range of 0.005 to 5 # m. For example, the composite material in the scope of patent application No. 1 includes a photocatalyst supported on the component ⑴, and as component (iv), one or more members selected from the group consisting of Zn, Ag, and Cu may be used. Antibacterial metal. 2. 3. 4. This paper size is in accordance with Chinese National Standard (CNS) A4 specifications (210 X 297) (please read the precautions on the back before filling out this page). 87. Scope of patent application A composite material according to the item, which comprises one or more selected from the group consisting of Ag, Cu, pd, ~, Cr, Co, Pt, Au & Rh in an amount that can sufficiently increase the oxidative decomposition force Metal as ingredient (iv). For example, the composite material of the scope of application for patent No. 1 contains one or more metals which are selected from the group consisting of u, Ca, Mg, and A1 as an ingredient in an amount that can sufficiently improve hydrophilicity. For example, the composite material of any one of items 4 to 6 of the patent application scope, wherein the weight of the component (iV) is expressed by c, and the weight of the photocatalyst of the component is c / d ^ 〇e〇〇〇〇1 〜〇〇5 〇 As for the composite material of the scope of application for patent No. 1, wherein the surface layer has a surface state that satisfies the following conditions, (2) any conditions; (1) the film thickness of the surface layer 0.01 ~ 3.0 / zm; (2) Let the intensity of ultraviolet rays on the surface layer be 1 2mw / cm2 when the 1% silver nitrate solution is attached to the surface layer, before and after ultraviolet irradiation for 5 minutes on the surface layer The surface layer color difference Δ ^ is 1 to 50. ′ The composite material according to item 1 of the patent application scope, wherein an adhesive is provided between the surface layers. 10. The composite material according to item i of the application, wherein the adhesive is polymerized or melted at a temperature below the deterioration temperature of the substrate, and the surface layer is fixed on the substrate. U. The composite material according to item 10 of the application, wherein the adhesive is an axon or a coating. ’'6 · (Please read the notes on the back before filling out this page) 8. 9. 訂_ 88 A8 B8 C8 〜----___ 申請專利範圍 12·如申請專利範圍第1項之複合材料，其中該基材為瓷碑 0 U·如申請專利範圍第丨項之複合材料，其中該基材為木材 、矽鈣板、混凝土板、水泥板、水泥擠壓成形板、石 膏板或蒸壓養護混凝土。 14·如申請專利範圍第1項之複合材料，其中係於該表面層 之表面上固著有發揮抗菌性之金屬或金屬化合物。 15· —種配合物，係用以形成申請專利範圍第1項之複合材 料之表面層的配合物，其包含·· ^_—成分⑴一受到光之照射即可產生觸媒作用之光 觸媒； 成分(ii)—選自由 A1203、ZnO、SrO、BaO、MgO 、CaO、Rb20、Na20、K20及P205所組成之群中的一 者或一者以上的金屬氧化物；以及 成分（iii) —選自由 Si02、Al2〇3、Zr02、Ge02及 Th02 所組成之群中的一者或一者以上的金屬氧化物。 16·如申請專利範圍第15項之配合物，其中當該成分（u) 之金屬氧化物的重量以a表示，該成分⑴之光觸媒之重 里以b表示時’ a/(a+b)係滿足0.001〜0.8 〇 17·如申請專利範圍第15項之配合物，該其中該成分⑴之 光觸媒及該成分（ii)之金屬氧化物係以0.005〜〇.5 # m 之粒徑範圍内的粒子配合。 18.如申請專利範圍第15項之配合物，其中包含載持於該 成分⑴之光觸媒上，作為成分（iv)之一者或一者以上 本紙張尺度適用中國國家標準（CNS) A4規格（210 X 297公釐） (請先閲讀背面之注意事項再填寫本頁) 、可| 89 A8 B8 C8 D8 、申請專利範圍 (請先閲讀背面之注意事項再填寫本頁) 選自於Zn、Ag及Cu組成之組群的發揮抗菌性之金屬。 19·如申請專利範圍第15項之配合物，其中包含可充分提 兩氧化分解力之量的一者或一者以上選自於下述物質 組成之組群的作為成分（iv)的金屬：Ag、Cu、Pd、Fe 、Ni、Cr、Co、Pt、Au及 Rh。 20·如申請專利範圍第15項之配合物，其中包含可充分提 高親水性之量的一者或一者以上選自於Li、Ca、Mg 及A1組成之組群中之作為成分（iv)的金屬。 21·如申請專利範圍第18項之配合物，其中當該成分（iv) _____之重量以c表色:該成分⑴之光觸媒的重量以d表示哮 ，c/d為 0.00001 〜〇·〇5 〇 訂丨 22· —種製造如申請專利範圍第1項之複合材料的方法，其 特徵在於包含有： 一準備步驟，係用以準備如申請專利範圍第丨5項 之配合物或由分散該配合物形成之分散溶膠； 4 一應用步驟，係將該配合物或分散溶膠應用至該 基材上；及 一形成步驟，係將已被應用該配合物或分散溶膠 之基材乾燥或加熱以形成該表面層。 23·如申請專利範圍第22項之方法，其中該配合物或分散 溶膠在該基材上的應用係以载置、塗抹或印刷之步驟 進行。 24· —種製造如申請專利範圍第1項之複合材料的方法，其 特徵在於包含有： 本紙張尺度適用中國國家標準（CNS) Α4規格（210X 297公釐） -90 495384 A8 B8 C8 D8 申請專利範圍 準備步驟，係用以準備如申請專利範圍第15項 之配合物或由分散該配合物形成之分散溶膠； 一形成步驟，係於該基材上形成黏著劑層； 一應用步驟，係將該配合物或分散溶膠應用至該 黏著劑層上；及 形成步驟，係將已被應用該配合物或分散溶膠 之該黏著劑層乾燥或加熱以形成該表面層。. 25·如申請專利範圍第以項之方法，其中該黏著劑係由釉 藥形成，將已被應用該配合物或分散溶劑之基材，在 iji：化溫度高30°C以上至300。(：以下之範 (請先閲讀背面之注意事項再填寫本頁) 訂— 圍内且遠比該基材的變質溫度低之溫度下加熱，以成 表面層。 6·如申叫專利範闺第25項之方法，其中該遠比該釉藥之 軟化溫度高30°C以上至300°C以下之範圍内且遠比該 基材的變質溫度低之溫度為150〜1300。(：。 # 2入如申請專利範圍第22項之方法，其中該形成該表面層 之形成步驟後，接著包含： 一塗抹步驟，其係於該形成表面層之表面上塗抹 刀政有發揮抗菌性之金屬或金屬化合物之溶液；及 一固著步驟，係可將該金屬或金屬氧化物固著於 該表面層之表面上者。 28·如申請專利範圍第22項之方法，其中於應用該配合物 或分散溶膠後，包含一塗抹分散有發揮抗菌性之金屬 或金屬化合物之溶液的步驟。Order _ 88 A8 B8 C8 ~ ----___ Application scope of patent12. For example, the composite material of the scope of patent application No.1, where the substrate is a porcelain tablet 0 U. For composite materials of the scope of patent application No. 丨, where The substrate is wood, silica-calcium board, concrete board, cement board, cement extruded board, gypsum board or autoclaved curing concrete. 14. The composite material according to item 1 of the patent application scope, wherein a metal or a metal compound exhibiting antibacterial properties is fixed on the surface of the surface layer. 15 · —A kind of complex, which is used to form the surface layer of the composite material of the scope of application for patent No. 1, which contains ... ^ _— a photocatalyst that can produce a catalytic effect upon exposure to light; Component (ii)-a metal oxide selected from one or more of the group consisting of A1203, ZnO, SrO, BaO, MgO, CaO, Rb20, Na20, K20, and P205; and component (iii)-selected One or more metal oxides from the group consisting of Si02, Al203, Zr02, Ge02, and Th02. 16. The complex according to item 15 of the scope of patent application, wherein when the weight of the metal oxide of the component (u) is expressed as a, and the weight of the photocatalyst of the component ⑴ is expressed as b 'a / (a + b) is Satisfy 0.001 ~ 0.8 〇17. If the compound of the scope of patent application No. 15, the photocatalyst of the component ⑴ and the metal oxide of the component (ii) are in the particle size range of 0.005 ~ 0.5.5 # m Particle fit. 18. If the complex in the scope of application for patent No. 15 includes a photocatalyst carried on the component ⑴, as one or more of the component (iv), this paper size applies the Chinese National Standard (CNS) A4 specification ( 210 X 297 mm) (Please read the notes on the back before filling this page), OK | 89 A8 B8 C8 D8, patent application scope (please read the notes on the back before filling this page) Selected from Zn, Ag A group consisting of Cu and metals exhibiting antibacterial properties. 19. The complex according to item 15 of the scope of patent application, which contains one or more metals that can sufficiently increase the oxidative decomposition power, as a component (iv), selected from the group consisting of the following substances: Ag, Cu, Pd, Fe, Ni, Cr, Co, Pt, Au and Rh. 20. The complex according to item 15 of the scope of patent application, which contains one or more of an amount sufficient to increase hydrophilicity as a component selected from the group consisting of Li, Ca, Mg and A1 (iv) Metal. 21 · The complex according to item 18 of the scope of patent application, wherein when the weight of the component (iv) _____ is expressed in c: the weight of the photocatalyst of the component 以 is expressed as d, and c / d is 0.00001 ~ 〇 · 〇 〇Order 丨 22 · — A method for manufacturing a composite material as described in the scope of patent application No. 1, which includes: a preparation step for preparing a complex as described in scope of patent application No. 丨 5 or by dispersion A disperse sol formed by the complex; 4 an application step in which the complex or disperse sol is applied to the substrate; and a formation step in which the substrate to which the complex or disperse sol has been applied is dried or heated To form the surface layer. 23. The method of claim 22, wherein the application of the complex or dispersing sol on the substrate is performed by a step of placing, painting or printing. 24 · —A method for manufacturing a composite material such as the scope of application for patent No.1, which is characterized by: The paper size is applicable to China National Standard (CNS) A4 specification (210X 297 mm) -90 495384 A8 B8 C8 D8 Application The patent range preparation step is used to prepare a complex such as the scope of patent application No. 15 or a dispersed sol formed by dispersing the complex; a forming step is to form an adhesive layer on the substrate; an application step is to Applying the complex or dispersed sol to the adhesive layer; and a forming step of drying or heating the adhesive layer to which the complex or dispersed sol has been applied to form the surface layer. 25. If the method according to item 1 of the scope of patent application, wherein the adhesive is formed of glaze, the base material to which the complex or the dispersing solvent has been applied will be at a temperature higher than 30 ° C to 300 ° C. (: The following norms (please read the precautions on the back before filling in this page) Order-heating within a temperature range much lower than the deterioration temperature of the substrate to form a surface layer. The method of item 25, wherein the temperature far in the range of 30 ° C to 300 ° C higher than the softening temperature of the glaze and lower than the deterioration temperature of the base material is 150 to 1300. (: # 2 Enter the method according to item 22 of the scope of patent application, wherein the forming step of forming the surface layer then includes: an application step, which is to apply a knife or a metal having antibacterial properties on the surface of the forming surface layer. A solution of a metal compound; and a fixing step, which can fix the metal or metal oxide on the surface of the surface layer. 28. The method of claim 22 in the scope of patent application, in which the complex or Dispersing the sol includes a step of applying a solution in which a metal or a metal compound exhibiting antibacterial properties is dispersed. 91 六、申請專利範圍 29·如申請專利範圍第22項之方法，#中於該形成表面層 之步驟後，接著包含： 一塗抹步驟，其係於該形成表面層之表面上塗抹 一含有發揮抗菌性之金屬離子的溶液；及 一載置/固定步驟，係用以紫外線照射於前述表面 層上，利用該金屬離子對光觸媒的光還原作用，使該 金屬載持/固定於該表面層中之光觸媒上者。 30· —種製造如申請專利範圍第丨8項之配合物的方法，包 含準備一至少分散有成分⑴之溶膠，於該溶膠中混合 -一該成分（iv)，持於該光觸媒之表面上。 31. 如申請專利範圍第3〇項之方法，包含將載持於該光觸 媒之表面的該成分（iv)與該成分（iv)之鹽及該光觸媒 共沈。 32. 如申請專利範圍第3〇項之方法，其中該成分（iv)在光 觸媒表面上的載持作用，係藉由將該溶膠及該成分 之混合物經由紫外線照射，利用該光觸媒之光還原作 用使该成分（iv)載持於該光觸媒之表面上而進行。 本紙張尺度適用中國國家標準（CNS) A4規格（210 X 297公釐） -92 -91 VI. Application for Patent Scope 29 · If the method for applying for the scope of patent application No. 22, after the step of forming the surface layer in #, the following steps include: an application step, which is applied on the surface of the surface layer to form a layer containing A solution of antibacterial metal ions; and a mounting / fixing step for irradiating the aforementioned surface layer with ultraviolet rays, and using the photoreduction effect of the metal ions on the photocatalyst, the metal is supported / fixed in the surface layer Light photocatalyst. 30 · —A method for manufacturing a complex as described in the scope of patent application No. 丨 8, comprising preparing a sol having at least the component ⑴ dispersed therein, mixing in the sol-a component (iv), and holding it on the surface of the photocatalyst . 31. The method of claim 30, including co-precipitating the component (iv) carried on the surface of the photocatalyst with the salt of the component (iv) and the photocatalyst. 32. The method of claim 30, wherein the supporting effect of the component (iv) on the surface of the photocatalyst is the photoreduction of the photocatalyst by irradiating the mixture of the sol and the component with ultraviolet rays. This component (iv) is carried on the surface of the photocatalyst. This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) -92-