JP4011705B2

Photocatalyst compound, photocatalyst-containing material, material having photocatalytic function and production thereof

Abstract

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Term

Term ended

Expired 10 December 2017, 8.8 years ago.

26 claims: 24 independent, 2 dependent

1
基材と、表面層とを少なくとも有してなる、前記表面層が親水性でかつ自己浄化能を備えてなる、表面に時折雨が降り注ぐ環境において大気中の窒素酸化物、アンモニア、および/または二酸化硫黄を削減するために用いられる複合材であって、前記表面層が、成分(i)光の照射を受けると触媒として機能する光触媒と、成分(ii)A1 2 O 3 、ZnO、SrO、BaO、MgO、CaO、Rb 2 O、Na 2 O、およびK 2 Oからなる群から選択される少なくとも一の金属酸化物と成分(iii)SiO 2 、ZrO 2 、GeO 2 、およびThO 2 からなる群から選択される少なくとも一の金属酸化物と、成分(iv ) A gおよび Cuからなる群から選択される少なくとも一の抗菌性を発揮する金属とを含んでなり、前記成分(iv)が前記(i)の光触媒に担持されてなり、前記成分(iv)の重量をc、前記(i)の光触媒の重量をbと表したとき、c/bが0.00001~0.05である、複合材。
2
基材と、表面層とを少なくとも有してなる、前記表面層が親水性でかつ自己浄化能を備えてなる、表面に時折雨が降り注ぐ環境において大気中の窒素酸化物、アンモニア、および/または二酸化硫黄を削減するために用いられる複合材であって、前記表面層が、成分(i)光の照射を受けると触媒として機能する光触媒と、成分(ii)A1 2 O 3 、ZnO、SrO、BaO、MgO、CaO、Rb 2 O、Na 2 O、およびK 2 Oからなる群から選択される少なくとも一の金属酸化物と成分(iii)SiO 2 、ZrO 2 、GeO 2 、およびThO 2 からなる群から選択される少なくとも一の金属酸化物を成分(iv) Ag、Cu、Pd、Fe、Ni、Cr、Co、Pt、Au、Rh、およびRu からなる群から選択される少なくとも一の金属とを含んでなり、前記成分(iv)の重量をc、前記(i)の光触媒の重量をbと表したとき、c/bが0.00001~0.05である、複合材。
3
前記(ii)の金属酸化物重量をa、前記(i)の光触媒の重量をbと表したとき、a/(a+b)が0.0001~0.8を満足する、請求項1または2に記載の複合材。
4
前記(i)の光触媒および前記(ii)の金属酸化物が0.005~0.5μmの粒径の粒子として含んでなる、請求項1~3のいずれか一項に記載の複合材。
5
前記表面層が、下記の(1)または(2)のいずれかの条件を満たす表面性状を有するものである、請求項1~ 4 のいずれか一項に記載の複合材:(1)表面層膜厚が0.01~3.0μmである。(2)1%の硝酸銀溶液を表面層に付着させた状態で、該表面層上における紫外線強度が1.2mW/cm 2 で前記表面層に紫外線を5分間照射した際の紫外線照射前と紫外線照射後の表面層の色差△Eが1~50である。
6
前記基材層と、前記表面層との間にバインダが介在されてなる、請求項1~ 5 のいずれか一項に記載の複合材。
7
前記バインダが、前記基材の変形温度以下の温度において、重合または溶融して前記基材上に前記表面層を固着可能なものである、請求項1~ 6 のいずれか一項に記載の複合材。
8
前記バインダが釉薬または塗料である、請求項 7 に記載の複合材。
9
前記基材がタイルである、請求項1~ 8 のいずれか一項に記載の複合材。
10
前記基材が、陶器、木材、珪カル板、コンクリート、セメント板、セメント押し出し成形板、石膏ボード、またはオートクレーブ養生軽量コンクリート板である、請求項1~ 8 のいずれか一項に記載の複合材。
11
前記表面層の表面に、抗菌性を発揮する金属または金属化合物が固着されてなる、請求項1~ 10 のいずれか一項に記載の複合材。
12
請求項1 および3 ~ 11 のいずれか一項に記載の複合材の表面層を形成可能な配合物であって、該配合物が、成分(i)光の照射を受けると触媒として機能する光触媒と、成分(ii)A1 2 O 3 、ZnO、SrO、BaO、MgO、CaO、Rb 2 O、Na 2 O、およびK 2 Oからなる群から選択される少なくとも一の金属酸化物と成分(iii)SiO 2 、ZrO 2 、GeO 2 、およびThO 2 からなる群から選択される少なくとも一の金属酸化物と成分(iv ) A gおよび Cuからなる群から選択される少なくとも一の抗菌性を発揮する金属とを含んでなり、前記成分(iv)が前記(i)の光触媒に担持されてなり、前記成分(iv)の重量をc、前記(i)の光触媒の重量をbと表したとき、c/bが0.00001~0.05である、配合物。
13
請求項 2 ~ 11 のいずれか一項に記載の複合材の表面層を形成可能な配合物であって、該配合物が、成分(i)光の照射を受けると触媒として機能する光触媒と、成分(ii)A1 2 O 3 、ZnO、SrO、BaO、MgO、CaO、Rb 2 O、Na 2 O、およびK 2 Oからなる群から選択される少なくとも一の金属酸化物と成分(iii)SiO 2 、ZrO 2 、GeO 2 、およびThO 2 からなる群から選択される少なくとも一の金属酸化物と成分(iv)として、Ag、Cu、Pd、Fe、Ni、Cr、Co、Pt、Au、Rh、およびRuからなる群から選択される少なくとも一の金属とを含んでなり、前記成分(iv)の重量をc、前記(i)の光触媒の重量をbと表したとき、c/bが0.00001~0.05である、配合物。
14
前記(ii)の金属酸化物重量をa、前記(i)の光触媒の重量をbと表したとき、a/(a+b)が0.0001~0.8となるように配合されてなる、請求項 12 または 13 に記載の配合物。
15
前記(i)の光触媒および前記(ii)の金属酸化物が0.005~0.5μmの粒径の粒子として配合されてなる、請求項 12 ~ 14 のいずれか一項に記載の配合物。
16
請求項1~ 11 のいずれか一項に記載の複合材の製造法であって、請求項 12 ~ 15 のいずれか一項に記載の配合物またはこの配合物を分散してなる分散ゾルを準備する工程と、前記配合物または分散ゾルを、基材上に適用する工程と、前記配合物または分散ゾルが適用された基材を乾燥または加熱して、表面層を形成する工程とを少なくとも含んでなる、方法。
17
前記配合物または分散ゾルの基材への適用を、載置、塗布、または印刷によって行う、請求項 16 に記載の方法。
18
請求項1~ 11 のいずれか一項に記載の複合材の製造法であって、請求項 12 ~ 15 のいずれか一項に記載の配合物またはこの配合物を分散してなる分散ゾルを準備する工程と、前記基材上にバインダ層を形成する工程と、前記バインダ層上に、前記配合物または分散ゾルを適用する工程と、前記配合物または分散ゾルが適用された基材を乾燥または加熱して、表面層を形成する工程とを少なくとも含んでなる、方法。
19
前記バインダ層が釉薬からなり、前記配合物または分散ゾルが適用された基材を、前記釉薬の軟化温度よりも30°C以上300°C以下の範囲で高い温度で、かつ前記基材の変形温度よりも低い温度で加熱して、表面層を形成する、請求項 18 に記載の方法。
20
前記釉薬の軟化温度よりも30°C以上300°C以下の範囲で高い温度で、かつ前記基材の変形温度よりも低い温度が、150°C~1300°Cである、請求項 19 に記載の方法。
21
前記表面層を形成する工程に続いて、前記形成された表面層の表面に抗菌性を発揮する金属または金属酸化物が分散された溶液を塗布する工程と、前記金属または金属酸化物を前記表面層の表面に固着させる工程をさらに含んでなる、請求項 16 ~ 20 のいずれか一項に記載の方法。
22
前記配合物または分散ゾルを適用した後、抗菌性を発揮する金属または金属化合物が分散された溶液を塗布する工程をさらに含んでなる、請求項 16 ~ 20 のいずれか一項に記載の方法。
23
前記表面層を形成する工程に続いて、前記形成された表面層の表面に抗菌性を発揮する金属のイオンを含んでなる水溶液を塗布する工程と、前記表面層に紫外線を照射して前記金属イオンを、光還元を利用して前記表面層における光触媒に担持または固着させる工程をさらに含んでなる、請求項 16 ~ 20 のいずれか一項に記載の方法。
24
請求項 12 ~ 15 のいずれか一項に記載の配合物の製造法であって、少なくとも成分(i)が分散されてなるゾルを用意し、該ゾルに前記成分(iv)を混合し、前記光触媒の表面に前記成分(iv)を担持させることを含んでなる、方法。
25
前記光触媒の表面への前記成分(iv)の担持を、前記成分(iv)の塩と、前記光触媒とを共沈させることにより行う、請求項 24 に記載の方法。
26
前記光触媒の表面への前記成分(iv)の担持を、前記ゾルと前記成分(iv)との混合物に紫外線を照射し、前記光触媒の光還元により前記光触媒の表面に前記成分(iv)を担持させることにより行う、請求項 24 に記載の方法。

Independent claims26

223 paragraphs, as filed

[Technical Fields to which the Invention belongs] The present invention comprises a photocatalyst formulation containing a photocatalyst that functions as a catalyst when irradiated with light, and a photocatalyst function exhibiting material and a photocatalyst formulation using this photocatalyst formulation. Regarding the manufacturing method.

[0002] Conventionally, the use of this type of photocatalyst is expanding because the energy used for the catalytic reaction is inexhaustible due to the light energy such as sunlight. For example, titanium dioxide (TiO), which is a type of photocatalyst.2 ), Especially in the crystalline type of anatase-type titanium dioxide, excited electrons and holes are generated by the energy of the irradiated light (ultraviolet rays), and the generated excited electrons and holes cause the presence of oxygen and water on the catalyst surface. O below2Produces reactive oxygen species such as-, O-, and OH ( indicates unpaired electrons and means radical species). Then, by utilizing the radical properties of this active oxygen species, nitrogen oxides (NOx) in the atmosphere are subjected to an oxidation reaction by the active oxygen species to make them harmless reactants (nitrate). , Decomposition of bacteria through oxidation of organic components, so-called antibacterial use, etc. have been proposed.

[0003] [Problems to be Solved by the Invention] By the way, in the process in which nitrogen oxides undergo an oxidation reaction by reactive oxygen species, nitrogen dioxide (NO)2 ) Is produced as an intermediate product, and this dinitrogen oxide is further oxidized to nitric acid. Then, the production of nitric acid reduces nitrogen oxides in the atmosphere and purifies the atmosphere. Therefore, in order to increase the efficiency of reducing nitrogen oxides, it is indispensable that active oxygen species and nitrogen oxides or nitrogen dioxide coexist. However, since nitrogen dioxide is a chemically relatively stable compound (gas), the produced nitrogen dioxide escapes from the reaction system and the efficiency of the oxidation reaction by reactive oxygen species decreases, resulting in a reduction. The efficiency will also decrease. Although it is conceivable to suppress the release of nitrogen dioxide by using a porous adsorbent such as activated carbon, it is not always effective as described below.

[0004] With such an adsorbent, once the nitrogen dioxide that has been released is adsorbed, the nitrogen dioxide may remain adsorbed in the pores of the adsorbent and not be released. Therefore, the adsorbed nitrogen dioxide may be placed outside the system of the oxidation reaction by the active oxygen species and not subjected to this oxidation reaction to become nitric acid, which is the final product. Therefore, the nitrogen oxides do not finally change to nitric acid, and the reduction efficiency is hindered. However, nitrogen dioxide adsorbed by the adsorbent is oxidized to nitric acid in the region in the reaction system that can coexist with the active oxygen species, that is, in the region close to the photocatalyst, but the region close to the photocatalyst is adsorbed. Since it is very limited to the entire adsorption region (including pores) of the substance in the agent, it can be said that the proportion of nitrogen dioxide that is not oxidized to nitric acid is high. In other words, even if an adsorbent is used, it only adsorbs and retains dinitrogen oxides, and it seems that the reduction of nitrogen oxides through the transition to nitric acid is not sufficient.

[0005] The present invention has been made to solve the above problems, to further improve the efficiency of a catalytic reaction involving a photocatalyst, or to obtain a final product of a reaction product subjected to this catalytic reaction. The purpose is to improve the reduction efficiency through the transition. Another purpose is to complement the function of the photocatalyst.

[Means for Solving the Problems and Their Actions and Effects] In order to solve the problems, the present inventionLight ofThe catalyst formulation isA formulation capable of forming a surface layer of a composite material The formulation is Component (i) A photocatalyst that functions as a catalyst when irradiated with light, component(ii) A12O3, ZnO, SrO, BaO, MgO, CaO, Rb2O, Na2O, and K2With at least one metal oxide selected from the group consisting of O component(iii) SiO2, ZrO2, GeO2, And ThO2With at least one metal oxide selected from the group consisting ofIs included.That is, the photocatalyst formulation of the present inventionWith a photocatalyst that functions as a catalyst when exposed to lightcomponent(ii)and(iii)Is a photocatalyst compound containing the above.component(ii)When the reaction product subjected to the catalytic reaction involving the photocatalyst undergoes the catalytic reaction and undergoes a chemical change to change to the final product defined by the structure of the reaction product and the catalytic reaction. It is characterized by being a compound that functions to increase the degree of transition from the reaction product to the final product in the coexistence with a photocatalyst.

[0007] The present invention having the above configurationLight ofAccording to the catalyst compound, the degree of transition from the reaction product to the final product is increased, so that the reduction efficiency of the reaction product can be improved.

[0008] The present invention having the above configurationLight ofThe following aspects can be taken in the catalyst formulation.According to a preferred embodiment of the present inventionSaidcomponent(ii)Is a compound that chemically binds to the product to be reacted or an intermediate product produced before the product to be reacted undergoes the catalytic reaction and is transformed into the final product.

[0009] ThisStateIn the same way, the reaction or intermediate product was formulated with a photocatalyst.component(ii)It is chemically bound to and retained. Then, the reaction product or the intermediate product is retained.component(ii)Does not have a porous structure, so these reactants or intermediate products are not placed outside the system of the catalytic reaction involving the photocatalyst, that is, in a region away from the photocatalyst. Place these reactants or intermediate products in the system of catalytic reaction through their adjacencies. Moreover, since the bond with the reaction product or the intermediate product is chemical, the reaction product or the intermediate product can be surely kept in the system of the catalytic reaction. As a result, thisStateAccording to such a photocatalytic formulation, the opportunity for the reaction product to be subjected to the catalytic reaction and the opportunity for the intermediate product to be further subjected to the catalytic reaction can be surely secured, and the catalytic reaction can proceed more efficiently. be able to. Then, since the degree of transition from the reaction product to the final product is increased through the improvement of the efficiency of the catalytic reaction, the reduction efficiency of the reaction product can be improved.

【0010】According to a preferred embodiment of the present inventionThe photocatalyst is a photocatalyst that generates excited electrons and holes by the energy of irradiated light, and generates active oxygen species by the excited electrons and holes in the presence of oxygen and water on the surface of the catalyst.

[0011] ThisStateAccording to the above, the reactants or intermediate products are placed in the system of catalytic reaction based on the active oxygen species generated by the photocatalyst, and the opportunity for these reactants to be subjected to the catalytic reaction and the intermediate products are further increased. The opportunity to be subjected to this catalytic reaction can be surely secured, and the catalytic reaction can proceed more efficiently. Therefore, the reduction efficiency of the reaction product can be increased.

[0012] In this case, the photocatalyst is titanium dioxide (T).iO2,), Zinc oxide (ZnO), Vanadium oxide (V)2O5), Tungsten trioxide (WO3 ) Etc. can be exemplified. These photocatalysts are not limited to their crystal type, and for example, titanium dioxide having an anatase type, rutile type, or brookite type crystal type may have any crystal type. Most preferably, anatase-type titanium dioxide is preferable from the viewpoint of easy availability. In addition, the reaction products to be subjected to the catalytic reaction based on the active oxygen species, their intermediate products, and the final products include nitrogen oxides, nitrogen dioxide and nitric acid, sulfur oxides, sulfur dioxide and sulfuric acid or sulfite. Examples thereof include carbon oxide, carbon dioxide, and carbon dioxide. Ammonia can also be exemplified as a reaction product, and the intermediate products and final products in this case are nitric oxide, nitrogen dioxide and nitric acid produced from ammonia.

【0013】According to a preferred embodiment of the present inventionSaidcomponent(ii)Is at least one metal of an amphoteric metal oxide, a basic metal oxide or an acidic metal oxide that chemically binds to the reaction product or the intermediate product subjected to the catalytic reaction based on the active oxygen species. It is an oxide.

[0014] ThisStateAccording to the above, when a reaction product or an intermediate product is placed in a system of catalytic reaction based on an active oxygen species generated by a photocatalyst, if the reaction product or the intermediate product is acidic, the so-called base point Can be formed with a specific atom due to the atomic arrangement of the basic metal oxide, and the basic metal oxide and the reaction product or the intermediate product can be reliably chemically bonded at this base point. Further, when the reaction product or the intermediate product is basic, a so-called acid point can be formed by a specific atom due to the atomic arrangement of the acidic metal oxide, and the acid point is reacted with the acidic metal oxide. The product or intermediate product can be reliably chemically bonded. Furthermore,component(ii)If is an amphoteric metal oxide, a specific atom resulting from the atomic arrangement of the amphoteric metal oxide can be set as a base point or an acid point suitable for the properties of the reaction product or the intermediate product. Regardless of whether the product or intermediate product is basic or acidic, the amphoteric metal oxide can be reliably chemically bonded to the reaction product or intermediate product.

[0015] In this case, the amphoteric metal oxide is alumina (Al).2O3), Zinc oxide (ZnO), tin oxide (SnO, SnO)2 ) Etc. can be exemplified. The basic metal oxides include strontium oxide (SrO), barium oxide (BaO), magnesium oxide (MgO), calcium oxide (CaO), and rubidium oxide (Rb).2O), sodium oxide (Na)2O), potassium oxide (K)2O) etc. can be exemplified. Furthermore, as an acidic metal oxide, phosphorus oxide (P)2O5) Etc. can be exemplified. The formation of base points or acid points in these metal oxides is due to the difference in electronegativity between the metal atoms and oxygen atoms that make up the metal oxide and the atomic arrangement of the metal atoms and oxygen atoms on the surface of the metal oxide. To do. Then, the above-mentioned basic metal oxide, acid metal oxide, and amphoteric metal oxide are appropriately selected in correspondence with the above-mentioned reaction product and its intermediate product to be subjected to the catalytic reaction based on the active oxygen species. Just do it. Since zinc oxide is a photocatalyst and an amphoteric metal oxide, it goes without saying that when zinc oxide is selected as the photocatalyst, zinc oxide is not selected as the amphoteric metal oxide.

[0016] Here, a case where the photocatalyst is titanium dioxide, the compound is alumina which is an amphoteric metal oxide, and the reaction object is nitrogen oxide (nitrogen monoxide) is taken as an example, and the state of the catalytic reaction and the alumina are used. The state of bonding will be described. In this case, nitric oxide is oxidized by the active oxygen species produced by titanium dioxide to become nitrogen dioxide as an intermediate product. As schematically shown in FIG. 1, when nitric oxide comes into contact with or is in close proximity to titanium dioxide, which is a photocatalyst, this nitric oxide is an active oxygen species produced by titanium dioxide when irradiated with light. It is oxidized to nitric oxide (gas) by acid radicals (Fig. 1 (a)). Since this nitrogen dioxide is acidic due to its molecular structure, and alumina is an amphoteric metal oxide and its oxygen atom is used as a base point for an acidic gas, nitrogen dioxide is attracted to this oxygen atom and chemically. It binds to and is retained in alumina (Fig. 1 (b)). The force that attracts nitrogen dioxide to the oxygen atom is the Coulomb force, and the bond is chemical.

Nitrogen dioxide bonded to the oxygen atom of alumina is retained in close proximity to titanium dioxide, which is a photocatalyst, and is therefore in the system of oxidation reaction (catalytic reaction) caused by hydroxyl radical OH (FIG. 1). (b)). Therefore, the opportunity for nitrogen dioxide to be oxidized by the hydroxyl radical OH is surely secured, and the oxidation of nitrogen dioxide proceeds efficiently. It is said that the oxidized nitrogen dioxide becomes nitrate ion and is bonded and retained with the hydrogen atom in hydroxyl radical OH and the oxygen atom of alumina which is the above-mentioned base point in the form of nitric acid (final product). It is possible (Fig. 1 (c)).

[0018] In this case, if nitrogen dioxide is present from the beginning, that is, if nitrogen dioxide is the object to be reacted, this nitrogen dioxide is directly oxidized by the reactive oxygen species produced by titanium dioxide, and as described above. Nitrogen dioxide chemically bound to alumina will also be oxidized by this reactive oxygen species. In other words, in such a case, alumina chemically bonds nitrogen dioxide as a reaction product.

[0019] Next, the state of bonding by alumina when sulfur monoxide (SO) and carbon monoxide (CO) are oxidized by the active oxygen species produced by titanium dioxide will be described. When these oxides are oxidized, they become sulfur dioxide and carbon dioxide, and also become acid gas. Therefore, as schematically shown in FIG. 2, sulfur dioxide is a base point of alumina, which is an amphoteric metal oxide, and is chemically bonded to an adjacent oxygen atom to be retained in alumina. Further, as schematically shown in FIG. 3, since carbon dioxide can be bonded with a bond order different from that of the carbon atom and the oxygen atom, it can be bonded to a single oxygen atom serving as a base point as described above (Fig. 3 (a)). ), Or it becomes a base point and chemically bonds with an adjacent oxygen atom (Fig. 3 (b)) and is retained in alumina. Then, the sulfur dioxide bonded and retained in this way further reacts with the active oxygen species (hydroxyl radicals / OH) generated by titanium dioxide to become sulfuric acid or sulfurous acid (final product), and carbon dioxide becomes carbonic acid (final). Product). It is also considered that carbon dioxide is transformed into methane and methanol by a reaction based on the radical hydrogen atom generated during the generation of hydroxyl radical OH, which is an active oxygen species, and the active oxygen species. In this case, this methane and methanol can also be said to be final products.

【0020】According to a preferred embodiment of the present inventionSaidcomponent(ii)Is compounded so that a / (a + b) is about 0.0001 to 0.8 when the weight is expressed as a and the weight of the photocatalyst is expressed as b.

[0021] ThisStateIf a / (a + b) is about 0.0001 or more, it is represented by a.component(ii)(Amphoteric metal oxide, basic metal oxide, acidic metal oxide) is preferable because it secures the chemical bond of the reaction product or the intermediate product and does not reduce the efficiency of the catalytic reaction. If a / (a + b) is about 0.8 or less, the amount of photocatalyst represented by b is as described above.component(ii)It is preferable because it is not too small and does not reduce the efficiency of the catalytic reaction.

[0022] In this case, the amount of the photocatalyst is about 20 to 95 wt with respect to the total amount of the above compound, which is a compound of the photocatalyst and other compounds, and the other compound, if any. It may be about%.

【0023】According to a preferred embodiment of the present inventionThe photocatalyst and thecomponent(ii)Is adjusted and blended in a particle size range of about 0.005 to 0.5 μm.

[0024] ThisofAs in the aspect, with a photocatalystcomponent(ii)If the particle size of (amphoteric metal oxide, basic metal oxide, acid metal oxide) is in the range of about 0.005 to 0.5 μm, the particle size can be easily adjusted by an existing pulverizer such as a ball mill or the sol gel method. Is preferable. Also, thisStateAccording to the photocatalystcomponent(ii)Since there is no significant difference in the particle size of the photocatalystcomponent(ii)Are close to each other with particles of almost the same size. Therefore, thiscomponent(ii)It is preferable that the reaction product or the intermediate product chemically bonded to the photocatalyst can be brought close to the photocatalyst, and the efficiency can be improved by ensuring a sufficient opportunity for the catalytic reaction to proceed.

【0025】According to a preferred embodiment of the present inventionThe photocatalyst and thecomponent(ii)In addition, a compound that has the property of chemically adsorbing hydroxyl groupscomponent(iii)The hydroxyl group is provided as the photocatalyst and the photocatalyst.component(iii)It is chemically adsorbed and retained on the surface of the compound as a compound, and exhibits hydrophilicity due to the retained hydroxyl group.

[0026] ThisStateIn the same way, the hydroxyl groups generated through the catalytic reaction of the photocatalyst are not only the photocatalyst but alsocomponent(iii)It is chemically adsorbed and retained on the surface of the compound. Since the water content (water vapor in the air, rainwater, etc.) on the surface of the catalyst does not become zero, it can be said that hydroxyl groups are constantly generated while the light is irradiated. Therefore, the hydroxyl groups are held at an extremely high density, and the holding is performed by a bond called chemisorption, so that it can be said that the hydroxyl groups are firmly held. On the other hand, while the light is not irradiated, the hydroxyl group generated by the photocatalyst does not occur, but the hydroxyl groups generated up to that point are the photocatalyst.component(iii)It is firmly retained on the surface of the compound, and the hydroxyl group is not inadvertently removed. Moreover, if the light is irradiated again, even if the density of the hydroxyl groups has decreased by then, the state of holding the high density is quickly restored. Therefore, thisStateBy fixing such a photocatalyst formulation to the surface of some base material, the surface of the base material can be surely made highly hydrophilic, and this high hydrophilicity can be surely maintained for a long period of time. In other words, thisStateSuch a photocatalyst formulation is a hydrophilicity-imparting material that imparts high hydrophilicity to the surface of the base material.

[0027] Here, the effect of hydrophilicity will be described. Hydrophilicity is strongly related to the contact angle with water, and the higher the hydrophilicity, the smaller the contact angle. On the other hand, if the contact angle is small, it becomes difficult for water to stay on the surface, so that dirt adhering to the surface flows down together with the water and is removed from the surface. Therefore, if hydrophilicity capable of exhibiting a contact angle lower than the contact angle of urban dust containing a large amount of lipophilic components and inorganic dust such as clay minerals can be obtained, these dusts can be removed without exhibiting affinity. it can. Moreover, as the contact angle approaches zero degrees, the hydrophilicity increases, and water diffuses into a film on the surface of the base material and easily flows. Therefore, not only the above-mentioned urban dust but also inorganic dust easily flows down from the surface of the base material together with water. In this case, in order to enhance the stain prevention effect, it is more preferable that the contact angle is about 20 ° or less and close to zero.

[0028] Therefore, thisStateBy fixing such a photocatalyst compound to the surface of the inner and outer walls of a building or the surface of a vehicle body such as an automobile or a train, it is possible to obtain a high antifouling effect with the high hydrophilicity imparted in this way. In this case, if it rains occasionally on these surfaces, the dust and pollutants on the surface will be washed away from the surface together with the rainwater due to the high hydrophilicity imparted to these surfaces, and these surfaces will be self-cleaned. .. That is, so-called rain streak stains in which dust and the like remain in streaks along the flow of water are effectively suppressed. Also, thisStateBy fixing such a photocatalyst formulation to the surface of glass, a lens, a mirror, or the like, it is possible to obtain a high antifogging effect with high hydrophilicity.

【0029】According to a preferred embodiment of the present inventionSaidcomponent(iii)Is a compound having a moist heat equal to or higher than that of the photocatalyst.

[0030] Wet heat can be regarded as an index showing the retention characteristics of hydroxyl groups on the surface of a substance in which hydroxyl groups can be present on the surface, and the higher the heat of wetness, the higher the degree of hydroxyl group retention and the higher the hydroxyl group density. Therefore, thisStateAccording to the report, the hydroxyl groups generated by the photocatalyst are more effective and denser.component(iii)It can be chemically adsorbed and retained on the compound of, and can impart high hydrophilicity to the surface of the base material more reliably and for a long period of time. In this case, the wet heat of titania, which is particularly preferable as a photocatalyst, is 320 to 512x10 in the anatase type.-3Jm-2, Rutile type 293 ~ 645x10-3Jm-2Because it is 500x10-3Jm-2It is more preferable that the compound has the above wet heat.

[0031] In the formulation of the present invention, the compound as the component (iii) is SiO.2, ZrO2 , GeO2, ThO2 , At least one metal oxide selected from ZnO.

[0032] Since these metal oxides have a moist heat equal to or higher than the moist heat of titania, which is particularly preferable as a photocatalyst, the retention density of hydroxyl groups is further increased, which is preferable. In particular, silica (SiO)2), GeO2 , ThO2 Has an upper limit of 1000x10 in the range of wet heat-3Jm-2It is more preferable because it exceeds.

【0034】According to a preferred embodiment of the present inventionThe photocatalyst and thecomponent(ii)And saidcomponent(iii)In addition to the compound ascomponent(iv)Prepared as described abovecomponent(iv)The metal as is supported on the photocatalyst.

[0035] ThisStateIn the same way, the antibacterial function that the photocatalyst itself can perform while being irradiated with light can be fulfilled by the metal supported on the photocatalyst while it is not irradiated with light. Therefore, the antibacterial function of the photocatalyst can be complemented, and the metal exhibiting antibacterial activity and the photocatalyst can exhibit synergistic antibacterial activity.

【0036】According to a preferred embodiment of the present inventionSaidcomponent(iv)The metal as is a metal having a reduction potential equal to or higher than the potential of the free electrons emitted by the photocatalyst.

[0037] ThisStateIn the same way, the metal can be easily supported on the photocatalyst by the reduction potential of the metal. In this case, if at least one metal selected from Ag, Cu, Pd, Fe, Ni, Cr, Co, Pt, Au, Li, Ca, Mg, Al, Zn, Rh, and Ru is used, the reduction potential is as described above. Ag, Cu, Pd, Pt, and Au are particularly preferable because they have a positive reduction potential, so that reduction carrying is likely to occur. Andcomponent(iv)When the weight of the metal selected as is c and the weight of the photocatalyst is d, it is preferable that the metal is blended so that c / d is about 0.00001 to 0.05. That is,component(iv)If the amount of metal is 0.00001 (= c / d) or more, the situation that the metal is too small to exhibit synergistic antibacterial properties does not occur, and if it is 0.05 (= c / d) or less, the relevant metal is applicable. It is preferable that the excess metal does not adversely affect the catalytic reaction of the photocatalyst.

[0038] The present inventionLight ofThe catalyst-containing material is a photocatalyst-containing material having a photocatalyst that functions as a catalyst when irradiated with light, and the present invention described above.Light ofThe catalyst formulation or the photocatalyst formulation of each aspect thereof is mixed and dispersed in a paint or a glaze.

[0039] The present invention having the above configuration.Light ofFor paints and glazes that are catalyst-containing materials, the present inventionLight ofSimilar to the catalyst formulation, it is possible to increase the efficiency of reducing the reaction product and to ensure that the reaction product or the intermediate product is kept in the system of the catalytic reaction. Therefore, the reaction object can be efficiently reduced on the surface of the one coated with this paint or on the surface of the one coated with the glaze. Further, on these surfaces, the opportunity for the reaction product to be subjected to the catalytic reaction and the opportunity for the intermediate product to be further subjected to the catalytic reaction can be surely secured, and the catalytic reaction can proceed more efficiently. ..

[0040] In this case, the paint or glaze to be mixed and dispersed with the photocatalyst and the compound may be an existing one, and in the case of a glaze, the photocatalyst and the compound are contained together with a glaze raw material such as a frit such as feldspar or potassium carbonate. It is dispersed in the solution. When the photocatalyst and the compound are dispersed and mixed, they may be blended together with the above-mentioned glaze raw materials in the process of producing the glaze, or may be blended into the completed glaze prior to the glaze.

[0041] The present invention described above.Light ofIn the catalyst-containing material, the photocatalyst generates excited electrons and holes by the energy of the irradiated light, and generates active oxygen species by the excited electrons and holes in the presence of oxygen and water on the surface of the catalyst. And saidcomponent(ii)Is at least one metal of an amphoteric metal oxide, a basic metal oxide or an acidic metal oxide that chemically binds to the reaction product or the intermediate product subjected to the catalytic reaction based on the active oxygen species. A photocatalyst-containing material (paint or glaze), which is an oxide, has the following advantages.

[0042] According to this photocatalyst-containing material, the present invention.Light ofSimilar to the above-described aspect of the catalyst formulation, the reaction product or intermediate product is reliably bound and retained at the base point or acid point, and the reaction product or the reaction product or the reaction product is contained in the system of the catalytic reaction based on the reactive oxygen species. Intermediate products can be placed. Therefore, the catalytic reaction can proceed more efficiently on the surface of the one coated with the paint as the photocatalyst-containing material, or on the surface of the one coated with the glaze, thereby increasing the efficiency of reducing the reactants. be able to. Also,component(iii)Using a photocatalyst formulation containing the compound ofBy, It is preferable that a high antifouling effect based on high hydrophilicity can be exhibited on these surfaces. Furthermore, the present inventionLight ofCatalyst formulationSuitableLike the aspectcomponent(iv)When a photocatalyst formulation having the above metal is used, it is preferable that the metal exhibiting antibacterial activity and the photocatalyst exhibit synergistic antibacterial activity on these surfaces.

[0043] Further, the present inventionLight ofFor catalyst-containing materials, especially paints, the paint is used to form a coating film of photocatalyst-containing materials on the inner and outer walls of existing buildings such as buildings, houses and bridges, and existing structures such as road guard rails and sound insulation walls. it can. Therefore, the existing structure can be easily modified into a structure having a high efficiency of reducing the reaction object and a high antifouling effect.

[0044] The present inventionCompositeThe material isNitrogen oxides, ammonia, and / or atmospheric nitrogen oxides, ammonia, and / or in an environment with occasional rain on the surface, which comprises at least a substrate and a surface layer, the surface layer being hydrophilic and self-cleaning. A composite material used to reduce sulfur dioxide The surface layer Component (i) A photocatalyst that functions as a catalyst when irradiated with light, component(ii) A12O3, ZnO, SrO, BaO, MgO, CaO, Rb2O, Na2O, and K2With at least one metal oxide selected from the group consisting of O component(iii) SiO2, ZrO2, GeO2, And ThO2At least one metal oxide selected from the group consisting ofIs included.That is, the composite material of the present invention isA material having a base material layer and a surface layer formed on the surface thereof and exhibiting a photocatalytic function when irradiated with light, and as the surface layer, the present invention described above.Light ofA surface layer composed of a catalyst compound or a photocatalytic compound of each aspect thereof, or the present invention described above.Light ofHas a surface layer made of catalyst-containing materialcompositeIt is a material.

The present inventionCompositeThe material iscomponent(iii)Compound as, or thiscomponent(iii)In addition tocomponent(iv)In the case of having a surface layer made of a photocatalyst compound or a photocatalyst-containing material, the surface layer has a surface property that satisfies any of the following conditions (1) and (2). can do. (1) Surface layer film thickness: Approximately 0.01 to approximately 3.0 μm (2) With a 1% silver nitrate solution attached to the surface layer, the ultraviolet intensity on the surface layer is 1.2 mW / cm.2 Color difference between the surface layer before and after ultraviolet irradiation when the surface layer is irradiated with ultraviolet rays for 5 minutes ΔE: 1 to 50 [0046] This embodimentCompositeIn the material, on the surface layercomponent(iii)Because it will contain the compound ascomponent(iii)According to the compound of the present inventionLight ofCatalyst formulationSuitableAs in the embodiment, in this surface layer, the contact angle is reduced, the hydrophilicity is improved, and a high stain prevention effect can be exhibited. When the film thickness of the surface layer is about 0.01 μm or more, the film (surface layer) is not too thin, so that the contact angle of the surface layer itself can be reliably exhibited as this material, which is preferable. That is, even if the base material has a large contact angle, the contact angle is reduced by the surface layer formed on the base material, and a high stain prevention effect can be obtained. On the other hand, when the film thickness of the surface layer is about 3.0 μm or less, the adhesion of the surface layer to the substrate can be maintained, so that the surface layer peeling (film peeling) can be suppressed, which is preferable.component(iii)In addition to the compound ascomponent(iv)The same applies to those having a metal as.

Further, the silver ions in the silver nitrate solution adhering to the surface layer are reduced and precipitated by receiving excited electrons from the photocatalyst that has been excited by ultraviolet rays, and develops color. Therefore, a color difference ΔE is observed before and after the ultraviolet irradiation. Therefore, the more excited electrons are generated, the larger this color difference ΔE becomes. Since the amount of excited electrons generated is a factor that determines the magnitude of photocatalytic activity, the magnitude of photocatalytic activity can be evaluated using the color difference ΔE. Since excited electrons of the photocatalyst generate active oxygen species such as hydroxyl radicals and OH in the air, the larger the photocatalytic activity, that is, the larger the color difference ΔE, the more active oxygen species such as hydroxyl radicals and OH are generated. ..

[0048] By the way, it is contained in the surface layer.component(iii)The compound has a role of retaining hydroxyl radicals / OH generated by excited electrons of the photocatalyst, and the larger the amount of generated hydroxyl radicals / OH, the more.component(iii)The hydroxyl group density on the surface of the compound is also increased, the contact angle of water is reduced, and the hydrophilicity is increased. Further, as the amount of hydroxyl radicals and OH increases, the amount of decomposition of organic compounds in the surface layer increases, which is advantageous for hydrophilicity. Therefore, if the surface layer has a color difference ΔE of 1 or more, it has sufficient photocatalytic activity to form a high hydroxyl group density, and the contact angle of the surface layer due to this has a degree of antifouling effect. It seems that it can be surely made smaller, which is preferable. On the other hand, if the amount of the photocatalyst with respect to the binder per unit area of surface area increases, the color difference ΔE increases, but in this case, it is considered that the adhesion to the substrate is lowered and the surface layer is likely to be peeled off. Therefore, a surface layer having a color difference ΔE of 50 or less is preferable from the viewpoint of suppressing peeling of the surface layer.

【0049】According to a preferred embodiment of the present inventionOf the present inventioncompositeThe material has a base material layer and a surface layer formed on the surface thereof, and exhibits a photocatalytic function when irradiated with light. The surface layer is the above-mentioned main source.MingIt is a photocatalyst function exhibiting material which is a surface layer formed on the surface of the base material layer by interposing a binder in the photocatalyst compound or the photocatalyst compound of each aspect thereof.

[0050] ThisAspectIn the photocatalyst function exhibiting material of the above, the binder may be a binder that is polymerized or melted at a temperature equal to or lower than the alteration temperature of the base material of the base material layer to adhere the photocatalyst compound to the surface of the base material layer, or a glaze or a paint. Is preferable.

【0051】According to a preferred embodiment of the present inventionOf the present inventioncompositeThe material has a base material layer and a surface layer formed on the surface thereof, and exhibits a photocatalytic function when irradiated with light, and the surface layer is TiO as a photocatalyst.2 In addition to Al2O3And SiO2 It is a photocatalytic function exhibiting material containing a metal exhibiting antibacterial properties.

[0052] The present invention having the above configurationcompositeIn the material, the present invention is provided on the surface of the surface layer formed on the base material layer.Light ofSimilar to the catalyst formulation, it is possible to increase the efficiency of reducing the reaction product and to ensure that the reaction product or the intermediate product is kept in the system of the catalytic reaction. Therefore, on the surface of the surface layer of the photocatalytic function exhibiting material, the reaction product can be efficiently reduced, and the opportunity for the reaction product to be subjected to the catalytic reaction and the opportunity for the intermediate product to be further subjected to the catalytic reaction are ensured. And the catalytic reaction can proceed even more efficiently. Further, since the surface layer contains a metal exhibiting antibacterial properties, it is preferable that the metal exhibiting antibacterial properties and the photocatalyst can exhibit synergistic antibacterial properties in this surface layer.

[0053] The above-mentioned invention of the present invention.compositeIn the material, the photocatalyst is a photocatalyst that generates excited electrons and holes by the energy of the irradiated light, and generates active oxygen species by the excited electrons and holes in the presence of oxygen and water on the surface of the catalyst. , Saidcomponent(ii)Is at least one metal of an amphoteric metal oxide, a basic metal oxide or an acidic metal oxide that chemically binds to the reaction product or the intermediate product subjected to the catalytic reaction based on the active oxygen species. A photocatalytic function exhibiting material, which is an oxide, has the following advantages.

[0054] According to this photocatalytic function exhibiting material, the present invention.Light ofSimilar to the above-described aspect of the catalyst formulation, the reaction product or intermediate product is reliably bound and retained at the base point or acid point, and the reaction product or the reaction product or the reaction product is contained in the system of the catalytic reaction based on the reactive oxygen species. Intermediate products can be placed. Therefore, the catalytic reaction can be promoted more efficiently on the surface of the surface layer of the photocatalytic function exhibiting material, and the reduction efficiency of the reaction product can be enhanced through this. Also,component(iii)Using a photocatalyst formulation or photocatalyst-containing material containing the above compoundBy, It is preferable that a high antifouling effect based on high hydrophilicity can be exhibited on these surfaces. Furthermore, the present inventionLight ofCatalyst formulationSuitableLike the aspectcomponent(iv)When a photocatalyst formulation or a photocatalyst-containing material having the above metal is used, it is preferable that the metal exhibiting antibacterial activity and the photocatalyst exhibit synergistic antibacterial activity on these surfaces.

[0055] The above-mentioned invention of the present invention.compositeThe following aspects can be adopted in the material.According to a preferred embodiment of the present inventionThe base material layer is made of any of ceramic, resin, metal, glass, pottery, wood, siliceous board, concrete board, cement board, cement extruded orthopedic board, gypsum board or autoclave curing lightweight concrete board. .. According to this aspect, nitrogen oxides, sulfur oxides, and carbon dioxide gas exert a photocatalytic function in places where these base materials are used, for example, inside and outside walls of building structures such as buildings, houses, and bridges, and roads. It is possible to purify the air by decomposing environmental pollutants such as. Furthermore,component(iii)When a photocatalyst compound containing the above compounds is used, a high antifouling effect based on high hydrophilicity can be exhibited on the inner and outer walls of these building structures, roads, and the like.

【0056】According to a preferred embodiment of the present inventionThe surface layer is formed by heat treatment, for example, firing. According to this aspect, the surface layer can be firmly formed on the base material layer.

【0057】According to a preferred embodiment of the present inventionA metal or metal compound exhibiting antibacterial properties is fixed to the surface of the surface layer. According to this aspect, the antibacterial function that the photocatalyst in the surface layer can perform while irradiated with light, and this antibacterial function while not irradiated with light, the metal or metal oxidation of the surface of the surface layer. It can be fulfilled by things. Therefore, the antibacterial function of the photocatalyst can be complemented. In addition to the photocatalyst, the surface layer has the abovecomponent(ii)In addition to the antibacterial function, it is possible to decompose environmental pollutants and purify the atmosphere by improving the efficiency of the catalytic reaction involving the above-mentioned photocatalyst. Also,component(iii)Using a photocatalyst formulation or photocatalyst-containing material containing the above compoundBy, These surface layers are preferable because they can exert a high antifouling effect based on high hydrophilicity. The present inventionLight ofCatalyst formulationSuitableLike the aspectcomponent(iv)When a photocatalyst compound or a photocatalyst-containing material having the above metal supported is used, thiscomponent(iv)Since synergistic antibacterial properties can be exhibited even with the metal of the above, the amount of metal or metal compound to be adhered to the surface of the surface layer can be very small. Also,component(iv)If the synergistic antibacterial property of the metal is high, the adhesion of the metal or the metal compound to the surface of the surface layer can be omitted.

[0058] Of the present inventioncompositeThe method for producing a material is a method for producing a material having a base material layer and a surface layer formed on the surface thereof and exhibiting a photocatalytic function when irradiated with light.Light ofCatalyst formulationOr the process of preparing a dispersion sol obtained by dispersing this formulation, A step of applying the formulation or dispersion sol onto a substrate, and A step of forming a surface layer by drying or heating a substrate to which the formulation or dispersion sol is applied.Contain at leastIt is characterized by that.

[0059] In this case, the photocatalyst compound dispersion sol can be obtained by dispersing the photocatalyst compound in a solution of water, alcohol or the like.

[0060] The present inventionMade ofThe present invention does not require a special process according to the manufacturing method.Light ofAs described in the catalyst formulation, it is possible to easily produce a new photocatalytic function exhibiting material that causes a catalytic reaction with high efficiency in the surface layer by ensuring that the reaction object or intermediate product is placed in the catalytic reaction system. it can. At this time, in forming the surface layer, an appropriate method, for example, heat treatment or drying treatment can be adopted depending on the arranged photocatalyst compound or the photocatalyst compound dispersion sol.

The present inventionMade ofIn the manufacturing method, in the arrangement step, when the photocatalyst formulation or the photocatalyst formulation dispersion sol is arranged in a layer on the surface of the base material layer, the photocatalyst formulation or the photocatalyst formulation dispersion sol is subjected to the above. A method for producing a photocatalytic function exhibiting material, which comprises a step of placing, coating or printing in a layer on the surface of a base material layer, has the following advantages.

The present inventionMade ofAccording to the production method, it is possible to easily produce a novel photocatalytic function exhibiting material which is composed of a photocatalyst compound and causes a catalytic reaction with high efficiency in a surface layer having a substantially uniform thickness. The layered coating of the photocatalyst compound on the surface of the base material layer can be performed by an appropriate coating method such as spray coating, and the layered printing can be performed by an appropriate printing method such as roll printing.

[0063] Of the present inventioncompositeOf woodanotherThe production method is a method for producing a material having a base material layer and a surface layer formed on the surface thereof and exhibiting a photocatalytic function when irradiated with light.Light ofCatalyst formulationOr the process of preparing a dispersion sol obtained by dispersing this formulation, The step of forming a binder layer on the base material and The step of applying the formulation or the dispersion sol on the binder layer, and A step of forming a surface layer by drying or heating a substrate to which the formulation or dispersion sol is applied.Contain at leastIt is characterized by that.

[0064] The present inventionMade ofAccording to the manufacturing method, at the boundary between the binder layer and the surface layer, the photocatalyst compound in the surface layer can be held in a state of being embedded in the binder layer, and the surface layer can be formed on the surface of the binder layer. Therefore, the surface layer can be firmly fixed to the binder layer, and the photocatalyst compound can be effectively brought into contact with the outside air. And the present inventionLight ofAs described in the catalyst formulation, by ensuring that the reaction object or the intermediate product is kept in the catalytic reaction system, it is possible to produce a novel photocatalytic function exhibiting material that causes a catalytic reaction in the surface layer with high efficiency.

[0065] In this case, when the binder is used as a glaze and the surface layer is formed, the temperature is higher than the softening temperature of the glaze in a range of 30 ° C. or more and 300 ° C. or less, and the alteration temperature of the base material of the base material layer. The heat treatment can be performed in a lower temperature environment. Since the heating temperature is 30 ° C or more higher than the softening temperature of the binder (glaze), it is preferable that the softening of the glaze by heating does not inadvertently take a long time. In addition, since the heating temperature is not higher than the softening temperature of the glaze by more than 300 ° C, it is possible to avoid rapid melting of the glaze and cause problems such as excessive filling of the photocatalyst compound, generation of uneven surfaces, and generation of pinholes. Can be suppressed. Further, in forming the surface layer, it is preferable to perform heat treatment in a temperature environment of about 150 to about 1300 ° C. In this way, it is possible to produce a novel photocatalytic function exhibiting material that causes a catalytic reaction with high efficiency by using an existing heating device. If the heat treatment temperature is set to about 150 ° C. or higher, it matches the heat treatment temperature of the existing glaze, and it is not necessary to change the heat treatment conditions from the conventional one. Further, if the heat treatment temperature is set to about 1300 ° C or less, the heat treatment temperature is matched with the heat treatment temperature at the time of forming a base material requiring heat treatment, for example, tile or ceramics, and the heat treatment conditions do not need to be changed from the conventional ones.

[0066] Further, when the binder is used as a paint to form the surface layer, heat treatment can be performed in a temperature environment equal to or lower than the alteration temperature of the base material of the base material layer. This is preferable because the surface layer can be formed without deteriorating the base material.

[0067] Further, the present invention described above.Made ofIn the manufacturing method, following the step of forming the surface layer, a step of applying a solution in which a metal or a metal compound exhibiting antibacterial properties is dispersed on the surface of the formed surface layer, and the step of applying the metal or the metal oxide. Can be provided with a step of fixing the surface layer to the surface of the surface layer.

[0068] According to the method for producing a photocatalytic function exhibiting material of this embodiment, a novel photocatalyst that can exhibit antibacterial properties in the surface layer regardless of whether it is in a bright place or in a dark place and causes a catalytic reaction in the surface layer with high efficiency. The functional material can be easily manufactured. Moreover, the property of exhibiting antibacterial properties regardless of whether it is in a bright place or in a dark place can be imparted to the photocatalytic function exhibiting material on which the surface layer has been formed.

[0069] Further, the present invention described above.Made ofIn the manufacturing method, in the arrangement step, the photocatalyst formulation or the photocatalyst formulation dispersion sol is arranged in layers, and then the metal or metal exhibiting antibacterial properties.OxideIt is assumed that the step of applying the solution in which the powder is dispersed is provided, and the step of forming the surface layer includes a step of fixing the metal or the metal oxide to the surface of the surface layer at the same time as forming the surface layer. be able to.

[0070] According to the method for producing a photocatalytic function exhibiting material of this aspect, a novel property having both a property of exhibiting antibacterial properties and a property of causing a catalytic reaction with high efficiency in both bright and dark places from the beginning. A photocatalytic function exhibiting material can be easily produced.

[0071] Further, the present invention described above.Made ofIn the manufacturing method, following the step of forming the surface layer, a step of applying a metal salt aqueous solution containing metal ions exhibiting antibacterial properties to the surface of the formed surface layer, and a step of irradiating the surface layer with ultraviolet rays. Then, it is possible to have a step of supporting and fixing the metal to the photocatalyst in the surface layer by utilizing the photoreduction of the metal ion to the photocatalyst.

[0072] According to the method for producing a photocatalytic function exhibiting material of this embodiment, a novel photocatalyst that can exhibit antibacterial properties in the surface layer regardless of whether it is in a bright place or in a dark place and causes a catalytic reaction in the surface layer with high efficiency. The functional material can be easily manufactured. Moreover, since the metal that contributes to the complementation of antibacterial properties is supported and fixed to the photocatalyst in the surface layer by utilizing photoreduction, the metal is less likely to fall off. Therefore, the complementary performance of antibacterial properties can be maintained for a long period of time. In addition, the property of exhibiting antibacterial properties regardless of whether it is in a bright place or in a dark place can be imparted to the photocatalytic function exhibiting material on which the surface layer has been formed. The present inventionLight ofCatalyst formulationSuitableLike the aspectcomponent(iv)When a photocatalyst formulation having the above metal supported is used, thiscomponent(iv)Since synergistic antibacterial properties can be exhibited even with the metal of the above, the amount of metal supported on the surface of the surface layer can be reduced to a very small amount through the application of an aqueous metal salt solution and the subsequent irradiation with ultraviolet rays. Also,component(iv)If the synergistic antibacterial property of the metal is high, the support of this metal on the surface of the surface layer can be omitted.

[0073] The present inventionLight ofThe method for producing the catalyst compound isPrepare a sol in which at least component (i) is dispersed, The component (iv) Is mixed, and the component (iv) Consists of supportingIt is characterized by that.That is, the method for producing a photocatalyst formulation of the present invention is:A photocatalyst that functions as a catalyst when exposed to light and the abovecomponent(ii)And saidcomponent(iii)Compound as and saidcomponent(iv)This is a method for producing a photocatalyst formulation in which the above-mentioned metal and the above-mentioned photocatalyst are blended.component(ii)And saidcomponent(iii)A method for preparing a photocatalyst-dispersed sol in which at least the photocatalyst is dispersed, and a method for producing a photocatalyst compound containing a photocatalyst that functions as a catalyst when irradiated with light.Light ofCatalyst formulationThing isThe step of preparing the dispersed photocatalyst compound dispersion sol and the metal salt aqueous solution containing the ion of the metal exhibiting antibacterial properties are mixed with the photocatalyst compound dispersion sol, and the metal is mixed.component(iv)It is characterized by having a step of supporting the photocatalyst.

【0074】According to a preferred embodiment of the present inventionA photocatalyst that functions as a catalyst when exposed to light and the abovecomponent(ii)And saidcomponent(iii)Compound as and saidcomponent(iv)This is a method for producing a photocatalyst formulation in which the above-mentioned metal and the above-mentioned photocatalyst are blended.component(ii)And saidcomponent(iii)A step of preparing a photocatalyst-dispersed sol in which at least the photocatalyst is dispersed, and a metal salt aqueous solution containing a metal ion exhibiting antibacterial properties is mixed with the photocatalyst-dispersed sol, and then the metal salt and the above-mentioned compound. The metal is co-precipitated with the photocatalyst formulation.component(iv)It is characterized by having a step of supporting the photocatalyst.

【0075】According to a preferred embodiment of the present inventionA photocatalyst that functions as a catalyst when exposed to light and the abovecomponent(ii)And saidcomponent(iii)Compound as and saidcomponent(iv)This is a method for producing a photocatalyst formulation in which the above-mentioned metal and the above-mentioned photocatalyst are blended.component(ii)And saidcomponent(iii)A step of preparing a photocatalyst-dispersed sol in which at least the photocatalyst is dispersed, and a metal salt aqueous solution containing metal ions exhibiting antibacterial properties are mixed with the photocatalyst-dispersed sol and then irradiated with ultraviolet rays. Use the photoreduction of metal ions to remove the metalcomponent(iv)It is characterized by having a step of supporting the photocatalyst.

[0076] According to the method for producing these photocatalyst formulations, the surface layer formed by using these photocatalyst formulations exhibits antibacterial properties regardless of whether it is in a bright place or in a dark place, and is high in this surface layer. A novel photocatalytic formulation that causes a catalytic reaction with efficiency can be easily produced. Moreover, according to the production method of the present invention, when the metal that contributes to the complementation of antibacterial properties is previously supported and fixed to the photocatalyst, it is sufficient to mix the photocatalyst dispersion sol and the metal salt aqueous solution, so that the process is simplified. be able to. In addition, the production method according to the preferred embodiment of the present invention utilizes coprecipitation or photoreduction when supporting and fixing the metal that contributes to the complementation of antibacterial properties to the photocatalyst in advance, so that the metal is less likely to fall off from the photocatalyst. , Antibacterial complementary performance can be maintained for a long period of time. Further, of the present invention10th manufacturing methodIs merely irradiating ultraviolet rays when supporting and fixing the metal, and does not require any chemicals or the like, so that the process can be simplified.

【0077】According to a preferred embodiment of the present inventionPhotocatalyst dispersion sol with photocatalystcomponent(ii)Whencomponent(iii)A sol in which all the compounds of the above are dispersed, that is, the present invention.Light ofCatalyst formulationThing isIt can be a dispersed sol. Also, in the photocatalyst dispersion sol after metal supportcomponent(ii)Whencomponent(iii)It is also possible to disperse the compound as. Furthermore, for convenience of storage, etc., in order to prepare a powdered photocatalyst compound,component(iv)As a metal-supported photocatalystcomponent(ii)Whencomponent(iii)The sol in which the compound as is dispersed may be dried.

[Other Aspects of the Invention] The present invention may adopt other embodiments such as the following, and the first other embodiment contains a photocatalyst that functions as a catalyst when irradiated with light. In the method for producing the compound, the step (A) of preparing the first sol in which the particles of the photocatalyst are dispersed, and the reaction product or the product to be reacted undergo the catalytic reaction to produce the final product. The above, which chemically binds to an intermediate product produced before it is transformed into a substance.component(ii)It is characterized by including a step (B) of preparing a second sol in which the particles of the above particles are dispersed, and a step (C) of mixing the first sol and the second sol.

[0079] According to the production method of the first other aspect, the photocatalyst can be easily obtained by mixing the first and second sol.component(ii)Can be dispersed in a solvent. Then, in the mixed sol that has undergone the step (C), only the photocatalyst is aggregated and exists, orcomponent(ii)With a photocatalyst that forms a photocatalyst formulation without the presence of only aggregatescomponent(ii)Is a sol that is mixed and dispersed almost uniformly. Therefore, this mixed sol is suitable for use as a photocatalyst compound dispersion sol, and can be used as a photocatalyst for materials used in a liquid state, such as paints and glazes.component(ii)Is easy to mix. Furthermore, since it is in the form of a sol, it is easy to weigh the first and second sol, so that it can be easily used as a photocatalyst through the weighing of each sol.component(ii)The mixing ratio of can be adjusted. In addition, if the solvent in the mixed sol is removed by a method such as drying, it can be used as a photocatalyst.component(ii)Is a solid, granular formulation that is mixed almost uniformly.

[0080] In this case, it is preferable to use the same solvent for the first sol and the second sol, or to use a so-called familiar solvent.

[0081] In the production method of the first other aspect described above, in the step (A), excited electrons and holes are generated by the energy of the irradiated light, and in the presence of oxygen and water on the catalyst surface. It has a step of adjusting the particles of the photocatalyst that generates active oxygen species by the excited electrons and holes, and the step (B) is the reaction product or the object to be subjected to the catalytic reaction based on the active oxygen species. At least one metal oxide of an amphoteric metal oxide, a basic metal oxide or an acidic metal oxide that chemically bonds with the intermediate product is described.component(ii)It is possible to have a step of adjusting the particles of the metal oxide.

[0082] According to this second other aspect, the reaction product or the intermediate product is reliably bound and retained at the base point and the acid point with the photocatalyst that causes a catalytic reaction based on the reactive oxygen species.component(ii)It is possible to easily obtain a photocatalyst formulation in which and is mixed almost uniformly.

[0083] Further, in the production method of the first other aspect described above, in the step (C), when the weight of the metal oxide is expressed as a and the weight of the photocatalyst is expressed as b, a / (a +] It is possible to have a step of blending the first sol and the second sol so that b) becomes about 0.0001 to 0.8.

[0084] According to the third other aspect, the amount of the metal oxide (amphoteric metal oxide, basic metal oxide, acidic metal oxide) is not too small, and the amount of the photocatalyst is the above. It is possible to easily obtain a photocatalyst formulation which is not too small with respect to the metal oxide of the above and does not cause a decrease in the efficiency of the catalytic reaction.

[0085] Further, in the production method of the first other aspect described above, the step (A) includes a step of adjusting the photocatalyst to particles having a particle size range of about 0.005 to 0.5 μm, and the step (A). B) may have a step of adjusting the metal oxide to particles having a particle size range of about 0.005 to 0.5 μm.

[0086] According to the fourth other aspect, the photocatalyst and the metal oxide (amphoteric metal oxide, basic metal oxide, acidic metal oxide) are subjected to an existing pulverizer such as a ball mill or a sol-gel method. It is preferable that the particle size can be easily adjusted. In addition, it is possible to easily obtain a photocatalyst compound that does not separate the reaction product or the intermediate product from the photocatalyst and does not reduce the efficiency of the catalytic reaction. Further, according to this aspect, the photocatalyst and the metal compound can be brought close to each other by particles having substantially the same size, and the reaction product or the intermediate product can be brought close to the photocatalyst, and the photocatalyst compounding with high efficiency of the catalytic reaction. You can easily get things.

[Embodiments of the Invention] Next, the embodiments of the present invention will be described.ExampleIt will be explained based on.

[0088] First,referenceThe formulation of the photocatalyst formulation used in the example will be described. Anatase-type titanium dioxide was used as the photocatalyst, and alumina, which is an amphoteric metal oxide, and strontium oxide and barium oxide, which are basic metal oxides, were used as the metal oxide to be blended with the photocatalyst. Then, the following steps were taken when preparing the photocatalyst formulation.

[0089] 1) Procurement of photocatalyst and metal oxide particles The raw materials for titanium dioxide, alumina, strontium oxide and barium oxide described above are procured and each is crushed with a crushing device such as a ball mill, or by the sol-gel method. Obtain fine particles of titanium dioxide, alumina, strontium oxide and barium oxide. At this time, the particle size is adjusted so that the particle size of each particle is in the particle size range of about 0.005 to 0.5 μm.

2) Preparation of sol Next, each compounding material prepared as described above is dispersed in a solvent such as water or alcohol, and a sol for each compounding material is prepared. In this case, the amount of dispersion of the dispersant in each sol (for example, the weight / solvent volume of the compounding material) is specified.

3) Adjustment of Photocatalyst Formulation After that, the prepared titanium dioxide sol (photocatalyst sol) is mixed with a metal oxide sol of alumina sol, strontium oxide sol, and barium oxide sol, and a titanium dioxide / alumina mixed sol (Ti / Al) is mixed. Sol), titanium dioxide / strontium oxide mixed sol (Ti / Sr sol) and titanium dioxide / barium oxide mixed sol (Ti / Ba sol) are obtained. In this case, when adjusting each of the above mixed sol, the mixed amount of the photocatalyst sol and the mixed amount of the metal oxide sol are weighed, and the mixing ratio of the photocatalyst and the metal oxide is various values by changing each weighing amount. The mixed sol that takes is adjusted. That is, when the weight of the metal oxide in each mixed sol is expressed as a and the weight of the photocatalyst is expressed as b, the blending ratio represented by a / (a + b) (hereinafter, this a / (a + b) is used. The mixing ratio determination ratio) is adjusted in various ways.

[0092] In addition to the above steps 1) to 3), particles such as alumina whose particle size has been adjusted can be added to the prepared photocatalyst sol and dispersed to obtain a Ti / Al sol or the like. Further, it is also possible to alternately or simultaneously disperse the photocatalyst particles whose particle size has been adjusted and the particles such as alumina in the above solvent to obtain a Ti / Al sol or the like in which the photocatalyst particles and the particles such as alumina are dispersed from the beginning.

Next, a photocatalytic function exhibiting material that exerts a photocatalytic function by using the photocatalyst compound (a mixed sol of Ti / Al sol, Ti / Sr sol, and Ti / Ba sol) prepared as described above will be described. .. BookreferenceExample (1streferenceIn Example), this photocatalytic function exhibiting material was used as a tile and manufactured as follows.

[0094] An glaze-free tile is prepared as a base material, and each of the above-mentioned mixed sol having a specified concentration is spray-coated on the surface of the tile. In this spray coating, the coating amount, that is, the spray time is adjusted so that the film thickness of the photocatalyst mixture on the tile surface after firing is about 0.85 μm. Next, a temperature that takes into account the melting temperature of silica and the like blended for fixing the photocatalyst and the melting temperature of titanium dioxide and each of the above metal oxides (book).referenceIn the example, by firing the tile after spray application of the mixed sol at about 800 ° C) for about 60 minutes, the above-mentioned sol neutral component (photocatalyst, photocatalyst,) is formed on the surface of the base material (tile). A final photocatalyst functioning material (photocatalyst functioning tile) having a surface layer containing (alumina, etc.) was used. Here, the evaluation will be described. The evaluation was made based on the presence or absence of the effect of reducing nitrogen oxides, ammonia, and sulfur dioxide, which are desired to be reduced as harmful substances in the air or indoors. The outline of the test is as follows. First, nitrogen oxide reduction will be described. Of course, instead of spray coating of the mixed sol, a method such as spin coating or dip coating can be adopted.

(1-1) Evaluation Test 1: Effect of Alumina, etc. on Reduction of Nitrogen Oxides First, the present inventionreferenceIn order to compare with the example product, a photocatalyst functioning tile (comparative example tile) using a photocatalyst compound containing only titanium dioxide without any alumina, strontium oxide and barium oxide.referenceExample photocatalytic function tile (referenceExample tile) was prepared as follows. The comparative example tile is a tile in which a photocatalytic sol containing 7.5 wt% of titanium dioxide is spray-coated on the tile surface and fired under the above firing conditions (about 800 ° CX 60 minutes). During this spray application, the weight of titanium dioxide on the tile surface after firing is approximately 3.3X10.-4g / cm2 The coating time and the like were set so as to be (the film thickness of titanium dioxide in this case is about 0.85 μm).referenceExample tiles are the following Ti / Al tiles, Ti / Sr tiles and Ti / Ba tiles.

[0096] The Ti / Al tile has a blending ratio determination ratio a / (a + b) of 1/11 with respect to the photocatalytic sol in which titanium dioxide occupies a ratio of 7.5 wt% as in the comparative example tile. This is a tile obtained by spray-coating and firing a Ti / Al sol in which the blending ratio of alumina is adjusted (a Ti / Al sol in which the weight ratio of alumina to titanium dioxide is 0.1) under the same conditions as the above-mentioned Comparative Example tile. The Ti / Sr tile is a tile in which a Ti / Sr sol containing titanium dioxide and strontium oxide in the same blending ratio as the Ti / Al tile is spray-coated and fired under the same conditions as the above comparative example tile. The same is true for Ti / Ba tiles. That is, since the comparative example tile has only titanium dioxide on the tile surface and exerts a reference catalytic function on the comparative control, this comparative example tile and each of the abovereferenceBy comparing the example tiles, the presence or absence and the degree of improvement in the catalytic function obtained by blending each metal oxide can be clarified. And the comparative example tile has a surface layer consisting only of titanium dioxide on the tile surface, and has.referenceThe example tile will have a surface layer consisting of a formulation containing titanium dioxide and alumina or strontium oxide or barium oxide.

[0097] This comparative example tile and eachreferenceThe example tiles were tested as follows. For the test, comparative example tiles and eachreferenceUsing a 10 cm square sample piece of the example tile, the nitrogen oxide reduction effect was measured with the test equipment shown in Fig. 4. This test device is provided with a cylinder 12 in which a constant concentration of nitrogen monoxide gas is sealed upstream of a sealed glass cell 10 on which a sample piece is placed, and the NO gas from this cylinder is sucked by an air pump 14. The atmosphere adjusted by the humidity regulator 15 is mixed by the flow rate adjusting valve 16, and a fixed amount (1 liter / min) of NO gas (1 liter / min) is added to the glass cell 10 from the flow rate adjusting valve 16 at a predetermined concentration (about 0.95 ppm). Test gas) is poured. Further, downstream of the glass cell 10, a concentration side regulator (NOx sensor) 18 for measuring the concentration of nitrogen oxides in the gas passing through the cell is provided. This NOx sensor 18 has NO concentration and nitrogen dioxide concentration in gas (NO).2 Concentration) is measured at any time, and in addition to the measured NO concentration and NO2 concentration, the sum of both concentrations is output as the nitrogen oxide concentration (NOx concentration). Further, the test apparatus has a lamp 20 that irradiates the inside of the glass cell 10 with ultraviolet rays (wavelength 300 to 400 nm). In this case, the lamp 20 has an ultraviolet intensity of 1.2 mW / cm on the sample piece.2 Lighting is controlled so as to be. Then, a sample piece is placed on the glass cell 10 of this test device and placed in an environment exposed to ultraviolet rays, and the comparative example tile and each are placed.referenceFor example tiles, NO for each elapsed time since the start of test gas pouring2 The concentration and NOx concentration were plotted. The results are shown in Fig. 5. The lamp 20 was turned on after the NOx concentration (NO concentration) on the outlet side became stable after the start of pouring the test gas.

[0098] In this evaluation test 1, if the reaction for oxidizing nitric oxide does not occur, for example, if the glass cell 10 is placed in a dark room and there is no generation of reactive oxygen species by titanium dioxide in the surface layer and no catalytic reaction occurs, then. The test gas flows to the NOx sensor 18 without any reaction. Therefore, the output of the NOx sensor 18 at this time is the same as the test gas concentration (CNO / in) for the NO concentration (CNO / out), and NO.2 Concentration (CNO2 / out) is zero, and NOx concentration (CNOx / out) is the same as CNO / out, that is, CNO / in. However, if NO is oxidized by a catalytic reaction based on the reactive oxygen species produced by titanium dioxide in the surface layer, the NO concentration decreases from CNO / in by the amount of the oxidation. Also, NO produced by NO oxidation2 If is detached from the tile surface, the detached NO2 Only for2 The concentration will increase. Then, the decrease in NO concentration due to NO oxidation and the generated NO2 NO due to detachment from the tile surface2 The degree of NOx reduction is determined from the relationship with the increase in concentration.

[0099] As shown in FIG. 5, in the comparative example tile, the NOx concentration sharply decreased at the start of the test, and after about 5 minutes from the start of the test, the NOx concentration started to increase and became the test gas concentration. Get closer. In addition, in this comparative example tile, gradually NO after the start of the test.2 The concentration increased to about 0.18 ppm after 30 minutes. This trend of increasing NOx concentration and NO2 The tendency of increasing concentration is almost the same. From these facts, in the comparative example tile, the photocatalytic reaction by titanium dioxide in the surface layer proceeds, NO is oxidized, and the NO concentration decreases, but NO2 As the concentration increases, the overall NOx reduction will not progress. Therefore, in the comparative example tile, NO2 NO to break off the tile surface2 It can be said that further oxidation on the tile surface of the tile has not occurred so much. Since the NOx concentration after 30 minutes was about 0.66 ppm, the NOx reduction efficiency in this comparative example tile was about 30.5% ((0.95-0.66) /0.95).

[0100] On the other hand, Ti / Al tiles, Ti / Sr tiles, and Ti / Ba tiles, respectively.referenceIn the example tiles, as in the comparative example tiles, the NOx concentration decreased sharply at the start of the test, and remained at a concentration slightly higher than the decreased minimum concentration. Also, eachreferenceFor example tiles, NO from the start of the test2 The concentration was low, reaching only about 0.05 ppm after 30 minutes. From these things, eachreferenceIn the example tile, first of all, it can be said that the photocatalytic reaction by titanium dioxide in the surface layer proceeds to oxidize NO and reduce the NO concentration. Also, NO2 Is bound to alumina, strontium oxide, and barium oxide and relatively does not separate from the tile surface, and this NO due to titanium dioxide2 Further oxidation of the active progress, NO2 It can be said that the concentration does not increase. Therefore, eachreferenceAccording to the example tile, it can be said that NOx can be reduced with extremely high efficiency. And since the NOx concentration after 30 minutes is about 0.45 ppm, eachreferenceThe NOx reduction efficiency of the example tile was about 52.6% ((0.95-0.45) /0.95), which was almost twice that of the comparative example tile. In addition, thesereferenceContinuing the above tests on the example tiles revealed that the NOx reduction efficiency remained high. Also, after 12 hours, the test was completed.referenceExample: When the tile surface was washed with water and the substances contained in the washing water were analyzed, the presence of nitric acid was confirmed.

[0101] In addition, eachreferenceThe surface condition of each of the example tiles was excellent with no abnormalities observed in the degree of unevenness. Moreover, when a sliding wear test using a plastic eraser was attempted in accordance with JIS-A6808, eachreferenceIt was also found that the surface layer of the example tiles did not deteriorate or peel off even after about 40 reciprocating slides, and was excellent in abrasion resistance. This means that the photocatalyst formulation produced by the above-mentioned method of mixing sol can be applied not only to firing paints and glazes, but also to firing, printing, binders and the like. Further, it can be said that a photocatalyst formulation or a photocatalyst function exhibiting material capable of obtaining a high nitrogen oxide reduction efficiency by the photocatalyst function as described above can be easily produced by the method of mixing the sol described above.

(1-2) Evaluation Test 1: Effect of Alumina, etc. on Ammonia Reduction For ammonia, comparative example tiles, Ti / Al tiles and Ti / Sr tiles are used with the same equipment and method as the above-mentioned nitrogen oxides. We investigated the state of reduction by. In this case, the test gas poured into the glass cell 10 was about 4 ppm of ammonia gas, and the concentration of ammonia in the gas passing through the cell was measured with a concentration side regulator (gas detector tube) downstream of the cell. And with the comparative example tilereferenceFor the example tiles (Ti / Al tiles, Ti / Sr tiles), the ammonia concentration was plotted for each elapsed time from the start of the test gas inflow. The results are shown in Fig. 6.

[0103] As shown in FIG. 6, the comparative example tile,referenceIn both example tiles, the ammonia concentration decreased with the start of the test. And over the measurement periodreferenceThe concentration of the example tile is lower, and about 10 minutes after the start of the test, the concentration of each tile becomes almost constant, about 3.5 ppm for the comparative example tile, about 2.5 ppm for the Ti / Al tile, and about about 2.5 ppm for the Ti / Sr tile. It was 2.6 ppm. Therefore, the reduction efficiency of ammonia is about 12.5% ((4-3.5) / 4) for the comparative example tile, about 37.5% ((4-2.5) / 4) for the Ti / Al tile, and about 35 for the Ti / Sr tile. It was% ((4-2.6) / 4). From this, in the comparative example tile, the photocatalytic reaction by titanium dioxide in the surface layer proceeds, and ammonia is NO, NO.2 Ammonia is reduced to some extent by chemical changes such as, but either Ti / Al tile or Ti / Sr tilereferenceIn the example tile, the ammonia reduction efficiency was superior to that of the comparative example tile. The reason for this can be inferred as follows.

[0104] If a reaction (chemical change) that transfers ammonia to another substance does not occur, the test gas flows into the gas detector tube without causing any reaction, and the measured ammonia concentration is the same as that of the test gas. However, if ammonia is transferred to another substance by a catalytic reaction based on the reactive oxygen species produced by titanium dioxide in the surface layer, the ammonia concentration will decrease from the concentration in the test gas by the amount of the change. Therefore, comparative example tiles,referenceIn both tiles, the ammonia concentration decreased immediately after the start of the test. In this case, since ammonia undergoes a catalytic reaction based on reactive oxygen species, the nitrogen that constitutes ammonia is oxidized, and NO or NO2 Is produced as an intermediate product. And this NO is NO depending on the active oxygen species as described above.2 Oxidized to this NO2 Is further oxidized by reactive oxygen species and chemically converted to nitric acid, ammonia undergoes a catalytic reaction based on reactive oxygen species, and NO or NO2 It is presumed that the degree of chemical change will increase and the efficiency of ammonia reduction will increase.

【0105】referenceExample tiles are NO as mentioned above2 Combine with NO from the tile surface2 It differs from the comparative example tile in that it contains alumina and strontium oxide to prevent the tiles from coming off. Therefore, in the comparative example tile, NO produced from ammonia2 NO due to detachment from the tile surface2 Is further oxidized by reactive oxygen species and chemically changed to nitric acid, and the reaction does not proceed much. On the contrary,referenceIn the example tile, NO produced from ammonia2 Do not separate from the tile surface, this NO2 The active oxygen species further promotes the reaction of oxidizing nitric acid. For this reason,referenceIn the example tile, the ammonia reduction efficiency was increased as described above, and it is considered that the ammonia reduction efficiency was superior or inferior.

(1-3) Evaluation Test 1: Effect of Alumina, etc. on Sulfur Dioxide Reduction Regarding sulfur dioxide, reduction by comparative example tiles and Ti / Al tiles using the same equipment and method as the above-mentioned nitrogen oxides. I checked the situation. In this case, the test gas poured into the glass cell 10 was about 10 ppm sulfur dioxide gas, and the sulfur dioxide concentration in the gas passing through the cell was measured with a concentration side regulator (gas detector tube) downstream of the cell. And with the comparative example tilereferenceFor the example tiles (Ti / Al tiles), the sulfur dioxide concentration for each elapsed time from the start of the test gas pouring was plotted. The results are shown in Fig. 7.

[0107] As shown in FIG. 7, a comparative example tile,referenceFor example tiles, the sulfur dioxide concentration decreased with the start of the test. And over the measurement periodreferenceThe concentration of the example tile was lower, and about 30 minutes after the start of the test, the concentration was about 7.7 ppm for the comparative example tile and about 2.7 ppm for the Ti / Al tile. Therefore, the sulfur dioxide reduction efficiency was about 23% ((10-7.7) / 10) for the comparative example tile and about 73% ((10-2.7) / 10) for the Ti / Al tile. From this, in the comparative example tile, the photocatalytic reaction by titanium dioxide in the surface layer proceeds and the sulfur dioxide is chemically changed to sulfuric acid or sulfurous acid, and the sulfur dioxide is reduced to some extent, but the Ti / Al tile (Ti / Al tile)referenceIn the example tile), the ammonia reduction efficiency was superior to that of the comparative example tile. The reason for this can be inferred as follows.

[0108] Comparative example tile,referenceAs in the case of nitric oxide and ammonia, the sulfur dioxide concentration decreases in both tiles because sulfur dioxide is transformed into sulfuric acid or sulfurous acid by a catalytic reaction based on the reactive oxygen species produced by titanium dioxide in the surface layer. This is because the ammonia concentration decreases from the concentration in the test gas by the amount of the transition. Sulfur dioxide, which is the reaction product in this evaluation test, is chemically bonded to and adsorbed on alumina, which is a basic metal oxide, as described with reference to FIG. 2 because it is an acid gas. Therefore, in the comparative example tile having no alumina, sulfur dioxide is oxidized by active oxygen species and chemically changed to sulfuric acid or sulfurous acid without being adsorbed on the tile surface, so that this reaction proceeds only relatively slowly. On the contrary,referenceIn the example tile, sulfur dioxide is adsorbed on the tile surface and oxidized to sulfuric acid or sulfurous acid by the active oxygen species, so that this reaction is promoted. For this reason,referenceIn the example tile, the sulfur dioxide reduction efficiency was increased as described above, and it is considered that the sulfur dioxide reduction efficiency was superior or inferior.

[0109] Next, the following two methods were used to evaluate the relationship between the degree of blending of alumina and the like blended with the photocatalyst and the effect of reducing nitrogen oxides. For this evaluation, alumina was taken as an example.

(2) Evaluation Test 2: Effect of Alumina Blending on Reduction of Nitrogen Oxides-Part 1 First, the present inventionreferenceIn order to compare with the example product, with the comparative example tile similar to the evaluation test 1 abovereferenceExample photocatalytic function tile (referenceExample tile) was prepared as follows. The comparative example tile is a tile in which a photocatalytic sol containing 7.5 wt% of titanium dioxide is spray-coated on the tile surface and fired under the above firing conditions (about 800 ° CX 60 minutes). When applying this spray, the weight of titanium dioxide on the tile surface after firing is approximately 3.3X10-4g / cm.2 The coating time was set so that the film thickness of titanium dioxide was about 0.85 μm.referenceThe example tiles are the following Ti / Al tiles.

[0111] The Ti / Al tile has a blending ratio determination ratio a / (a + b) in the range of 0.0001 to 0.8 with respect to the photocatalytic sol in which titanium dioxide occupies a ratio of 7.5 wt% as in the comparative example tile. This is a tile in which the Ti / Al sol in which the blending ratio of alumina is adjusted as described above is spray-coated and fired under the same conditions as the above-mentioned Comparative Example tile. That is, the weight of titanium dioxide on the tile surface after firing is about 3.3X10, which is the same as that of the comparative example tile.-4g / cm2 As it is, various Ti / Al tiles having different weights of alumina on the surface of the tile after firing were fired, and each Ti / Al tile was used in this evaluation test 2.referenceExample tile. When the mixing ratio determination ratio a / (a + b) is 0.01, a = b / 99, so the weight of alumina on the tile surface after firing is about 3.3X10.-6g / cm2 And when the compounding ratio determination ratio a / (a + b) is 0.5, a = b, so it is about 3.3X10.-4g / cm2 Will be. Even in this evaluation test 2, the comparative example tile exerts a standard catalytic function, so by comparing each Ti / Al tie with a different amount of alumina compounded with this comparative example tile, a fixed amount of photocatalyst was compounded. The effect of the amount of alumina compounded on the improvement of the catalytic function in the case is clarified.

[0112] In this evaluation test 2, using the same test equipment as in the evaluation test 1, 30 minutes from the start of the test in which a fixed amount of test gas was poured at a predetermined concentration (about 0.95 ppm) and the lamp 20 was turned on. NO after the lapse2 Concentration and NOx concentration, comparative example tile and eachreferenceMeasured for example tiles. Then, for each tile, the NOx removal amount obtained by subtracting the measured NOx concentration from the NO concentration of the test gas and the measured NO2 Concentration and was plotted. The results are shown in Fig. 8. Since the comparative example tile does not contain any alumina, the mixing ratio determination ratio a / (a + b) is zero.

[0113] In FIG. 8, the comparative example tile (a / (a + b) = 0) is plotted on the Y-axis of the graph and is NO.2 The concentration was about 0.17 ppm and the amount of NOx removed was about 0.3 ppm. In this way, the NOx concentration was lower than that of the test gas, but it was not contained in the test gas.2 As mentioned above, the concentration of is measured by the progress of the photocatalytic reaction by titanium dioxide in the surface layer and NO from the tile surface.2 This is because the withdrawal occurs.

[0114] On the other hand, in the Ti / Al tile in which the blending ratio determination ratio a / (a + b) is represented by the X-axis coordinates of the graph, the alumina blending amount is small and the blending ratio determination ratio a / (a + b). ) Is 0.01 and NO2 The concentration was about 0.15 ppm and the amount of NOx removed was about 0.4 ppm. In addition, for Ti / Al tiles in which the amount of alumina compounded is the same as that of titanium dioxide and the compounding ratio determination ratio a / (a + b) is 0.5, NO2 The concentration was about 0.14 ppm and the amount of NOx removed was about 0.43 ppm. And for Ti / Al tiles with a blending ratio determination ratio a / (a + b) in the range of 0.05 to 0.2, NO2 The concentration is about 0.06 to 0.13ppm, and the amount of NOx removed is about 0.44 to 0.46ppm, which is significantly NO compared to the comparative example tile.2 The concentration was low and the amount of NOx removed was large. Even with Ti / Al tiles with a blending ratio determination ratio a / (a + b) of 0.0001, results similar to those with a blending ratio determination ratio a / (a + b) of 0.01 were obtained (NO).2Concentration = about 0.155ppm, NOx removal amount = about 0.36ppm), and the X-axis coordinates for plotting this Ti / Al tile are omitted because they are close to zero.

[0115] As is clear from these facts, if the blending ratio determination ratio a / (a + b) is in the range of 0.0001 to 0.5, the blending of alumina is NO.2 It is possible to suppress the withdrawal of the tile, and the NO is higher than the comparative example tile.2 The reduction effect can be obtained as a result of NOx reduction effect. In particular, when the blending ratio determination ratio a / (a + b) is in the range of 0.05 to 0.2, a NOx reduction effect extremely higher than that of the comparative example tile can be obtained, which is preferable. Then, a high NOx reduction effect could be obtained even by blending a very small amount of alumina, such that the blending ratio determination ratio a / (a + b) was 0.0001.

[0116] Further, the surface condition of each Ti / Al tile in which the blending ratio determination ratio a / (a + b) was set to various values was also good, and the abrasion resistance was also excellent.

(3) Evaluation Test 3: Effect of Alumina Blending on Reduction of Nitrogen Oxides-Part 2 In this evaluation test 3, the total amount of titanium dioxide and alumina (the sum of the blending of both) as photocatalysts was kept constant, and the total amount was fixed. Among them, it was decided to investigate the effect of reducing nitrogen oxides when the blending amounts of titanium dioxide and alumina were various.

[0118] First, the present inventionreferenceIn order to compare with the example product, with the comparative example tile similar to the evaluation test 1 abovereferenceExample photocatalytic function tile (referenceExample tile) was prepared as follows. The comparative example tile is the same tile as in the above evaluation test 2, and the weight of titanium dioxide on the tile surface after firing is about 3.3X10.-4g / cm2 Is. In addition, the weight of alumina on the tile surface is about 3.3X10 for simple tiles (tiles that do not exhibit photocatalyst) that use a formulation that does not contain any photocatalyst and contains only alumina.-4g / cm2 I prepared what I said.referenceThe example tiles are the following Ti / Al tiles.

[0119] The Ti / Al tile has a blending ratio determination ratio a / (a + b) of 0.05 to 0.95 with respect to the photocatalytic sol in which the total amount of titanium dioxide and alumina accounts for 7.5 wt% as in the comparative example tile. This is a tile in which a Ti / Al sol whose blending ratio of alumina is adjusted so as to fall within the above range is spray-coated and fired under the same conditions as the above-mentioned Comparative Example tile. That is, the weight of titanium dioxide on the tile surface after firing is about 3.3X10 as the weight of alumina increases.-4g / cm2 Various Ti / Al tiles reduced from the above were fired, and each Ti / Al tile was used in this evaluation test 3.referenceExample tile. When the mixing ratio determination ratio a / (a + b) is 0.05, a + b is 3.3X10 above.-4g / cm2 Therefore, the weight a of alumina on the tile surface after firing is about 1.65X10.-5g / cm2 And the weight b of titanium dioxide is about 3.135X10-4g / cm2 Is. When the mixing ratio determination ratio a / (a + b) is 0.95, on the contrary, the weight a of alumina is about 3.135X10.-4g / cm2 And the weight b of titanium dioxide is about 1.65X10-5g / cm2 Is. Even in this evaluation test 3, the comparative example tile exerts a standard catalytic function. Therefore, by comparing this comparative example tile with each Ti / Al tie having different amounts of titanium dioxide and alumina, the catalytic function can be obtained. The effect of the blending amount of titanium dioxide and alumina on the improvement of

[0120] In this evaluation test 3, the same test equipment as in the evaluation test 1 was used, and the NO2 concentration and the amount of NOx removed were plotted in the same manner as in the evaluation test 2. The results are shown in Fig. 9. Since the comparative example tile does not contain any alumina, the mixing ratio determination ratio a / (a + b) is zero, and the above tile that does not exhibit a photocatalyst does not contain any titanium dioxide. , The compounding ratio determination ratio a / (a + b) is 1.

[0121] In FIG. 9, the comparative example tile (a / (a + b) = 0) is plotted on the Y-axis of the graph and is NO.2 The concentration was about 0.17 ppm and the amount of NOx removed was about 0.3 ppm. In this way, the NOx concentration was lower than that of the test gas, but it was not contained in the test gas.2 The concentration of is measured as described above for evaluation test 2. Also, the above mere tiles that do not exert a photocatalyst are plotted on the X-axis of the graph, NO.2 Naturally, both the concentration and the amount of NOx removed were zero.

[0122] On the other hand, in the Ti / Al tile in which the blending ratio determination ratio a / (a + b) is represented by the X-axis coordinates of the graph, the alumina blending amount is small and the blending ratio determination ratio a / (a + b). ) Is 0.05 and NO2 The concentration was about 0.07 ppm and the amount of NOx removed was about 0.46 ppm. In addition, for Ti / Al tiles in which the amount of alumina compounded is superior to the amount of titanium dioxide compounded and the compounding ratio determination ratio a / (a + b) is 0.8, NO.2 The concentration was about 0.13 ppm and the amount of NOx removed was about 0.32 ppm. And for Ti / Al tiles with a blending ratio determination ratio a / (a + b) in the range of 0.05 to 0.65, NO2 The concentration is about 0.07 to 0.09ppm, and the amount of NOx removed is about 0.43 to 0.52ppm, which is significantly NO compared to the comparative example tile.2 The concentration was low and the amount of NOx removed was large. In addition, for Ti / Al tiles in which the amount of alumina compounded is significantly higher than the amount of titanium dioxide compounded and the compounding ratio determination ratio a / (a + b) is 0.9 or more, NO equal to or less than that of the comparative example tile.2 It was the concentration and the amount of NOx removed.

[0123] As is clear from these facts, if the total amount of titanium dioxide and alumina is constant and the mixing ratio determination ratio a / (a + b) of these is in the range of 0.0001 to 0.8, the addition of alumina NO2 It is possible to suppress the withdrawal of the tile, and the NO is higher than the comparative example tile.2 The reduction effect can be obtained as a result of NOx reduction effect. In particular, when the blending ratio determination ratio a / (a + b) is in the range of 0.05 to 0.6, a NOx reduction effect extremely higher than that of the comparative example tile can be obtained, which is preferable. When the compounding ratio determination ratio a / (a + b) is less than 0.0001 or more than 0.8, the NOx reduction effect equivalent to that of the comparative example tile can be obtained, but in particular, the compounding ratio determination ratio a /. When (a + b) is 0.9 or more, it is expected that the amount of titanium dioxide as a photocatalyst is too small and the particles are surrounded by alumina particles without gaps and light does not reach, so that the photocatalytic function deteriorates.

[0124] Further, the surface condition of each Ti / Al tile in which the blending ratio determination ratio a / (a + b) was set to various values was also good, and the abrasion resistance was also excellent.

[0125] First of the abovereferenceIn the example, anatase-type titanium dioxide was used as the photocatalyst, and alumina, which is an amphoteric metal oxide, and strontium oxide and barium oxide, which are basic metal oxides, were used as the metal oxide to be blended with the photocatalyst. Of course, the NOx reduction effect described above can also be obtained by combining other photocatalysts and metal oxides. For example, even if titanium dioxide is used as a photocatalyst, titanium dioxide having a crystal type of rutile or brookite can be used. Also, ZnO, V2O5, WO3 , SnO2 , SrTiO3 , Bi2O3, Fe2O3Even if a photocatalyst such as the above is used, the NOx reduction effect can be achieved. Furthermore, as metal oxides that replace alumina, strontium oxide, and barium oxide, zinc oxide, tin oxide (above, amphoteric metal oxide), magnesium oxide, calcium oxide, rubidium oxide, sodium oxide, and potassium oxide (above, basic). Even if (metal oxide) is used, the NOx reduction effect can be achieved. When the basic gas is to be reduced, phosphorus oxide (acidic metal oxide) can be used in addition to the above amphoteric metal oxide.

[0126] Next, the secondreferenceAn example will be described. This secondreferenceIn the example, the procedure for forming a surface layer composed of a photocatalyst compound having a photocatalyst such as titanium dioxide and a specific metal oxide such as alumina on the tile surface is different. This secondreferenceExamplereferenceIn the example, first, a base material for forming a surface layer is prepared. The base material may be ceramic, resin, metal, glass, ceramic wood, siliceous board, concrete board, cement board, cement extruded orthopedic board, gypsum board, autoclave curing lightweight concrete board, etc., and may be used for buildings, houses and bridges. , A base material used for building structures such as road sound insulation walls is preferable because environmental pollutants such as nitrogen oxides can be reduced on the surface of these building structures to purify the atmosphere.

Next, a binder layer is formed on the surface of the prepared base material. The binder layer is formed by selecting a binder material whose softening temperature is lower than the alteration temperature of the base material and using this binder material by an appropriate method suitable for the properties of the binder. For example, when the base material is tile, enamel or ceramic, the glaze layer or printing layer for coloring the surface can be used as it is as the binder layer. After the binder layer is formed, the first described above is applied to the surface of the binder layer.referenceA photocatalyst that becomes a surface layer later by applying or printing a sol such as Ti / Al sol in the example, or spraying mixed particles of titanium dioxide particles and alumina particles obtained by removing the solvent from this sol. Form a compound layer. Alternatively, a photocatalyst compound layer may be formed on a separately produced binder layer, and the binder layer may be placed on the surface of the base material. In these cases, the photocatalyst compound layer may be formed in the binder layer so as not to be separated from the binder layer at the time of subsequent firing.

[0128] After that, when the binder layer is a glaze layer composed of a glaze, it is higher than the softening temperature of the binder material (glaze) in the range of 30 ° C. or higher and 300 ° C. or lower, and higher than the alteration temperature of the base material. Heat treatment in a low temperature environment. By undergoing this heat treatment, the binder material (glaze) is melted and solidified, the binder layer is firmly fixed to the tile surface, and the surface layer is formed from the photocatalyst compound layer. At this time, at the boundary with the binder layer, the particles (titanium dioxide particles, alumina particles) of the photocatalyst compound in the surface layer settle in the binder layer in the process of melting the binder material, and these particles are buried in the binder layer. It is held and firmly fixed to the binder layer. Further, in the photocatalyst compound layer, adjacent particles are bonded to each other by intermolecular force between the particles or sintering by firing to form a surface layer, and in this surface layer, titanium dioxide and alumina are respectively formed on the surface. Expose the particles. Therefore, the surface layer can be firmly fixed to the binder layer, and the particles of titanium dioxide and alumina can be effectively brought into contact with the outside air. Therefore, the second abovereferenceAccording to the production method in the example, it is possible to easily produce a building structure material or the like having a surface layer capable of causing a photocatalytic reaction with high efficiency.

[0129] In this case, since the heating temperature is higher than the softening temperature of the binder material by 30 ° C. or more, it is preferable that the softening of the binder material by heating does not inadvertently take a long time, and the particles of titanium dioxide and alumina are settled. It is preferable because it does not interfere with holding. In addition, since the heating temperature is not higher than the alteration temperature of the binder by more than 300 ° C, rapid melting of the binder material is avoided, and excessive sedimentation of titanium dioxide and alumina particles, generation of uneven surfaces, or pinholes occur. It is preferable because it can suppress problems such as occurrence. The heating temperature is preferably a temperature higher than the softening temperature of the binder material in the range of 50 ° C. or higher and 150 ° C. or lower.

[0130] The second abovereferenceEven in the example, as a photocatalyst, titanium dioxide having a crystal type of rutile or brookite, ZnO, V2O5, WO3 , SnO2 , SrTiO3 , Bi2O3, Fe2O3Etc. may be used. In addition, as a metal oxide that replaces alumina, if the target of reduction is an acidic gas such as NOx, zinc oxide, tin oxide (above, amphoteric metal oxide), magnesium oxide, calcium oxide, rubidium oxide, sodium oxide, etc. Potassium oxide (above, basic metal oxide) may be used, and when the basic gas is to be reduced, phosphorus oxide (acidic metal oxide) may be used in addition to the above amphoteric metal oxide. Good.

[0131] Next, the otherreferenceAn example will be described. The first and second mentioned abovereferenceAn example is a photocatalyst and a particular compound described above with a product to be reacted (eg NO) or an intermediate product (eg NO).2 ) Is retained in the catalytic reaction system to ensure that the reaction product is subjected to the catalytic reaction and the intermediate product is further subjected to the catalytic reaction, and the effect of reducing harmful substances such as NOx is ensured. To obtain, but explained belowreferenceIn the example, by adding a substance other than the specific compound described above, the NOx reduction effect can be further improved or a new effect can be obtained.

[0132] First, the thirdreferenceAn example will be described. This thirdreferenceAn example is for a photocatalytic function exhibiting material having an antibacterial function exhibited by a photocatalyst generating active oxygen species in addition to improving the efficiency of the catalytic reaction as described above. In its production, a Ti / Al sol in which alumina is blended with titanium dioxide at the above-mentioned blending ratio determination ratio that can achieve efficient catalytic reaction, copper (Cu), its oxide, silver (Ag), or the like. Prepare a third sol in which particles such as oxides are dispersed. Next, the Ti / Al sol is applied to the tile surface and fired to form this Ti / Al layer. Then, a third sol is applied to the surface of the Ti / Al layer on the tile surface, and the third sol component is immobilized on the surface by a method such as photoreduction. This tile is this thirdreferenceThis is an example tile, and this thirdreferenceAn example tile is a tile having a surface layer in which titanium dioxide as a photocatalyst is fixed together with alumina on the surface thereof, and particles such as Cu are further fixed on the upper surface thereof. When applying the third sol, the amount of the third sol applied is adjusted so that the photocatalyst is sufficiently irradiated with light. For example, the weight of Cu is about 0.8 to 2.0 μg / cm after firing.2 Is sufficient. This thirdreferenceThe following antibacterial properties were evaluated for the example tile and the comparative example tile used in the above evaluation test. The evaluation was based on the presence or absence of a bactericidal effect on Escherichia coli w3110 strain.

[0133] First, the thirdreferenceExamplereferenceThe surface of both the example tile and the comparative example tile is sterilized with 70% ethanol, and then 0.15 ml (1 to 5X10) of Escherichia coli solution is placed on the tile surface.4 CFU) was added dropwise. A glass plate was placed on the surface of the tile, and Escherichia coli was brought into close contact with the surface of the tile to use this as a sample, and a pair of this sample was prepared for each tile. Then the thirdreferenceExamplereferenceOne sample of the example tile and the comparative example tile was irradiated with a fluorescent lamp through a glass plate, and the other sample was placed in a light-shielded environment. Then, with the passage of irradiation time, the survival rate of Escherichia coli in the sample under fluorescent light irradiation (under bright place) and the sample under shading (under dark place) was measured, and the antibacterial rate (E. coli killed) converted from this survival rate. Or the rate at which growth was stopped) was plotted against the elapsed time. The results are shown in FIG. At the time of measurement, the bacterial solution of each sample was wiped with sterile gauze and collected in 10 ml of physiological saline, and the survival rate of Escherichia coli in this physiological saline was measured and used as the survival rate in the sample.

[0134] As is clear from FIG. 10, under fluorescent light irradiation, the thirdreferenceExamplereferenceHigh antibacterial effect was obtained for both the example tile and the comparative example tile. It is considered that this is because titanium dioxide in the surface layer actively produces active oxygen species under fluorescent light irradiation, and Escherichia coli is killed or stopped growing due to decomposition of its organic components by these active oxygen species. However, under shading, the comparative example tile has almost no antibacterial effect because it does not generate reactive oxygen species, whereas the third tile has almost no antibacterial effect.referenceExamplereferenceIn the example tile, a relatively high antibacterial effect was obtained even under shading. This is because the particles such as Cu fixed on the surface exerted an antibacterial function even under light shielding. Therefore, this thirdreferenceExamplereferenceAccording to the example tile, the antibacterial function that titanium dioxide as a photocatalyst cannot exert because it is under light shielding can be fulfilled by particles such as Cu under light shielding, and the antibacterial function performed by the photocatalyst can be complemented.

[0135] Third abovereferenceEven in the example, as a photocatalyst, titanium dioxide having a crystal type of rutile or brookite, ZnO, V2O5, WO3 , SnO2 , SrTiO3 , Bi2O3, Fe2O3As metal oxides instead of alumina, zinc oxide, tin oxide (above, amphoteric metal oxide), magnesium oxide, calcium oxide, rubidium oxide, sodium oxide, potassium oxide (above, basic metal oxidation) may be used. Product), phosphorus oxide (acidic metal oxide) may be used. Also, instead of Cu, its oxide, silver (Ag) or its oxide, etc., and metals such as Pd, Ni, Co, Pt, Au, Al, Fe, Zn, Cr, Rh, Ru, etc. It is preferable to use a metal itself having an antibacterial effect even slightly.

[0136] Next, the fourth and fifth embodiments will be described. This fourth embodiment is the first and secondreferenceAs in the example, the photocatalyst and the above-mentioned metal oxides such as alumina (amphoteric metal oxides, basic metal oxides, acidic metal oxides) are used, and other compounds and the above-mentioned third metal oxides are used.referenceAs in the example, it is a four-component system that uses metals such as Cu and Ag together. The fifth embodiment is a three-component system in which a photocatalyst and the above-mentioned metal oxides such as alumina (amphoteric metal oxides, basic metal oxides, acidic metal oxides) are used in combination with other compounds.

[0137] If the metal used in combination in the fourth embodiment is a metal having a reduction potential equal to or higher than the potential (-3.2V) of free electrons emitted by titanium dioxide as a photocatalyst, the metal is supported on titanium dioxide by the reduction potential ( It is preferable because it can be reduced and supported). Specifically, it is a transition metal such as Ag, Cu, Pd, Fe, Ni, Cr, Co, Pt, Au, Li, Ca, Mg, Al, Zn, Rh, Ru, among them, Ag, Cu, Since Pd, Pt, and Au have a positive reduction potential, reduction carrying is likely to occur, which is particularly preferable. A method of supporting the metal on a photocatalyst when these metals are used in combination will be described. Examples of the method for supporting the metal on the photocatalyst include the following methods.

[0138] 1) Simple mixing method: A method in which an aqueous metal salt solution containing a target metal species is added to a photocatalyst sol, the two are mixed, and metal ions are supported by adsorption on the surface of photocatalyst particles. 2) Coprecipitation method: After adding an aqueous metal salt solution containing the desired metal species to the photocatalyst sol, the metal salt and the photocatalyst are simultaneously precipitated by adding a precipitant or heating to achieve coprecipitation, and the metal ions are transferred to the photocatalyst particles. A method of supporting on the surface. 3) Pre-reduction support method: A method in which a metal salt aqueous solution containing a target metal species is added to a photocatalyst sol and then irradiated with ultraviolet energy to carry the metal ions by photoreduction to the surface of the photocatalyst particles. 4) Post-photoreduction support method: A method in which a metal salt aqueous solution containing a target metal species is applied on a photocatalyst film and then irradiated with ultraviolet energy to carry metal ions by photoreduction to the surface of the photocatalyst film. .. 5) Thin-film deposition method: A method of supporting metal particles or metal compounds by a chemical or physical thin-film deposition method. 6) Others: A method in which ions of the target metal species are added before granulating the photocatalyst particles using the sol-gel method, and then the photocatalyst / metal ions are atomized by the coprecipitation method or the like.

[0139] Further, the compound used in combination with the photocatalyst and the above-mentioned metal oxide such as alumina is silicon dioxide (silica: SiO).2 ). In addition, instead of silica, ZrO2 , GeO2 , ThO2 , ZnO and other oxides can also be used.

[0140] In this fourth embodiment, the above-mentioned simple mixing method, photoreduction pre-supporting method or coprecipitation method was adopted, and a metal-supported photocatalyst was used by this method.

[0141] The photocatalytic function exerting tile (Example tile) of the fourth embodiment is a photocatalyst sol in which a photocatalyst (titanium dioxide) supporting Ag and Cu is dispersed by a simple mixing method, a pre-reduction supporting method or a coprecipitation method. The above-mentioned firstreferenceFollowing the process described in Evaluation Test 1 of the example, the sol of the other two components (alumina and silica) is mixed and stirred with this metal-supported photocatalyst sol (photocatalyst / metal), and the mixed sol is spray-coated. -Manufactured after firing. The photocatalyst / metal (Ag or Cu) / alumina / silica four-component tile thus produced is the example tile of the fourth embodiment. At this time, in order to understand the influence of the newly blended metal and silica, tiles (reference tiles) were also manufactured for the photocatalyst / metal (Ag or Cu) two-component system. In addition, the example tile of the fifth embodiment is the firstreferenceUsing a photocatalyst sol containing only a photocatalyst (titanium dioxide) similar to the example, the above-mentioned firstreferenceFollowing the process described in Evaluation Test 1 of the example, the sol of the other two components (alumina and silica) was mixed and stirred with this photocatalytic sol, and the mixed sol was spray-coated and fired to produce the mixture. The photocatalyst / alumina / silica three-component tile thus produced is the example tile of the fifth embodiment. And the example tiles, reference tiles, and 1st of the 4th and 5th examples.referenceExamplereferenceThe NOx reduction efficiency was investigated for example tiles and comparative example tiles. In addition, the firstreferenceExamplereferenceExample tiles, comparative example tiles are the firstreferenceIt is as described in the evaluation test 1 of the example, and the firstreferenceExamplereferenceExample The tile compounding ratio determination ratio a / (a + b) is 1/11. In addition, the compounding ratio determination ratio of the example tiles of the fourth example (SIO)2 / (TiO2 + Al2O3+ SiO2)) Is 1/11, and the mixing ratio determination ratio (Al) of the example tiles of the fifth example.2O3/ (TiO2 + Al2O3+ SiO2 )) Is 1/11. Two-component reference tiles include metal and TiO2 The weight ratio of is 0.001 (Ag / TiO) for the reference tile of the two-component system containing Ag.2 ), Cu-blended two-component reference tile 0.01 (Cu / TiO)2 ).

[0142] For these tiles, the first test apparatus shown in FIG. 4 was used.referenceAs mentioned in Evaluation Test 1 of the example, CNO / out, CNO2 / out was measured. And this measured CNO / out, CNO2 From / out and the known test gas concentration (CNO / in), (CNO / in-CNO / out) and CNO 30 minutes after light irradiation2 Obtained / out and NOx reduction efficiency. The results are shown in Table 1.

[0143] [Table 1]<img file="JP4011705B2_D0001.tif" />[0144] (CNO / in-CNO / out), NO is NO2 Or NO3-It is the amount of oxidation (NO reduction amount), and is a value that is an index of the oxidizing power of NO. Also, CNO2/ out is NO2 Is the amount of by-production outside the system, and this CNO2 The smaller the value of / out, the more NO2 Do not let go out of the system, that is, NO2 Indicates that the adsorption force of is strong. Therefore, as is clear from Table 1, according to the example tile of the fourth embodiment, the firstreferenceIt was possible to exert NO oxidizing power equal to or higher than the example, and to obtain high NOx reduction efficiency. In particular, in the example tile of the fourth example containing Ag, the NO oxidizing power is high due to the large (CNO / in-CNO / out), and the small CNO.2 / out more powerful NO2 Since it has an adsorptive power, it was possible to achieve both an oxidizing power and an adsorptive power.

[0145] Further, from the result of the reference tile, if the photoreduction pre-supporting method is adopted, even if it is a two-component system of titanium dioxide and metal, the firstreferenceWe were able to obtain the same level of NO oxidizing power and NOx reduction efficiency as in the example. Furthermore, from the results of the example tiles of the fifth example, even if silica is blended, the firstreferenceSince we were able to obtain the same level of NO oxidizing power and NOx reduction efficiency as in the example, it was found that there were no problems with silica compounding regarding NOx reduction.

[0146] Even in the above-mentioned fourth and fifth examples, as the photocatalyst, titanium dioxide having a crystal type of rutile or brookite, ZnO, V, etc.2O5, WO3 , SnO2 , SrTiO3 , Bi2O3, Fe2O3Etc. may be used. In addition, as a metal oxide that replaces alumina, if the target of reduction is an acidic gas such as NOx, zinc oxide, tin oxide (above, amphoteric metal oxide), magnesium oxide, calcium oxide, rubidium oxide, sodium oxide, potassium oxide (Above, basic metal oxide) may be used, and when the basic gas is to be reduced, phosphorus oxide (acidic metal oxide) may be used in addition to the above-mentioned amphoteric metal oxide. Further, each of the above metals can be used instead of Ag and Cu, and each of the above oxides can be used instead of silica.

[0147] Next, the sixth and seventh embodiments will be described. In the sixth embodiment, similarly to the fourth embodiment described above, a photocatalyst typified by titanium dioxide, an amphoteric or basic or acidic metal oxide typified by alumina, Cu, Ag, Pd, Fe, Ni. , Cr, Co, Pt, Au, Rh, Ru, etc., which is a four-component system in which the metal described in the fourth example and other compounds (oxides) such as silica, etc. described in the fourth example are used in combination. Is. The seventh embodiment is a three-component system in which a photocatalyst, an amphoteric or basic or acidic metal oxide typified by alumina, and other compounds (oxides) described in the fourth embodiment such as silica are used in combination. It is a thing. Then, in the 6th and 7th examples, the decomposing power including the decomposing ability of environmental pollutants such as NOx was improved and the pollution was prevented.

[0148] In the sixth embodiment as well, as in the fourth embodiment, the photocatalyst sol in which the photocatalyst (titanium dioxide) supporting Ag and Cu was dispersed was used by the simple mixing method or the photoreduction pre-supporting method described above. .. And even in the example tile of the sixth embodiment, as in the fourth embodiment, the firstreferenceIt was manufactured by following the process described in Evaluation Test 1 of the example. The example tiles of the 7th example were produced by mixing and stirring the sol of other components (alumina, silica) with the photocatalytic sol and spray-coating and firing the mixed sol as in the 5th example. In addition, in order to understand the effects of newly blended metals and silica, a two-component system of photocatalyst / metal (Ag or Cu), a two-component system of photocatalyst / silica, and a three-component system of photocatalyst / metal (Ag or Cu) / silica We also manufactured tiles (reference tiles) for the system. In this case, when applying the photocatalytic sol to the base material (tile), a method such as spin coating or dip coating can be adopted instead of spray coating. In addition, the adhesion of the photocatalytic sol to the surface of the base material is the first.referenceThe process described in Evaluation Test 1 of the example was carried out by firing (baking type), or a method of mixing a silicone resin with a photocatalyst sol and curing the silicone resin at a relatively low temperature (paint type) was adopted. Then, the example tiles, reference tiles, and comparative example tiles of the 6th and 7th examples were evaluated. The comparative example tile is the firstreferenceIt is as described in the evaluation test 1 of the example.

[0149] Example tile blending ratio determination ratio of the sixth embodiment (SIO)2 / (TiO2 + Al2O3+ SiO2 )) Is 1/10, and the mixing ratio determination ratio of the example tiles of the 7th example (Al)2O3/ (TiO2 + Al2O3+ SiO2 )) Is 1/10. Photocatalyst / silica two-component reference tile compounding ratio determination ratio (SIO)2 / (TiO2 + SiO2 )) Is 1/5. Photocatalyst / metal two-component reference tiles include metal and TiO2 The weight ratio of is 0.001 (Ag / TiO) for the reference tile of the two-component system containing Ag.2 ), Cu-blended two-component reference tile 0.01 (Cu / TiO)2 ). In the reference tile of the photocatalyst / metal / silica three-component system, metal and TiO2 The weight ratio of is the same as the above reference tile (0.001 (Ag / TiO)2 ), 0.01 (Cu / TiO2 )), And its mixing ratio determination ratio (SIO)2 / (TiO2 + SiO2 )) Is 1/5.

[0150] First, in order to understand the influence of the newly blended metal, a reference tile of a photocatalyst / metal (Ag or Cu) two-component system will be described. For the baking type, this two-component reference tile contains various metal salts (Wako Pure Chemicals Reagent Special Grade) in titanium oxide sol (Ishihara Sangyo STS-11), 0.001 to 10% of the titanium oxide solid content in the titanium oxide sol. It was blended so as to be. Then, Ag or Cu was previously supported on the photocatalyst by a simple mixing method, a pre-reduction support method, or a coprecipitation method. In the pre-reduction carrier method, after mixing an aqueous metal salt solution of Ag or Cu with titanium oxide sol, 1 mW / cm2 The sol of the photocatalyst on which the metal was supported was obtained by irradiating with ultraviolet rays at the intensity of 2 hours. In the coprecipitation method, TiOSO4 Using the solution as a starting material, an aqueous metal salt solution was added to the solution and hydrolyzed to obtain a metal-supported photocatalyst sol. After that, these photocatalytic sol are spray-coated on the tile surface so that the film thickness after firing is about 0.8 μm, and firing is performed at 600 to 900 ° C (about 800 ° C in this reference tile), and a two-component system is used. I got a reference tile (baked type).

[0151] In the paint type, various metal salts (Wako Pure Chemicals Reagent Special Grade) were mixed with titanium oxide sol (Nissan Chemical TA-15) so as to be 0.001 to 1% of the titanium oxide solid content in the titanium oxide sol. .. Then, the photocatalytic sol on which Ag or Cu is supported by the simple mixing method or the photoreduction pre-supporting method and the silicone resin as a binder are mixed so that the solid content ratio of titanium oxide and the silicone resin is 7: 3. , The surface of the tile was spin-coated and heated at 150 ° C to obtain a two-component reference tile (paint type).

[0152] The following evaluation tests were conducted on the evaluation of the decomposing power of chemical substances for the reference tiles (baking type & paint type) of this two-component system. The decomposing power can be directly evaluated by the antibacterial power and the oil decomposition rate. Here, the antibacterial activity is the third mentioned above.referenceThe antibacterial rate against Escherichia coil w3110 described in the example was used, and the antibacterial activity exerted by the tile having a photocatalyst layer composed of a single photocatalyst (titanium dioxide) was evaluated as 1. The oil decomposition rate was determined as follows. 1 mg / 100 cm for specimen2 Just apply vegetable oil, 1mW / cm2 Was irradiated with ultraviolet rays for 7 days. Then, the gloss before oil application, immediately after oil application, and at the end of irradiation was measured, and the value obtained from the following formula 1 was taken as the oil decomposition rate.

[0153] [Number 1]<img file="JP4011705B2_D0002.tif" />[0154] Further, since the decomposition of the chemical substance by the photocatalyst is mainly due to the oxidizing action of the active oxygen species released from the photocatalyst on the substance, it can be used as an index of the decomposition ability of the chemical substance by the photocatalyst. It is possible to use the oxidizing power of the photocatalyst. Here, as a model reaction, nitric oxide (NO) to nitrogen dioxide (NO)2 The NO oxidizing power of various photocatalytic thin films was also evaluated based on the amount of conversion due to oxidation to). This NO oxidizing power was determined by using the test equipment shown in Fig. 4.referenceAs described in Evaluation Test 1 of the example, CNO / out was measured. Then, from the measured CNO / out and the known test gas concentration (CNO / in), the (CNO / in-CNO / out) for each elapsed time after light irradiation is obtained, and one hour elapses from the start of light irradiation. The number of moles of total NO oxidized up to this point was calculated from the above (CNO / in-CNO / out), and this was taken as the NO oxidizing power. However, the conditions at that time were that NO gas (test gas) was poured at 2 liters / min, and the sample piece had a size of 5 cm x 50 cm.

Table 2 shows the antibacterial activity, oil decomposition rate, and NO oxidizing ability of the above-mentioned two-component reference tile (baking type & paint type). The antibacterial activity, oil decomposition rate, and NO oxidizing activity in Table 2 are those when the tile is under a bright place, as is clear from the above explanation.

[0156] [Table 2]<img file="JP4011705B2_D0003.tif" />[0157] From Table 2, in the baking type reference tile, in the Cu addition system, Cu prepared by the pre-reduction carrier method was TiO.2 The one supporting 1% of the oil has the best antibacterial activity, oil decomposition rate, and NO oxidizing activity. In the Ag addition system, the photoreduction pre-supporting method is also superior in antibacterial activity, oil decomposition rate, and NO oxidizing activity to the simple mixing method. The addition of any of the metals in the table improves the antibacterial activity, oil decomposition rate, and NO oxidizing activity compared to those without the addition, and thus TiO2 Metals such as Cu, Ag, Pd, and Fe supported on TiO2 It was found that it contributes to the improvement of the decomposing power of. In the baking type, in the Cu addition system, Cu prepared by the photoreduction pre-supporting method is TiO.2 The one supporting 0.1 to 1% shows the highest antibacterial activity. It was also found that the Ag-added system exhibits higher antibacterial activity than the Cu-added system.

[0158] From the above results, in the baking type and paint type reference tiles, metals such as Cu, Ag, Pd, and Fe are TiO.2 It can be seen that the decomposing power is improved by supporting the product. That is, the above metal is TiO2 It can be concluded that it has a function to improve the decomposing power of. Further, it can be seen that the photoreduction pre-supporting method is superior to the simple mixing method as a method for supporting metal species in terms of decomposition power. Furthermore, by adjusting the supported amount of the above metal, TiO2 It can be said that the decomposition power of can be changed.

[0159] Further, when the antibacterial activity when this baking type two-component reference tile was placed in a dark place was investigated, Cu was TiO by a simple mixing method.2 The antibacterial activity of the reference tile supporting 0.1% was about 0.3. In addition, Cu is TiO by a simple mixing method.2 The antibacterial activity was about 0.3 even with the reference tile that supported 1% of the tile. Furthermore, Ag is TiO by a simple mixing method.2 The antibacterial activity was about 0.3 even with the reference tile supporting 0.1% of the total. As described above, in a dark place, the photocatalyst is not activated and its antibacterial activity is nothing but that of the metal itself carried. Considering that the antibacterial activity in the dark is almost zero with the tiles without metal added, that is, the tiles with only the photocatalyst, the antibacterial activity exhibited by the metal itself and the tiles with only the photocatalyst are exhibited in these reference tiles. It can exert antibacterial power that exceeds the antibacterial power (1 from Table 2) in bright light. For example, Cu is TiO by simple mixing method.2 The antibacterial activity of the reference tile supported by 0.1% is 1.5 from Table 2, but this value is the antibacterial activity of Cu itself (0.3) and the antibacterial activity of the tile with photocatalyst only (1). Exceeds the sum of. Therefore, Cu is TiO2 By supporting it against Cu and TiO2 It can be said that a greater effect can be obtained than a simple combination of.

[0160] Here, the example tiles of the sixth and seventh embodiments will be described based on the effects of the reference tiles described above. In the 6th and 7th examples, hydrophilicity, which is a new evaluation item, was also evaluated. First, the relationship between hydrophilicity and surface pollution will be described prior to the hydrophilicity test and the like.

[0161] In recent years, it has been discovered that the surface can be prevented from becoming dirty by making the surface hydrophilic (Polymer, Vol. 44, May 1995, p. 307). Hydrophilicity can be converted by the contact angle with water, and the smaller the contact angle, the better the wettability with water, and the more difficult it is for water that comes into contact with the hydrophilic surface to stay on the contact surface. If the water does not stop easily in this way, dirt components such as urban dust contained in rainwater or the like will flow down from the hydrophilic surface together with the water, and the dirt prevention effect will be enhanced.

[0162] Therefore, it has been proposed to apply a graft polymer imparted with hydrophilicity to the outer wall of a building or the like to prevent stains with a coating film of the graft polymer, but it is converted by the contact angle with water. Since the hydrophilicity is about 30 to about 40 °, water is relatively easy to stop on the surface, and the stain prevention effect and the antifogging effect are not always sufficient. In addition, inorganic dust represented by clay minerals has a contact angle with water of about 20 to about 50 °, so that it has an affinity with a graft polymer having the above contact angle and easily adheres to the surface of the graft polymer. .. Combined with this, it has been difficult for the graft polymer coating film or film to exhibit a high antifouling effect particularly against inorganic dust.

[0163] If the contact angle is made smaller than the contact angle of urban dust containing a large amount of lipophilic components and inorganic dust such as clay minerals, these dusts may exert an affinity on the surface of the base material. Therefore, the stain prevention effect can be further enhanced. Moreover, as the contact angle approaches zero degrees, the hydrophilicity increases, and water diffuses into a film on the surface of the base material and easily flows. Therefore, not only the above-mentioned urban dust but also inorganic dust easily flows down from the surface of the base material together with water. In this case, in order to enhance the stain prevention effect, it is more preferable that the contact angle is about 20 ° or less and close to zero.

[0164] When the examples (6th and 7th examples) of the present invention using a photocatalyst were examined in view of such problems, hydroxyl radicals and OH were generated by the catalytic reaction exhibited by the photocatalyst. As described above, the contact angle with water, which is an index of hydrophilicity, was investigated. The outline of the test is as follows.

[0165] For the example tiles of the sixth and seventh embodiments described above, the reference tiles of the two-component system and the three-component system, and the comparative example tiles, each of which is a baking type is prepared, and a sample piece of an appropriate size is prepared. Prepared. Then, a lamp that irradiates the contact angle of the water droplets dropped on the sample piece with ultraviolet rays after the tile is manufactured (the amount of light received by the sample piece is about 1 mW / cm at a wavelength of 320 to 380 nm).2 ) After irradiating with ultraviolet rays for about 24 hours (under a bright place) and after leaving it in a dark place for a time sufficient to almost completely stop the activity of this photocatalyst (under a dark place). did. The measurement results are shown in Table 3.

[0166] [Table 3]<img file="JP4011705B2_D0004.tif" />[0167] From the results of Table 3, the table of Cu, Ag, etc. is obtained even in the example tile of the 4-component system (6th example) as in the reference tile of the 2-component system in which the influence of the metal composition is investigated. By blending the metal inside, the antibacterial power, oil decomposition power, and NO oxidizing power were all improved, and the decomposition power could be enhanced. Moreover, it was possible to obtain an antibacterial activity exceeding the sum of the antibacterial activity exerted by the metal itself in the table such as Cu and Ag and the antibacterial activity of the comparative example tile containing only the photocatalyst or the example tile of the three-component system. Moreover, the Mohs hardness of the surface layer is equivalent to the Mohs hardness of a simple tile having no surface layer, and has practicality as a tile.

[0168] Further, since the contact angles of the 6th and 7th examples are smaller than those of the comparative example tiles in both light and dark times, TiO is formed on the surface layer.2 SiO compounded with2 Or Al2O3Alternatively, both of them have been clarified to contribute to the improvement of hydrophilicity of the tile surface through the adsorption of hydroxyl groups as described above. Moreover, it was found that by blending the metals in the table such as Cu and Ag, the contact angle did not increase, that is, the hydrophilicity did not decrease. From these facts, a functional thin film having both decomposing power and hydrophilicity or a functional material having such a thin film contributes to improvement of decomposing power Cu, Ag, Pd, Fe, Ni, Cr, Co, Pt, Au. , Rh, Ru and other metal TiO2 SiO which contributes to the support on the surface and the improvement of hydrophilicity2 Or Al2O3Or both TiO2 It can be manufactured after being blended into.

[0169] Further, the example tiles of the 6th and 7th examples have TiO on the surface layer thereof.2 In addition to Al2O3Because it contains, the first and secondreferenceOf course, as explained in the example, it has the effect of reducing harmful substances such as nitrogen oxides. The NO oxidizing power of the example tiles of the 7th example of the above-mentioned metal-free three-component system is the same as that of the comparative example tiles, but the example tiles of the 6th and 7th examples have the same NO oxidizing power. 1st, 2ndreferenceIntermediate products (NO) as explained in the example2 ) Is chemically changed to nitric acid to make this NO2To reduce even. Therefore, according to the example tiles of the 6th and 7th examples, NO and NO2 There is no contradiction in being able to exert the effect of reducing all harmful substances including.

[0170] When it was investigated whether the above-mentioned effect of improving the decomposing power could be obtained for the example tiles of the 6th and 7th examples of the paint type, the results shown in Table 4 were obtained. Therefore, even if it is a paint type, according to the example tiles of the 6th and 7th examples, the antibacterial power, the oil decomposing power, and the NO oxidizing power can be improved and the decomposing power can be enhanced by blending the metals in the table. It was proved that it was possible. Even in the example tiles of the 6th and 7th examples of this paint type, TiO is the same as the above-mentioned baking type example tiles.2 SiO compounded with2 Of course, it is possible to contribute to the improvement of hydrophilicity of the tile surface through the adsorption of hydroxyl groups. Further, even with this paint type, the surface layer has a pencil hardness of 4H, so that it has practicality as a tile.

[0171] [Table 4]<img file="JP4011705B2_D0005.tif" />[0172] Here, the blending amount of Cu, Ag, etc. described above will be described by taking the example tile of the sixth embodiment of the four-component system of photocatalyst / metal / alumina / silica as an example. The example tile of the sixth example has a compounding ratio determination ratio (SIO).2 / (TiO2 + Al2O3+ SiO2 )) Is constant at 1/10, and the weight of the metal is c, TiO2 When the weight of was expressed as d, a mixture was prepared so that c / d (metal compounding ratio) had various values. Then, for each example tile, the relationship between this metal compounding ratio and the antibacterial activity was investigated. The results are shown in FIGS. 11 and 12 separately for the baking type and the paint type. The antibacterial activity in this case is represented by 1 as the antibacterial activity exhibited by the example tile of the 7th example of the photocatalyst / alumina / silica three-component system.

[0173] As can be seen from FIGS. 11 and 12, if the metal compounding ratio of any of the metals Ag, Pd, Pt, Cu, and Cr is about 0.00001 or more for both the baking type and the paint type, " An antibacterial activity of "value 1" or higher could be obtained. In addition, the antibacterial activity peaked at about 0.001 for Ag, Pd, and Pt, and peaked at about 0.01 for Cu and Cr, and then the antibacterial activity tended to decrease. Therefore, it was found that metals such as Ag, Pd, Pt, Cu, and Cr should be blended so that the metal blending ratio is about 0.00001 to 0.05. In other words, if these metals are blended in a metal blending ratio of 0.00001 or more, it does not happen that the amount of metal is too small and does not contribute to the improvement of antibacterial activity at all, and if it is 0.05 or less, the photocatalyst (TiO)2 ), It is preferable that the metal does not become excessive and adversely affects the catalytic reaction of the photocatalyst. Further, it was found that the example tile of the surface layer containing Ag, Pd and Pt as the fourth component has superior antibacterial activity to the example tile of the surface layer containing Cu and Cr as the fourth component.

[0174] Here, regarding the surface texture of the surface layer formed on the tile surface using the above-mentioned photocatalyst sol, the tile and the photocatalyst / alumina of the sixth embodiment of the four-component system of photocatalyst / metal / alumina / silica / The example tile of the 7th example of the three-component system of silica will be taken as an example for explanation. In this case, the example tiles of the 6th and 7th examples have a blending ratio determination ratio (SIO).2 / (TiO2 + Al2O3+ SiO2 )) Was set to 1/10, and a surface layer having a surface layer so that the film thickness, which is one of the surface properties, had various values was prepared. Then, for each example tile, the relationship between the surface layer film thickness and the contact angle, antibacterial force, oil decomposition force or NO oxidizing force was investigated. The results are shown in FIGS. 13 to 17.

[0175] FIGS. 13 to 16 are for the example tile (baking type) of the sixth embodiment of the four-component system. FIG. 13 is a graph showing the relationship between the surface layer film thickness and the contact angle at light, FIG. 14 is a graph showing the relationship between the surface layer film thickness and the antibacterial activity, and FIG. 15 is the surface layer film thickness. It is a graph showing the relationship with the oil decomposition force, and FIG. 16 is a graph showing the relationship between the surface layer film thickness and the NO oxidizing force. The antibacterial activity in this case is expressed as 1 as the antibacterial activity exerted by the tile having a surface layer containing photocatalyst / alumina / silica. FIG. 17 is a graph showing the relationship between the surface layer film thickness and the contact angle at light in the example tile (baking type) of the seventh embodiment of the three-component system. The four-component example tiles contained Ag, Pd, Pt, Cu, and Cr in the surface layer, respectively, and were examined for a film thickness of 0.005 to 3 μm.

[0176] In the example tiles of the three-component system and the four-component system, SiO contributes to the improvement of hydrophilicity through the adsorption of hydroxyl groups on the surface layer thereof as described above.2 Because it contained2 The function (improvement of hydrophilicity) obtained by containing the above is required. The improvement in hydrophilicity in this case can be confirmed by the presence or absence of a low contact angle as described above, and the contact angle is preferably 20 ° or less. Considering FIGS. 13 and 17 from this point of view, in the example tiles of the baking type three-component system and four-component system, if the film thickness of the surface layer is about 0.01 μm or more, a small contact angle of 20 ° or less is obtained. It is preferable to obtain the effect of preventing stains through the improvement of hydrophilicity. When the surface layer film thickness is about 0.01 μm or more, a contact angle of 20 ° or less can be obtained because the film (surface layer) is not too thin, even if the base material has a large contact angle. It is considered that this is because the contact angle of the surface layer itself formed on the material (tile) can be exhibited.

[0177] As shown in FIGS. 13 and 17, if the surface layer film thickness is about 0.5 μm or more, the contact angle remains a small value. On the other hand, as the film thickness of the surface layer becomes thicker, the weight per contact area of the surface layer increases. Therefore, if the film thickness of the surface layer is too thick, the adhesion between the base material and the surface layer is lowered and the surface layer becomes formed. May peel off. Therefore, the surface layer film thickness is preferably about 3 μm or less from the viewpoint of maintaining the adhesion between the base material and the surface layer. Further, if the film thickness of the surface layer is too thick, ultraviolet rays do not penetrate into the lower layer of the surface layer at all and the function as a photocatalyst cannot be exhibited in the entire surface layer. Therefore, the film thickness of the surface layer is preferably about 3 μm or less. It can be said that.

[0178] Then, as shown in FIGS. 14 to 16, the antibacterial power, the oil decomposing power, and the NO oxidizing power are surely obtained within the surface layer film thickness range (about 0.01 to about 3 μm) defined as described above. It can be improved and is preferable.

[0179] In addition to the above surface layer film thickness, the following surface properties were also investigated.

[0180] When irradiated with ultraviolet rays, excited electrons are generated together with hydroxide radicals by the photocatalyst. Therefore, by identifying the phenomenon that occurs in the surface layer by these excited electrons and observing the state, the state of generation of these excited electrons, that is, the state of generation of hydroxyl radicals and OH can be clarified. The example tiles of the 6th and 7th examples have SiO that adsorbs and retains hydroxyl groups on its surface layer.2 Since it contains, the hydroxyl radical OH generated by the photocatalyst is this SiO.2 Is held in. Therefore, the more excited electrons are generated by the photocatalyst, the larger the amount of hydroxyl radicals and OH generated, resulting in SiO.2 It is considered that the hydroxyl group density on the surface of the water increases, the contact angle of water decreases, and the hydrophilicity increases. Therefore, if ultraviolet irradiation is performed with the silver nitrate solution attached to the surface layer, the charge of silver ions in the silver nitrate solution attached to the surface layer is changed by this excitation electricity, and a color reaction occurs before and after the ultraviolet irradiation. Color difference ΔE is observed at. This color difference ΔE increases as the number of excited electrons involved in the reaction increases, and thus serves as an index indicating the degree of hydrophilicity. Therefore, it was decided to observe the color difference ΔE as follows.

[0181] For the measurement of this color difference ΔE, a general 1% silver nitrate solution was used as a reagent exhibiting a color reaction. The silver ions contained in this solution are excited electrons (e) generated by a photocatalyst.- ) And is precipitated as silver. The reaction formula is as follows. By depositing silver in this way, the surface to which the silver nitrate solution is attached changes color to brown or black, and a color difference ΔE can be clearly obtained.

[0182] Ag+ + e- Ag [0183] Therefore, a 1% silver nitrate solution was attached to the surface layer of the tiles of the 6th example (4 components) and 7th example (3 components) of the paint type, and UV irradiation was performed in this state. Was performed, and the color difference ΔE was measured for each tile. Ultraviolet rays are 1.2 mW / cm on the surface layer2 Irradiation was performed so as to have the same intensity as, and the irradiation time was set to 5 minutes. Then, the relationship between the measured color difference ΔE and the contact angle, antibacterial force, oil decomposition force or NO oxidizing force was investigated. The results are shown in FIGS. 18 to 22. When measuring the color difference ΔE, the residual aqueous solution on the tile surface was wiped off with a Kim towel, and the difference between the silver coloration amount on the tile surface in this state and the silver coloration amount before the test (before ultraviolet irradiation) was determined. .. The color difference meter ND300A manufactured by Nippon Discoloration Industry Co., Ltd. was used to measure the amount of silver coloration, and conformed to JIS Z 8729 (1980) and JIS Z 8730 (1980).

[0184] FIGS. 18 to 21 are for the example tile (paint type) of the sixth embodiment of the four-component system. FIG. 18 is a graph showing the relationship between the color difference ΔE and the contact angle at light, FIG. 19 is a graph showing the relationship between the color difference ΔE and the antibacterial activity, and FIG. 20 is the surface layer film thickness and oil decomposition. It is a graph showing the relationship with the force, and FIG. 21 is a graph showing the relationship between the color difference ΔE and the NO oxidizing power. The antibacterial activity in this case is also expressed as 1 as the antibacterial activity exerted by the tile having a surface layer containing photocatalyst / alumina / silica. FIG. 22 is a graph showing the relationship between the color difference ΔE and the light contact angle in the example tile (paint type) of the seventh embodiment of the three-component system. It should be noted that the four-component example tiles were assumed to contain Ag in the surface layer, and the tiles having a color difference ΔE of 0 to 60 were investigated. In this case, a tile with zero color difference ΔE is a mere tile that does not generate excited electrons (a tile that has only a surface layer consisting of paint only).

[0185] From FIGS. 18 and 22, when the color difference ΔE is 1 or more, a small contact angle of 20 ° or less can be obtained, and a stain prevention effect through improvement of hydrophilicity can be obtained, which is preferable. Then, if the color difference ΔE is about 10 or more, the contact angle remains a small value. On the other hand, as the amount of photocatalyst increases, the generation of excited electrons becomes active, so the color difference ΔE increases, but the components other than the photocatalyst (Al)2O3, SiO2 Alternatively, it is considered that the amount of the photocatalyst relative to the total amount of these and the above-mentioned metal) increases, and as the amount of the photocatalyst increases, the adhesion to the substrate decreases and the surface layer is likely to be peeled off. Therefore, when the color difference ΔE is 50 or less, the amount of the photocatalyst is not too large with respect to the total amount of the components other than the photocatalyst, which is preferable from the viewpoint of suppressing surface layer peeling.

[0186] Then, as shown in FIGS. 19 to 21, the antibacterial power, the oil decomposing power, and the NO oxidizing power are surely obtained within the range of the color difference ΔE defined as described above (about 1 to about 50). It can be improved and is preferable.

Next, TiO2 SiO that contributes to the improvement of hydrophilicity of2 Or Al2O3The improvement of the superhydrophilic function by adding other components (metal oxides) such as the above will be described. First, a baking type embodiment (8th embodiment) will be described.

1) Procurement of photocatalytic and metal oxide sol; photocatalytic material / TiO2 Sol: Average particle size approx. 0.02 μm (Ishihara Sangyo STS-11) or average particle size approx. 0.01 μm (Taki Chemical A-6L) SnO2 Sol: Average particle size approx. 0.002 μm (Taki Chemical Co., Ltd.) [0189] In this eighth embodiment, anatase-type TiO that is harmless, chemically stable, and inexpensive.2 Besides, SnO2 A sol was used, but other photocatalytic material, crystalline TiO2 , SrTiO3 , ZnO, SiC, GaP, CdS, CdSe, MoS3 , V2O5, WO3 , SnO2 , Bi2O5, Fe2O3Can be used as an alternative substance.

[0190] Metal oxide / SiO2 Sol: Average particle size approx. 0.007 to approx. 0.009 μm (Nissan Chemical Industries Snowtex S) Al2O3Sol: Average particle size approx. 0.01 μm x approx. 0.1 μm (Nissan Chemical Alumina Sol 200, amorphous) or average particle size approx. 0.01 to approx. 0.02 μm (Nissan Chemical Alumina Sol 520, boehmite) SiO2 + K2O sol: (Nissan Chemical Snowtex K SiO2 / K2O molar ratio 3.3 ~ 4.0) SiO2 + LiO2 Sol: (Nissan Chemical Lithium Silica 35 / SiO2 / LiO2 molar ratio 3.5) ZrO2 Sol: Average particle size approx. 0.07 μm (Nissan Kagaku NZS-30B) [0191] All of the above sol used commercially available products, but a hydrolysis inhibitor such as hydrochloric acid or ethylamine was added to the metal alkoxide as a starting material. , After diluting with an alcohol such as ethanol or propanol, a solution in which hydrolysis is partially proceeded or completely hydrolyzed may be used. For example, in the case of titanium alkoxide, tetraethoxytitanium, tetraisopropoxytitanium, tetran-propoxytitanium, tetrabutoxytitanium, tetramethoxytitanium and the like can be mentioned. Other organometallic compounds (chelates, acetates), TiCl4 , Ti (SO)4)2It is also possible to use an inorganic metal compound such as the above as a starting material.

2) Adjustment of hydrophilicity-imparting material; The mixture of the photocatalytic substance and the sol of the metal oxide is diluted in advance so that the solid content concentration becomes 0.4% by weight, and the ratios shown in Table 5 below are shown. Each sol was mixed with and thoroughly stirred. The solid content weight ratio after mixing is the liquid weight ratio of each sol used.

[0193] 3) Fabrication of hydrophilic tiles; Glazed tile (made by TOTO) AB06E11) was prepared as a base material, and a predetermined amount of the mixed sol was spray-coated on the surface of the tile so that the film thickness was about 0.5 μm. This was fired with RHK (Roller Hers Kiln) at a maximum temperature of about 700 ° C to 900 ° C and a firing time of 60 minutes to produce the 8th Example tile. In this 8th Example tile, spray coating was performed, but flow coating, spin coating, dip coating, roll coating, brush coating, and other coating methods can be used as the coating method. In addition, although tiles were used as the base material in this 8th embodiment, metals, ceramics, ceramics, glass, plastics, wood, stone, cement, concrete or combinations thereof, and laminates thereof should be used. Is possible. In this eighth embodiment, since the sol used is the one described in the above-mentioned procurement of the sol, the photocatalyst, the amphoteric or basic or acidic metal oxide typified by alumina, and the second of silica and the like. It is a two-component system or a three-component system in which the other compounds (oxides) described in the four examples are combined. However, as shown in Table 5 described later, there are cases where a plurality of types of compounds (metal oxides) are used as one component.

4) Evaluation; The evaluation of hydrophilicity was based on the static contact angle of water. First, test tiles (8th Example tile and Comparative Example tile) have an ultraviolet intensity of about 1.5 mW / cm.2 After irradiating with a BLB fluorescent lamp (black light lamp manufactured by Sankyo Electric Co., Ltd., FL20BLB) for 24 hours, the contact angle with water was measured. Then, it was stored in the dark for 72 hours, and the contact angle with water was measured again. The results are shown in the table above. In addition, the film strength was evaluated using the Mohs hardness. The results are shown in Table 5.

[0195] [Table 5]<img file="JP4011705B2_D0006.tif" />[0196] From Nos. 2 to 14 in Table 5, TiO in hydrophilization by ultraviolet irradiation.2/ (TiO2 + SiO2 + Al2O3) 0.4, the contact angle with water is 10 degrees or less, and it can be seen that sufficient hydrophilicity is achieved. Also, after storage in the dark, TiO2If the amount of is the same, Al2O3It can be seen that the larger the amount of the addition, the higher the hydrophilicity is maintained. Also, SiO2 It can be seen that the hardness increases by adding the above amount and by increasing the amount of the addition. From these things, photocatalyst (TiO2 ) To SiO2 And Al2O3It was confirmed that the addition of the photocatalyst improved the hydrophilicity under light irradiation as compared with the photocatalyst alone, also improved the ability to maintain hydrophilicity in a dark place, and further improved the film hardness and denseness. Among these effects, when the sol shown in this example is used, the improvement in hydrophilicity is mainly Al.2O3The improvement in film hardness is brought about by the addition of SiO2It is thought that it is brought about by the addition of. No. 1 in Table 4 is the result for the above-mentioned glazed tile, and No. 2 is the result for the tile with only a photocatalyst (comparative example tile).

[0197] Nos. 15 to 18 in Table 5 are the same tests, but SiO2 Part of K2It is replaced with O. This result is also SiO2 , K2O, Al2O3By the addition of the above, the hydrophilic function and the film hardness are improved in the firing temperature range of about 700 ° C. to about 800 ° C. No. 19 is SiO2 Part of LiO2In this test, which was replaced with, the hydrophilic function and the improvement of the film hardness were similarly achieved.

[0198] No. 17 and No. 18 examined the raw material shape of alumina sol, and it was confirmed that the hydrophilic function was further improved by using alumina sol having an amorphous and feather-like structure. It is considered that a structure having many hydrophilic groups is particularly effective in improving the hydrophilic function rather than being in the form of particles.

[0199] No.20 is TiO2 To ZrO2 Is the result when. From now on ZrO2 However, it was found to be effective in improving hydrophilicity.

[0200] No. 21 and No. 22 are SnO as photocatalysts.2 It is the result of the test using. SnO2 Hydrophilization effect can be seen even by itself, and Al2O3It was confirmed that the hydrophilicity was improved by adding. At this time, there was no decrease in film hardness, and SnO2 It was confirmed that it also has a function as a binder by itself.

[0201] Also, from No.3 to No.14, Al2O3As the amount added increases, the contact angle becomes smaller and the hydrophilicity improves. Therefore, Al2O3The degree of hydrophilicity can be changed by adjusting the amount of addition. Then, from the results in Table 2, by adjusting the amount of metal such as Cu, Ag, Pd, Fe, etc. supported on the photocatalyst, TiO2 Considering that the decomposition power of can be changed, Al2O3By adjusting the amount of addition and the amount of metal supported as described above, the balance between hydrophilicity performance and decomposition power (decomposition performance) can be adjusted. As a result, when a strong decomposing power is required, it can be said that the required strong decomposing power can be exhibited while maintaining the hydrophilicity at a level equal to or higher than that that can be exhibited by the photocatalyst.

[0202] Combining hydrophilicity performance and decomposition performance in this way has the following advantages. The two-step process of removing stains based on hydrophilicity and removing stains based on decomposition performance can significantly improve the efficiency of removing adhered stains and improve the removal speed. In this case, depending on the type of dirt, the adhesion strength of a small amount of dirt left after removing the dirt based on hydrophilicity may be high, but due to the improvement of the decomposing power through the adjustment of the supported amount of the metal described above, such Even a small amount of dirt with high adhesion strength can be removed. Further, since the dirt is removed in this way, the light to the photocatalyst is not blocked, and the amount of light irradiated to the photocatalyst can be increased. Therefore, dirt removal based on hydrophilicity and dirt removal based on decomposition performance can be maintained extremely efficiently.

[0203] In summary, the photocatalyst is SiO2 , Al2O3, ZrO2 It was found that the addition of the above improves the contact angle under light irradiation and the ability to maintain hydrophilicity after holding in a dark place. It is considered that this effect is brought about by the hydrophilicity of these substances, and wet heat is mentioned as an index showing the hydrophilicity of the substances, which is preferable as a photocatalyst.2 Wet heat of anatase type is 320 ~ 512 × 10-3Jm-2, Rutile type 293 ~ 645 × 10-3Jm-2Is. From this, 500 × 10-3Jm-2It is preferable that the compound has the above wet heat, and in addition to the above three types of metal oxides, GeO2 , ThO2 , ZnO. It was found that these metal oxides are not only those having a crystal structure but also those having an amorphous shape, and the particle size range is 0.1 μm or less. Also, SiO2 It was found that the film hardness was improved by adding. SiO2Part of the amount of K added2O or LiO2 By setting the temperature, the film hardness could be improved even if the firing temperature was low. In particular, as a range where the above effects can be expected, TiO2 / (Total solid content of hydrophilicity imparting adjuster) 0.5, SiO2 / (Total solid content of hydrophilicity imparting adjuster) 0.5 condition.

Next, TiO2 SiO that contributes to the improvement of hydrophilicity of2 Or Al2O3The presence or absence of improvement of the superhydrophilic function and improvement of other functions (improvement of film hardness) by addition of other components (metal oxides) such as the above will be described in Examples of the paint type (9th Example).

1) Procurement of photocatalytic and metal oxide sol; photocatalytic material / TiO2 Sol: (Nissan Chemical TA-15) Also in this 9th example, anatase-type TiO which is harmless, chemically stable, and inexpensive.2 Besides, SnO2 A sol was used, but other photocatalytic material, crystalline TiO2 , SrTiO3 , ZnO, SiC, GaP, CdS, CdSe, MoS3, V2O5, WO3 , SnO2 , Bi2O5, Fe2O3Can be used as an alternative substance.

[0206] Metal oxide / SiO2 Sol: (Nippon Synthetic Rubber Glasska T2202) Al2O3Sol: Average particle size of about 0.01 to about 0.02 μm (Nissan Chemical Alumina Sol 520, boehmite) [0207] SiO2 Although a commercially available product was used, it is possible to use a coating film-forming element composed of silicone (organopolysiloxane) or a precursor of silicone. Also, TiO2 And Al2O3As for the sol, a commercially available product was used, but as in the eighth embodiment described above, these were subjected to the above-mentioned steps such as adding a hydrolysis inhibitor such as hydrochloric acid or ethylamine to the metal alkoxide as a starting material. It is also possible to prepare a sol.

[0208] 2) Adjustment of hydrophilicity-imparting material; The above raw materials were mixed at a constant ratio and then diluted 3-fold with ethanol to prepare a coating liquid. The component ratios of the prepared coating liquid are shown in Table 6 below.

[0209] [Table 6]<img file="JP4011705B2_D0007.tif" />[0210] 3) Preparation of hydrophilic tile; as in the eighth embodiment above, a glazed tile was prepared as a base material, coated by a spin coating method, and heated at 150 ° C. for 30 minutes to cure the coating film. .. In this ninth embodiment, spin coating was performed, but flow coating, spray coating, dip coating, roll coating, brush coating, and other coating methods can be used as the coating method. Also, in this ninth embodiment, in addition to tiles, metals, ceramics, ceramics, glass, plastics, wood, stone, cement, concrete or combinations thereof, and laminates thereof can be used as a base material. is there. In this ninth embodiment as well, the sol used is the one described in the above sol procurement, and the components shown in Table 5 are TiO.2, SiO2 Or Al2O3Therefore, a two-component system in which a photocatalyst, an amphoteric or basic or acidic metal oxide typified by alumina, and other compounds (oxides) described in the fourth embodiment such as silica are combined. It is a three-component system.

[0211] 4) Evaluation; For film hardness, a pencil hardness test (JIS K5400 paint general test) was performed on test tiles (9th Example tile and Comparative Example tile). The results are shown in Table 7. As for hydrophilicity, the static contact angle of water was measured for the test tiles (9th Example tile and Comparative Example tile) in the same manner as in the 8th Example above. The results are shown in Table 8. The UV intensity in this case is about 1.2 mW / cm.2 The irradiation time was 12 hours.

[0212] [Table 7]<img file="JP4011705B2_D0008.tif" />[0213] [Table 8]<img file="JP4011705B2_D0009.tif" />[0214] From this Table 7, SiO2 / TiO2 Binders (SiO) with a value of 0.1 or less2 It was found that the lack of sol) caused a decrease in film strength. Also, from Table 8, SiO2 / TiO2 In the range of 1/5 ~ 2, Al2O3/ TiO2 When was 1/12 to 2 it was found that the effect of improving the hydrophilicity rate by adding alumina was exhibited. This effect is also Al, as described in the eighth embodiment.2O3Although it is considered to be caused by the hydrophilicity of the substance, wet heat is mentioned as an index showing the hydrophilicity of the substance, and TiO which is preferable as a photocatalyst.2 Wet heat of anatase type is 320 ~ 512 × 10-3Jm-2, Rutile type 293 ~ 645 × 10-3Jm-2Is. From this, 500 × 10-3Jm-2It is preferable that the compound has the above wet heat, and even in this example, ZrO2 , GeO2 , ThO2 , ZnO. These metal oxides are not limited to those having a crystal structure, but may be amorphous.

[0215] Although the examples of the present invention have been described above, the present invention is not limited to the above examples and embodiments, and can be carried out in various embodiments without departing from the gist of the present invention. Of course.

[0216] For example, in producing a tile capable of supplementing the antibacterial function by fixing particles such as copper and its oxide, the Ti / Al sol is applied to the tile surface and fired in advance from the photocatalyst compound. A tile having a surface layer thereof may be produced, and a third sol may be applied to the surface layer of the tile again and fired.

BRIEF DESCRIPTION OF THE DRAWINGS [Fig. 1] When a nitrogen oxide is oxidized with titanium dioxide, which is a photocatalyst, the progress of the catalytic reaction when alumina is blended with the titanium dioxide, and an intermediate product of the catalytic reaction. The explanatory view which shows the state of bonding by alumina schematically.

FIG. 2 is an explanatory diagram schematically showing a state of bonding of an intermediate product of a catalytic reaction with alumina when alumina is mixed with titanium dioxide when sulfur oxide is oxidized with titanium dioxide as a photocatalyst.

FIG. 3 is an explanatory diagram schematically showing a state of bonding by alumina as an intermediate product of a catalytic reaction when alumina is mixed with titanium dioxide when carbon monoxide is oxidized with titanium dioxide as a photocatalyst.

FIG. 4 is the first aspect of the present invention.referenceIn the examplereferenceExample A schematic configuration diagram of the test equipment used to measure the nitrogen oxide reduction effect of tiles.

[Fig. 5] No. 1referenceIn the examplereferenceA graph showing the results of the reduction effect of nitrogen oxides by example tiles.

[Fig. 6] No. 1referenceIn the examplereferenceGraph to explain the effect of reducing ammonia by example tiles [Fig. 7] No. 1referenceIn the examplereferenceGraph to illustrate the sulfur dioxide reduction effect of example tiles.

[Fig. 8] No. 1referenceIn the examplereferenceA graph showing the results of the reduction effect of nitrogen oxides by example tiles.

[Fig. 9] No. 1referenceIn the examplereferenceA graph showing the results of the reduction effect of nitrogen oxides by example tiles.

FIG. 10 is a third aspect of the present invention.referenceIn the examplereferenceA graph showing the results of the antibacterial effect of an example tile.

FIG. 11 shows the weight of the metal supported on the example tile (baked type) of the sixth embodiment of the four-component system as c, TiO.2 A graph showing the relationship between c / d (metal compounding ratio) and antibacterial activity when the weight of is expressed as d.

FIG. 12 shows the weight of the metal supported in the example tile (paint type) of the sixth embodiment of the four-component system as c, TiO.2 A graph showing the relationship between c / d (metal compounding ratio) and antibacterial activity when the weight of is expressed as d.

FIG. 13 is a graph showing the relationship between the surface layer film thickness and the contact angle at light in the example tile (baking 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 antibacterial activity in the example tile (baking type) of the sixth embodiment of the four-component system.

FIG. 15 is a graph showing the relationship between the surface layer film thickness and the oil decomposition force in the example tile (baking type) of the sixth embodiment of the four-component system.

FIG. 16 is a graph showing the relationship between the surface layer film thickness and the NO oxidizing power in the example tile (baking type) of the sixth embodiment of the four-component system.

FIG. 17 is a graph showing the relationship between the surface layer film thickness and the contact angle at light in the example tile (baking type) of the seventh embodiment of the three-component system.

FIG. 18 is a graph showing the relationship between the color difference ΔE and the light contact angle in the example tile (paint type) of the sixth embodiment of the four-component system.

FIG. 19 is a graph showing the relationship between the color difference ΔE and the antibacterial activity in 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 ΔE and the oil decomposing power in the 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 ΔE and NO oxidizing power in the example tile (paint type) of the sixth embodiment of the four-component system.

FIG. 22 is a graph showing the relationship between the color difference ΔE and the light contact angle in the example tile (paint type) of the seventh embodiment of the three-component system.

[Code description] 10 Glass cell 12 Cylinder 14 Air pump 15 Humidity regulator 16 Flow control valve 18 NOx sensor 20 Lamp

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Citations
Document	Relation	Office	Cited during
US11594746B2	Cited by	United States of America	Search report
JP2018144003A	Cited by	Japan	Search report
JP11131261A	Cites	Japan	–
JP1160281A	Cites	Japan	–
WO9815600A1	Cites	World Intellectual Property Organization (WIPO)	–
WO9700134A1	Cites	World Intellectual Property Organization (WIPO)	–
JP975748A	Cites	Japan	–
JP8117606A	Cites	Japan	–

28 members in 12 offices

This recordMember, by publication datePriority claim2 more offices are in the list below

Priority claims12

Priority claims
Document	Office	Kind	Date
1996352005	Japan	–	1996-12-10
35200596	Japan	A	1996-12-10
35200596	Japan	A	1996-12-10
1997316377	Japan	–	1997-10-30
31637797	Japan	A	1997-10-30
31637797	Japan	A	1997-10-30
36207897	Japan	A	1997-12-10
1996352005	–	–	–
1997316377	–	–	–
JP19960352005	–	–	–
JP19970316377	–	–	–
JP19970362078	–	–	–

Members28

Family members, oldest first
Document	Office	Kind
JPH10237416A	Japan	A	1998-09-08
WO9929424A1	World Intellectual Property Organization (WIPO)	A1	1999-06-17
AU8748498A	Australia	A	1999-06-28
JPH11192436A	Japan	A	1999-07-21
BR9813433A	Brazil	A	2000-10-24
EP1053788A1	European Patent Office (EPO)	A1	2000-11-22
CN1281388A	China	A	2001-01-24
ID27059A	Indonesia	A	2001-02-22
KR20010015871A	Republic of Korea	A	2001-02-26
CZ20002151A3	Czechia	A3	2001-03-14
EP1053788A4	European Patent Office (EPO)	A4	2001-03-21
US2001036897A1	United States of America	A1	2001-11-01
EP1327475A2	European Patent Office (EPO)	A2	2003-07-16
EP1327475A3	European Patent Office (EPO)	A3	2003-08-13
EP1053788B1	European Patent Office (EPO)	B1	2003-10-08
DE69818866D1	Germany	D1	2003-11-13
KR100408470B1	Republic of Korea	B1	2003-12-06
US2004072684A1	United States of America	A1	2004-04-15
CN1148260C	China	C	2004-05-05
DE69818866T2	Germany	T2	2004-05-06
ES2209182T3	Spain	T3	2004-06-16
JP2004290974A	Japan	A	2004-10-21
JP4011705B2This record	Japan	B2	2007-11-21
US2009209410A1	United States of America	A1	2009-08-20
US7754648B2	United States of America	B2	2010-07-13
CZ301921B6	Czechia	B6	2010-07-28
US8034309B2	United States of America	B2	2011-10-11
BRPI9813433B1	Brazil	B1	2012-02-22

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