Substrate having antiviral thin film

A substrate with an antivirus thin film

0001The present invention relates to a substrate with an antivirus thin film.

0002From a sanitary viewpoint, the layer which consists of photocatalysts, such as a layer which becomes an article in which a microorganism may touch from metal, such as silver, copper, and zinc, or titanium oxide, may be provided. It is known that these metal and photocatalysts have antibacterial properties. By a displacement reaction with a cell membrane and a cytoplasmic organization substance, the above-mentioned metal deactivates a bacillus and demonstrates an antibacterial effect. The reactive oxygen species generated by irradiation of ultraviolet rays are attacking the cell wall of a bacillus, and a cell membrane, and the above-mentioned photocatalyst demonstrates an antibacterial effect.

0003A photocatalyst and metal are used together, cell walls, such as bacteria, are destroyed with a photocatalyst, and promoting the antibacterial function by metal is also known. For example, in patent documents 1, producing an antibacterial substrate is indicated by providing on a substrate the photocatalyst layer containing titanium oxide, and providing the island part which consists of copper etc. on this photocatalyst layer.

0004In patent documents 1, applying the produced antibacterial substrate to the article in which a virus may touch is also indicated.

0005Metal oxide particles revealing a photocatalyst operation in patent documents 2, and revealing the allergen inactivation operation based on this under existence of a copper divalent ion and chlorine ion, to them is indicated. Mixing concretely the solution of the partial hydrolysis condensation thing of tetra-ethoxy Silane and the dispersion liquid of the rutile type titanium dioxide particulates which supported copper 2 value salt in the Example 2 of patent documents 2, and producing a coating material is indicated.

0006Making a virus inactivate is indicated by the electron emitted to patent documents 3 when the copper compound particulates of 1 value become a copper ion of 2 values. The dispersion liquid of the copper compound particulates of 1 value are indicated by the example of patent documents 3.

<p num="0007"><patcit num="1"><text>International publication 2008th / No. 047810</text></patcit><patcit num="2"><text>JP,2011-111600,A</text></patcit><patcit num="3"><text>JP,2010-239897,A</text></patcit></p>

<p num="0008">When these people inquired, it turned out that it does not have an antibacterial substrate given in patent documents 1, a coating agent given in patent documents 2, and antiviral nature with sufficient all of the dispersion liquid of a statement for patent documents 3.</p>

<p num="0009">An object of the present invention is to provide the substrate with an antivirus thin film which has the outstanding antiviral nature in view of such a situation.</p><p num="0010">Present invention,<br />It has a substrate and the antivirus thin film formed on the above-mentioned substrate,<br />The above-mentioned antivirus thin film has a layer which makes titanium oxide the main ingredients, and an island part which are arranged on the surface of the above-mentioned layer and which makes material of a Cu system the main ingredients,<br />Cu (OH) to the number of Mol of all the Cu atoms in the above-mentioned island part₂The substrate with an antivirus thin film whose molar ratios which are ratios of the number of of Mol are 0.25-0.35,<br />It provides.</p><p num="0011">The present invention is from the another side,<br />It has a substrate and the antivirus thin film formed on the above-mentioned substrate,<br />The above-mentioned antivirus thin film has a layer which makes titanium oxide the main ingredients, and an island part which are arranged on the surface of the above-mentioned layer and which makes material of a Cu system the main ingredients,<br />Cu (OH) to the number of Mol of all the Cu atoms in the above-mentioned island part₂Molar ratio A which is a ratio of the number of of Mol is 0.15-0.35,<br />The number of Mol and Cu (OH) of CuO to the number of Mol of all the Cu atoms in the above-mentioned island part₂The substrate with an antivirus thin film whose molar ratio B which is a ratio of total of the number of of Mol is 0.70-0.95,<br />It provides.</p><p num="0012">In this specification, content uses the "main ingredients" as a term which points out the ingredient which occupies more than 50 mass % as common use. In this specification, the material of a Cu system means the compound containing the simple substance or Cu element consisting of Cu element.</p>

<p num="0013">According to the present invention, the substrate with an antivirus thin film which has the outstanding antiviral nature can be provided.</p>

0014<figref num="1">The sectional view showing an example of the typical composition of the substrate with an antivirus thin film of the present invention</figref><figref num="2">The sectional view showing another example of the typical composition of the substrate with an antivirus thin film of the present invention</figref><figref num="3">The key map showing how to form an island part</figref>

0015Hereinafter, the substrate with an antivirus thin film of the present invention is explained.

0016First, the antivirus thin film formed on a substrate is explained. An antivirus thin film is a film which demonstrates antiviral nature by being irradiated with light. An antivirus thin film has a layer (it may be hereafter indicated as a photocatalyst layer) which makes titanium oxide the main ingredients, and an island part which makes material of a Cu system the main ingredients.

0017A part of surface has exposed a photocatalyst layer. An antiviral effect is demonstrated by being irradiated with light. The photocatalyst layer of this embodiment generates an electric charge (an electron or an electron hole) by being irradiated with light.

0018As for the main ingredients of the viewpoint of improving the function as a photocatalyst of a photocatalyst layer to a photocatalyst layer, it is preferred that it is multi-crystal titanium oxide including a Anatase type crystal structure.

0019The photocatalyst layer may consist of titanium oxide substantially. A "real target" is the meaning that it is not what even the impurities mixed unescapable eliminate.

0020As long as a photocatalyst layer makes titanium oxide the main ingredients, other materials may be included, but a photocatalyst layer may contain metal, such as iron or aluminum, for example to such an extent that it does not produce disorder of a crystal structure. If a little metal is added by the photocatalyst layer, generating of a career will be promoted in a photocatalyst layer and the photocatalyst activity of a photocatalyst layer will increase. The suitable metal content of a photocatalyst layer is 0.001 to 1.0 mass %. If the amount of addition is less than this, an effect may not be acquired, when too large, it may become disorder of the crystal structure of a photocatalyst layer, and a cause of recombination center generation, and photocatalyst activity may fall.

0021A photocatalyst layer can be formed on a substrate with publicly known methods for film deposition, such as a chemical vapor deposition method (CVD method), the sputtering method, and a liquid phase method (for example, sol gel process). Especially, since a uniform film can be easily formed by a large area, the sputtering method and a CVD method are recommended.

0022When forming a photocatalyst layer by the sputtering method, a substrate may be heated during membrane formation of a photocatalyst layer, or a substrate may be heated after (heating membrane formation) and membrane formation of a photocatalyst layer (heating after membrane formation). Thereby, the crystallinity of titanium oxide of a photocatalyst layer increases and it can obtain the high photocatalyst layer of a photocatalyst function. Temperature in the case of heating after heating membrane formation and membrane formation is a temperature higher than room temperature. It is preferred that substrates are softening, modification, and the temperature not deteriorating. When adopting a glass board as a substrate, the temperature in the case of heating after heating membrane formation and membrane formation may be set, for example as 200-600 .

0023The island part is deposited in the state where it was dotted on the surface of the photocatalyst layer. The surface has exposed an island part. An antiviral effect is demonstrated by contacting a virus. Cu (OH) by which an island part is specifically contained in an island part mainly₂It is alike and demonstrates the originating antiviral action. Cu (OH) to the number of Mol of all the Cu atoms [ in / more specifically / an island part ]₂When the molar ratios which are ratios of the number of of Mol are 0.25-0.35, an antivirus thin film demonstrates good antiviral nature. As for the above-mentioned molar ratio, it is preferred that it is 0.26-0.35, and it is more preferred that it is 0.27-0.35. In example of another, the ranges of the above-mentioned molar ratio are 0.25-0.30, desirable ranges are 0.26-0.30, and more desirable ranges are 0.27-0.30. Cu (OH) in an island part₂Cu (OH) which computed the metal copper equivalent unit of Weight of by having broken it by area of the surface of a photocatalyst layer₂The amount of Loading is 1 ng/cm, for example.^２It is above and preferably is 4 ng/cm.^２It is above.

0024By the way, an antivirus thin film is Cu (OH) in an island part, while being irradiated with light, although it is a film which demonstrates antiviral nature by being irradiated with light (specifically ultraviolet rays or visible light).₂Cu [ in / it Generated and / an island part ] (OH)₂Ratio may increase. Thus, Cu (OH) generated in the island part while being irradiated with light₂It contributes to the antiviral nature of Also and an antivirus thin film. It is Cu (OH), when these artificers check and the ratio of CuO in the island part in front of light irradiation is high.₂It turned out that Ratio increases easily. Water in which this exists in the atmosphere for which a substrate with an antivirus thin film is used if an antivirus thin film is irradiated, or moisture (H)₂O) etc. and CuO react and it is Cu (OH).₂It is thought that it is because it Generated. That is, CuO is Cu (OH) by light irradiation.₂By it being alike and converting, it can be said that antiviral nature can be gained in late-coming. However, Cu (OH) limit to when the ratio of CuO in an island part is high, and according to light irradiation₂increase of will become effective. Cu (OH) of CuO₂When it takes into consideration being affected about the intensity etc. of the light irradiated with the conversion through which it passes etc., in the island part in front of light irradiation, it is Cu (OH) more than a fixed ratio in CuO.₂To exist is desired. Cu (OH) to the number of Mol of all the Cu atoms in an island part if these are taken into consideration, in order to reveal good antiviral nature₂ofmol -- the mol of all the Cu atoms [ in / molar ratio A which is a ratio of a number is 0.15 or more and 0.15 to 0.35, for example, 0.15 to 0.30, and less than 0.25, and / an island part ] -- the mol of CuO to a number -- a number and Cu (OH)₂It is preferred that molar ratio B which is a ratio of total of the number of of Mol is 0.70-0.95. As for molar ratio B, 0.75-0.95 are preferred, and 0.80-0.95 are more preferred. As for molar ratio C which is a ratio of the number of Mol of CuO to the number of Mol of all the Cu atoms in an island part, 0.50-0.85 are preferred, 0.65-0.85 are preferred, and 0.70-especially 0.80 are preferred. The metal copper equivalent unit and Cu (OH) of weight of CuO in an island part₂CuO and Cu (OH) which computed total of the metal copper equivalent unit of Weight of by having broken it by area of the surface of a photocatalyst layer₂Total of the amount of Loading is 3 ng/cm, for example.^２It is above and preferably is 10 ng/cm.^２It is above.

0025The island part may consist of material of a Cu system substantially. However, the island part may contain the addition metal of a quantity (on mass standard) smaller than the material of a Cu system. As an addition metal, at least one sort chosen from tin (Sn), iron (Fe), zirconium (Zr), chromium (Cr), zinc (Zn), titanium (Ti), manganese (Mn), etc. is mentioned. By addition of such metal, the improvement of the corrosion resistance of an island part is expectable.

0026As for an island part, it is preferred at least one, for example, 100-3000 pieces, preferably that 250-750 pieces exist all over the arbitrary fields of 1x1 micrometer of width in the surface of a photocatalyst layer. According to this feature, an antiviral effect can be uniformly revealed in a field.

0027The height in particular of an island part is not limited. As for the maximum height of an island part, from avoiding connection in the island part of objects, such as a dustcloth, and there being a viewpoint of improving the abrasion resistance of an island part, 20 nm or less is preferred. On the other hand, as for the maximum height of an island part, from a viewpoint of securing antiviral nature, it is preferred that it is 1 nm or more. That is, from both the above-mentioned viewpoints, as for the maximum height of an island part, 1-20 nm is preferred, its 1-10 nm is more preferred, and especially its 2-5 nm is preferred.

0028An island part can be formed on a photocatalyst layer by the sputtering method so that the following may describe in detail. Since the sputtering process for forming the sputtering process and island part for forming a photocatalyst layer can be carried out by the same production line when forming both a photocatalyst layer and an island part by the sputtering method, improvement in productivity is expected.

0029The antiviral nature which an antivirus thin film has is based on both the operation of a photocatalyst layer, and the operation of an island part. When an island part contacts a virus, antiviral nature is demonstrated, and when the electric charge which occurred in the photocatalyst layer by a photocatalyst layer being irradiated moves to an island part, more specifically, it is thought that the antiviral action originating in an island part is promoted notably. If both generating operations of the electric charge based on a photocatalyst layer are combined with the antiviral nature based on an island part with sufficient balance, the antiviral nature of the whole antivirus thin film can be improved. When it observes along the thickness direction of an antivirus thin film from this viewpoint, That is, as for the ratio of total of the area of the island part to the area of an antivirus thin film when an antivirus thin film is observed from the upper part of an island part, 0.01-0.20 are preferred, 0.03-0.15 are more preferred, and 0.05-0.12 are more preferred.

0030In the substrate with an antivirus thin film of this embodiment, it is formed so that it may be dotted with the island part which makes material of a Cu system the main ingredients on the photocatalyst layer which makes titanium oxide the main ingredients. A certain amount of [ when an island part is formed like this embodiment / each field of the exposure side of the photocatalyst layer (surrounded by the straight line which connects three adjoining island parts) divided by the island part / each ] collected area (for example, 500-2000 nm)²It has. Thereby, a photocatalyst layer can generate an electric charge effectively. Since the island part of this embodiment fully faces the open air compared with the material etc. of a Cu system which was doped by titanium oxide and taken in during the crystal of titanium oxide, it is easy to contact a virus. Unlike the film produced by fixing the particles of the material of a Cu system with a binder, with the substrate with an antivirus thin film of this embodiment, the exposure sides of an island part do not decrease in number with obstacles, such as a binder.

0031Although the size in particular of each island part is not limited, when each island part is too small, there is a possibility that the quantity which the exposure area of the island part to the volume of an island part becomes large too much, and it dissolves in water, acid, alkali, etc. may become large, and may become insufficient [ weatherability and chemical resistance ]. Therefore, as for each island part, it is preferred to have a diameter of 1 nm or more. On the other hand, when each island part is too large, the number of the viruses which the exposure area of the island part to the volume of an island part can become small too much, and can contact an island part decreases, and there is a possibility that antiviral nature may not fully be demonstrated. Therefore, as for each island part, it is preferred to have a diameter of 20 nm or less. That is, from both the above-mentioned viewpoints, as for the diameter of an island part, 1-20 nm is preferred, its 1-10 nm is more preferred, and especially its 2-5 nm is preferred.

0032As a method of checking island shape being dotted with the island part, evaluation by the scanning electron microscope (SEM) image and a transmission electron microscope (TEM) image, etc. are mentioned.

0033Next, a substrate is explained. Although a substrate in particular is not limited, it is preferred to have light transmission nature. One sort or two sorts or more of materials chosen from the group which consists of a glass board, a plastic sheet, and a resin film as a substrate which has light transmission nature are mentioned. As a glass board, the float plate glass, template glass and wired sheet glass which are marketed, and the glass board which carried out various kinds of coloring to them can be used. Glass boards, such as borosilicate glass and alumino silicate glass, can also be used. The substrate of light reflex nature, such as a mirror, can also be used.

0034A substrate is transparent, and when it has light transmission nature, it is preferred to stop the rate of Hayes in the visible light range (for example, 380-760-nm wavelength band) of a substrate with an antivirus thin film to 0.5% or less. Thereby, good design nature can be obtained.

0035The substrate may contain the main part of a substrate, and the foundation layer formed so that the main part of a substrate might be touched. As for a foundation layer, when the main part of a substrate is a glass board, it is preferred to have the function to prevent diffusion of the alkali component in a glass board.

0036As for a foundation layer, it is preferred that at least one chosen from the group which consists of a compound oxide of oxidization silicon, silicon nitride, tin oxide, a zinc oxide, a zirconium dioxide and zinc, and tin is included. Fluoride may be doped by tin oxide when tin oxide is included as a foundation layer. Sufficient effect will be acquired if the range of the thickness of a foundation layer is 5-10 nm. A foundation layer can be formed on the main part of a substrate in advance of formation of a photocatalyst layer or an island part with publicly known methods for film deposition, such as a chemical vapor deposition method, the sputtering method, and a liquid phase method.

0037As for a foundation layer, when forming a photocatalyst layer and a foundation layer by the sputtering method, it is preferred to have a film containing a multi-crystal zirconium dioxide including a monoclinic crystal structure. The grating constant of a monoclinic zirconium dioxide is close to the grating constant of Anatase type titanium oxide. Therefore, the titanium oxide layer formed on it can be made into the layer to which heteroepitaxial growth of the Anatase type crystal structure was carried out by providing the film containing a monoclinic zirconium dioxide as a foundation layer. Thereby, the high photocatalyst layer of a photocatalyst effect can be formed.

0038The foundation layer may comprise a plurality of layers. From the main part side of a substrate, an oxidization silicon film can be adopted as the 1st foundation layer, and it can adopt zirconium oxide membrane as the 2nd foundation layer, for example, when it constitutes a foundation layer from two-layer.

0039The art of heating membrane formation and the art of heating after membrane formation can be applied also when providing a foundation layer. That is, the main part of a substrate may be heated during membrane formation of a foundation layer, or the main part of a substrate may be heated after membrane formation of a foundation layer.

0040When using the glass board manufactured by a float process as a body part (main part of a substrate) of a substrate, the photocatalyst layer which makes a foundation layer and titanium oxide the main ingredients with the heat CVD method using the heat at the time of glass formulation may be formed. Generally the heat CVD method using the heat at the time of float glass formation is called an on-line CVD method (or CVD method in a bus). According to the on-line CVD method, the CVD device for forming a foundation layer and a photocatalyst layer on the forming line of the glass by a float process (for example, inside of a float bus) is installed. According to the on-line CVD method, since fabrication of the glass by a float process and formation of the foundation layer by a CVD method and a photocatalyst layer can be performed continuously, it excels in economical efficiency.

0041Next, some typical composition of a substrate with an antivirus thin film is shown in a drawing.

0042Drawing 1 is a sectional view showing an example of the typical composition of the substrate with an antivirus thin film of the present invention. Antivirus thin film 21 is formed in the surface of soda lime glass board 11 as a substrate which has light transmission nature in substrate 1 with an antivirus thin film of this example. That is, photocatalyst layer 22 is formed in the surface of soda lime glass board 11, and a plurality of island parts 23 (group of island part 23) are formed in the surface of photocatalyst layer 22. The surface of island part 23 is exposed and the surface of photocatalyst layer 22 is exposed except for a contact surface with island part 23. As shown in Drawing 1, while securing both the antiviral nature based on photocatalyst layer 22, and the antiviral nature based on island part 23 by making island shape deposit island part 23, The color tone and light transmission nature originating in titanium oxide which is the material of glass board 11 and the main ingredients of a photocatalyst layer can be kept good.

0043As shown in Drawing 2, substrate 101 with an antivirus thin film may be constituted by forming foundation layer 14 in the surface of soda lime glass board 11 (main part of a substrate), and forming antivirus thin film 21 in the surface of foundation layer 14.

0044Next, the concrete manufacturing method of an island part is explained.

0045An island part can be formed by the sputtering method. The quantity of the material which constitutes the island part made to deposit by the sputtering method can be controlled highly.

0046The sputtering method can be enforced under the gas atmosphere containing inactive gas and oxygen, such as argon. Island shape can be made to deposit the material which constitutes an island part (for example, thing to set it as 0.1-1.0 nm) by adjusting the standard film thickness by the sputtering method. Here, standard film thickness says the film thickness of the continuation film at the time of the whole quantity of the material which constitutes an island part converting having constituted the continuation film with uniform film thickness, and does not show the actual height of the formed island part itself.

0047This standard film thickness can be defined as follows, for example. First, the membrane formation conditions (a film deposition system, membrane formation atmosphere gas, a degree of vacuum, substrate temperature, membrane formation power, etc.) of an island part are defined. The continuation film which consists of material which forms membranes over comparatively long time and constitutes an island part from the membrane formation conditions is formed. Only membrane formation time is changed, membranes are formed several times, and several continuation films in which film thickness differs are obtained. The film thickness of the obtained continuation film is measured and it asks for the relation between film thickness and membrane formation time. The film thickness of a continuation film can be measured by the sensing pin type level difference film thickness meter or an ellipsometer. From the relation between film thickness and membrane formation time, the predicted value of the film thickness to predetermined membrane formation time can be calculated, and this predicted value can be used as standard film thickness. That is, the membrane formation time equivalent to predetermined standard film thickness is computed beforehand, and the membrane formation time of an island part is set to this computed membrane formation time. It becomes possible to make island shape deposit the material which constitutes an island part with such a procedure. In an in-line type sputtering system (device which conveys a substrate continuously, passes a target field (field where the metal flipped off from the target may reach a substrate), and forms membranes), membrane formation time is equivalent to time for each portion of a substrate to exist in a target field.

0048By the way, a characteristic relation between the oxyecoia partial pressure at the time of carrying out sputtering and composition of the island part formed is. If oxyecoia partial pressure is raised from 0, performing sputtering, the target surface will be maintained at a metaled state and, as for this field, the island part of a metaled state will mainly be formed in the beginning. it is called metal mode -- having -- if oxyecoia partial pressure exceeds a predetermined threshold, discharge voltage will change discontinuously (mode changes), it will be oxidized by the target surface, and an island part with a high ratio of an oxide will come (this field is called oxide mode) to be formed. Oxyecoia partial pressure is reduced from this state, and if less than the oxyecoia partial pressure to which mode changes took place, it will return to metal mode (reverse changes). A hysteresis arises between the oxyecoia partial pressure under mode changes and the relation of composition of an island part formed, and the relation of composition between the oxyecoia partial pressure under reverse changes, and the island part formed. The direction where discharge voltage changes before and after mode changes changes with metal kinds of a target. Although the voltage in oxide mode becomes higher in Ti, it becomes reverse more low in Cu and Si.

0049Cu [ in / in the suitable manufacturing conditions of an island part / an island part ] (OH)₂There are the 1st manufacturing conditions suitable for improving Ratio and the 2nd manufacturing conditions suitable for improving the ratio of CuO in an island part. The 1st manufacturing conditions are manufacturing conditions which make oxyecoia partial pressure the oxyecoia partial pressure of the low side field in the above-mentioned metal mode. Although the ranges of the suitable oxyecoia partial pressure on the 1st manufacturing conditions differ for every film deposition system, when it expresses by the ratio of the flow of oxygen to the flow of inactive gas contained in sputtering gas, 3:97-10:90 are preferred and it is more preferred that it is 4:96-7:93.

0050The 2nd manufacturing conditions are manufacturing conditions made into the oxyecoia partial pressure which can be set they to be [ any in the quantity side field, changes mode, and oxide mode ], while being able to set oxyecoia partial pressure in metal mode higher than the case of the 1st manufacturing conditions -. However, in changes mode, since the mode changes frequently between metal mode and oxide mode, membrane formation is not stabilized. moreover -- oxide mode -- a membrane formation rate -- low (1/10 or less [ of metal mode ]) -- a sake -- productivity -- falling . When these are taken into consideration, it is preferred to be the oxyecoia partial pressure in metal mode, and to make oxyecoia partial pressure under sputtering into the oxyecoia partial pressure of the field near changes mode. Although it differs for every film deposition system, when the range of desirable oxyecoia partial pressure is expressed by the ratio of the flow of oxygen to the flow of inactive gas contained in sputtering gas, 12:88-27:73 are preferred and it is more preferred that it is 15:80-25:75.

0051An example of the sputtering system for forming an island part in Drawing 3 is shown. In sputtering system 50 shown in Drawing 3, where glass board 31 with a photocatalyst layer with which the photocatalyst layer was formed for career 43 on the substrate is put in order, it moves. On the other hand, from outlet 41, the sputtering gas containing inactive gas (argon etc.) and oxygen is supplied. Then, metal Cu flipped off by the collision of the ionized sputtering gas from target 33 reaches on glass board 31 with a photocatalyst layer through the opening slot formed by two parallel shield plates 42. Thereby, the material which constitutes an island part deposits on glass board 31 with a photocatalyst layer.

0052A membrane formation rate is controllable by adjusting the width of the opening slot formed by shield plate 42. The width of an opening slot can be adjusted, for example in about 1-150 mm. A membrane formation rate may be controlled by replacing with adjusting the width of an opening slot, or making quick the bearer rate of glass board 31 with a photocatalyst layer, or stopping injection power low with this. When sputtering conditions are changed, membrane formation standard film thickness and membrane formation efficiency may be considered, and the width of an opening slot may be adjusted.

0053Target 33 may contain a proper quantity of addition metal other than metal Cu. As an addition metal, at least one sort chosen from tin (Sn), iron (Fe), zirconium (Zr), chromium (Cr), zinc (Zn), titanium (Ti), manganese (Mn), etc. may be contained in target 33. Thereby, the improvement of the corrosion resistance of an island part is expectable.

0054In order to explain the present invention still in detail, an example and a comparative example are shown.

0055&lt;Example 1-3&gt;<br />(Example 1)<br />In Example 1, the float glass board (soda lime glass board) with a thickness [ as a main part of a substrate ] of 3.0 mm was prepared first. Next, the oxidization silicon film as a foundation layer (the 1st foundation layer) was formed on the surface of a float glass board. Membrane formation of the oxidization silicon film was performed by the sputtering method using product [ made by ULVAC ] in-line type sputter device MLH-6215. It was 5x15 inches in size, and in order to give conductivity, specifically, the oxidization silicon film was formed by the reactive sputtering method under oxygen containing gas atmosphere using the silicon target which doped Lynn. The main part of a substrate was not heated at the time of membrane formation. The interval of the main part of a substrate and a target was about 60 mm. The details of the sputtering conditions of an oxidization silicon film are as follows.

0056Oxidization silicon (SiO)₂The sputtering conditions at the time of membrane formation<br />- Target : Si (P dope)<br />- Gas pressure : 0.4 Pa<br />- Sputtering type of gas : oxygen (O)₂80%+ argon (Ar)20%<br />- Injection power : DC pulse 2.0kW (power density : 4.13W/(cm))²）<br />- Film thickness : 10 nm<br />however, oxygen of the item of a sputtering type of gas and the percentage of argon are the ratios of the flow to the flow of the whole sputtering gas (the following -- the same).

0057Next, the zirconium oxide membrane as a foundation layer (the 2nd foundation layer) was formed on the oxidization silicon film. Membrane formation of zirconium oxide membrane was performed by the sputtering method using product [ made by ULVAC ] in-line type sputter device MLH-6215. Specifically, zirconium oxide membrane was formed by the reactive sputtering method under oxygen gas atmosphere using the metallic target with a size of 5x15 inches. The main part of a substrate was not heated at the time of membrane formation. The interval of the main part of a substrate and target in which the 1st foundation layer was formed was about 60 mm. The details of the sputtering conditions of zirconium oxide membrane are as follows.

0058Zirconium oxide membrane (ZrO)₂The sputtering conditions at the time of membrane formation<br />- Target : zirconium (Zr)<br />- Gas pressure : 1.33 Pa<br />- Sputtering type of gas : oxygen (O)₂）１００％<br />- Injection power : DC2.6kW (power density : 5.54W/(cm))²）<br />- Film thickness : 10 nm

0059Next, the photocatalyst layer was formed on the surface of zirconium oxide membrane. Membrane formation of the photocatalyst layer was performed by the sputtering method using product [ made by ULVAC ] in-line type sputter device MLH-6215. Specifically, the photocatalyst layer was formed by the reactive sputtering method under oxygen gas atmosphere using the metallic target with a size of 5x15 inches. The main part of a substrate was not heated at the time of membrane formation. The interval of the main part of a substrate and target in which the 1st foundation layer and the 2nd foundation layer were formed was about 60 mm. The details of the sputtering conditions of a photocatalyst layer are as follows.

0060The sputtering conditions of a photocatalyst layer<br />- Target : titanium (Ti)<br />- Gas pressure : 2.67 Pa<br />- Sputtering type of gas : oxygen (O)₂）１００％<br />- Injection power : DC3.0kW (power density : 6.40W/(cm))²）<br />- Film thickness : 10 nm

0061Next, the island part was formed on the surface of a photocatalyst layer. It carried out to formation of the island part by the sputtering method using product made from ULVAC in-line type sputter device SCH-3030. The size of the target was 5x20 inches. The interval of the substrate and target in which the photocatalyst layer was formed was about 65 mm. In order to reduce a membrane formation rate, as shown in Drawing 3, it is between the main part of a substrate, and a target, and installed the shield plate in a 50-mm position from the main part of a substrate. The long and slender crevice which extends with a shield plate in the longitudinal direction of a target, parallel and the conveyance direction, and the direction that intersects perpendicularly as shown in Drawing 3 was made. The width of the crevice could be 15 mm. The main part of a substrate was not heated at the time of membrane formation.

0062The details of sputtering conditions at the time of forming an island part are as follows.<br />- Target : Cu<br />- Gas pressure : 0.67 Pa<br />- Sputtering type of gas : oxygen (O)₂5%+ argon (Ar)95%<br />- Injection power : DC250W (0.51W/(cm))²）<br />- Bearer rate : 1000 mm/min (according to the membrane formation rate of a target, it tunes finely)<br />- Standard film thickness : 0.5 nm

0063As shown in Drawing 3, the outlet of sputtering gas was installed so that gas might be emitted between a shield plate and a target.

0064The conditions of sputtering of an island part performed separately sputtering which uses a target as metal Cu, and made an about 20-nm continuation film deposit, and it defined them by analyzing composition of this continuation film by the In-planeXRD method.

0065The sample of Example 1 was produced in the above procedure.

0066Next, Cu, Cu which are contained in the island part of the produced sample₂O, CuO, and Cu (OH)₂The The presence of ratio was analyzed by the XPS method (X ray photoelectron spectroscopy). The sample was irradiated with X-rays (an aluminum-Kalpha line, output 150W) in the vacuum, and, specifically, the X ray photoelectron spectral device (the ULVAC phi company make, ESCA-5600i) detected Cu in the island part of a sample, O, and Ti. Cu, Cu [ as opposed to / about Cu perform waveform separation of a spectrum and / all the Cu atoms ]₂O, CuO, and Cu (OH)₂The rate of an abundance ratio of Each of (molar ratio) was calculated. The spectrum of Cu and Cu₂Since it is similar and separation of each spectrum is difficult, the spectra of O are Cu and Cu.₂About O, they are a molar ratio of Cu, and Cu.₂It asked for total of the molar ratio of O. The molar ratio of Cu, and Cu₂In total of the molar ratio of O, the molar ratios of 0.218 and CuO are 0.510 and Cu (OH).₂The of molar ratio was 0.272. The gross weight of metal copper conversion of the material of a Cu system in an island part was measured by the chemical analysis. The chemical analysis was conducted by ICP optical emission spectrometry. "SPS3520UV" by S eye eye nanotechnology incorporated company was used for the ICP optical-emission-spectrometry device. Impression electric power was set as 1.2 kW, the measurement wavelength was set as 324.847 nm for the conditions of the device, and, specifically, the quantitative analysis was carried out based on the analytical curve of Cu using the standard solution which diluted suitably the Cu1000ppm standard solution for atomic absorption analysis (made by Kanto Kagaku, Inc.), and produced it. Cu from the measured rate of an abundance ratio, gross weight, and the area of the surface of a photocatalyst layer, Cu₂O, CuO, and Cu (OH)₂The amount of support which is Metal copper equivalent weight (metal copper equivalent weight per unit area of a photocatalyst layer) was calculated. Cu and Cu₂Total of the amount of support of O is 75 ng/cm.^２The amount of support of CuO is 175 ng/cm.^２Cu (OH)₂The amount of Loading is 93 ng/cm.^２It came out. It is Cu (OH) to the island part formed in spite of not having contained in the sputtering rig gas in Example 1 the substance which has H atom.₂It is thought that it is because the moisture contained in the atmosphere reacted to the sample when that of Contains rare ing takes out a sample from a sputter device after membrane formation of an island part.

0067The average diameter of the island part was measured by TEM observation. Specifically accelerating voltage was set as 200 kV, it was made one 200,000 times the magnification of this using EM-002B made from TOPCON, and the TEM photograph was taken. The size of the particles which change the view at the time of photography, carry out same photography 3 times, and can recognize it was measured. The average diameter of the island part was about 2.8 nm.

0068Next, the following procedures estimated the antiviral nature of the sample of Example 1.

0069First, coli phage (Escherichia coli phage) Qbeta is prepared as an examination virus, this is diluted, and concentration is 4x10.⁹The phage liquid of Pieces/ml was prepared. Coli phage Qbeta is general-purpose as substitution of an influenza virus in antivirus evaluation.

0070Next, this phage liquid 100mul was dropped on the antivirus thin film of a sample. Next, the transparent plastic sheet (what cut the commercial OHP sheet on a 40-mm square) for the prevention from dry was put on the sample which trickled coli phage. Thus, phage liquid was held between the sample and the plastic sheet.

0071Next, the petri dish was covered with the filter paper made to become wet with pure water, and the piece of glass has been arranged on this filter paper. Next, the plastic sheet has arranged the sample by which -ed was carried out to this glass Kataue, and it covered the petri dish with the silica glass board. Thus, the state where the humidity in a petri dish was maintained and filter paper did not touch a sample was acquired.

0072Next, it irradiated with ultraviolet rays from on the silica glass board. Specifically, intensity is 0.25mW/cm by a black lamp (Toshiba Lighting &amp; Technology Corp. make BLB-20S).²It irradiated with UV for 10 minutes.

0073Next, the sample and the plastic sheet were moved to another container, and phosphate buffered saline (0.1wt% of a surface-active agent (Tween20) is included to full weight) washed. The diluted solutions diluted 100 times on the basis of the volume of the dropped phage liquid by this were collected.

0074Next, it is this diluted solution by the above-mentioned phosphate buffered saline Further 10¹～１０⁵It diluted twice and prepared test liquid.

0075Next, the host liquid which contains coliform bacillus with a superfluous size to the coli phage contained in this test liquid was prepared. Next, test liquid 100mul and host liquid were mixed, and the mixed-solution was obtained. About the obtained mixed-solution, it is the upper agar medium (Nutrient Agar 5 g/l). It mixed to Nutrient Broth8 g/l and NaCl 0.5wt%, and applied to the lower layer agar medium (Nutrient Agar 15 g/l, Nutrient Broth 8 g/l, NaCl 0.5wt%) currently beforehand fixed to the petri dish.

0076Next, this petri dish was warmed in the homoiothermal layer set as 37 for 15 hours or more. Next, the number of the plaques which occurred was visually counted from the bottom side of a petri dish, and the concentration (PFU/ml) of the coli phage which did not lose infectious capacity among the coli phage contained in the phage liquid dropped from the number and dilution magnification of the plaque was computed. The concentration of the coli phage which did not lose infectious capacity is 1.0x10.³It was below PFU/ml.

0077What sterilized with the auto crepe sterilization machine and UV sterilization machine was used for all the instruments except phage liquid and host liquid.

0078In evaluation of the sample of Example 1, composition of the island part after an ultraviolet exposure was also analyzed. Specifically the same sample as the sample of Example 1 was prepared, this sample was irradiated with ultraviolet rays on the same conditions as the ultraviolet exposure in the above-mentioned antivirus evaluation, and composition of the island part of this sample was analyzed like the above after the ultraviolet exposure. The molar ratio of Cu, and Cu₂In total of the molar ratio of O, the molar ratios of 0.215 and CuO are 0.510 and Cu (OH).₂The of molar ratio was 0.274. Cu, Cu₂O, CuO, and Cu (OH)₂The amount of Loading was changing by the rate of change of a molar ratio, and the same rate of change (also setting this point to a below-mentioned example and comparative example the same).

0079In the above-mentioned antivirus evaluation, evaluation of the sample of Example 1 also estimated antiviral nature when it changes into ultraviolet rays and intensity irradiates with the visible light (light source: the usual fluorescent light) of 800lx for 60 minutes. The concentration of coli phage after irradiating with visible light is 5.0x10.³It was PFU/ml. Composition of the island part after visible light irradiation was analyzed by the same method as analysis of composition of the island part after an ultraviolet exposure. The molar ratio of Cu, and Cu₂In total of the molar ratio of O, the molar ratios of 0.218 and CuO are 0.507 and Cu (OH).₂The of molar ratio was 0.275.

0080In the above-mentioned antivirus evaluation, evaluation of the sample of Example 1 also estimated the antiviral nature after neglecting a petri dish in a darkroom for 180 minutes instead of irradiating with ultraviolet rays or visible light. The concentration of the coli phage in this case is 5.2x10.⁷It was PFU/ml. Composition of the island part after neglecting it in a darkroom was analyzed by the same method as analysis of composition of the island part after an ultraviolet exposure. The molar ratio of Cu, and Cu₂In total of the molar ratio of O, the molar ratios of 0.214 and CuO are 0.509 and Cu (OH).₂The of molar ratio was 0.277.

0081The rate of Hayes was measured about the sample of Example 1. Specifically, the rate of Hayes was measured using the Hayes meter (Nippon Denshoku Industries NDH2000) by entering light (wavelength band: 380-760 nm) from the glass board side. The rate of Hayes of the sample of Example 1 was 0.2%. Visually, Hayes of this sample has not been recognized. That light transmission nature is high has recognized this sample visually.

0082(Example 2)<br />In Example 2, flow rate of oxygen in the sputtering gas at the time of forming an island part was made 4% (0.04). The sample was produced like Example 1 except it. The molar ratio of Cu and Cu in the island part of the sample of Example 2₂In total of the molar ratio of O, the molar ratios of 0.278 and CuO are 0.471 and Cu (OH).₂The of molar ratio was 0.251. Cu and Cu₂Total of the amount of support of O is 91 ng/cm.^２The amount of support of CuO is 155 ng/cm.^２Cu (OH)₂The amount of Loading is 83 ng/cm.^２It came out. In Example 2, the sample was irradiated with ultraviolet rays like Example 1, and antivirus evaluation was performed. The concentration of the coli phage which did not lose infectious capacity is 5.2x10.⁵It was PFU/ml. The molar ratio of Cu and Cu in the island part after an ultraviolet exposure₂In total of the molar ratio of O, the molar ratios of 0.273 and CuO are 0.474 and Cu (OH).₂The of molar ratio was 0.253.

0083(Example 3)<br />In Example 3, the thickness of the photocatalyst layer was 50 nm. The sample was produced like Example 1 except it. The molar ratio of Cu and Cu in the island part of the sample of Example 3₂In total of the molar ratio of O, the molar ratios of 0.216 and CuO are 0.508 and Cu (OH).₂The of molar ratio was 0.276. Cu and Cu₂Total of the amount of support of O is 73 ng/cm.^２The amount of support of CuO is 173 ng/cm.^２Cu (OH)₂The amount of Loading is 94 ng/cm.^２It came out. In Example 3, the sample was irradiated with ultraviolet rays like Example 1, and antivirus evaluation was performed. The concentration of the coli phage which did not lose infectious capacity is 1.0x10.³It was below PFU/ml. The molar ratio of Cu and Cu in the island part after an ultraviolet exposure₂In total of the molar ratio of O, the molar ratios of 0.212 and CuO are 0.510 and Cu (OH).₂The of molar ratio was 0.278.

0084The result of Example 1-3 is summarized in Table 1.

0085<tables num="1"><img file="WO2013038705A1_D0001.tif" /></tables>

0086(Example 4)<br />In Example 4, flow rate of oxygen in sputtering gas was made 20% (0.20). The sample was produced like Example 1 except it. The molar ratio of Cu and Cu in the island part of the sample of Example 4₂In total of the molar ratio of O, the molar ratios of 0.110 and CuO are 0.735 and Cu (OH).₂The of molar ratio was 0.156. Cu and Cu₂Total of the amount of support of O is 39 ng/cm.^２The amount of support of CuO is 262 ng/cm.^２Cu (OH)₂The amount of Loading is 56 ng/cm.^２It came out. About the sample obtained in Example 4, antivirus evaluation after neglect was performed like Example 1 after an ultraviolet exposure and visible light irradiation and in a darkroom. The concentration of the coli phage which did not lose infectious capacity after irradiating the sample of Example 4 with ultraviolet rays is 1.0x10.³It was below PFU/ml. The molar ratio of Cu and Cu after an ultraviolet exposure₂In total of the molar ratio of O, the molar ratios of 0.091 and CuO are 0.629 and Cu (OH).₂The of molar ratio was 0.279. The concentration of the coli phage which did not lose infectious capacity after irradiating the sample of Example 4 with visible light is 6.0x10.³It was PFU/ml. The molar ratio of Cu and Cu in the island part after visible light irradiation₂In total of the molar ratio of O, the molar ratios of 0.080 and CuO are 0.660 and Cu (OH).₂The of molar ratio was 0.260. The concentration of the coli phage which did not lose infectious capacity after neglecting the sample of Example 4 in a darkroom is 6.2x10.⁸It was PFU/ml. The molar ratio of Cu and Cu in the island part after neglecting it in a darkroom₂In total of the molar ratio of O, the molar ratios of 0.114 and CuO are 0.733 and Cu (OH).₂The of molar ratio was 0.153.

0087The result of Example 4 is summarized in Table 2.

0088<tables num="2"><img file="WO2013038705A1_D0002.tif" /></tables>

0089&lt;Comparative example 1-3&gt;<br />(Comparative example 1)<br />In comparative example 1, flow rate of oxygen in the sputtering gas at the time of forming an island part was made 3% (0.03). The sample was produced like Example 1 except it. The molar ratio of Cu and Cu in the island part of the sample of comparative example 1₂In total of the molar ratio of O, the molar ratios of 0.310 and CuO are 0.450 and Cu (OH).₂The of molar ratio was 0.240. Cu and Cu₂Total of the amount of support of O is 102 ng/cm.^２The amount of support of CuO is 148 ng/cm.^２Cu (OH)₂The amount of Loading is 79 ng/cm.^２It came out. In comparative example 1, the sample was irradiated with ultraviolet rays like Example 1, and antivirus evaluation was performed. The concentration of the coli phage which did not lose infectious capacity is 4.1x10.⁷It was PFU/ml. The molar ratio of Cu and Cu in the island part after an ultraviolet exposure₂In total of the molar ratio of O, the molar ratios of 0.315 and CuO are 0.446 and Cu (OH).₂The of molar ratio was 0.239.

0090(Comparative example 2)<br />In comparative example 2, oxygen in sputtering gas was made 2% (0.02). The sample was produced like Example 1 except it. The molar ratio of Cu and Cu in the island part of the sample of comparative example 2₂In total of the molar ratio of O, the molar ratios of 0.419 and CuO are 0.379 and Cu (OH).₂The of molar ratio was 0.202. Cu and Cu₂Total of the amount of support of O is 138 ng/cm.^２The amount of support of CuO is 125 ng/cm.^２Cu (OH)₂The amount of Loading is 66 ng/cm.^２It came out. In comparative example 2, the sample was irradiated with ultraviolet rays and visible light like Example 1, respectively, and antivirus evaluation was performed. The concentration of the coli phage which did not lose infectious capacity after the ultraviolet exposure is 6.1x10.⁷It was PFU/ml. The molar ratio of Cu and Cu in the island part after an ultraviolet exposure₂In total of the molar ratio of O, the molar ratios of 0.415 and CuO are 0.380 and Cu (OH).₂The of molar ratio was 0.205. The concentration of the coli phage which did not lose infectious capacity after visible light irradiation is 8.1x10.⁷It was PFU/ml. The molar ratio of Cu and Cu after visible light irradiation₂In total of the molar ratio of O, the molar ratios of 0.422 and CuO are 0.376 and Cu (OH).₂The of molar ratio was 0.201.

0091(Comparative example 3)<br />In comparative example 3, oxygen in sputtering gas was made 0%. The sample was produced like Example 1 except it. The molar ratio of Cu and Cu in the island part of the sample of comparative example 3₂In total of the molar ratio of O, the molar ratios of 0.700 and CuO are 0.180 and Cu (OH).₂The of molar ratio was 0.120. Cu and Cu₂Total of the amount of support of O is 211 ng/cm.^２The amount of support of CuO is 54 ng/cm.^２Cu (OH)₂The amount of Loading is 36 ng/cm.^２It came out. In comparative example 3, the sample was irradiated with ultraviolet rays like Example 1, and antivirus evaluation was performed. The concentration of the coli phage which did not lose infectious capacity is 2.5x10.⁸It was PFU/ml. The molar ratio of Cu and Cu in the island part after an ultraviolet exposure₂In total of the molar ratio of O, the molar ratios of 0.699 and CuO are 0.177 and Cu (OH).₂The of molar ratio was 0.124.

0092The result of comparative example 1-3 is summarized in Table 3.

0093<tables num="3"><img file="WO2013038705A1_D0003.tif" /></tables>

0094&lt;Comparative example 4-7&gt;<br />(Comparative example 4)<br />In comparative example 4, the standard film thickness in sputtering which sets a target to Cu was 5 nm. The sample was produced like Example 1 except it. In comparative example 4, the island part of a Cu system was not formed but the continuation film (Cu film) of a Cu system was formed. The molar ratio of Cu and Cu in Cu film of the sample of comparative example 4₂In total of the molar ratio of O, the molar ratios of 0.202 and CuO are 0.547 and Cu (OH).₂The of molar ratio was 0.251. Cu and Cu₂Total of the amount of support of O is 211 ng/cm.^２The amount of support of CuO is 1882 ng/cm.^２Cu (OH)₂The amount of Loading is 865 ng/cm.^２It came out. In comparative example 4, the sample was irradiated with ultraviolet rays like Example 1, and antivirus evaluation was performed. The concentration of the coli phage which did not lose infectious capacity is 8.3x10.⁷It was PFU/ml. The molar ratio of Cu and Cu in the island part after an ultraviolet exposure₂In total of the molar ratio of O, the molar ratios of 0.202 and CuO are 0.547 and Cu (OH).₂The of molar ratio was 0.251.

0095(Comparative example 5)<br />A photocatalyst layer was not provided in comparative example 5. The sample was produced like Example 1 except it. The molar ratio of Cu and Cu in the island part of the sample of comparative example 5₂In total of the molar ratio of O, the molar ratios of 0.214 and CuO are 0.512 and Cu (OH).₂The of molar ratio was 0.273. Cu and Cu₂Total of the amount of support of O is 68 ng/cm.^２The amount of support of CuO is 162 ng/cm.^２Cu (OH)₂The amount of Loading is 88 ng/cm.^２It came out. In comparative example 5, the sample was irradiated with ultraviolet rays like Example 1, and antivirus evaluation was performed. The concentration of the coli phage which did not lose infectious capacity is 5.8x10.⁷It was PFU/ml. The molar ratio of Cu and Cu in the island part after an ultraviolet exposure₂In total of the molar ratio of O, the molar ratios of 0.214 and CuO are 0.511 and Cu (OH).₂The of molar ratio was 0.276.

0096(Comparative example 6)<br />An island part was not provided in comparative example 6. The sample was produced like Example 1 except it. In comparative example 6, the sample was irradiated with ultraviolet rays like Example 1, and antivirus evaluation was performed. The concentration of the coli phage which did not lose infectious capacity is 2.9x10.⁹It was PFU/ml.

0097(Comparative example 7)<br />Only the glass board was made into the sample in comparative example 7. In comparative example 7, the sample was irradiated with ultraviolet rays like Example 1, and antivirus evaluation was performed. The concentration of the coli phage which did not lose infectious capacity is 3.5x10.⁹It was PFU/ml.

0098The result of comparative example 4-7 is summarized in Table 4.

0099<tables num="4"><img file="WO2013038705A1_D0004.tif" /></tables>

0100&lt;Comparative example 8-10&gt;<br />(Comparative example 8)<br />The rutile type titanium dioxide (MT-150A by TAYCA CORP.) was made suspended in addition in distilled water, in comparative example 8, so that the rate to this distilled water may become 10 mass %. It is Cu (NO) to this suspension.₃）₂3H₂Agitating [ added O (made by Wako Pure Chemical Industries, Ltd.) so that the rate to the rutile type titanium dioxide of a copper ion might become 0.1 mass %, and ] it, it heated at 90 and held for 1 hour. Next, after carrying out suction filtration of this suspension, the rutile type titanium dioxide particulates which supported copper 2 value salt were obtained by distilled water's washing a residual substance and carrying out drying by heating of this residual substance at 110 further.

0101It settled for 24 hours, after having added to distilled water so that the rate to this distilled water might become 10 mass % after powder-izing this copper 2 value salt support rutile type titanium dioxide in a mortar, and making it suspended by ultrasonic dispersion. By extracting a supernatant fluid, copper 2 value salt support rutile type titanium dioxide particulate dispersion liquid was obtained from the liquid after this settlement. When drying by heating of a part of these dispersion liquid was carried out and the content of the copper 2 value salt support rutile type titanium dioxide particulates in dispersion liquid was checked, it was 6.1 mass %.

0102Next, they are 5 mass parts of tetra-ethoxy Silane (made by Wako Pure Chemical Industries, Ltd.) in a reaction vessel, 0.8 mass part of ion exchange water, 0.07 mass part of HCl solution of concentration 0.1 mol/l, and 94.13 mass parts of ethanol were mixed, and the solution of the partial hydrolysis condensation polymer of tetra-ethoxy Silane was obtained by agitating for 16 hours.

0103100 mass parts of the above-mentioned copper 2 value salt support rutile type titanium dioxide particulate dispersion liquid was mixed with 100 mass parts of solution of the partial hydrolysis condensation polymer of this tetra-ethoxy Silane, and the coating material was obtained by agitating for 1 hour.

0104This coating material was applied with the spin coat on the 3.0-mm-thick glass board, and the sample by which the coating film was formed on the glass board was obtained by heating for 30 minutes and making it dry and harden at 100 .

0105The coating film in the obtained sample was 80 nm. The rate of Hayes measured by the same method as Example 1 about this sample was 2.1%. Hayes of this sample has been recognized visually. This sample has recognized visually that light transmission nature is also low. Therefore, this sample is unsuitable for the use which requires light transmission nature, design nature, etc.

0106(Comparative example 9)<br />In comparative example 9, it is diluting water and ethanol with a weight ratio 11 times with solution mixed at a rate of 1:1, applying with a spin coat on a glass board, heating for 30 minutes, and drying and stiffening the coating material of comparative example 8 at 100 , The sample by which the coating film was formed on the glass board was obtained.

0107The coating film in the obtained sample was 7 nm. When converting it from composition of a coating film, the mass of the titanium oxide contained in this coating film is equivalent to the mass which a 5-nm-thick titanium oxide film has. The molar ratio of Cu and Cu in the coating film of the sample of comparative example 9₂In total of the molar ratio of O, the molar ratios of 0.000 and CuO are 0.630 and Cu (OH).₂The of molar ratio was 0.370. Cu and Cu₂Total of the amount of support of O is 0 ng/cm.^２The amount of support of CuO is 345 ng/cm.^２Cu (OH)₂The amount of Loading is 203 ng/cm.^２It came out. About this sample, the sample was irradiated with ultraviolet rays like Example 1, and antivirus evaluation was performed. The concentration of the coli phage which did not lose infectious capacity is 3.2x10.⁷It was PFU/ml. The molar ratio of Cu and Cu in the coating film after an ultraviolet exposure₂In total of the molar ratio of O, the molar ratios of 0.000 and CuO are 0.632 and Cu (OH).₂The of molar ratio was 0.368. The rate of Hayes measured by the same method as Example 1 about this sample was 0.6%.

0108The result of comparative example 9 is summarized in Table 5.

0109<tables num="5"><img file="WO2013038705A1_D0005.tif" /></tables>

0110(Comparative example 10)<br />In comparative example 10, an oxidization silicon film, zirconium oxide membrane, and a photocatalyst layer were formed on the float glass like Example 1. Next, copper chloride (I) powder (first class by Wako Pure Chemical Industries, Ltd. in Kazumitsu, 40.9 micrometers of particle diameter) was made suspended to water 100mul, and the suspension of concentration 1.0 mass % was obtained. This suspension was sprayed on the photocatalyst layer with the spray, and the sample was obtained by making it dry at normal temperature. Although the sample was irradiated with ultraviolet rays like Example 1 and antivirus evaluation was performed about the sample obtained by comparative example 10, there was no antiviral nature of the sample of comparative example 10.

0111&lt;Example 5-6&gt;<br />(Example 5)<br />In Example 5, the island part was formed on the same conditions as Example 1 on the commercial glass board with a photocatalyst layer (made by ACTIV;Pilkington Group Limited). TiO in which this glass board with a photocatalyst was formed by the glass board and the CVD method_２The film is included.

0112The molar ratio of Cu and Cu in the island part of the sample of Example 5₂In total of the molar ratio of O, the molar ratios of 0.148 and CuO are 0.601 and Cu (OH).₂The of molar ratio was 0.251. Cu and Cu₂Total of the amount of support of O is 31 ng/cm.^２The amount of support of CuO is 126 ng/cm.^２Cu (OH)₂The amount of Loading is 52 ng/cm.^２It came out. The diameter of the island part was about 2.8 nm. About the sample obtained in Example 5, antivirus evaluation after neglect was performed like Example 1 after an ultraviolet exposure and visible light irradiation and in a darkroom. The concentration of the coli phage which did not lose infectious capacity after irradiating the sample of Example 5 with ultraviolet rays is 1.0x10.³It was below PFU/ml. The concentration of the coli phage which did not lose infectious capacity after irradiating the sample of Example 5 with visible light is 1.0x10.³It was below PFU/ml. The concentration of the coli phage which did not lose infectious capacity after neglecting the sample of Example 5 in a darkroom is 1.1x10.⁸It was PFU/ml. The molar ratio of Cu and Cu in the island part of the sample of Example 5₂The molar ratio and Cu (OH) of total of the molar ratio of O, and CuO₂A of molar ratio was hardly changing, before and after neglecting it in an ultraviolet exposure, visible light irradiation, and a darkroom (even the sample of Example 6 of this point is the same).

0113(Example 6)<br />In Example 6, the island part was formed on the same conditions as Example 1 on the commercial glass board with a photocatalyst layer (clear Tect; made by Nippon Sheet Glass Co., Ltd.). TiO in which this glass board with a photocatalyst was formed of the glass board and the sol gel process_２The film is included.

0114The molar ratio of Cu and Cu in the island part of the sample of Example 6₂In total of the molar ratio of O, the molar ratios of 0.267 and CuO are 0.495 and Cu (OH).₂The of molar ratio was 0.238. Cu and Cu₂Total of the amount of support of O is 32 ng/cm.^２The amount of support of CuO is 58 ng/cm.^２Cu (OH)₂The amount of Loading is 28 ng/cm.^２It came out. About the sample obtained in Example 6, antivirus evaluation after neglect was performed like Example 1 after an ultraviolet exposure and visible light irradiation and in a darkroom. The concentration of the coli phage which did not lose infectious capacity after irradiating the sample of Example 6 with ultraviolet rays is 1.0x10.³It was below PFU/ml. The concentration of the coli phage which did not lose infectious capacity after irradiating the sample of Example 6 with visible light is 1.0x10.³It was below PFU/ml. The concentration of the coli phage which did not lose infectious capacity after neglecting the sample of Example 6 in a darkroom is 5.1x10.⁸It was PFU/ml.

0115The result of Examples 5 and 6 is summarized in Table 6.

0116<tables num="6"><img file="WO2013038705A1_D0006.tif" /></tables>

0117&lt;Example 7-13&gt;<br />In Examples 7, 8, and 12, the sample was produced like Example 1 except having made small the amount of support of the material (island part) of a Cu system. In Example 9-11 and 13, the sample was produced like Example 4 except having made small the amount of support of the material of a Cu system. About each sample of Example 7-13, evaluation carried out to the sample of Example 1 and same evaluation were carried out. About each sample of Example 7-13, the carried-out evaluation result is summarized in Drawing 7, and is shown.<br /><tables num="7"><img file="WO2013038705A1_D0007.tif" /></tables>

0118&lt;Example 14-17&gt;<br />In Example 14, it united according to the process commonly used by the person skilled in the art using the sample (substrate with an antivirus thin film) of Example 1, glass was produced, and it was considered as the sample. In Example 15, it united using the sample of Example 5, glass was produced, and it was considered as the sample. In Example 16, using the sample of Example 1, double-glazed glass was produced and it was considered as the sample according to the process commonly used by the person skilled in the art. In Example 17, double-glazed glass was produced using the sample of Example 5, and it was considered as the sample. About each sample of Example 14-17, antivirus evaluation carried out to the sample of Example 1 and same antivirus evaluation were carried out. About each sample of Example 14-17, the carried-out evaluation result is summarized in Table 8, and is shown. As shown in Table 8, when a substrate with an antivirus thin film is set and it applies to glass or double-glazed glass, the molar ratio of the various materials of a Cu system may change. Although this reason is not understood in detail, there is a possibility that the heat etc. which are applied to glass in the process of the common use which unites and produces glass and double-glazed glass have contributed.<br /><tables num="8"><img file="WO2013038705A1_D0008.tif" /></tables>

0119&lt;Analysis of an example and a comparative example&gt;<br />Cu (OH) in the island part in front of the process (irradiation process) of an island part being formed on a photocatalyst layer and irradiating with ultraviolet rays or visible light as shown in Table 1₂In the sample of Example 1-3 in which the of molar ratio (molar ratio A) is over 0.25, the quantity of the virus decreased or less to 1/1000 according to the irradiation process. In the sample of Examples 1 and 3 whose molar ratio A in the island part in front of an irradiation process is 0.26 or more, reduction in a virus was more remarkable.

0120It turns out that molar ratio A has the flow rate which is a ratio of the flow of oxygen to the flow of the whole sputtering gas, and correlation from Table 1. That is, in order for antiviral nature to produce a high substrate with an antivirus thin film, while inactive gas and oxygen constitute sputtering gas, it is preferred to set up the flow rate which is a ratio of the flow of oxygen to the flow of the whole gas more than 4% (0.04). When the ratio of the flow of oxygen to the flow of inactive gas contained in sputtering gas is made about into 4:96 to 10:90 from Table 1, it can be said that antiviral nature can produce a high substrate with an antivirus thin film.

0121Not only when the sample of Example 1 irradiates with ultraviolet rays, but when it irradiates with visible light, demonstrating good antiviral nature is grasped.

0122As shown in Table 2, antiviral nature also with a good sample of Example 4 was shown. In the sample of Example 4, although molar ratio A in the island part in front of an irradiation process was less than 0.25, after the irradiation process, 0.25 or more had been the molar ratio A. the mol of all the Cu atoms [ in / on the other hand / at the sample of Example 4 / the island part in front of an irradiation process ] -- the mol of CuO to a number -- although the ratio (molar ratio C) of the number was 0.735 and was [ 0.20 or more ] high compared with the case of Example 1-3, after the irradiation process, it fell or more by 0.07. At these to Example 4, CuO is Cu (OH) during irradiation of ultraviolet rays or visible light.₂It is alike, and it changes and it is thought that it came to reveal good antiviral nature. It is thought from Table 1 and 2 that the flow rate which is a ratio of the flow [ as opposed to / C / in front of an irradiation process / molar ratio / the flow of the whole sputtering gas in the high reason ] of oxygen is 20% (0.20), and it is because it was high compared with Example 1-3.

0123CuO is Cu (OH), also when it irradiates with ultraviolet rays and irradiates with visible light from the result of Example 4.₂CuO of many although it was alike, and it changed, when it irradiates with ultraviolet rays compared with the case where it irradiates with visible light is Cu (OH).₂It is alike, and it changes and it can be said that higher antiviral nature is obtained.

0124In the sample of comparative example 1-7, the quantity of the virus did not decrease like the case of an example. Cu [ in / in comparative example 1-3 and the sample of 6 / an island part ] (OH)₂It can be said that it is because a photocatalyst layer or island part does not have [ that a of molar ratio is low, that the photocatalyst layer has not exposed the sample of comparative example 4, that the sample of comparative example 5 does not have a photocatalyst layer, and ] the sample of comparative example 7, either.

0125Although the sample of comparative example 9 had high molar ratio A, antiviral nature was hardly shown. This is considered that it is one cause that molar ratio A is too high slightly with the sample of comparative example 9. The partial hydrolysis condensation polymer of tetra-ethoxy Silane becomes an obstacle, and it is also thought that it is the causes that the copper 2 value salt which has contacted the virus was restricted, and for this partial hydrolysis condensation polymer to have interrupted ultraviolet rays, and to have not been irradiated with the ultraviolet rays of sufficient quantity for titanium oxide.

0126It can be said that the substrate with an antivirus thin film which has good antiviral nature is obtained from Example 1, Example 5, and Example 6 even if it forms a photocatalyst layer by any of the sputtering method, a CVD method, and a sol gel process.

0127The amount of support of the various materials of a Cu system of the substrate with an antivirus thin film of Example 7-13 to this embodiment is number ng/cm.^２Even if it is a grade, it is grasped that antiviral nature is shown. Material of a Cu system which antivirus exertion takes the sample of Example 7-13 (for example, Cu (OH))_２The minimum of the amount of support is number ng/cm.^２It can be said that it expresses that it is below a grade.

0128Even if a substrate with an antivirus thin film is set and it applies to glass or double-glazed glass from Examples 1 and 5 and 14-17, it can be said that antiviral nature does not change substantially (degradation). the process which similarly is commonly used by the person skilled in the art in the substrate with an antivirus thin film of the present invention -- tempered glass -- it may bend and may apply to secondary elaboration articles, such as glass.

0129On all the articles in which, as for the substrate with an antivirus thin film of the present invention, a virus may touch, and a concrete target, The windowpane for construction, the glass for partitions, door glass, glass for cars, It is applicable to the glass for a display, a mirror, the transparent substrate for DNA analysis, a solar cell, an information portable device, health, medical science, electronic equipment, an optical component, the glassware for a biochemistry experiment, the inspection chip for medical science, and a medical endoscope and the optical fiber for an operation.

0130Since breeding of the virus in a hospital, a nursing home, a residence, etc. can be controlled if the substrate with an antivirus thin film of the present invention is used, reduction of a problem the health which made the virus the cause, and sanitary is expected.