Base with 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 photocatalyst layer and an island part which makes the main ingredients material of a Cu system arranged directly in contact with the surface top of the photocatalyst layer,<br />The above-mentioned photocatalyst layer contains Anatase type titanium oxide,<br />Cu (OH) to the number of Mol of all the Cu atoms in the above-mentioned island part_２The substrate with an antivirus thin film whose molar ratio A which is a ratio of the number of of Mol is 0.80 or less more greatly than 0.35,<br />It provides.</p><p num="0011">Another mode of the 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 photocatalyst layer and an island part which makes the main ingredients material of a Cu system arranged directly in contact with the surface top of the photocatalyst layer,<br />The above-mentioned photocatalyst layer contains Anatase type titanium oxide,<br />Cu (OH) in the above-mentioned island part_２Cu (OH) which computed the quantity which converted Weight of into metal copper by having broken it by area of the surface of the above-mentioned layer_２The amount of Loading is 70 ng/cm.^２The substrate with an antivirus thin film which it is above,<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 photocatalyst layer and an island part which makes material of a Cu system the main ingredients.

0017A photocatalyst layer generates an electric charge (an electron or an electron hole) by being irradiated with light. The function as a photocatalyst of a photocatalyst layer is brought about with Anatase type titanium oxide. As for this Anatase type titanium oxide, it is preferred that they are many crystalline material. The electric charge which arose by the photocatalyst layer acts with the island part which makes material of a Cu system the main ingredients, and a photocatalyst layer and an island part demonstrate an antiviral effect as an antivirus thin film.

0018The 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.

0019The titanium oxide contained in a photocatalyst layer may be made to contain metal, such as iron, aluminum, and tungsten, in small quantities intentionally as a dopant. In a photocatalyst layer, generating of a career is promoted with a dopant, and the photocatalyst activity of a photocatalyst layer increases. 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.

0020A 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.

0021The 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 mainly_２It 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 ]_２The molar ratio (molar ratio A) which is a ratio of the number of of Mol exceeds 0.35, and when it is 0.80 or less, an antivirus thin film demonstrates good antiviral nature. As for the above-mentioned molar ratio A, it is preferred that it is 0.37-0.70, and it is more preferred that it is 0.38-0.60.

0022Cu (OH) in an island part_２Cu (OH) which computed the quantity which converted Weight of into metal copper by having broken it by area of the surface of a photocatalyst layer_２The amount of Loading is 1 ng/cm, for example.^２It is above and preferably is 4 ng/cm.^２It is above and more preferably is 40 ng/cm.^２It is above and, still more preferably is 70 ng/cm.^２It is above.

0023Cu [ in / preferably / an island part ] (OH)_２ofmol -- the mol of a number and CuO -- the mol of all the Cu atoms in the island part of the sum with a number -- the molar ratios (molar ratio B) to a number are 0.70-0.95. That is, in an island part, a part of Cu is Cu (Cu of a metal state), or Cu._２Living together in the state of O is preferred.

0024The above-mentioned Cu (OH)_２The amount of Loading is 70 ng/cm.^２When it is above, an antivirus thin film demonstrates antiviral nature good as another aspect.

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.

00261x1 micrometer [ in / in an island part / the surface of a photocatalyst layer ]^２All over the arbitrary fields of Width of, it is preferred at least one, for example, 100-3000 pieces, preferably that 250-750 pieces exist. 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.

0028It is preferred for an island part to form on a photocatalyst layer by the sputtering method so that the following may describe in detail. According to especially the reactive sputtering method, it is easy to control the number of Price of Cu in the material of a Cu system with the distribution, and it is preferred.

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 still 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 total exposure area of the island part to the whole island part product 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 total exposure area of the island part to the whole island part product 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. 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 1.0% or less, and it is good to consider it as 0.5% or less more preferably. 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.

0037The 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.

0038When 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.

0039Next, some typical composition of a substrate with an antivirus thin film is shown in a drawing.

0040Drawing 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. Photocatalyst layer 22 has the shape of a flat film. The surface (surface specifically excluding a contact surface with photocatalyst layer 22 of island part 23) 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.

0041As 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.

0042Next, the concrete manufacturing method of an island part is explained.

0043An 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.

0044The 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.

0045This 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.

0046The target which makes metal copper the main ingredients is used, and it is Cu (OH)._２When forming, in order to oxidize copper in a metal state and to form hydroxide, an oxidizer and moisture materials are needed. In the present invention, it is preferred to carry out the moisture materials of the water which makes an oxidizer the oxygen contained in sputtering gas, and exists in a membrane formation chamber. Although the moisture which is sticking to the wall in a chamber or material for membranes to be formed may be sufficient as moisture in a membrane formation chamber, it may introduce moisture into a membrane formation chamber positively as vapor.

0047Cu [ in / on the present invention and / an island part ] (OH)_２In order to adjust appropriately of molar ratio A and the amount of support, it differs for every film deposition system, but as for the ratio (oxyecoia partial pressure) of the flow of oxygen to the flow of inactive gas contained in sputtering gas, 5:95-22:78 may be preferred, and they may be 12:88-18:82. Moisture in a membrane formation chamber is one to 3x10, when expressing it with the partial pressure of the water in a membrane formation chamber.^－２It is preferred that it is Pa.

0048An example of the sputtering system for forming an island part in Drawing 3 is shown. In sputtering system 50 shown in Drawing 3, glass board 31 with a photocatalyst layer with which the photocatalyst layer was formed on the substrate moves with conveyance roller 43. 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.

0049A 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.

0050Target 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.

0051In order to explain the present invention still in detail, an example and a comparative example are shown.

0052(EXAMPLE)<br />(Formation of an antivirus thin film)<br />In all the examples of the present invention, the island part was formed by the reactive sputtering method on the surface of the photocatalyst layer using the commercial photocatalyst cleaning glass board with which the photocatalyst layer is formed on the glass board.

0053The photocatalyst cleaning glass board of this marketing is a product made by ACTIV;Pilkington Group Limited. In this photocatalyst cleaning glass board, the photocatalyst film is formed on the glass board by a float process, and the photocatalyst layer in the outermost surface of that photocatalyst film makes Anatase type titanium oxide the main ingredients.

0054Even if it uses the thing originating in other processes which are not things of CVD method origin as a photocatalyst film, it is as above-mentioned that the antivirus thin film of the present invention can be obtained. For example, it may replace with ACTIV and may use clear Tect S (Nippon Sheet Glass Co., Ltd. make; a glass board and the Anatase type titanium oxide film of the sputtering method origin formed on the glass board are included).

0055The sputter device used for reactive sputtering membrane formation is an in-line type sputter device (G-38 type; made by Airco), and is a device of the industrial scale which has a target side with a size of about 3 m x 30 cm. In this device, like the common in-line type sputter device, a series of vacuum chamber groups are furnished by the airtight door between chambers so that atmosphere can be separated. Between a membrane formation chamber which forms membranes by sputtering, and the device exterior, a hold chamber is formed as one of the above-mentioned vacuum chambers of a series of. A glass board in atmospheric pressure atmosphere can be introduced into a membrane formation chamber, without affecting a degree of vacuum and a sputtering gas atmosphere of a membrane formation chamber by passing this hold chamber.

0056Specifically, it is as follows. After washing and washing a photocatalyst cleaning glass board using neutral detergent and a brush and draining water with the air knife, it introduced into the membrane formation chamber through the hold chamber, and the island part was formed by the sputtering method.

0057The size of the target was 3097x280 mm. The interval of the substrate and target in which the photocatalyst layer was formed was about 100 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 100 mm. The main part of a substrate was not heated at the time of membrane formation.

0058When forming an island part, the conditions which changed the standard sputtering conditions shown below were adopted.<br />- Target : Cu<br />- Gas pressure : 0.20 Pa<br />- Sputtering type of gas : oxygen (O)_２16%+ argon (Ar) 84%<br />- Injection power : DC1,000W (power density of 0.0012W/cm)^２）<br />- Bearer rate : 3,500 mm/min (according to the membrane formation rate of a target, it tunes finely)<br />- Standard film thickness : 0.2 nm

0059As shown in Drawing 3, the outlet of sputtering gas was installed so that gas might be emitted between a shield plate and a target.

0060The 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.

0061(Evaluation of the rate of an abundance ratio of Cu system material of an island part)<br />Cu, Cu which are contained in the island part of the produced sample_２O, CuO, and Cu (OH)_２The The presence of ratio was analyzed by the XPS method (X ray photoelectron spectroscopy). The used analysis devices are the ULVAC phi company make and ESCA-5600i, and irradiation X-rays are an aluminum-Kalpha line. Cu, Cu [ as opposed to / 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 Cu_２Since 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.

0062(Evaluation of the quantity which converted Cu system material of the island part into metal copper)<br />Measurement of the gross weight of metal copper conversion of the material of a Cu system in an island part was performed according to the ICP emission spectrometry using the analytical curve by standard solution. The used analysis device is "SPS3520UV" by S eye eye nanotechnology incorporated company. Cu from the measured rate of an abundance ratio, gross weight, and the area of the surface of a photocatalyst layer, Cu_２O, CuO, and Cu (OH)_２The amount of support was calculated as Metal copper equivalent weight (metal copper equivalent weight per unit area of a photocatalyst layer). However, about the sample in which the photocatalyst layer is not formed, it replaced with the area of the surface of a photocatalyst layer, and calculated metal copper equivalent weight (the amount of support) using the area of the surface of a glass board.

0063(Measurement of the ratio of the average diameter of an island part, and the area of an island part)<br />The 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 area of the island part was computed from the diameter of the measured island part, and the ratio of the area which the island part to the area of a thin film has covered was computed.

0064(Antivirus evaluation)<br />Coli phage (Escherichia coli phage) Qbeta used widely by substitution of an influenza virus in antivirus evaluation was used for antivirus evaluation as an examination virus. Antivirus evaluation performed predetermined light irradiation to the phage liquid of predetermined concentration, and it performed it by measuring the concentration of the phage which holds infectious capacity after light irradiation.

0065Specifically, it is as follows. Concentration 4x10^９100microL of the above-mentioned phage liquid prepared to Pieces/mL was dropped on the antivirus thin film of the sample cut on a 50-mm square. The area which makes uniform thickness of the solution layer of the phage liquid on an antivirus thin film and to which phage liquid touches an antivirus thin film by putting the OHP sheet of marketing cut on a 40-mm square on it was provided in a 40-mm square.

0066In order to prevent phage liquid volatilizing in light irradiation, the sample was held in the petri dish with which humidity was maintained. That is, the bottom of the petri dish was covered with the filter paper made to become wet with pure water, the piece of glass was placed on it, the sample was placed on it, and the petri dish was covered with the silica glass board.

0067The following three kinds of processings were added to the sample held in the petri dish.<br />- Ultraviolet exposure : use a black lamp (Toshiba Lighting &amp; Technology Corp. make BLB-20S), and it is the intensity of 0.25mW/cm from the outside of the lid of a silica glass board.^２It irradiates with UV for 10 minutes.<br />- Visible light irradiation : irradiate with the visible light of illumination 800Lx for 60 minutes from the outside of the lid of a silica glass board using the usual fluorescent light.<br />- Dark place storage : don't irradiate with light but keep a petri dish in a darkroom for 180 minutes.

0068The whole quantity was collected by fully washing a sample and an OHP sheet for the phage liquid after light irradiation. It is dilution magnification 10 about this recovering liquid.^３～１０^８It diluted one by one twice. Thus, a series of test liquid was prepared. The adjusted test liquid was respectively mixed with the coliform bacillus host liquid prepared separately, and a series of mixed-solutions were prepared. This mixed-solution was inoculated and cultivated to the agar medium prepared separately. The number of the plaques which arose after that was counted visually. Based on the number of plaques, and dilution magnification, it asked for the concentration of the phage which holds infectious capacity after the light irradiation in phage liquid as PFU/mL.

0069Washing and dilution were made to contain coliform bacillus with a superfluous size to phage using the phosphate buffered saline which contains 0.1wt% of a surface-active agent (Tween20) to full weight in coliform bacillus host liquid.

0070About inoculation to a culture medium, the above-mentioned mixed-solution was mixed to the upper agar medium, and it applied to the lower layer agar medium beforehand fixed to the petri dish. The upper agar medium of an ingredient of a culture medium is Nutrient Agar5 g/L, Nutrient Broth 8 g/L, and NaCl 0.5wt%. A lower layer agar medium is Nutrient Agar 15 g/L, Nutrient Broth 8 g/L, and NaCl 0.5wt%.

0071Cultivation was performed by warming the inoculated petri dish in the homoiothermal layer set as 37 for 15 hours or more.

0072What sterilized with the auto crepe sterilization machine and UV sterilization machine was used for all the instruments except phage liquid and host liquid.

0073(Measurement of the rate of Hayes)<br />Using the Hayes meter (Nippon Denshoku Industries NDH2000), light (wavelength band: 380-760 nm) was entered in measurement of the rate of Hayes, and it measured from the glass board side to it.

0074(Example 1)<br />Except for the following points, sputtering was performed according to the above-mentioned standard sputtering conditions. This obtained the sample of Example 1.<br />- Sputtering type of gas : oxygen (O)_２5%+ argon (Ar) 95%<br />- Partial pressure of the water in a membrane formation chamber : 1.8x10^－２Pa

0075The rate of an abundance ratio and each metal copper equivalent weight of Cu system material of the island part were as follows.<br />Kind of Cu system material Molar ratio Metal copper equivalent weight<br />Cu and Cu_２Total of O 0.090 24 ng/cm^２<br />CuO 0.517 140ng/cm^２<br />Cu(OH)_２0.393 107ng/cm^２

0076The diameter of the island part by TEM observation was about 2.8 nm. The ratio of the area which the island part to the area of a thin film has covered was 0.12.

0077The antivirus evaluation result was as follows.<br />Conditions of light irradiation Concentration of the phage which is maintaining infectious capacity after irradiation<br />Ultraviolet exposure 1.0x10^３Below PFU/mL<br />Visible light irradiation 1.0x10^３Below PFU/mL<br />Dark place storage 1.9x10^８PFU/mL

0078The rate of Hayes was 0.2%, and Hayes has not been recognized visually but it has recognized that light transmission nature is high.

0079(Examples 2-6)<br />In Examples 2-6, the following points were changed among the above-mentioned standard sputtering conditions, and sputtering was performed. This obtained the sample of Examples 2-6.<br />Rate of oxygen in sputtering gas Partial pressure of the water in a membrane formation chamber<br />Example 2 8% 2.8x10^－２Pa<br />Example 3 12% 2.0x10^－２Pa<br />Example 4 16% 1.8x10^－２Pa<br />Example 5 18% 2.4x10^－２Pa<br />Example 6 22% 2.1x10^－２Pa

0080The result of having measured the rate of an abundance ratio of each Cu system material in an island part, the metal copper equivalent weight of each Cu system material in an island part, and antiviral nature about the sample of Examples 1-6 is shown in Table 1. The notation of nE+m in Table 1 is nx10.^+mIt means.

0081Also in any of the sample of Examples 1-6, the diameter of the island part was in the range of 1-20 nm, the ratio of the area which the island part to the area of a thin film has covered was in the range of 0.01-0.20, and the rate of Hayes was 1.0% or less.

0082(Comparative examples 1 and 2)<br />At comparative examples 1 and 2, it is the partial pressure of water [ in / respectively / for the rate of oxygen in sputtering gas / 2%, 0%, and a membrane formation chamber ] respectively 0.94x10^－２Pa, 0.56x10^－２The above-mentioned standard sputtering conditions were adopted except for the point changed into Pa. This obtained the sample of comparative examples 1 and 2.

0083(Comparative example 3)<br />In comparative example 3, the following points were changed among the sputtering conditions of Example 1, and sputtering was performed. This obtained the sample of comparative example 3.<br />- Standard film thickness : 5 nm<br />- Partial pressure of the water in a membrane formation chamber : 1.2x10^－２Pa<br />In comparative example 3, Cu system material by which sputtering was carried out formed not island shape but the continuation film.

0084(Comparative example 4)<br />In comparative example 4, the float glass (photocatalyst layer is not formed) board with which coating is not made at all was used instead of the photocatalyst cleaning glass board used in the example. The sample was produced like Example 1 except it.

0085The result of having measured the rate of an abundance ratio of each Cu system material in an island part, the metal copper equivalent weight of each Cu system material in an island part, and antiviral nature about the sample of comparative examples 1-4 is shown in Table 1.

0086(Comparative example 5)<br />In comparative example 5, an island part was not provided in the photocatalyst cleaning glass board used in the example at all. That is, only the photocatalyst cleaning glass board was made into the sample of comparative example 5.

0087(Comparative example 6)<br />In comparative example 6, the float glass board which is not coated at all was prepared. An island part was not provided in this float glass board at all. That is, only the float glass board was made into the sample of comparative example 6.

0088The evaluation result of the sample of comparative examples 5 and 6 is also collectively shown in Table 1.

0089(Comparative example 7)<br />Comparative example 7 made the sample what fixed copper 2 value salt support rutile type titanium dioxide particulates on the float glass board by the sol gel process which uses silica as a binder. The sample was obtained in the following procedures.

009010 weight sections of rutile type titanium dioxides (MT-150A by TAYCA CORP.) are made suspended to 100 weight sections of distilled water, and also it is Cu (NO)._３2.3H_２It held at 90 for 1 hour, agitating [ 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.

0091The rutile type titanium dioxide particulates which supported copper 2 value salt were obtained by washing the residual substance after the suction filtration of this suspension with distilled water, and also carrying out drying by heating at 110 .

0092It settled for 24 hours, after adding 10 weight sections of this copper 2 value salt support rutile type titanium dioxide to 100 weight sections of distilled water 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. 6.1 mass % According to evaporation to dryness, copper 2 value salt support rutile type titanium dioxide particulates were contained in these dispersion liquid.

0093Next, 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.

0094100 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.

0095This coating material was applied with the spin coat on the 3.0-mm-thick float 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 .

0096The coating film in the obtained sample was 80 nm. The rate of Hayes of this sample was 2.1%, became cloudy clearly and 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.

0097(Comparative example 8)<br />In the same coating material as comparative example 7, comparative example 8 is made equivalent to the mass in which a 5-nm-thick titanium oxide film has the mass of the titanium oxide contained in a coating film.

0098It 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 7 at 100 , The sample by which the coating film of 7 nm of film thickness was formed on the float glass board was obtained.

0099The rate of Hayes of this sample was 0.6%, and the rate of an abundance ratio and each metal copper equivalent weight of Cu system material of the coating film were as follows.<br />Kind of Cu system material Molar ratio Metal copper equivalent weight<br />Cu and Cu_２Total of O 0.000 0 ng/cm^２<br />CuO 0.630 345ng/cm^２<br />Cu(OH)_２0.370 203ng/cm^２

0100The antivirus evaluation was as follows.<br />Conditions of light irradiation Concentration of the phage which is maintaining infectious capacity after irradiation<br />Ultraviolet exposure 3.2x10^７PFU/mL

0101(Comparative example 9)<br />Comparative example 9 made the sample what sprayed and fixed copper chloride (I) fine powder instead of the island part which makes material of a Cu system of an example the main ingredients. The sample was obtained in the following procedures.

0102The copper chloride (I) (first class [ in Kazumitsu ] by Wako Pure Chemical Industries, Ltd., powder of 40.9 micrometers of particle diameter) suspension of concentration 1.0 mass % which considers water as suspension intermediation was sprayed with the spray on the photocatalyst cleaning glass board used in the example, and was dried at normal temperature, and the sample was obtained.

0103Although antivirus evaluation by an ultraviolet exposure was performed, there was no antiviral nature.

0104The various measurement results about the sample of comparative examples 1-6, and 8 are shown in Table 1.

0105<tables num="1"><img file="WO2014112345A1_D0001.tif" /></tables>

0106&lt;Analysis of an example and a comparative example&gt;<br />Cu [ in / as shown in Table 1, an island part is formed on a photocatalyst layer, and / an island part ] (OH)_２In the sample of Examples 1-6 in which the of molar ratio is over 0.35, the quantity of the virus decreased or less to 1/1000 by irradiation of purple outdoor daylight or visible light. At the sample of Examples 1-6, it is Cu (OH) so that I may be understood from Table 1._２A metal copper equivalent unit (the amount of support) is 40 ng/cm.^２It was above. At the sample of Examples 1-5, it is Cu (OH)._２A metal copper equivalent unit is 70 ng/cm.^２It was above.

0107In the sample of comparative examples 1-9, the quantity of the virus did not decrease like the case of an example. Cu [ in / in the sample of comparative examples 1-3 / an island part ] (OH)_２It is thought 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 3, that the sample of comparative example 4 does not have a photocatalyst layer, that the sample of comparative example 5 does not have an island part, and ] the sample of comparative example 6, either.

0108Cu [ in / in the sample of comparative example 8 / a coating film ] (OH)_２Although the of molar ratio was high, antiviral nature was hardly shown. This is considered that it is a cause to have used the rutile [ not a Anatase type but ] type thing as titanium oxide. That the copper 2 value salt which the partial hydrolysis condensation polymer of tetra-ethoxy Silane became an obstacle, and has contacted the virus was restricted, and Cu and Cu_２It may also be the cause that O does not exist.

0109On 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 vehicles, It is applicable to the glass for cars, 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.

0110Since 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.