WO2014112345A1 - Base ayant un film mince antiviral - Google Patents

Base ayant un film mince antiviral Download PDF

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Publication number
WO2014112345A1
WO2014112345A1 PCT/JP2014/000098 JP2014000098W WO2014112345A1 WO 2014112345 A1 WO2014112345 A1 WO 2014112345A1 JP 2014000098 W JP2014000098 W JP 2014000098W WO 2014112345 A1 WO2014112345 A1 WO 2014112345A1
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Prior art keywords
thin film
antiviral
island
antiviral thin
substrate
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PCT/JP2014/000098
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English (en)
Japanese (ja)
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木島　義文
哲男 皆合
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日本板硝子株式会社
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Priority to JP2014557389A priority Critical patent/JP5955984B2/ja
Publication of WO2014112345A1 publication Critical patent/WO2014112345A1/fr

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    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N59/00—Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
    • A01N59/16—Heavy metals; Compounds thereof
    • A01N59/20—Copper
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
    • B01J21/063—Titanium; Oxides or hydroxides thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/72—Copper
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • B01J35/39—Photocatalytic properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • B01J35/391—Physical properties of the active metal ingredient
    • B01J35/392—Metal surface area
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • B01J35/391—Physical properties of the active metal ingredient
    • B01J35/393—Metal or metal oxide crystallite size

Definitions

  • the present invention relates to a substrate with an antiviral thin film.
  • an article that may come into contact with microorganisms may be provided with a layer made of a metal such as silver, copper, or zinc, or a layer made of a photocatalyst such as titanium oxide.
  • a metal such as silver, copper, or zinc
  • a photocatalyst such as titanium oxide.
  • These metals and photocatalysts are known to have antibacterial properties. Said metal inactivates a microbe by substitution reaction with a cell membrane and a cytoplasm constituent substance, and exhibits an antibacterial effect.
  • the above-mentioned photocatalyst exhibits an antibacterial effect by reactive oxygen species generated by ultraviolet irradiation attacking the cell walls and cell membranes of bacteria.
  • Patent Document 1 describes that an antibacterial substrate is prepared by providing a photocatalyst layer containing titanium oxide on a base material and providing an island portion made of copper or the like on the photocatalyst layer. Yes.
  • Patent Document 1 also describes that the produced antibacterial substrate is applied to an article that may come into contact with a virus.
  • Patent Document 2 describes that in the presence of copper divalent ions and chloride ions, metal oxide particles exhibit a photocatalytic action and an allergen inactivating action based on the photocatalytic action.
  • a solution of a partial hydrolysis condensate of tetraethoxysilane and a dispersion of rutile titanium dioxide fine particles supporting a copper divalent salt are mixed to form a coating material. The production is described.
  • Patent Document 3 describes that a virus is inactivated by electrons emitted when monovalent copper compound fine particles become divalent copper ions.
  • a dispersion of monovalent copper compound fine particles is disclosed.
  • an object of the present invention is to provide a substrate with an antiviral thin film having excellent antiviral properties.
  • the present invention A base material, and an antiviral thin film formed on the base material,
  • the antiviral thin film has a photocatalyst layer, and an island part mainly composed of a Cu-based material disposed in direct contact with the surface of the photocatalyst layer,
  • the photocatalyst layer contains anatase type titanium oxide,
  • a base material with an antiviral thin film having a molar ratio A which is a ratio of the number of moles of Cu (OH) 2 to the number of moles of all Cu atoms in the island portion is greater than 0.35 and not more than 0.80 I will provide a.
  • a base material, and an antiviral thin film formed on the base material The antiviral thin film has a photocatalyst layer, and an island part mainly composed of a Cu-based material disposed in direct contact with the surface of the photocatalyst layer,
  • the photocatalyst layer contains anatase type titanium oxide,
  • Anti-viral properties in which the amount of Cu (OH) 2 supported is 70 ng / cm 2 or more, calculated by dividing the amount of Cu (OH) 2 in the island portion converted to metallic copper by the surface area of the layer.
  • Substrate with thin film, I will provide a.
  • main component is used as a term indicating a component occupying 50% by mass or more as usual.
  • the Cu-based material refers to a simple substance made of Cu element or a compound containing Cu element.
  • a substrate with an antiviral thin film having excellent antiviral properties can be provided.
  • Sectional drawing which shows an example of the typical structure of the base material with an antiviral thin film of this invention
  • Sectional drawing which shows another example of the typical structure of the base material with an antiviral thin film of this invention
  • Conceptual diagram showing how to form islands
  • the antiviral thin film formed on the substrate is a film that exhibits antiviral properties when irradiated with light.
  • the antiviral thin film has a photocatalyst layer and an island part mainly composed of a Cu-based material.
  • the photocatalyst layer generates charges (electrons or holes) when irradiated with light.
  • the function of the photocatalyst layer as a photocatalyst is brought about by anatase-type titanium oxide.
  • the anatase type titanium oxide is preferably polycrystalline.
  • the electric charge generated by the photocatalyst layer acts on an island portion mainly composed of a Cu-based material, and the photocatalyst layer and the island portion exhibit an antiviral effect as an antiviral thin film.
  • the photocatalyst layer may be substantially made of titanium oxide. “Substantially” means that impurities that are inevitably mixed are not excluded.
  • the titanium oxide contained in the photocatalytic layer may intentionally contain a small amount of a metal such as iron, aluminum or tungsten as a dopant.
  • a metal such as iron, aluminum or tungsten
  • the generation of carriers in the photocatalyst layer is promoted by the dopant, and the photocatalytic activity of the photocatalyst layer is increased.
  • the preferred metal content of the photocatalyst layer is 0.001 to 1.0% by mass. If the addition amount is less than this, the effect may not be obtained. If the addition amount is too large, the photocatalytic activity may be lowered due to disorder of the crystal structure of the photocatalyst layer and generation of recombination centers.
  • the photocatalytic layer can be formed on the substrate by a known film formation method such as a chemical vapor deposition method (CVD method), a sputtering method, or a liquid phase method (for example, a sol-gel method).
  • CVD method chemical vapor deposition method
  • sputtering and CVD are recommended because a uniform film with a large area can be easily formed.
  • the islands are deposited in a scattered manner on the surface of the photocatalytic layer.
  • the surface of the island is exposed and exhibits an antiviral effect when in contact with the virus.
  • the island part exhibits an antiviral action mainly derived from Cu (OH) 2 contained in the island part.
  • the molar ratio (molar ratio A) which is the ratio of the molar number of Cu (OH) 2 to the molar number of all Cu atoms in the island part, is more than 0.35 and not more than 0.80
  • the antiviral thin film exhibits good antiviral properties.
  • the molar ratio A is preferably 0.37 to 0.70, and more preferably 0.38 to 0.60.
  • the amount of Cu (OH) 2 supported is, for example, 1 ng / cm 2 or more. , preferably 4 ng / cm 2 or more, more preferably 40 ng / cm 2 or more, further preferably 70 ng / cm 2 or more.
  • the molar ratio (molar ratio B) of the sum of the number of moles of Cu (OH) 2 and the number of moles of CuO in the island part to the number of moles of all Cu atoms in the island part is 0.70 to 0. .95. That is, it is preferable that a part of Cu coexists in the state of Cu (Cu in a metal state) or Cu 2 O in the island portion.
  • the antiviral thin film exhibits good antiviral properties as another aspect.
  • the island part may be substantially made of a Cu-based material.
  • the island part may contain an additional metal (on a mass basis) in an amount smaller than that of the Cu-based material.
  • the additive metal include at least one selected from tin (Sn), iron (Fe), zirconium (Zr), chromium (Cr), zinc (Zn), titanium (Ti), manganese (Mn), and the like. The addition of these metals can be expected to improve the corrosion resistance of the islands.
  • At least one island portion for example, 100 to 3000, preferably 250 to 750, is present in an arbitrary region having an area of 1 ⁇ 1 ⁇ m 2 on the surface of the photocatalyst layer.
  • the antiviral effect can be expressed uniformly in the plane.
  • the height of the island is not particularly limited. From the viewpoint of avoiding catching of an object such as a dust cloth on the island part and enhancing the wear resistance of the island part, the maximum height of the island part is preferably 20 nm or less. On the other hand, from the viewpoint of ensuring antiviral properties, the maximum height of the island is preferably 1 nm or more. That is, from the above viewpoints, the maximum height of the island is preferably 1 to 20 nm, more preferably 1 to 10 nm, and particularly preferably 2 to 5 nm.
  • the island is preferably formed on the photocatalyst layer by a sputtering method as described in detail below.
  • the reactive sputtering method is preferable because it is easy to control the valence of Cu in the Cu-based material together with its distribution.
  • the antiviral properties of the antiviral thin film are based on both the action of the photocatalytic layer and the action of the islands. More specifically, the antiviral property is exerted when the island part comes into contact with the virus, and the charge generated in the photocatalyst layer is transferred to the island part by irradiating the photocatalyst layer with light. It is considered that the antiviral action is significantly promoted. If both the antiviral property based on the island portion and the charge generation action based on the photocatalyst layer are combined in a well-balanced manner, the antiviral property of the entire antiviral thin film can be enhanced.
  • the ratio of the total area of the island portion to the area of the antiviral thin film when observed along the thickness direction of the antiviral thin film, that is, when the antiviral thin film is observed from above the island portion Is preferably 0.01 to 0.20, more preferably 0.03 to 0.15, and even more preferably 0.05 to 0.12.
  • island portions mainly composed of a Cu-based material are scattered on a photocatalyst layer mainly composed of titanium oxide.
  • each area of the exposed surface of the photocatalyst layer partitioned by the island part is a certain area. (For example, 500 to 2000 nm 2 ).
  • a photocatalyst layer can generate an electric charge effectively.
  • the island portion of the present embodiment is sufficiently exposed to the outside air, and thus is easily in contact with the virus.
  • the exposed surface of the island portion is reduced by the obstacle such as the binder in the base material with the antiviral thin film of the present embodiment. There is nothing.
  • each island part preferably has a diameter of 1 nm or more.
  • each island part has a diameter of 20 nm or less. That is, from both viewpoints, the diameter of the island is preferably 1 to 20 nm, more preferably 1 to 10 nm, and particularly preferably 2 to 5 nm.
  • a base material is not specifically limited, It is preferable to have translucency.
  • a base material which has translucency the 1 type, or 2 or more types of raw material chosen from the group which consists of a glass plate, a plastic plate, and a resin film is mentioned.
  • a light-reflective substrate such as a mirror can also be used.
  • the substrate when the substrate is transparent and translucent, it is preferable to suppress the haze ratio in the visible light region (for example, a wavelength region of 380 to 760 nm) of the substrate with an antiviral thin film to 1.0% or less, More preferably, it is 0.5% or less. Thereby, a favorable design property can be obtained.
  • the base material may include a base material body and a base layer formed so as to be in contact with the base material body.
  • the underlayer preferably has a function of preventing the diffusion of alkali components in the glass plate.
  • the undercoat layer preferably contains at least one selected from the group consisting of silicon oxide, silicon nitride, tin oxide, zinc oxide, zirconium oxide, and a composite oxide of zinc and tin.
  • the tin oxide may be doped with fluorine. Further, a sufficient effect can be obtained if the thickness of the underlayer is in the range of 5 to 10 nm.
  • the underlayer Prior to the formation of the photocatalyst layer and the island portion, the underlayer can be formed on the substrate body by a known film formation method such as a chemical vapor deposition method, a sputtering method, or a liquid phase method.
  • the underlayer may be composed of a plurality of layers.
  • a silicon oxide film can be adopted as the first underlayer and a zirconium oxide film can be adopted as the second underlayer from the substrate body side.
  • the photocatalyst which has a base layer and a titanium oxide as a main component by the thermal CVD method using the heat
  • the thermal CVD method using heat at the time of forming the float glass is generally called an on-line CVD method (or in-bus CVD method).
  • a CVD apparatus for forming an underlayer and a photocatalyst layer is installed on a glass forming line (for example, in a float bath) by a float method.
  • the glass forming by the float method and the formation of the underlayer and the photocatalyst layer by the CVD method can be performed continuously.
  • FIG. 1 is a cross-sectional view showing an example of a typical configuration of a substrate with an antiviral thin film of the present invention.
  • an antiviral thin film 21 is formed on the surface of a soda lime glass plate 11 as a base material having translucency. That is, the photocatalyst layer 22 is formed on the surface of the soda lime glass plate 11, and a plurality of island portions 23 (groups of island portions 23) are formed on the surface of the photocatalyst layer 22.
  • the photocatalyst layer 22 has a flat membrane shape.
  • the surface of the island part 23 (specifically, the surface excluding the contact surface with the photocatalyst layer 22 of the island part 23) is exposed, and the surface of the photocatalyst layer 22 is exposed except for the contact surface with the island part 23. ing.
  • the island portion 23 in an island shape, both the antiviral property based on the photocatalytic layer 22 and the antiviral property based on the island portion 23 are ensured, and the material of the glass plate 11 and the photocatalytic layer
  • the color tone and translucency derived from titanium oxide, which is the main component, can be kept good.
  • the underlayer 14 is formed on the surface of the soda lime glass plate 11 (base material main body), and the antiviral thin film 21 is formed on the surface of the underlayer 14.
  • the substrate 101 with a conductive thin film may be configured.
  • the island can be formed by sputtering.
  • the amount of material constituting the islands deposited by sputtering can be highly controlled.
  • the sputtering method can be performed in a gas atmosphere containing an inert gas such as argon and oxygen. Further, by adjusting the reference film thickness by the sputtering method (for example, by setting it to 0.1 to 1.0 nm), the material constituting the island portion can be deposited in an island shape.
  • the reference film thickness means the film thickness of the continuous film when the total amount of the material constituting the island portion is converted to a continuous film having a uniform film thickness. It does not indicate the actual height itself.
  • the reference film thickness can be determined as follows, for example. First, the film forming conditions (film forming apparatus, film forming atmosphere gas, degree of vacuum, substrate temperature, film forming power, etc.) of the island part are determined. Under these film formation conditions, film formation is performed for a relatively long time, and a continuous film made of a material constituting the island portion is formed. Only a film formation time is changed, and film formation is performed several times to obtain a plurality of continuous films having different film thicknesses. The film thickness of the obtained continuous film is measured, and the relationship between the film thickness and the film formation time is determined. The film thickness of the continuous film can be measured by a stylus type step thickness meter or an ellipsometer.
  • a predicted value of the film thickness for a predetermined film formation time can be obtained, and this predicted value can be used as a reference film thickness. That is, a film formation time corresponding to a predetermined reference film thickness is calculated in advance, and the film formation time on the island is set to the calculated film formation time. By such a procedure, it becomes possible to deposit the material which comprises an island part in island shape.
  • the film formation time Corresponds to the time during which each part of the substrate is present in the target area.
  • an oxidizing agent and a moisture raw material are required to oxidize copper in a metallic state to form a hydroxide.
  • oxygen contained in the sputtering gas as an oxidant and water existing in the film forming chamber as a moisture source.
  • the moisture in the film formation chamber may be moisture adsorbed on the inner wall of the chamber and the film formation material, but moisture may be positively introduced into the film formation chamber as water vapor.
  • the flow rate of oxygen contained in the sputtering gas and the inert gas is preferably 5:95 to 22:78, and may be 12:88 to 18:82.
  • the moisture in the film formation chamber is preferably 1 to 3 ⁇ 10 ⁇ 2 Pa when expressed in terms of the partial pressure of water in the film formation chamber.
  • FIG. 3 shows an example of a sputtering apparatus for forming islands.
  • the glass plate 31 with the photocatalyst layer in which the photocatalyst layer is formed on the substrate is moved by the transport roller 43.
  • an inert gas such as argon
  • a sputtering gas containing oxygen are supplied from the discharge port 41.
  • the metal Cu bounced off from the target 33 by the collision of the ionized sputtering gas reaches the glass plate 31 with the photocatalyst layer through the opening groove formed by the two parallel shield plates 42.
  • the material which comprises an island part accumulates on the glass plate 31 with a photocatalyst layer.
  • the film forming rate can be controlled by adjusting the width of the opening groove formed by the shield plate 42.
  • the width of the opening groove can be adjusted within a range of about 1 to 150 mm, for example.
  • the film formation rate may be controlled by increasing the conveyance speed of the glass plate 31 with a photocatalyst layer or by keeping the input power low.
  • the width of the opening groove may be adjusted in consideration of the film formation guide film thickness and the film formation efficiency.
  • the target 33 may contain an appropriate amount of additive metal in addition to the metal Cu.
  • the target 33 includes at least one selected from tin (Sn), iron (Fe), zirconium (Zr), chromium (Cr), zinc (Zn), titanium (Ti), manganese (Mn), and the like. It may be. Thereby, the improvement of the corrosion resistance of an island part can be expected.
  • Example (Formation of antiviral thin film)
  • a commercially available photocatalyst cleaning glass plate having a photocatalyst layer formed on a glass plate was used, and an island portion was formed on the surface of the photocatalyst layer by a reactive sputtering method.
  • This commercially available photocatalyst cleaning glass plate is manufactured by ACTIV; Pilkington Group Limited.
  • a photocatalyst film is formed on a glass plate by a float method, and the photocatalyst layer on the outermost surface of the photocatalyst film is mainly composed of anatase type titanium oxide.
  • the antiviral thin film of the present invention can be obtained even if a photocatalytic film derived from another manufacturing method not derived from the CVD method is used.
  • a photocatalytic film derived from another manufacturing method not derived from the CVD method is used.
  • Cleartect S manufactured by Nippon Sheet Glass Co., Ltd .; including a glass plate and a sputtering method-derived anatase-type titanium oxide film formed on the glass plate
  • Cleartect S manufactured by Nippon Sheet Glass Co., Ltd .; including a glass plate and a sputtering method-derived anatase-type titanium oxide film formed on the glass plate
  • the sputtering apparatus used for reactive sputtering film formation is an in-line type sputtering apparatus (G-38 type; manufactured by Airco), which is an industrial scale apparatus having a target surface of about 3 m ⁇ 30 cm in size.
  • G-38 type manufactured by Airco
  • a series of vacuum chamber groups are installed so that the atmosphere can be separated by an airtight door between the chambers.
  • a hold chamber is provided as one of the series of vacuum chambers between the film forming chamber for forming a film by sputtering and the outside of the apparatus, and the degree of vacuum of the film forming chamber is set via the hold chamber.
  • a glass plate in an atmospheric pressure atmosphere can be introduced into the deposition chamber without affecting the sputtering gas atmosphere.
  • the photocatalyst cleaning glass plate was washed with a neutral detergent and a brush, washed with water, drained with an air knife, introduced into the film formation chamber through a hold chamber, and an island portion was formed by sputtering.
  • the target size was 3097 ⁇ 280 mm.
  • the distance between the substrate on which the photocatalyst layer was formed and the target was about 100 mm.
  • a shield plate was installed between the base body and the target at a position 50 mm from the base body.
  • the shield plate created an elongated gap extending in the direction parallel to the longitudinal direction of the target and perpendicular to the transport direction.
  • the width of the gap was 100 mm.
  • the base-material main body was not heated at the time of film-forming.
  • the sputtering gas outlet was installed so that gas was released between the shield plate and the target.
  • the sputtering conditions for the island were determined by separately performing sputtering using a metal Cu as a target, depositing a continuous film of about 20 nm, and analyzing the composition of the continuous film by the In-plane XRD method.
  • the average diameter of the island part was measured by TEM observation. Specifically, a TEM photograph was taken using an EM-002B manufactured by TOPCON, with an acceleration voltage set to 200 kV and a magnification of 200,000. Similar imaging was performed three times with the visual field at the time of imaging changed, and the size of recognizable particles was measured. Moreover, the area of the island part was calculated from the measured diameter of the island part, and the ratio of the area covered by the island part to the area of the thin film was calculated.
  • Antiviral evaluation For the antiviral evaluation, Escherichia coli phage Q ⁇ , which is widely used as a test virus in place of influenza virus in the antiviral evaluation, was used. Antiviral properties were evaluated by performing predetermined light irradiation on a phage solution having a predetermined concentration, and measuring the concentration of phage that retains infectivity after light irradiation.
  • the sample was held in a petri dish kept at a high humidity. That is, a filter paper moistened with pure water was laid on the bottom of the petri dish, a glass piece was placed thereon, a sample was placed thereon, and the petri dish was covered with a quartz glass plate.
  • UV irradiation Using a black lamp (BLB-20S manufactured by Toshiba Lighting & Technology Corporation), UV irradiation with an intensity of 0.25 mW / cm 2 was applied for 10 minutes from the outside of the lid of the quartz glass plate.
  • -Visible light irradiation Using a normal fluorescent lamp, visible light with an illuminance of 800 Lx is irradiated for 60 minutes from the outside of the lid of the quartz glass plate.
  • -Dark storage Do not irradiate light and store petri dishes in a dark room for 180 minutes.
  • the phage solution after the light irradiation was recovered in its entirety by thoroughly washing the sample and the OHP sheet. This recovered solution was diluted serially at a dilution ratio of 10 3 to 10 8 times. In this way, a series of test solutions was prepared.
  • the prepared test solution was mixed with a separately prepared E. coli host solution to prepare a series of mixed solutions. This mixed solution was inoculated and cultured in a separately prepared agar medium. Thereafter, the number of plaques produced was visually counted. Based on the number of plaques and the dilution factor, the concentration of phage that retains infectivity after light irradiation in the phage solution was determined as PFU / mL.
  • phosphate buffered saline containing 0.1 wt% surfactant (Tween 20) based on the total weight was used, and the E. coli host solution contained a large excess of E. coli relative to the phage. Oita.
  • the above mixed solution was mixed with the upper layer agar medium and applied to the lower layer agar medium previously fixed to the petri dish.
  • the components of the culture medium are: Nutrient Agar 5 g / L, Nutrient Broth 8 g / L, NaCl 0.5 wt%, Upper Agar Medium: Nutrient Agar 15 g / L, Nutrient Broth 8 g / L, NaCl 0.5 wt% It is.
  • Cultivation was performed by heating the inoculated petri dish for 15 hours or more in a constant temperature layer set at 37 ° C.
  • the haze ratio was measured by using a haze meter (NDH2000 manufactured by Nippon Denshoku Industries Co., Ltd.) and making light (wavelength range: 380 to 760 nm) incident from the glass plate side.
  • Example 1 Except for the following points, sputtering was performed according to the standard sputtering conditions described above. Thereby, the sample of Example 1 was obtained. Sputtering gas type: oxygen (O 2 ) 5% + argon (Ar) 95% ⁇ Partial pressure of water in the deposition chamber: 1.8 ⁇ 10 ⁇ 2 Pa
  • the abundance ratio of the Cu-based material in the island portion and the weight in terms of metal copper were as follows.
  • Type of Cu-based material Molar ratio Metal copper equivalent weight Total of Cu and Cu 2 O 0.090 24 ng / cm 2 CuO 0.517 140 ng / cm 2 Cu (OH) 2 0.393 107 ng / cm 2
  • the diameter of the island part by TEM observation was about 2.8 nm.
  • the ratio of the area covered by the island to the area of the thin film was 0.12.
  • the haze ratio was 0.2%, haze could not be recognized visually, and it was recognized that translucency was high.
  • Example 2 to 6 sputtering was performed by changing the following points among the standard sputtering conditions described above. As a result, samples of Examples 2 to 6 were obtained.
  • Oxygen ratio in sputtering gas Partial pressure of water in film formation chamber
  • Example 2 8% 2.8 ⁇ 10 ⁇ 2 Pa Example 3 12% 2.0 ⁇ 10 ⁇ 2 Pa
  • Example 4 16% 1.8 ⁇ 10 ⁇ 2 Pa
  • Example 5 18% 2.4 ⁇ 10 ⁇ 2 Pa
  • Example 6 22% 2.1 ⁇ 10 ⁇ 2 Pa
  • Table 1 shows the results of measuring the abundance ratio of each Cu-based material in the island portion, the metal copper equivalent weight of each Cu-based material in the island portion, and the antiviral properties of the samples of Examples 1 to 6.
  • the notation of nE + m in Table 1 means n ⁇ 10 + m .
  • the diameter of the island portion is in the range of 1 to 20 nm, and the ratio of the area covered by the island portion to the area of the thin film is in the range of 0.01 to 0.20.
  • the haze ratio was 1.0% or less.
  • Comparative Examples 1 and 2 In Comparative Examples 1 and 2, the oxygen ratio in the sputtering gas was changed to 2% and 0%, respectively, and the partial pressure of water in the film forming chamber was changed to 0.94 ⁇ 10 ⁇ 2 Pa and 0.56 ⁇ 10 ⁇ 2 Pa, respectively. Except for this point, the standard sputtering conditions described above were employed. Thereby, samples of Comparative Examples 1 and 2 were obtained.
  • Comparative Example 3 (Comparative Example 3)
  • sputtering was performed by changing the following points among the sputtering conditions of Example 1. Thereby, a sample of Comparative Example 3 was obtained.
  • ⁇ Standard film thickness 5nm
  • Partial pressure of water in the film formation chamber 1.2 ⁇ 10 ⁇ 2 Pa
  • the sputtered Cu-based material formed a continuous film rather than an island shape.
  • Comparative Example 4 In Comparative Example 4, a float glass plate without any coating (no photocatalyst layer formed) was used in place of the photocatalyst cleaning glass plate used in the examples. Otherwise, a sample was prepared in the same manner as in Example 1.
  • Table 1 shows the results of measuring the abundance ratio of each Cu-based material in the island part, the metal copper equivalent weight of each Cu-based material in the island part, and antiviral properties for the samples of Comparative Examples 1 to 4.
  • Comparative Example 5 In Comparative Example 5, no island portion was provided on the photocatalyst cleaning glass plate used in the example. That is, only the photocatalyst cleaning glass plate was used as the sample of Comparative Example 5.
  • Comparative Example 6 (Comparative Example 6) In Comparative Example 6, a float glass plate that was not coated at all was prepared. This float glass plate was not provided with any islands. That is, only the float glass plate was used as the sample of Comparative Example 6.
  • Comparative Example 7 a sample in which copper divalent salt-supported rutile titanium dioxide fine particles were fixed on a float glass plate by a sol-gel method using silica as a binder was used. Samples were obtained by the following procedure.
  • rutile-type titanium dioxide (MT-150A manufactured by Teika Co., Ltd.) is suspended in 100 parts by weight of distilled water, and further Cu (NO 3 ) 2 .3H 2 O (manufactured by Wako Pure Chemical Industries, Ltd.) It added so that the ratio with respect to a rutile type titanium dioxide of a copper ion might be 0.1 mass%, and it hold
  • the copper divalent salt-supported rutile titanium dioxide 10 parts by weight was added to 100 parts by weight of distilled water, suspended by ultrasonic dispersion, and allowed to stand for 24 hours. By collecting the supernatant from the liquid after standing, a copper divalent salt-supported rutile-type titanium dioxide fine particle dispersion was obtained. According to evaporation to dryness, the dispersion contained 6.1% by mass of copper divalent salt-supported rutile titanium dioxide fine particles.
  • This coating material was applied onto a float glass plate having a thickness of 3.0 mm by spin coating, heated at 100 ° C. for 30 minutes, and dried / cured to obtain a sample in which a coating film was formed on the glass plate. .
  • the coating film in the obtained sample was 80 nm. Moreover, the haze rate of this sample was 2.1%, and it was also recognized visually that it was clearly cloudy and had low translucency. Therefore, this sample is unsuitable for applications requiring translucency, design properties, and the like.
  • Comparative Example 8 In Comparative Example 8, in the same coating material as in Comparative Example 7, the mass of titanium oxide included in the coating film is made to correspond to the mass of the titanium oxide film having a thickness of 5 nm.
  • the coating material of Comparative Example 7 was diluted 11 times with a solution in which water and ethanol were mixed at a weight ratio of 1: 1, applied onto a glass plate by spin coating, dried at 100 ° C. for 30 minutes and dried. -By curing, a sample in which a 7 nm thick coating film was formed on a float glass plate was obtained.
  • the haze ratio of this sample was 0.6%, and the abundance ratio of the Cu-based material in the coating film and the weight in terms of metallic copper were as follows.
  • Type of Cu-based material Molar ratio Metal copper equivalent weight Total of Cu and Cu 2 O 0.000 0 ng / cm 2 CuO 0.630 345 ng / cm 2 Cu (OH) 2 0.370 203 ng / cm 2
  • Antiviral evaluation was as follows. Conditions of light irradiation Concentration of phages that maintain infectivity after irradiation UV irradiation 3.2 ⁇ 10 7 PFU / mL
  • Comparative Example 9 a sample obtained by spraying and fixing copper (I) chloride fine powder instead of the island part mainly composed of the Cu-based material of the example was used as a sample. Samples were obtained by the following procedure.
  • Photocatalyst cleaning using a suspension of copper (I) chloride (Wako Pure Chemical Industries, Ltd., Wako first grade, 40.9 ⁇ m particle size) suspension with water as a suspension medium in the examples The sample was sprayed on a glass plate with a spray and dried at room temperature to obtain a sample.
  • the antiviral property was evaluated by ultraviolet irradiation, but there was no antiviral property.
  • Table 1 shows various measurement results for the samples of Comparative Examples 1 to 6 and 8.
  • the amount of virus did not decrease as much as in the example.
  • the samples of Comparative Examples 1 to 3 have a low Cu (OH) 2 molar ratio in the island, the sample of Comparative Example 3 has no exposed photocatalyst layer, and the sample of Comparative Example 4 has a photocatalytic layer. This is probably because the sample of Comparative Example 5 does not have an island part, and the sample of Comparative Example 6 does not have a photocatalyst layer or an island part.
  • Comparative Example 8 showed little antiviral properties although the molar ratio of Cu (OH) 2 in the coating film was high. This is considered to be due to the use of rutile type titanium oxide instead of anatase type. It may also be caused by the limited hydrolysis of copper divalent salts that could be brought into contact with the virus due to the partial hydrolysis and condensation polymerization of tetraethoxysilane, and the absence of Cu or Cu 2 O. .
  • the substrate with an antiviral thin film of the present invention can be used for any article that may come into contact with a virus, specifically, architectural window glass, partition glass, door glass, vehicle glass, automotive glass, and display. Glass, mirrors, transparent substrates for DNA analysis, solar cells, portable information devices, hygiene, medical care, electronic equipment, optical components, glass products for biochemical experiments, medical test chips, medical endoscopes and surgical instruments Applicable to optical fiber.
  • the substrate with an antiviral thin film of the present invention is used, the propagation of viruses in hospitals, nursing homes, houses, etc. can be suppressed, so that reduction in health and hygiene problems caused by viruses is expected.

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Abstract

L'invention concerne une base ayant un film antiviral qui est doté d'une base et d'un film antiviral qui est formé sur la base. Le film antiviral a une couche qui est principalement composée d'oxyde de titane et une partie île qui est disposée sur la surface de la couche et est principalement composée d'une matière à base de Cu. Le rapport molaire A, qui est le rapport du nombre de moles de Cu(OH)2 par rapport au nombre de moles de tous les atomes de Cu dans la partie île, est plus de 0,35 mais de 0,80 ou moins.
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WO2015040558A1 (fr) * 2013-09-17 2015-03-26 Theta Chemicals Limited Film antimicrobien à double action
CN105680790A (zh) * 2016-04-01 2016-06-15 华北电力大学（保定） 一种全天候除霾光电池板装置
JP2017000655A (ja) * 2015-06-16 2017-01-05 日本板硝子株式会社 抗ウイルス性薄膜つき基材
JP2020066187A (ja) * 2018-10-25 2020-04-30 株式会社Uacj 抗菌シート及びその製造方法
GB202011249D0 (en) 2020-07-21 2020-09-02 Pilkington Group Ltd Antimicrobial substrate
JP6996650B1 (ja) 2020-10-15 2022-01-17 凸版印刷株式会社 プリント化粧金属板、及びドア
WO2022090708A1 (fr) 2020-10-26 2022-05-05 Pilkington Group Limited Utilisation de substrats revêtus
CN115243545A (zh) * 2020-03-27 2022-10-25 三菱综合材料株式会社 抗菌部件
WO2023281788A1 (fr) * 2021-07-05 2023-01-12 公立大学法人奈良県立医科大学 Matériau antiviral

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JP2010239897A (ja) * 2009-04-06 2010-10-28 Nbc Meshtec Inc ウイルス不活化剤
JP2011111600A (ja) * 2009-11-30 2011-06-09 Panasonic Electric Works Co Ltd 可視光応答型光触媒コーティング材、コーティング処理物及びアレルゲン不活性化方法
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Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2015040558A1 (fr) * 2013-09-17 2015-03-26 Theta Chemicals Limited Film antimicrobien à double action
JP2017000655A (ja) * 2015-06-16 2017-01-05 日本板硝子株式会社 抗ウイルス性薄膜つき基材
CN105680790A (zh) * 2016-04-01 2016-06-15 华北电力大学（保定） 一种全天候除霾光电池板装置
JP7084846B2 (ja) 2018-10-25 2022-06-15 株式会社Uacj 抗菌シート及びその製造方法
JP2020066187A (ja) * 2018-10-25 2020-04-30 株式会社Uacj 抗菌シート及びその製造方法
CN115243545A (zh) * 2020-03-27 2022-10-25 三菱综合材料株式会社 抗菌部件
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WO2021260370A1 (fr) 2020-06-23 2021-12-30 Pilkington Group Limited Substrat antimicrobien
GB202011249D0 (en) 2020-07-21 2020-09-02 Pilkington Group Ltd Antimicrobial substrate
JP6996650B1 (ja) 2020-10-15 2022-01-17 凸版印刷株式会社 プリント化粧金属板、及びドア
JP2022065607A (ja) * 2020-10-15 2022-04-27 凸版印刷株式会社 プリント化粧金属板、及びドア
WO2022090708A1 (fr) 2020-10-26 2022-05-05 Pilkington Group Limited Utilisation de substrats revêtus
WO2023281788A1 (fr) * 2021-07-05 2023-01-12 公立大学法人奈良県立医科大学 Matériau antiviral

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