JPWO2018021106A1 - Antimicrobial, antiviral and / or algal material comprising inorganic / organic hybrid compound and method for producing the same - Google Patents

Abstract

Conventional types of anti-microbial, anti-viral and / or anti-algal materials that fix the active ingredient to a solid are of the type in which the active ingredient is incorporated into a conventional plastic (organic polymer), but in that case the surface There is a problem that the active ingredient is easily detached, and the one embedded inside can not sufficiently exhibit the action. The present invention relates to an anti-microbial agent, an antiviral agent, in which a metal or a compound of silver or copper as an active ingredient is fixed to an inorganic / organic hybrid compound in which an inorganic oxide or a derivative thereof and an organic polymer having a hydroxyl group are chemically bonded. And / or anti-algal material. The hybrid compound has both water resistance and water absorbency, and since the active ingredient stably fixed thereto is fine active particles such as nanoparticles, extra detachment and release of the active ingredient is achieved. Without it, a high anti-microbial, anti-viral and / or anti-algal material effect can be obtained, and all the fixed active ingredients can be fully used up.

Description

  The present invention relates to novel anti-microbial, anti-viral and / or anti-algal materials.

  Conventionally, sterilization and antibacterial treatment have been performed for the purpose of improving the living environment such as homes and buildings. For example, for housing equipment, there are various methods such as an ultraviolet irradiation method using an ultraviolet lamp, an ozone oxidation method, and a cleaning method using a sodium hypochlorite solution, which are respectively selected according to the purpose. Products that have bactericidal and / or bactericidal properties include organic bactericidal agents, and bactericidal and bactericidal materials such as silver and copper, and various devices for imparting bactericidal or bactericidal properties to provide a clean environment There is.

  Among these methods, the physical method of irradiating electromagnetic waves (light) such as gamma rays, electron beams, ultraviolet rays, microwaves etc. is very effective, but an apparatus and a power source for this are necessary, It can only be used in a originally limited place, such as in a dedicated facility of a factory or in a housing equipment. The ozone oxidation method also requires an apparatus and a power source to generate it, and the situation does not change much. Moreover, although the heat sterilization method is also available as a simpler method, it still requires some equipment for heating. These methods of electromagnetic wave irradiation, ozone oxidation, heating and the like also often involve not only the antimicrobial effect, but also the deterioration of the object in many cases, and there are many cases where this method can not be applied.

  As a method of indirectly utilizing light, there is also a method of causing an antimicrobial or antiviral action by applying light to the light using photocatalyst such as titanium oxide. In this case, the effect can be expressed by natural light or lighting in the living environment, and a dedicated device or power source is not necessarily required, but it is also used in the place of use and application in that some light sources are required. There is also a limit.

  Antimicrobial agents, antiviral agents and algae-protecting agents by chemical substances (drugs) are widely used methods because they do not require an apparatus, a power source and a light source, and there are few restrictions on the place of use. The environment where bacteria are most likely to grow is reservoir water, circulating water, around water, and a wet environment, but for example, chlorine has long been used to sterilize tap water. In addition, chlorine and chlorine compounds, isothiazoline compounds, etc. are used for the antibacterial activity of cooling water in factories and buildings, swimming pools, bath water in hot water facilities, water in paper making process of paper and pulp industry using water, etc. The method of direct dissolution in water is taken. These methods are effective in that the antibacterial action is widely spread because they are dissolved in water, but if they are dissolved at a high concentration to obtain a higher antibacterial effect, health hazards may arise, and drainage There are also concerns about the negative impact on the environment. In addition, there is a concern that the effect of the chemical on the oxidizing property and pH may accelerate the corrosion of equipment components and equipment.

  On the other hand, as a method for anti-microbial and anti-viral of parts that contact skin regularly such as fittings, furniture, stationery, toys, beauty tools, etc., the active ingredient is kneaded into the constituent material or coated on the material surface Methods are taken. That is, the active ingredient is in a state of being fixed to the solid material. For example, an antimicrobial or antiviral composition in which an active ingredient such as a thiabendazole compound or silver is supported on silica, alumina, zeolite, zirconium phosphate or the like is kneaded into a constituent material or coated on the material surface Methods are taken. These methods are applicable to all kinds of anti-microbial and solid substances that require antiviral action, such as anti-microbial, anti-viral filter (mask), net, sheet, film, fiber, etc. . These anti-microbial and anti-viral active ingredients of the type fixed on solid can also be applied to the above reservoir water, circulating water, around water, and in a wet environment, and the drug is dissolved in water. There is also a possibility that anti-microbial and anti-viral effects can be realized.

The following is disclosed as an example of the anti-microbial and solid substance fixed with anti-viral component.
For example, in the case of a plastic sheet or a resin molded product, the bactericidal or antibacterial property is maintained by kneading an organic type antibacterial agent such as a diphenyl ether type bactericide or a chlorhexidine type bactericide into the resin or coating it on the surface. (See Patent Document 1).
Also, a film or a plastic sheet obtained by kneading or coating an inorganic antibacterial agent in which a metal material such as silver, copper, and zinc is supported on a mineral carrier such as zeolite, silica gel, and glass; The fibers are made to retain bactericidal or antibacterial properties (see Patent Document 2, Patent Document 3, Patent Document 4).
In addition, a film-like antimicrobial laminate is disclosed in which silver ions are vapor-deposited by an ion deposition method to form an antimicrobial layer on a biaxially stretched PET film, and polyester or the like is coated on the antimicrobial layer (Patent Document 5) reference).
In addition, inorganic compounds having antibacterial properties such as silver, silver nanoparticles, copper, zinc, and gold using a polymer compound such as a cellulose derivative, a urethane resin, an acrylic resin, and a polyvinyl alcohol resin as a binder, and chlorhexidine and triclosan etc. An antimicrobial laminate structure in which an organic antimicrobial agent and a preservative or an antibiotic agent are used in combination is disclosed (see Patent Document 6).
In addition, it is disclosed that a film having algal protection is obtained by applying a coating treatment to the film surface of silica or alumina particles in which silver is supported on an acrylic resin (see Patent Document 7).
In all of these prior art references, anti-microbial and anti-viral solid substances, that is, base materials for immobilizing active ingredients are existing organic polymers (plastics).

  By the way, some of the inventors of the present invention have so far disclosed an inorganic / organic hybrid compound which is a new material different from a pure organic polymer and a pure inorganic oxide. This is an inorganic / organic hybrid compound in which polyvinyl alcohol having a hydroxyl group is chemically bonded to an inorganic oxide at a molecular level, and it has low chemical stability and low cost, reflecting the properties of the inorganic oxide. It has been shown to be excellent in heat resistance and applicable in several fields (without anti-microbial, anti-viral and / or anti-algal materials).

  For example, these inorganic / organic hybrid compounds can be used as proton (or hydroxide ion) conductive solid electrolytes, and various fuel cells, various electrolytic devices, sensors, batteries, electrochromic devices, dehumidifiers, etc. Applications to applications have been proposed. The inorganic / organic hybrid compounds that can be used as these solid electrolytes are, specifically, inorganic / organic hybrid compounds consisting of a silicate compound and polyvinyl alcohol (see Patent Document 8), and inorganic / organic hybrid compounds consisting of a zirconate compound and polyvinyl alcohol (Patent Document) 9, 10) and so on. Alternatively, a catalyst for organic synthesis is also disclosed in which an inorganic / organic hybrid compound composed of a zirconate compound and polyvinyl alcohol contains metal nanoparticles such as palladium (see Patent Document 11). A solid electrolyte composed of these hybrid compounds is produced through the process of neutralizing the salt of the inorganic oxide with an acid or an alkali in the state where the salt of the inorganic oxide and the polyvinyl alcohol coexist.

Japanese Patent Publication No. 2010-510819 JP 2011-500306 gazette International Publication No. 2012/098742 JP 2011-530400 gazette WO 2007/132919 Japanese Patent Publication No. 2010-509791 Unexamined-Japanese-Patent No. 2003-327730 Patent No. 4832670 Patent No. 3848882 Patent No. 4081343 PCT / JP2011 / 065129

  The object of the present application is to provide novel anti-microbial, anti-viral and / or anti-algal materials. Preferably, the present invention provides an anti-microbial, anti-viral and / or anti-algal material which solves the following problems.

  As described above, sterilization using a physical method such as electromagnetic wave (light) irradiation, ozone oxidation, or heating requires a dedicated device, a power source, a light source, etc., and places and uses that can be originally used are limited. Therefore, although antimicrobial and antiviral treatments using chemical substances (drugs) with few restrictions on places and environments where they can be used are widely used, drugs used for stored water and circulating water are of the type that is dissolved in water In addition to being the mainstream, there are concerns about adverse effects on the human body and the environment, and corrosion of parts and equipment that come in contact with it may also be a problem. Therefore, in order to apply to reservoir water, circulating water, etc., it is desirable to use an antimicrobial or antiviral material in which the active ingredient is fixed to a solid. That is, the member that comes in contact with water itself is made of an anti-microbial, anti-viral material, or a filter or the like is formed of a material in which the active ingredient is fixed to a solid. There is also a method to carry out virus treatment.

  The antimicrobial and antiviral active ingredients to be immobilized on solid substances are organic compounds such as thiabendazole compounds, metals such as silver and copper, metal fine particles (nanoparticles), or metal compounds such as salts, oxides and complexes is there. In the case of metal, the inorganic solid particle support is often used by being fixed to a solid in a state of being supported by inorganic solid particles such as silica, alumina, zeolite and zirconium phosphate. In order to make the member in contact with water have an antimicrobial and antiviral effect, a method is conceivable in which these active ingredients are kneaded into the member. However, in that case, it is easier to form a coat film on which the active ingredient is fixed on the surface of the member, since there is a certain restriction on the selection of constituent materials that can be used for the member. Or the method of affixing the film-form thing which fixed the active ingredient on the member surface is also considered. On the other hand, when a filter is formed of a material in which the active ingredient is fixed to a solid and water is brought into contact with the filter to carry out an antimicrobial or antiviral treatment, the structure of a porous body such as a filter net, mesh or non-woven fabric The active ingredient may be kneaded into the member itself, or a coat film on which the active ingredient is fixed may be formed on the surface of the member.

  By the way, when the method of mixing the anti-microbial and anti-viral active ingredients into a solid member, the constituent material is almost limited to the plastic (organic polymer) in that the mixing process can be easily performed. In addition, even in the case of forming a coated film in which the active ingredient is fixed on the solid surface, the coated film must be flexible, and thus is formed of an organic polymer. Even when the film-like material having the active ingredient fixed thereto is attached to a solid, the film-like material needs to be flexible and is formed of an organic polymer. For example, even in Patent Documents 1 to 7, it is a common organic polymer such as polyester that the active ingredient is fixed. Although the above-mentioned antimicrobial and antiviral metal components are supported on inorganic solid particles such as silica, alumina, zeolite and zirconium phosphate, the active ingredient is directly fixed to the inorganic solid particles. Finally, the particles are used by being incorporated into the organic polymer.

  When these active ingredients are mixed into an organic polymer, they are fixed by wrapping the active ingredient in the organic polymer. Even in the case of the coated film formed on the solid surface, the active ingredient is eventually fixed by being encased in the organic polymer constituting the coated film. By the way, in order for anti-microbial, anti-viral or anti-algal effects to be expressed, microorganisms, viruses, algae, etc. need to be in contact with the active ingredient, and in many cases a small amount of the immobilized active ingredient elutes. Efficacy is thought to be manifested by contact with microorganisms, viruses and algae. Thus, while the active ingredient is encased in solid organic polymer, it also needs to be exposed. However, since the elution and desorption rates of the active ingredient in the exposed part are large in water, loss of the active ingredient is likely to occur when the degree of exposure is too high, and a large anti-microbial and antiviral effect can be obtained initially However, the effect will not last. Alternatively, the elution of the active ingredient at a high concentration may contaminate the surrounding environment, and the elution of the active ingredient in a large amount wastefully is not preferable from the viewpoint of material cost. However, conversely, if the active ingredient is excessively embedded so as not to be easily detached, sufficient antimicrobial and antiviral effects can not be obtained, and too many active ingredients are used by kneading too Become. In the fixed type of the active ingredient, it is necessary to adjust the contradictory conditions to an appropriate state, but the adjustment is actually difficult.

  As mentioned above, although the solid that fixes the active ingredient is often an organic polymer, the common organic polymers used are hydrophobic, insoluble in water and do not absorb water. When a water-soluble organic polymer is used, it dissolves itself in water, and a natural organic polymer which is naturally hydrophobic is selected because of its stability in water. However, the active ingredient embedded and immobilized in a hydrophobic organic polymer is substantially inactivated against antimicrobial, antiviral or algal action since the contact with water is blocked. I will. Elution and desorption rates are very high in the part where the active ingredient is exposed, so it is difficult to adjust these contradictory conditions to a suitable state, and it has high activity against antimicrobial, antiviral, or algal action and active ingredient It is extremely difficult to make it compatible with desorption control (durability). In addition, it is inevitable that a large amount of waste of the active ingredient is automatically generated by the deactivation of the active ingredient in the embedded part in the first place. These problems apply to anti-microbial, anti-viral or anti-algal treatment generally in an aqueous environment such as stored water, circulating water, around water, or in a wet environment.

  Antimicrobial and antiviral effects are required not only in the water environment, but also in the daily dry environment such as fixtures, furniture, stationery, toys, beauty products, etc. that are in daily contact with the skin. Also in this case, as in the above, the antimicrobial or antiviral active ingredient is kneaded into the component, a coated film on which the active ingredient is immobilized is formed on the surface, or a film on which the active ingredient is immobilized is attached In general, what is fixed is an organic polymer. As described above, it is believed that the anti-microbial and anti-viral effects are produced by microelution of the fixed active ingredient, and that the effect is manifested by contact with microorganisms and viruses. Therefore, unlike the water environment, when used in a normal dry state, the effect is inherently less effective. It functions by the minute amount of adsorbed moisture on the surface of the organic polymer derived from atmospheric moisture or moisture emitted from the human body, excreted sweat, etc. As described above, commonly used organic polymers Since it is hydrophobic and it is easy to repel adsorbed water, its anti-microbial and anti-viral effects are difficult to develop.

  In the case of an antimicrobial or antiviral material on the surface of which a coating film to which an active ingredient is fixed is formed, if the component of the base is an organic polymer, it is familiar and the bonding stability is good. The material is not necessarily an organic polymer. For example, when it is made of inorganic materials such as glass, tiles, pottery such as a toilet bowl, cement material, etc., the coat film made of organic polymer is not well-matched, so long-term bonding stability of the coat film itself It will cause problems.

  The present invention comprises an inorganic / organic hybrid compound in which an inorganic oxide or a derivative thereof and an organic polymer having a hydroxyl group are chemically bonded, and the inorganic / organic hybrid compound contains silver or copper metal or its compound inside. It is a solid which does not dissolve in water, and can absorb water.

  The inorganic / organic hybrid compound is particularly one in which the inorganic oxide or the derivative thereof contains an oxide of zirconium or a derivative thereof, and the organic polymer having a hydroxyl group contains a polyvinyl alcohol. The metal of silver or copper contained in the inorganic / organic hybrid compound or the compound thereof contains particles having a diameter of 10 nm or less, and in the diffraction intensity-diffraction angle diagram obtained by the X-ray diffraction method using a CuΚα ray, It is characterized in that the half width of the highest peak attributed to the metal of silver or copper or the compound thereof is 2 (2θ °) or more or no peak.

  The antimicrobial, antiviral and / or anti-algal material of the present invention is immersed in the material so that the amount of silver or copper in the material is 1 mg / L or more to water at ordinary temperature and is immersed for 24 hours or more Characterized in that the concentration of silver or copper dissolved out of the material in water is less than 0.05 mg / L.

  The anti-microbial, anti-viral and / or anti-algal material of the present invention can be a film, and the film can be a coated film coated on the solid surface. The coating film can be coated on solid surfaces such as fixtures, furniture, stationery, toys, beauty tools, trash containers, drainage members, toilet bowls, vinyl sheets for plastic greenhouses, switch of equipment, medical tools, outer surface of ship bottom etc. . The solid that coats the coating film is a porous material and can be a net, mesh, woven fabric, non-woven fabric, and can be used as a filter or a mask. Furthermore, when the material of the present invention is in the form of a film, the metal of silver or copper contained in the inorganic / organic hybrid compound or the compound thereof has a concentration gradient with respect to the thickness direction of the film. I assume.

  The anti-microbial, anti-viral and / or anti-algal material of the present invention can be brought into contact with a liquid to suppress an increase in the population of microorganisms and viruses in the liquid or reduce the population. In that case, the liquid can be brought into contact while being forcibly circulated, and the liquid to be applied may be a pool, a bath, a water reservoir for housing, a water tank for breeding, an industrial water reservoir, circulating water for industry, tap water , Septic tanks, cooling towers, and water used for ballast water of transport vessels. When the material is brought into contact with a gas, the increase in the population of microorganisms and viruses in the gas can be suppressed or the population can be reduced. In this case, the gas can be brought into contact while being forcibly circulated.

  In the anti-microbial, anti-viral and / or anti-algal material of the present invention, the zirconium salt or oxyzirconium salt is neutralized by alkali in the coexistence of polyvinyl alcohol and a silver or copper salt, and the zirconate compound and the polyvinyl alcohol It is manufactured through the process of forming a chemically bonded inorganic / organic hybrid compound. In that case, in the process of forming the inorganic / organic hybrid compound in which the zirconate compound and the polyvinyl alcohol are chemically bonded, the solvent is removed from the solution in which the zirconium salt or oxyzirconium salt and the polyvinyl alcohol and the silver or copper salt coexist. To form a solid, which is contacted with alkali to neutralize the zirconium or oxyzirconium salt in the solid.

  In the method of producing an anti-microbial, anti-viral and / or anti-algal material of the present invention, silver or an inorganic / organic hybrid compound containing a silver or copper compound, in which a zirconate compound and a polyvinyl alcohol are chemically bonded is formed. The copper compound can be reduced to silver or copper in the metallic state by reduction with a reducing agent.

Although overlapping with the above, the present invention is shown below.
[Invention 1]
The inorganic oxide or derivative thereof and an organic polymer having an hydroxyl group are chemically bonded to each other, and the inorganic / organic hybrid compound contains a silver or copper metal or a compound thereof and is not soluble in water. An anti-microbial, anti-viral and / or anti-algal material characterized in that it is solid and capable of absorbing water.
[Invention 2]
The antimicrobial, antiviral and / or algal material according to Invention 1, wherein the inorganic oxide is an oxide of zirconium, silicon, titanium or tungsten.
[Invention 3]
The antimicrobial, antiviral and / or algal material according to Invention 2, wherein the inorganic oxide is an oxide of zirconium.
[Invention 4]
The antimicrobial, antiviral and / or algal material according to Invention 1, wherein the organic polymer having a hydroxyl group is polyvinyl alcohol.
[Invention 5]
The antimicrobial, antiviral, and / or antialgal agent according to any one of Inventions 1 to 4, wherein the metal of silver or copper contained in the inorganic / organic hybrid compound or the compound thereof comprises particles having a diameter of 10 nm or less material.
[Invention 6]
In the diffraction intensity-diffraction angle diagram obtained by X-ray diffraction method using Cu Κ α ray, the half width of the highest peak among the peaks attributed to the metal of silver or copper contained in the inorganic / organic hybrid compound or the compound is The antimicrobial, antiviral, and / or anti-algal material according to any one of Inventions 1 to 4, which is 2 (2θ) or more, or has no peak.
[Invention 7]
Silver or copper dissolved in water when immersed in water at room temperature where the amount of silver or copper in the antimicrobial, antiviral and / or anti-algal material is 1 mg / L or more for 24 hours or more The anti-microbial, anti-viral, and / or anti-algal material according to any one of Inventions 1 to 4, wherein the concentration of
[Invention 8]
The antimicrobial, antiviral, and / or anti-algal material according to any one of Inventions 1 to 4, which is a film-like material.
[Invention 9]
The anti-microbial, anti-viral and / or anti-algal material according to Invention 8, wherein the film-like material is a coated film coated on a solid surface.
[Invention 10]
The invention is characterized in that the solid coated with a coating film on the surface is a fixture, furniture, stationery, toy, beauty tool, trash container, drainage member, toilet bowl, vinyl sheet for vinyl house, switch of equipment, medical tool The anti-microbial, anti-viral and / or anti-algal material as described in 9.
[Invention 11]
The antimicrobial, antiviral, and / or antialgal material according to Invention 9, wherein the solid substance is a porous material.
[Invention 12]
The antimicrobial, antiviral, and / or algal material as set forth in claim 11, wherein the porous material is a net, a mesh, a woven fabric, or a non-woven fabric.
[Invention 13]
The antimicrobial, antiviral, and / or antialgal material according to Invention 11, wherein the porous material is a filter or a mask.
[Invention 14]
The antimicrobial, antiviral, and antifungal agent according to invention 8, wherein the silver or copper metal contained in the inorganic / organic hybrid compound or the compound thereof has a concentration gradient with respect to the thickness direction of the film-like material And / or algae protection material.
[Invention 15]
In the inventions 1-5, the antimicrobial, antiviral and / or antialgal material is brought into contact with the liquid to suppress an increase in the number of microorganisms and viruses in the liquid or to reduce the number of individuals. Antimicrobial, antiviral, and / or anti-algal material according to any one of the preceding claims.
[Invention 16]
The antimicrobial, antiviral, and / or antialgal material according to invention 15, characterized in that the liquid is brought into contact while being forced to circulate.
[Invention 17]
The liquid is a water used for a pool, a bath, a water storage tank for collective housing, a breeding water tank, an industrial water storage tank, industrial circulating water, tap water, a septic tank, a cooling tower, and ballast water for transport vessels. The anti-microbial, anti-viral, and / or anti-algal material according to Invention 15.
[Invention 18]
In the inventions 1-4, the antimicrobial, antiviral and / or antialgal material is brought into contact with a gas to suppress an increase in the number of microorganisms and viruses in the gas or to reduce the number of individuals. Antimicrobial, antiviral, and / or anti-algal material according to any one of the preceding claims.
[Invention 19]
The antimicrobial, antiviral, and / or antialgal material according to Invention 18, characterized in that the gas is brought into contact while being forced to circulate.
[Invention 20]
By neutralizing the zirconium salt or oxyzirconium salt with an alkali in the coexistence of polyvinyl alcohol and a silver or copper salt, and forming an inorganic / organic hybrid compound in which the zirconate compound and the polyvinyl alcohol are chemically bonded The manufacturing method which obtains the antimicrobial of the invention 3 or 4, an antiviral, and / or an anti-algal material.
[Invention 21]
The process of forming the inorganic / organic hybrid compound in which the zirconate compound and the polyvinyl alcohol are combined forms a solid by removing the solvent from the solution in which the zirconium salt or oxyzirconium salt and the polyvinyl alcohol and the silver or copper salt coexist. A process for producing the anti-microbial, anti-viral and / or anti-algal material according to the invention 20, which is carried out by forming it and bringing it into contact with alkali to neutralize the zirconium salt or oxyzirconium salt in the solid.
[Invention 22]
After forming an inorganic / organic hybrid compound in which a zirconate compound containing a silver or copper compound and a polyvinyl alcohol are chemically bonded, the silver or copper compound is reduced to silver or copper in a metallic state by reducing with a reducing agent. A method for producing the anti-microbial, anti-viral and / or anti-algal material of the invention 20, characterized in that

  The material of the present invention exerts an antimicrobial, antiviral and / or algal effect. Preferably, the anti-microbial, anti-viral and / or anti-algal material of the present invention is a solid that is not soluble in water, and is characterized by being capable of absorbing water. In the present invention, the release rate of the active ingredient such as silver or copper can be easily controlled to suppress excessive release, and the active ingredient can be used without waste, so the effect can be maintained over a long period of time, and the cost merit is large. In addition, active ingredients such as silver or copper are present in a fine and active state such as nanoparticles in the inorganic / organic hybrid compound, and particles on the surface are brought into direct contact with high anti-microbial, anti-viral and / or antiviral agents. It exhibits antialgal activity, and it is also possible to take small virus etc. into the material and attack it. Furthermore, even when used as a coated film, it exhibits stable bonding to a wide range of materials, regardless of whether it is an organic material or an inorganic material.

  That is, first, inorganic / organic hybrid compounds in which an inorganic oxide and an organic polymer are chemically bonded to each other as active ingredients such as metals and metal compounds of silver and copper having antimicrobial, antiviral and / or antialgal effects like nanoparticles. Can be stably fixed as fine particles. These active ingredients of silver and copper remain in a fine state such as nanoparticles in many cases so that they are simultaneously generated inside the solid when the hybrid compound is formed, and are active states without large growth and inactivation. It is maintained by Since the inorganic / organic hybrid compound of the present invention has the property of absorbing water internally, if there is water in the environment, it will be in a state of being absorbed in the molecular gap of the hybrid compound. In that state, the active components of silver and copper diffuse through the intermolecular space of the hybrid compound absorbed in water, and are gradually supplied to the surface. The active ingredients of silver and copper that reach the surface come in contact with microorganisms, viruses, etc. there and exhibit antimicrobial, antiviral and / or algal action, but at this time the supply of the active ingredient to the surface is a hybrid compound By being limited by the slow internal diffusion within, the rate can be controlled appropriately and excessive release of the active ingredient can be avoided. This eliminates useless consumption of the active ingredient. Such an effect can be realized by using a highly hydrophilic organic polymer based on a water-soluble organic polymer even if it is an organic polymer, but in that case it is difficult to obtain a stable material in a water environment . The material of the present invention can realize such an effect by applying an inorganic / organic hybrid compound which has high hydrophilicity but does not dissolve in water and maintains high stability in water.

  In addition, since the active ingredient is in a state of fine and always high activity such as nanoparticles inside the hybrid compound, it can be used without exhaustive of the active ingredient, so that high antimicrobial, antiviral and / or long-term effects can be obtained. Alternatively, the antialgal activity can be stably maintained. As described above, in the conventional antimicrobial, antiviral and / or anti-algal materials of the type that fixes the active ingredient to a solid, desorption and elution occur excessively at the exposed part of the active ingredient, and conversely at the embedding site. There is a problem that it is totally inactive. On the other hand, this material is composed of an inorganic / organic hybrid compound, so it can be hydrophilic and absorb water while being a stable material even in water, and the active ingredient can be controlled in rate by internal diffusion in the material. By being able to supply to the surface in the state, the problem of the conventional material can be solved. While having such an effect, the hybrid compound also has flexible physical properties like organic polymers.

  The active ingredient of silver or copper is also present not only inside the hybrid compound but also on the surface, and is in direct contact with microorganisms, viruses, etc., but the active ingredient on these surfaces is also highly active in the nanoparticles. It exerts anti-microbial, anti-viral and / or algal action. Furthermore, the absorption of water widens the interstitial space of the hybrid compound, but the small virus enters inside, where it contacts the nanoparticles and is attacked. That is, it is also possible to obtain an antiviral effect without releasing the active ingredient.

  Inorganic / organic hybrid compounds are water-absorbable, not only in the water environment, but also for anti-microbial and anti-viral treatments of fixtures, furniture, stationery, toys, beauty products, etc. that are in daily contact with the skin Is also important. As described above, although it is generally the organic polymer to which the active ingredient is fixed, the organic polymer is hydrophobic, and in a normal dry environment which is not a water environment or a wet environment, an antimicrobial and antiviral action is developed. Hateful. On the other hand, since the inorganic / organic hybrid compound of the present invention is water-absorbent, it absorbs moisture from the atmosphere, moisture emitted from the human body, moisture derived from sweat etc. secreted, etc. It is possible to realize a state of holding water even under various environments. The portion of the inorganic / organic hybrid compound can be maintained in a water environment, a state similar to a wet state, an anti-microbial effect, or an anti-viral effect, thereby obtaining a high effect.

  In the conventional method of fixing the active ingredient to the organic polymer, there is also a method of enhancing the activity by exposing the active ingredient to the surface as much as possible, but in such a case, the active ingredient will become wet if it gets wet during use. Is easily removed. In addition, the active ingredient can be easily removed when it is used for touching by people without getting wet with water. However, in the material of the present invention, the mechanism by which the active ingredient originally existing inside diffuses to the surface works by the hygroscopicity of the inorganic / organic hybrid compound, so the effect is exhibited even if the surface exposure of the active ingredient is small can do. Alternatively, when the virus is incorporated inside and attacked, the active ingredient does not have to be exposed on the surface.

  Silver or copper is often used as a general active ingredient of anti-microbial, anti-viral and / or anti-algal materials, and they are also used in the present invention, but compounds such as their oxides are highly oxidative. Strong However, in general, organic polymers are weak to oxidation and may be degraded by their oxidation when they carry a silver or copper compound. On the other hand, the inorganic / organic hybrid compound of the present invention reflects the extremely high oxidation resistance property of the inorganic oxide, and is less likely to be deteriorated even when carrying a silver or copper compound having a strong oxidizing action.

  In addition, the material of the present invention is composed of an inorganic / organic hybrid compound having high affinity to both inorganic and organic substances. Therefore, when forming a coating film on the surface of a solid, even if the constituent material of the solid is an organic polymer or an inorganic substance such as a ceramic, it can be stably joined.

Diffraction intensity-diffraction angle figure (45 kV, 40 mA, scan rate 0.002 ° s ⁻¹⁾ obtained by X-ray diffraction method using CuΚα ray of the antimicrobial, antiviral and / or anti-algal material according to the present invention ) (A) Material containing silver, (b) Material containing copper BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a system diagram schematically showing a representative embodiment (first embodiment) of an antimicrobial, antiviral and / or algal material according to the present invention. 2 is a system diagram schematically showing a representative embodiment (second embodiment) of the anti-microbial, anti-viral and / or anti-algal material according to the present invention. FIG.

In the present application, "consisting of" and "consisting of" mean that it may include components other than the components described.

  Hereinafter, embodiments of the anti-microbial, anti-viral and / or anti-algal material according to the present invention will be described. The present invention comprises an inorganic / organic hybrid compound in which an inorganic oxide or a derivative thereof and an organic polymer having a hydroxyl group are chemically bonded, and the inorganic / organic hybrid compound contains a silver or copper metal or its compound inside. It is a solid that does not dissolve in water and that it can absorb water. In the present invention, the inorganic oxide or the derivative thereof is preferably an oxide of zirconium or a derivative thereof. Here, the oxide of zirconium or its derivative is a compound containing ZrO 2 as a basic unit, and refers to zirconic acid which can be represented by zirconium hydroxide, the general formula ZrO 2 · x H 2 O, or all of their derivatives. In addition, as other inorganic oxides, oxides of silicon or derivatives thereof can also be used, in which case the oxides of silicon or derivatives thereof are compounds containing SiO 2 as a basic unit and have a general formula of SiO 2 · x H 2 O It refers to silicic acid that can be represented by or their derivatives in general. Other inorganic oxides such as titanium and tungsten may be used. These inorganic oxides or their derivatives may be partially substituted with another metal element, and deviations from the stoichiometric composition or addition of additives may be tolerated.

  The inorganic / organic hybrid compound in the present invention is obtained by chemically bonding the above-mentioned inorganic oxide or its derivative with an organic polymer molecule. Therefore, the organic polymer molecule needs a way to bond with the inorganic oxide, and an organic polymer having a hydroxyl group is used as the hand for the bond. For example, when an inorganic oxide or derivative thereof forms an organic polymer having an hydroxyl group and an inorganic / organic hybrid compound, both entangle each other at the molecular level, and firmly by hydrogen bond or dehydration condensation via the hydroxyl group of the organic polymer. It is connected. Hybrid compounds are distinguished from mixtures by physical mixing of organic polymers and inorganic oxides or derivatives thereof. That is, unlike the mixture, the chemical properties of the components constituting the hybrid compound are not necessarily retained after hybridization. For example, even if the organic polymer having a hydroxyl group is water-soluble alone, it is basically insoluble in water in the state of forming a hybrid compound with an inorganic oxide or a derivative thereof. Thus, the change in chemical properties after hybridization can indicate that it is a hybrid compound different from a mixture by physical mixing. In addition, this inorganic / organic hybrid compound is insoluble in water but is highly hydrophilic and has water absorption. As described above, the present invention relates to high activity, control of active ingredient release rate, etc. for antimicrobial, antiviral and / or algal materials, by combining the water resistance and water absorbency of this inorganic / organic hybrid compound for fixing the active ingredient. Produces various effects.

  These compounds, such as oxides of silver or copper, which are often used as active ingredients of anti-microbial, anti-viral and / or anti-algal materials, are very oxidative, so the common organic polymers loaded with them deteriorate There is a possibility. On the other hand, the inorganic / organic hybrid compound of the present invention reflects the extremely high oxidation resistance property of the inorganic oxide, and is less likely to be deteriorated even when carrying a silver or copper compound having a strong oxidizing action. That is, application of the inorganic / organic hybrid compound as a compound for fixing the active ingredient is, in addition to the point that the water resistance and the water absorption as described above are compatible, in that it can withstand the strong oxidation action of the silver or copper compound. It is also important.

  In the present invention, the polymerization degree of the organic polymer having a hydroxyl group constituting the inorganic / organic hybrid compound is not particularly limited. For example, it is 500-100000, Preferably it is 1000-20000, More preferably, it is 2000-5000. The degree of polymerization is measured, for example, in accordance with JIS K 6726: 1994.

  In the present invention, the organic polymer having a hydroxyl group constituting the inorganic / organic hybrid compound is more preferably polyvinyl alcohol. The polyvinyl alcohol here does not need to be perfect and can be used if it essentially functions as a polyvinyl alcohol. For example, those in which a part of hydroxyl groups is substituted with another group, and those in which another polymer is copolymerized in part can also function as polyvinyl alcohol. For example, the polyvinyl alcohol of the organic polymer of the present invention is preferably composed of 50 mol% or more, more preferably 70 mol% or more, still more preferably 90 mol% or more of monomer units of vinyl alcohol or its derivative. For example, monomer units of the vinyl alcohol or derivative thereof are not substituted at least 70%, preferably at least 80%, more preferably at least 85% of the hydroxyl groups with other groups. In addition, since similar effects can be obtained by passing polyvinyl alcohol in the production process of the present invention, polyvinyl acetate or the like, which is a raw material of polyvinyl alcohol, can be used as a starting material. For example, polyvinyl alcohol obtained by saponifying at least 70%, preferably at least 80%, more preferably at least 85% of polyvinyl acetate can be used. The degree of saponification is measured, for example, in accordance with JIS K 6726: 1994.

  For polyvinyl alcohol, other polymers, for example, polyolefin polymers such as polyethylene and polypropylene, polyacrylic acid polymers, polyether polymers such as polyethylene oxide and polypropylene oxide, polyethylene terephthalate, as long as the function is sufficiently expressed. Polyester polymers such as polybutylene terephthalate, fluorine polymers such as polytetrafluoroethylene and polyvinylidene fluoride, sugar chain polymers such as methyl cellulose, polyvinyl acetate polymers, polystyrene polymers, polycarbonate polymers, epoxy resin polymers or Other organic and inorganic additives can also be mixed. For example, the organic polymer of the present invention preferably comprises 50% by weight or more, more preferably 70% by weight or more, still more preferably 90% by weight or more of polyvinyl alcohol.

  In the antimicrobial, antiviral and / or algal materials of the present invention, when the amount of the inorganic oxide or the derivative thereof to the organic polymer in the inorganic / organic hybrid compound is too small, the water resistance and the oxidation resistance become insufficient. On the contrary, when the amount of the inorganic oxide or its derivative is too large, the amount of absorbed water decreases and the swelling decreases, so that the diffusion rate of the active ingredient and the virus decreases, and the antimicrobial, antiviral and / or antialgal The effect is reduced, and the inorganic / organic hybrid compound becomes hard and brittle, and breakage easily occurs. Therefore, it is preferable to control the weight ratio of the inorganic oxide or the derivative thereof in the hybrid compound to the weight of the organic polymer to be 0.1 to 10.

  In the present invention, the inorganic / organic hybrid compound contains a silver or copper metal or a compound thereof as an active ingredient having an antimicrobial, antiviral and / or antialgal activity. In the case of silver, in addition to the metallic state, compounds such as silver oxides, silver salts such as silver chloride, and complexes of silver can be used. In the case of copper, in addition to the metal state, compounds such as copper oxide and complexes of copper can be used. These may be contained alone or in combination of two or more species. When these are contained as solid particles in the inorganic / organic hybrid compound, they are preferably nanoparticles, and in particular, it is desirable to include particles with a diameter of 10 nm or less. As a result, since the active ingredient is always in a highly active state, it can be fully utilized when the active ingredient is supplied to the surface by internal diffusion in the inorganic / organic hybrid compound, and has a high anti-microbial activity over a long period of time, The antiviral and / or algal activity can be stably maintained. In addition, the fine nanoparticles exhibit high activity when particles present on the surface directly contact and attack microorganisms and viruses, and also exhibit high activity when incorporating and attack viruses and the like. The existence of these silver or copper metals or their compounds as sufficiently small particles is a peak attributed to those metals or compounds in the diffraction intensity-diffraction angle diagram obtained by the X-ray diffraction method using CuΚα rays. Among these, it can be shown by the fact that the half width of the highest peak is 2 (2θ °) or more or that there is no peak. In the anti-microbial, anti-viral and / or anti-algal material of the present invention, a metal of silver or copper or a compound thereof is at least 0.1 wt%, more preferably at least 0.5 wt%, more preferably in terms of metal atoms. It is preferable that 1 wt% or more is contained. Although there is no upper limit, a content of, for example, 15 wt% or less in terms of metal atoms, and 5 wt% or less is desirable from the viewpoint of suppressing metal elution.

  Diffraction intensity-diffraction angle diagram is generally obtained as a result of X-ray diffraction, and shows the relationship between the diffraction angle 2θ and the count number of X-rays. When the substance is crystalline, the regular stacking of crystal planes causes the diffraction phenomenon of X-rays, the count number of X-rays becomes extremely high at a specific diffraction angle corresponding to the plane spacing of crystal planes, and the diffraction intensity A sharp peak is obtained at the diffraction angle position in the diffraction angle diagram. When the particles are small and the number of stacked crystal planes is not large, the peak has a low height and a broad broad peak, so the half width (peak width at half the height of the peak of the diffraction peak is 2θ Of the angular unit of 2θ °). In addition, in the case of fine particles (nanoparticles) which are so small that a substance can not form crystals, no diffraction peak appears at all at the diffraction angle at which the peak should originally occur when the substance is a crystal. That is, the half width becomes infinite. Therefore, the half width can be regarded as a scale that represents the degree of the fine particles (nanoparticles), and the larger the value is, the lower the crystallinity is, which indicates that it is more fine particles. In the present invention, in the diffraction intensity-diffraction angle diagram of the inorganic / organic hybrid compound, among the peaks attributed to the metal of silver or copper contained therein or the compound thereof, the half width of the highest peak is 2 (2θ °) If it is above, there will be no diffraction peak. FIG. 1 shows a typical diffraction intensity-diffraction angle diagram of X-ray diffraction of the material containing silver and copper of the present invention (Panalytical X‘Part Pro, using CuΚα ray). No sharp diffraction peak is observed in the diffraction intensity-diffraction angle diagrams of any of the materials, and none have a half width of less than 2 (2θ °).

  The present invention is characterized in that the active ingredient silver or copper metal or its compound is contained in the inorganic / organic hybrid compound having water absorbency in the form of fine particles (nanoparticles), whereby It is possible to control the rate at which the active ingredient diffuses to the material surface and is released. That is, the minimum amount of the active ingredient necessary for the antimicrobial, antiviral and / or antialgal action is gradually released, and the active ingredient to be contained is in the form of microparticles (nanoparticles), so the supply of the active ingredient is It can be maintained constantly until it is used up, and it is excellent in durability. In addition, it is possible to minimize the pollution of the surrounding environment and the pollution to the contacting person. In addition, the particles of the active ingredient immobilized on the surface are highly active fine particles (nanoparticles), and thus exhibit high anti-microbial, anti-viral and / or anti-algal activity by direct contact with microorganisms, viruses, etc. . Furthermore, it is also possible to obtain an effect by extremely reducing the release of the active ingredient by showing high activity even when attacking by taking in a virus or the like. The release rate of these active ingredients can be controlled in such a way that the amount of silver or copper in the anti-microbial, anti-viral and / or anti-algal material of the present invention is 1 mg / L or more. It is possible to immerse by immersing the anti-algal material for 24 hours or more and measuring the concentration of silver or copper dissolved out in water. In the present invention, the value is desirably less than 0.05 mg / L.

  The anti-microbial, anti-viral and / or anti-algal material of the present invention can be used as a solid of a suitable form and dipped in water to be treated as it is. The preferred form is a membrane. In that case, for example, it is possible to immerse the membranous substance in water as it is, or to mount it on some kind of support material, or to round it and insert it into a column. It is also possible to cut finely and use it as a small piece, and it is also possible to use the small piece packed in a column for use. Moreover, it is also possible to stick and use it on the surface of the solid object which makes a film-like object.

  The anti-microbial, anti-viral and / or anti-algal material of the present invention can also be used by coating on the surface of the target solid. Also in that case, it is a film-like substance on the surface. In the case of coating, the form of the target solid may be any form, and all targets are applicable. In addition, since this material is based on an inorganic / organic hybrid compound having both inorganic and organic properties, it can be stably bonded to any inorganic or organic compound, and organic polymers ( It can be stably coated on plastic, wood, paper, glass, ceramics, metals and the like. For example, by coating the material of the present invention on the surface of a porous material such as net, mesh, woven fabric, non-woven fabric, it can be used as a filter having antimicrobial, antiviral and / or algal action. . Alternatively, the material of the present invention may be coated on the surface of particles or other solid matter such as beads, and may be used as an anti-microbial, anti-viral and / or anti-algal material of the type to be stored in water.

  When the material is a film-like material, the silver or copper metal of the active ingredient contained in the inorganic / organic hybrid compound or the compound thereof can have a concentration gradient with respect to the thickness direction of the film-like material. For example, when used in a water environment, excessive release of the active ingredient is likely to occur. Therefore, the method of suppressing the release rate is effective by lowering the concentration of the active ingredient on the surface side of the film like compared to the inner side. is there. On the other hand, when used in a normal dry environment, the release of the active ingredient is less likely to occur and the effect is less likely to occur, so the concentration of the active ingredient on the surface side of the film is rather higher than that on the inner side. It is valid.

  The material of the present invention can be used in any application as an antimicrobial, antiviral and / or algal material. There are storage water and circulating water as a place where bacteria and algae are likely to grow, but as described above, the present invention is effective in anti-microbial, anti-viral and / or prevention without polluting water by elution of the extra active ingredients. It can be used for all reservoir water and circulating water to express algal action. For example, because the pool, bath water in a hot-water bath facility, water in a water reservoir for collective housing, tap water, etc. touch the human body directly or ingested by the human body, it is an application where you do not want to use medicine is there. In addition, a breeding aquarium for culture or appreciation is also an application that does not want to use or can not use medicines because it has an influence on breeding animals such as fish. Because the ballast water of transport vessels is ultimately discarded to the sea, it is also an application where it is desirable to avoid the use of drugs from the viewpoint of environmental pollution. In addition, for example, industrial water storage and circulating water such as water used for paper making process of paper and pulp industry, water of cooling towers of factories and buildings, etc. influence the oxidizing property and pH of the drug when using the drug. , There is a concern to promote the corrosion of equipment components and equipment. In addition, in the case of industrial water, there is also the concern of drug contamination of the product. In these applications, it is possible to take advantage of the feature which suppresses the elution of the extra active ingredient of the material of the invention.

  When the material of the present invention is applied to these uses, basically, if the material is in contact with water, an antimicrobial, antiviral and / or algal effect can be obtained, so any use A form is also possible. The simplest is to dip the material of the present invention directly into water. From the viewpoint of effectively functioning the active ingredient, a film-like or fiber-like having a relatively large specific surface area is preferable, but a film-like is most preferable from the viewpoint of easiness of production, easiness of recovery after use, strength and the like. There is also a method of sticking a film-like material of the material of the present invention to a member in contact with water or coating the surface of the member. In addition, in the case of reservoir water, the material of the present invention is coated on solid matter such as glass beads, stones, ceramic blocks, ceramic pieces, etc., and then it is sunk or coated on a plastic ball or the like and floated. There is also a method such as For example, in a culture tank for culture or appreciation, it is necessary to prevent infection of a living organism such as fish with a virus, or to prevent algae (carp) from growing on the glass of the breeding case. It is necessary to apply an anti-microbial, anti-viral and / or anti-algal treatment so as not to affect the organism. For example, pebbles coated with the material of the present invention may be spread on the bottom of the water tank, or the glass inner surface of the breeding case may be coated with the material of the present invention.

  However, unlike the method in which the drug is dissolved in water, the active ingredient is distributed uniformly throughout the water, in the case of the material of the present invention, the effect is only on the water in contact with the material. That is, if the material is placed only in very limited places and the water is not moving so much, the anti-microbial, anti-viral and / or anti-algal effect does not extend to the whole water. Therefore, it is necessary to cover the bottom with a coating of the present material or to coat the entire surface of the constituent material in contact with water, but in such a case, the cost may be considerable. Therefore, it is effective to circulate the entire water when the material is used as reservoir water. In that case, it is effective to construct a column packed with this material in an appropriate form, pass water through it, or paste or coat this material on the surface of the stirring blade of the stirring device. It can be processed.

  The anti-microbial, anti-viral and / or anti-algal material of the present invention can be used for preventing shellfish and algae such as barnacles from adhering and growing on the outer surface of the bottom of the ship and increasing resistance during propulsion. . In that case, there is a method of coating the material on the outer surface of the bottom of the ship or attaching a film. As in the conventional method, there is also a method of mixing and applying an active ingredient such as a copper compound to a paint, but in such a case, excessive elution of the active ingredient is likely to occur, resulting in environmental pollution such as oceans, rivers and lakes. It is easy to happen. The material of the present invention is effective without elution of the extra active ingredient, so that less contamination is required.

  The material of the present invention can be used as an antimicrobial, antiviral and / or antialgal material not only in an environment always immersed in water, such as stored water and circulating water, but also in water and in a wet environment. In these applications, the method of coating the material on the surface of an article in such an environment is central. For example, bathroom walls, floors, drains, or anything used therein. Most of them are usually made of organic polymers (plastics), but the materials can form a stable coated film on their surface. In addition, since the material of the present invention is made of an inorganic / organic hybrid compound and has high affinity to inorganic substances, walls, floors, baths, windows, etc. are inorganic such as cement, tile, pottery, glass, etc. The material can also be coated stably if it is made of a material. Other items used in the kitchen, washroom, toilet water area, basins, baskets, tubs, buckets, rubbish bins, etc. are also covered. Also in this case, a stable coat film can be formed against a sink of a toilet made of pottery which is an inorganic substance, a toilet bowl, and the like. It can also be used for cooking utensils and other so-called kitchen utensils, and can also be used for packing water bottles, lunch containers and the like.

  In addition, there is a problem that algae sheets are easily grown on vinyl sheets used in vinyl houses as those used in a wet environment, and the light necessary for plant growth is impeded. There is a conceivable way to keep

  The materials according to the invention can also be used as anti-microbial, anti-viral and / or anti-algal materials, even under normal atmospheric conditions, but not in wet environments. For example, it can be applied to anything that routinely comes in contact with the skin, such as fittings, furniture, stationery, toys, beauty products, and switches of equipment. Especially when applied to those in the hospital, it is effective in suppressing nosocomial infections. Moreover, it is also possible to utilize for various medical instruments. For these applications, film-like materials of the present invention are attached to their surfaces, or materials of the present invention are coated on their surfaces and used.

  For example, in livestock, birds, and other breeding grounds for animals, if the material is coated on the surface or pasted on anything used there, it helps to prevent infection of bacteria and viruses. In particular, infection with diseases such as avian influenza caused by the flight of birds carrying bacteria and viruses from the outside may be prevented by taking a method such as enclosing this material in a coated net.

  By coating the material of the present invention on the surface of a porous material such as net, mesh, woven fabric or non-woven fabric, it can be used as a filter having an antimicrobial, antiviral and / or algal action. Passing through the filter while contacting the gas while forcibly circulating the gas can prevent or reduce the increase of bacteria and viruses in the air. Therefore, it can be used as an air filter of an air purifier. Moreover, it is also possible to use for a mask by the same effect | action.

  Next, the process for producing the anti-microbial, anti-viral and / or anti-algal material according to the present invention will be described. FIG. 2 is a system diagram schematically showing a first embodiment of the manufacturing process of the present material. First, a solvent is prepared in step 1 as a raw material, a silver or copper salt in step 2, an inorganic salt other than a silver or copper salt in step 3 or an oxo acid salt, and an organic polymer having a hydroxyl group in step 4 Then, these raw materials are mixed in step 5 to obtain a mixed solution in which silver or copper salts and other inorganic salts or oxo acid salts and an organic polymer having a hydroxyl group coexist in a solvent. The order of the preparation steps of steps 1 to 4 is not limited, and the order of mixing the raw materials in step 5 is also not limited. Preferably the solvent comprises water. The silver or copper salt, the other inorganic salt, the oxo acid salt, or the organic polymer containing a hydroxyl group may have any composition, but it is preferably soluble in water. For example, silver nitrate, copper chloride and the like can be used as the silver or copper salt in step 2, and their hydrates may be used. In Step 3, zirconium salts, oxyzirconium salts, silicates and the like can be used as inorganic salts or oxo acid salts other than silver or copper salts. Also, for example, in the case of using polyvinyl alcohol as the organic polymer having a hydroxyl group in step 4, in order to be able to perform the step of removing water and forming in a later step within a practical time range for production. In the mixed solution of step 5, it is desirable that the concentration of polyvinyl alcohol is 5% by weight or more, more preferably 10% by weight or more. When a silver salt is used, it is preferable to block the light in this step to prevent the silver salt from being reduced by light.

  Next, if the inorganic salt or oxo acid salt other than the silver or copper salt in step 3 can be neutralized with an alkali, such as a zirconium salt or oxyzirconium salt, then silver or copper in the mixed solution in step 6 The salt, other inorganic salts or oxo acid salts are neutralized with alkali to obtain a raw material solution after neutralization in step 7. If the inorganic salt or oxo acid salt other than the silver or copper salt in step 3 can be neutralized with an acid such as a silicate, then the inorganic salt or oxo salt other than the silver or copper salt in the mixed solution in step 6 The acid salt is neutralized with acid to obtain the raw material solution after neutralization in step 7. The solvent is then removed in step 8 and in step 9 a compact of the material of the invention is obtained. In the case where an unnecessary salt generated by neutralization is present in the raw material solution after the neutralization in Step 7, after the molded product is obtained in Step 9, the unnecessary salt can be removed by washing with water.

  In the raw material liquid of step 5 of FIG. 2, the salt of silver or copper, the inorganic salt other than that, or the oxo acid salt and the organic polymer having a hydroxyl group are dissolved and mixed at the molecular level. In this state, when the neutralization operation is performed in step 6, the inorganic salt or oxo acid salt is neutralized to be an inorganic oxide or a derivative thereof. Small new-born inorganic oxides or derivatives thereof are unstable, and if there is an organic polymer having a hydroxyl group in the vicinity, they bind to the hydroxyl group. In this way, an inorganic / organic hybrid compound is formed in which an inorganic oxide or a derivative thereof and an organic polymer are chemically bonded. At this time, the inorganic oxide or the derivative thereof is inhibited from growing because it chemically bonds with the organic polymer, and remains in the nanoparticles. Silver or copper salts are incorporated into inorganic / organic hybrid compounds in the form of oxides, hydroxides, etc. when the neutralization operation in step 6 is carried out with alkali, or they are themselves either organic polymers or chemically It is bound but in any case remains in the nanoparticles. When the neutralization operation in step 6 is carried out with an acid, a silver or copper salt is incorporated into the inorganic / organic hybrid compound in the form of a salt even after neutralization. Thus, in this case the silver or copper salt may be added later than before the neutralization operation. In either case, the silver or copper compound is formed in the inorganic / organic hybrid compound and does not form large particles.

  The acid for neutralizing the inorganic salt or oxo acid salt in the raw material solution in step 6 may be any acid as long as it can neutralize these. For example, hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, acetic acid, proton type cation exchange resin, etc. can be used. The alkali for neutralizing the inorganic salt or oxo acid salt in the raw material solution in step 6 may be any alkali capable of neutralizing these. For example, sodium hydroxide, potassium hydroxide, lithium hydroxide, ammonia, calcium hydroxide, strontium hydroxide, barium hydroxide, carbonate, hydroxide ion type anion exchange resin, etc. can be used. These acids and alkalis may be used alone or in combination.

  In the case of coating this material on the surface of an existing solid, after applying the raw material solution of step 7 to the surface of the object, the solvent is removed (dried) in step 8 and a coated film of this material is obtained in step 9 . For example, when forming a coated film of this material on the surface of the net, the raw material solution in step 7 may be directly applied or sprayed, or the net may be dipped in the raw material liquid and pulled up to remove the solvent by heating ( It can implement by methods, such as drying.

  FIG. 3 is a system diagram schematically showing a second embodiment of the manufacturing process of the present material. Through the same steps as in FIG. 2, a mixed solution in which a silver or copper salt, and other inorganic salts or oxoacid salts and an organic polymer having a hydroxyl group coexist is obtained in step 5. Next, in step 6, the solvent is removed. In step 7, a silver or copper salt, and a mixture of other inorganic salts or oxo acid salts and an organic polymer having a hydroxyl group are formed into a shaped solid. In step 8, it is contacted with an acid or alkali to neutralize the inorganic salt or oxo acid salt. In step 9, a molded body of the material is obtained. As a method of contacting with acid or alkali in step 8, there is a method of immersing in an acid or alkali solution, applying or spraying acid or alkali solution on the mixture of step 7, or exposing to a vapor. Hybridization proceeds in the neutralization step of step 8 of FIG. 3 in the same manner as in the case of FIG. 2, and the compound of silver or copper or the other inorganic oxide or its derivative is fine as nanoparticles. Stay in the particles.

  In the case of coating this material on the surface of the existing solid according to the second embodiment, after applying the mixed solution of step 5 to the surface of the object, the solvent is removed (dried) in step 6, and the step 7 is performed. A coated film of a silver or copper salt and a mixture of other inorganic salts or an oxo acid salt and an organic polymer having a hydroxyl group is formed on the surface of the object. In step 8, it is contacted with an acid or alkali to neutralize the inorganic salt or oxo acid salt, and in step 9, a coated film of the present material is obtained. In step 8, as a method of contacting with acid or alkali, there is a method of immersing in an acid or alkali solution, applying or spraying an acid or alkali solution on a coated film of the mixture of step 7, or exposing to a vapor. is there.

  An inorganic / organic hybrid compound in which an inorganic oxide or a derivative thereof and an organic polymer having a hydroxyl group are chemically bonded can be produced by the method as shown in FIG. 2 or FIG. This hybrid compound is not soluble in water because the organic polymer is crosslinked by the nanoparticles of the inorganic oxide or its derivative. And, it is highly hydrophilic due to the action of nanoparticles of an inorganic oxide or its derivative, or a hydroxyl group left without bonding of an organic polymer, and has a property of absorbing water. As described above, by the coexistence of the water resistance and the water absorbability, a good antimicrobial, antiviral and / or algal action can be realized. In addition, when a method of incorporating already-made silver, copper or a compound thereof is adopted later, those particles can not be made very fine, but as in the method of the present invention, silver and copper components are used as raw materials By introducing from the liquid stage and simultaneously forming these compounds during the formation of the inorganic / organic hybrid compounds, it is possible to make very fine particles such as nanoparticles. As described above, this causes exhaustion of the active ingredient to the end, enhances the activity when particles immobilized on the surface attack microorganisms and viruses directly, and enhances the activity when viruses are taken inside and attacked, etc. The effect of The degree of fine particles (nanoparticles) of the silver or copper metal or compound is as in step 6 of FIG. 2 or step 8 of FIG. 3 as in the case where the inorganic oxide of the inorganic / organic hybrid compound is a zirconium oxide. The sum operation is carried out with alkali, and silver or copper salts are also finer when neutralized. From this point of view, an oxide of zirconium is particularly preferable as the inorganic oxide, and in that case, the second embodiment of FIG. 3 is preferable as a manufacturing method.

  By continuing heating at 80 to 170 ° C. even after forming a molded body at the stage of step 9 in FIG. 2 or FIG. 3, the hybridization reaction can be further advanced to improve the strength of the present material. Also, the silver or copper compound in the inorganic / organic hybrid compound produced by the method of FIG. 2 or 3 can be converted to a metal state by reduction with an appropriate reducing agent.

  In order to obtain a film-like material of this material, the material solution of step 7 of FIG. 2 or the mixed solution of step 5 of FIG. 3 is cast on a flat substrate or coated on the surface of the object to be coated. . In this case, the second layer can be further cast or coated in a state in which the solvent is removed to some extent, and this can be repeated to coat a plurality of layers. It is also possible to change the composition of each layer, for example, to make the concentration gradient in the thickness direction of the film-like material by changing the concentration of silver or copper in each layer. When used in a water environment, excessive release of the active ingredient is likely to occur, so a method of suppressing the release rate is effective by lowering the concentration of the active ingredient on the surface side of the film-like substance than in the inner side. The state can be realized by making the concentration of the silver or copper component of the layer on the surface side lower than that of the layer on the inner side. On the other hand, when used in a normal dry environment, the release of the active ingredient is less likely to occur and the effect is less likely to occur. Rather, the concentration of the active ingredient in the layer on the surface side of the film is higher than that on the inner side. Is effective. The state can be realized by making the concentration of the silver or copper component of the layer on the surface side higher than that of the layer on the inner side.

  Hereinafter, examples of the anti-microbial, anti-viral and / or anti-algal material according to the present invention will be described. The present invention is not limited to the contents described in these embodiments.

Example 1
A film which is an anti-microbial, anti-viral and / or anti-algal material of the present invention containing silver as an active ingredient is prepared according to the third embodiment, and the silver component has a concentration gradient with respect to the thickness direction of the film The inside was made the one whose concentration of the silver component is higher than the surface.

Silver nitrate saponification degree of the 86 to 90% polyvinyl alcohol aqueous solution of 10 weight percent 90g in polymerization degree of 3100~3900 _(AgNO 3) 0.7g and zirconium oxychloride octahydrate _{(ZrCl 2 O · 8H 2 O} ) 4g The mixture solution A was prepared by heating at 50 ° C. for 1 hour while stirring while being shielded from light by aluminum foil in order to prevent photoreduction of silver nitrate. In addition, 4 g of zirconium oxychloride octahydrate (ZrCl ₂ O · 8 H ₂ O) is added to 90 g of a 10 wt% aqueous solution of polyvinyl alcohol having a degree of polymerization of 3100 to 3900 and a degree of saponification of 86 to 90% while stirring The mixture solution B was prepared by heating at 50 ° C. for 1 hour. That is, the silver solution was contained in the mixed solution A, and the silver compound was not contained in the mixed solution B.

  Next, this mixed solution is coated on a smooth pedestal of a coating device (K Control Coater 202, manufactured by RK Print Coat Instruments Ltd.) equipped with a blade whose gap with the pedestal can be adjusted using a micrometer. The mixed solution B was cast on the film. At this time, the pedestal was heated to 70 ° C. while being controlled. After casting the mixed solution B on the pedestal, a blade whose gap was adjusted to 0.4 mm was swept at a constant speed over the mixed solution B to make a constant thickness. Furthermore, by standing with heating at 70 ° C., the water is removed by leaving it at a stage where the fluidity almost disappears, the mixed solution A is cast one on top of the mixture solution and cast, and the blade whose gap is adjusted to 0.6 mm is fixed again. It swept over mixed solution A at speed. In addition, water is removed by standing with heating at 70 ° C., and when the fluidity is almost lost, mixed solution B is again cast from the top and cast, and the blade whose gap is adjusted to 0.4 mm is fixed immediately. The raw material solution B was swept at a speed. Moisture was removed by standing at 70 ° C. while heating, and the temperature of the pedestal was raised to 130 ° C. when fluidity was almost lost, and heat treatment was carried out for 1.5 hours while maintaining that state. Then, after peeling the film | membrane produced | generated on the base and immersed in 0.2 N sodium hydroxide aqueous solution for 18 hours at normal temperature, it wash | cleaned in 60 degreeC-70 degreeC hot water for about 30 minutes. After drying at room temperature, heat treatment was performed at 120 ° C. for 1 hour, and the film 1 was washed again in hot water of 90 ° C. for about 1 hour, to prepare a membrane 1. Film 1 contained 1.3 wt% of silver on average.

  As in this example, a film is prepared by applying three layers of the present material, and by making only the inner layer into a mixed solution A having a silver compound, a film having a high concentration of silver component inside and a low concentration near the surface Can be produced.

Example 2
A film which is an anti-microbial, anti-viral and / or anti-algal material of the present invention containing silver as an active ingredient is prepared according to the third embodiment, and the silver component has a concentration gradient with respect to the thickness direction of the film The surface was made to have a higher concentration of silver component than the inside.

Add ₂ g of zirconium oxychloride octahydrate (ZrCl ₂ O 8 H ₂ O) and 0.05 g of silver nitrate to 90 g of a 10% by weight aqueous solution of polyvinyl alcohol having a degree of polymerization of 3100 to 3900 and a degree of saponification of 86 to 90% In order to prevent photoreduction of silver nitrate, the mixture solution A was prepared by heating at 50 ° C. for 1 hour while stirring in a state shielded from light by aluminum foil. Further, ₂ g of zirconium oxychloride octahydrate (ZrCl ₂ O · 8 H ₂ O) is added to 90 g of a 10 wt% aqueous solution of polyvinyl alcohol having a degree of polymerization of 3100 to 3900 and a degree of saponification of 86 to 90% while stirring The mixture solution B was prepared by heating at 50 ° C. for 1 hour. That is, the silver solution was contained in the mixed solution A, and the silver compound was not contained in the mixed solution B.

  Next, this mixed solution is coated on a smooth pedestal of a coating device (K Control Coater 202, manufactured by RK Print Coat Instruments Ltd.) equipped with a blade whose gap with the pedestal can be adjusted using a micrometer. The mixed solution A was cast on the film. At this time, the pedestal was heated to 70 ° C. while being controlled. After casting the mixed solution A on the pedestal, a blade whose gap was adjusted to 0.3 mm was swept at a constant speed over the mixed solution A to make a constant thickness. Furthermore, by standing with heating at 70 ° C., the water is removed by leaving it at a stage where the fluidity almost disappears, the mixed solution B is cast one on top of the mixture solution and cast, and the blade whose gap is adjusted to 0.6 mm is constant again. It swept over mixed solution B at speed. Furthermore, by standing with heating at 70 ° C., the water is removed by leaving it at a stage where the fluidity almost disappears, mixed solution A is again cast from the top again and cast, and the blade whose gap is adjusted to 0.4 mm is fixed immediately. It swept over mixed solution A at speed. Moisture was removed by standing at 70 ° C. while heating, and the temperature of the pedestal was raised to 130 ° C. when fluidity was almost lost, and heat treatment was carried out for 1.5 hours while maintaining that state. Then, after peeling the film | membrane produced | generated on the base and immersed in 0.2 N sodium hydroxide aqueous solution for 18 hours at normal temperature, it wash | cleaned in 60 degreeC-70 degreeC hot water for about 30 minutes. After drying at room temperature, heat treatment was performed at 120 ° C. for 1 hour, and the film 2 was washed again in hot water of 90 ° C. for about 1 hour to prepare a membrane 2.

  As in this example, by preparing three layers of this material and preparing only the layer on the surface side into the mixed solution A having a silver compound, the concentration of the silver component near the surface is high and the concentration is low inside Membranes can be produced.

Example 3
The antimicrobial, antiviral and / or antialgal material film of the present invention containing copper as an active ingredient was prepared according to the third embodiment.

90 g of a 10% by weight aqueous solution of polyvinyl alcohol having a polymerization degree of 3100 to 3900 and a saponification degree of 86 to 90%, 6 g of zirconium oxychloride octahydrate (ZrCl ₂ O · 8 H ₂ O), and copper chloride dihydrate ( 0.3 g of CuCl ₂ · 2 H ₂ O) was added, and the mixture was heated at 50 ° C. for 1 hour while stirring to prepare a mixed solution. Next, this mixed solution is coated on a smooth pedestal of a coating device (K Control Coater 202, manufactured by RK Print Coat Instruments Ltd.) equipped with a blade whose gap with the pedestal can be adjusted using a micrometer. The mixed solution was cast on a film. At this time, the pedestal was heated to 70 ° C. while being controlled. Immediately after casting the mixed solution on the pedestal, a blade whose gap was adjusted to 0.5 mm was swept over the mixed solution at a constant speed to make a constant thickness. Furthermore, by standing while heating at 70 ° C., the moisture was removed, and at the stage when the fluidity almost disappeared, the temperature of the pedestal was raised to 130 ° C. and heat treatment was performed for 1.5 hours while maintaining that state. Then, after peeling the film | membrane produced | generated on the base and immersed in 0.1 N sodium hydroxide aqueous solution at normal temperature for 18 hours, it wash | cleaned in 60 degreeC-70 degreeC hot water for about 30 minutes. After drying at room temperature, heat treatment was performed at 120 ° C. for 1 hour, and the film 3 was washed again in hot water of 90 ° C. for about 1 hour. The film 3 contained 1.2 wt% of copper on average.

Example 4
A film which is an antimicrobial, antiviral and / or anti-algal material of the present invention containing silver as an active ingredient was prepared according to the third embodiment and coated on the surface of a polypropylene mesh (net).

Add 4 g of zirconium oxychloride octahydrate (ZrCl ₂ O 8 H ₂ O) and 0.4 g of silver nitrate to 90 g of a 10% by weight aqueous solution of polyvinyl alcohol having a degree of polymerization of 3100 to 3900 and a degree of saponification of 86 to 90% In order to prevent photoreduction of silver nitrate, the mixture solution was prepared by heating at 50 ° C. for 1 hour while stirring while being shielded from light by aluminum foil. A polypropylene mesh (mesh for net) was immersed in this mixed solution for 1 hour. After taking it out, the excess mixed solution was removed by air blow and heat treatment was performed at 130 ° C. for 1 hour. Then, after immersing in 0.2N sodium hydroxide aqueous solution at normal temperature for 18 hours, it wash | cleaned in 60 degreeC-70 degreeC hot water for about 30 minutes. After drying at room temperature, heat treatment was carried out at 120 ° C. for 1 hour, and the film was washed again in hot water of 90 ° C. for about 1 hour to produce a polypropylene mesh (PP mesh) coated with the membrane of the present invention.

Example 5
(Test Example 1 Dissolution Test)
The membrane of the present invention was added to each test water and the elution amount of silver and copper was measured by ICP emission analysis.
We prepared 800 ml of each test water of sterile water, phosphate buffer, and phosphate buffer (phosphate buffer + bacteria) to which bacterial solution containing Staphylococcus aureus and E. coli was added so that the number of bacteria was 10 ⁵ CFU / ml. . The film 1 or 3 was added to each test water and stirred so that the content of silver or copper was about 1 mg / L or more. Thereafter, the concentration of silver or copper in each test water was measured before, 3 hours, 6 hours, and 24 hours after film introduction. Silver and copper were not detected in any of the membrane 1 and the membrane 3, indicating that the membrane was stably immobilized. The measurement results are shown in Tables 1 and 2. Both the membrane 1 and the membrane 3 showed swelling of the membrane when immersed in any water and became soft, but after measurement, they were taken out and left to dry in the air, the original size, hardness Returned to From this, it was confirmed that these films absorb water clearly. Further, when both the membrane 1 and the membrane 3 were immersed in any water, although they absorbed water, they did not dissolve, and deterioration of the membrane was not observed.

Example 6
(Test Example 2 Antibacterial Activity Test)
The prepared membrane was subjected to the antibacterial force evaluation test by the shake flask method in accordance with the test method of the Antimicrobial Product Technology Council.

For each of Staphylococcus aureus and Escherichia coli, 30 ml of the test solution is prepared by adding the solution to sterile phosphate buffered saline (KH2PO4) so that the number of bacteria is about 10 ⁴ to 10 ⁵ CFU / mL. did. It was added to a 200 ml sterilized Erlenmeyer flask, and the membrane 1 or the membrane 3 was cut and charged so as to be 1 mg / L or more as silver or copper, and shaken at 25 ± 5 ° C., 320 to 340 rpm. Thereafter, the number of viable bacteria was measured at each elapsed time (0 hour, 1 hour, 3 hours, 24 hours, 72 hours, 168 hours) to evaluate the antibacterial activity. In addition, what did not add a microbe liquid by said operation was set as control. In addition, a comparative film containing no silver and copper was prepared, and a film weight approximately equal to that of the film 1 or 3 was added and evaluated (comparative example 1). The results are shown in Tables 3 and 4. Both membrane 1 and membrane 3 showed excellent bactericidal effects.
The following two strains were used in the test.
Staphylococcus aureus NBRC12732
Escherichia coli NBRC3972

Example 7
(Test example 3 Algae test)
Chlorella a vulgaris C-135 (hereinafter referred to as Chlorella), which is a green algae, was used to evaluate the algicidal effect of Membrane 1 and Membrane 3.

A preculture solution of Chlorella in MDM medium is diluted with distilled water so that the value at absorbance ₄₂₀ is 0.25 to 0.28, and HEPES (N-2-hydroxyethylpiperazine-N is added thereto). The '-2- ethane sulfonic acid) was introduced and dissolved to make the concentration of HEPES 50 mM. To this was added caustic soda to adjust the pH to 8.5. 10 ml of this test solution was dispensed into an L-shaped test tube and placed in a light-irradiated shaking-constant temperature aqueous layer. Membrane 1 and membrane 3 were cut, and each was charged so as to be 6 mg / L or more as silver or copper. Also, the same comparative film as prepared in Example 6 was prepared, cut, and the same amount as film 1 or film 3 was added as the film weight, and it was evaluated. The shaking culture was carried out under conditions of 30 ° C. and 10 KLx (light: 12 hours, dark: 12 hours), and observation was carried out for 2 days by visual observation. The algicidal effect was evaluated by the criteria described in Table 5, and the test results are shown in Table 6.

Example 8
Test Example 4 Virus Inactivation Test
Next, the evaluation of the virus inactivation performance of the mesh made of PP made of silver nano membrane prepared in Example 4 was performed.

The PP mesh of Example 4 was cut into a size of about 3 cm × 3 cm, and four sheets were stacked to obtain a PP mesh test piece to be evaluated. Moreover, the test piece of the glass plate was used as a comparison control. The influenza virus culture solution after cell culture of influenza virus (influenza A virus (H1N1) A / PR / 8/34 ATCC VR-1469) is centrifuged and the obtained supernatant is diluted 10 times with purified water. The virus solution was prepared. Each test piece was inoculated with 0.2 ml of virus solution and stored at room temperature for 3 hours, 6 hours, and 24 hours. After storage, the virus infectivity titer (TCID ₅₀ / mL) was measured. The results are shown in Table 7.

  In addition, evaluation of virus infectivity titer is expressed by [R = log B-log A] (A: virus infectivity titer of the test piece of the glass plate as a comparison control, B: virus infectivity titer of the PP mesh test piece to be evaluated) When the inactivation effect R was 2 or more, it was judged that there was an inactivation effect. As a result, the test piece showed a virus inactivation effect after 24 hours of contact.

The anti-microbial, anti-viral and / or anti-algal material of the present invention takes advantage of the feature of achieving a high effect without extra release of the active ingredient, and it can be used in swimming pools, baths, water reservoirs for collective housing, breeding aquariums, It can be used as an anti-microbial, anti-viral and / or anti-algal material for water used in industrial reservoirs, industrial circulating water, tap water, septic tanks, cooling towers, transport vessel ballast water. Also, anti-microbial, anti-microbial, anti-microbial, anti-microbial, anti-microbial, anti-microbial, anti-microbial, etc. used to coat fittings, furniture, stationery, toys, beauty tools, waste containers, drainage members, toilet bowls, vinyl sheets for plastic greenhouses, equipment switches, medical tools, air filters, masks, etc. It can also be used as a virus and / or as an algicidal material.

Claims (22)

  The inorganic oxide or derivative thereof and an organic polymer having an hydroxyl group are chemically bonded to each other, and the inorganic / organic hybrid compound contains a silver or copper metal or a compound thereof and is not soluble in water. An anti-microbial, anti-viral and / or anti-algal material characterized in that it is solid and capable of absorbing water.   The antimicrobial, antiviral, and / or antialgal material according to claim 1, wherein the inorganic oxide is an oxide of zirconium, silicon, titanium, or tungsten.   The antimicrobial, antiviral and / or algal material according to claim 2, wherein the inorganic oxide is an oxide of zirconium.   The antimicrobial, antiviral, and / or antialgal material according to claim 1, wherein the organic polymer having a hydroxyl group is polyvinyl alcohol.   5. The antimicrobial, antiviral, and / or preventive agent according to any one of claims 1 to 4, wherein the metal of silver or copper contained in the inorganic / organic hybrid compound or the compound thereof comprises particles of 10 nm or less in diameter. Algae material.   In the diffraction intensity-diffraction angle diagram obtained by X-ray diffraction method using Cu Κ α ray, the half width of the highest peak among the peaks attributed to the metal of silver or copper contained in the inorganic / organic hybrid compound or the compound is The antimicrobial, antiviral, and / or anti-algal material according to any one of claims 1 to 4, which is 2 (2θ) or more, or has no peak.   Silver or copper dissolved in water when immersed in water at room temperature where the amount of silver or copper in the antimicrobial, antiviral and / or anti-algal material is 1 mg / L or more for 24 hours or more The anti-microbial, anti-viral, and / or anti-algal material according to any one of claims 1 to 4, wherein the concentration of S is less than 0.05 mg / L.   The antimicrobial, antiviral, and / or anti-algal material according to any one of claims 1 to 4, which is a film-like material.   9. The anti-microbial, anti-viral, and / or anti-algal material according to claim 8, wherein the film-like material is a coated film coated on a solid surface.   Solids coated with a coating on the surface are fittings, furniture, stationery, toys, beauty tools, waste containers, drainage members, toilet bowls, vinyl sheets for plastic greenhouses, switches for equipment, and medical devices. Item 10. The antimicrobial, antiviral and / or antialgal material according to item 9.   10. The anti-microbial, anti-viral and / or anti-algal material according to claim 9, characterized in that the solid is a porous material.   The antimicrobial, antiviral and / or algal material as claimed in claim 11, wherein the porous material is a net, a mesh, a woven fabric, or a non-woven fabric.   The antimicrobial, antiviral and / or algal material as claimed in claim 11, wherein the porous material is a filter or a mask.   9. The antimicrobial or antiviral agent according to claim 8, wherein the silver or copper metal contained in the inorganic / organic hybrid compound or the compound thereof has a concentration gradient with respect to the thickness direction of the film-like material. And / or algae protection material.   The method according to any one of claims 1 to 5, characterized in that the antimicrobial, antiviral and / or antialgal material is brought into contact with the liquid to suppress an increase in the number of microorganisms and viruses in the liquid or to reduce the number of individuals. Antimicrobial, antiviral, and / or anti-algal material according to any one of the preceding claims.   The anti-microbial, anti-viral, and / or anti-algal material according to claim 15, characterized in that the liquid is brought into contact while being forced to circulate.   The liquid is a water used for a pool, a bath, a water storage tank for collective housing, a breeding water tank, an industrial water storage tank, industrial circulating water, tap water, a septic tank, a cooling tower, and ballast water for transport vessels. The anti-microbial, anti-viral and / or anti-algal material as claimed in claim 15.   The antimicrobial, antiviral and / or antialgal material is brought into contact with a gas to suppress an increase in the number of microorganisms and viruses in the gas or reduce the number of individuals. Antimicrobial, antiviral, and / or anti-algal material according to any one of the preceding claims.   The anti-microbial, anti-viral, and / or anti-algal material according to claim 18, characterized in that the gas is brought into contact while being forced to circulate.   By neutralizing the zirconium salt or oxyzirconium salt with an alkali in the coexistence of polyvinyl alcohol and a silver or copper salt, and forming an inorganic / organic hybrid compound in which the zirconate compound and the polyvinyl alcohol are chemically bonded A method of producing the anti-microbial, anti-viral and / or anti-algal material of claim 3 or 4.   The process of forming the inorganic / organic hybrid compound in which the zirconate compound and the polyvinyl alcohol are combined forms a solid by removing the solvent from the solution in which the zirconium salt or oxyzirconium salt and the polyvinyl alcohol and the silver or copper salt coexist. 21. A process for producing an anti-microbial, anti-viral and / or anti-algal material according to claim 20, which is carried out by forming and contacting it with alkali to neutralize zirconium or oxyzirconium salts in the solid. After forming an inorganic / organic hybrid compound in which a zirconate compound containing a silver or copper compound and a polyvinyl alcohol are chemically bonded, the silver or copper compound is reduced to silver or copper in a metallic state by reducing with a reducing agent. 21. A method of producing the anti-microbial, anti-viral and / or anti-algal material of claim 20, characterized in that