TW202002789A - Agent having effect similar to effect realized under irradiation with light even when not irradiated with light, and method for preparing said agent - Google Patents

Abstract

Provided is an agent having an effect similar to an effect realized under intermittent irradiation with light over a long period of time even when not irradiated with light, the agent moreover making it possible to accomplish this effect in a short period of time. The agent having an effect similar to an effect realized under irradiation with light even when not irradiated with light according to one embodiment of the present application is characterized by including: composite particles in which silver particles and either titanium oxide or tungsten oxide particles are physically combined; (1) particles of at least one non-silver metal or metal oxide selected from among copper, copper oxide, nickel, zinc, tungsten, tungsten oxide, molybdenum, and molybdenum oxide; (2) a silver halide; and (3) at least one material selected from among silver-ion-supported zeolites.

Description

Formulation and its preparation method without light irradiation and still having the same effect as that under light irradiation

The present invention relates to a method that can be installed on the surface of paper, fabric, resin, metal, ceramics, composites and other substrates, such as bacteria, viruses, allergens, fungi, odorous substances or harmful substances, etc., without light irradiation A preparation and its preparation method that can exert the same effect as that under light irradiation for a long period of time, and can exert the effect in a short time.

Previously, bactericides and deodorants in solid or liquid form are well known. Among the solid bactericides and deodorants, there are many photocatalyst related technologies that use the redox ability of photocatalysts. Generally, the photocatalyst can work for a long time because it is insoluble, but it only works when there is ultraviolet light, but it does not work in dark places. In addition, because the photocatalyst is solid, it is caused by bacteria, viruses, allergens, and organic substances that cause various odors when it contacts and exerts a sterilizing and deodorizing effect. Therefore, it is more expensive until the sterilizing effect or deodorizing effect is exerted on the surrounding environment. Time. In contrast, liquid sterilants or deodorants such as alcohol and hypochlorite usually work without light, and immediately exert an excellent sterilization or deodorization effect on the surrounding environment, but due to immediate vaporization or evaporation, the Only works for a short time. Furthermore, in general, most liquid bactericides are still toxic, and therefore have the disadvantage of putting a load on the environment.

The previous photocatalyst has, for example, a structure in which metallic silver is supported on a carrier containing titanium dioxide. The free radicals generated by the redox reaction generated on the surface of the photocatalyst in the presence of ultraviolet light, bacteria, viruses, allergens, cause Organic substances of various odors are decomposed, thereby having sterilization effect and deodorization effect. However, the oxidation-reduction reaction only occurs at the boundary surface of the silver and titanium dioxide of the photocatalyst, and the reaction is very weak under visible light, so it is considered that there is a problem that the photocatalyst does not function in a darker environment.

On the other hand, Patent Documents 1 and 2 disclose the invention of a preparation containing silver particles and titanium dioxide particles, which exerts a sterilizing effect and a deodorizing effect even in the absence of light. This preparation is different from the one in which silver particles are supported on the surface of titanium dioxide particles, and it is a physical combination in which silver particles and titanium dioxide particles bite into each other. [Prior Technical Literature] [Patent Literature]

Patent Document 1: Japanese Patent No. 5995100 Patent Document 2: Japanese Patent Laid-Open No. 2016-199560 Patent Document 3: Japanese Patent No. 5129897 Patent Document 4: Japanese Patent Laid-Open No. 2014-193433 [Non-patent literature]

Non-Patent Literature 1: "Nihon Univ. Sch. Pham.", Vol. 55, pp. 1-18

[Problems to be solved by the invention]

According to the invention of the preparation disclosed in Patent Documents 1 and 2 above, there is no doubt as long as it is a place where there is light, and it exerts a specific sterilization or deodorizing effect even in the dark place where there is no light, and it can maintain the long-term maintenance of the Excellent effect. However, since the preparations disclosed in the above-mentioned Patent Documents 1 and 2 are solid, they exist until they exert a specific effect on the surrounding environment when compared with liquid bactericides or deodorants such as alcohol or hypochlorous acid. A more time-consuming subject.

Furthermore, in the above Patent Document 3, there is disclosed a titanium oxide having a rutile titanium oxide content of 50 mol% or more, and a monovalent copper compound and a divalent copper compound supported on the surface of the titanium oxide The copper compound supports the invention of titanium oxide photocatalyst. In addition, Patent Document 4 discloses an invention of a visible light-responsive hybrid photocatalyst obtained by subjecting copper ion-supported tungsten oxide particles and zeolite to a mechanochemical reaction. However, the above Patent Documents 3 and 4 do not show the provision of silver particles or copper particles, and are related to photocatalysts exhibiting catalytic activity under indoor light, but not those exhibiting catalytic activity even in the absence of light .

The inventors have repeatedly conducted various studies on the conditions disclosed in Patent Documents 1 and 2 to shorten the time until a specific effect is exhibited, and as a result, completed the present invention. That is, an object of the present invention is to provide a preparation that has the same effects as those under light irradiation for a long period of time without light irradiation, and can exert such effects in a short time. [Technical means to solve the problem]

The above-mentioned object of the present invention is achieved by the following configuration. That is, the preparation of the first aspect of the present invention which does not require light irradiation and still has the same effect as that under light irradiation is characterized by comprising: Composite particles formed by physically combining silver particles with titanium oxide or tungsten oxide particles, and At least one material selected from the following: (1) At least one metal or metal oxide particle other than silver selected from copper, copper oxide, nickel, zinc, tungsten, tungsten oxide, molybdenum, and molybdenum oxide, (2) Silver salt, (3) Silver ion supports zeolite.

The preparation of the first aspect of the present invention not only contains composite particles formed by physically combining silver particles with titanium oxide or tungsten oxide particles, but also contains at least one material selected from the following: (1) At least one metal or metal oxide particle other than silver selected from copper, copper oxide, nickel, zinc, tungsten, tungsten oxide, molybdenum, and molybdenum oxide, (2) Silver salt, (3) Silver ion supports zeolite.

Among them, composite particles in which silver particles and titanium oxide or tungsten oxide particles are physically combined are known components as preparations that have the same effect as that under light irradiation without light irradiation. The titanium oxide includes anatase type, rutile type, or brookite type, and may be any type of titanium oxide, or a mixture of two or more types.

In addition, in the material of (1), copper, nickel, and zinc are all metals that have a higher ionization tendency than silver. Therefore, if moisture is present in the surroundings, they will elute in the form of metal ions before silver. Similarly, tungsten and molybdenum are oxidized on a part of the surface in the air to form tungsten oxide and molybdenum oxide. If moisture exists in the surroundings, they are dissolved out in the form of tungstate ions or molybdate ions. Similarly, if water is present around the copper oxide, a part of the surface is hydrated and dissolved out in the form of copper ions.

Moreover, as the silver salt of (2), for example, soluble silver salts such as silver nitrate or silver acetate, silver oxide, silver hydroxide, silver molybdate, silver tungstate, silver carbonate, silver phosphate, silver sulfate, chromate, Insoluble silver salts such as silver halide and silver oxalate. In the case of easily soluble silver salts, if water exists around, it will immediately dissolve to generate silver ions, and in the case of insoluble silver salts, if water exists around, it will be determined by the solubility product of each compound. The amount of silver ions (and anions). In either case, if water is present in the surrounding area, silver ions are generated, so the initial bactericidal effect can be improved, especially in the case of soluble silver salts, if water is present in the surrounding area, it will immediately dissolve to generate silver ions, so Immediate effectiveness. Among them, for example, silver nitrate is designated as a hazardous substance according to the Toxic and Hazardous Substances Control Law in Japan. It is necessary to pay attention to the use of a very small amount. Furthermore, the silver ion-supported zeolite system of (3) is well-known as a silver-based inorganic antibacterial agent, and examples include Zeomic (manufactured by Sinanen Zeomic Co., Ltd.), Novaron (manufactured by Toa Synthetic Co., Ltd.), and the like. The silver ion-carrying zeolite also dissolves silver ions if moisture exists around it.

The ions formed by using at least one material selected from the above (1) to (3) all have an effect on the surroundings first compared to the effect of the composite particles, so as a result, the silver particles and titanium oxide or oxide The composite particles formed by the physical combination of tungsten particles exhibit specific effects in a shorter period of time. In addition, if at least one material selected from the above (1) to (3) exhibits a specific effect when moisture is present around it, even if it is in a dry state, it can be combined with the first state of the invention Moisture in materials contacted by such preparations, such as microorganisms, viruses, etc., internally produces the above-mentioned effects and exerts specific effects.

Furthermore, the effect of the preparation of the first aspect of the present invention is formed by ions formed by using composite particles and at least one material selected from the above (1) to (3), and the composite particles accompanying them As a result of the generation of free radicals in the process, the formation rate of these ions is relatively slow, so it becomes a long-term permanent effect, without biological toxicity, and it is not excellent for producing resistant bacteria.

In the preparation of this aspect that does not require light irradiation and still has the same effect as that under light irradiation, the composite particles are preferably combined in such a manner that the silver particles bite into the titanium oxide or tungsten oxide particles. The state in which one of the silver particles and the titanium oxide or tungsten oxide particles is not easy to bite into the other, or the one and the other bite into each other can also appear to be chimeric, and the physical bonding includes such bonding Appearance.

If the physical combination of silver particles and titanium oxide or tungsten oxide particles bites into place, there is no doubt when there is light irradiation, and when there is no light irradiation, it can also play better than when there is light irradiation. The effect is the same.

Furthermore, in the preparation of this aspect that does not require light irradiation and still has the same effect as that under light irradiation, at least one of the materials selected above may be carried on the composite particles, or may be further combined with Particles are physically combined.

If the silver particles in the composite particles are physically combined with the titanium oxide or tungsten oxide particles, then when it is deemed that at least one of the materials selected above is carried on the surface of the composite particles, when it is deemed that they are physically combined, There is no doubt that when there is light irradiation, the same effect as when there is light irradiation can also be exerted when there is no light irradiation.

In addition, in the preparation of this aspect that does not require light irradiation and still has the same effect as that under light irradiation, it is preferable that the particle diameter of the silver particles and the at least one material selected above is 100 nm to 1 μm .

The particle size of the silver particles and the at least one material selected above does not necessarily have a critical limit, and as long as it is in the range of 100 nm to 1 μm, the above effects are exhibited satisfactorily. Furthermore, if the particle size of the silver particles and the at least one selected material does not reach 100 nm, the dissolution rate of the silver particles and the at least one selected material becomes faster if moisture is present around it. The time until a specific effect is shortened, but especially because at least one of the materials selected above disappears in advance, the long-term effect is shortened. In addition, if the particle size of the silver particles and the at least one material selected above exceeds 1 μm, the long-term effect becomes good, but the time from the initial stage until the specific effect is exerted is extended.

In the preparation of this aspect that does not require light irradiation and still has the same effect as that under light irradiation, it is preferable that the content ratio of the silver particles in the composite particles is 100 parts by mass of titanium oxide or tungsten oxide particles 0.1 to 5.0 parts by mass, and the content ratio of the at least one material selected above is 2 to 7 parts by mass with respect to 100 parts by mass of titanium oxide or tungsten oxide particles.

If the content ratio of the silver particles in the composite particles is less than 0.1 parts by mass relative to 100 parts by mass of the titanium oxide or tungsten oxide particles, the content of the silver particles is too small to easily exert a specific effect. In addition, even if the content ratio of silver particles exceeds 5 parts by mass with respect to 100 parts by mass of titanium oxide, the effect is saturated and silver is expensive, which causes waste. The content ratio of the better silver particles in the composite particles is 0.2 to 3 parts by mass relative to 100 parts by mass of titanium oxide.

In addition, if the content ratio of the at least one selected material is less than 0.2 parts by mass with respect to 100 parts by mass of the titanium oxide or tungsten oxide particles, the content ratio of the at least one selected material is too small to exert a specific effect. Moreover, even if the content ratio of the at least one material selected above exceeds 7 parts by mass with respect to 100 parts by mass of titanium oxide or tungsten oxide particles, the effect is saturated. More preferably, the content ratio of the at least one material selected above is 2.5 to 4 parts by mass with respect to 100 parts by mass of titanium oxide or tungsten oxide particles.

In the preparation of this aspect that does not require light irradiation and still has the same effect as that under light irradiation, it is preferable to further contain 5 to 50 parts by mass of the adsorbent with respect to 100 parts by mass of titanium oxide or tungsten oxide particles. As the adsorbent, hydroxyapatite is preferred.

In the preparation of this aspect that does not require light irradiation and still has the same effect as that under light irradiation, whether or not an adsorbent is present, it is harmful to bacteria, fungi, viruses, allergens, odor substances and harmful substances. At least one of them works. In particular, if the adsorbent coexists, the adsorbent can adsorb bacteria, fungi, viruses, allergens, odor substances, harmful substances, etc. (hereinafter, these are sometimes collectively referred to as "objects to be processed"), so they can be combined The object to be treated is left in the vicinity of the particles and the at least one material selected above, and the above effects are exhibited satisfactorily. In addition, when hydroxyapatite is used as an adsorbent, the adsorption effect of the object to be treated is good, so the above effect is more effectively exhibited. In addition, the effect against bacteria, fungi and viruses is also called bactericidal effect.

In addition, the content ratio of the adsorbent is not a critical limit, and it is preferably 5 to 50 parts by mass with respect to 100 parts by mass of titanium oxide or tungsten oxide particles. If the content ratio of the adsorbent is less than 5 parts by mass with respect to 100 parts by mass of the titanium oxide or tungsten oxide particles, the effect of adding the adsorbent is not exerted. In addition, if the content ratio of the adsorbent exceeds 50 parts by mass with respect to the titanium oxide or tungsten oxide particles, the content ratio of the composite particles and at least one of the materials selected above is relatively reduced, so the above effects are reduced. In the case of using hydroxyapatite as the adsorbent, the content ratio of the better adsorbent is 20 to 30 parts by mass relative to 100 parts by mass of the titanium oxide or tungsten oxide particles.

Moreover, the material of the second aspect of the present invention is characterized in that it contains any of the preparations of the first aspect described above, and is provided for the following: (a) Woven fabric, non-woven fabric or paper, wood, resin, metal, ceramic, (b) Compounds containing any two or more of woven fabric, non-woven fabric, paper, wood, resin, metal and ceramic, (c) Any of paint, resin film, water, cleaning liquid, air filter, and printing ink.

According to the material of the second aspect of the present invention, a material that can exert any of the effects of the first aspect described above can be provided.

Among the materials of this aspect, the above-mentioned materials may be any of paint, resin film, or wallpaper applied to the surface of residential materials used indoors.

According to the material of this aspect, since the paint, resin film, or wallpaper can exhibit any of the effects of the above-mentioned first aspect, the surface of the residential materials used indoors can also exhibit any of the effects of the above-mentioned first aspect.

In the material of this aspect, the aforementioned material may be woven fabric, non-woven fabric or paper, and the aforementioned formulation may be impregnated or coated on the aforementioned material.

According to the material of this aspect, a woven fabric, non-woven fabric, or paper that can exert any of the effects of the first aspect described above can be obtained.

Among the materials in this aspect, the above-mentioned materials may be any of those used for drinking water, rainwater, hot springs, cooling towers, hydroponic cultivation, soil improvement, vegetable washing, food preservation, and food preservation.

According to the material of this aspect, it can be set to each supply target, and any effect of the above-mentioned first aspect can be exhibited.

Furthermore, the product of the third aspect of the present invention contains any one of the above-mentioned first formulations, and can be regarded as ・Choose from cushions, sheets, pillowcases, towels, handkerchiefs, face towels, curtains, quilt covers, blanket covers, chair covers, floor cushion covers, covers, tablecloths, carpets, air purification filters, water purification filters, air conditioners or Among the vehicles, ・Medical supplies selected from medical materials, medical materials, medical products, or medical equipment, ・Bad wounds, ointments, lotions, cosmetics and hand creams, gauze, catheters, endoscopes, bandages, white clothes, masks, air bags, buttons for medical instruments, or resin products for the medical field, ・A medicament for at least any of the diseases secondary to tinea pedis, burns, bedsores, atopic dermatitis, skin or epidermal damage, Furthermore, it can be used as a person having a sterilizing effect.

The product according to this aspect can be set to each product, and can exhibit any of the effects of the first aspect described above.

In addition, the preparation method of the fourth aspect of the present invention, which does not require light irradiation and still has the same effect as that under light irradiation, is characterized by having the following steps: The first step is to obtain composite particles formed by physically combining silver particles with titanium oxide or tungsten oxide particles; and The second step is to mix or stir the above composite particles with at least one material selected from the following: (1) At least one metal or metal oxide particle other than silver selected from copper, copper oxide, nickel, zinc, tungsten, tungsten oxide, molybdenum, and molybdenum oxide, (2) Silver salt, (3) Silver ion supports zeolite.

In the preparation method of the preparation which does not require light irradiation and still has the same effect as that under light irradiation, an adsorbent such as hydroxyapatite particles may be further added.

According to this aspect of the preparation that does not require light irradiation and still has the same effect as that under light irradiation, if the adsorbent coexists, the adsorbent can adsorb the object to be processed, so the composite particles and at least the selected The object to be treated is left near a material, and the above-mentioned effects are exerted well. In addition, if hydroxyapatite is used as an adsorbent, the adsorption effect of the object to be processed is good, so the above effect is exhibited more satisfactorily.

In the preparation method of the fourth aspect of the present invention which does not require light irradiation and still has the same effect as the effect under light irradiation, as the first step, it may include a group selected from the group consisting of the following steps step: (1) Through the steps of maintaining a high temperature area; (2) The steps of using ball mills to pressurize each other; and (3) The steps of simultaneously performing the operation of heating and mutual pressurization using any of the ball mill, high-temperature roller, and high-temperature ultrasonic compression bonding method.

In addition, in the step (1), the temperature may be a temperature higher than the melting point of silver (962°C), and may be, for example, about 1000°C to 3200°C. In this case, if the temperature of the area is high, the required composite particles can be produced in a very short time. When the temperature of the area is low, it takes enough time to produce the required composite particles, so the area The passing time may be appropriately set according to the temperature of the area.

In the preparation method of the preparation that does not require light irradiation and still has the same effect as that under light irradiation, in the step (2) or (3) above, it can be further added by adding to the ball mill An adsorbent, such as hydroxyapatite particles, is mixed or stirred to prepare.

If this method is adopted, there is no need to separately provide a step of mixing or stirring the hydroxyapatite particles and the composite particles, so the preparation step is simplified.

Furthermore, the preparation method of the fifth aspect of the present invention which does not require light irradiation and still has the same effect as that under light irradiation is characterized by: Silver particles, Titanium oxide or tungsten oxide particles, and At least one material selected from the following: (1) At least one metal or metal oxide particle other than silver selected from copper, copper oxide, nickel, zinc, tungsten, tungsten oxide, molybdenum, and molybdenum oxide, (2) Silver salt, (3) Silver ion supported zeolite Mix or stir in a ball mill to obtain a formulation in which at least silver particles are physically combined with titanium oxide or tungsten oxide particles.

In the preparation method of the preparation that does not require light irradiation and still has the same effect as that under light irradiation, the adsorbent particles, such as hydroxyapatite particles, can be added and mixed into the ball mill. And stir to prepare.

According to this aspect, a preparation method of a preparation that does not require light irradiation and still has the same effect as that under light irradiation, by oxidizing only silver particles, titanium oxide or tungsten oxide particles, and metals or metals other than silver The particles are mixed and stirred in the ball mill. Furthermore, by also mixing and stirring the hydroxyapatite particles in the ball mill, the invention can be prepared in one step without light irradiation. A preparation with the same effect.

Furthermore, the sixth aspect of the present invention includes a material having a bactericidal effect including a preparation that does not require light irradiation and still has the same effect as that under light irradiation: The above preparation has composite particles formed by physically combining metal particles with titanium oxide or tungsten oxide particles, The aforementioned metal particles are selected from gold, silver, platinum, copper, or a mixture of these, and The above-mentioned composite particles are included in the presence of soft water having a hardness of 60 or less and are adsorbed or coated on woven fabric, non-woven fabric, or paper.

According to this aspect, a material having a bactericidal effect including a preparation that does not require light irradiation and still has the same effect as that under light irradiation, and the composite particles are included in the presence of soft water with a hardness of 60 or less to be adsorbed or coated on the fabric For cloth, non-woven fabric or paper, the composite particles will not aggregate on the fiber surface of the woven fabric, non-woven fabric or paper, but will be substantially uniformly attached to the surface of the fiber. The material containing the woven fabric, non-woven fabric or paper with good sterilization effect can be obtained.

Furthermore, if the hardness of the soft water exceeds 60, the composite particles are easily aggregated, which is not good. More preferably, the hardness of the soft water system is 40 or less. As the hardness decreases, the composite particles become less likely to agglomerate, so the adsorption or coating time can be extended to allow more composite particles to be uniformly attached to the fiber surface of the woven fabric, non-woven fabric, or paper, and a better sterilization effect can be obtained. Materials of woven, non-woven or paper.

In this aspect, a material having a bactericidal effect including a preparation that does not require light irradiation and still has the same effect as that under light irradiation can be adsorbed together with adsorbent particles such as hydroxyapatite particles Or coated on woven, non-woven or paper.

According to the material having a sterilization effect according to this aspect, if adsorbent particles, such as hydroxyapatite, are used as the adsorbent, the adsorption effect of the object to be treated becomes good, so that a woven fabric containing a more excellent sterilization effect can be obtained , Non-woven or paper materials.

The material having a bactericidal effect in this aspect can be set to have an effect against at least one of allergens, odor substances, and harmful substances.

In the material having a sterilizing effect of this aspect, the above-mentioned composite particles can not only exert a sterilizing effect, but also exert an effect against at least one of allergens, odor substances, and harmful substances.

In the seventh aspect of the present invention, which contains a material having a sterilization effect and has a sterilization effect, the above-mentioned product can be selected from the group consisting of bedding, bed sheets, pillowcases, towels, handkerchiefs, face towels, curtains, and quilt covers , Blanket covers, chair covers, floor cushion covers, covers, tablecloths, carpets, air purification filters, or water purification filters; or selected from gauze, bandages, white clothes, masks.

In addition, the eighth aspect of the present invention includes a preparation method of a material having a bactericidal effect including a preparation that does not require light irradiation and still has the same effect as that under light irradiation: The above preparation has composite particles formed by physically combining metal particles with titanium oxide or tungsten oxide particles, The aforementioned metal particles are selected from gold, silver, platinum, copper, or a mixture of these, and After the woven fabric, non-woven fabric or paper is washed or wetted with soft water having a hardness of 60 or less, the composite particles are brought into contact with the composite particles before drying, thereby adsorbing or coating the composite particles on the woven fabric, non-woven fabric or paper.

In the method for preparing a material having a bactericidal effect that includes a preparation that does not require light irradiation and still has the same effect as that under light irradiation, the composite particles and the adsorbent can be adsorbed together or It is prepared by coating on the woven fabric, non-woven fabric, or paper.

Furthermore, in the method of preparing a material having a bactericidal effect, which includes a preparation that does not require light irradiation and still has the same effect as that under light irradiation, by the action of the above-mentioned composite particles, Non-woven fabric or paper can not only have a bactericidal effect, but also have an effect against at least one of allergens, odor substances and harmful substances. [Effect of invention]

As described above, the preparation according to the present invention that does not require light irradiation and still has the same effect as that under light irradiation can obtain at least one of bacteria, fungi, viruses, allergens, odor substances, and harmful substances It does not require light irradiation, and it still has the same effect as that under light irradiation for a long period of time, and it can exert these effects in a short time.

Hereinafter, the preparation of the present invention that does not require light irradiation and still has the same effect as that under light irradiation and the method of forming the same will be described in detail using various experimental examples. However, the various experimental examples shown below are examples for embodying the technical idea of the present invention, and it is not intended to specify the present invention as those shown in these experimental examples. The present invention can also be applied to other embodiments included in the scope of patent application.

[Preparation of the preparation of Experimental Example 1] In Experimental Example 1, first, according to the methods disclosed in the above-mentioned Patent Documents 1 and 2, composite particles in which silver particles and titanium dioxide particles were physically combined so as to bite in were prepared. As the adsorbent, for example, zeolite, sepiolite, apatite, activated carbon, etc. can be used, and because not only adsorbs and retains bacteria, fungi, viruses, allergens, but also adsorbs and retains unpleasant odor substances and harmful Substances and other objects can be used in the preparation of the present invention. In particular, the present invention uses hydroxyapatite which functions as an adsorbent. The size of the hydroxyapatite particles in the present invention is particularly preferably 0.3 to 50 μm in order to secure a wider surface area and to achieve good operation. The mixing ratio of the ceramic combined with the metal and the hydroxyapatite as the adsorbent is 100:1~50 in mass ratio, for example, it is ideal for playing bacteria, viruses, allergens, fungi, odor substances or harmful substances. The effect is especially good: 100:1~30. The preparation of the present invention can be prepared by mixing a ceramic combined with a metal and an adsorbent.

Furthermore, ceramics bonded to metals can be prepared using (1) the thermal bonding method shown in FIG. 1, (2) the pressure bonding method shown in FIG. 2, and (3) the thermal/pressure bonding method shown in FIG. 3.

In the thermal bonding method of (1), particles of ceramic (TiO ₂ ) and metal (silver) are bonded through the high-temperature region shown in FIG. 1. The purity of the silver used is 80-99.9%, and the purity of titanium dioxide is about 90-99%. During this process, part of the metal is ingrown into the interior of the ceramic particles. In this way, the metal particles and the ceramic particles are combined by one biting into the other, or the one biting into the other is biting into each other (or also appears to be fitted), that is, physical bonding. The temperature in the high-temperature region is substantially, for example, about 1000°C to 3200°C. By microscopic observation, it was confirmed that the obtained composite particles physically engaged with the silver particles and the titanium dioxide particles.

Furthermore, in the pressure bonding method of (2), ceramic and metal are combined by using the ball mill shown in FIG. 2. The ball mill has very hard balls containing materials such as alumina or zirconium. The balls are, for example, about 0.1 mm, 0.004 mg. Furthermore, in the thermal/compression bonding method of (3), as shown in FIG. 3, by simultaneously applying heating and pressurization, the particles of ceramic and metal can be combined. Furthermore, as a method of combining metal and ceramic, other methods such as a high-temperature roller and a high-temperature ultrasonic compression bonding method can also be used.

In Experimental Example 1, 0.5 g of silver particles with an average particle diameter of 300 nm, 80 g of anatase titanium dioxide particles with an average particle diameter of 250 nm, and hydroxyapatite with an average particle diameter of 1 μm (hereinafter, sometimes (Abbreviated as "Hy") 20 g was stirred and mixed for 1 to 2 hours in a laboratory ball mill using zirconia balls to prepare the preparation of Experimental Example 1 containing silver particles-titania particles-Hy particles. The rotation speed of the ball mill at this time is to rotate at a low speed in such a way that the titanium dioxide particles are not finely pulverized and become a physical bond between the silver particles and the titanium dioxide particles. There are also cases where the silver particles are in contact with the copper particles. In addition, the time when the hydroxyapatite is charged into the ball mill may be the same time as the silver particles and the titanium dioxide particles, or may be a specific time after the time when the silver particles and the titanium dioxide particles are charged. In addition, as described in the following modification 3, the adsorbent such as hydroxyapatite may be omitted.

The silver content in the preparation of Experimental Example 1 obtained corresponds to 0.6 parts by mass with respect to 100 parts by mass of titanium dioxide, and the content of hydroxyapatite corresponds to 25 parts by mass with respect to 100 parts by mass of titanium dioxide. 35 g of the obtained preparation of Experimental Example 1 was dispersed in 65 mL of distilled water to prepare a stock solution of the preparation of Experimental Example 1 having a solid content concentration of 35%.

[Preparation of the preparation of Experimental Example 2] In Experimental Example 2, with respect to 100.5 g of the preparation containing silver particles-titania particles-Hy particles prepared in the same manner as in Experimental Example 1, 1.5 g of copper particles with an average particle diameter of 300 nm were added and stirred in a ball mill Or mix for a few minutes. The silver particles-copper particles-titanium dioxide particles-Hy particles obtained in the above manner are physically combined by the way in which the silver particles and the titanium dioxide particles bite in, and the copper becomes attached to the surface of the titanium dioxide or hydroxyapatite, which essentially becomes a burden The state of being carried on the surface of titanium dioxide or hydroxyapatite. In addition, there is a part of copper and silver that are in contact, but they are not in a state of melting with each other. FIG. 4 is a schematic conceptual diagram showing the binding state of each component of the preparation obtained in Experimental Example 2. FIG.

The silver content in the preparation of Experimental Example 2 obtained corresponds to 0.6 parts by mass relative to 100 parts by mass of titanium dioxide, the same copper content corresponds to 1.8 parts by mass relative to 100 parts by mass of titanium dioxide, and the same content of hydroxyapatite corresponds to 100 parts by mass of titanium dioxide corresponds to 25 parts by mass. 35 g of the obtained preparation of Experimental Example 2 was dispersed in 65 mL of distilled water, and a stock solution of the preparation of Experimental Example 2 having a solid content concentration of 35% was prepared and used in various microbiological tests.

[Preparation of the preparation of Experimental Example 3] In Experimental Example 3, except that the addition amount of copper was set to 3.0 g, a preparation containing silver particles-copper particles-titania particles-Hy particles was prepared in the same manner as in the case of Experimental Example 2. The conceptual conceptual diagram of the obtained preparation of Experimental Example 3 is substantially the same as Experimental Example 2 shown in FIG. 4. The silver content in the preparation of Experimental Example 3 obtained corresponds to 0.6 parts by mass relative to 100 parts by mass of titanium dioxide, the same copper content corresponds to 3.6 parts by mass relative to 100 parts by mass of titanium dioxide, and the same content of hydroxyapatite corresponds to 100 parts by mass of titanium dioxide corresponds to 25 parts by mass. 35 g of the obtained preparation of Experimental Example 3 was dispersed in 65 mL of distilled water, and a stock solution of the preparation of Experimental Example 3 with a solid content concentration of 35% was prepared and used in various microbiological tests.

Table 1 summarizes the composition of the preparations of Reference Examples and Experimental Examples 1 to 3 prepared by the above method. In addition, the reference example is a water-only sample (blank). [Table 1]

[Measurement of bactericidal effect against Staphylococcus aureus] Using the preparations containing the silver particles-copper particles-titanium dioxide particles-Hy particles prepared in the above experimental examples 1 to 3, the effect against Staphylococcus aureus was measured . First, dilute the original solutions of the preparations of Experimental Examples 1 to 3 by 10 times, prepare 10 mL of the test solution of the preparations of Experimental Examples 1 to 3 with a solid content concentration of 3.5%, and further prepare 10 mL of distilled water as a reference example ( Blank) sample. To the blank sample obtained in the above manner and each sample of Experimental Examples 1 to 4, 0.1 mL of a 9.0×10 ⁷ cfu Staphylococcus aureus solution was mixed and kept in a thermostatic bath maintained at 25°C, shading on one side , While maintaining for 0 hours, 0.5 hours and 2 hours, the number of Staphylococcus aureus in each sample at this time was measured by the plate agar culture method. The results are summarized in Table 2, Figure 5 and Figure 6. In addition, FIG. 5 is a graph showing the relationship between contact time and the number of bacteria detected, and FIG. 6 is a graph showing the relationship between contact time and log (number of bacteria).

[Table 2]

If the results of Experimental Example 1 against Staphylococcus aureus are compared with the results of the preparations of Experimental Examples 2 and 3, the following will be known. That is, if not only silver and titanium dioxide are added, but copper is also added, it is confirmed that the initial sterilization effect is improved. Regarding the sterilization rate after 0.5 hours, Experimental Example 1 was 27.3%, compared with 39.1% for Experimental Example 2 and 84.0% for Experimental Example 3, and the sterilization effect was greatly improved. However, the improvement effect of the initial sterilization effect became stable with the passage of time. In the preparation of Experimental Example 3 with the largest amount of copper added, it became the substance of the preparation of Experimental Example 1 without copper after 2 hours. The same effect. The result of the preparation of Experimental Example 2 with a small amount of added copper became slightly worse than the bactericidal effect of the preparation of Experimental Example 1 without copper after 2 hours.

It is considered that the reason is that copper has a higher ionization tendency than silver, so if water is present in the surroundings, copper becomes copper ions and elutes. Therefore, in addition to the sterilization effect produced by silver and titanium dioxide, the sterilization effect produced by copper ions also increases. The effect of increasing the initial sterilization effect. However, the results of the preparations of Experimental Examples 2 and 3 after 2 hours became the same bactericidal effect (Experiment Example 3) as the preparation of Experimental Example 1 without copper (Experiment Example 3) or worse than the bactericidal effect (Experiment Example 2). It is speculated that the reason may be that the surface of the copper particles is heterogeneous, and there are parts that are easy to dissolve and parts that are difficult to dissolve. In the initial stage, they dissolve from the parts that are easily dissolved, so the sterilization effect is improved, and the parts that are easily dissolved by copper gradually disappear. Therefore, the sterilization effect produced by silver and titanium dioxide accounts for a large proportion.

Furthermore, from the results shown in Table 1, it can be seen that if the copper content ratio is 2 parts by mass or more with respect to 100 parts by mass of the titanium dioxide particles, a good sterilization effect is exhibited, and the greater the amount of copper added, the more the initial sterilization effect is confirmed Although the effect is too high, it saturates even if too much effect. Therefore, the content ratio of copper is preferably 7 parts by mass or less with respect to 100 parts by mass of the titanium dioxide particles. If these results are interpolated, it is considered that the better copper content ratio is 2.5 to 4 parts by mass relative to 100 parts by mass of titanium dioxide.

[Measurement of bactericidal effect against Escherichia coli] Using the preparations of Experimental Examples 1 to 3 prepared by the above method each containing silver particles-copper particles-titania particles-Hy particles, the effect against E. coli was measured. First, dilute the original solutions of the preparations of Experimental Examples 1 to 3 by 10 times, and prepare 10 mL of the test solution of the preparations of Experimental Examples 1 to 3 with a solid content concentration of 3.5%, respectively, and further prepare 10 mL of distilled water as a reference example (Blank) sample. To each of the blank samples obtained in the above manner and the samples of Experimental Examples 1 to 4, 0.1 mL of 5.0×10 ⁶ cfu of E. coli solution was mixed in a thermostatic bath maintained at 25° C. The number of Escherichia coli bacteria in the samples maintained at 0 hours, 0.5 hours and 2 hours was measured by the plate agar culture method. The results are summarized in Table 3, FIG. 7 and FIG. 8. Furthermore, FIG. 7 is a graph showing the relationship between contact time and the number of bacteria detected, and FIG. 8 is a graph showing the relationship between contact time and log (number of bacteria).

[table 3]

The results of Experimental Example 1 against E. coli and the results of the preparations of Experimental Examples 2 and 3 were obtained substantially the same as those against Staphylococcus aureus. That is, if not only silver and titanium dioxide are added, but copper is also added, it is confirmed that the initial sterilization effect is improved. Regarding the sterilization rate after 0.5 hours, Experimental Example 1 was 27.3%, compared with Experimental Example 2 was 39.1%, Experimental Example 3 was 84.5% and the sterilization effect was greatly improved. Among them, the improvement effect of this initial bactericidal effect becomes stable with time. In the preparation of Experimental Example 3 with the largest amount of copper added, it became the preparation of Experimental Example 1 without copper after 2 hours. Essentially the same effect. The result of the preparation of Experimental Example 2 with a small amount of added copper became slightly worse than the bactericidal effect of the preparation of Experimental Example 1 without copper after 2 hours. Regarding the reason, it is also believed that the difference in the addition of copper to Staphylococcus aureus is due to the same reason as the difference in bactericidal effect, and the preferred copper content ratio is also considered to be 100 parts by mass relative to the titanium dioxide particles It is preferably 7 parts by mass or less, and more preferably 2.5 to 4 parts by mass relative to 100 parts by mass of titanium dioxide.

In addition, according to the description of Non-Patent Document 1, the bactericidal effect against E. coli in water, in the case of silver ions, exhibits a sufficient sterilizing effect at a concentration of 5 ppm, in the case of copper ions In the case of 625 ppm, which is 100 times or more the silver ion concentration, it is shown that the sterilization effect is the same as when the silver ion concentration is 5 ppm. However, in the preparations of Experimental Examples 2 and 3 of this case, copper coexists with silver metal in the form of metal, and both copper metal and silver metal dissolve only a very small amount (or hardly dissolve) in about 2 hours. The concentration of copper ions in the test sample is also a few ppm to tens of ppm, and it is speculated that the concentration of silver ions is much less than it. That is, the preparation according to the present invention has extremely low copper ion concentration and silver ion concentration compared with those disclosed in the above-mentioned non-patent document 1, but as in the case of the above-mentioned non-patent document 1, it exerts a bactericidal effect against E. coli By using the form of the preparation of the present invention, a synergistic effect that cannot be predicted at all by using the aforementioned preparations such as Non-Patent Document 1 is exerted.

[Variation 1~3] In the above Experimental Examples 2 and 3, first, a preparation containing silver particles-titania particles-Hy particles (Experiment Example 1) was prepared, and then copper particles were added and stirred or mixed in a ball mill to prepare silver particles- Preparation of copper particles-titanium dioxide particles-Hy granules. However, the preparation of the present invention is not limited to such a composition. First, the titanium dioxide particles and the silver particles can be stirred or mixed in a ball mill, thereby preparing composite particles containing silver particles-titanium dioxide particles, and then adding copper particles. Next, hydroxyapatite particles were added to prepare a preparation of Variation 1 containing silver particles-copper particles-titanium dioxide particles-Hy particles. In the preparation of Modification 1, the titanium dioxide particles and the silver particles are physically bonded, and the copper particles are substantially supported on the titanium dioxide. In addition, the hydroxyapatite particles are bound in a state supported on titanium dioxide, silver particles, or copper particles.

In addition, first, the titanium dioxide particles, silver particles, and copper particles are stirred or mixed in a ball mill, thereby preparing composite particles including silver particles-copper particles-titanium dioxide particles, and then by carrying hydroxyapatite particles, The preparation of Variation 2 containing silver particles-copper particles-titanium dioxide particles-Hy particles can be prepared. In the preparation of Variation 2, the silver particles and the titanium dioxide particles are physically bonded by way of most bite, but copper is harder than silver, so part of the copper particles and titanium dioxide particles are physically bonded by way of bite, the remaining The copper particles are bonded in a state supported on the surface of titanium dioxide. In addition, hydroxyapatite is bonded in a state supported on the surface of titanium dioxide, silver particles, or copper particles.

Furthermore, first, the titanium dioxide particles and the silver particles can be stirred or mixed in a ball mill, thereby preparing composite particles containing silver particles-titania particles, and then adding copper particles to prepare a modified example containing silver particles-copper particles-titania particles. 3's preparation. That is, adsorbents such as hydroxyapatite are not combined with the preparation of Modification 3. In the preparation of Modification 3, the titanium dioxide particles and the silver particles are physically bonded by biting, and the copper particles are substantially bonded while being supported on the titanium dioxide. In Variation 3, for example, bacteria, viruses, allergens, fungi, odorous substances, or harmful substances can also be obtained, and the same effects as those under light irradiation can be continuously obtained for a long period of time without light irradiation, and Preparations that can exert these effects in a short time. Furthermore, the adsorbent such as hydroxyapatite may be omitted from the preparation of the above-mentioned modification 1 or modification 2. The schematic conceptual diagrams of the combined state of the components of the preparations of the modified examples 1 to 3 are shown in FIGS. 9 to 11.

In addition, in the above Experimental Examples 2 and 3, examples of using 300 nm as the particle diameter of silver particles and the average particle diameter of copper particles are shown, but the critical limits of these particle diameters are not clear as long as The range from 100 nm to 1 μm is sufficient. Furthermore, an example in which the content of silver particles is set to 6 parts by mass relative to 100 parts by mass of titanium dioxide is shown, but the critical limit of the content is not clear. In terms of operational effects and economic efficiency, it is relative to titanium dioxide 100 The mass parts may be in the range of 0.1 to 5 parts by mass, and more preferably 0.2 to 2 parts by mass.

In addition, in each of the above experimental examples, an example in which titanium dioxide particles are used as the metal oxide forming the composite particles together with the silver particles is shown, but even if tungsten oxide particles are used instead of titanium dioxide particles, it is the same as when titanium dioxide is used. There is no doubt that there is light irradiation, and when there is no light irradiation, the same effect as that when there is light irradiation can be exerted better.

In addition, in each of the above experimental examples, an example in which hydroxyapatite is used as the adsorbent is shown, but other well-known adsorbents such as zeolite, sepiolite, apatite, and activated carbon can also be used. The critical limit of the particle size of the adsorbent is not clear, but for example, when hydroxyapatite is used as the adsorbent, in order to ensure a wider surface area and to achieve good function, it is particularly preferably 0.3 to 50 μm.

Furthermore, the content ratio of the adsorbent is not critical, and it is preferably 10 to 50 parts by mass relative to 100 parts by mass of titanium dioxide or tungsten oxide particles. If the content ratio of the adsorbent is less than 10 parts by mass with respect to 100 parts by mass of the titanium dioxide or tungsten oxide particles, the effect of adding the adsorbent is not exerted. Furthermore, if the content ratio of the adsorbent exceeds 50 parts by mass with respect to the titanium dioxide or tungsten oxide particles, the content ratio of the composite particles and at least one of the materials selected above is relatively reduced, so the above effect is reduced. In the case of using hydroxyapatite as the adsorbent, the content ratio of the better adsorbent is 20 to 30 parts by mass relative to 100 parts by mass of the titanium dioxide or tungsten oxide particles.

In addition, in the above experimental examples, an example of using copper as at least one material selected from the following is shown: (1) At least one metal or metal oxide particle other than silver selected from copper, copper oxide, nickel, zinc, tungsten, tungsten oxide, molybdenum, and molybdenum oxide, (2) Silver salt, (3) Zeolite supported by silver ions, However, when other materials are used from these materials, for example, bacteria, viruses, allergens, fungi, odorous substances or harmful substances can be obtained without light exposure. A preparation that has the same effect and can exert these effects in a short time.

The preparation of the present invention may be applied by coating or the like in order to be used for objects such as wood, cloth, resin, metal, ceramics, concrete, etc., and these may also be used as an inner filler. The preparation of the present invention also becomes a beneficial material by being dispersed in water, organic solvents, adhesives and other dispersing agents during the period of such action.

In addition to the above-mentioned forms, the preparation of the present invention can also take the form of printing inks and paints. The purpose of these forms is also to provide sterilization, deodorization and decorative effects. The printing ink and other forms of the present invention are not limited to ceramics combined with metals and hydroxyapatite as an adsorbent, and at least also include colored materials and carriers. The printing ink also contains other ingredients if necessary. As the colored material, not only inorganic dyes (pigments) and organic pigments (pigments) (that is, colored materials commonly used as printing inks), but also dyes such as solvent dyes (organic solvent-dissolving dyes) and disperse dyes can be cited. As a carrier, the following can be mentioned as an example.

Examples include: dry oils such as linseed oil (linseed oil), semi-drying oils such as soybean oil, non-drying oils such as castor oil, or natural resins (rosin (rosin), modified rosin (modified Rosin), hard asphalt, etc.), natural resin-derived products, phenol resin, alkyd resin, xylene resin, urea resin, melamine resin, polyamide resin, acrylic resin, epoxy resin, ketone resin, petroleum resin, Resins such as polyvinyl chloride resins, vinyl acetate resins, urethane resins, chlorinated polypropylene, chlorinated rubber, cyclized rubber, cellulose-based derivatives, reactive resins, or plasticizers.

Examples of other materials include: natural wax, wax in synthetic wax, desiccant, dispersant, wetting agent, crosslinking agent, gelling agent, thickener, Anti-skin agent, stabilizer, flattening agent, defoaming agent, color unevenness preventing agent, antifungal agent, etc.

There is no critical limit for the mixing ratio of these ingredients, and the mixing ratio in common printing inks in the market can be used. Printing inks have bactericidal properties, in order to exert effects such as removing odors, so as to ensure proper printing ability, preferably 3 to 80% of the total mass of printing inks, preferably 10 to 80% The preparation of the present invention is added in a manner.

The form or type of printing ink is not particularly limited. It can be paste ink, oily ink, or solvent free ink. It can also be used as offset printing ink, lithographic printing ink, gravure printing ink, screen printing ink, letterpress printing ink or special printing ink. In order to achieve the best purpose of the invention, the screen printing ink is, for example, among the above types, preferably a screen printing ink for paper, a screen printing ink for resin, a screen printing ink for glass, Screen printing ink for metal, screen printing ink for cloth, etc.

In addition, other usage forms of the preparation of the present invention are shown below. The coating contains not only the preparation of the present invention, but also at least the film-forming component and the dispersant. If necessary, it may contain other ingredients. Examples of the film-forming component include cellulose-based derivatives, phthalate resins, phenol resins, alkyd resins, amine alkyd resins, acrylic resins, epoxy resins, urethane resins, and polychlorinated resins. Synthetic resins such as vinyl resins, silicone resins, fluororesins, emulsions (latex), water-soluble resins, vegetable dry oils, etc.

Examples of the dispersant include petroleum solvents, aromatic solvents, alcohol solvents, ester solvents, ketone solvents, cellosolve solvents, and water. In the case of powder coating, there is no need to be a solvent for the dispersant.

As other components, pigments (pigments) include, for example, inorganic pigments (pigments) such as titanium dioxide, lead chromate, iron red (Indian red), chromium oxide, and carbon black; Hansa yellow, Novoperm orange, and quinacridone violet , Copper phthalocyanine and other organic pigments (pigments); precipitated calcium carbonate, barium sulfate, talc, clay, white carbon and other physical pigments; zinc chromate, strontium chromate, zinc phosphate, aluminum phosphate, etc. Anti-corrosion pigments represent special functional pigments (pigments).

Furthermore, the following can be incorporated as auxiliary materials, for example, a desiccant that accelerates the drying of the paint film, a polymerization catalyst, a wetting agent, a pigment dispersant, a color unevenness preventing agent, and a pigment (pigment) Dispersion promoting non-hardener, tackifier, shaker, anti-sagging agent for fluidity adjustment of pigments (pigments), leveling agent, anti-foaming agent, anti-cracking for adjustment of painted surface Agent, anti-floating agent, anti-skin agent, antistatic agent, anti-friction agent, anti-blocking agent, ultraviolet light inhibitor, antifouling agent, antiseptic, antifungal agent, etc. There is no specific blending ratio of these ingredients, as long as it is appropriately determined according to the technical knowledge of those skilled in the art.

In this case, the ratio of common paints on the market can be used. The paint has bactericidal properties. In order to exert effects such as odor removal and to ensure proper paint properties, the preferred content of the preparation of the present invention is 3 to 80% of the total mass of the paint, particularly preferably 10 to 80% .

The coating method for coating is not particularly limited. Methods such as paint brush coating, air spray coating, non-air spray coating, electrostatic spray coating, powder coating, electroplating coating, shower screen coating, and roller brush coating can be used. The required area of the preparation of the present invention is not particularly limited, but varies according to the use of the preparation.

The preparation of the present invention can also be used in combination with liquids or preparations represented by ointments or lotions, which can be used on the human body or other surfaces, and is more effective for sterilization or deodorization. For example, it can also be used as cosmetics, hand cream 11, ointment, therapeutic ointment (secondary disease of tinea pedis, burns, bedsores, atopic dermatitis, wounds and other diseases related to the skin and epidermis ) And other products are mixed with liquid or agent.

In addition, the preparation of the present invention can be mixed not only with liquid solvents or agents, but also with resins, ceramics, adhesives and other products, and with raw materials for material production.

Furthermore, the preparation of the present invention can be attached to various materials such as paper, wood, cloth, resin, metal, concrete, and sterilized, and is more effective for removing odor and the like. In addition, the preparation of the present invention can also exert a decorative effect by printing into a desired shape or figure, and can be used for various decorations and other purposes when the use of light irradiation cannot be assumed. Furthermore, the preparation of the present invention can be attached to ceramics, metals, or composites, for example, for the purification of drinking water 12 shown in FIG. 12 (FIG. 13), the preservation of drinking water 12, the preservation of rainwater (FIG. 14), rainwater Reuse, storage tanks, ponds, washing of vegetables, hydroponic cultivation, cooling towers, baths, hot springs shown in Figure 15, soil improvement shown in Figure 16, food preservation, food preservation, drainage outlets, Figure 12 Various products such as the tile 13 shown, the humidifier 14 shown in FIG. 12, medical equipment, and the filler of the column.

In addition, the preparation of the present invention is attached to paper as a package for food preservation, filters, medical materials, medical products, wallpaper 15 shown in FIG. 12, sliding paper, partition paper, and furniture 16 shown in FIG. Materials such as materials, various kinds of wrapping paper, leather bags and other residential materials for products are more useful. In addition, by adhering to resin, resin products used in the medical field such as decorative films, protective films, food packaging films and other films, catheters, endoscopes, air bags, buttons for instruments, and personal computers 30 shown in FIG. 12, The telephone 17 shown in FIG. 12, the Jet Towel 18 shown in FIG. 12, products such as amusement facilities, the guardrail 19 shown in FIG. 12, and the ceiling materials 28 shown in FIG. 12 are useful for residential materials, etc. Materials required for other products are equally useful. In addition, it is also useful as a paste (focusing agent) contained in the raw materials of paper, woven fabric or non-woven fabric.

The preparation of the present invention is attached to a cloth (fabric material) and a woven cloth, and the cloth 21 shown in FIG. 12, the food materials shown in FIG. 12, the agricultural materials, the medical materials, and the wound plaster 22 shown in FIG. 12 , Gauze, bandages, white clothes 23 shown in FIG. 12, uniforms, masks 24 shown in FIG. 12, curtains 25 shown in FIG. 12, bed sheets, quilt covers, blanket covers, pillow covers, etc. shown in FIG. 12 (seat covers, floors Cushion covers, etc.), tablecloths, carpets 26, towels, handkerchiefs and other products are useful. It can also be used as a material for the air purification filter 27 shown in FIG. 12 or the water purification filter 29 shown in FIG. In addition, the preparation of the present invention can also be used for the air conditioner 31 and the vehicle 32 shown in FIG. 12. For example, it can also be used for filters of air conditioners 31, air conditioners of vehicles 32, seats, seat covers, interiors, etc. Furthermore, it can be used for the coating of buildings and other structures, the coating of various products, the addition of low-pollution paint to ships, bridges, docks (bridge posts), etc., to expel (avoid) barnacles, dragon insects Aquatic animals such as Surpula and Mussels. It can also be used to prevent the production of algae.

[Experiment example 4] In Experimental Example 4, the behavior when the preparation prepared in Experimental Example 1 and water having various hardnesses were impregnated or applied to woven fabric, non-woven fabric, or paper was investigated. First, prepare 12 kinds of commercially available mineral water and other water filled in PET bottles as water of various hardness. The hardness of the 12 types of water varies according to the place of origin or brand, and is distributed from 1612 to 9.9. For example, those with a hardness of 1612 are commercially available in the form of "Courmayeur" (trade name (the same below)), those with a hardness of 304 are commercially available in the form of "Evian", and those with a hardness of 60 are "Volvik" is available on the market. Those with a hardness of 30 are on the market in the form of "Natural Water of the Southern Alps", and those with a hardness of 9.9 are on the market in the form of "Natural Water of Kumano Ancient Road" On sale. In addition, pure water obtained by ion exchange resin is used for water with a hardness of 0.

First, at room temperature, 13 kinds of water with a hardness of 1612 to 0 are separately injected into the measuring cylinder so as to become 200 mL. Then, 10 mL of the stock solution of the preparation obtained in Experimental Example 1 was gradually added to each measuring cylinder, mixed thoroughly and allowed to stand, and the height (mm) of the preparation that aggregated and precipitated over time was measured. Table 4 summarizes the results.

[Table 4]

Then, 200 mL of water with hardness of 85, 60, and 30 was poured into the three beakers, and 10 mL of the original solution of the preparation obtained in Experimental Example 1 was added to each beaker. The sample was immersed for 5 minutes, after which excess water was wiped off with filter paper, and dried at 70°C for 5 minutes, thereby obtaining 3 pieces of cloth samples processed by the preparation of the present invention. Then, each of the three cloth samples obtained was observed with an electron microscope at a magnification of 1,000 times. The results are summarized in Figure 17. 17A is an electron microscope photograph when using the preparation of the present invention and water with a hardness of 85, FIG. 17B is an electron microscope photograph when using the preparation of the present invention and water with a hardness of 60, and FIG. 17C is a diagram using the preparation of the present invention and Electron microscope photograph of water with a hardness of 30.

From the results shown in Table 4, it can be seen that if the water hardness of the preparation obtained in Experimental Example 1 exceeds 60, it coagulates and precipitates after about 3 minutes, and coagulates and precipitates largely after 5 minutes. On the other hand, if the hardness of the water is 60 or less, it hardly aggregates even after 5 minutes, and substantially no precipitation is observed. In particular, if the hardness is 40 or less, there is almost no aggregation even after 10 minutes have passed, and substantially no precipitation is observed. In addition, the result shown in FIG. 17A shows that there is a large amount of agglomeration, and it becomes a defective product as a product. The result shown in FIG. 17B shows that there is little agglomeration, and it can be sufficiently applied as a commodity. Furthermore, according to the result shown in FIG. 17C, it can be seen that there is even less aggregation, and a product with good quality can be obtained.

Furthermore, when the preparation of Embodiment 1 is adsorbed or adhered, for example, impregnated or coated on fibers such as woven fabric, non-woven fabric, or paper, if the treatment time is about 1 minute and extremely short, regardless of the hardness of the coexisting water, It is not easy to cause agglomeration, but if the time spent in the drying and heat treatment steps after treatment is also considered, there may be agglomeration at this step, which may eventually adversely affect the quality of the product. Therefore, if the results shown in Table 4 and FIGS. 17A to 17C are considered together, it can be seen that in order to ensure the treatment time of 5 minutes or more, the hardness of the coexisting water is preferably set to 60 or less. In order to ensure a longer treatment time, the preferred water hardness is below 40. Furthermore, if the hardness of the water is 30 or less, the agglomeration is further reduced, which is better.

Next, the mechanism for adsorbing or adhering the preparation of the present invention to fibers such as woven fabric, non-woven fabric, or paper will be described using FIGS. 18 to 20. Furthermore, FIG. 18A is a conceptual diagram showing the steps of using a processing device with a drum-type washing machine to attach the preparation of the present invention and water of a specific hardness to the sewn clothes, and FIG. 18B is an example of the processing device of FIG. 18A. Concept map. Fig. 19 is a schematic view of a continuous processing apparatus for attaching the preparation of the present invention and specific soft water to the original sheet of the fiber product. Fig. 20 is a schematic view of a continuous processing apparatus for attaching the preparation of the present invention and specific soft water to the original sheet of the fiber product by the screen printing method.

The processing device 40 shown in FIG. 18A includes, for example, a drum-type washing machine used in a coin laundry, etc., and is provided in an internal drum 41 for supplying and discharging the preparation of the present invention. The organization of the specific mixed solution 42 of soft water. In a commercially available drum-type washing machine, although the illustration is omitted, a water supply line for supplying tap water and a drain line for discharging water from inside are provided. Therefore, as long as the water supply pipeline and the drain pipeline are connected halfway between the pipeline for supplying the mixed solution of the preparation of the present invention and a specific soft water, and the pipeline for discharging the mixed solution of the internal use agent, the electromagnetic Valves and electric pumps can control the inflow and outflow of each mixed solution. In addition, the preparation of the present invention and specific soft water are preferably prepared and supplied before use.

When processing the preparation of the present invention on the washed clothes or the clean and dry clothes before processing 43, as long as the clothes before processing 43 are put into the drum 41, a specific amount of the preparation of the present invention and specific The mixed solution 42 of soft water and the drum 41 are rotated in the same way as in the case of normal washing, so that the clothes 43 before processing can be sufficiently wetted with the mixed solution 42. Therefore, the number of rotations of the drum may be several times, and the rotation time may be several minutes, for example, about 2 to 3 minutes.

After the clothes 43 are fully wetted with the mixed solution 42 of the preparation of the present invention and the specific soft water before processing, the mixed solution 42 remaining in the drum 41 is recovered, and then subjected to dehydration treatment in the same manner as the normal washing. After the dehydration treatment is completed, the dehydrated clothes are taken out from the processing device 40 and dried by the drying device 44 at about 70°C, thereby obtaining the clothes 45 processed by the preparation of the present invention. The drying device 44 used for drying is not particularly limited as long as it can be statically heated to about 70°C. Furthermore, if a drum-type washing and drying device or a drum-type drying device is used for the drying process, the preparation of the present invention adhering or adsorbed to clothes may fall off, which is not preferable.

An example of such a processing device 40 having a tumble dryer will be described using FIG. 18B. The processing device 40 has a drum-type washing machine 50 equipped with a drum 41, and a tank 51 for storing a mixed solution of the preparation of the present invention and specific soft water. An opening 51a is formed in the upper portion of the tank 51, and the raw solution of the preparation of the present invention, specific soft water, adjusted mixed solution, or mixed solution stored in another container after use is injected into the tank 51 through the opening 51a. The stock solution of the preparation of the present invention is obtained by mixing the preparation of the present invention into a specific soft water so as to have a specific concentration. The drum type washing machine 50 can directly use a commercially available drum type, and is provided with a water supply line 52 for supplying tap water for washing and a drain line 53 for discharging water from the inside.

In the tank 51, for example, a mixed solution supply line 55 is provided for supplying the mixed solution 42 stored in the tank 51 to the drum-type washing machine 50 through the two ports of the three-way valve 54 from the bottom. The mixed solution supply line 55 is connected to the drum-type washing machine 50 via a liquid feed pump 56. In addition, the remaining ports of the 3-directional valve 54 are connected to an external drain pipe (not shown) via the drain channel 57. In addition, the liquid feed pump 56 and the 3-directional valve 54 of the mixed solution supply line 55 are connected to the liquid discharge tray 60 via the stop valve 58 and the discharge line 59.

In addition, the drain line 53 of the drum-type washing machine 50 is connected to the upper part of the tank 51 via the two ports of the filter 61, the return pump 62, the three-way valve 63, and the return flow path 64. The filter 61 is provided with a filter element (not shown) for filtering wire chips and the like, and a container 65 for catching water leakage is provided in the lower part. In addition, the filter 61 and the return pump 62 are connected to the drain tray 60 via a stop valve 66 and a drain line 67.

In addition, the remaining port of the three-way valve 63 is connected to another container 70 via a stop valve 68 and a discharge line 69. Furthermore, a water supply line 71 for supplying water of a specific hardness or tap water is connected to the upper portion of the tank 51. In addition, when the tap water system has a specific hardness, the water supply line 71 may be connected to the tap water pipe and directly supply tap water, or may be configured to switch between supplying tap water and soft water of a specific hardness.

The operation of the processing device 40 is performed as follows. First, the three-way valve 54 is switched so that the lower part of the tank 51 is connected to the mixed solution supply line 55 from the drain channel 57. Then, a specific amount of the stock solution of the preparation of the present invention is supplied from the opening 51a provided in the upper portion of the tank 51, and a specific amount of soft water is supplied from the soft water supply line 71, which is thoroughly stirred to prepare a mixed solution 42 containing a preparation of a specific concentration in advance .

The stop valves 58, 66, and 68 are closed in advance, the liquid feed pump 56 and the return pump 62 are closed in advance, and the filter element of the filter 61 (not shown) is removed in advance. Here, the laundry 43 to be treated (see FIG. 18A) is put into the drum 41, and if the power switch of the drum washing machine 50 is turned on, the drum 41 rotates, and the water remaining in the drum washing machine 50 passes through The drain line 53 and the filter 61 are sufficiently discharged into the container 65. An operation panel 50 a is provided on the drum-type washing machine 50. An operation mode switch (not shown) is provided on the operation panel 50a, for example. With the operation mode switch, for example, the following operation modes can be selected: (1) Stirring (2) Thin fabrics with a processing capacity of less than 10 kg (3) Thin fabric processing capacity 10 kg~15 kg (4) Thick fabric with a processing capacity of 10 kg or less (5) Thick fabric processing capacity 10~15 kg (6) Wash.

In the (1) stirring mode, as preparation for processing, the mixed solution 42 is injected into the drum-type washing machine 50 from the tank 51 by the liquid-feeding pump 56 while rotating the drum 41 to the mixed solution 42 in the drum-type washing machine 50 Stir. In the modes (2)~(5), the processing time or the rotation speed of the drum are automatically set according to the state of the processed object. (6) The washing mode is a mode in which the water supplied from the water supply line 52 is used to wash the drum-type washing machine 50 after the end of the process or before the start of the process. Furthermore, during the processing, the rotation direction of the drum is alternately switched to the forward rotation direction and the reverse rotation direction every certain time.

In addition to the operation mode switch, for example, an operation time setting switch, a drum rotation speed setting switch, etc. are provided on the operation panel 50a. By manual input using these switches, the processing conditions set by the operation mode switch can be adjusted. After the water remaining in the drum-type washing machine 50 is sufficiently discharged, a filter element is installed in the filter 61, and if the operation mode switch is set to agitation and the liquid feed pump 56 is turned on, the mixed solution 42 stored in the tank 51 will be stored It is automatically supplied to the drum-type washing machine 50 via the three-way valve 54, the mixed solution supply line 55, and the liquid feed pump 56, while stirring. Next, the laundry 43 is put into the drum-type washing machine 50, and the operation mode switch is selected to perform processing.

After the processing is temporarily ended, the clothes 43 that have completed the processing are taken out and dried in the dryer 44 (see FIG. 18A). Then, when the following processing is continued, after the clothes 43 to be processed are put into the drum 41 again, the same processing as described above is performed.

The laundry 43 is processed a certain number of times. When the laundry 43 is processed, the mixed solution 42 must be recovered so as not to deposit inside. The recovery process of the mixed solution is performed by turning off the liquid feed pump 56 and turning on the reflux pump 62. The mixed solution 42 in the drum-type washing machine 50 is recovered by the reflux pump 62 through the drain line 53, the filter 61, the three-way valve 63, and the reflux flow path 64 to the tank 51. In addition, the mixed solution 42 in the tank 51 may be transferred to an external storage tank (not shown) and stored.

In this case, there is no particular limitation, and the following operations can be performed: (1) The piping from the outlet side of the liquid feed pump 56 is switched to the storage tank, and the mixed solution 42 is transferred from the tank 51 to the liquid feed pump 56 Storage tank; (2) Switch the piping of the reflux pump 62, connect the piping of the inlet side of the reflux pump 62 to the tank 51, connect the piping of the outlet side of the reflux pump 62 to the storage tank, and use the reflux pump 62 to connect the mixed solution 42 Transfer from the tank 51 to the storage tank; (3) Use another pump (not shown) to transfer the mixed solution 42 from the tank 51 to the storage tank or the like.

The mixed solution 42 can be used for repeated processing multiple times, but in order to maintain the processing quality, a specific limit use number is determined. The mixed solution 42 exceeding the limit use number is passed through the discharge line 67, the discharge line 69, the discharge line 59 or The drain channel 57 etc. drains to an external drain pipe or the like.

Furthermore, tap water may be supplied into the drum-type washing machine 50 and the tank 51 through the water supply pipes 51 and 71 to wash the inside. The washing water after washing the drum-type washing machine 50 is drained to the drain tray 60 or an external drain pipe (not shown) through the drain line 67, for example. In addition, the washing water after washing the tank 51 is drained to an external drain pipe or the like via the drain channel 57, for example.

Furthermore, when only the clean and dry clothes are processed using the preparation of the present invention, as shown in FIGS. 18C and 18D, a spray nozzle 76 may be provided on the door 75 of the drum-type washing machine 50 to A mixed solution 77 of the preparation and specific soft water is sprayed and supplied from the spray nozzle 76 into the drum 41. In this case, the mixed solution of the preparation of the present invention and the specific soft water is immediately absorbed in the clothes 43 or attached to the surface of the clothes 43. In this way, specific bactericidal properties are imparted to the fiber products. In addition, the spray nozzle 76 is provided with a tank for storing the mixed solution 77, and all of the spray nozzle 76, or a part of its groove portion, etc. are set to a cylinder type, whereby replacement is possible, and mixing to the spray nozzle 76 can be omitted The piping of solution 77.

In addition, in the continuous processing device 80 shown in FIG. 19 for attaching the preparation of the present invention and specific soft water to the original sheet of the fiber product, the unprocessed original sheet 81 which is folded and supplied is passed through the roller 82 To the dipping tank 83. In the dipping tank 83, a mixed solution 84 of the preparation of the present invention and specific soft water is stored. The preparation of the present invention and specific soft water are absorbed or attached to the dipping tank 83, and the excess soft water is removed by the squeeze roller 85, and then the preparation of the present invention is fixed to the inside or the surface of the original sheet through the drying and heat treatment section 86. Thereby, the processed original sheet 87 is given a specific sterilization property, and is folded into a specific shape, or is omitted from the illustration, and wound into a roll shape by a roll.

In addition, in the continuous processing device 90 which uses the screen printing method to attach the preparation of the present invention and specific soft water to the original sheet of the fiber product, the unprocessed original sheet 91 supplied by folding is passed through The roller 92 passes through the stage 94 of the screen printing device 93. The screen printing device 93 is provided with a screen mask 95 forming a specific pattern on the bottom, and a mixed solution 96 of the preparation of the present invention and specific soft water is stored on the upper part. The unprocessed original 91 passes between the stage 94 of the screen printing device 93 and the screen mask 95. To the mixed solution 96 of the preparation of the present invention and specific soft water used here, a pre-specified pigment (pigment or dye) may be mixed.

In the continuous processing device 90, the unprocessed original film moves intermittently. The unprocessed original film that is still on the table 94 of the screen printing device 93 is displayed by the screen printing device 93 to be sandwiched between the table 94 and the screen mask 95. In this state, the doctor blade 96 is driven to The untreated original film is printed in a specific pattern using a mixed solution 95 of the preparation of the present invention and a specific soft water. This operation is the same as the usual screen printing.

Using the screen printing device 93, the original film printed by the mixed solution 66 of the preparation of the present invention and a specific soft water in a specific pattern is intermittently passed through the drying and heat treatment section 97 to fix the preparation of the present invention to the original film Internal or surface. As a result, the original sheet 98 after the sterilization is given to a specific pattern is folded into a specific shape, or the illustration is omitted, and the roll is wound up by a roll. In the continuous processing device 90, a specific pigment is preliminarily mixed into the mixed solution 66 of the preparation of the present invention and specific soft water, thereby not only forming sterilization on the untreated original sheet, but also forming a specific pattern Pattern, so it is more useful if the plain color is used as the unprocessed original film.

In addition, FIGS. 18-20 shows the structure which sterilizes a fiber product or an original sheet mechanically, but it is not limited to this, and sterilization can be given to a fiber product or an original sheet manually. For example, as shown in FIG. 21A, the preparation of the present invention, specific soft water and spray can be injected into a spray can, and the preparation of the present invention and specific soft water can be sprayed in a spray form toward the surface of the fiber product or original sheet. Drying, thereby imparting sterilization to specific fiber products or original sheets. Furthermore, as shown in FIG. 21B, the preparation of the present invention and specific soft water may be poured into a container such as a bucket or a basin, immersed in a specific fiber product or original sheet, dehydrated, and dried to thereby remove the specific fiber product Or the original film imparts bactericidal properties.

In addition, in Experimental Example 4, the preparation prepared in Experimental Example 1 is described as an example, but even if the preparation prepared in Experimental Example 2, Experimental Example 3, or Variation Examples 1 to 3, etc. is used, Similarly, the preparation is adsorbed or attached, for example, impregnated or coated on fibers such as woven cloth, non-woven cloth or paper.

As described above, the preparation of the present invention adsorbs to bacteria, fungi, and viruses in the same manner as malodorous substances or toxic substances. Following or simultaneously with this adsorption, bacteria, fungi, viruses, etc. decompose. Furthermore, even if the effect of the preparation of the present invention is not decomposed, its growth can be stopped or not approached. In addition, the preparation of the present invention does not require light irradiation and still has the same effect as light irradiation at room temperature for humans living on the earth at room temperature. Furthermore, bacteria, fungi, viruses, etc. containing proteins are decomposed and annihilated, so the above effect does not decrease over time and continues semi-permanently.

The proliferation of bacteria and fungi prefer high temperature and high humidity conditions. The preparation of the present invention is particularly effective under high temperature and high humidity conditions, so it is more effective against bacteria and fungi. The bactericidal ingredient in the preparation of the present invention is insoluble. The preparation of the present invention can be used for killing and inhibiting bacteria, fungi, and other undesirable microorganisms. In the case of residential, hospitals, nursing facilities, public places, food factories, water plants and other places that require public health, bacterial management, odor management, etc., it is difficult to cope with the situation using only one product, by applying the preparation of the present invention It is used together with a plurality of products, and these products can be freely combined and used as a "system" according to needs, which can sterilize and deodorize extremely efficiently. In order to obtain further effects in a wider field, the preparation of the present invention can be used as a novel with immediate effect and sustainability by using (combining) both existing pharmaceuticals, various products or systems used Sterilization system (sterilization method). For example, after first sterilizing with alcohol, the preparation of the present invention can be used to maintain a sterilized state for a long time.

In addition, since the preparation of the present invention does not substantially dissolve, it does not put a load on the environment. Previously, there were various medicines used to deodorize viruses, deactivate allergens, and deodorize allergens. However, such medicines have the fact that the more effective they are, the more internally they cause damage to the human body and nature. However, since the preparation of the present invention is insoluble in water and effective for a long time, it does not cause adverse effects on the environment. Furthermore, there is no need for light irradiation to have long-term and continuous effects under light irradiation and the same effects under natural light, and the application range is wide, which is helpful to the industry.

11‧‧‧Hand Cream 12‧‧‧ drinking water 13‧‧‧ Tile 14‧‧‧Humidifier 15‧‧‧ wallpaper 16‧‧‧furniture 17‧‧‧Telephone 18‧‧‧Jet Towel 21‧‧‧ cloth 22‧‧‧Stumbling plaster 23‧‧‧White 24‧‧‧ mask 25‧‧‧ curtains 26‧‧‧Carpet 27‧‧‧Air purification filter 28‧‧‧Ceiling materials 29‧‧‧Water purification filter 30‧‧‧PC 31‧‧‧Air conditioning 32‧‧‧Vehicle 40‧‧‧Processing device 41‧‧‧Roller 42‧‧‧ Mixed solution 43‧‧‧ Clothes before processing 44‧‧‧Drying device 45‧‧‧ Clothes after processing 50‧‧‧Drum washing machine 50a‧‧‧Operation panel 51‧‧‧slot 51a‧‧‧(slot) opening 52‧‧‧Water supply pipeline 53‧‧‧Drainage pipeline 54‧‧‧Three-way valve 55‧‧‧ Mixed solution supply line 56‧‧‧Liquid delivery pump 57‧‧‧Drainage flow path 58‧‧‧Stop valve 59‧‧‧Discharge line 60‧‧‧Drain tray 61‧‧‧filter 62‧‧‧Backflow pump 63‧‧‧Three-way valve 64‧‧‧Return flow path 65‧‧‧Container 66‧‧‧Stop valve 67‧‧‧Discharge line 68‧‧‧Stop valve 69‧‧‧Discharge line 70‧‧‧Container 71‧‧‧Water supply pipeline 75‧‧‧ door 76‧‧‧ spray nozzle 80‧‧‧Continuous processing device 81‧‧‧ unprocessed original film 82‧‧‧Roll 83‧‧‧Immersion tank 84‧‧‧ Mixed solution 85‧‧‧Squeeze roller 86‧‧‧Drying and heat treatment department 87‧‧‧The original film after processing 90‧‧‧Continuous processing device 91‧‧‧ unprocessed original film 92‧‧‧roll 93‧‧‧ Screen printing device 94‧‧‧ 95‧‧‧ screen mask 96‧‧‧ Mixed solution 97‧‧‧Drying and heat treatment department 98‧‧‧The original film after processing

FIG. 1 is a diagram showing a method of thermally bonding a ceramic and a metal of the present invention. Fig. 2 is a diagram showing a method of pressure bonding ceramic and metal of the present invention. Fig. 3 is a diagram showing a method of applying heat/pressure bonding to the ceramic and metal of the present invention. 4 is a schematic conceptual diagram showing the binding state of each component in the preparation of Experimental Example 2. FIG. 5 is a graph showing the bactericidal effect of Staphylococcus aureus using the preparations of various experimental examples. FIG. 6 is a graph showing the vertical axis of FIG. 5 as log (number of bacteria (cfu/mL)). 7 is a graph showing the bactericidal effect of E. coli using the preparations of various experimental examples. FIG. 8 is a graph showing the vertical axis of FIG. 7 as log (number of bacteria (cfu/mL)). 9 is a schematic conceptual diagram showing the binding state of each component in the preparation of Modification 1. FIG. FIG. 10 is a schematic conceptual diagram showing the binding state of each component in the preparation of Modification 2. FIG. 11 is a schematic conceptual diagram showing the combined state of the components in the preparation of Modification 3. FIG. Fig. 12 is a diagram of the preparation of the present invention used in various products. Fig. 13 is a diagram of the preparation of the present invention used in drinking water. Fig. 14 is a diagram of the preparation of the present invention used in the preservation of drinking water. Fig. 15 is a diagram of the preparation of the present invention used in storage for cooling towers. Fig. 16 is a diagram of the preparation of the present invention used in soil improvement. FIG. 17A is an electron microscope photograph when using the preparation of the present invention and water with hardness 85, FIG. 17B is an electron microscope photograph when using the preparation of the present invention and water with hardness 60, and FIG. 17C is a diagram using the preparation of the present invention and hardness 30 Electron microscope photo of water time. Fig. 18A is a conceptual diagram showing the steps of attaching the preparation of the present invention and water of a specific hardness to the sewn clothes using a processing device with a drum-type washing machine, and Fig. 18B is a conceptual diagram showing an example of the processing device of Fig. 18A. Fig. 18C is a plan view of a processing apparatus for supplying the preparation of the present invention and water of a specific hardness by spray, and Fig. 18D is a side cross-sectional view of Fig. 18C. Fig. 19 is a schematic view of a continuous processing apparatus for attaching the preparation of the present invention and specific soft water to the original sheet of the fiber product. Fig. 20 is a schematic view of a continuous processing apparatus for attaching the preparation of the present invention and specific soft water to the original sheet of a fiber product by a screen printing method. Fig. 21A is a diagram showing an example in which the preparation of the present invention and water of a specific hardness are supplied to a fiber product using a spray can, and Fig. 21B is a diagram showing an example in which the fiber product is immersed in the same container.

Claims (37)

A preparation that does not require light irradiation and still has the same effect as that under light irradiation, is characterized by comprising: Composite particles formed by physically combining silver particles with titanium oxide or tungsten oxide particles, and At least one material selected from the following: (1) At least one metal or metal oxide particle other than silver selected from copper, copper oxide, nickel, zinc, tungsten, tungsten oxide, molybdenum, and molybdenum oxide, (2) Silver salt, (3) Silver ion supports zeolite. A preparation as claimed in claim 1 that does not require light irradiation and still has the same effect as that under light irradiation, wherein the composite particles perform one of the silver particles and the titanium oxide or tungsten oxide particles into the other A combination, or a combination in which one bites into another. The preparation as claimed in claim 1 or 2 which does not require light irradiation and still has the same effect as that under light irradiation, wherein at least one of the materials selected above is carried on or physically combined with the composite particles. The preparation as claimed in any one of claims 1 to 3, which does not require light irradiation and still has the same effect as that under light irradiation, wherein the particle diameter of the above silver particles and at least one selected material is 100 nm~ 1 μm. A preparation as claimed in any one of claims 1 to 4 which does not require light irradiation and still has the same effect as that under light irradiation, wherein the content ratio of the silver particles in the composite particles relative to the titanium oxide or oxidation 100 parts by mass of tungsten particles are 0.1 to 5.0 parts by mass, and The content ratio of the at least one material selected above is 2-7 parts by mass with respect to 100 parts by mass of the titanium oxide or tungsten oxide particles. The preparation according to any one of claims 1 to 5 which does not require light irradiation and still has the same effect as that under light irradiation, which contains the adsorbent 5 relative to 100 parts by mass of the above-mentioned titanium oxide or tungsten oxide particles ~50 parts by mass. A preparation as claimed in any one of claims 1 to 6 which does not require light irradiation and still has the same effect as that under light irradiation, wherein the above effects are directed against bacteria, viruses, allergens, fungi, odorous substances and harmful substances The effect of at least one of the substances. A material comprising the preparation according to any one of claims 1 to 7. If the materials in claim 8, the above materials are any of the following: (a) Woven fabric, non-woven fabric, paper, wood, resin, metal or ceramic, (b) Compounds containing any two or more of woven fabric, non-woven fabric, paper, wood, resin, metal and ceramic, (c) Paint, resin film, aqueous solution, cleaning solution or printing ink. The material according to claim 8, wherein the above-mentioned material is any one of paint, resin film or wallpaper applied to the surface of residential materials used indoors. The material according to claim 8, wherein the above-mentioned material is woven fabric, non-woven fabric or paper, and the above-mentioned preparation is impregnated or coated on the above-mentioned material. The material according to claim 8, wherein the above-mentioned materials are used for drinking water, rainwater, hot springs, cooling towers, hydroponic cultivation, soil improvement, vegetable washing, food preservation, and food preservation. An article comprising the preparation according to any one of claims 1 to 7. The product according to claim 13, wherein the product is selected from the group consisting of bedding, bed sheets, pillowcases, towels, handkerchiefs, face towels, curtains, quilt covers, blanket covers, chair covers, floor cushion covers, covers, tablecloths, carpets, and air purification Filters, water purification filters, air conditioners, or vehicles. The product according to claim 13, wherein the above product is a medical product selected from medical materials, medical materials, medical products, or medical equipment. The product according to claim 15, wherein the above product is selected from the group consisting of a plaster, ointment, lotion, cosmetics and hand cream, gauze, catheter, endoscope, bandage, white coat, mask, air bag, medical button or medical device Resin products used in the field. The product according to claim 15, wherein the above-mentioned product is selected from the group consisting of agents for at least any one of diseases secondary to tinea pedis, burns, bedsores, atopic dermatitis, skin or epidermal damage. The product according to claim 15, wherein the above product has a bactericidal effect. A preparation method of a preparation that does not require light irradiation and still has the same effect as that under light irradiation is characterized by the following steps: The first step is to obtain composite particles formed by physically combining silver particles with titanium oxide or tungsten oxide particles; and The second step is to mix or stir the above composite particles with at least one material selected from the following: (1) At least one metal or metal oxide particle other than silver selected from copper, copper oxide, nickel, zinc, tungsten, tungsten oxide, molybdenum, and molybdenum oxide, (2) Silver salt, (3) Silver ion supports zeolite. The preparation method of the preparation of claim 19 that does not require light irradiation and still has the same effect as that under light irradiation, in which adsorbent particles are further added. If the preparation method of claim 19 does not require light irradiation and still has the same effect as the effect under light irradiation, the above-mentioned first step includes a step selected from the group consisting of: (1) Through the steps of maintaining a high temperature area; (2) The steps of using ball mills to pressurize each other; and (3) The steps of simultaneously performing the operation of heating and mutual pressurization using any of the ball mill, high-temperature roller, and high-temperature ultrasonic compression bonding method. If the preparation method of claim 21 does not require light irradiation and still has the same effect as the effect under light irradiation, in the step (2) or (3) above, the adsorbent particles are further added to the ball mill And mix or stir. A preparation method of a preparation that does not require light irradiation and still has the same effect as that under light irradiation, is characterized by: Titanium oxide or tungsten oxide particles, and At least one material selected from the following: (1) At least one metal or metal oxide particle other than silver selected from copper, copper oxide, nickel, zinc, tungsten, tungsten oxide, molybdenum, and molybdenum oxide, (2) Silver salt, (3) Silver ion supported zeolite Mix or stir in a ball mill to obtain a formulation in which at least silver particles are physically combined with titanium oxide or tungsten oxide particles. The preparation method of the preparation of claim 23 which does not require light irradiation and still has the same effect as that under light irradiation, wherein the adsorbent particles are further added to the above-mentioned ball mill and mixed or stirred. A material having a bactericidal effect that contains a preparation that does not require light irradiation and still has the same effect as that under light irradiation, characterized in that the preparation has a composite of metal particles and titanium oxide or tungsten oxide particles physically combined particle, The aforementioned metal particles are selected from gold, silver, platinum, copper, or a mixture of these, and The above-mentioned material is contained in the presence of water with a hardness of 60 PPM or less, and the above-mentioned preparation is adsorbed or adhered to a fiber containing at least one kind of woven fabric, non-woven fabric, or paper. The material having a bactericidal effect according to claim 25, wherein the above-mentioned preparation is adsorbed or attached to the above-mentioned fiber together with the adsorbent. The material having bactericidal effect according to claim 25 or 26 further has an effect against at least one of allergens, odor substances and harmful substances. A product having a bactericidal effect, which comprises the material having a sterilizing effect according to any one of claims 25 to 27. The product with sterilization effect according to claim 28, wherein the above-mentioned products are selected from the group consisting of bedding, bed sheets, pillowcases, towels, handkerchiefs, face towels, curtains, quilt covers, blanket covers, chair covers, floor cushion covers, covers, tablecloths, Carpets, air purification filters, water purification filters, gauze, bandages, white clothing, or masks. A method for preparing a material having a bactericidal effect including a preparation that does not require light irradiation and still has the same effect as that under light irradiation, characterized in that the preparation has metal particles and titanium oxide or tungsten oxide particles physically combined Into composite particles, The aforementioned metal particles are selected from gold, silver, platinum, copper, or a mixture of these, and The above-mentioned preparation method is to adsorb or attach the above-mentioned preparation to fibers containing at least one of woven cloth, non-woven cloth, or paper in the presence of water having a hardness of 60 PPM or less. The method for preparing a material having a bactericidal effect according to claim 30, wherein the preparation and the adsorbent are adsorbed or attached to the fiber. A method for preparing a material having a bactericidal effect according to claim 30 or 31, wherein the above-mentioned material further has an effect against at least one of allergens, odor substances, and harmful substances. A material having a bactericidal effect that contains a preparation that does not require light irradiation and still has the same effect as that under light irradiation, characterized in that the preparation includes: Composite particles formed by physically combining titanium oxide or tungsten oxide particles, and At least one material selected from the following: (1) At least one metal or metal oxide particle other than silver selected from copper, copper oxide, nickel, zinc, tungsten, tungsten oxide, molybdenum, and molybdenum oxide, (2) Silver salt, (3) Silver ion supported zeolite; and The above-mentioned material is contained in the presence of water with a hardness of 60 PPM or less, and the above-mentioned preparation is adsorbed or adhered to a fiber containing at least one kind of woven fabric, non-woven fabric, or paper. The material with bactericidal effect according to claim 33, wherein the above-mentioned preparation is adsorbed or attached to the above-mentioned fiber together with the adsorbent. The material having sterilization effect according to claim 33 or 34, in turn, has an effect against at least one of allergens, odor substances and harmful substances. A product having a bactericidal effect, which comprises the material having a sterilizing effect according to any one of claims 33 to 35. A method for preparing a material having a bactericidal effect comprising a preparation that does not require light irradiation and still has the same effect as that under light irradiation, characterized in that the preparation includes: Composite particles formed by physically combining silver particles with titanium oxide or tungsten oxide particles, and At least one material selected from the following: (1) At least one metal or metal oxide particle other than silver selected from copper, copper oxide, nickel, zinc, tungsten, tungsten oxide, molybdenum, and molybdenum oxide, (2) Silver salt, (3) Silver ion supported zeolite; and The above-mentioned preparation method is to adsorb or attach the above-mentioned preparation to fibers containing at least one of woven cloth, non-woven cloth, or paper in the presence of water having a hardness of 60 PPM or less.

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