JP6838034B2 - Antiviral member - Google Patents

Description

The present invention relates to antimicrobial components.

In recent years, so-called "pandemics", in which infectious diseases mediated by various microorganisms that are pathogens spread rapidly in a short time, have become a problem, such as SARS (Severe Acute Respiratory Syndrome), norovirus, and bird flu. Deaths from viral infections have also been reported.

Therefore, antiviral agents that exert antiviral activity against various viruses are being actively developed, and antiviral agents composed of metals such as Pd and organic compounds that actually have antiviral activity on various members. It is practiced to apply a resin or the like containing the above-mentioned material, or to manufacture a member containing a material on which an antiviral agent is carried.

Patent Document 1 is characterized in that it is a molded product having a layer made of a curable resin containing an inorganic antibacterial agent and a metal oxide on its surface, and the inorganic antibacterial agent is a fatty acid-modified metal ultrafine particle. The molded product to be used is disclosed.

Patent Document 2 discloses an antibacterial base material to which antibacterial activity is imparted by forming a plurality of antibacterial metal islands on the surface of the base material.

Japanese Unexamined Patent Publication No. 2015-105252 Republished 2008-47810

However, in the molded product described in Patent Document 1, the layer made of the curable resin is a continuous layer formed on the surface of the molded product, and the color, pattern, arrangement, etc. of the surface of the molded product are decorative. When the above-mentioned resin layer is formed on the surface of the devised molded product, there is a problem that the aesthetic appearance of the above-mentioned molded product is spoiled.

In the antibacterial base material described in Patent Document 2, it is disclosed that antibacterial metal islands having an average diameter of 5 to 500 nm are fixed to the surface of the base material, but sufficient antibacterial properties commensurate with the fixed amount of the antibacterial metal. , There was a problem that antiviral activity was not obtained.

The present invention has been made in view of such a problem, has high antimicrobial activity per unit area of an antimicrobial binder cured product, and has characteristics such as color and pattern formed on the surface of a substrate. It is an object of the present invention to provide an antimicrobial member that can be maintained as it is without damaging the above.

The antimicrobial member of the present invention is characterized in that a cured binder containing an antimicrobial component is fixed to the surface of the base material, and the cured binder covers 10 to 55% of the surface of the base material. And.

The antimicrobial component in the antimicrobial member of the present invention is a concept including antiviral, antibacterial, antifungal, and antifungal. Therefore, the antimicrobial component is a concept including an antiviral component, an antibacterial component, an antifungal component, and an antifungal component, and the antimicrobial agent includes an antiviral agent, an antibacterial agent, an antifungal agent, and an antifungal agent. It is a concept, and the antimicrobial composition is a concept including an antiviral composition, an antibacterial composition, an antifungal composition, and an antifungal composition.

In the present specification, the antimicrobial member may be a member exhibiting any one of antiviral, antibacterial, antifungal and antifungal activity, and among antiviral, antibacterial, antifungal and antifungal members. , A member exhibiting any two types of activity, a member exhibiting any three types of activity, or a member exhibiting all four types of activity.
Among the antimicrobial properties of the antimicrobial member of the present invention, it is particularly effective for antiviral and antifungal, and the antiviral has the highest activity.

In the antimicrobial member of the present invention, a binder cured product containing an antimicrobial component is formed on the surface of the substrate so as to expose a part of the surface of the substrate. On the surface of the base material, a region in which a cured binder containing an antimicrobial component is formed and a region in which a cured binder is not formed are mixed, and in particular, the cured binder is scattered in an island shape. Is desirable. This is because the total surface area of the cured binder can be increased by forming the cured binder in an island shape, and the design of the base material is not impaired.

In the antimicrobial member of the present invention, the binder cured product containing the antimicrobial component is scattered in an island shape on the surface of the base material, or the area where the binder cured product containing the antimicrobial component is formed and the binder cured product are formed. Since the cured binder covers 10 to 55% of the surface of the base material, the cured binder does not become thick and the surface area can be increased. It is possible to provide an antimicrobial member having high antimicrobial activity per unit area of an antimicrobial binder cured product.
Therefore, sufficient antimicrobial performance can be realized with the minimum necessary antimicrobial composition.
Further, since the surface area of the cured binder showing antimicrobial properties can be increased, the contact probability between the cured binder showing antimicrobial properties and microorganisms such as viruses can be increased, and between the cured binders. Since it is possible to easily trap microorganisms such as viruses in the gaps between the two, it is easy to inactivate microorganisms such as viruses.

Further, in the antimicrobial member of the present invention, the cured binder material covers 10 to 55% of the surface of the base material, and a considerable amount of the area of the portion not covered with the cured binder material exists. When a design or the like having a predetermined pattern is formed on the surface, the appearance or aesthetic appearance of the design or the like is not impaired.

Further, in the antimicrobial member of the present invention, the binder cured product does not exist on the entire surface of the base material and is scattered in an island shape, or the region where the binder cured product containing the antimicrobial component is formed and the binder curing. Regions where no material is formed are mixed, and the contact area of the cured binder with the surface of the base material can be reduced, and the residual stress of the cured binder can be suppressed, which is high with the base material. It is a binder cured product that has adhesiveness and does not easily come off from the base material.

In the present specification, the island shape means that the cured binder on the surface of the base material exists in an isolated state in which it does not come into contact with other cured binders. The shape of the cured binder material scattered in an island shape is not particularly limited, and when the contour is viewed in a plane, it may be a shape composed of curves such as a circle and an ellipse, and a shape such as a polygon. It may be a shape in which a circular shape, an elliptical shape, or the like are connected to each other through a thin portion.

In the antimicrobial member of the present invention, if the coverage of the cured binder to the surface of the substrate is less than 10%, the coverage is too low and the antimicrobial activity is lowered. On the other hand, if the coating ratio of the cured binder to the surface of the substrate exceeds 55%, the total surface area of the cured binder decreases, so that the probability of contact with microorganisms such as viruses decreases, and the cured binder decreases. The antimicrobial activity per unit area is reduced. Further, since the coverage of the cured binder is too high, when a design or the like having a predetermined pattern is formed on the surface of the base material, the appearance or aesthetic appearance of the design or the like is impaired.

In the antimicrobial member of the present invention, it is desirable that the cured binder contains at least one selected from the group consisting of an inorganic antimicrobial agent and an organic antimicrobial agent as the antimicrobial component.

In the antimicrobial member of the present invention, it is definitely high if the cured binder contains at least one selected from the group consisting of an inorganic antimicrobial agent and an organic antimicrobial agent as the antimicrobial component. It is possible to realize an antimicrobial member having antimicrobial activity.

In the antimicrobial member of the present invention, the inorganic antimicrobial agent is a silver, copper, zinc, platinum, zinc compound, a silver compound, a copper compound, a metal oxide catalyst carrying a metal or a metal oxide, or a metal ion. It is desirable that it is at least one selected from the group consisting of an ion-exchanged zeolite and a copper complex.

In the antimicrobial member of the present invention, the inorganic antimicrobial agent is a metal oxide catalyst or metal ion carrying silver, copper, zinc, platinum, zinc compound, silver compound, copper compound, metal or metal oxide. When at least one selected from the group consisting of ion-exchanged zeolite and a copper complex, the antimicrobial agent can be in the form of particles, and the inorganic antimicrobial agent is exposed from the cured binder. It is an antimicrobial member that is easy to use and has higher antimicrobial activity.

In the antimicrobial member of the present invention, the organic antimicrobial agent is at least one selected from the group consisting of an antimicrobial resin, a sulfonic acid-based surfactant, a copper alkoxide, and a bis-type quaternary ammonium salt. Is desirable.

In the antimicrobial member of the present invention, the organic antimicrobial agent is at least one selected from the group consisting of an antimicrobial resin, a sulfonic acid surfactant, a copper alkoxide, and a bis-type quaternary ammonium salt. Then, the organic antimicrobial agent easily spreads over the entire binder cured product, and becomes an antimicrobial member having high antimicrobial activity.

In the antimicrobial member of the present invention, it is desirable that the cured binder contains an inorganic binder and / or a cured product of an electromagnetically curable resin.

In the antimicrobial member of the present invention, when the binder cured product contains an inorganic binder and / or a cured product of an electromagnetic wave curable resin, a binder cured product having excellent adhesion is relatively easily formed by fixing to the surface of the base material. Can be made to.

In the antimicrobial member of the present invention, the electromagnetic wave curable resin is at least one selected from the group consisting of acrylic resin, urethane acrylate resin, polyether resin, polyester resin, epoxy resin, and alkyd resin. desirable.

In the antimicrobial member of the present invention, the electromagnetic wave curable resin is at least one selected from the group consisting of acrylic resin, urethane acrylate resin, polyether resin, polyester resin, epoxy resin, and alkyd resin. The cured binder has not only transparency but also excellent adhesion to the substrate.

In the antimicrobial member of the present invention, it is desirable that the inorganic binder is at least one selected from the group consisting of silica sol, alumina sol, titania sol, zirconia sol and sodium silicate.

In the antimicrobial member of the present invention, when the inorganic binder is at least one selected from the group consisting of silica sol, alumina sol, titania sol, zirconia sol and sodium silicate, water is dispersed according to the type of antimicrobial component. A sol or the like used as a medium or a sol using a solvent as a dispersion medium can be used properly, and a binder cured product in which antimicrobial components are well dispersed can be formed.

In the antimicrobial member of the present invention, the maximum width of the cured binder in the direction parallel to the surface of the substrate is 0.1 to 500 μm, and the average thickness thereof is 0.1 to 20 μm. desirable.

In the antimicrobial member of the present invention, by setting the maximum width of the binder cured product in the direction parallel to the surface of the base material to 0.1 to 500 μm, the surface of the base material is not covered with the binder cured product. Even when a design or the like having a predetermined pattern is formed on the surface of the base material, it is possible to prevent the appearance and aesthetic appearance of the design or the like from being spoiled.

In the antimicrobial member of the present invention, it is technically difficult to form a binder cured product having a maximum width of less than 0.1 μm in a direction parallel to the surface of the binder cured product, and the binder cured product. The coverage of the surface of the base material is also lowered, and the antimicrobial activity per unit carrying amount is lowered. On the other hand, if the maximum width of the cured binder product in the direction parallel to the surface of the base material exceeds 500 μm, the size of one cured binder product becomes too large, and a design or the like having a predetermined pattern is formed on the surface of the base material. If this is the case, the cured binder obstructs the design and the like, making it difficult to see the design and the like, and the appearance and appearance of the design and the like are impaired.

In the antimicrobial member of the present invention, when the average value of the thickness of the cured binder is 0.1 to 20 μm, the cured binder is thin, so that it is difficult to form a continuous layer of the cured binder, and the cured binder is formed. It becomes easy to be scattered in an island shape, it is possible to prevent the appearance and aesthetics of the design and the like from being spoiled, and high antimicrobial activity can be obtained.
In the antimicrobial member of the present invention, it is technically difficult to form a binder cured product having an average thickness of less than 0.1 μm, and the coverage of the surface of the binder cured product is also low. The antimicrobial activity is reduced per load. On the other hand, if the average thickness of the cured binder material exceeds 20 μm, the cured binder product is too thick. Therefore, if a design or the like having a predetermined pattern is formed on the surface of the base material, the cured binder product interferes with the design or the like. Is hard to see, and the appearance and aesthetics of the design etc. are spoiled.

In the antimicrobial member of the present invention, the arithmetic mean roughness (Ra) of the surface containing the binder cured product of the substrate on which the binder cured product containing the antimicrobial component is fixed is 0.1 according to JIS B 0601. It is desirable that it is ~ 5 μm.

In the antimicrobial member of the present invention, the arithmetic average roughness (Ra) of the surface containing the binder cured product of the substrate on which the binder cured product containing the antimicrobial component is fixed is 0 in accordance with JIS B 0601. If it is 1 to 5 μm, the surface area and unevenness of the surface of the base material containing the cured binder will be in an appropriate range, the probability of contact between microorganisms such as viruses and antimicrobial components will increase, and the valleys of the unevenness of the surface will increase. , Microorganisms such as viruses are easily trapped, and as a result, microorganisms such as viruses are easily inactivated.

In the antimicrobial member of the present invention, when Ra is less than 0.1 μm, the surface area and unevenness of the surface of the base material containing the cured binder are reduced, and the probability of contact between microorganisms such as viruses and the antimicrobial component is reduced. In addition, since the surface irregularities are reduced, microorganisms such as viruses are less likely to be trapped, and as a result, the antimicrobial activity is reduced.
On the other hand, when Ra exceeds 5 μm, the unevenness becomes too large, and microorganisms such as viruses come into preferential contact with the antimicrobial agent in the concave portion of the unevenness, so that the antimicrobial agent in the vicinity of the convex portion does not easily exert antimicrobial activity. Become. Further, it is considered that fine foreign substances other than microorganisms such as viruses are likely to be deposited in the recesses, resulting in insufficient contact between the antimicrobial agent and microorganisms such as viruses, and as a result, the antimicrobial activity is lowered.

In the antimicrobial member of the present invention, when the binder cured product is scattered and fixed in an island shape, the island-shaped binder cured product is 0.05 × 10 ⁸ to 30 × 10 ^{8 per square meter of the surface of the base material.} It is desirable that there are one.

In the antimicrobial member of the present invention, when the island-shaped cured binder is ^{present in 0.05 × 10 8} to 30 × 10 ⁸ per square meter of the surface of the base material, the size of the cured binder is appropriately set. Therefore, it is possible to prevent the appearance and aesthetic appearance of the design and the like formed on the surface of the base material from being spoiled, and the antimicrobial member has high antimicrobial activity per unit carrying amount.

In the antimicrobial member of the present invention, the number of the islands of binder cured product, if it is 0.05 × 10 than ⁸ per surface 1 m2 of the substrate, the coverage of the substrate surface of the binder cured product 10 In order to make it ~ 55%, it is necessary to increase the area of each binder cured product, the total surface area of the binder cured product becomes smaller, and the contact probability between the binder cured product and microorganisms such as viruses decreases. The antimicrobial activity deteriorates.
On the other hand, if the number of the binder cured product 30 × 10 more than ^eight, because the number of the binder cured product is too large, easily overlap binder cured together, design, etc. of a predetermined pattern on the substrate surface is formed In that case, the appearance and aesthetics of the design or the like formed on the surface of the base material are impaired.
Patent Document 2 describes that one or more antibacterial metal islands are required for an area of 1 μm × 1 μm, which ^{corresponds to 10 12} / m ^2, and the number of antibacterial agents is the present invention. Much more than, but not so high in antibacterial activity.

In the antimicrobial member of the present invention, a cured product of an electromagnetic wave curable resin containing an antimicrobial component is fixed to the surface of the base material, and the cured product of the electromagnetic wave curable resin is 10 to 55% of the surface of the base material. It is desirable that the antimicrobial member is characterized by covering the above.

The electromagnetic wave curable resin is cured by electromagnetic waves by adhering an antimicrobial composition composed of an uncured electromagnetic wave curable resin having antimicrobial properties to the surface of a base material constituting an existing building such as a wall or a toilet. This is because the cured product having antimicrobial properties can be fixed to the surface of the base material simply by allowing it to be allowed to adhere.

In the antimicrobial member of the present invention, the cured product of the electromagnetic wave curable resin covers 10 to 55% of the surface of the base material, and the cured product of the electromagnetic wave curable resin having antimicrobial activity is island-shaped. Antibacterial because the region is scattered or the region where the cured product of the electromagnetic wave curable resin containing the antimicrobial component is formed and the region where the cured product of the electromagnetic wave curable resin is not formed are mixed. The total surface area of the cured product of the electromagnetic wave curable resin exhibiting microbial activity increases, the probability of contact with microorganisms such as viruses increases, and between the protrusions of the cured product of the electromagnetic wave curable resin exhibiting antimicrobial activity. This is because microorganisms such as viruses are trapped in the formed recesses, and the microorganisms such as viruses are easily inactivated.

It is desirable that the cured product of the electromagnetic wave curable resin contains at least one selected from the group consisting of an inorganic antimicrobial agent and an organic antimicrobial agent as the antimicrobial component.

The antimicrobial component contained in the cured product of the electromagnetic wave curable resin is a copper compound, and the copper compounds are Cu (I) and Cu (Cu (I)) in the range of 925 to 955 eV by X-ray photoelectron spectroscopy. It is desirable that the coexistence of Cu (I) and Cu (II) is confirmed by measuring the binding energy corresponding to II) for 5 minutes. This is because the coexistence of Cu (I) and Cu (II) has higher antimicrobial activity than the case where each of them exists alone.

The antimicrobial component contained in the cured product of the electromagnetic wave curable resin is a copper compound, and the copper compounds are Cu (I) and Cu (Cu (I)) in the range of 925 to 955 eV by X-ray photoelectron spectroscopic analysis. The ratio of the number of ions of Cu (I) and Cu (II) contained in the copper compound calculated by measuring the binding energy corresponding to II) for 5 minutes (Cu (I) / Cu (II). )) Is preferably 0.4 to 50.

The antimicrobial component contained in the cured product of the electromagnetic wave curable resin is preferably a bis-type quaternary ammonium salt. This is because it has high antimicrobial performance.

In the antimicrobial member of the present invention, it is desirable that the cured product of the electromagnetic wave curable resin further contains a polymerization initiator. This is because it has a function of promoting the polymerization reaction and the cross-linking reaction of the electromagnetic wave curable resin and reducing copper (II) to copper (I) having high antimicrobial performance.

In the anti-microbial member of the present invention, the above-mentioned polymerization initiator contains an alkylphenone-based polymerization initiator and a benzophenone-based polymerization initiator, and the ratio of the alkylphenone-based polymerization initiator to the benzophenone-based polymerization initiator is determined. It is desirable that the alkylphenone-based polymerization initiator / benzophenone-based polymerization initiator = 1/1 to 4/1 in terms of weight ratio. This is because the crosslink density of the cured product of the electromagnetic wave curable resin becomes high.

In addition, the cured product of the electromagnetic wave curable resin was immersed in boiled toluene for 8 hours and dried, and the crosslink density was measured at (weight of cured product after immersion / weight of cured product before immersion) × 100%. The crosslink density of the antiviral members 1 and 5 is 97%. On the other hand, when the same resin as in Examples 1 and 5 is used and the ratio of the alkylphenone-based polymerization initiator / benzophenone-based polymerization initiator is 0.5 / 1 and 5/1, the crosslink density is up to 91%, respectively. descend. That is, it is optimal that the alkylphenone-based polymerization initiator / benzophenone-based polymerization initiator = 1/1 to 4/1 (crosslink density 95% or more) in terms of weight ratio.

In the antimicrobial member of the present invention, it is desirable that the antimicrobial member is an antiviral member or an antifungal member.
This is because the antimicrobial member of the present invention has antiviral, antibacterial, antifungal and antifungal properties, but is excellent in antiviral activity and antifungal activity, and in particular, antiviral has the highest activity.

FIG. 1A is a cross-sectional view schematically showing an embodiment of the antimicrobial member of the present invention, and FIG. 1B is a plan view of the antimicrobial member shown in FIG. 1A. .. FIG. 2 is an optical micrograph showing the antiviral member obtained in Example 1. FIG. 3 is a graph showing the results of antiviral activity per unit area of the binder cured product of the antiviral member obtained in Examples 1 to 4 and Comparative Examples 1 to 3. FIG. 4 is a graph showing the results of antiviral activity of the binder cured product of the antiviral member obtained in Examples 1 to 4 and Comparative Examples 1 to 3.

(Detailed description of the invention)
Hereinafter, the antimicrobial member of the present invention will be described in detail.
In the following description, the case where the binder cured product containing the antimicrobial component is scattered in an island shape on the surface of the base material will be described as an example, but the region where the binder cured product containing the antimicrobial component is formed on the surface of the base material The same applies to the case where the binder cured product is fixedly formed in a state where the regions where the binder cured product is not formed are mixed.
In the antimicrobial member of the present invention, the binder cured product containing the antimicrobial component is scattered in an island shape on the surface of the base material, or the binder cured product is formed with the region where the binder cured product containing the antimicrobial component is formed. The binder cured product is fixedly formed in a state where the non-existing regions are mixed, and the binder cured product covers 10 to 55% of the surface of the base material.

FIG. 1A is a cross-sectional view schematically showing an embodiment of the antimicrobial member of the present invention, and FIG. 1B is a plan view of the antimicrobial member shown in FIG. 1A. ..

As shown in FIG. 1, in the antimicrobial member 10 of the present invention, the binder cured product 12 containing the antimicrobial component is scattered in an island shape on the surface of the base material 11, and the binder cured product 12 is the surface of the base material. Covers 10 to 55% of.

In the antimicrobial member of the present invention, the cured binder containing the antimicrobial component is scattered on the surface of the base material in an island shape, and the cured binder covers 10 to 55% of the surface of the base material. A large surface area can be secured without thickening the binder cured product, and an antimicrobial member having high antimicrobial activity per unit loading amount can be provided.

Further, in the antimicrobial member of the present invention, the cured binder material covers 10 to 55% of the surface of the base material, and a considerable amount of the area of the portion not covered with the cured binder material exists. When a design or the like having a predetermined pattern is formed on the surface, the appearance or aesthetic appearance of the design or the like is not impaired.

Further, in the antimicrobial member of the present invention, the cured binder does not exist on the entire surface of the base material but is scattered in an island shape, so that the contact area of the cured binder with the surface of the base material is reduced. It is possible to suppress the residual stress of the cured binder product, and the cured binder product has high adhesion to the base material and is not easily peeled off from the base material.

The material of the base material constituting the antimicrobial member of the present invention is not particularly limited, and examples thereof include ceramics such as metal and glass, resins, fiber woven fabrics, and wood.
Further, the member serving as a base material constituting the antimicrobial member of the present invention is not particularly limited, and may be an interior material, a wall material, a window glass, a door, etc. inside a building, such as office equipment and the like. It may be furniture or the like, and may be a decorative board or the like used for various purposes in addition to the above-mentioned interior material.

The decorative board has a substrate and a surface resin layer laminated on the surface of the substrate.
The substrate used for the decorative board is not particularly limited, and a noncombustible board such as core paper or magnesia cement generally used for the decorative board can be used. The core paper may be used alone or as a laminated body in which a plurality of core papers are laminated. The number of core papers is not particularly limited, but may be 1 to 20. As the core paper, for example, aluminum hydroxide papermaking can be used. The core paper can be impregnated with phenol resin. Further, the core paper and the magnesia cement non-combustible plate can be laminated to form a substrate.

The magnesia cement non-combustible plate can be used alone, or can be laminated on the center of the core paper to form a substrate. The magnesia cement non-combustible plate is manufactured by mixing magnesium oxide (MgO) and magnesium chloride (MgCl ₂ ), further adding aggregate and water, kneading, and forming into a plate shape. As the aggregate, inorganic fibers such as rock wool and glass wool and organic fibers such as wood chips and pulp can be used. Further, in order to increase the strength of the magnesia cement non-combustible plate, a glass fiber layer formed in a mesh shape or the like can be provided as an intermediate layer.

The resins that can be used for the surface resin layer constituting the decorative board include melamine resin, diallyl phthalate (DAP) resin, polyester resin, olefin resin, vinyl chloride resin, acrylic resin, epoxy resin, urethane resin, and phenol. Examples thereof include resins, silicone resins, fluororesins, and guanamine resins. Among these, it is desirable to use a melamine resin.

The melamine resin is a resin having improved dimensional stability and toughness without impairing optical and visual characteristics such as translucency. As the melamine resin, any known resin can be adopted as long as it is a resin using melamine and its derivative as a monomer. Further, the melamine resin may be a resin composed of a single monomer or a copolymer composed of a plurality of monomers. Examples of the melamine derivative include derivatives having a functional group such as an alkoxymethyl group such as an imino group, a methylol group, a methoxymethyl group and a butoxymethyl group. Further, a compound obtained by reacting a melamine derivative having a methylol group with a lower alcohol to partially or completely etherify it can be used as a monomer. Derivatives having a methylol group such as monomethylol melamine, dimethylol melamine, trimethylol melamine, tetramethylol melamine, pentamethylol melamine, hexamethylol melamine (hereinafter referred to as "methylolated melamine") are copolymerized with melamine as a cross-linking agent. A melamine resin can be used.

The surface resin layer may be a decorative layer in which a printing paper on which a pattern or a color is printed is impregnated with a resin, and an overlay that becomes translucent when the amount of the filler is 15% or less and the resin is impregnated. An overlay layer in which paper is impregnated with resin may be used. When the surface resin layer is an overlay layer, the decorative layer is provided below the overlay layer.
The filler is an inorganic particle (filler) for adjusting whiteness and smoothness by adding it to paper, and at least one selected from calcium carbonate, talc, clay and kaolin is desirable. Since the filler is an inorganic particle, the content of the filler can be calculated from the weight of the paper and the weight of the ash remaining after the paper is heated strongly.

In the antimicrobial member of the present invention, it is desirable that the cured binder contains at least one selected from the group consisting of an inorganic antimicrobial agent and an organic antimicrobial agent as the antimicrobial component.
The binder cured product may contain only one type of the above-mentioned inorganic antimicrobial agent, or may contain two or more types of the above-mentioned inorganic antimicrobial agent, and the above-mentioned organic antimicrobial agent. May be contained in only one kind, or two or more kinds of organic antimicrobial agents may be contained. Further, the binder cured product may contain two or more types of the inorganic antimicrobial agent and the inorganic antimicrobial agent.

Further, in the antimicrobial member of the present invention, the inorganic antimicrobial agent is a metal oxide catalyst or metal in which silver, copper, zinc, platinum, zinc compound, silver compound, copper compound, metal or metal oxide is supported. It is desirable that it is at least one selected from the group consisting of an ion-exchanged zeolite and a copper complex.

Examples of the inorganic antimicrobial agent contained in the cured binder include a metal composed of at least one of silver, copper, zinc and platinum.
The cured binder may contain silver, copper, zinc and platinum particles alone, and may contain two or more kinds of metal particles among silver, copper, zinc and platinum. For example, metal particles of an alloy containing at least two of silver, copper, zinc and platinum may be fixed.

Examples of the inorganic antimicrobial agent contained in the cured binder include copper compounds such as copper carboxylates, copper complexes, and water-soluble inorganic salts of copper, zinc compounds, and silver compounds.
As the carboxylic acid salt of copper, an ionic compound of copper can be used, and examples thereof include copper acetate, copper benzoate, and copper phthalate.
As the water-soluble inorganic salt of copper, an ionic compound of copper can be used, and examples thereof include copper nitrate and copper sulfate.
Examples of other copper compounds include copper (methoxydo), copper ethoxydo, copper propoxide, copper butoxide and the like, and copper covalent compounds include copper oxide and copper hydroxide. .. Copper carboxylate and copper hydroxide have high affinity with organic binders and inorganic binders, and are not eluted with water, so they have excellent water resistance.
Examples of the copper carboxylate include copper (II) acetate, copper (I) acetate, copper (I) oxalate, copper (II) benzoate, and copper (II) phthalate.
Examples of the copper complex include a complex of acetylacetone and copper, a complex of β-diketone such as 5-methyl-2,4-hexanedione and copper, copper (I) (1-butanethiolate), and copper ( I) (Hexafluoropentandionate cyclooctadiene) and the like can be mentioned.
Examples of the water-soluble inorganic salt of copper include copper (II) nitrate and copper (II) sulfate. Examples of other copper compounds include copper (II) (methoxide), copper (II) ethoxydo, copper (II) propoxide, copper (II) butoxide and the like.

As a metal oxide catalyst in which the metal or metal oxide contained in the cured binder is supported, for example, platinum group such as platinum, palladium, rhodium, ruthenium, silver, copper or the like is supported on titanium oxide or the like. Examples include metal. Specific examples of the metal oxide catalyst carrying a metal or metal oxide include a platinum-supported titania catalyst, a copper-supported titania catalyst, a silver-supported titania catalyst, a platinum-supported nitrogen-doped titania catalyst, and a platinum-supported sulfur-doped titania catalyst. , Carbon-doped titanium dioxide catalyst, copper-supported titanium oxide catalyst, silver-supported titanium oxide catalyst, and other visible light-responsive photocatalysts. Examples of the copper-supported titania catalyst include CuO described in JP-A-2006-232729. / TIO ₂ (% by weight) = copper-containing anatase-type titanium oxide in the range of 1.0 to 3.5, sub-copper oxide (copper (I) oxide (I): Cu) described in JP2012-210557A. _A photocatalyst composition in which 2O) and titanium oxide are composited, titanium oxide having a surface containing a mixture containing a monovalent copper compound and a divalent copper compound described in JP2013-166705, and international publication. Examples thereof include copper and titanium-containing compositions containing titanium oxide containing crystalline rutyl-type titanium oxide and a divalent copper compound described in No. 2013/094573.

Further, as the inorganic antimicrobial agent, particles of a metal oxide or a metal hydrate containing at least one metal selected from silver, copper, zinc, titanium, tungsten and the like can also be used. Specific examples of the inorganic antimicrobial agent include copper (I) oxide (copper oxide), copper (II) oxide, copper (II) carbonate, copper (II) hydroxide, copper (II) chloride, and nano. Alumina carrying at least one of silver and copper, silica carrying at least one of nanosilver and copper, zinc oxide carrying at least one of nanosilver and copper, nanosilver and at least one of copper were carried. Examples thereof include inorganic particles such as titanium oxide or calcium phosphate in which at least one of tungsten oxide, nanosilver and copper is supported. The zeolite exchanged at least one of the silver ion and the copper ion may be further exchanged with another metal ion such as zinc ion. Further, the inorganic antimicrobial agent of the present invention is preferably a copper complex.

In the antimicrobial member of the present invention, the organic antimicrobial agent is at least one selected from the group consisting of an antimicrobial resin, a sulfonic acid-based surfactant, a copper alkoxide, and a bis-type quaternary ammonium salt. Is desirable.

In the anti-microbial member of the present invention, examples of the organic anti-microbial agent include halocarban, chlorophenesine, lysozyme chloride, alkyldiaminoethylglycine hydrochloride, isopropylmethylphenol, timol, hexachlorophene, berberine, tioxolone, salicylic acid and the like. Derivatives of them, benzoic acid, sodium benzoate, paraoxybenzoic acid ester, parachlormethacresol, benzalkonium chloride, phenoxyethanol, isopropylmethylphenol, phenolic acid, sorbic acid, potassium sorbate, hexachlorophene, chlorhexidine chloride, trichlorocarbani Lido, thiantol, hinokithiol, triclosan, trichlorohydroxydiphenyl ether, chlorhexidine phenolate, phenoxyethanol, resorcin, azulene, salicylic acid, zincpyrythion, mononitroguanacol sodium, uikyo extract, sansho extract, cetylpyridinium chloride, benzethonium chloride and undecylene acid derivatives, Examples thereof include alkylbenzene sulfonic acid or a salt thereof. Of these, alkylbenzene sulfonic acid or a salt thereof is preferable.

In the antimicrobial member of the present invention, the antimicrobial resin comprises an acidic functional group and a resin substrate. Examples of the acidic functional group include a sulfonic acid group, a phosphoric acid group, a carboxyl group, a hydroxyl group, a nitro group and the like. Of these, a sulfonic acid group, a phosphoric acid group, and a carboxyl group are preferable.

The resin substrate is preferably a polymer of a monomer having a vinyl group.
Since the polymer of the monomer having a vinyl group is synthesized by addition polymerization, there is no by-product such as water, and a highly transparent antimicrobial resin can be obtained. Therefore, the influence on the design of the base material can be reduced.

The monomer having a vinyl group is preferably one or more monomers selected from styrene, methacrylic acid, methacrylic acid ester, divinylbenzene, and trivinylbenzene.
Styrene, methacrylic acid, methacrylic acid ester, divinylbenzene, and trivinylbenzene can be used to obtain an antimicrobial resin having particularly high transparency. Further, divinylbenzene and trivinylbenzene can be crosslinked by adding them to a monomer to form a three-dimensional network structure. By forming a three-dimensional network structure, it becomes difficult to disassemble and durability can be increased.

In the antimicrobial member of the present invention, the antimicrobial resin composed of the acidic functional group and the resin substrate is not particularly limited, but for example, the cation exchange resin may be used as it is or after being pulverized to be finely divided. Can be done. The cation exchange resin also has an acidic functional group on the resin substrate, and can be used as the antimicrobial resin of the present invention.

Examples of the bis-type quaternary ammonium salt include a bis-type pyridinium salt represented by the following general formula (1), a bis-type quinolinium salt, a bis-type thiazolium salt, and a compound represented by the following general formula (2). Is desirable.

（上記一般式（１）中、Ｒ^１及びＲ^２は、同一または異なっていてもよいアルキル基、Ｒ^３はエーテル結合を含んでもよい有機基であり、Ｘ⁻は、ハロゲン陰イオンを示す。）

(In the above general formula (1), R ¹ and R ² are alkyl groups which may be the same or different, R ³ is an organic group which may contain an ether bond, and X ⁻ represents a halogen anion. )

（上記一般式（２）中、Ｒ^４は、官能基を有してもよいアルキル基を表し、Ｒ^５、Ｒ^６、Ｒ^７、Ｒ^８、Ｒ^９及びＲ^１０は、アルキル基を表す。）

(In the above general formula (2), R ⁴ represents an alkyl group which may have a functional group, and R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ represent an alkyl group. )

First, the bis-type pyridinium salt represented by the general formula (1) will be described.
In the bis-type pyridinium salt represented by the general formula (1), examples of ^{X − include Cl −} , Br ⁻ , I ^{− and the} like.
R ¹ and R ² are preferably alkyl groups having 1 to 20 carbon atoms, and the alkyl groups may have a side chain.
In the above general formula (1), the ^{organic group represented by R 3} is -CO-O- (CH ₂ ) _6- O-CO-, -CONH- (CH ₂ ) _6- CO-, -NH-CO. -(CH ₂ ) _4- CO-NH-, -S-Ph-S-, -CONH-Ph-NHCO-, -NHCO-Ph-CONH-, _{-O- (CH 2} ) _6- O- or -CH ^{It is desirable that it is represented by 2-} O- (CH ₂ ) _4- O-CH _2- (where Ph represents a phenylene group).

上記一般式（３）中、Ｒ^１１は、Ｃ_ｎＨ_２ｎ＋１で表されるアルキル基であり、ｎは、８、１０、１２、１４、１６または１８が望ましい。また、ｍは、３、４、６、８、１０が望ましい。以下に示す化合物の置換基Ｒ^１１についても、同様である。 Specifically, examples of the bis-type pyridinium salt include those represented by the following general formulas (3) to (10).

In the above general formula (3), R ¹¹ is _{an alkyl group represented by C n} H _{2n + 1} , and n is preferably 8, 10, 12, 14, 16 or 18. Further, m is preferably 3, 4, 6, 8 and 10. Substituents R ¹¹ of the compound shown below is also the same.

Further, as the bis-type pyridinium salt, 1,1'-didecyl-3,3'-[butane-1,4-diylbis (oxymethylene)] dipyridinium = dibromid represented by the following general formula (11). Is particularly desirable.

Next, the bis-type thiazolium salt will be described.
Further, examples of the bis-type thiazolium salt include bis-type thiazolium salts represented by the following general formula (12).

Next, the bis-type quinolinium salt will be described.
As the bis-type quinolinium salt, the pyridinium group represented by the following general formula (13) constituting the bis-type pyridinium salt represented by the general formulas (3) to (10) is used in the following general formula (14). ), A bis-type quinolinium salt having a chemical structure substituted with the quinolium group shown in) can be mentioned. In the above bis-type quinolinium salt, other substituents and the like are the same as those of the bis-type pyridinium salt represented by the general formulas (3) to (10).

上記一般式（２）中、Ｒ^４は、官能基を有してもよいアルキル基を示す。アルキル基は、側鎖を有してもよく、その炭素数は、１〜２０が望ましい。上記官能基としては、ヒドロキシル基、アルデヒド基、カルボキシル基、シアノ基、ニトロ基、アミノ基、エーテル基等が挙げられる。また、Ｒ^５、Ｒ^６、Ｒ^７、Ｒ^８、Ｒ^９及びＲ^１０は、アルキル基を表し、上記アルキル基は、側鎖を有してもよく、その炭素数は、１〜２０が望ましい。 Further, the compound represented by the general formula (2) used in the present invention will be described.

In the above general formula (2), R ⁴ represents an alkyl group which may have a functional group. The alkyl group may have a side chain, and the number of carbon atoms thereof is preferably 1 to 20. Examples of the functional group include a hydroxyl group, an aldehyde group, a carboxyl group, a cyano group, a nitro group, an amino group, an ether group and the like. Further, R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ represent an alkyl group, and the above alkyl group may have a side chain, and the number of carbon atoms thereof is preferably 1 to 20. ..

Examples of the compound represented by the general formula (2) include 2,3-bis (hexadecyldimethylammonium bromide) -1-propanol and the like.

In the anti-microbial member of the present invention, it is desirable that the cured binder is an organic binder, an inorganic binder, an organic / inorganic hybrid binder and / or a cured product of an electromagnetic curable resin. An organometallic compound can be used as the binder of the organic / inorganic hybrid.
In the antimicrobial member of the present invention, as the antimicrobial component, at least one selected from the group consisting of an inorganic antimicrobial agent and an organic antimicrobial agent, and an organic binder, an inorganic binder, and an organic / inorganic hybrid which are binders. A binder cured product can be obtained by curing a mixture of the binder and at least one of the electromagnetic curable resins.

Next, a cured product of the electromagnetic wave curable resin in the antimicrobial member of the present invention will be described.
After forming island-shaped droplets on the surface of the substrate using an anti-microbial composition containing a monomer or oligomer which is an uncured electromagnetically curable resin, a polymerization initiator, various additives, and an anti-microbial component, an electromagnetic wave is generated. By irradiating with, the polymerization initiator causes reactions such as cleavage reaction, hydrogen abstraction reaction, electron transfer, etc., and the photoradical molecules, photocation molecules, photoanion molecules, etc. generated thereby attack the above-mentioned monomer and the above-mentioned oligomer. Then, the polymerization reaction and the cross-linking reaction of the monomer and the oligomer proceed, and an island-shaped binder cured product containing an anti-microbial component is formed. The resin constituting the binder cured product of the present invention produced by such a reaction is called an electromagnetic wave curable resin.
In the present invention, a method for producing a binder cured product scattered in an island shape will be described in detail later.

In the present invention, the polymerization initiator can be used as a reducing agent for copper. Therefore, a polymerization initiator may be added to the antimicrobial composition consisting of an inorganic binder, a copper compound and a dispersion medium. The polymerization initiator is preferably a photopolymerization initiator. Copper (II) can be reduced to copper (I) with a polymerization initiator. Copper (I) has higher antimicrobial performance than copper (II).

As such an electromagnetic curable resin, at least one selected from the group consisting of, for example, acrylic resin, urethane acrylate resin, polyether resin, polyester resin, epoxy resin, and alkyd resin is desirable.

Examples of the acrylic resin include epoxy-modified acrylate resin, urethane acrylate resin (urethane-modified acrylate resin), and silicon-modified acrylate resin.
Examples of the polyester resin include polyethylene terephthalate (PET) and polybutylene terephthalate (PBT).

Examples of the epoxy resin include alicyclic epoxy resin, alicyclic epoxy resin, alicyclic epoxy resin, glycidyl ether type epoxy resin, glycidyl ether type epoxy resin, and oxetane resin.
Examples of the alkyd resin include polyester alkyd resin and the like.
These resins have transparency and are also excellent in adhesion to a base material.

Next, the cured product of the inorganic binder in the antimicrobial member of the present invention will be described.
The antimicrobial component is obtained by mixing an inorganic binder, an antimicrobial component, and if necessary, various additives and dispersion media to form island-shaped droplets on the surface of the substrate using the antimicrobial composition, and then drying the mixture. An island-shaped hardened binder (hardened inorganic binder) is formed.

The inorganic binder is preferably at least one selected from the group consisting of silica sol, alumina sol, titania sol, zirconia sol and sodium silicate. The content ratio of the inorganic oxide such as silica in the above-mentioned inorganic binder is preferably 2 to 80% by weight in terms of solid content.
Since there are two types of the above-mentioned inorganic binders, one using water and the other using an organic solvent as the dispersion medium, the inorganic binder can be selected in consideration of the type of the antimicrobial component to be added, and the antimicrobial component can be selected. The above-mentioned antimicrobial composition in which is uniformly dispersed can be obtained.

In the antimicrobial member of the present invention, the maximum width of the cured binder in the direction parallel to the surface of the substrate is 0.1 to 500 μm, and the average thickness thereof is 0.1 to 20 μm. desirable.
In the antimicrobial member of the present invention, when the average value of the thickness of the cured binder is 0.1 to 20 μm, the cured binder is thin, so that it is difficult to form a continuous layer of the cured binder, and the cured binder is formed. It becomes easy to be scattered in an island shape, it is possible to prevent the appearance and aesthetics of the design and the like from being spoiled, and high antimicrobial activity can be obtained.
Further, by setting the maximum width of the cured binder material in the direction parallel to the surface of the base material to 0.1 to 500 μm, the proportion of the portion where the surface of the base material is not covered with the cured binder material is appropriately maintained. Therefore, even when a design or the like having a predetermined pattern is formed on the surface of the base material, it is possible to prevent the appearance and aesthetic appearance of the design or the like from being impaired.
The maximum width in the direction parallel to the surface of the substrate of the cured binder and the average value thereof can be measured by using a scanning microscope or a laser microscope.
Specifically, by using a scanning microscope or a laser microscope equipped with image analysis / image measurement software, or by using an image analysis / image measurement software to analyze an image obtained by the scanning microscope or a laser microscope. By performing the above, the maximum width in the direction parallel to the surface of the substrate of the cured binder and the average value of the thickness can be obtained.

In the antimicrobial member of the present invention, it is technically difficult to form a binder cured product having an average thickness of less than 0.1 μm, and the coverage of the surface of the binder cured product on the substrate surface is also lowered. Microbial activity is reduced. On the other hand, if the average thickness of the cured binder material exceeds 20 μm, the cured binder product is too thick. Therefore, if a design or the like having a predetermined pattern is formed on the surface of the base material, the cured binder product interferes with the design or the like. Is hard to see, and the appearance and aesthetics of the design etc. are spoiled.

In the antimicrobial member of the present invention, it is technically difficult to form a binder cured product having a maximum width of less than 0.1 μm in a direction parallel to the surface of the binder cured product, and the binder cured product. The coverage of the surface of the base material is also lowered, and the antimicrobial activity is lowered. On the other hand, if the maximum width of the cured binder product in the direction parallel to the surface of the base material exceeds 500 μm, the size of one cured binder product becomes too large, and a design or the like having a predetermined pattern is formed on the surface of the base material. If this is the case, the cured binder obstructs the design and the like, making it difficult to see the design and the like, and the appearance and appearance of the design and the like are impaired.

In the antimicrobial member of the present invention, the arithmetic mean roughness (Ra) of the surface containing the binder cured product of the base material in which the binder cured product containing the antimicrobial component is scattered in an island shape on the surface according to JIS B 0601. Is preferably 0.1 to 5 μm.
The arithmetic mean roughness (Ra) can be obtained by measuring with a measurement length of 8 mm using HANDYSURF, which is a contact type surface roughness measuring machine manufactured by Tokyo Seimitsu Co., Ltd.

In the antimicrobial member of the present invention, the arithmetic average roughness (Ra) of the surface containing the binder cured product of the base material in which the binder cured product containing the antimicrobial component is scattered in an island shape on the surface according to JIS B 0601. ) Is 0.1 to 5 μm, the surface area of the substrate surface containing the cured binder is in an appropriate range, the probability of contact between microorganisms such as viruses and antimicrobial components is high, and the surface irregularities are uneven. Microorganisms such as viruses are likely to be trapped in the valley, and as a result, microorganisms such as viruses are likely to be inactivated.

In the antimicrobial member of the present invention, when Ra is less than 0.1 μm, the surface area of the surface of the base material containing the cured binder is reduced, the probability of contact between microorganisms such as viruses and the antimicrobial component is reduced, and the antimicrobial component is less likely to come into contact with each other. Since the surface unevenness is reduced, microorganisms such as viruses are less likely to be trapped, and as a result, the antimicrobial activity is reduced.
On the other hand, when Ra exceeds 5 μm, the unevenness becomes too large, and microorganisms such as viruses come into preferential contact with the antimicrobial agent in the concave portion of the unevenness, so that the antimicrobial agent in the vicinity of the convex portion does not easily exert antimicrobial activity. Become. Further, it is considered that fine foreign substances other than microorganisms such as viruses are likely to be deposited in the recesses, resulting in insufficient contact between the antimicrobial agent and microorganisms such as viruses, and as a result, the antimicrobial activity is lowered.
At the same time, the convex parts of the cured binder are easily worn and damaged by a physical load such as wiping and cleaning, so that the antimicrobial component is lost, so that the uneven parts become large and the height of the convex parts is high. If it becomes too much, the durability will decrease.

In the antimicrobial member of the present invention, it is desirable that the above-mentioned island-shaped cured binder is ^{present in 0.05 × 10 8} to 30 × 10 ^{8 per square meter of the surface of the base material.}

In the antimicrobial member of the present invention, when the island-shaped cured binder is ^{present in 0.05 × 10 8} to 30 × 10 ⁸ per square meter of the surface of the base material, the size of the cured binder is appropriately set. Therefore, it is possible to prevent the appearance and aesthetic appearance of the design and the like formed on the surface of the base material from being spoiled, and the antimicrobial member has high antimicrobial activity per unit carrying amount.

Keep the antimicrobial member of the present invention, the number of the islands of binder cured product, if it is 0.05 × 10 than ⁸ per surface 1 m2 of the substrate, the coverage of the substrate surface of the binder cured In order to make it 10 to 55%, it is necessary to increase the area of each binder cured product, the total surface area of the binder cured product becomes small, and the contact probability between the binder cured product and microorganisms such as viruses decreases. As a result, the antimicrobial activity deteriorates.
On the other hand, if the number of the binder cured product 30 × 10 more than ^eight, because the number of the binder cured product is too large, easily overlap binder cured together, design, etc. of a predetermined pattern on the substrate surface is formed In that case, the appearance and aesthetics of the design or the like formed on the surface of the base material are impaired.
In addition, the average diameter of the cured binder is reduced, which not only impairs the adhesion, but also the convex portion of the cured binder is relatively large, and the cured binder is worn and damaged during wiping and cleaning, resulting in antimicrobial activity. Since the property is reduced, the physical durability of the antimicrobial performance is also reduced.

According to the antimicrobial member of the present invention, for example, for interior materials, wall materials, windowpanes, doors, kitchen utensils, etc. inside buildings, office equipment, furniture, etc., decorative boards used for various purposes, etc. The antimicrobial function can be added without changing the pattern, color, design, color tone, etc. formed on the surface.

Next, the method for producing the above-mentioned antimicrobial member will be described.
First, a case where an electromagnetic wave curable resin is used as a binder will be described.
When producing the antimicrobial member, first, a spraying step of spraying an antimicrobial composition containing an antimicrobial component, an uncured electromagnetically curable resin, a dispersion medium, and a polymerization initiator is performed on the surface of the base material. This is followed by a drying step of drying the antimicrobial composition sprayed by the spraying step to remove the dispersion medium, and finally the above-mentioned antimicrobial composition in the antimicrobial composition from which the dispersion medium has been removed in the drying step. An uncured electromagnetically curable resin is irradiated with an electromagnetic wave to cure the electromagnetically curable resin, and a binder cured product containing an antimicrobial component is scattered on the surface of the base material in an island shape, resulting in a binder cured product. An antimicrobial member that covers 10 to 55% of the surface of the substrate can be obtained.

(1) Spraying Step When producing the antimicrobial member of the present invention, first, as a spraying step, an antimicrobial component, an uncured electromagnetic wave curable resin, a dispersion medium, and a polymerization initiator are applied to the surface of the base material. Spray the containing antimicrobial composition.

The material of the base material to be sprayed is not particularly limited, and examples thereof include ceramics such as metal and glass, resins, textile fabrics, and wood.
Further, the member to be a base material is not particularly limited, and may be an interior material, a wall material, a window glass, a door, etc. inside a building, an office equipment, furniture, etc. In addition to the interior material, it may be a decorative board or the like used for various purposes.

Examples of the antimicrobial component include at least one selected from the group consisting of inorganic antimicrobial agents and organic antimicrobial agents.
The inorganic antimicrobial agents include silver, copper, zinc, platinum, zinc compounds, silver compounds, copper compounds, metal oxide catalysts carrying metals or metal oxides, zeolite ion-exchanged with metal ions, and It is desirable that the organic antimicrobial agent is at least one selected from the group consisting of copper complexes, and the organic antimicrobial agent is an antimicrobial resin, a sulfonic acid-based surfactant, a copper alkoxide, and a bis-type quaternary ammonium. It is desirable that it be at least one selected from the group consisting of salts.

The electromagnetic wave curable resin is preferably at least one selected from the group consisting of acrylic resin, urethane acrylate resin, polyether resin, polyester resin, epoxy resin, and alkyd resin.

The type of the dispersion medium is not particularly limited, but it is preferable to use alcohols or water in consideration of stability. Examples of alcohols include alcohols such as methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, and sec-butyl alcohol in consideration of lowering the viscosity. Among these alcohols, methyl alcohol and ethyl alcohol, which do not easily increase in viscosity, are preferable, and a mixed solution of alcohol and water is preferable.

In the present invention, the polymerization initiator can be used as a reducing agent for copper. Therefore, a polymerization initiator may be added to the antimicrobial composition consisting of an inorganic binder, a copper compound and a dispersion medium. The polymerization initiator is preferably a photopolymerization initiator. Copper (II) can be reduced to copper (I) with a polymerization initiator. Copper (I) has higher antimicrobial performance than copper (II).
Specifically, the polymerization initiator is preferably at least one selected from the group consisting of an alkylphenone type, a benzophenone type, an acylphosphine oxide type, an intramolecular hydrogen abstraction type, and an oxime ester type.

Examples of the alkylphenone-based polymerization initiator include 2,2-dimethoxy-1,2-diphenylethane-1-one, 1-hydroxy-cyclohexyl-phenyl-ketone, and 2-hydroxy-2-methyl-1-. Phenyl-propane-1-one, 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propane-1-one, 2-hirodoxy-1- {4- [4] -(2-Hydroxy-2-methyl-propionyl) -benzyl] phenyl} -2-methyl-propane-1-one, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropane-1-one , 2-Benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1,2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4) -Morhonyl) phenyl] -1-butanone and the like.

Examples of the acylphosphine oxide-based polymerization initiator include 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide and the like.

Examples of the intramolecular hydrogen abstraction type polymerization initiator include phenylglycilic acid methyl ester, oxyphenyl succinate, 2- [2-oxo-2-phenylacetoxyethoxy] ethyl ester tooxyphenylacetic acid and 2- (2). Examples thereof include a mixture with −hydroxyethoxy) ethyl ester.

Examples of the oxime ester-based polymerization initiator include 1,2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyloxime)], etanone, 1- [9-ethyl-6-. (2-Methylbenzoyl) -9H-carbazole-3-yl]-, 1- (0-acetyloxime) and the like can be mentioned.

In the anti-microbial member of the present invention, the above-mentioned polymerization initiator contains an alkylphenone-based polymerization initiator and a benzophenone-based polymerization initiator, and the ratio of the alkylphenone-based polymerization initiator to the benzophenone-based polymerization initiator is determined. It is desirable that the alkylphenone-based polymerization initiator / benzophenone-based polymerization initiator = 1/1 to 4/1 in terms of weight ratio. This is because the crosslink density of the cured product of the electromagnetic wave curable resin becomes high.

The content ratio of the antimicrobial component in the antimicrobial composition is preferably 2.0 to 30.0% by weight, and the content ratio of the uncured electromagnetic wave curable resin (monomer or oligomer) is 15 to 40% by weight. Desirably, the content ratio of the dispersion medium is preferably 30 to 80% by weight.

If necessary, the antimicrobial composition may contain an ultraviolet absorber, an antioxidant, a light stabilizer, an adhesion accelerator, a rheology adjuster, a leveling agent, an antifoaming agent and the like.

When preparing the above antimicrobial composition, after adding the antimicrobial component, the monomer or oligomer and the polymerization initiator to the dispersion medium, the mixture is sufficiently stirred with a mixer or the like, and the antimicrobial component and the uncured electromagnetic wave curable resin are prepared. It is desirable to prepare a composition in which the polymerization initiator is dispersed at a uniform concentration, and then spray the composition.

As used herein, spraying refers to adhering the antimicrobial composition to the surface of a substrate in a divided state.
Examples of the spraying method include a spray method, a two-fluid spray method, an electrostatic spray method, an aerosol method and the like.

In the present invention, the spray method refers to spraying an antimicrobial composition in a mist state using a gas such as high-pressure air or mechanical movement (finger, piezo element, etc.), and the antimicrobial composition on the surface of the substrate. It means to attach the droplets of.
In the present invention, the two-fluid spray method is a kind of spray method, in which a gas such as high-pressure air and an antimicrobial composition are mixed and then sprayed from a nozzle in a mist state to the surface of the base material. Adhering droplets of microbial composition.
In the present invention, the electrostatic spray method is a spraying method using a charged antimicrobial composition, in which the antimicrobial composition is sprayed in a mist state by the above spray method, but the antimicrobial composition is atomized. There are a gun type in which the antimicrobial composition is sprayed with a sprayer and an electrostatic atomization method using the repulsion of the charged antimicrobial composition, and the gun type is further charged. There are a method of spraying the antimicrobial composition and a method of applying a charge to the sprayed atomized antimicrobial composition by corona discharge from an external electrode. Since the mist-like droplets are charged, they easily adhere to the surface of the base material, and the antimicrobial composition can be satisfactorily adhered to the surface of the base material in a finely divided state.
In the present invention, the aerosol method is a method of spraying a mist of a physically and chemically produced antimicrobial composition containing a metal compound onto an object.

By the above spraying step, the antimicrobial composition containing the antimicrobial component, the uncured electromagnetic wave curable resin, the dispersion medium, and the polymerization initiator is scattered on the surface of the base material in an island shape.

(2) Drying Step The antimicrobial composition containing the antimicrobial component sprayed on the surface of the base material by the spraying step, the uncured electromagnetically curable resin, the dispersion medium and the polymerization initiator is dried, and the dispersion medium is evaporated. , The binder cured product containing the antimicrobial component can be temporarily fixed to the surface of the substrate, and the antimicrobial component can be exposed from the surface of the binder cured product by shrinkage of the binder cured product. The drying conditions are preferably 60 to 100 ° C. and 0.5 to 5.0 minutes.

(3) Curing Step When producing the anti-microbial member, as a curing step, the monomer or oligomer which is the uncured electromagnetically curable resin in the anti-microbial composition from which the dispersion medium has been removed in the drying step is used. The electromagnetic wave curable resin is cured by irradiating it with an electromagnetic wave to obtain a binder cured product.
In the method for producing an antimicrobial member of the present invention, the electromagnetic wave irradiating the uncured electromagnetic wave curable resin is not particularly limited, and for example, ultraviolet rays (UV), infrared rays, visible rays, microwaves, and electron beams (Electron Beam). : EB) and the like, but among these, ultraviolet rays (UV) are desirable.

Further, the electromagnetic wave has a function of exciting a photopolymerization initiator and reducing a copper compound. Therefore, copper (II) can be reduced to increase the amount of copper (I) to increase the antimicrobial activity.

In the anti-microbial member of the present invention, the binding energies corresponding to Cu (I) and Cu (II) in the range of 925 to 955 eV are measured for 5 minutes by X-ray photoelectron spectroscopic analysis to obtain Cu in the copper compound. It is desirable that the coexistence of (I) and Cu (II) is confirmed. This is because Cu (I) and Cu (II) have higher antimicrobial activity when they coexist than when they are used alone.

In the anti-microbial member of the present invention, the copper is calculated by measuring the bond energies corresponding to Cu (I) and Cu (II) in the range of 925 to 955 eV for 5 minutes by X-ray photoelectron spectroscopic analysis. The ratio of the number of ions of Cu (I) and Cu (II) contained in the compound (Cu (I) / Cu (II)) is preferably 0.4 to 50.
Further, since the copper of Cu (I) is superior in antimicrobial properties to the copper of Cu (II), the first antimicrobial member of the present invention is subjected to X-ray photoelectron spectroscopic analysis to show that 925 to 5 Ions of Cu (I) and Cu (II) contained in the copper compound calculated by measuring the binding energy corresponding to Cu (I) and Cu (II) in the range of 955 eV for 5 minutes. When the ratio of the number (Cu (I) / Cu (II)) is 1.0 to 4.0, the anti-microbial member has more excellent anti-microbial properties.
By these steps, the cured binder containing an antimicrobial component is scattered on the surface of the substrate in an island shape, and the cured binder covers 10 to 55% of the surface of the substrate. Members can be manufactured.

Since the above-mentioned polymerization initiator is added to the above-mentioned antimicrobial composition, the polymerization reaction, the cross-linking reaction, and the like of the monomer or oligomer which is an uncured electromagnetically curable resin proceed by irradiating with electromagnetic waves. A binder cured product containing a copper compound is formed.
Since the antimicrobial composition sprayed by the above spraying step is scattered in an island shape, the obtained binder cured product is also scattered in an island shape.

The coverage of the cured binder on the substrate surface can be determined by controlling the concentration of the dispersion medium in the antimicrobial composition, the concentration of the antimicrobial component, the spraying pressure, the ejection speed of the coating liquid, the spraying time, and the like. , Can be adjusted. By manufacturing the antimicrobial member so that the cured binder covers 10 to 55% of the surface of the base material, the cured binder does not become thick and a large surface area can be secured, and a large surface area can be secured per unit loading amount. It is possible to provide an antimicrobial member having high antimicrobial activity.

Next, a method for producing an antimicrobial member when an inorganic binder is used as the binder will be described.
When producing the antimicrobial member, first, a spraying step of spraying an antimicrobial composition containing an antimicrobial component, an inorganic binder and a dispersion medium is performed on the surface of the base material, and then spraying is performed by the spraying step. The antimicrobial composition was dried to remove the dispersion medium, and a drying / curing step was performed to cure the antimicrobial composition, so that the cured binder containing the antimicrobial component was formed into islands on the surface of the base material. Scattered antimicrobial components can be obtained.

(1) Spraying Step When producing the antimicrobial member of the present invention, first, as a spraying step, an antimicrobial composition containing an antimicrobial component, an inorganic binder and a dispersion medium is sprayed on the surface of the base material.

The material of the base material to be sprayed is not particularly limited, and examples thereof include ceramics such as metal and glass, resins, textile fabrics, and wood.
Further, the member to be a base material is not particularly limited, and may be an interior material, a wall material, a window glass, a door, etc. inside a building, an office equipment, furniture, etc. In addition to the interior material, it may be a decorative board or the like used for various purposes.

Examples of the antimicrobial component include at least one selected from the group consisting of inorganic antimicrobial agents and organic antimicrobial agents.
The inorganic antimicrobial agents include silver, copper, zinc, platinum, zinc compounds, silver compounds, copper compounds, metal oxide catalysts carrying metals or metal oxides, zeolite ion-exchanged with metal ions, and It is desirable that the organic antimicrobial agent is at least one selected from the group consisting of copper complexes, and the organic antimicrobial agent is an antimicrobial resin, a sulfonic acid-based surfactant, a copper alkoxide, and a bis-type quaternary ammonium. It is desirable that it be at least one selected from the group consisting of salts.

The inorganic binder is preferably at least one selected from the group consisting of silica sol, alumina sol, titania sol, zirconia sol and sodium silicate.

The type of the dispersion medium is not particularly limited, but it is preferable to use alcohols or water. Examples of alcohols include alcohols such as methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, and sec-butyl alcohol in consideration of lowering the viscosity.

The content ratio of the antimicrobial component in the antimicrobial composition is preferably 2 to 30% by weight, the content ratio of the inorganic binder is preferably 15 to 60% by weight, and the content ratio of the dispersion medium is 30 to 80% by weight. Is desirable. In this case, the content ratio of the inorganic oxide such as silica in the antimicrobial composition is 5 to 20% by weight.

If necessary, the antimicrobial composition may contain a pH adjuster, an adhesion accelerator, a rheology adjuster, a leveling agent, an antifoaming agent, and the like.
When preparing the above antimicrobial composition, after adding the antimicrobial component, the inorganic binder, etc. to the dispersion medium, the composition is sufficiently stirred with a mixer or the like to disperse the antimicrobial component, the inorganic binder, etc. at a uniform concentration. It is desirable to spray immediately after making a product.

Examples of the spraying method include a spray method, a two-fluid spray method, an electrostatic spray method, an aerosol method and the like. Moreover, you may use a roller or a brush.

In the present invention, the spray method refers to spraying an antimicrobial composition in a mist state using a gas such as high-pressure air or mechanical movement (finger, piezo element, etc.), and the antimicrobial composition on the surface of the substrate. It means to attach the droplets of.
In the present invention, the two-fluid spray method is a kind of spray method, in which a gas such as high-pressure air and an antimicrobial composition are mixed and then sprayed from a nozzle in a mist state to the surface of the base material. Adhering droplets of microbial composition.
In the present invention, the electrostatic spray method is a spraying method using a charged antimicrobial composition, in which the antimicrobial composition is sprayed in a mist state by the above spray method, but the antimicrobial composition is atomized. There are a gun type in which the antimicrobial composition is sprayed with a sprayer and an electrostatic atomization method using the repulsion of the charged antimicrobial composition, and the gun type is further charged. There are a method of spraying the antimicrobial composition and a method of applying a charge to the sprayed atomized antimicrobial composition by corona discharge from an external electrode. Since the mist-like droplets are charged, they easily adhere to the surface of the base material, and the antimicrobial composition can be satisfactorily adhered to the surface of the base material in a finely divided state.
In the present invention, the aerosol method is a method of spraying a mist of a physically and chemically produced antimicrobial composition containing a metal compound onto an object. Alternatively, it may be applied with a roller or a brush.

By the above spraying step, the antimicrobial composition containing the antimicrobial component, the inorganic binder and the dispersion medium is in a state of being scattered on the surface of the base material in an island shape.

(2) Drying / Curing Step The antimicrobial composition containing the antimicrobial component sprayed by the spraying step, the inorganic binder and the dispersion medium is dried, and the dispersion medium is evaporated and removed to cure the antimicrobial component. The cured binder containing the binder is fixed to the surface of the substrate. The drying conditions are preferably 20 to 100 ° C. and 0.5 to 5 minutes.
Before and after drying, the antimicrobial composition or the cured product may be irradiated with electromagnetic waves to excite the photopolymerization initiator. The electromagnetic wave is not particularly limited, and examples thereof include ultraviolet rays (UV), infrared rays, visible rays, microwaves, electron beams (EB), and the like, and among these, ultraviolet rays (UV) are preferable.
The electromagnetic wave has a function of exciting a photopolymerization initiator and reducing a copper compound. Therefore, copper (II) can be reduced to increase the amount of copper (I) to increase the antimicrobial activity.

For the coverage of the cured binder on the substrate surface, the concentration of the antimicrobial component in the antimicrobial composition, the concentration of the dispersion medium, the spraying pressure, the ejection speed of the coating liquid, the coating time, etc. are controlled. Can be adjusted by When spraying with a spray gun, adjust the coverage of the cured binder by changing the air pressure of the spray gun, the spray application width, the moving speed of the spray gun, the ejection speed of the coating liquid, and the coating distance. Can be done.

(Example 1)
(1) Dissolve cupric acetate (II) monohydrate powder (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) in pure water so that the concentration of copper acetate is 6.0 wt%, and then use a magnetic stirrer. A copper acetate aqueous solution was prepared by stirring at 600 rpm for 15 minutes. The ultraviolet curable resin solution is prepared by mixing a photoradical polymerization type acrylate resin (UCECOAT7200 manufactured by Daicel Ornex) and a photopolymerization initiator (OmnIrad500 manufactured by IGM) at a weight ratio of 98: 2, and stirring at 8000 rpm for 30 minutes using a homogenizer. And prepared. The 6.0 wt% copper acetate aqueous solution and the ultraviolet curable resin solution were mixed at a weight ratio of 1.9: 1.0 and stirred at 600 rpm for 2 minutes using a magnetic stirrer to prepare an antiviral composition.
The OmniIrad 500 manufactured by IGM is the same as the IRGACURE 500 manufactured by BASF, and is a 1: 1 mixture of 1-hydroxy-cyclohexyl-phenyl-ketone (alkylphenone) and benzophenone in a weight ratio of 1: 1. That is, the alkylphenone-based polymerization initiator and the benzophenone-based polymerization initiator are present in a weight ratio of 1: 1. This photopolymerization initiator is insoluble in water and exhibits reducing power by ultraviolet rays.

(2) Next, on a black glossy melamine plate having a size of 500 mm × 500 mm, ^{an antiviral composition equivalent to 2} g / m 2 was sprayed with a spray gun (with a dispersion medium at a ejection rate of 7.5 g / min). Using FINER SPOT G12) manufactured by Meiji Kikai Seisakusho, sprayed in a mist form at an air pressure of 0.1 MPa and a stroke speed of 30 cm / sec, and droplets of the antiviral composition were scattered on the surface of a black glossy melamine plate in an island shape. It was.

(3) After that, the black glossy melamine plate is dried at 80 ° C. for 3 minutes, and further irradiated with ultraviolet rays at an irradiation intensity of ^{30 mW / cm 2 for 80 seconds using an ultraviolet irradiation device (MP02 manufactured by COATTEC).} An anti-virus member in which a cured binder containing a copper compound was scattered in an island shape on the surface of a black glossy melamine plate, which was a material, was obtained. On the surface of the black glossy melamine plate, white letters having a size as large as that written on newspaper were written.

The ratio of the number of ions of Cu (I) and Cu (II) (Cu (I) / Cu (II)) was measured with respect to the copper compound contained in the cured binder obtained in Example 1 by the following method. did. As a result, Cu (I) / Cu (II) = 1.9. Since Examples 2 to 4 and Comparative Examples 2 and 3 also have the same compound, composition, and curing conditions, Cu (I) / Cu (II) = 1.9.

(Cu (I) / Cu (II) measurement test)
The ratio of the number of ions of Cu (I) and Cu (II) was measured by X-ray photoelectron spectroscopy (XPS analysis method). The measurement conditions are as follows.
・ Equipment: ULVAC-PHI PHI 5000 Versa probeII
-X-ray source: Al Kα 1486.6 eV
・ Detection angle: 45 °
・ Measurement diameter: 100 μm
-Charge neutralization: Yes-Wide scan-Measurement step: 0.8 eV
・ Pass energy: 177.8eV
-Narrow scan / measurement step: 0.1 eV
-Pass energy: 46.9 eV
The measurement time is 5 minutes, the peak position of Cu (I) is 932.5 eV ± 0.3 eV, the peak position of Cu (II) is 933.8 eV ± 0.3 eV, and the areas of the respective peaks are integrated. From the ratio, Cu (I) / Cu (II) was obtained.

(Example 2)
The antiviral composition in which the cured binder containing the copper compound is scattered in an island shape in the same manner as in Example 1 except that the amount of the antiviral composition sprayed in the form of a mist using a spray gun is ^{changed to 4 g / m 2.} A sex member was obtained.

(Example 3)
The antiviral composition in which the cured binder containing the copper compound is scattered in an island shape in the same manner as in Example 1 except that the amount of the antiviral composition sprayed in the form of a mist using a spray gun is ^{changed to 6 g / m 2.} A sex member was obtained.

(Example 4)
The antiviral composition in which the cured binder containing the copper compound is scattered in an island shape in the same manner as in Example 1 except that the amount of the antiviral composition sprayed in the form of a mist using a spray gun is ^{changed to 8 g / m 2.} A sex member was obtained.

(Comparative Example 1)
The antiviral composition was not sprayed on the black glossy melamine plate.

(Comparative Example 2)
The antiviral composition in which the cured binder containing the copper compound is scattered in an island shape in the same manner as in Example 1 except that the amount of the antiviral composition sprayed in the form of a mist using a spray gun is ^{changed to 12 g / m 2.} A sex member was obtained.

(Comparative Example 3)
The antiviral composition in which the cured binder containing the copper compound is scattered in an island shape in the same manner as in Example 1 except that the amount of the antiviral composition sprayed in a mist form using a spray gun ^{was changed to 16 g / m 2.} A sex member was obtained.

(Test Example 1)
(1) After suspending copper (I) chloride powder (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) in pure water so that the concentration of copper (I) chloride becomes 0.34 wt%, use a magnetic stirrer. , 600 rpm for 15 minutes to prepare a copper chloride suspension. The 0.34 wt% copper (I) chloride suspension and polyvinyl alcohol are mixed at a weight ratio of 1.9: 1.0 and stirred at 600 rpm for 2 minutes using a magnetic stirrer to prepare an antiviral composition. ..
(2) Next, prepare a glass plate having a size of 300 mm × 300 mm, and when the antiviral composition is applied to the surface of the glass plate by spraying, the cured product of the antiviral composition is applied to the surface of the glass plate. Is sprayed until 36.3% covered.
(3) After that, the glass plate is dried at room temperature for 24 hours, and an antiviral member in which a binder cured product containing a copper compound is fixedly formed so that a part of the surface of the glass plate as a base material is exposed. To get.

(Comparative Example 4)
An aqueous solution having a concentration of copper (II) acetate of 6 wt% was applied to the surface of a black glossy melamine plate having a size of 300 mm × 300 mm until the dried product covered the surface of the black glossy melamine plate by 36.3% when dried. II) The aqueous solution is sprayed and adhered. Then, it is dried at room temperature for 48 hours without irradiation with ultraviolet rays.

(Example 5)
(1) A photoradical polymerization type acrylate resin (UCECOAT7200 manufactured by Daicel Ornex), a photopolymerization initiator (OmnIrad500 manufactured by IGM) and a photopolymerization initiator (OmnIrad184 manufactured by IGM) are mixed at a weight ratio of 97: 2: 1. Then, using a homogenizer, the mixture is stirred at 8000 rpm for 10 minutes to prepare an ultraviolet curable resin solution. The OmniIrad500 manufactured by IGM is the same as the IRGACURE500 manufactured by BASF, and is a 1: 1 mixture of 1-hydroxy-cyclohexyl-phenyl-ketone (alkylphenone) and benzophenone. This photopolymerization initiator is insoluble in water and exhibits reducing power by absorbing ultraviolet rays. On the other hand, the photopolymerization initiator (OmnIrad184 manufactured by IGM) is 1-hydroxy-cyclohexyl-phenyl-ketone (alkylphenone), and after all, as the photopolymerization initiator, alkylphenone and benzophenone have a weight ratio of 2: 1. It exists in proportion.
(2) Water, bis-type quaternary ammonium salt (1,1'-didecyl-3,3'-[butane-1,4-diylbis (oxymethylene)] dipyridinium = dibromid) and the above ultraviolet curable resin solution. Mix at a weight ratio of 19: 0.51 / 10 and stir at 600 rpm for 2 minutes using a magnetic stirrer to prepare an antiviral composition.
(3) Next, on a black glossy melamine plate having a size of 500 mm × 500 mm, ^{an antiviral composition equivalent to 2} g / m 2 was sprayed with a spray gun (with a dispersion medium at a ejection rate of 7.5 g / min). Using FINER SPOT G12) manufactured by Meiji Kikai Seisakusho, spray the antiviral composition in a mist form at an air pressure of 0.1 MPa and a stroke speed of 30 cm / sec, and disperse the droplets of the antiviral composition on the surface of the black glossy melamine plate in an island shape. ..
(4) After that, the black glossy melamine plate is dried at 80 ° C. for 3 minutes, and further irradiated with ultraviolet rays at an irradiation intensity of ^{30 mW / cm 2 for 80 seconds using an ultraviolet irradiation device (MP02 manufactured by COATTEC).} An anti-virus member in which a cured binder containing a copper compound is scattered in an island shape on the surface of a black glossy melamine plate, which is a material, is obtained.

(Example 6)
Similar to Example 5, the antiviral composition in which the cured binder containing the copper compound is scattered in an island shape, except that the amount of the antiviral composition sprayed in the form of a mist using a spray gun is ^{changed to 4 g / m 2.} Obtain a sex member.

(Example 7)
Similar to Example 5, the antiviral composition in which the cured binder containing the copper compound is scattered in an island shape, except that the amount of the antiviral composition sprayed in the form of a mist using a spray gun is ^{changed to 6 g / m 2.} Obtain a sex member.

(Example 8)
The antiviral composition in which the binder cured product containing the copper compound is scattered in an island shape in the same manner as in Example 5 except that the amount of the antiviral composition sprayed in the form of a mist using a spray gun is ^{changed to 8 g / m 2.} Obtain a sex member.

(Comparative Example 5)
The antiviral composition was not sprayed on the black glossy melamine plate.

(Comparative Example 6)
The amount of the antiviral composition sprayed in a mist form using a spray gun ^{was changed to 12 g / m 2} , and in the same manner as in Example 5, the binder cured product containing the copper compound was scattered in an island shape. Obtain a sex member.

(Evaluation of the shape of the antiviral member and the dispersed state of the binder cured product)
The obtained antiviral member was photographed with an optical microscope (Microscope VHX-5000 manufactured by KEYENCE CORPORATION). FIG. 2 is an optical micrograph showing the antiviral member obtained in Example 1. It can be seen that the binder cured product 1 is scattered in an island shape on the surface of the black glossy melamine plate which is the base material.
Further, with respect to the antiviral members obtained in Examples 1 to 4 and Comparative Examples 1 to 3, the island-shaped binder cured product shown on the surface of the base material per 2410000 ^{μm 2 (1552 μm) was obtained by binarizing the images.} Three points were measured and the average surface coverage was calculated. The results are shown in Table 1.

(Antiviral evaluation using feline calicivirus)
This antiviral test was carried out as follows.
In order to evaluate the antiviral properties of the antiviral members obtained in Examples 1 to 4 and Comparative Examples 1 to 3, JIS Z 2801 antibacterial processed product-antibacterial test method-a method modified in antibacterial effect was used. .. The modification is that "inoculation of test bacterial solution" was changed to "inoculation of test virus". All changes due to the use of viruses were made based on the antiviral test method for JIS L 1922 textile products. The measurement results are based on JIS L 1922 Annex B for the antiviral members obtained in Examples 1 to 4 and Comparative Examples 1 to 3, and the concentration of feline calicivirus that has lost the ability to infect CRFK cells is not feline calicivirus. Display as activity. Here, the concentration of the virus inactivated to the CRFK cells (virus inactivity) was used as an index of the virus concentration, and the antiviral activity value was calculated based on the virus inactivity.

The procedure will be described in detail below.
(1) the antiviral member obtained in Examples 1 to 4 and Comparative Examples 1 to 3, place the test sample cut into a square having one side 50mm angle sterilized plastic Petri dish, test virus solution (> 10 ⁷ Inoculate 0.4 mL of PFU / mL).
Test virus solution is used after diluting 10-fold stock of ¹⁰ 8 PFU / mL with purified water.
(2) Prepare a 50 mm square polyethylene film as a control sample and inoculate the virus solution in the same manner as the test sample.

(3) Cover the inoculated virus solution with 40 mm square polyethylene, inoculate the test virus solution evenly, and then react at 25 ° C. for a predetermined time.
(4) Immediately after inoculation or after the reaction, add 10 mL of SCDLP medium and wash away the virus solution.
(5) Obtain the virus infection value according to JIS L 1922 Annex B.

(6) Calculate the antiviral activity value using the following formula.
Mv = Log (Vb / Vc)
Mv: Antiviral activity value Log (Vb): Logistic value of the infection value after the reaction of the polyethylene film for a predetermined time Log (Vc): Logistic reference standard of the infection value after the reaction of the test sample for a predetermined time JIS L 1922, JIS Z 2801
The measuring method was a plaque measuring method.
In addition, FelIne calcIvIrus; StraIn: F-9 ATCC VR-782 was used as the test virus.
The obtained antiviral activity values are shown in Table 1.

Table 1 shows the coating rate (%) of the surface of the substrate of the cured binder, the average surface coverage (%), the surface roughness Ra (μm) of the surface of the substrate after spraying and curing the antivirus composition. Ry (μm), Rz (μm), average surface roughness Ra (μm) averaged at 3 points, circle equivalent diameter (μm) of binder cured product, average circle equivalent diameter (μm), coating of antivirus composition The average value of the three-point actual measurement value of the area (nm ² ) and the three-point actual measurement value of the anti-virus composition coating area (nm ^{2 ), that is, the average coating area (nm 2} ) of the anti-virus composition, and the binder cured product. Number, area per binder cured product (nm ² ), average value of area per binder cured product (nm ² ), antivirus activity value, unit of binder cured product in one binder cured product The anti-virus activity value (× 10 ^-6 ) per area is shown.

FIG. 3 is a graph showing the results of antiviral activity per unit area of the binder cured product of the antiviral member obtained in Examples 1 to 4 and Comparative Examples 1 to 3. The horizontal axis in FIG. 3 is the coverage of the cured binder on the surface of the substrate, and the vertical axis is the antiviral activity value per unit area of the cured binder.
Since the island-shaped cured binder is generally uniform, the value obtained by dividing the antiviral activity value by the coverage area of one island of the cured binder is substituted as the antiviral activity value per unit carrying amount of the antiviral component. can do.
According to Tables 1 and 3 above, it can be seen that the antiviral activity value per unit area of the cured binder product in one island is most excellent in the range of 10 to 55% coverage on the surface of the substrate.

FIG. 4 is a graph showing the results of antiviral activity of the binder cured product of the antiviral member obtained in Examples 1 to 4 and Comparative Examples 1 to 3.
According to FIG. 4, it can be seen that the antiviral activity value of the cured binder is best in the range of 10 to 55% of the coverage on the surface of the base material. It is presumed that this is because the total surface area of the antiviral binder cured product has increased, the probability of contact with viruses has increased, and the virus has been trapped in the unevenness, making it easier to inactivate the virus. doing.

(Design on the surface of the base material)
It was confirmed whether or not the characters on the surface of the base material could be visually recognized with respect to the base material made of the black glossy melamine plate to which the island-shaped binder cured product produced in Examples 1 to 4 and Comparative Examples 1 to 3 was adhered. As a result, the characters could be visually recognized in Examples 1 to 4 and Comparative Example 1, but the characters could not be visually recognized in Comparative Examples 2 and 3.

In general, the infectivity of the virus, such as norovirus and influenza viruses, emissions of patients (saliva splash, feces) per 1g, 10 and ⁸ is said to be present, also, viral contamination range of the palm of the hand, It is assumed to be in the range of 10 cm x 10 cm. Feces or saliva splashes adhere to the palm, assuming that contaminate the range of 10 cm × 10 cm of the wall or desk surface, in order to deactivate the 10 ⁸ virus, calculated per area of 10 cm × 10 cm Therefore, antiviral activity having a value of 8 or more as an antiviral activity value is required. On the other hand, since the vertical axis of the graph in FIG. 3 is ^{the antiviral activity per 2410000 μm 2} (2.41 mm ² ), the fact that the antiviral activity value converted per area of 10 cm × 10 cm is 8 or more is shown in FIG. When converted to the graph of, an antiviral activity value of 8 × 2.41 / 10000 ≈ 0.002 or more is required. In the present invention, if it is 0.002 (2000 × ^10-6 ) or more, it is considered to be within a range that can withstand practical use, and such antiviral activity is used to increase the coverage of the surface of the cured binder binder with 10%. It was realized by adjusting to ~ 55%.
Further, in the antiviral member of the present invention, the unit carrying amount (unit) of the binder cured product in one antiviral binder cured product is adjusted by adjusting the coverage of the antiviral binder cured product on the surface of the base material. Since the antiviral activity per area) can be increased, a practical antiviral activity can be obtained with a minimum antiviral composition.
Further, according to the graph of FIG. 4, the practical antiviral activity value 3 is obtained by adjusting the coverage from 10 to 55% based on the relationship between the coverage of the surface of the binder cured product and the antiviral activity. It can be seen that the above can be achieved.

The antiviral activity values of Test Example 1 and Comparative Example 4 were 3.3 and 1.5, respectively, which are lower than those of Example 3 having the same coverage, but Test Example 1 Then, only Cu (I) is present in the cured product, the antioxidant effect of Cu (I) of Cu (II) does not work, and in Comparative Example 4, only Cu (II) is present in the dried product. Since it does not contain a binder, it is presumed that the surface area of the cured binder showing antiviral properties is small and the antiviral activity is low.

Further, with respect to the antiviral members of Examples 5 to 8 and Comparative Examples 5 and 6, the average surface coverage was determined in the same manner as in Examples 1 to 4 and Comparative Examples 1 to 3, and the antiviral using feline calicivirus was used. An antiviral activity value was obtained by a sex test. The results are shown in Table 2.

As is clear from Table 2, the antiviral members of Examples 5 to 8 can achieve an antiviral activity of 4 or more with a coverage of 10% to 55%, but the members of Comparative Example 5 have antiviral activity. No viral activity is observed, and even if the coverage is too high as in the antiviral member of Comparative Example 6, sufficient antiviral activity cannot be obtained.

According to the above-mentioned Examples and Comparative Examples, in the antiviral members obtained in Examples 1 to 8, binder cured products containing an antiviral component were scattered in an island shape on the surface of a black glossy melamine plate as a base material. Moreover, since the cured binder covers 10 to 55% of the surface of the base material, it has been proved that it is an antiviral member having high antiviral activity per unit carrying amount.

(Evaluation of antibacterial properties using Staphylococcus aureus)
Antibacterial evaluation using Staphylococcus aureus was carried out as follows.
(1) The antiviral members obtained in Examples 1 to 3 and 5 to 8 and Comparative Examples 1 to 3, 5 and 6 were cut into a 50 mm square and a test sample was placed in a sterilized plastic petri dish for testing. Inoculate 0.4 mL of the bacterial solution (number of bacteria 2.5 × 10 ⁵ to 10 × 10 ^{5 / mL).}
For the test bacterial solution, the cultured bacteria pre-cultured in the incubator at a temperature of 35 ± 1 ° C. for 16 to 24 hours are further transplanted to the slope medium and pre-cultured in the incubator at a temperature of 35 ± 1 ° C. for 16 to 20 hours. The one that has been appropriately adjusted with 1/500 NB medium is used.
(2) Prepare a 50 mm square polyethylene film as a control sample, and inoculate the test bacterial solution in the same manner as the test sample.
(3) Cover the inoculated test bacterial solution with a 40 mm square polyethylene film, inoculate the test bacterial solution evenly, and then react at a temperature of 35 ± 1 ° C. for 8 ± 1 hour.
(4) Immediately after inoculation or after the reaction, add 10 mL of SCDLP medium and wash out the test bacterial solution.
(5) The wash-out solution is appropriately diluted and mixed with a standard agar medium to prepare a petri dish for measuring the viable cell count. After culturing at a temperature of 35 ± 1 ° C. for 40 to 48 hours, the number of colonies is measured.
(6) Calculation of viable cell count The viable cell count is calculated using the following formula.
N = C × D × V
N: Number of viable bacteria C: Number of colonies D: Dilution ratio V: Liquid volume (mL) of SCDLP medium used for washing out
(7) Calculate the antibacterial activity value using the following formula.
R = (Ut-U0)-(At-U0) = Ut-At
R: Antibacterial activity value U0: Mean value of log value of viable cell count immediately after inoculation of unprocessed test piece Ut: Mean value of log value of viable cell count 24 hours after inoculation of unprocessed test piece At: Antibacterial processed test piece Reference standard JIS Z 2801
Staphylococcus aureus NBRC12732 was used as the test bacterium.
The evaluation results are shown in Tables 3 and 4.

(Evaluation of antifungal properties using Aspergillus niger)
The antifungal property evaluation using Aspergillus niger was carried out as follows.
(1) The test samples obtained by cutting out the antiviral members obtained in Examples 1 to 4, 5 to 8 and Comparative Examples 1, 3, 5 and 6 into 50 mm square squares were placed in a sterilized plastic petri dish, and spores were placed. Inoculate 0.4 mL of the suspension (spore concentration> 2x10 ^{5 cells / ml).}
(2) Prepare a 50 mm square polyethylene film as a control sample, and inoculate the spore suspension in the same manner as the test sample.
(3) Cover the inoculated spore suspension with a 40 mm square polyethylene film, inoculate the spore suspension evenly, and then react for 42 hours while irradiating light of about 900 LUX at a temperature of 26 ° C.
(4) Immediately after inoculation or after the reaction, the amount of ATP is measured according to the measurement of JIS L 1921 13 luminescence amount.
(5) Calculate the antifungal activity value using the following formula.
A _a = (LogC _t- LogC ₀ )-(LogT _t- LogT ₀ )
A _a : Antifungal activity value LogC ₀ : Arithmetic mean of ATP amount of 3 control samples immediately after inoculation LogC _t : Arithmetic mean of ATP of 3 control samples after culture LogT ₀ : Arithmetic mean of the ATP amount of the three test samples immediately after inoculation LogT _t : Common logarithmic reference standard of the arithmetic mean of the ATP amount of the three test samples after culture JIS Z 2801, JIS L 1921
Aspergillus nIger NBRC105649 was used as the test mold.
The evaluation results are shown in Tables 3 and 4.

As described above, the antiviral member according to the embodiment of the present invention exhibits excellent antiviral performance when the coverage of the cured binder is 10 to 55%, and the surface of the substrate is covered with the cured binder. When the rate is 10 to 55%, it can be seen that the antifungal property is also excellent. The same applies to antibacterial properties.
When the coverage of the substrate surface with the cured binder is 10 to 55%, the unevenness of the surface of the substrate containing the cured binder will be in an appropriate range and the total surface area will be large, so spores of viruses, bacteria and molds will increase. It is presumed that the contact probability with is high and that it is excellent in antiviral, antibacterial, and antifungal properties.
It should be noted that the effect of improving the antimicrobial activity by adjusting the coating ratio of the surface of the cured binder material is higher in antiviral and antifungal properties than in antibacterial properties, and the effect of the present invention is particularly high. I can say. As described above, the antiviral members of Examples 1 to 8 can also be used as antibacterial and antifungal members. That is, the antimicrobial member of the present invention has excellent antimicrobial performance.

10 Antimicrobial member 11 Base material 12 Binder cured product

Claims (1)

A binder cured product containing a copper compound as an antiviral component is fixed to the surface of the base material, and the binder cured product is composed of a cured product of an electromagnetic wave curable resin.
The binder cured product is scattered on the surface of the base material in an island shape, or a region in which the binder cured product is formed and a region in which the binder cured product is not formed are mixed. Is fixed and formed,
Antiviral member to which the binder cured product, characterized in that covering the 10-55% of the coating area of the substrate surface.

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