JP2021075559A - Antimicrobial member - Google Patents

Abstract

To provide an antimicrobial member that has high antimicrobial activity per unit amount of carrying even when it is wiped and cleaned.SOLUTION: An antimicrobial member has a binder cured product containing an antimicrobial component fixedly formed on the base material surface, wherein the binder cured product coats the base material surface in a range of more than 55% to 95% or less.SELECTED DRAWING: Figure 3

Description

The present invention relates to an antimicrobial member.

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 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.

Republished 2008-47810

However, in the antibacterial base material described in Patent Document 1, 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 the antibacterial metal is attached by sputtering. However, if the surface is wiped clean with a cloth or the like, there is a problem that the antibacterial and antiviral activities are lowered.

The present invention has been made in view of such a problem, and an object of the present invention is to provide an antimicrobial member having high antimicrobial activity per unit carrier amount even when wiped and cleaned.

In the antimicrobial member of the present invention, a cured binder containing an antimicrobial component is fixedly formed on the surface of the base material, and the cured binder covers a range of more than 55% and 95% or less of the surface of the base material. It is characterized by being.

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 fixedly formed on the surface of the base material, and the binder cured product covers a range of more than 55% and 95% or less of the base material surface. Therefore, the convex part composed of the hardened binder is relatively small, and it is difficult to be damaged by wear. Therefore, the force and friction of peeling from the surface of the base material are applied to the hardened binder by wiping and cleaning. Even in this case, the cured binder is not lost from the surface of the base material, and an antimicrobial member having high antimicrobial activity per unit carrying amount can be provided.
When the uneven surface of the cured binder is wiped off and cleaned, a frictional force is concentrated on the convex portion, and the convex portion is likely to be damaged. However, in the present invention, the coverage of the cured binder is high and flattened. Therefore, the relative amount of the convex portion is reduced, and as a result, it is possible to prevent the binder cured product from being lost due to wear.
In the present invention, since the antimicrobial activity per unit loading amount can be increased, sufficient antimicrobial performance can be realized with the minimum necessary antimicrobial composition.

In the present specification, the binder cured product covers more than 55% and 95% or less of the surface of the base material, and the binder cured product forming region in which the binder cured product is formed and the binder in which the binder cured product is not formed are formed. It suffices as long as it is in a state where the cured product non-forming region and the cured product non-forming region are mixed. That is, the binder cured product is fixedly formed on the surface of the base material so as to expose a part of the surface of the base material. The cured binder may be formed in an island shape, and a region in which the cured binder is fixedly formed on the surface of the base material and a region in which the cured binder is not fixedly formed are provided in a mixed state. There may be.

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 hardened binder scattered in an island shape is not particularly limited, and when the contour is viewed in a plan view, 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 in the shape of a circle, an ellipse, or the like connected to each other through a thin portion, or it may be in the shape of an amoeba. In addition, the islands may be adjacent to each other without being intricately in contact with each other.
Further, the binder cured product is formed in a film shape, and a binder cured product in a state in which a region in which the cured product is not formed is mixed in the formed region of the film-shaped binder cured product and an island-shaped cured product. The hardened binder formed in the above may be mixed.

In the antimicrobial member of the present invention, when the coverage of the cured binder with respect to the surface of the base material is 55% or less, the surface area per one cured binder becomes small and the contact area with the surface of the base material decreases. At the same time that the hardened binder is easily removed, the convex part occupies a relatively large area as a whole, so that the convex part is worn and damaged by a physical load such as wiping and cleaning. As a result, the binder cured product containing the antimicrobial component is lost, and the antimicrobial activity is reduced. That is, the durability of the antimicrobial activity is reduced. On the other hand, if the coverage of the cured binder to the surface of the substrate exceeds 95%, the area of the peripheral side surface of the cured binder becomes small and the probability of contact with microorganisms such as viruses decreases, so that per unit area. The antimicrobial activity is also reduced.
As described above, in the present invention, the coating ratio of the cured binder to the surface of the base material is adjusted to exceed 55% and 95% or less, and the relative amount of the convex portion of the cured binder is reduced to make it slippery. By doing so, the physical load such as wiping and cleaning is prevented from being concentrated, the binder cured product is prevented from being worn and damaged, and the antimicrobial activity is not reduced even by wiping and cleaning. It improves the durability of microbial activity.
Further, by adjusting the coverage of the cured binder to the surface of the base material so as to exceed 55% and 95% or less, it is possible to form an uneven shape due to the cured binder, and the binder exhibits antimicrobial properties. Since the surface area of the cured product can be increased, the contact probability between the cured binder that exhibits antimicrobial properties and microorganisms such as viruses can be increased, and microorganisms such as viruses can be placed in the gaps between the cured binders. Since it can be easily trapped, it is easy to inactivate microorganisms such as viruses.

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 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-based 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 electromagnetic wave 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, the binder cured product having excellent adhesion is relatively easily fixed to the surface of the base material. be able 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 an organic 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 substrate surface 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 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 aesthetic 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 thickness of 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. The design is easily dispersed in an island shape, or a region in which the cured binder is fixedly formed on the surface of the base material and a region in which the cured binder is not fixedly formed are provided in a mixed state. It is possible to prevent the appearance and aesthetics of the above from being spoiled, and it is possible to obtain high antimicrobial activity.

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, the arithmetic mean roughness (Ra) of the surface of the base material on which the binder cured product containing the antimicrobial component is adhered is 0.1 to 5 μm in accordance with JIS B 0601. Is desirable.

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 on which the binder cured product containing the antimicrobial component is adhered to the surface is based on JIS B 0601. If it is 0.1 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 unevenness of the surface will increase. 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 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, it becomes difficult for microorganisms such as viruses to be trapped, and as a result, the antimicrobial activity is lowered.
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, when the binder cured product is scattered 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 to exist.

In the antimicrobial member of the present invention, when the cured binder is scattered in an island shape, the cured binder in the island shape is 0.05 × 10 ⁸ to 30 × 10 ^{8 per square meter of the surface of the base material.} If there are individual binders, the size of the cured binder is set appropriately, and it is possible to prevent the appearance and aesthetics of the design, etc. formed on the surface of the base material from being spoiled, and per unit carrying amount. It is an antimicrobial member with high antimicrobial activity.

Keep the antimicrobial member of the present invention, when the binder cured product are scattered like islands, the number of the islands of binder cured product, the surface per square meter 0.05 × 10 than ⁸ base If there is, in order to reduce the coverage of the surface of the cured binder to 95% or less, it is necessary to increase the area of the cured binder per piece, the total surface area of the cured binder becomes smaller, and the binder becomes smaller. The contact probability between the cured product and a microorganism such as a virus decreases, and 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 lost during wiping and cleaning, resulting in antimicrobial activity. Since the property is reduced, the physical durability of the antimicrobial performance is also reduced.

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 55 to 95 on the surface of the base material. It is desirable that it is an antimicrobial member characterized by covering%.

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 55 to 95% of the surface of the base material, and the cured product of the electromagnetic wave curable resin having antimicrobial activity is island-shaped. A state in which a region is dispersed and fixed to the surface of the base material, or a region in which a cured product of an electromagnetic wave curable resin containing an antimicrobial component is formed and a region in which a cured product of an electromagnetic wave curable resin is not formed are mixed. Therefore, the total surface area of the cured product of the electromagnetic wave curable resin exhibiting antimicrobial activity is increased, the contact probability with microorganisms such as viruses is increased, and the electromagnetic wave curable resin exhibiting antimicrobial activity is cured. This is because microorganisms such as viruses are trapped in the convex portions of the object and the concave portions formed between the convex portions, and the microorganisms such as viruses are easily inactivated.
Further, since the coverage of the cured product of the electromagnetic wave curable resin is high and flattened, the relative amount of the convex portion is reduced, and as a result, it is possible to suppress the loss of the cured product of the electromagnetic wave curable resin due to wear.

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 reducing copper (II) to copper (I) having high antimicrobial performance while advancing the polymerization reaction and the cross-linking reaction.

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 is increased, and the durability against stress and abrasion generated during wiping and cleaning is improved.
The cured product was immersed in boiled toluene for 8 hours to dry, and the crosslink density was measured by measuring the weight of the cured product after immersion / the weight of the cured product before immersion × 100%. The crosslink density of each member is 97%. On the other hand, when the same resin as in Examples 1 and 3 is used and the ratio of the alkylphenone-based polymerization initiator / benzophenone-based polymerization initiator is 0.5 / 1 and 5/1, the cross-linking densities are 91%, respectively. Drops to. 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 used in a manner in which a wiping and cleaning treatment is performed. This is because it has excellent durability against stress and abrasion generated during wiping and cleaning. That is, it is used in a mode in which the antimicrobial member is wiped and cleaned.

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, and antifungal (including antifungal) properties, but is excellent in antiviral activity and antifungal activity, and in particular, antiviral has the highest activity.

FIG. 1 is a plan view schematically showing an embodiment of the antimicrobial member of the present invention. 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 antiviral member obtained in Examples 1 and 2 and Comparative Examples 1 and 2. FIG. 4 is a graph showing the results of the antiviral activity of the antiviral members obtained in Examples 1 and 2 and Comparative Examples 1 and 2.

(Detailed description of the invention)
Hereinafter, the antimicrobial member of the present invention will be described in detail.
In the antimicrobial member of the present invention, a cured binder containing an antimicrobial component is fixedly formed on the surface of the base material, and the cured binder covers a range of more than 55% and 95% or less of the surface of the base material. It is characterized by being.

FIG. 1 is a plan view schematically showing an embodiment of the antimicrobial member of the present invention.

As shown in FIG. 1, in the antimicrobial member 10 of the present invention, the binder cured product is provided on the surface of the base material 11 in the film forming region 12 in which the antimicrobial binder cured product is formed in a film shape. The non-film-formed region 13 is in a mixed state.

In the anti-microbial member of the present invention, the binder cured product does not exist on the entire surface of the base material, and the binder cured product forming region where the binder cured product is formed and the binder cured product non-forming where the binder cured product is not formed are formed. Since the regions are mixed, 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 hard to peel 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 paper 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 inorganic particles, 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 silver, copper, zinc, platinum, zinc compound, silver compound, copper compound, metal or metal oxide particles carrying a metal oxide, or a metal. 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 copper water-soluble inorganic salts.
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 acetate (II), copper acetate (I), copper oxalate (I), copper benzoate (II), copper phthalate (II) and the like.
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) ethoxide, 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. Anatase-type titanium oxide containing copper in the range of / TiO ₂ (% by weight) = 1.0 to 3.5, and cuprous 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, for example, copper (I) oxide (copper oxide), copper (II) oxide, copper (II) carbonate, copper (II) hydroxide, copper (II) chloride, and silver. At least one of the exchanged zeolite, nanosilver and copper, alumina with at least one of the ions and copper ions, silica with at least one of the nanosilver and copper, nanosilver and copper were supported. Examples thereof include titanium oxide in which at least one of zinc oxide, nanosilver and copper is supported, or inorganic particles such as tungsten oxide, calcium phosphate in which at least one of 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, velverine, tioxolone, salicylic acid and 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, mononitroguayacol 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 provide 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 by pulverization. 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, a 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 general formula (14). Examples thereof include a bis-type quinolinium salt having a chemical structure substituted with the quinolium group shown in. 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 and an ether group. 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 antimicrobial 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 electromagnetically 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 droplets on the surface of the substrate using an antimicrobial composition containing a monomer or oligomer which is an uncured electromagnetically curable resin, a polymerization initiator, various additives, and an antimicrobial component, the substrate is irradiated with electromagnetic waves. As a result, the polymerization initiator causes reactions such as cleavage reaction, hydrogen abstraction reaction, and electron transfer, and the photoradical molecule, photocation molecule, photoanion molecule, etc. generated thereby attack the monomer and the oligomer, and the monomer. And the polymerization reaction and the cross-linking reaction of the oligomer proceed, and a binder cured product containing an antimicrobial 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, 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 an alicyclic epoxy resin, an alicyclic epoxy resin, an alicyclic epoxy resin, a glycidyl ether type epoxy resin, a glycidyl ether type epoxy resin, and an 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.
Binder curing containing antimicrobial component is performed by mixing an inorganic binder, an antimicrobial component and, if necessary, various additives and dispersion media to form droplets on the surface of a substrate using an antimicrobial composition, and then drying the mixture. An object (a cured product of an inorganic binder) is formed.

When the droplets are isolated and adhere to the surface of the base material, the hardened binder becomes island-like, and when the droplets are superimposed on the surface of the base material and adhere, the hardened binder becomes a film, and the hardened binder becomes hardened with the binder. The form is a mixture of a product-forming region and a non-forming region in which a binder cured product is not formed. This is the same for the electromagnetic wave curable resin described above.

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 substrate surface 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 thickness of 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 make the region scattered in an island shape or the region where the cured binder is fixedly formed on the surface of the base material and the region where the cured binder is not fixedly formed. It is possible to prevent the appearance from being spoiled and to obtain high antimicrobial activity.

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.

Further, in the antimicrobial member of the present invention, the surface of the binder cured product is covered with the binder cured product 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. It is possible to appropriately maintain the proportion of the non-existent portion, and 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.

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 aesthetic appearance of the design and the like are impaired.

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 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, the arithmetic mean roughness (Ra) of the surface of the base material on which the binder cured product containing the antimicrobial component is adhered is 0.1 to 5 μm in accordance with JIS B 0601. Is desirable.
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) according to JIS B 0601 of the surface on which the cured binder containing the antimicrobial component is adhered is 0.1 to 5 μm. , The surface area of the substrate surface containing the cured binder is within an appropriate range, the probability of contact between microorganisms such as viruses and antimicrobial components is high, and microorganisms such as viruses are likely to be trapped in the valleys of the surface irregularities. 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 of the substrate surface 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 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.
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, when the cured binders are scattered in an island shape, the cured binders in the island shape are 0.05 × 10 ⁸ to 30 × 10 ^{8 per square meter of the surface of the base material.} It is desirable to exist.

In the antimicrobial member of the present invention, when the cured binder is scattered in an island shape, the cured binder in the island shape is 0.05 × 10 ⁸ to 30 × 10 ^{8 per square meter of the surface of the base material.} If there are individual binders, the size of the cured binder is set appropriately, and it is possible to prevent the appearance and aesthetics of the design, etc. formed on the surface of the base material from being spoiled, and per unit carrying amount. It is an antimicrobial member with high antimicrobial activity.

Keep the antimicrobial member of the present invention, when the binder cured product are scattered like islands, the number of the islands of binder cured product, the surface per square meter 0.05 × 10 than ⁸ base If there is, in order to increase the coverage of the surface of the cured binder material to more than 55% and 95% or less, it is necessary to increase the area of the cured binder material per piece, and the total surface area of the cured binder material is increased. Is reduced, the contact probability between the cured binder and microorganisms such as viruses is reduced, and the antimicrobial activity is deteriorated.
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 lost 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 electromagnetic wave 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. A curing step is performed in which the uncured electromagnetic wave curable resin is irradiated with electromagnetic waves to cure the electromagnetic wave curable resin, and a binder cured product containing an antimicrobial component adheres to the surface of the base material to form a binder cured product. It is possible to obtain an antimicrobial member which covers a range of more than 55% and 95% or less of the surface of the base material.

(1) Spraying Step When producing the antimicrobial member of the present invention, first, as a spraying step, an antimicrobial component, an uncured electromagnetically 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, fiber woven fabrics, and wood.
Further, the member used as 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)], ethanone, 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 is increased, and the durability against stress and abrasion generated during wiping and cleaning is improved.

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 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 spray method described above, 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.

A state in which the antimicrobial composition containing the antimicrobial component, the uncured electromagnetic wave curable resin, the dispersion medium, and the polymerization initiator is isolated on the surface of the base material or a part of the surface of the base material is exposed by the above spraying step. It becomes a state where it is superimposed and adhered.

(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 the photopolymerization initiator and reducing the 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 binding 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, a cured binder containing an antimicrobial component adheres to the surface of the base material, and the cured binder covers a range of more than 55% and 95% or less of the surface of the base material. The antimicrobial member of the present invention can be produced.

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 isolated on the surface of the base material or superposed on the surface of the base material in an exposed state, the obtained binder cured product can be obtained. The region where the binder cured product is formed and the region where the binder cured product is not formed are mixed.

The coverage of the cured binder on the substrate surface can be determined by controlling 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 spraying time, and the like. , Can be adjusted. When spraying using a spray gun, the coverage of the cured binder can be adjusted by changing the air pressure of the spray gun, the spray coating width, the moving speed of the spray gun, the spraying speed of the coating liquid, and the coating distance.

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 a binder cured product containing an antimicrobial component was adhered to the surface of the base material. A microbial member 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 a 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, fiber woven fabrics, and wood.
Further, the member used as 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.

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 spray method described above, 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, droplets of the antimicrobial composition containing the antimicrobial component, the inorganic binder and the dispersion medium are superposed on the surface of the substrate in an isolated state or with a part of the surface of the substrate exposed and superimposed. Adhere to.

(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.

The coverage of the cured binder on the substrate surface can be determined by controlling 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 spraying time, and the like. , Can be adjusted. When spraying using a spray gun, the coverage of the cured binder can be adjusted by changing the air pressure of the spray gun, the spray coating width, the moving speed of the spray gun, the spraying speed of the coating liquid, and the coating distance.

(Example 1)
(1) Dissolve copper (II) acetate / monohydrate powder (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) in pure water so that the concentration of copper acetate is 0.7 wt%, and then use a magnetic stirrer. , 600 rpm for 15 minutes to prepare an aqueous cupric acetate solution. 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 0.7 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 Omnirad 500 manufactured by IGM is the same as the IRGACURE 500 manufactured by BASF, and is a 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, an antiviral composition equivalent to ^{12.0 g / m 2} was placed on a black glossy melamine plate having a size of 3000 mm × 3000 mm and containing a dispersion medium at an ejection rate of 7.5 g / min. Using a spray gun (FINER SPOT G12 manufactured by Meiji Kikai Seisakusho), spray the liquid in a mist form with an air pressure of 0.1 MPa, a liquid ejection amount of 0.02 g / sec, and a stroke speed of 30 cm / sec. Droplets were attached to the surface of a black glossy melamine plate.

(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 antiviral member was obtained in which a cured binder containing a copper compound was fixedly formed on the surface of a black glossy melamine plate, which is a material, so that a part of the surface was exposed.

Further, regarding the copper compound contained in the cured binder obtained in Example 1, the ratio of the number of ions of Cu (I) and Cu (II) (Cu (I) / Cu (II)) by the following method. Was measured. As a result, Cu (I) / Cu (II) = 1.9. Since Example 2 and Comparative Examples 1 and 2 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 area of each peak is integrated. Then, Cu (I) / Cu (II) was obtained from the ratio.

(Example 2)
Similar to Example 1, the binder cured product containing the copper compound was black glossy melamine, except that the amount of the antiviral composition sprayed in the form of a mist using a spray gun ^{was changed to 18.5 g / m 2.} An antiviral member fixed to the surface of the plate so as to expose a part of the surface was obtained.

(Comparative Example 1)
A binder cured product containing a copper compound was applied to the surface of the substrate 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 7.8 g / m 2.} A fixed antiviral member was obtained.

(Comparative Example 2)
Using the same antiviral composition as in Example 1, it was applied to the entire surface of the substrate with a No. 9 coat bar. After that, in the same manner as in Example 1, the mixture was 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) to form a film.} An antiviral member in which a cured binder containing a copper compound was fixedly formed on the surface of a substrate 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. To do.
(2) Next, prepare a glass plate having a size of 300 mm × 300 mm, and when the antiviral composition is cured on the surface of the glass plate by spraying, the cured product of the antiviral composition is formed on the glass plate. Spray until 75% of the surface is 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 3)
An aqueous solution having a concentration of copper (II) acetate of 0.7 wt% is placed on a black glossy melamine plate having a size of 300 mm × 300 mm, and acetic acid is applied to the surface of the melamine plate until the dried product covers the surface of the melamine plate by 75% when dried. An aqueous solution of copper (II) is sprayed by mist to adhere. Then, it is dried at room temperature for 48 hours without irradiation with ultraviolet rays.

(Example 3)
(1) A photoradical polymerization type acrylate resin (UCECOAT7200 manufactured by Daicel Ornex), a photopolymerization initiator (Omnirad500 manufactured by IGM) and a photopolymerization initiator (Omnirad 184 manufactured by IGM) are mixed at a weight ratio of 97: 2: 1. , Using a homogenizer, stir at 8000 rpm for 10 minutes to prepare an ultraviolet curable resin solution. The Omnirad 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. This photopolymerization initiator is insoluble in water and exhibits reducing power by absorbing ultraviolet rays. On the other hand, the photopolymerization initiator (Omnirad 184 manufactured by IGM) is 1-hydroxy-cyclohexyl-phenyl-ketone (alkylphenone), and as a 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, an antiviral composition equivalent to ^{12.0 g / m 2} was placed on a black glossy melamine plate having a size of 500 mm × 500 mm and containing a dispersion medium at an ejection rate of 7.5 g / min. Using a spray gun (FINER SPOT G12 manufactured by Meiji Kikai Seisakusho), spray the droplets of the antiviral composition on the surface of the black glossy melamine plate in a mist form at an air pressure of 0.1 MPa and a stroke speed of 30 cm / sec. Scatter in a 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 antiviral member is obtained in which a cured binder containing a copper compound adheres to the surface of a base material on the surface of a black glossy melamine plate which is a material.

(Example 4)
Antiviral property in which the binder cured product adhered to the surface of the substrate in the same manner as in Example 3 except that the amount of the antiviral composition sprayed in a mist form using a spray gun ^{was changed to 18.5 g / m 2.} Get the member.

(Example 5)
Antiviral property in which the binder cured product adhered to the surface of the substrate in the same manner as in Example 3 except that the amount of the antiviral composition sprayed in a mist form using a spray gun ^{was changed to 20.0 g / m 2.} Obtain a member.

(Comparative Example 4)
Antiviral property in which the binder cured product adhered to the surface of the substrate in the same manner as in Example 3 except that the amount of the antiviral composition sprayed in a mist form using a spray gun ^{was changed to 7.0 g / m 2.} Obtain a member.

(Comparative Example 5)
Using the same antiviral composition as in Example 3, the coating bar No. 9 is applied to the entire surface of the substrate.

(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 2. It can be seen that the binder cured product is fixedly formed on the surface of the black glossy melamine plate which is the base material so as to expose a part of the surface.
FIG. 2 shows a mixture of a region in which a cured binder is formed and a region in which a cured binder is not formed.

Further, with respect to the antiviral members obtained in Examples 1 and 2 and Comparative Example 1, the area of the cured binder shown on the surface of the substrate per 241291 ^{μm 2 (1552 μm □) was determined by binarizing the images.} The measurement was performed and the average surface coverage was calculated. ^{Moreover, the coating area (nm 2} ) of the binder cured product per ^{1 mm 2} was calculated from the observation range and the area of the binder cured product. Furthermore, the virus inactivity after the wiping test is divided by the coating area per ^{1 mm 2 (μm 2} ) to calculate the virus inactivity per unit coating area (× 10 ^-6 ), and the results are shown in the table. Shown in 1. In this example, it is ^{divided by the coating area per 1 mm 2} , but since the area of the melamine plate is the same in Examples 1 and 2 and Comparative Examples 1 and 2, it is divided by the coating area per ^{1 mm 2.} By comparing the values, the virus inactivity (antiviral activity) per unit coating area can be compared.
For Comparative Example 2, it was confirmed that there were no defects such as holes in the film of the cured binder, and the area coverage was calculated as 100%.

(Wipe off the surface of antiviral material)
The antiviral members obtained in Examples 1 and 2 and Comparative Examples 1 and 2 were wiped 5475 times at a pressure of 150 Pa using a microfiber cloth impregnated with tap water.

(Antiviral evaluation using phage virus)
This antiviral test was carried out as follows.
In order to evaluate the antiviral property of the antiviral members obtained in Examples 1 and 2 and Comparative Examples 1 and 2 after the surface wiping treatment, JIS Z 2801 antibacterial processed product-antibacterial test method / antibacterial effect was introduced. A modified method 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 and 2 and Comparative Examples 1 and 2, and the concentration of the phage virus that has lost the ability to infect Escherichia coli is displayed as the virus inactivity. To do. Here, the concentration of the virus inactivated against Escherichia coli (virus inactivity) was used as an index of the virus concentration, and the antiviral activity value was calculated based on this virus inactivity.

The procedure will be described in detail below.
(1) The antiviral members obtained in Examples 1 and 2 and Comparative Examples 1 and 2 were subjected to the above-mentioned surface wiping treatment, and then the antiviral members were cut into squares having a side of 50 mm square for testing. It was used as a sample. Place the test specimen in sterilized plastic Petri dish, test virus solution ^(> 10 7 PFU / mL) to 0.4mL inoculation.
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 infection value after reaction for a predetermined time of polyethylene film Log (Vc): Logistic value reference standard of infection value after reaction for a predetermined time of test sample JIS L 1922, JIS Z 2801
The measuring method was a plaque measuring method.
The obtained antiviral activity values are shown in Table 1.

Table 1 shows the coverage (%) of the substrate surface of the cured binder, the average surface coverage (%), the coating area of the antiviral composition measured at three points (μm ² ), and the antiviral composition. Average coating area of 3 points (μm ² ), measuring range of microscope (micron field) (μm ² ), measuring range of microscope (micron field) (mm ² ), coating per ^{1 mm 2} of antiviral composition The area (μm ² / mm ² ), anti-virus activity value, and anti-virus activity value per unit area of the binder cured product (× ^10-6 ) are shown.

FIG. 3 is a graph showing the results of antiviral activity per unit area of the binder cured product after wiping the surface of the antiviral member obtained in Examples 1 and 2 and Comparative Examples 1 and 2. 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.
FIG. 4 is a graph showing the results of the antiviral activity of the antiviral members obtained in Examples 1 and 2 and Comparative Examples 1 and 2. In FIG. 4, the horizontal axis is the coverage of the cured binder on the substrate surface, and the vertical axis is the antiviral activity value.
Since the binder cured product is generally uniform, the value obtained by dividing the antiviral activity value by the covering area of the binder cured product (× ^10-6 ) is substituted as the antiviral activity value per unit carrying amount of the antiviral component. be able to.

According to Table 1, FIG. 3 and FIG. 4, the antiviral activity value per unit area of the binder cured product after the surface wiping treatment is most in the range of 95% or less, with the coverage on the substrate surface exceeding 55%. It turns out to be excellent.
In FIG. 3, the vertical axis is the antiviral activity value per unit area of the binder cured product per ^{1 mm 2 , but since a base material having an area of 1 m 2} or more is used in practical use, the actual antiviral activity value. is 10 ⁶ times. After the wiping treatment, if the antiviral activity value is 3 or more, that is, if there is enough antiviral activity to reduce the amount of virus to 1/1000 or less, virus infection can be prevented and it is practically usable. Therefore, in the present invention, a range in which the antiviral activity value per unit area of the binder cured product per ^{1 mm 2 is 3 × 10 -6} or more is a practically effective range.
Further, the antiviral member of the present invention adjusts the coverage of the antiviral binder cured product on the surface of the base material to prevent the virus per unit carrying amount (unit area) of the antiviral binder cured product. Since the activity can be increased, practical antiviral activity can be obtained with a minimum amount of antiviral composition.
Further, also in FIG. 4, the antiviral activity value per unit area of the binder cured product after the surface wiping treatment is best in the range of 95% or less, with the coverage on the substrate surface exceeding 55%. I understand.

The antiviral activity values of Test Example 1 and Comparative Example 3 after the wiping treatment were 3.0 and 0.1, respectively, and the antiviral activity was higher than that of Example 2 (75.3%) having the same coverage. However, in Test Example 1, only Cu (I) was present in the cured product, the antioxidant effect of Cu (I) of Cu (II) did not work, and in Comparative Example 3, it was in the dried product. Since only Cu (II) is present in the product and does not contain a binder, it is considered that all the copper acetate has been removed by the wiping process.

With respect to the antiviral members of Examples 3 to 5 and Comparative Examples 4 and 5, the average surface coverage was determined and the antiviral test using a phage virus was performed in the same manner as in Examples 1 and 2 and Comparative Examples 1 and 2. The antiviral activity value was obtained. The results are shown in Table 2.

As is clear from Table 2, the antiviral members of Examples 3 to 5 have a coverage of 55% to 95% and can achieve an antiviral activity of 3 or more even after the wiping treatment, but in Comparative Example 4. In the member, the antiviral binder is worn or dropped by the wiping process, and sufficient antiviral performance cannot be obtained. Further, even if the coverage is too high as in the antiviral member of Comparative Example 5, sufficient antiviral activity cannot be obtained.

According to the above-mentioned Examples and Comparative Examples, in the antiviral members obtained in Examples 1 to 5, a binder cured product containing an antiviral component was fixedly formed on the surface of a black glossy melamine plate as a base material, and Since the cured binder material covers more than 55% and 95% or less of the surface of the base material, even if stress such as wiping and cleaning is applied to the surface of the antiviral base material, a binder containing an antiviral component. It has been proved that the cured product does not easily fall off or wear out and is not easily damaged, and that it becomes 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 test sample obtained by cutting out the antiviral members obtained in Examples 1 to 5 and Comparative Examples 1 to 2, 4 and 5 into a square of 50 mm square was placed in a sterilized plastic petri dish, and the test bacterial solution (bacteria) was placed. Number 2.5 x 10 ⁵ to 10 x 10 ⁵ / mL) is inoculated with 0.4 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, mixed with a standard agar medium to prepare a petri dish for measuring the viable cell count, cultured at a temperature of 35 ± 1 ° C. for 40 to 48 hours, and then 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: Average logarithmic number of viable cells immediately after inoculation of the unprocessed test piece Ut: Average logarithmic number of viable cells 24 hours after inoculation of the unprocessed test piece At: Antibacterial processed test piece Average value of logarithmic counts of viable cells after 24 hours of reference 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) A test sample obtained by cutting out the antiviral members obtained in Examples 1 to 5 and Comparative Examples 1 to 2, 4 and 5 into a square of 50 mm square was placed on a sterilized plastic petri dish, and a spore suspension (spore suspension). Inoculate 0.4 mL of 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 culturing 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 even after wiping treatment when the coverage of the substrate surface with the binder cured product exceeds 55% and is 95% or less. Further, when the coverage of the surface of the base material with the cured binder exceeds 55% and is 95% or less, it can be seen that the antifungal property is excellent even after the wiping treatment. The same applies to antibacterial properties.
When the coverage of the surface of the base material with the cured binder exceeds 55% and is 95% or less, the portion corresponding to the convexity of the cured antimicrobial binder becomes close to a flat shape, so that the surface becomes smooth and wiped off. It is presumed that the loss of the cured anti-microbial binder due to wear during time will be reduced, and that it will be excellent in antiviral, antibacterial, and antifungal properties even after wiping. The effect of improving the antimicrobial activity after wiping treatment by adjusting the coverage 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. Can be said to be particularly high. As described above, the antiviral members of Examples 1 to 5 can also be used as antibacterial and antifungal members.

10 Antimicrobial member 11 Base material 12 Membrane-forming region 13 Membrane-non-forming region

Claims (25)

A binder cured product containing an antimicrobial component is fixedly formed on the surface of the base material, and the binder cured product covers a range of more than 55% and 95% or less of the surface of the base material. Microbial member. The antimicrobial member according to claim 1, wherein the binder cured product contains at least one selected from the group consisting of an inorganic antimicrobial agent and an organic antimicrobial agent as the antimicrobial component. The inorganic antimicrobial agent includes 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 The antimicrobial member according to claim 2, which is at least one selected from the group consisting of copper complexes. The second aspect of claim 2, wherein 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. Antimicrobial member. The antimicrobial member according to any one of claims 1 to 4, wherein the cured binder contains an inorganic binder and / or a cured product of an electromagnetic wave curable resin. The antimicrobial member according to claim 5, wherein the electromagnetic wave curable resin is at least one selected from the group consisting of an acrylic resin, a urethane acrylate resin, a polyether resin, a polyester resin, an epoxy resin, and an alkyd resin. The antimicrobial member according to claim 5, wherein the inorganic binder is at least one selected from the group consisting of silica sol, alumina sol, titania sol, zirconia sol and sodium silicate. The antimicrobial member according to any one of claims 1 to 7, wherein a region in which the binder cured product is formed and a region in which the binder cured product is not formed are provided in a mixed manner. The cured binder is scattered on the surface of the base material in an island shape, or a region in which the cured binder is fixedly formed on the surface of the base material and a region in which the cured binder is not formed are provided in a mixed manner. The antimicrobial member according to any one of claims 1 to 8. Claims 1 to 9, wherein the binder cured product is formed in a film shape, and a region in which the binder cured product is not formed is mixed and provided in the region where the film of the binder cured product is formed. The antimicrobial member according to any one of the following items. The antimicrobial member according to any one of claims 1 to 10, wherein the antimicrobial member is an antiviral member. The antimicrobial member according to any one of claims 1 to 10, wherein the antimicrobial member is an antifungal member. 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 covers a range of more than 55% and 95% or less of the surface of the base material. An antimicrobial member characterized by being plastic. The antimicrobial member according to claim 13, wherein 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 is a copper compound, and the copper compound measures the binding energy corresponding to Cu (I) and Cu (II) in the range of 925 to 955 eV for 5 minutes by X-ray photoelectron spectroscopy. The antimicrobial member according to any one of claims 13 or 14, wherein the coexistence of Cu (I) and Cu (II) is confirmed. The antimicrobial component is a copper compound, and the copper compound measures the binding energy 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 claim that the ratio of the number of ions of Cu (I) and Cu (II) contained in the copper compound (Cu (I) / Cu (II)) calculated by the above is 0.4 to 50. Item 3. The anti-microbial member according to any one of Items 13 to 15. The antimicrobial member according to any one of claims 13 to 16, wherein the antimicrobial component is a bis-type quaternary ammonium salt. The antimicrobial member according to any one of claims 13 to 17, wherein the cured product of the electromagnetic wave curable resin is scattered on the surface of the base material in an island shape. The cured product of the electromagnetic wave curable resin is a state in which a region in which a cured product of the electromagnetic wave curable resin containing an antimicrobial component is formed and a region in which a cured product of the electromagnetic wave curable resin is not formed are mixed. Item 3. The antimicrobial member according to any one of Items 13 to 18. The antimicrobial member according to any one of claims 13 to 19, wherein the cured product of the electromagnetic wave curable resin further contains a polymerization initiator. The 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 the weight ratio of the alkylphenone-based polymerization initiator. The anti-microbial member according to claim 20, wherein the agent / benzophenone-based polymerization initiator = 1/1 to 4/1. The antimicrobial member according to any one of claims 13 to 21, wherein the antimicrobial member is an antiviral member. The antimicrobial member according to any one of claims 13 to 21, wherein the antimicrobial member is an antifungal member. The antimicrobial member according to any one of claims 1 to 23, wherein the antimicrobial member is used in a mode in which a wiping and cleaning treatment is performed. Use in an embodiment in which the antimicrobial member according to any one of claims 1 to 23 is wiped and cleaned.

Images