JP2021006588A - Antimicrobial member - Google Patents

Abstract

To provide an antimicrobial member which dispenses with expensive synthetic equipment, and continuously and simply exhibits antimicrobial performance such as antiviral properties having high reliability to a constructed installed product by on-site construction.SOLUTION: An antimicrobial member has a binder cured product containing an antimicrobial component stuck and formed on a surface of a base material, in which glossiness according to JIS Z 8741 of the surface of the base material containing the binder cured product is less than 45%.SELECTED DRAWING: Figure 1

Description

The present invention relates to an antimicrobial member having antimicrobial properties and at the same time being durable against wiping.

It is well known that trace amounts of metal ions such as silver, copper and zinc have antibacterial and antifungal effects, and such antibacterial metal ions are sterilized in the form of a metal salt such as silver nitrate. It is added to agents, disinfectants, etc. and is widely used in various fields. However, since such metal salts are handled in an aqueous solution, their uses are limited, and silver nitrate has strong mucosal irritation to the human body, and there are many problems in its safety.
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 the virus infection have also been reported.

Therefore, antimicrobial agents such as antibacterial, antifungal, and antiviral agents are being actively developed, and Patent Document 1 has a surface layer having antibacterial activity on at least one side, and the glossiness on the surface layer side is high. More than 100% antibacterial synthetic films are disclosed.

Further, Patent Document 2 describes a layer composed of a polymer substance in which an organic antibacterial agent component is bonded to a main chain or a side chain, a hydrophilic substance in which the organic antibacterial agent component is mixed or bonded to the polymer substance, and a composition containing a curing agent. Is disclosed as an antibacterial laminated film in which is laminated on at least one surface of a base film and the glossiness of the laminated surface is 65% or less.
Further, Patent Document 3 discloses an antiviral coating agent composed of cuprous oxide and a sugar having a reducing property.

Japanese Unexamined Patent Publication No. 10-86290 Japanese Unexamined Patent Publication No. 2000-263706 Japanese Patent No. 581248

However, the antibacterial synthetic resin stretched film of Patent Document 1 did not have sufficient antibacterial and antiviral performance. Further, the antibacterial laminated film of Patent Document 2 has a problem that when stress is applied to the surface of the antimicrobial layer during wiping and cleaning, the antimicrobial layer is worn and the antimicrobial performance is deteriorated. Further, even with the antiviral coat of Patent Document 3, sufficient antibacterial and antiviral performance could not be obtained. Therefore, there has been a demand for an antimicrobial member having excellent antimicrobial performance such as antibacterial, antiviral, and antifungal properties, and capable of continuously exhibiting antimicrobial performance.
Further, an antimicrobial member having high cost and high coatability has been desired.

The present invention has been made in view of such a problem, and does not require expensive synthetic equipment, and has high reliability and antiviral properties, etc. by on-site construction even for easily installed installation products. It is an object of the present invention to provide an antimicrobial member that continuously exhibits the antimicrobial performance of the above.

As a result of diligent research, the present inventors have newly found that the glossiness of a surface portion exhibiting antimicrobial properties such as antibacterial properties, antiviral properties, and antifungal properties contributes to antimicrobial properties, and the present invention has been made. Was completed.
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 surface of the base material containing the cured binder has a glossiness of less than 45% in accordance with JIS Z 8741. 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 fixed to the surface of the base material on the surface, and the glossiness of the base material surface containing the binder cured product according to JIS Z 8741 is 45. Since irregularities are formed on the surface of the base material containing the cured binder so as to be less than%, the surface area of the cured binder having antimicrobial activity becomes large, and microorganisms such as flowing viruses, fungi, and molds increase. The contact probability between the above-mentioned binder and the cured product is increased, and microorganisms such as viruses, bacteria, and molds can be inactivated.

Further, when the glossiness of the surface of the base material containing the cured binder is less than 45%, the amount of the cured binder containing the antimicrobial component adhered to the surface of the base material increases, and the unevenness becomes smooth. , The slipperiness of the surface of the cured binder becomes high, and even if the surface of the cured binder containing antimicrobial components is stressed during wiping and cleaning, the cured binder does not break due to wear, and the antibacterial of the cured binder has. The microbial activity does not decrease.
That is, it is desirable that the antimicrobial member of the present invention is used in a manner in which a wiping treatment is performed. Further, the present invention may be used in a mode in which the antimicrobial member of the present invention is wiped off.
Further, since the cured binder having microbial activity is formed in an uneven shape, microorganisms such as viruses are easily trapped in the concave portions having an uneven shape, and the microorganisms such as viruses can be reliably inactivated. The glossiness is particularly preferably 10% or more and less than 45%. This is because it can exhibit durability enough to maintain antimicrobial performance such as antiviral performance even when the force of abrasion such as wiping and cleaning works.
In the present invention, the glossiness is a value that can be measured according to JIS Z 8741 (1997), and as the measuring device, CM-25cG manufactured by Konica Minolta can be specifically used. The incident angle of the measurement light when measuring the glossiness is 60 °. The notation of glossiness is (%).

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 is fixed on the surface of the base material in a film form or dispersed in an island shape. It is desirable that the region is fixed to the surface of the base material, or the region where the cured binder is formed and the region where the cured binder is not formed are mixed and provided on the surface of the base material.

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 is dispersed in an island shape and fixed to the surface of the base material. Since the region where the binder cured product is formed and the region where the binder cured product is not formed are provided on the surface of the base material in a mixed manner, the surface of the base material is composed of a binder cured product composed of an antimicrobial component. Unevenness is formed. For this reason, the total surface area of the cured binder containing the antimicrobial component is larger than that in the case where the cured binder is formed into a film, so that the probability of contact with microorganisms such as viruses is increased, and viruses and the like are not present. Since microorganisms can be trapped between the cured binders, high antimicrobial activity can be obtained. In addition, since the anti-microbial component is contained in the cured binder, it has excellent adhesion to the base material and can be prevented from falling off by wiping and cleaning.
In the antimicrobial member of the present invention, when the cured binder is adhered to the surface of the substrate in the form of a film, the surface of the film is subjected to polishing treatment, blasting treatment, transfer treatment using a shaping plate, or the like. It is preferable to form an uneven shape to adjust the glossiness.

In the present specification, it is desirable that the binder cured product covers 10% or more and 95% or less of the surface of the base material, and the binder cured product forming region on which the binder cured product is formed and the binder cured product are formed. It suffices as long as it is in a state in which a non-cured binder region is 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, or may be provided in a state in which a region in which the cured binder is formed and a region in which the cured binder is not formed are mixed.

The island shape means that the cured binder on the surface of the base material exists in an isolated state so as not to come into contact with other cured binders. The shape of the cured binder material scattered in an island shape is not particularly limited, and when the contour is viewed in a 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 a binder cured product in which a region in which a binder cured product is formed and a region in which a binder cured product is not formed are provided in a mixed state, and a binder cured product formed in an island shape. And may be mixed.

In the antimicrobial member of the present invention, it is desirable that 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.

In the antimicrobial member of the present invention, it is surely high when 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. It is possible to realize an antimicrobial member having antimicrobial activity.

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

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

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

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

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

In the antimicrobial member of the present invention, it is desirable that the cured binder contains at least one cured binder selected from an organic binder, an inorganic binder and an organic / inorganic hybrid binder.

It is desirable that the organic binder is at least one selected from the group consisting of thermosetting resins and electromagnetic wave curable resins.

In the antimicrobial member of the present invention, it is desirable that the thermosetting resin is at least one selected from the group consisting of epoxy resin, polyimide resin, and melamine resin. It is desirable that 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.

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 anti-microbial 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. 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. It is easy to make it in a state where the binder cured product is scattered in an island shape or 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 binder cured product is formed. Therefore, it is possible to prevent the appearance and aesthetic appearance of the design and the like from being impaired, 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 exceeds 20 μm, the cured binder is too thick. Therefore, when a design or the like having a predetermined pattern is formed on the surface of the substrate, the cured binder interferes with the design or the like. Is hard to see, and the appearance and aesthetics of the design etc. are spoiled.

The anti-microbial member of the present invention contains a copper compound as an inorganic anti-microbial agent, and the copper compound corresponds to Cu (I) and Cu (II) 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 (Cu (I) / Cu (II)) calculated by measuring the binding energy to be formed for 5 minutes is It is preferably 0.4 to 50.

Further, since copper of Cu (I) is superior in antimicrobial performance to copper of Cu (II), the antimicrobial member of the present invention contains a copper compound as an inorganic antimicrobial agent, and the copper is described above. The compound coexists with Cu (I) and Cu (II) by measuring 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. Is desirable to be confirmed.
Specifically, in the copper compound 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 spectroscopy. When the ratio of the number of ions of Cu (I) and Cu (II) contained (Cu (I) / Cu (II)) is 1.0 to 4.0, the anti-microorganism having more excellent anti-microbial performance It becomes a member.

Note that Cu (I) means that the ionic valence of copper is 1, and may be expressed as Cu +. On the other hand, Cu (II) means that the ionic valence of copper is 2, and may be expressed as Cu2 +. In general, the binding energy of Cu (I) is 932.5 eV ± 0.3 (932.2 to 932.8 eV), and the binding energy of Cu (II) is 933.8 eV ± 0.3 (933). It is .5 to 934.1 eV).

In the antimicrobial member of the present invention, the arithmetic mean roughness (Ra) according to JIS B 0601 of the surface of the base material on which the cured binder containing the antimicrobial component is fixedly formed is 0.1 to 5 μm. desirable.

In the anti-microbial member of the present invention, the arithmetic average roughness (Ra) of the surface of the base material on which the cured binder containing the anti-microbial component is fixedly formed is 0.1 to 5 μm in accordance with JIS B 0601. The surface area and unevenness of the surface of the base material containing the cured binder are within an appropriate range, the probability of contact between microorganisms such as viruses and anti-microbial components is high, and microorganisms such as viruses are formed in the valleys of the irregularities on the surface. Is more likely to be trapped, and as a result, more likely to inactivate microorganisms such as viruses.

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 anti-microbial member of the present invention, when the cured binder is scattered in an island shape, the cured island-shaped binder is 0.05 × 10 ⁸ to 30 × 10 ⁸ per square meter of the surface of the base material. If there are one, the size of the cured binder is set appropriately, and it is possible to prevent the appearance and aesthetic appearance of the design, etc. formed on the surface of the base material from being spoiled, and per unit carrying amount. It is an anti-microbial member with high anti-microbial activity.

In the antimicrobial member of the present invention, it is desirable that the antimicrobial member is an antiviral member.

Further, it is desirable that the antimicrobial member of the present invention is an antimicrobial member used in a mode of being wiped off.
The present invention is also used in a mode in which the antimicrobial member of the present invention is wiped off.

FIG. 1 is a plan view schematically showing an embodiment of the antimicrobial member of the present invention. FIG. 2A is a sectional view schematically showing another embodiment of the antimicrobial member of the present invention, and FIG. 2B is a sectional view of the antimicrobial member shown in FIG. 2A. Is.

(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 surface containing the cured binder has a glossiness of less than 45% in accordance with JIS Z 8741. It is characterized by that. The binder cured product may be fixed to the surface of the base material in a film shape, dispersed in an island shape and fixed to the surface of the base material, or a region where the cured binder product is formed on the surface of the base material. The regions where the cured binder is not formed are mixed and provided, and irregularities are formed on the surface of the anti-microbial member. In the present invention, it is desirable that the cured binder covers 10% or more and 95% or less of the surface of the base material.

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 in the binder cured product, is the binder cured product fixed to the surface of the base material in a film form? , The region is dispersed in an island shape and fixed to the surface of the base material, or the region where the cured binder is formed and the region where the cured binder is not formed are provided in a mixed manner on the surface of the base material. Concavities and convexities are formed so that the glossiness of the surface of the base material containing the binder cured product in accordance with JIS Z 8741 is less than 45%. For this reason, the total surface area of the cured binder containing the antimicrobial component is increased, so that the probability of contact with microorganisms such as viruses is high, and microorganisms such as viruses can be trapped between the cured binders, resulting in high antimicrobial properties. The activity is obtained. In addition, since the anti-microbial component is contained in the cured binder, it has excellent adhesion to the base material and can be prevented from falling off by wiping and cleaning.
In the antimicrobial member of the present invention, when the cured binder is adhered to the surface of the substrate in the form of a film, the surface of the film is subjected to polishing treatment, blasting treatment, transfer treatment using a shaping plate, or the like. It is preferable to form an uneven shape to adjust the glossiness.

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 binder cured product of the antimicrobial agent is formed in a film shape. There is no film non-forming region 13 in a mixed state.

FIG. 2A is a sectional view schematically showing another embodiment of the antimicrobial member of the present invention, and FIG. 2B is a sectional view of the antimicrobial member shown in FIG. 2A. Is.
In the antimicrobial member 20 of the present invention shown in FIGS. 2A and 2B, an antimicrobial binder cured product 22 is formed in an island shape on the surface of the base material 21.

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 hardened binder and the stress generated during the thermal cycle, and the hardened binder has high adhesion to the base material and is hard to peel off from the base material. In addition, unlike islands made of antibacterial metal formed by spattering, it does not peel off by wiping and cleaning.

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 a protective film for a touch panel or a film for a display, and may be an interior material or a wall inside a building. It may be a material, a window glass, a handrail, or the like. It may also be a doorknob, a toilet slide key, or the like. Further, it may be office equipment, furniture, etc., and may be a decorative board or the like used for various purposes in addition to the above-mentioned interior material.

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

The magnesia cement non-combustible plate can be used alone, or can be laminated and arranged in 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 heating the paper.

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. 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 kinds of the inorganic antimicrobial agent and the organic antimicrobial agent.

Further, in the antimicrobial member of the present invention, the inorganic antimicrobial agent is a metal oxide catalyst or metal in which silver, copper, zinc, platinum, zinc compound, silver compound, copper compound, metal or metal oxide is supported. It is desirable that it is at least one selected from the group consisting of a zeolite ion-exchanged with an ion 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 metal particles of 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 oxide, copper hydroxide, copper carboxylate, copper complex, and water-soluble inorganic salt of copper. And so on.
Examples of the copper carboxylate include copper (II) acetate, copper (I) acetate, copper (I) oxalate, copper (II) benzoate, and copper (II) phthalate.
Examples of the copper complex include a complex of acetylacetone and copper, a complex of β-diketone such as 5-methyl-2,4-hexanedione and copper, copper (I) (1-butanthiolate), 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. As the other copper compound, a divalent copper compound is desirable, and examples thereof include copper (II) (methoxide), copper (II) ethoxydo, copper (II) propoxide, copper (II) butoxide and the like. It is desirable to add the copper compound (II) to the uncured binder and reduce the copper compound to monovalent with a polymerization initiator.

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 platinum-supported titania catalyst, copper-supported titania catalyst, silver-supported titania catalyst, platinum-supported nitrogen-doped titania catalyst, and 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 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. Zeolites exchanged at least one of silver and copper ions may be further exchanged with other metal ions such as zinc ions. Further, the inorganic antimicrobial agent of the present invention is preferably a copper complex.

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

In the anti-microbial member of the present invention, examples of the organic anti-microbial agent include halocarban, chlorophenesine, lysozyme chloride, alkyldiaminoethylglycine hydrochloride, isopropylmethylphenol, timol, hexachlorophene, berberine, tioxolone, salicylic acid and 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 member. 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 member is preferably a polymer of a monomer having a vinyl group.
Since the polymer of the monomer having a vinyl group is synthesized by addition polymerization, there is no by-product such as water, and a highly transparent antimicrobial resin can be obtained. Therefore, the influence on the design of the base material can be reduced.

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

In the antimicrobial member of the present invention, the antimicrobial resin composed of an acidic functional group and a resin member 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 in the resin member, 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 that may be the same or different, R ³ is an organic group that 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 R3 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 ₂ It is desirable that it is represented by −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.

また、上記ビス型ピリジニウム塩としては、下記の一般式（１１）で表される１，１′−ジデシル−３，３′−［ブタン−１，４−ジイルビス（オキシメチレン）］ジピリジニウム＝ジブロミドが特に望ましい。

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。 Furthermore, 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 binder 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, electron transfer, etc., and the photoradical molecules, photocation molecules, photoanion molecules, 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 composed 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.
Since copper (I) has higher antimicrobial performance than copper (II), the antimicrobial performance of the antimicrobial composition can be enhanced by the polymerization initiator.
Further, the polymerization initiator may be added not only to the electromagnetic wave curable resin but also to the antimicrobial composition composed of an inorganic binder, a copper compound and a dispersion medium.

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 silicone-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, a glycidyl ether type epoxy resin, and an oxetane resin in combination.
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 anti-microbial component is performed by mixing an inorganic binder, an anti-microbial component and, if necessary, various additives and dispersion media to form droplets on the surface of a substrate using an anti-microbial 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 cured binder becomes island-like, and when the droplets are superimposed on the surface of the base material and adhere to the surface of the base material, the cured binder becomes a film, and the cured binder becomes a 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 also applies to 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 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 is easy to make it in a state where the binder cured product is scattered in an island shape or 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 binder cured product is formed. Therefore, it is possible to prevent the appearance and aesthetic appearance of the design and the like from being impaired, 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 exceeds 20 μm, the cured binder is too thick. Therefore, when a design or the like having a predetermined pattern is formed on the surface of the substrate, the cured binder 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 missing 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 anti-microbial 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. 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 thereof can be measured by using a scanning microscope or a laser microscope.
Specifically, by using a scanning microscope or a laser microscope equipped with image analysis / image measurement software, or by using an image analysis / image measurement software to analyze an image obtained by the scanning microscope or a laser microscope. By performing the above, the maximum width in the direction parallel to the surface of the substrate of the cured binder and the average value of the thickness can be obtained.

In the antimicrobial member of the present invention, the arithmetic mean 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 fixed is 0 in accordance with JIS B 0601. .1 to 5 μm 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) of the surface containing the binder cured product of the base material having the binder cured product containing the antimicrobial component adhered to the surface is based on JIS B 0601. When it is 0.1 to 5 μm, the surface area of the substrate surface containing the cured binder is in an appropriate range, the probability of contact between microorganisms such as viruses and antimicrobial components is high, and the valleys of surface irregularities are high. , Microorganisms such as viruses are easily trapped, and as a result, microorganisms such as viruses are easily inactivated.

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

According to the antimicrobial member of the present invention, for example, the pattern, color, design, color tone, etc. formed on the surface of a knob, slide key, handle, handle, handrail, etc., which human hands frequently come into contact with, are changed. The antimicrobial function can be added without any need. In addition, patterns, colors, and designs formed on the surface of interior materials, wall materials, windowpanes, doors, kitchen utensils, office equipment, furniture, etc., and decorative boards used for various purposes inside buildings. , Antimicrobial function can be added without changing the color tone and the like.

Next, the method for producing the above-mentioned antimicrobial member will be described.
When producing the antimicrobial member, first, a spraying step of spraying an antimicrobial composition containing an antimicrobial component, an uncured binder, a dispersion medium and a polymerization initiator is performed on the surface of the base material, followed by a spraying step. If necessary, the antimicrobial composition sprayed on the surface of the base material is dried by the spraying step to remove the dispersion medium, and finally the mixing is carried out by removing the dispersion medium in the drying step. A curing step is performed to cure the uncured binder in the antimicrobial composition, the cured binder containing the antimicrobial component adheres to the surface of the substrate, and the cured binder is a part of the surface of the substrate. It is possible to obtain an antimicrobial member that is coated so as to be exposed. The binder may be cured at the same time as drying. The antimicrobial component is preferably a divalent copper compound. This is because copper (II) can be reduced to copper (I) by a polymerization initiator so that copper (II) and copper (I) can coexist.

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

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

Examples of the antimicrobial component include at least one selected from the group consisting of an inorganic antimicrobial agent and an organic antimicrobial agent.
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 a copper complex, 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 binder comprises at least one selected from an organic binder, an inorganic binder and an organic / inorganic hybrid binder, and the organic binder is at least one selected from the group consisting of a thermosetting resin and an electromagnetic wave curable resin. It is desirable to have.

It is desirable that the thermosetting resin is at least one selected from the group consisting of epoxy resin, polyimide resin, and melamine resin. It is desirable that 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.

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.

The type of the dispersion medium is not particularly limited, but alcohols and water are preferably used 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.

Specifically, the polymerization initiator is preferably at least one selected from the group consisting of alkylphenone type, benzophenone type, acylphosphine oxide type, intramolecular hydrogen abstraction type, and oxime ester type. The polymerization initiator is used to reduce the copper compound (II). When an electromagnetic wave curable resin is used as a binder, it has a function of polymerizing monomers and oligomers.

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

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

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

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

The content ratio of the antimicrobial component in the antimicrobial composition is preferably 2 to 30% by weight, the content ratio of the uncured binder is preferably 15 to 60% by weight, and the content ratio of the dispersion medium is 30 to 80%. 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 to polymerize the antimicrobial component, the uncured binder and the like. It is desirable to make a composition in which the initiator is dispersed at a uniform concentration, and then spray the composition.

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

By the above spraying step, the antimicrobial composition containing the antimicrobial component, the uncured binder, the dispersion medium and the polymerization initiator is superposed on the surface of the substrate in an isolated state or with a part of the surface of the substrate exposed. It becomes an attached state.

(2) Drying Step The antimicrobial composition containing the antimicrobial component sprayed on the surface of the substrate by the spraying step, the uncured binder, the dispersion medium and the polymerization initiator is dried, and the dispersion medium is evaporated and removed. , 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.
In the case of an anti-microbial composition consisting of an inorganic binder, a copper compound, a dispersion medium and a polymerization initiator added as needed, the inorganic binder is cured by removing the dispersion medium by drying. In the case of this antimicrobial composition, the drying step and the curing step proceed at the same time.
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 uncured binder is cured by irradiating it with an electromagnetic wave to obtain a cured binder.
In the method for producing an antimicrobial member of the present invention, when the uncured binder is an electromagnetic wave curable resin, the electromagnetic wave to be irradiated for curing is not particularly limited, and for example, ultraviolet rays (UV), infrared rays, and visible light. Examples thereof include light rays, microwaves, and electron beams (EB). Among these, ultraviolet rays (UV) are preferable.
By these steps, the cured binder containing an antimicrobial component adheres to the surface of the substrate, and the cured binder is coated so as to expose a part of the surface of the substrate. Antimicrobial components can be produced.

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, Cu (I) and Cu are measured by measuring 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. It is desirable that the coexistence of (II) is confirmed.
Further, Cu contained in the copper compound 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 (Cu (I) / Cu (II)) between (I) and Cu (II) is preferably 0.4 to 50.
Further, since copper of Cu (I) is superior in antimicrobial properties to copper of Cu (II), the first antimicrobial member of the present invention is subjected to X-ray photoelectron spectroscopy to 925 to 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 is more excellent in anti-microorganism. This is because the coexistence of Cu (I) and Cu (II) has higher antimicrobial activity as compared with the case where Cu (I) and Cu (II) are present alone.

The glossiness of the surface of the antimicrobial member is controlled by controlling the concentration of the antimicrobial component in the antimicrobial composition, the average particle size of the particles to be added, the concentration of the dispersion medium, the ejection speed of the coating liquid, the time required for spraying, and the like. By doing so, it can be adjusted. When spraying with a spray gun, the glossiness of the surface of the anti-microbial member is adjusted by changing the air pressure of the spray gun, the spray application width, the moving speed of the spray gun, the ejection speed of the coating liquid, and the coating distance. it can. Further, the glossiness of the surface of the base material itself may be adjusted to adjust the glossiness of the surface of the antimicrobial member.

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 application width, the moving speed of the spray gun, the ejection speed of the coating liquid, and the coating distance.

The antimicrobial member of the present invention is preferably used in a wiping mode, such as a toilet wall, a door knob, a slide key, a strap, a chair armrest, a kindergarten or school classroom wall, or a desk mouth. It can be suitably used on a surface or the like.

(Example 1)
(1) Dissolve copper acetate (II) monohydrate powder (manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.) in pure water so that the concentration of copper acetate is 1.75 wt%, and then use a magnetic stirrer. A copper acetate aqueous solution was prepared by stirring at 600 rpm for 15 minutes. The UV curable resin solution is a photoradical polymerization type acrylate resin (UCECOAT7200 manufactured by Daicel Ornex), a photopolymerization initiator (Omnirad 500 manufactured by IGM), and a photopolymerization initiator (Omnirad 184 manufactured by IGM) in a weight ratio of 97: 2: It was prepared by mixing in 1 and stirring at 8000 rpm for 30 minutes using a homogenizer. The 1.75 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 antimicrobial composition.
The Omnirad 500 manufactured by IGM is the same as the IRGACURE 500 manufactured by BASF, and is a mixture containing 1-hydroxy-cyclohexyl-phenyl-ketone (alkylphenone) and benzophenone in a weight ratio of 1: 1. This photopolymerization initiator is insoluble in water and exhibits reducing power by ultraviolet rays. The photopolymerization initiator (Omnirad 184 manufactured by IGM) is 1-hydroxy-cyclohexyl-phenyl-ketone (alkylphenone), and the photopolymerization initiator is an alkylphenone and a benzophenone in a weight ratio of 2: 1. It is a mixture containing in proportion.

(2) Next, an antimicrobial composition corresponding to 45.0 g / m ² is sprayed on a black glossy melamine substrate having a size of 300 mm × 300 mm at a ejection rate of 1.2 g / min and containing a dispersion medium. Using a gun (LPH-50 manufactured by Anest Iwata), the mixture was sprayed in a mist form at an air pressure of 0.1 MPa and a stroke speed of 30 cm / sec to attach droplets of the antimicrobial composition to the surface of a black glossy melamine substrate.

(3) After that, the black glossy melamine substrate 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 antimicrobial member was obtained in which a cured binder containing a copper compound was fixedly formed on the surface of a melamine substrate, which is a material, so that a part of the surface was exposed.
(Example 2)
After applying the anti-microbial composition of Example 1 to a black glossy melamine substrate in a film form with a brush, the black glossy melamine substrate is dried at 80 ° C. for 3 minutes, and further using an ultraviolet irradiation device (MP02 manufactured by COATTEC). The ultraviolet curable resin was cured by irradiating ultraviolet rays at an irradiation intensity of 30 mW / cm ² for 80 seconds to obtain an antimicrobial member according to Example 2.

(Example 3)
Anti-microbial composition according to Example 3 in the same manner as in Example 1 except that an anti-microbial composition corresponding to 30.0 g / m ² was attached to the surface of a black glossy melamine substrate using a spray gun in a state containing a dispersion medium. A microbial member was obtained.
(Example 4)
Antimicrobial composition according to Example 4 in the same manner as in Example 1 except that an antimicrobial composition corresponding to 20.0 g / m ² was adhered to the surface of a black glossy melamine substrate using a spray gun in a state containing a dispersion medium. A microbial member was obtained.
(Example 5)
(1) A photoradical polymerization type acrylate resin (UCECOAT7200 manufactured by Daicel Ornex), a photopolymerization initiator (Omnirad 500 manufactured by IGM) and a photopolymerization initiator (Omnirad 184 manufactured by IGM) are mixed at a weight ratio of 97: 2: 1. Then, using a homogenizer, the mixture was stirred 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. The photopolymerization initiator (Omnirad 184 manufactured by IGM) is 1-hydroxy-cyclohexyl-phenyl-ketone (alkylphenone), and the photopolymerization initiator is an alkylphenone and a benzophenone in a weight ratio of 2: 1. It is a mixture containing 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. The mixture was mixed at a weight ratio of 19: 0.51: 10 and stirred at 600 rpm for 2 minutes using a magnetic stirrer to prepare an antimicrobial composition.
(3) Next, an antimicrobial composition corresponding to 18.0 g / m ² was sprayed on a black glossy melamine plate having a size of 500 mm × 500 mm at a ejection rate of 7.5 g / min and containing a dispersion medium. Using a gun (FINERSPOT G12 manufactured by Meiji Kikai Seisakusho), sprayed in a mist form with an air pressure of 0.1 MPa and a stroke speed of 30 cm / sec, and droplets of the antimicrobial composition were scattered in an island shape on the surface of a black glossy melamine plate. I let you.
(4) After that, the black glossy melamine plate is dried at 80 ° C. for 3 minutes, and further irradiated with ultraviolet rays at an irradiation intensity of 30 mW / cm ² for 80 seconds using an ultraviolet irradiation device (MP02 manufactured by COATTEC). An anti-microbial member was obtained in which a cured binder containing a bis-type quaternary ammonium salt was adhered to the surface of a black glossy melamine substrate which was a material.

(Example 6)
(1) A photoradical polymerization type acrylate resin (UCECOAT7200 manufactured by Daicel Ornex), a photopolymerization initiator (Omnirad 500 manufactured by IGM) and a photopolymerization initiator (Omnirad 184 manufactured by IGM) are mixed at a weight ratio of 97: 2: 1. Then, using a homogenizer, the mixture was stirred 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. The photopolymerization initiator (Omnirad 184 manufactured by IGM) is 1-hydroxy-cyclohexyl-phenyl-ketone (alkylphenone), and the photopolymerization initiator is an alkylphenone and a benzophenone in a weight ratio of 2: 1. It is a mixture containing 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. The mixture was mixed at a weight ratio of 19: 0.51: 10 and stirred at 600 rpm for 2 minutes using a magnetic stirrer to prepare an antimicrobial composition.
(3) Next, the antimicrobial composition was applied in a film form on the surface of the black glossy melamine plate with a bar coater on a black glossy melamine plate having a size of 500 mm × 500 mm.
(4) After that, the black glossy melamine plate is dried at 80 ° C. for 3 minutes, and further irradiated with ultraviolet rays at an irradiation intensity of 30 mW / cm ² for 80 seconds using an ultraviolet irradiation device (MP02 manufactured by COATTEC). An anti-microbial member was obtained in which a cured binder containing a bis-type quaternary ammonium salt was adhered to the surface of a black glossy melamine substrate which was a material. Next, shot blasting was performed using # 100 alumina particles to adjust the glossiness to 10%.

(Test Example 1)
Anti-microbial composition according to Test Example 1 in the same manner as in Example 1 except that an anti-microbial composition corresponding to 15.0 g / m ² was adhered to the surface of a black glossy melamine substrate using a spray gun in a state containing a dispersion medium. A microbial member was obtained.

(Test Example 2)
(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 antimicrobial composition. did.
(2) Next, prepare a black glossy melamine decorative board having a size of 300 mm × 300 mm, and use a mist to apply the antimicrobial composition to the surface of the black glossy melamine decorative board, and the cured product of the antimicrobial composition adheres to the surface. The surface of the black glossy melamine decorative board was sprayed so that the glossiness was 35%.
(3) After that, the glass plate to which the antimicrobial composition is attached is dried at room temperature for 24 hours, and the binder containing copper (I) chloride is cured so that a part of the surface is exposed on the surface of the glass plate as the base material. An antimicrobial member on which an object was fixedly formed was obtained.

(Test Example 3)
(1) 50.0 g of potassium oleate was heated and dissolved in 2000 g of water, and 82.5 g of a 17.7% copper nitrate aqueous solution was added thereto to obtain a suspension of copper oleate. Suspension particles were separated by suction filtration of this suspension, washed with water, and then vacuum dried to obtain 45.7 g of copper oleate. In a 1 L 4-port flask equipped with a stirrer, 500 g of methyl isobutyl ketone was placed as an organic solvent, and 42.5 g of methyl methacrylate and 4.5 g of diethylene glycol dimethacrylate were added and dissolved therein, and then the above solution was added to the solution. 10.8 g of copper oleate was added to prepare a suspension, and 0.5 g of benzoyl peroxide, which is a thermal polymerization initiator, was further added as a polymerization catalyst to prepare an anti-microbial composition.
(2) Next, a black glossy melamine decorative plate glass plate having a size of 300 mm × 300 mm was prepared, and the cured product of the antimicrobial composition was fixed by spraying the antimicrobial composition onto a black glossy melamine substrate. The surface of the black glossy melamine decorative board was sprayed so that the glossiness was 35%.
(3) After that, the black glossy melamine decorative plate to which the antimicrobial composition is attached is heated to 60 ° C. while degassing by nitrogen substitution, and subjected to a heat polymerization reaction for 10 hours to contain copper (II) chloride. An antimicrobial member to which a cured binder was fixed was obtained.

(Test Example 4)
Instead of the shot blasting treatment using # 100 alumina, a polishing roughening treatment was performed using a diamond slurry having an average particle diameter of 2 μm, and the surface glossiness was adjusted to 47% in the same manner as in Example 6. An antimicrobial member according to Test Example 4 was obtained.

(Comparative Example 1)
The antimicrobial composition was not adhered onto the black glossy melamine substrate.

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

(Gloss measurement)
The glossiness was measured according to JIS Z 8741 (1997). The measuring device was CM-25cG manufactured by Konica Minolta. The incident angle of the measurement light was measured at 60 °. The notation of glossiness is (%).

(Wipe off the surface of antimicrobial material)
Tap water was applied to the antimicrobial members obtained in Examples 1, 2, 3, 4, 5, 6 and Test Examples 1, 2, 3 and 4, and the black glossy melamine substrate used in Comparative Example 1. Using the impregnated microfiber cloth, the wiping treatment was carried out 11,000 times at a pressure of 150 Pa. The following antiviral evaluation, antibacterial evaluation, and antifungal evaluation were performed on the antimicrobial member after this wiping treatment.

(Antiviral evaluation using phage virus)
This antiviral test was performed as follows.
JIS Z 2801 antibacterial processed product-antibacterial test in order to evaluate the antiviral properties of the examples and the antimicrobial members obtained in the test examples, and the black glossy melamine substrate used in the comparative example after the wiping treatment. Method-A method with modified antibacterial effect was used.
The modification is that "inoculation of test bacterial solution" was changed to "inoculation of test virus". All changes due to the use of viruses were made based on the antiviral test method for JIS L 1922 textile products.
The measurement results are based on JIS L 1922 Annex B for the antimicrobial members obtained in 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.
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) With respect to the antimicrobial member obtained in Examples and Test Examples and the black glossy melamine substrate used in Comparative Example, the antimicrobial member and the black glossy melamine substrate are squared with a side of 50 mm square. It was cut out into a test sample. Place this test sample in a sterile plastic petri dish and inoculate 0.4 mL of test virus solution (> 107 PFU / mL). The test virus solution used was a stock of 108 PFU / mL diluted 10-fold with purified water.
(2) A 50 mm square polyethylene film was prepared as a control sample, and the virus solution was inoculated in the same manner as the test sample.
(3) A 40 mm square polyethylene was covered over the inoculated virus solution, the test virus solution was evenly inoculated, and then the reaction was carried out at 25 ° C. for a predetermined time.
(4) Immediately after inoculation or after the reaction, 10 mL of SCDLP medium was added to wash away the virus solution.
(5) The virus infection value was determined by JIS L 1922 Annex B.
(6) The antiviral activity value was calculated using the following formula.
Mv = Log (Vb / Vc)
Mv: Antiviral activity value Log (Vb): Logistic value of infection value after reaction of polyethylene film for a predetermined time Log (Vc): Logistic reference standard of infection value after reaction of 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.

(Evaluation of antibacterial properties using Staphylococcus aureus)
Antibacterial evaluation using Staphylococcus aureus was carried out as follows.
(1) The antimicrobial members obtained in Examples and Test Examples, and the black glossy melamine substrate used in Comparative Examples were cut into 50 mm square squares and used as test samples. This test sample was placed in a sterilized plastic petri dish and inoculated with 0.4 mL of the test bacterial solution (number of bacteria 2.5 × 10 ⁵ to 10 × 10 ⁵ / mL). For the test bacterial solution, the cultured bacteria pre-cultured in the incubator at a temperature of 35 ± 1 ° C. for 16 to 24 hours are further transplanted to a slope medium and pre-cultured in the incubator at a temperature of 35 ± 1 ° C. for 16 to 20 hours. The one prepared with 1/500 NB medium was used.
(2) A 50 mm square polyethylene film was prepared as a control sample, and the test bacterial solution was inoculated in the same manner as the test sample.
(3) A 40 mm square polyethylene film was put on the inoculated test bacterial solution, the test bacterial solution was evenly inoculated, and then the reaction was carried out at a temperature of 35 ± 1 ° C. for 24 ± 1 hour.
(4) Immediately after inoculation or after the reaction, 10 mL of SCDLP medium was added and the test bacterial solution was washed out.
(5) The wash-out solution was appropriately diluted and mixed with a standard agar medium to prepare a petri dish for measuring the viable cell count. After culturing at a temperature of 35 ± 1 ° C. for 40 to 48 hours, the number of colonies was measured.
(6) Calculation of viable cell count The viable cell count was 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) The antibacterial activity value was calculated using the following formula.
R = (Ut-U0)-(At-U0) = Ut-At
R: Antibacterial activity value U0: Mean value of log value of viable cell count immediately after inoculation of unprocessed test piece Ut: Mean value of log value of viable cell count 24 hours after inoculation of unprocessed test piece At: Antibacterial processed test piece Average value of logarithmic counts of viable bacteria after 24 hours Reference standard JIS Z 2801
As the test bacterium, Staphylococcus aureus NBRC12732 was used.
The obtained antibacterial activity values are shown in Table 1.

(Evaluation of antifungal properties using Aspergillus niger)
The antifungal property evaluation using Aspergillus niger was carried out as follows.
(1) The antimicrobial members obtained in Examples and Test Examples, and the black glossy melamine substrate used in Comparative Examples were cut into 50 mm square squares and used as test samples. This test sample was placed in a sterilized plastic petri dish and inoculated with 0.4 mL of spore suspension (spore concentration> 2x10 ⁵ pieces / ml).
(2) A 50 mm square polyethylene film was prepared as a control sample, and a spore suspension was inoculated in the same manner as the test sample.
(3) A 40 mm square polyethylene film was put on the inoculated spore suspension, and the spore suspension was inoculated evenly, and then the reaction was carried out at a temperature of 26 ° C. for 42 hours while irradiating with light of about 900 LUX.
(4) Immediately after inoculation or after the reaction, the amount of ATP was measured according to the measurement of JIS L 1921 13 luminescence amount.
(5) The antifungal activity value was calculated using the following formula.
Aa = (LogCt-LogC0)-(LogTt-LogT0)
Aa: Antifungal activity value LogC0: Arithmetic average of the ATP amount of the three control samples immediately after inoculation LogCt: Arithmetic average of the ATP amount of the three control samples after inoculation LogT0: Test immediately after inoculation Arithmetic average of the ATP amount of the three samples LogTt: Common logarithmic reference standard of the arithmetic average of the ATP amount of the three sample samples after culturing JIS Z 2801, JIS L 1921
Aspergillus niger NBRC105649 was used as the test mold.
The obtained antifungal activity values are shown in Table 1.

From the evaluation results of the above Examples, Comparative Examples, and Test Examples, the antiviral activity value, antibacterial activity value, and antifungal activity value of the antimicrobial member having a glossiness of less than 45% are all even after the wiping treatment. , The practical range can be maintained. That is, even after the wiping treatment, excellent effects were confirmed in all of the antiviral activity, the antibacterial activity and the antifungal activity.
That is, in the present invention, by adjusting the glossiness to 10% or more and less than 45%, an antimicrobial member having excellent durability, antiviral performance, antibacterial performance, and antifungal performance can be obtained. In addition, since antimicrobial activity including antiviral activity can be easily imparted by simply applying with a spray, on-site construction can be realized at low cost without the need for special synthetic equipment.

10, 20 Antimicrobial members 11, 21 Base material 12 Membrane-forming region 13 Membrane-non-forming region 22 Binder cured product

Claims (12)

A binder cured product containing an antimicrobial component is fixedly formed on the surface of the base material, and the glossiness of the base material surface containing the binder cured product in accordance with JIS Z 8741 is less than 45%. Microbial member. The binder cured product is formed by being fixed to the surface of the base material in a film shape, dispersed in an island shape and fixed to the surface of the base material, or a region in which the cured binder product is formed on the surface of the base material. The antimicrobial member according to claim 1, wherein the binder and the region in which the cured binder is not formed are mixed and provided. The antimicrobial member according to claim 1 or 2, 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 compound, silver compound, copper compound, metal oxide catalyst carrying metal or metal oxide, zeolite ion-exchanged with metal ions, and The anti-microbial member according to claim 3, which is at least one selected from the group consisting of copper complexes. The third aspect of claim 3, 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 antibacterial product according to any one of claims 1 to 5, wherein the cured binder contains at least one cured product selected from the group consisting of an organic binder, an inorganic binder, and an organic / inorganic hybrid binder. Microbial member. The antimicrobial member according to claim 6, wherein the organic binder is at least one selected from the group consisting of a thermosetting resin and an electromagnetic wave curable resin. The antimicrobial member according to claim 6, 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 binder cured product contains a copper compound as the inorganic antimicrobial agent, and the copper compound corresponds to Cu (I) and Cu (II) in the range of 925 to 955 eV by X-ray photoelectron spectroscopy. The antimicrobial member according to claim 4, wherein the coexistence of Cu (I) and Cu (II) is confirmed by measuring the binding energy for 5 minutes. The antimicrobial member according to any one of claims 1 to 9, 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 used in a mode of being wiped off. Use in a mode in which the antimicrobial member according to any one of claims 1 to 10 is wiped off.

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