JP7229216B2 - antiviral component - Google Patents

Description

The present invention relates to antimicrobial components.

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 metal salts 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 the form of an aqueous solution, their applications are limited, and silver nitrate is highly irritating to the human mucous membranes and has many safety problems.
In recent years, the so-called "pandemic", in which infectious diseases mediated by various pathogenic microorganisms spread rapidly in a short period of time, has become a problem. deaths from viral infections have also been reported.

Therefore, the development of antimicrobial agents such as antibacterial, antifungal, and antiviral agents has been actively carried out. 100% or more antimicrobial synthetic films have been disclosed.

Further, in Patent Document 2, a layer composed of a composition containing a polymeric substance having an organic antibacterial agent component bound to its main chain or side chain, a hydrophilic substance mixed or bound to the polymeric substance, and a curing agent is laminated on at least one surface of a base film, and the glossiness of the laminated surface is 65% or less.
Furthermore, Patent Document 3 discloses an antiviral coating agent comprising cuprous oxide and a reducing sugar.

JP-A-10-86290 JP-A-2000-263706 Japanese Patent No. 5812488

However, the antibacterial synthetic resin stretched film of Patent Document 1 did not have sufficient antibacterial and antiviral properties. In addition, the antibacterial laminated film of Patent Document 2 is a composition containing a polymer substance in which an antibacterial substance is bound to a polymer main chain and side chains, a hydrophilic substance mixed or bound to the polymer substance, and a curing agent. is formed from Therefore, it is necessary to synthesize an antibacterial polymer in which an antibacterial substance is bound to the main chain and side chains of the polymer. Furthermore, even the antiviral coat of Patent Document 3 could not provide sufficient antibacterial and antiviral performance. Accordingly, there has been a demand for an antimicrobial member that is excellent in antimicrobial properties such as antibacterial, antiviral, and antifungal properties, is low in cost, and has good workability.

The present invention has been made in view of such problems, and does not require expensive synthesis equipment, and can be easily applied to already-constructed fixtures by on-site construction. An object of the present invention is to provide an antimicrobial member that exhibits the antimicrobial performance of

As a result of intensive research, the present inventors newly found that the glossiness of the surface portion exhibiting antimicrobial performance such as antibacterial, antiviral, and antifungal properties contributes to the antimicrobial properties. completed.
In the antimicrobial member of the present invention, a cured binder containing an antimicrobial component is fixed to the surface of a substrate, and the surface of the substrate containing the cured binder has a glossiness of 45% or more according to JIS Z 8741. , less than 100%.

Antimicrobial in the antimicrobial member of the present invention is a concept including antivirus, antibacterial, antifungal, and antifungal. Therefore, antimicrobial component is a concept including antiviral component, antibacterial component, antifungal component, and antifungal component, and antimicrobial agent includes antiviral agent, antibacterial agent, antifungal agent, and antifungal agent. An antimicrobial composition is a concept including antiviral compositions, antibacterial compositions, antifungal compositions, and antifungal compositions.

In the present specification, the antimicrobial member may be a member exhibiting any one of antiviral, antibacterial, antifungal and antifungal activities. , it may be a member that exhibits any two types of activity, a member that exhibits any three types of activity, or a member that exhibits all four types of activity.
Among the antimicrobial properties of the antimicrobial member of the present invention, it is particularly effective against viruses and fungi, and has the highest antiviral activity.

In the antimicrobial member of the present invention, a cured binder containing an antimicrobial component is adhered to the surface of a substrate, and the surface of the substrate containing the cured binder has a glossiness of 45 according to JIS Z 8741. % or more and less than 100%, the surface of the base material containing the binder cured product is formed with unevenness, so that the surface area of the binder cured product having antimicrobial activity is increased, and viruses, fungi, and molds flow. Such microorganisms are more likely to come into contact with the hardened binder material, so that microorganisms such as viruses, bacteria, and molds can be deactivated.

If the glossiness of the surface of the substrate containing the cured binder is 100% or more, the unevenness becomes small, the probability of contact with microorganisms such as viruses and bacteria decreases, and sufficient antimicrobial activity cannot be obtained. may not.
In addition, since the hardened binder having antimicrobial activity is formed in an uneven shape on the surface of the substrate containing the hardened binder, microorganisms such as viruses are easily trapped in the concave portions of the uneven shape. sure to be deactivated. The glossiness is preferably 45% or more and 90% or less, more preferably 45% or more and 80% or less, from the viewpoint of exhibiting antimicrobial performance.
In the present invention, the glossiness is a value obtained by measuring according to JIS Z 8741 (1997), and as a measuring instrument, specifically, Konica Minolta (CM-25cG) can be used. can. The incident angle of the measurement light for measuring the glossiness is 60°. Glossiness is expressed in (%).

The antimicrobial member of the present invention comprises a cured binder containing an antimicrobial component adhered to the surface of a base material, and the cured binder is adhered to the surface of the base material in the form of a film or dispersed in the form of islands. It is desirable that the binder is fixed to the surface of the base material as described above, or that the area on which the cured binder is formed and the area on which the cured binder is not formed are mixed on the surface of the base material.

In the antimicrobial member of the present invention, a cured binder containing an antimicrobial component is adhered to the surface of a base material, and the cured binder is dispersed in islands and adhered to the surface of the base material, or Since the area where the hardened binder is formed and the area where the hardened binder is not formed are mixed on the surface of the base material, the hardened binder made of the antimicrobial component is formed on the surface of the base material. Unevenness is formed. Therefore, the total surface area of the cured binder containing the antimicrobial component is increased compared to the case where the cured binder is formed into a film. Since the microorganisms can be trapped between the binder hardened materials, high antimicrobial activity can be obtained. In addition, since the antimicrobial component is contained in the binder cured product, it has excellent adhesion to the base material and can be prevented from coming off due to wiping and cleaning.
In the antimicrobial member of the present invention, when the hardened binder is adhered to the base material surface in the form of a film, the film surface is subjected to polishing treatment, blasting treatment, transfer treatment using a shaping plate, etc. It is preferable to adjust the glossiness by forming an uneven shape.

In this specification, the cured binder preferably covers 10% or more and 95% or less of the surface of the base material. It suffices if the binder hardened material non-formation region and the binder hardened material non-formation region are mixed. That is, the binder cured product is fixedly formed on the surface of the base material so as to expose a part of the surface of the base material. The binder cured product may be formed in an island shape, or the binder cured product is formed in a film shape, and regions where the binder cured product is formed and regions where the binder cured product is not formed are mixed. It may be in a state in which it is provided.

The island shape means that the binder cured product on the surface of the base material exists in an isolated state without contact with other binder cured products. The shape of the cured binder that is scattered like islands is not particularly limited. It may have a shape such as a circular shape, an elliptical shape, or the like connected through a thin portion, or an amoeba-like shape. Also, the islands may be adjacent to each other without being intricate and in contact with each other.
In addition, the binder cured product includes a binder cured product in which a region in which the binder cured product is formed and a region in which the binder cured product is not formed are mixed, and a binder cured product formed in an island shape. may be mixed.

In the antimicrobial member of the present invention, the cured binder preferably contains at least one selected from the group consisting of inorganic antimicrobial agents and organic antimicrobial agents as the antimicrobial component.

In the antimicrobial member of the present invention, when the binder cured product contains at least one selected from the group consisting of inorganic antimicrobial agents and organic antimicrobial agents as the antimicrobial component, the An antimicrobial member having antimicrobial activity can be achieved.

In the antimicrobial member of the present invention, the inorganic antimicrobial agent is a metal oxide or metal hydrate containing at least one metal selected from the group consisting of silver, copper, zinc, titanium, tungsten, etc. can also be used. Specific examples of inorganic antimicrobial agents include copper (I) oxide (cuprous oxide), copper (II) oxide, copper (II) carbonate, copper (II) hydroxide, copper (II) chloride, nano Alumina supporting at least one of silver and copper, silica supporting at least one of nano-silver and copper, zinc oxide supporting at least one of nano-silver and copper, and at least one of nano-silver and copper supported Inorganic particles such as calcium phosphate on which at least one of titanium oxide, tungsten oxide, nano-silver and copper is supported. The zeolite exchanged with at least one of silver ions and copper ions may be further exchanged with other metal ions such as zinc ions. Moreover, 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, a zinc compound, a silver compound, a copper compound, a metal oxide catalyst supporting a metal or a metal oxide, or a metal ion. At least one selected from the group consisting of ion-exchanged zeolites and copper complexes is desirable.

In the antimicrobial member of the present invention, the inorganic antimicrobial agent is silver, copper, zinc, platinum, a zinc compound, a silver compound, a copper compound, a metal or metal oxide-supported metal oxide catalyst, or a metal ion. When it is at least one selected from the group consisting of ion-exchanged zeolite and a copper complex, the inorganic antimicrobial agent can be made into particles, and the inorganic antimicrobial agent is a cured binder material. It is easy to be exposed from, and it becomes an antimicrobial member with higher antimicrobial activity.

In the antimicrobial member of the present invention, the organic antimicrobial agent is at least one selected from the group consisting of antimicrobial resins, sulfonic acid surfactants, copper alkoxides, and bis-type quaternary ammonium salts. is desirable.

In the antimicrobial member of the present invention, the organic antimicrobial agent is at least one selected from the group consisting of antimicrobial resins, sulfonic acid surfactants, copper alkoxides, and bis-type quaternary ammonium salts. Then, the organic antimicrobial agent spreads easily over the entire cured binder, and the antimicrobial member has high antimicrobial activity.

In the antimicrobial member of the present invention, the cured binder preferably contains at least one cured binder selected from the group consisting of an organic binder, an inorganic binder, and an organic/inorganic hybrid binder.

The organic binder is preferably at least one selected from the group consisting of thermosetting resins and electromagnetic wave curing resins.

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

In the antimicrobial member of the present invention, the electromagnetic wave curable resin is at least one selected from the group consisting of acrylic resins, urethane acrylate resins, polyether resins, polyester resins, epoxy resins, and alkyd resins. The binder cured product has transparency and excellent adhesion to the substrate.

In the antimicrobial member of the present invention, the inorganic binder is desirably 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 using a medium or a sol using an organic solvent as a dispersion medium can be selectively used, and a cured binder material in which the antimicrobial component is well dispersed can be formed.

In the antimicrobial member of the present invention, the maximum width in the direction parallel to the substrate surface of the hardened binder 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, the surface of the base material is not covered with the cured binder by setting the maximum width of the cured binder material in the direction parallel to the surface of the base material to 0.1 to 500 μm. can be properly maintained, and even when a design or the like of a predetermined pattern is formed on the surface of the base material, it is possible to prevent the appearance and beauty of the design or the like from being impaired.

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

In the antimicrobial member of the present invention, when the average thickness of the binder cured product is 0.1 to 20 μm, the thickness of the binder cured product is thin, so it is difficult to form a continuous layer of the binder cured product. Scattered islands, or a state in which the binder cured product is formed in the form of a film, and a region in which the binder cured product is not formed is mixed with a region in which the cured binder film is formed. Therefore, it is possible to prevent the appearance and beauty of the design from being spoiled, and it is possible to obtain high antimicrobial activity.

In the antimicrobial member of the present invention, it is technically difficult to form a binder cured product having an average thickness of less than 0.1 μm, and the coverage of the base material surface of the binder cured product is low. Microbial activity decreases. On the other hand, if the average thickness of the binder cured product exceeds 20 μm, the binder cured product is too thick. becomes difficult to see, and the appearance and beauty of the design are impaired.

The antimicrobial member of the present invention contains a copper compound as an 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. It is desirable to confirm the coexistence of Cu(I) and Cu(II) by measuring the binding energy for 5 minutes.
Further, specifically, the copper compound is calculated 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 spectroscopy. The ratio of the numbers of Cu(I) and Cu(II) ions contained therein (Cu(I)/Cu(II)) is preferably 0.4-50.

In addition, since copper of Cu(I) is superior in antimicrobial performance compared to copper of Cu(II), the antimicrobial member of the present invention has a range of 925 to 955 eV by X-ray photoelectron spectroscopy. The ratio of the number of ions of Cu(I) and Cu(II) contained in the copper compound, calculated by measuring the binding energy corresponding to Cu(I) and Cu(II) in the copper compound for 5 minutes When (Cu(I)/Cu(II)) is from 1.0 to 4.0, the antimicrobial member has more excellent antimicrobial performance.

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

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

In the antimicrobial member of the present invention, the arithmetic mean roughness (Ra) conforming to JIS B 0601 of the surface of the substrate to which the cured binder containing the antimicrobial component is fixed is 0.1 to 5 μm. With this, the surface area and unevenness of the surface of the base material containing the cured binder material are in an appropriate range, and the probability of contact between microorganisms such as viruses and the antimicrobial component increases. Microorganisms are easily trapped, and as a result, microorganisms such as viruses are easily deactivated.

In the antimicrobial member of the present invention, when the cured binder is scattered like islands, the island-shaped cured binder is 0.05×10 ⁸ to 30×10 ⁸ per square meter of the substrate surface. Existence is desirable.

In the antimicrobial member of the present invention, when the cured binder is scattered like islands, the cured islands of the binder are 0.05×10 ⁸ to 30×10 ⁸ per square meter of the substrate surface. If there are individual particles, the size of the binder cured product is appropriately set, and it is possible to prevent the appearance and beauty of the design formed on the base material surface from being impaired. It becomes an antimicrobial member having high antimicrobial activity.

In the antimicrobial member of the present invention, the antimicrobial member is preferably an antiviral member.

FIG. 1 is a plan view schematically showing one embodiment of the antimicrobial member of the present invention. FIG. 2(a) is a cross-sectional view schematically showing another embodiment of the antimicrobial member of the present invention, and FIG. 2(b) is a cross-sectional view of the antimicrobial member shown in FIG. 2(a). is. 3 is an optical micrograph showing the antimicrobial member obtained in Example 1. FIG.

(Detailed description of the invention)
The antimicrobial member of the present invention will be described in detail below.
In the antimicrobial member of the present invention, a hardened binder containing an antimicrobial component is adhered to the surface of a base material, and the surface including the hardened binder has a glossiness in accordance with JIS Z 8741 of 45% or more and 100%. %. The cured binder is adhered to the surface of the base material in the form of a film, dispersed in the form of islands and adhered to the surface of the base material, or formed on the surface of the base material with the cured binder area. Regions where the hardened binder is not formed are mixedly provided, and irregularities are formed on the surface of the antimicrobial member.
In the present invention, the cured binder preferably covers 10% or more and 95% or less of the substrate surface.

The antimicrobial member of the present invention is formed by fixing a cured binder containing an antimicrobial component to the surface of a base material, and the cured binder is formed by fixing the cured binder to the surface of the base material in the form of a film. , dispersed in islands and fixed to the surface of the base material, or provided on the surface of the base material in a mixture of areas where the cured binder is formed and areas where the cured binder is not formed, Concavities and convexities are formed so that the glossiness of the surface of the base material containing the binder cured product conforming to JIS Z 8741 is 45% or more and less than 100%. Therefore, since the total surface area of the cured binder containing the antimicrobial component is increased, the probability of contact with microorganisms such as viruses increases. Activity is obtained. In addition, since the antimicrobial component is contained in the binder cured product, it has excellent adhesion to the base material and can be prevented from coming off due to wiping and cleaning.
In the antimicrobial member of the present invention, when the hardened binder is adhered to the base material surface in the form of a film, the film surface is subjected to polishing treatment, blasting treatment, transfer treatment using a shaping plate, etc. It is preferable to adjust the glossiness by forming an uneven shape.

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

As shown in FIG. 1, in the antimicrobial member 10 of the present invention, the hardened binder is provided in the film-forming region 12 in which the hardened antimicrobial binder is formed in the form of a film on the surface of the substrate 11 . The film non-formation region 13 is mixed.

FIG. 2(a) is a cross-sectional view schematically showing another embodiment of the antimicrobial member of the present invention, and FIG. 2(b) is a cross-sectional view of the antimicrobial member shown in FIG. 2(a). is.
In the antimicrobial member 20 of the present invention shown in FIGS. 2(a) and 2(b), the hardened antimicrobial binder 22 is formed on the surface of the substrate 21 in the form of islands.

In the antimicrobial member of the present invention, the hardened binder does not exist on the entire surface of the base material, and the hardened binder forming region where the hardened binder is formed and the cured binder non-formation where the hardened binder is not formed are formed. Since the regions are mixed, it is possible to suppress the residual stress of the binder cured product and the stress generated during the thermal cycle. In addition, unlike islands made of antibacterial metal formed by sputtering or the like, they are not peeled off by wiping or cleaning.

The material of the substrate constituting the antimicrobial member of the present invention is not particularly limited, and examples thereof include metals, ceramics such as glass, resins, fiber fabrics, and wood.
In addition, the member to be the 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, an interior material inside a building, a wall materials, window glass, handrails, and the like. It may also be a doorknob, a toilet slide key, or the like. Further, it may be office equipment, furniture, and the like, and may be a decorative board or the like used for various purposes in addition to the above-mentioned interior materials.

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 core paper generally used for decorative boards, noncombustible boards such as magnesia cement, and the like can be used. The core paper may be used alone, or may be a laminate obtained by laminating a plurality of core papers. The number of core sheets is not particularly limited, but can be 1 to 20 sheets. As the core paper, for example, aluminum hydroxide paper can be used. The core paper can be impregnated with phenolic resin. Alternatively, a core paper and a magnesia cement noncombustible board may be laminated to form a substrate.

The magnesia-cement incombustible board can be used alone or can be laminated to the center of the core paper to constitute the substrate. The magnesia-cement incombustible plate is produced by mixing magnesium oxide (MgO) and magnesium chloride (MgCl ₂ ), adding aggregate and water, kneading the mixture, and molding into a plate. 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 incombustible board, a glass fiber layer formed in a mesh shape or the like can be provided as an intermediate layer.

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

Melamine resin is a resin that has improved dimensional stability and toughness without impairing optical and visual properties such as translucency. As the melamine resin, known resins containing melamine and its derivatives as monomers can be employed. Moreover, the melamine resin may be a resin composed of a single monomer, or a copolymer composed of a plurality of monomers. Derivatives of melamine include, for example, derivatives having functional groups such as imino groups, methylol groups, methoxymethyl groups, and alkoxymethyl groups such as butoxymethyl groups. Also, a compound obtained by reacting a melamine derivative having a methylol group with a lower alcohol to partially or completely etherify can be used as a monomer. A derivative having a methylol group such as monomethylolmelamine, dimethylolmelamine, trimethylolmelamine, tetramethylolmelamine, pentamethylolmelamine, hexamethylolmelamine (hereinafter referred to as "methylolated melamine") is copolymerized with melamine as a cross-linking agent. It is possible to use a melamine resin consisting of

The surface resin layer may be a decorative layer in which printed paper on which a pattern or color is printed is impregnated with resin, and when the amount of filler is 15% or less and the resin is impregnated, the overlay becomes translucent. It may be an overlay layer in which paper is impregnated with resin. When the surface resin layer is an overlay layer, the decorative layer is provided below the overlay layer.
A filler is an inorganic particle (filler) added to paper to adjust whiteness and smoothness, and is preferably at least one selected from calcium carbonate, talc, clay and kaolin. Since the fillers are inorganic particles, the filler content can be calculated from the weight of the paper and the weight of the ash remaining after the paper is ignited.

In the antimicrobial member of the present invention, the cured binder preferably contains at least one selected from the group consisting of inorganic antimicrobial agents and organic antimicrobial agents as the antimicrobial component.
The binder cured product may contain only one type of the inorganic antimicrobial agent described above, may contain two or more types of inorganic antimicrobial agents, and may contain the above organic antimicrobial agents. may contain only one type, or may contain two or more types of organic antimicrobial agents. Furthermore, two or more kinds of the inorganic antimicrobial agent and the organic antimicrobial agent may be contained in the binder cured product.

In the antimicrobial member of the present invention, the inorganic antimicrobial agent includes silver, copper, zinc, platinum, zinc compounds, silver compounds, copper compounds, metal or metal oxide-supported metal oxide catalysts, metal At least one selected from the group consisting of ion-exchanged zeolites and copper complexes is desirable.

Examples of inorganic antimicrobial agents contained in the binder cured product include metals comprising at least one of silver, copper, zinc and platinum.
The cured binder may contain particles of silver, copper, zinc and platinum alone, or may contain particles of two or more kinds of metals selected from 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 inorganic antimicrobial agents contained in the binder cured product include copper compounds such as copper oxides, copper hydroxides, copper carboxylates, copper complexes, and water-soluble inorganic salts of copper. etc.
Examples of the copper carboxylate include copper (II) acetate, copper (I) acetate, copper (I) oxalate, copper (II) benzoate, and copper (II) phthalate.
Examples of the copper complex include a complex of acetylacetone and copper, a complex of β-diketone such as 5-methyl-2,4-hexanedione and copper, copper (I) (1-butanethiolate), copper ( I) (Hexafluoropentanedionate cyclooctadiene) and the like.
Examples of the water-soluble inorganic salt of copper include copper (II) nitrate and copper (II) sulfate. Other copper compounds are preferably divalent copper compounds such as copper (II) (methoxide), copper (II) ethoxide, copper (II) propoxide, copper (II) butoxide and the like. Desirably, the copper compound (II) is added to the uncured binder and the copper compound is monovalently reduced by the polymerization initiator.

As the metal oxide catalyst in which the metal or metal oxide contained in the binder cured product is supported, for example, titanium oxide or the like is supported with a platinum group metal such as platinum, palladium, rhodium, or ruthenium, silver, copper, or the like. and so on. Specific examples of metal oxide catalysts supporting metals or metal oxides include platinum-supported titania catalysts, copper-supported titania catalysts, silver-supported titania catalysts, platinum-supported nitrogen-doped titania catalysts, and platinum-supported sulfur-doped titania catalysts. , carbon-doped titania catalysts, copper-supported tungsten oxide catalysts, silver-supported tungsten oxide catalysts, and other visible light-responsive photocatalysts. /TiO ₂ (weight% ratio) = Anatase titanium oxide containing copper in the range of 1.0 to 3.5, cuprous oxide (copper oxide (I): Cu ₂ O) and titanium oxide composite photocatalyst composition, titanium oxide having a mixture containing a monovalent copper compound and a divalent copper compound described in JP 2013-166705 supported on the surface, and international publication A copper- and titanium-containing composition containing titanium oxide, including crystalline rutile-type titanium oxide, and a divalent copper compound, described in No. 2013/094573, and the like.

As the inorganic antimicrobial agent, metal oxide or metal hydrate particles containing at least one metal selected from silver, copper, zinc, titanium, tungsten and the like can also be used. Specific examples of inorganic antimicrobial agents include copper (I) oxide (cuprous oxide), copper (II) oxide, copper (II) carbonate, copper (II) hydroxide, copper (II) chloride, silver Zeolite exchanged with at least one of ions and copper ions, alumina supporting at least one of nano-silver and copper, silica supporting at least one of nano-silver and copper, at least one of nano-silver and copper supported Titanium oxide supporting at least one of zinc oxide, nano-silver and copper, or inorganic particles such as calcium phosphate supporting at least one of tungsten oxide, nano-silver and copper can be used. The zeolite exchanged with at least one of silver ions and copper ions may be further exchanged with other metal ions such as zinc ions. Moreover, 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 antimicrobial resins, sulfonic acid surfactants, copper alkoxides, and bis-type quaternary ammonium salts. is desirable.

In the antimicrobial member of the present invention, the organic antimicrobial agents include, for example, halocarban, chlorophenesin, lysozyme chloride, alkyldiaminoethylglycine hydrochloride, isopropylmethylphenol, thymol, hexachlorophene, berberine, thioxolone, salicylic acid and Derivatives thereof, benzoic acid, sodium benzoate, parahydroxybenzoic acid ester, parachlormetacresol, benzalkonium chloride, phenoxyethanol, isopropylmethylphenol, carbolic acid, sorbic acid, potassium sorbate, hexachlorophene, chlorhexidine chloride, trichlorocarbani Lido, thianthol, hinokitiol, triclosan, trichlorohydroxydiphenyl ether, chlorhexidine gluconate, phenoxyethanol, resorcinol, azulene, salicylic acid, zinc pyrithione, sodium mononitroguaiacol, fennel extract, Japanese pepper extract, cetylpyridinium chloride, benzethonium chloride and undecylenic acid derivatives, Alkyl benzene sulfonic acid or its salt etc. are mentioned. Among these, alkylbenzenesulfonic acids or salts thereof are preferred.

In the antimicrobial member of the present invention, the antimicrobial resin comprises an acidic functional group and a resin member. Examples of acidic functional groups include sulfonic acid groups, phosphoric acid groups, carboxyl groups, hydroxyl groups, and nitro groups. Among these, a sulfonic acid group, a phosphoric acid group, and a carboxyl group are preferred.

The resin member is desirably a polymer of a monomer having a vinyl group.
Polymers of monomers having a vinyl group are synthesized by addition polymerization, so that there is no by-product such as water, and a highly transparent antimicrobial resin can be obtained. Therefore, it is possible to reduce the influence on the design of the substrate.

The vinyl group-containing monomer is desirably one or more monomers selected from styrene, methacrylic acid, methacrylic acid esters, divinylbenzene, and trivinylbenzene.
Styrene, methacrylic acid, methacrylic acid esters, divinylbenzene, and trivinylbenzene can yield antimicrobial resins with particularly high transparency. Moreover, divinylbenzene and trivinylbenzene can be crosslinked to form a three-dimensional network structure by being added to the monomer. By forming a three-dimensional network structure, it becomes difficult to decompose, and durability can be enhanced.

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. can be done. The cation-exchange resin, similarly having a structure having an acidic functional group in the resin member, can be used as the antimicrobial resin of the present invention.

Examples of the bis-type quaternary ammonium salt include bis-type pyridinium salts, bis-type quinolinium salts, bis-type thiazolium salts represented by the following general formula (1), compounds represented by the following general formula (2), and the like. 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 general formula (1) above, R ¹ and R ² are alkyl groups which may be the same or different, R ³ is an organic group which may contain an ether bond, and X- represents a halogen anion. )

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

(In general formula (2) above, 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 alkyl groups. )

First, the bis-pyridinium salt represented by the general formula (1) will be described.
In the bis-type pyridinium salt represented by the general formula (1), X- includes, for example, 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 side chains.
In the above general formula (1), the organic group represented by R ³ is -CO-O-(CH ₂ ) ₆ -O-CO-, -CONH-(CH ₂ ) _6- CO-, -NH-CO -(CH ₂ ) ₄ -CO-NH-, -S-Ph-S-, -CONH-Ph-NHCO-, -NHCO-Ph-CONH-, -O-(CH ₂ ) ₆ -O- or -CH It is preferably represented by ₂ -O-(CH ₂ ) ₄ -O-CH ₂ - (where Ph represents a phenylene group).

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

In general formula (3) above, R ¹¹ is an alkyl group represented by C _n H _2n+1 , and n is desirably 8, 10, 12, 14, 16 or 18. Also, m is desirably 3, 4, 6, 8, or 10. The same applies to the substituent R ¹¹ of the compounds shown below.

Further, as the bis-type pyridinium salt, 1,1′-didecyl-3,3′-[butane-1,4-diylbis(oxymethylene)]dipyridinium=dibromide 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 salts represented by general formulas (3) to (10) is and a bis-type quinolinium salt having a chemical structure in which the quinolium group shown in is substituted. Other substituents and the like in the bis-type quinolinium salt are the same as those of the bis-type pyridinium salts represented by 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 explained.

In general formula (2) above, R ⁴ represents an alkyl group which may have a functional group. The alkyl group may have a side chain, and preferably has 1 to 20 carbon atoms. 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. In addition, R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ each represent an alkyl group, the 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.

In the antimicrobial member of the present invention, the binder cured product is preferably an organic binder, an inorganic binder, an organic/inorganic hybrid binder and/or a binder cured product of an electromagnetic wave curing type resin. An organic metal compound can be used as the organic/inorganic hybrid binder.
In the antimicrobial member of the present invention, as the antimicrobial component, at least one selected from the group consisting of inorganic antimicrobial agents and organic antimicrobial agents, and an organic binder, an inorganic binder, an organic/inorganic hybrid, which is a binder. A binder cured product can be obtained by curing a mixture of the binder and at least one of the electromagnetic radiation curable resin.

Next, the cured product of the electromagnetic wave curing resin in the antimicrobial member of the present invention will be described.
After forming droplets on the substrate surface using an antimicrobial composition containing a monomer or oligomer that is an uncured electromagnetic wave curable resin, a polymerization initiator, various additives, and an antimicrobial component, the composition is irradiated with an electromagnetic wave. As a result, the polymerization initiator causes reactions such as cleavage reaction, hydrogen abstraction reaction, electron transfer, etc., and photoradical molecules, photocationic molecules, photoanion molecules, etc., thus generated attack the above-mentioned monomers and oligomers to form monomers. Polymerization reaction and cross-linking reaction of oligomers and oligomers proceed to form a cured binder containing an antimicrobial component. 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.
For this reason, a polymerization initiator may be added to an antimicrobial composition comprising an inorganic binder, a copper compound and a dispersion medium.
The polymerization initiator is desirably a photopolymerization initiator.
The polymerization initiator can reduce copper(II) to copper(I).
Since copper(I) has higher antimicrobial performance than copper(II), the polymerization initiator can enhance the antimicrobial performance of the antimicrobial composition.
Moreover, a polymerization initiator may be added to an antimicrobial composition comprising an inorganic binder, a copper compound, and a dispersion medium, without being limited to the electromagnetic wave curable resin.

At least one selected from the group consisting of, for example, acrylic resins, urethane acrylate resins, polyether resins, polyester resins, epoxy resins, and alkyd resins is desirable for such electromagnetic wave curing resins.

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

Examples of the epoxy resin include alicyclic epoxy resins, alicyclic epoxy resins, and combinations of glycidyl ether type epoxy resins and oxetane resins.
Examples of alkyd resins include polyester alkyd resins.
These resins have transparency and excellent adhesion to substrates.

Next, the cured inorganic binder in the antimicrobial member of the present invention will be described.
An inorganic binder, an antimicrobial component, and optionally various additives and dispersion media are mixed to form droplets on the substrate surface using the antimicrobial composition, and then dried to cure the binder containing the antimicrobial component. A product (cured product of inorganic binder) is formed.

When the droplets are isolated and adhere to the substrate surface, the cured binder becomes island-shaped, and when the droplets overlap and adhere to the substrate surface, the cured binder becomes film-shaped. This results in a form in which a product formation region and a non-formation region in which the binder cured product is not formed are mixed. This also applies to the above-described electromagnetic wave curing resin.

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 of inorganic oxides such as silica in the inorganic binder is preferably 2 to 80% by weight in terms of solid content.
Since the inorganic binder includes those using water and those using an organic solvent as a dispersion medium, the inorganic binder can be selected in consideration of the type of antimicrobial component to be added. is uniformly dispersed in the above antimicrobial composition.

In the antimicrobial member of the present invention, the maximum width in the direction parallel to the substrate surface of the hardened binder 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 thickness of the binder cured product is 0.1 to 20 μm, the thickness of the binder cured product is thin, so it is difficult to form a continuous layer of the binder cured product. Scattered islands, or a state in which the binder cured product is formed in the form of a film, and a region in which the binder cured product is not formed is mixed with a region in which the cured binder film is formed. Therefore, it is possible to prevent the appearance and beauty of the design from being spoiled, and it is possible to obtain high antimicrobial activity.

In the antimicrobial member of the present invention, it is technically difficult to form a binder cured product having an average thickness of less than 0.1 μm, and the coverage of the base material surface of the binder cured product is low. Microbial activity decreases. On the other hand, if the average thickness of the binder cured product exceeds 20 μm, the binder cured product is too thick. becomes difficult to see, and the appearance and beauty of the design are impaired.

In the antimicrobial member of the present invention, the surface of the substrate is coated with the cured binder by setting the maximum width of the cured binder in the direction parallel to the surface of the substrate to 0.1 to 500 μm. It is possible to appropriately maintain the proportion of the non-coated portion, and even when a predetermined pattern of design or the like is formed on the surface of the base material, it is possible to prevent the appearance or beauty of the design or the like from being spoiled.

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

The maximum width in the direction parallel to the substrate surface and the average thickness of the binder cured product can be measured by using a scanning microscope or a laser microscope.
Specifically, by using a scanning microscope or laser microscope equipped with image analysis/image measurement software, or by using image analysis/image measurement software for images obtained with a scanning microscope or laser microscope. etc., the maximum width in the direction parallel to the surface of the base material and the average value of the thickness of the binder cured product can be obtained.

In the antimicrobial member of the present invention, the arithmetic mean roughness (Ra) according to JIS B 0601 of the surface containing the cured binder of the substrate to which the cured binder containing the antimicrobial component is adhered is 0. .1 to 5 μm is desirable.
The above arithmetic mean roughness (Ra) can be obtained by measuring with a measuring length of 8 mm using a HANDYSURF contact surface roughness measuring machine manufactured by Tokyo Seimitsu.

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 to which the binder cured product containing the antimicrobial component is fixed on the surface according to JIS B 0601 is , When it is 0.1 to 5 μm, the surface area of the substrate surface containing the binder cured product is in an appropriate range, and the probability of contact between microorganisms such as viruses and the antimicrobial component increases. , viruses and other microorganisms are easily trapped, and as a result, the viruses and other microorganisms are easily deactivated.

In the antimicrobial member of the present invention, when the cured binder is scattered like islands, the cured islands of the binder are 0.05×10 ⁸ to 30×10 ⁸ per square meter of the surface of the substrate. Existence is desirable.

In the antimicrobial member of the present invention, when the cured binder is scattered like islands, the cured islands of the binder are 0.05×10 ⁸ to 30×10 ⁸ per square meter of the substrate surface. If there are individual particles, the size of the binder cured product is appropriately set, and it is possible to prevent the appearance and beauty of the design formed on the base material surface from being impaired. It becomes an antimicrobial member having high antimicrobial activity.

According to the antimicrobial member of the present invention, for example, the pattern, color, design, color tone, etc. formed on the surface of knobs, slide keys, handles, handles, handrails, etc. that are frequently touched by human hands can be changed. antimicrobial function can be added without In addition, patterns, colors, and designs formed on the surface of interior materials, wall materials, window glass, doors, kitchen utensils, etc., office equipment, furniture, etc., and decorative boards used for various purposes inside buildings , the antimicrobial function can be added without changing the color tone, etc.

Next, a method for manufacturing the above 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 on the surface of a base material is performed, followed by If necessary, a drying step of drying the antimicrobial composition sprayed on the substrate surface in the spraying step to remove the dispersion medium is performed, and finally the antimicrobial composition from which the dispersion medium is removed in the drying step is performed. A curing step is performed to cure the uncured binder in the microbial composition, and the cured binder containing the antimicrobial component adheres to the surface of the substrate, and the cured binder is part of the surface of the substrate. An antimicrobial component can be obtained that is exposed to the coating. Curing of the binder may be performed simultaneously with drying. The antimicrobial component is preferably a divalent copper compound. This is because copper(II) can be reduced to copper(I) by the polymerization initiator so that copper(II) and copper(I) can coexist.

(1) Spraying step When manufacturing 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 applied to the surface of a base material. Spray the composition.

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

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

The binder is at least one selected from organic binders, inorganic binders and organic/inorganic hybrid binders, and the organic binder is at least one selected from the group consisting of thermosetting resins and electromagnetic wave curing resins. It is desirable to have

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

The inorganic binder is desirably 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, preferred are methyl alcohol and ethyl alcohol, which tend not to increase in viscosity, and preferred is a mixture of alcohol and water.

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

Examples of the alkylphenone-based polymerization initiator include 2,2-dimethoxy-1,2-diphenylethan-1-one, 1-hydroxy-cyclohexyl-phenyl-ketone, 2-hydroxy-2-methyl-1- Phenyl-propan-1-one, 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propan-1-one, 2-hydroxy-1-{4-[4 -(2-hydroxy-2-methyl-propionyl)-benzyl]phenyl}-2-methyl-propan-1-one, 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one , 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1,2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4 -morphonyl)phenyl]-1-butanone and the like.

Acylphosphine oxide-based polymerization initiators include, for example, 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide and bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide.

Intramolecular hydrogen abstraction type polymerization initiators include, for example, phenylglyoxylic acid methyl ester, oxyphenylsuccinate, 2-[2-oxo-2-phenylacetoxyethoxy]ethyl ester and 2-(2 -hydroxyethoxy)ethyl ester.

Examples of oxime ester polymerization initiators include 1,2-octanedione, 1-[4-(phenylthio)-, 2-(O-benzoyloxime)], ethanone, 1-[9-ethyl-6- (2-methylbenzoyl)-9H-carbazol-3-yl]-, 1-(0-acetyloxime) and the like.

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

If necessary, the antimicrobial composition may contain ultraviolet absorbers, antioxidants, light stabilizers, adhesion promoters, rheology modifiers, leveling agents, antifoaming agents, and the like.

When preparing the antimicrobial composition, after adding the antimicrobial component, the monomer or oligomer, and the polymerization initiator to the dispersion medium, sufficiently stirring with a mixer or the like, the antimicrobial component, the uncured binder, etc. are polymerized. It is desirable to disperse the composition after forming a composition in which the initiator is dispersed at a uniform concentration.

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

In the present invention, the spraying method involves spraying the antimicrobial composition in a mist state using a gas such as high-pressure air or mechanical movement (such as a finger or a piezo element), and applying the antimicrobial composition to the surface of the substrate. It refers to attaching droplets of substances.
In the present invention, the two-fluid spray method is a type of spray method, in which a gas such as high-pressure air is mixed with an antimicrobial composition, and then sprayed in a mist state from a nozzle, and the antimicrobial composition is applied to the surface of the substrate. It refers to depositing droplets of the microbial composition.
In the present invention, the electrostatic spray method is a spraying method using a charged antimicrobial composition, and the antimicrobial composition is sprayed in a mist state by the above-described spray method. There are a gun type that sprays the antimicrobial composition with a sprayer and an electrostatic atomization system that uses the repulsion of a charged antimicrobial composition. There are a method of spraying the antimicrobial composition and a method of imparting electric charge to the atomized antimicrobial composition by corona discharge from an external electrode. Since the atomized droplets are electrically charged, they easily adhere to the surface of the substrate, and the finely divided antimicrobial composition can adhere to the surface of the substrate satisfactorily.
In the present invention, the aerosol method is a method of spraying an object in the form of a mist that is physically and chemically produced from an antimicrobial composition containing a metal compound.

By the spraying step, the antimicrobial composition containing the antimicrobial component, the uncured binder, the dispersion medium, and the polymerization initiator is isolated on the substrate surface, or superimposed on the substrate surface in a partially exposed state. It will be in a sticky state.

(2) Drying step The antimicrobial composition containing the antimicrobial component, uncured binder, dispersion medium and polymerization initiator sprayed on the surface of the substrate in the spraying step is dried to evaporate and remove the dispersion medium. In addition, the hardened binder containing the antimicrobial component can be temporarily fixed on the surface of the substrate, and the cured antimicrobial component can be exposed from the surface of the hardened binder due to the shrinkage of the cured binder.
In the case of an antimicrobial composition comprising an inorganic binder, a copper compound, a dispersion medium, and optionally a polymerization initiator, the inorganic binder is cured by removing the dispersion medium by drying. In the case of this antimicrobial composition, the drying and curing steps proceed simultaneously.
Desirable drying conditions are 60 to 100° C. and 0.5 to 5.0 minutes.

(3) Curing step When manufacturing the above antimicrobial member, in the curing step, the uncured electromagnetic wave curable resin monomer or oligomer in the antimicrobial composition from which the dispersion medium has been removed in the drying step is The uncured binder is cured by irradiation with electromagnetic waves to obtain a binder cured product.
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 examples include ultraviolet (UV), infrared, and visible light. Light rays, microwaves, electron beams (EB) and the like can be used, and among these, ultraviolet rays (UV) are preferable.
By these steps, the cured binder containing the antimicrobial component adheres to the surface of the substrate, and the cured binder coats the surface of the substrate so as to partially expose the present invention. of antimicrobial components can be manufactured.

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) and increase the antimicrobial activity.
The antimicrobial member of the present invention contains a copper compound as an 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. It is desirable to confirm the coexistence of Cu(I) and Cu(II) by measuring the binding energy for 5 minutes.
Further, the copper compound is calculated 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 spectroscopy. The ratio of the numbers of Cu(I) and Cu(II) ions contained therein (Cu(I)/Cu(II)) is preferably 0.4-50.
In addition, since copper of Cu(I) is superior in antimicrobial properties to copper of Cu(II), the antimicrobial member of the first aspect of the present invention contains a copper compound as an inorganic antimicrobial agent. , The copper compound is calculated 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 spectroscopy. When the ratio of the number of Cu (I) and Cu (II) ions contained in the (Cu (I) / Cu (II)) is 1.0 to 4.0, the antimicrobial excellent in antimicrobial become a component. This is because the coexistence of Cu(I) and Cu(II) provides higher antimicrobial activity than when Cu(I) and Cu(II) are present alone.

The glossiness of the surface of the antimicrobial member is controlled by 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, etc. can be adjusted by doing When spraying with a spray gun, the glossiness of the surface of the antimicrobial member can be adjusted by changing the air pressure of the spray gun, the spray application width, the movement speed of the spray gun, the ejection speed of the coating liquid, and the coating distance. can. Alternatively, the glossiness of the surface of the antimicrobial member may be adjusted by adjusting the glossiness of the surface of the base material itself.

The coating rate of the hardened binder material 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 pressure of spraying, the ejection speed of the coating liquid, the spraying time, etc. , can be adjusted.
When spraying with a spray gun, the coverage of the cured binder can be adjusted by changing the air pressure of the spray gun, the width of the spray application, the movement speed of the spray gun, the ejection speed of the coating liquid, and the coating distance.

(Example 1)
(1) Copper (II) acetate monohydrate powder (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) was dissolved in pure water so that the concentration of copper acetate was 1.75 wt%, and then a magnetic stirrer was added. and stirred at 600 rpm for 15 minutes to prepare an aqueous solution of copper acetate. The UV curable resin liquid is composed of a photo-radical polymerizable acrylate resin (UCECOAT7200 manufactured by Daicel Allnex), a photopolymerization initiator (Omnirad500 manufactured by IGM) and a photopolymerization initiator (Omnirad184 manufactured by IGM) at a weight ratio of 97:2. 1 and stirred at 8000 rpm for 30 minutes using a homogenizer. The above 1.75 wt % copper acetate aqueous solution and the above UV 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.
Note that Omnirad 500 manufactured by IGM is the same as IRGACURE 500 manufactured by BASF, and is a mixture containing 1-hydroxy-cyclohexyl-phenyl-ketone and benzophenone at a weight ratio of 1:1. This photopolymerization initiator is insoluble in water and exhibits reducing power when exposed to ultraviolet rays. Omnirad 184 manufactured by IGM is 1-hydroxy-cyclohexyl-phenyl-ketone (alkylphenone), and is a mixture containing alkylphenone and benzophenone in a weight ratio of 2:1 as photopolymerization initiators.

(2) Then, on a glossy black melamine substrate having a size of 300 mm x 300 mm, an antimicrobial composition equivalent to 15.0 g/m ² containing a dispersion medium is sprayed at an ejection speed of 1.2 g/min. Using a gun (LPH-50 manufactured by Anest Iwata), the antimicrobial composition was atomized at an air pressure of 0.1 MPa and a stroke speed of 30 cm/sec to adhere droplets of the antimicrobial composition to the surface of the glossy black melamine substrate.

(3) After that, the glossy black melamine substrate was dried at 80° C. for 3 minutes, and then irradiated with ultraviolet rays for 80 seconds at an irradiation intensity of 30 mW/cm ² using an ultraviolet irradiation device (MP02 manufactured by COATTEC). An antimicrobial member was obtained in which a hardened binder containing a copper compound was adhered to the surface of a melamine substrate as a material so that a part of the surface was exposed.

(Example 2)
The antimicrobial composition according to Example 2 was prepared in the same manner as in Example 1 except that the antimicrobial composition corresponding to 10.0 g / m ² in the state containing the dispersion medium was attached to the surface of the glossy black melamine substrate using a spray gun. A microbial member was obtained.
(Example 3)
The antimicrobial composition according to Example 3 was prepared in the same manner as in Example 1 except that the antimicrobial composition corresponding to 5.0 g / m ² in the state containing the dispersion medium was attached to the surface of the glossy black melamine substrate using a spray gun. A microbial member was obtained.
(Example 4)
(1) A photoradical polymerizable acrylate resin (UCECOAT7200 manufactured by Daicel-Ornex), a photopolymerization initiator (Omnirad500 manufactured by IGM) and a photopolymerization initiator (Omnirad184 manufactured by IGM) are mixed at a weight ratio of 97:2:1. Then, using a homogenizer, the mixture was stirred at 8000 rpm for 10 minutes to prepare an ultraviolet curable resin liquid. Omnirad 500 manufactured by IGM is the same as 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 composed of alkylphenone and benzophenone in a weight ratio of 2:1. It is a mixture containing proportions.
(2) water, bis-type quaternary ammonium salt (1,1′-didecyl-3,3′-[butane-1,4-diylbis(oxymethylene)]dipyridinium=dibromide) and the above UV curable resin liquid An antimicrobial composition was prepared by mixing at a weight ratio of 19:0.51:10 and stirring at 600 rpm for 2 minutes using a magnetic stirrer.
(3) Next, the antimicrobial composition was applied to the surface of a glossy black melamine plate having a size of 500 mm×500 mm in the form of a film using a bar coater.
(4) After that, the black glossy melamine plate was dried at 80° C. for 3 minutes, and further irradiated with ultraviolet rays for 80 seconds at an irradiation intensity of 30 mW/cm ² using an ultraviolet irradiation device (MP02 manufactured by COATTEC) to obtain a substrate. An antimicrobial member was obtained in which a hardened binder containing a bis-type quaternary ammonium salt adhered to the surface of a glossy black melamine substrate. Next, the surface was roughened by polishing with colloidal silica of 100 nm to adjust the surface glossiness to 90%.

(Example 5)
An antimicrobial member according to Example 5 was obtained in the same manner as in Example 4, except that the diamond slurry having an average particle size of 1 μm was used to roughen and adjust the glossiness to 47%.

(Comparative example 1)
No antimicrobial composition was deposited on the black gloss melamine substrate.

(Test example 1)
After applying the antimicrobial composition of Example 1 to a glossy black melamine substrate with a brush, the melamine substrate was dried at 80° C. for 3 minutes, and further irradiated with an ultraviolet irradiation device (manufactured by COATTEC, MP02) at 30 mW/cm ² . After curing the UV-curable resin by irradiating with UV rays for 80 seconds at an irradiation intensity, the resin surface was mirror-polished using colloidal silica to obtain an antimicrobial member according to Test Example 1.

(Test example 2)
(1) Copper (I) chloride powder (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) was suspended in pure water so that the concentration of copper (I) chloride was 0.34 wt%, and then stirred using a magnetic stirrer. , 600 rpm for 15 minutes to prepare a copper chloride suspension. The above 0.34 wt% copper (I) chloride suspension and polyvinyl alcohol 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. bottom.
(2) Next, a glossy black melamine decorative board with a size of 300 mm x 300 mm was prepared, and the antimicrobial composition was applied to the surface of the black melamine decorative board using a sprayer, and the cured product of the antimicrobial composition was fixed. It was sprayed so that the glossiness of the surface of the black glossy melamine decorative board became 55%.
(3) After that, the black glossy decorative melamine board to which the antimicrobial composition is attached is dried at room temperature for 24 hours, and copper chloride ( An antimicrobial member was obtained in which the cured binder containing I) was fixedly formed.

(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 copper oleate suspension. This suspension was subjected to suction filtration to separate suspended particles, which were washed with water and vacuum dried to obtain 45.7 g of copper oleate. 500 g of methyl isobutyl ketone as an organic solvent was placed in a 1 L four-necked flask equipped with a stirrer, and 42.5 g of methyl methacrylate and 4.5 g of diethylene glycol dimethacrylate were added and dissolved. 10.8 g of copper oleate was added to obtain 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 antimicrobial composition.
(2) Next, a 300 mm × 300 mm black glossy melamine decorative glass plate was prepared, and the above antimicrobial composition was sprayed onto the black glossy melamine substrate to fix the cured product of the antimicrobial composition. It was sprayed so that the glossiness of the surface of the black glossy melamine decorative board became 55%.
(3) After that, the black glossy melamine decorative board to which the antimicrobial composition has adhered is heated to 60 ° C. while degassing by nitrogen replacement, and subjected to a thermal polymerization reaction for 10 hours to contain copper (II) chloride. An antimicrobial member was obtained in which the hardened binder was fixed.

(Test example 4)
The antimicrobial composition according to Test Example 4 was prepared in the same manner as in Example 1 except that the antimicrobial composition corresponding to 18.0 g / m ² in the state containing the dispersion medium was attached to the surface of the glossy black melamine substrate using a spray gun. A microbial member was obtained.

(Test Example 5)
An antimicrobial member according to Test Example 5 was obtained in the same manner as in Example 4 except that the surface was roughened by polishing with a diamond slurry having an average particle size of 2 μm to adjust the glossiness of the surface to 35%.

(Cu(I)/Cu(II) measurement test)
The ratio of the numbers of Cu(I) and Cu(II) ions was measured by X-ray photoelectron spectroscopy (XPS analysis). The measurement conditions are as follows.
・Equipment: PHI 5000 Versa probe II manufactured by ULVAC-Phi
・X-ray source: Al Kα 1486.6 eV
・Detection angle: 45°
・Measurement diameter: 100 μm
・Electrification neutralization: Yes - wide scan ・Measurement step: 0.8 eV
・Pass energy: 187.8 eV
-Narrow scan/measurement step: 0.1 eV
・Pass energy: 46.9 eV
The measurement time was 5 minutes, the peak position of Cu(I) was 932.5 eV ±0.3 eV, the peak position of Cu(II) was 933.8 eV ±0.3 eV, and the area of each peak was integrated. and obtained Cu(I)/Cu(II) from the ratio.

(Evaluation of the shape of the antimicrobial member and the dispersion state of the cured binder)
The antimicrobial member obtained in Example 1 was photographed with an optical microscope (Keyence Microscope VHX-5000).
3 is an optical micrograph showing the antimicrobial member obtained in Example 1. FIG.
It can be seen that the hardened binder is fixedly formed on the surface of the glossy black melamine decorative board, which is the base material, so that a part of the surface is exposed.
FIG. 3 shows a mixture of regions in which the cured binder is formed and regions in which the cured binder is not formed.

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

(Antiviral evaluation using phage virus)
This antiviral test was performed as follows.
In order to evaluate the antiviral properties of the antimicrobial members obtained in Examples and Test Examples and the glossy black melamine substrate used in Comparative Examples, JIS Z 2801 Antibacterial processed products-Antibacterial test method/Antibacterial effect A modified method was used.
The modified point 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 JIS L 1922 Antiviral Test Method for Textile Products.
The measurement results are based on JIS L 1922 Appendix B for the antimicrobial members obtained in Examples 1 and 2, and the phage virus concentration at which the ability to infect E. coli is lost is indicated as virus inactivity.
Here, the concentration of virus inactivated against Escherichia coli (virus inactivation) was used as an index of virus concentration, and the antiviral activity value was calculated based on this virus inactivation.

The procedure will be specifically described below.
(1) Regarding the antimicrobial members obtained in Examples and Test Examples and the glossy black melamine substrate used in Comparative Examples, the antimicrobial member and the glossy black melamine substrate are squares of 50 mm on each side. It was cut out into pieces and used as a test sample. This test sample is placed in a sterilized plastic Petri dish and inoculated with 0.4 mL of test virus solution (>107 PFU/mL). A 108 PFU/mL stock diluted 10-fold with purified water is used as the test virus solution.
(2) As a control sample, a 50 mm square polyethylene film was prepared and inoculated with the virus solution in the same manner as the test sample.
(3) The inoculated virus solution was covered with polyethylene of 40 mm square, and the test virus solution was evenly inoculated, followed by reacting at 25° C. for a predetermined time.
(4) Immediately after inoculation or after reaction, 10 mL of SCDLP medium was added to wash off the virus solution.
(5) The virus infection value was determined according to JIS L 1922 Appendix B.
(6) The antiviral activity value was calculated using the following formula.
Mv=Log(Vb/Vc)
Mv: Antiviral activity value Log (Vb): Logarithmic value of infection value after reacting for a predetermined time on polyethylene film Log (Vc): Logarithmic value of infection value after reacting for a predetermined time on test sample Reference standards JIS L 1922, JIS Z 2801
The measurement method was the plaque measurement method.
Table 1 shows the obtained antiviral activity values.

(Antibacterial evaluation using Staphylococcus aureus)
Antibacterial evaluation using Staphylococcus aureus was performed as follows.
(1) The antimicrobial members obtained in Examples and Test Examples and the glossy black melamine substrate used in Comparative Examples were each cut into 50 mm squares to prepare test samples. This test sample was placed in a sterilized plastic petri dish and inoculated with 0.4 mL of a test bacterial solution (bacteria count: 2.5×10 ⁵ to 10×10 ⁵ /mL). The test bacterial solution is prepared by pre-cultivating the cultured bacteria in an incubator at a temperature of 35±1°C for 16-24 hours, transplanting them to a slant medium, and pre-cultivating them in an incubator at a temperature of 35±1°C for 16-20 hours. 1/500 NB medium was used.
(2) A polyethylene film of 50 mm square was prepared as a control sample and inoculated with the test bacterial solution in the same manner as the test sample.
(3) A polyethylene film of 40 mm square was placed on the inoculated test bacterial solution, and the test bacterial solution was evenly inoculated, followed by reaction at a temperature of 35±1° C. for 24±1 hours.
(4) Immediately after inoculation or after reaction, 10 mL of SCDLP medium was added to wash out the test bacterial solution.
(5) The washing solution was appropriately diluted and mixed with a standard agar medium to prepare a petri dish for measuring the viable cell count.
(6) Calculation of viable count The viable count was obtained 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
(7) The antibacterial activity value was calculated using the following formula.
R=(Ut-U0)-(At-U0)=Ut-At
R: Antibacterial activity value U0: Average value of logarithmic value of viable count immediately after inoculation of unprocessed test piece Ut: Average value of logarithmic value of viable count of unprocessed test piece after 24 hours At: Antibacterial processed test piece Average value of the logarithmic value of the number of viable bacteria after 24 hours Reference standard JIS Z 2801
Staphylococcus aureus NBRC12732 was used as the test fungus.
Table 1 shows the obtained antibacterial activity values.

(Anti-mold property evaluation using Aspergillus niger)
Antifungal evaluation using Aspergillus niger was carried out as follows.
(1) The antimicrobial members obtained in Examples and Test Examples and the glossy black melamine substrate used in Comparative Examples were each cut into 50 mm squares to obtain test samples. The test sample was placed in a sterilized plastic petri dish and inoculated with 0.4 mL of a spore suspension (spore concentration>2×10 ⁵ /ml).
(2) A polyethylene film of 50 mm square was prepared as a control sample and inoculated with a spore suspension in the same manner as the test sample.
(3) The inoculated spore suspension was covered with a polyethylene film of 40 mm square and evenly inoculated with the spore suspension, followed by reaction at 26° C. for 42 hours while irradiating light of about 900 LUX.
(4) Immediately after inoculation or after reaction, the amount of ATP was measured according to JIS L 1921-13 luminescence measurement.
(5) The antifungal activity value was calculated using the following formula.
Aa = (LogCt-LogC0) - (LogTt-LogT0)
Aa: Antifungal activity value LogC0: Common logarithm value of arithmetic mean of ATP amount of 3 control samples immediately after inoculation LogCt: Arithmetic mean of ATP amount of 3 control samples after culture LogT0: Test immediately after inoculation Common logarithm value of arithmetic mean of ATP amount of 3 samples LogTt: Common logarithm value of arithmetic mean of ATP amount of 3 test samples after culture Reference standard JIS Z 2801, JIS L 1921
Aspergillus niger NBRC105649 was used as the test fungus.
Table 1 shows the obtained antifungal activity values.

From the evaluation results of the above examples, comparative examples, and test examples, for the antimicrobial members according to the examples having a glossiness of 45% or more and less than 100%, the antiviral activity value, the antibacterial activity value, and the antifungal activity value are It is possible to maintain the practical range. That is, excellent effects were confirmed for all of antiviral activity, antibacterial activity and antifungal activity.
In the present invention, it was confirmed that an antimicrobial member having excellent antiviral performance, antibacterial performance, and antifungal performance can be obtained by adjusting the glossiness to 45% or more and 90% or less.
In addition, antimicrobial activity including antiviral activity can be imparted simply by spraying, so no special synthesis facility is required and on-site construction can be realized at low cost.

10, 20 Antimicrobial members 11, 21 Base material 12 Film forming region 13 Film non-forming region 22 Binder hardened material

Claims (7)

The base material surface contains a copper compound as an antiviral component, and the copper compound is exposed to a binding energy corresponding to Cu(I) and Cu(II) in the range of 925 to 955 eV for 5 minutes by X-ray photoelectron spectroscopy. Coexistence of Cu(I) and Cu(II) was confirmed by the measurement, and a binder cured product containing no fatty acid-coated monovalent copper compound particles was fixedly formed, and the binder cured product An antiviral member, characterized in that the surface of a base material comprising JIS Z 8741 has a glossiness of 45% or more and less than 100%. The antiviral component according to claim 1, wherein the antiviral component does not contain _TiO2 . 3. The antiviral member according to claim 1, wherein the copper compound does not contain a mixture of a monovalent copper compound and a divalent copper compound supported on the surface of the photocatalytic substance. The binder cured product is adhered to the base material surface in the form of a film, dispersed in islands and adhered to the base material surface, or a region in which the binder cured product is formed on the base material surface. 4. The antiviral member according to any one of claims 1 to 3, wherein the antiviral member is provided with a mixture of the region and the region where the binder cured product is not formed. 5. The binder according to any one of claims 1 to 4, wherein the binder cured product contains at least one binder cured product selected from the group consisting of an organic binder, an inorganic binder, and an organic/inorganic hybrid binder. virus component. The antiviral member according to claim 5, wherein the organic binder is at least one selected from the group consisting of thermosetting resins and electromagnetic wave curing resins. The antiviral member according to claim 5, wherein the inorganic binder is at least one selected from the group consisting of silica sol, alumina sol, titania sol, zirconia sol, and sodium silicate.

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