JP7304377B2 - Antiviral member manufacturing method, handle manufacturing method, chair armrest manufacturing method, and table edge manufacturing method - Google Patents

Description

The present invention relates to a method for manufacturing an antiviral member, a method for manufacturing a handle, a method for manufacturing an armrest of a chair, and a method for manufacturing a table edge .

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 due to viral infections have also been reported.

Therefore, the development of antiviral agents that exhibit antiviral activity against various viruses has been actively carried out. Coating with a resin or the like containing an antiviral agent or manufacturing a member containing a material carrying an antiviral agent has been performed. In particular, there are many industrial products consisting of the base material itself or a base material having a polypropylene resin on the surface, and the range of applications is wide.

Patent Literature 1 discloses a method for producing an antibacterial member in which a polymer base material such as polypropylene is coated with an antibacterial layer containing antibacterial particles and a protective layer containing alumina on the base material.

Japanese Patent Publication No. 8-505858

However, in Patent Document 1, the base material surface is covered with a homogeneous antibacterial / protective layer film, so if there is a load of residual stress and changes in the temperature of the outside air and the surrounding environment, the coefficient of thermal expansion of the base material itself There is a problem that cracks, peeling, etc. of the surface coating occur due to the difference in thermal expansion coefficient between the antibacterial and protective layers, and it is impossible to provide an antimicrobial member with high adhesion.

The present invention has been made in view of such problems, and has a high antimicrobial activity. By forming a discontinuous region with a mixture of non-bonded regions, cracks, peeling, swelling, etc. of the surface film can be prevented due to differences in the surrounding environment due to heat, pressure, etc., deformation of the base material, etc. It is an object of the present invention to provide an antimicrobial member having high adhesiveness without reducing antimicrobial activity.

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 made of polypropylene resin, and the cured binder is dispersed in islands and adhered to the surface of the base material. Alternatively, a region where the binder cured product is formed and a region where the binder cured product is not formed are mixedly provided on the substrate surface.

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 an antiviral composition, an antibacterial composition, an antifungal composition, and an antifungal composition.

In the present specification, the antimicrobial member may be a substrate exhibiting any one of antiviral, antibacterial, antifungal and antifungal activities. It may be a substrate that exhibits any two types of activity, a substrate that exhibits any three types of activity, or a substrate 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 binder hardened material containing an antimicrobial component is fixedly formed on the surface of a base material made of polypropylene resin (hereinafter also simply referred to as the base material surface), and the hardened binder material is shaped like islands. It is dispersed and fixed to the surface of the base material, or the area where the cured binder is formed and the area where the cured binder is not formed are mixedly provided on the surface of the base material. Concavities and convexities composed of a hardened material containing an antimicrobial component are formed on the surface. 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, it is possible to suppress the residual stress of the binder cured product and the stress generated during thermal cycles, and the binder cured product has high adhesion to the base material and is difficult to peel off from the base material. Therefore, it is possible to provide a more reliable antimicrobial member that does not cause peeling or cracking due to differences in thermal stress, etc., compared to the above-described antibacterial member uniformly coated on the base material. In addition, the binder cured product can disperse the stress generated at the interface with the base material due to the deformation of the base material, and does not cause peeling or blistering. It is possible to solve the problem that the cured product exhibiting antimicrobial activity is dropped and the antimicrobial activity is reduced.

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, and the binder cured product is formed in the form of a film, and a region where the binder cured product is not formed is mixed with a region where the binder cured product is formed. It may be in a state in which it is provided as

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 is formed in a film shape, and the binder cured product in a state in which a region in which the cured product is not formed is mixed in the formation region of the film-shaped binder cured product, and an island-shaped binder cured product. may be mixed with the binder cured product formed in the above.

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 agents include silver, copper, zinc, platinum, zinc compounds, silver compounds, copper compounds, titanium, tungsten, metal oxide catalysts supporting metals or metal oxides. , zeolite ion-exchanged with metal ions, and metal oxide or metal hydrate particles containing at least one metal selected from copper complexes 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, 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 antimicrobial agent can be particulate, and the inorganic antimicrobial agent is exposed from the cured binder. It is easy to use and results in an antimicrobial component 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 material selected from organic binders, inorganic binders and organic/inorganic hybrid binders. An organic metal compound can be used as the 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.

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.

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 and unevenness of the surface of the substrate containing the cured binder are in an appropriate range, the probability of contact between microorganisms such as viruses and the antimicrobial component increases, and the unevenness of the surface. Microorganisms such as viruses are easily trapped in the valleys, and as a result, the 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.

The antimicrobial member of the present invention is desirably an antiviral member.
The antimicrobial component of the present invention has antiviral, antibacterial, antifungal and antifungal properties, but in particular has the highest antiviral activity.

The handle of the present invention is a handle whose surface is made of polypropylene resin, and is formed by fixing a cured binder containing an antimicrobial component to the surface of the polypropylene resin constituting the handle, and the cured binder has an island shape. It is dispersed in the substrate surface and fixed to the substrate surface, or the substrate surface is provided with a region in which the binder cured product is formed and a region in which the binder cured product is not formed. and
A hardened binder containing an antimicrobial component is adhered to the surface of the handle, so that microorganisms such as viruses attached to the handle can be deactivated, so that microorganisms such as viruses can be prevented from infecting humans who touch the handle. can be prevented. In addition, even if a person who has microorganisms such as viruses touches the handle, the cured binder containing the antimicrobial component can deactivate the microorganisms such as viruses, and the next person who touches the handle will be infected with viruses. of microorganisms can be prevented from being transmitted. In addition, since the cured binder containing the antimicrobial component has excellent adhesion to the handle, it will not fall off even if it is touched by human hands one after another and even if it is wiped off.

The chair armrest of the present invention is a chair armrest having a surface made of polypropylene resin, wherein a hardened binder containing an antimicrobial component is fixedly formed on the surface of the polypropylene resin constituting the armrest of the chair, and the binder The cured product is dispersed in islands and adhered to the surface of the base material, or is provided on the surface of the base material in a mixture of regions where the cured binder is formed and regions where the cured binder is not formed. It is characterized by being made.
Since the cured binder containing the antimicrobial component is adhered to the surface of the armrest of the chair, it is possible to inactivate microorganisms such as viruses adhering to the armrest of the chair. Infection by microorganisms such as viruses can be prevented. In addition, even if a person having microorganisms such as viruses touches the armrest of the chair, the hardened binder containing the antimicrobial component can deactivate the microorganism such as the virus. In addition, it is possible to prevent the transmission of microorganisms such as viruses. In addition, since the cured binder containing the antimicrobial component has excellent adhesion to the armrests of the chair, it does not come off even if it is touched by human hands or elbows one after another and even if it is wiped off.

The table edge of the present invention is a table edge whose surface is made of polypropylene resin, and is formed by fixing and forming a binder hardened material containing an antimicrobial component on the surface of the polypropylene resin constituting the table edge, and the binder hardened material is , dispersed in the form of islands and fixed to the surface of the base material, or provided on the surface of the base material in a mixture of regions where the cured binder is formed and regions where the cured binder is not formed. It is characterized by
Since the hardened binder containing the antimicrobial component is adhered to the surface of the table edge, it is possible to inactivate microorganisms such as viruses adhering to the table edge. Microorganism infection can be prevented. In addition, even if a person carrying microorganisms such as viruses touches the edge of the table, the hardened binder containing the antimicrobial component can deactivate the microorganisms such as viruses. It is possible to prevent the infection of microorganisms such as viruses. In addition, since the cured binder containing the antimicrobial component has excellent adhesion to the table edge, it will not fall off even if it is touched by human hands one after another and even if it is wiped clean.

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. FIG. 4(a) is a cross-sectional view schematically showing an embodiment of the handle of the present invention, and FIG. 4(b) is a perspective view of the handle shown in FIG. 4(a). FIG. 5(a) is a perspective view schematically showing one embodiment of the armrest of the chair of the present invention, and FIG. 5(b) is the armrest A of the chair of the present invention shown in FIG. 5(a). -A sectional view. FIG. 6(a) is a perspective view schematically showing one embodiment of the table edge of the present invention, and FIG. 6(b) is a side view of the table edge of the present invention shown in FIG. 6(a). be.

(Detailed description of the invention)
The antimicrobial member of the present invention will be described in detail below.
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 made of polypropylene resin, and the cured binder is dispersed in islands and adhered to the surface of the base material. Alternatively, the surface of the substrate is provided with a mixture of a region where the cured binder is formed and a region where the cured binder is not formed.
In the present invention, the cured binder preferably covers 10% or more and 95% or less of the substrate surface.

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, a hardened binder containing an antimicrobial component is fixedly formed on the surface of the base material, and the hardened binder is dispersed in islands and fixed to the surface of the base material, or Since the area where the binder cured product is formed and the area where the binder cured product is not formed are mixed on the substrate surface, the substrate surface has unevenness composed of the cured product composed of the antimicrobial component. 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, it is possible to suppress the residual stress of the binder cured product and the stress generated during the thermal cycle, and the binder cured product has high adhesion to the base material and is difficult to peel off from the base material. Therefore, it is possible to provide a more reliable antimicrobial member that does not cause peeling or cracking due to differences in thermal stress, etc., compared to the above-described antibacterial member uniformly coated on the base material. In addition, the binder cured product can disperse the stress generated at the interface with the base material due to the deformation of the base material, and does not cause peeling or swelling, so the binder cured product exhibiting antimicrobial activity falls off. However, it is possible to solve the problem of a decrease in antimicrobial activity caused by thermal deformation that tends to occur in polypropylene substrates.

The base material constituting the antimicrobial member of the present invention is polypropylene.
Polypropylene is not particularly limited, and includes homopolypropylene, random polypropylene, block polypropylene and the like.
Homopolypropylene may be isotactic, atactic or syndiotactic. Examples of random polypropylene or block polypropylene include copolymers of propylene and other olefins having 2 to 20 carbon atoms.
These polypropylenes may be used alone or as a mixture.
Polypropylene may also contain inorganic fine particles such as silica, talc, calcium carbonate, glass, and barium sulfate.

Further, even if the inside of the base material is metal or ceramic, the base material may be coated with polypropylene on its surface. In addition, the use of the polypropylene base material constituting the antimicrobial member of the present invention is not particularly limited. It can be applied to a wide range of applications, such as handles, armrests of chairs, table edges, toilet seats and lids, which are frequently installed in facilities. In addition, packaging products such as packaging films and industrial films, food containers, miscellaneous goods containers, detergent containers, buckets, chemical resistant containers, containers such as containers, CD cases, suitcases, book binders, PET bottle caps, etc. Representative daily necessities, laboratory equipment such as centrifuge tubes and tips for micropipettors are also included.
The polypropylene substrate that constitutes the antimicrobial member of the present invention may be colored or decorated for surface protection and design improvement by means of printing, painting, or the like. As described above, the present invention is based on the effect exhibited by the mixture of the binder-cured product forming region in which the binder cured product is formed and the binder-cured product non-formation region in which the binder cured product is not formed. It does not relate to the interaction between the cured product and its interface (polypropylene surface, painted surface).

In the antimicrobial member of the present invention, the cured binder preferably contains, as the antimicrobial component, at least one selected from the group consisting of inorganic antimicrobial agents and organic antimicrobial agents.
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 carboxylates, copper complexes, copper hydroxides, copper oxides, and water-soluble inorganic salts of copper. A copper compound etc. are mentioned.
As the carboxylate of copper, an ionic compound of copper can be used, including copper acetate, copper benzoate, copper phthalate, and the like.
As the water-soluble inorganic salt of copper, an ionic compound of copper can be used, and examples thereof include copper nitrate and copper sulfate.
Other copper compounds include, for example, copper (methoxide), copper ethoxide, copper propoxide, copper butoxide, and the like, and covalent compounds of copper include copper oxides, copper hydroxides, and the like. . Copper carboxylates and copper hydroxides have high affinity with organic binders and inorganic binders and are not eluted with water, so they are excellent in water resistance.
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.
As the water-soluble inorganic salt of copper, an ionic compound of copper can be used, and examples thereof include copper (II) nitrate and copper (II) sulfate.
Other copper compounds include, for example, copper (II) (methoxide), copper (II) ethoxide, copper (II) propoxide, and copper (II) butoxide. oxides, hydroxides of copper, and the like.

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 (I) oxide: 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, mononitroguaiacol sodium, 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 base. 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 substrate 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 base is not particularly limited. can be done. The cation-exchange resin, similarly having an acid functional group on the resin base, 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, and bis-type thiazolium salts represented by the following general formula (1). Compounds represented by the following general formula (2), etc. desirable.

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

(In the above general formula (1), R ¹ and R ² are alkyl groups which may be the same or different, R ³ is an organic group which may contain an ether bond, and X ^{1 -} 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-pyridinium salt represented by the general formula (1), X ^{2 −} 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 cured binder is desirably an organic binder, an inorganic binder, an organic/inorganic hybrid binder and/or a cured electromagnetic wave curable 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 wave curing 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 forming 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). Copper(I) has higher antimicrobial performance than copper(II).

At least one selected from the group consisting of 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 the substrate.

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.

Further, 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 the handle of a vehicle or building, the armrest of a chair, the edge of a table, etc. Functions can be added.

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 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 The curing step of curing the uncured binder is performed so that the cured binder containing the antimicrobial component adheres to the surface of the base material, and the cured binder is partially exposed on the surface of the base material. A coated antimicrobial component can be obtained. Curing of the binder may be performed simultaneously with drying.

(1) Sprinkling step When producing the antimicrobial member of the present invention, first, as a spreading step, an antimicrobial component, an uncured binder, a dispersion medium, and a polymerization initiator are applied to the surface of a base material made of polypropylene resin. Apply an antimicrobial composition comprising

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 polymerization initiator is used to reduce the copper compound. 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.

UV absorbers, antioxidants, light stabilizers, adhesion promoters, rheology modifiers, leveling agents, antifoaming agents and the like may be blended in the antimicrobial composition, if necessary.

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.
In the antimicrobial member of the present invention, the copper The ratio of the numbers of Cu(I) and Cu(II) ions contained in the compound (Cu(I)/Cu(II)) is preferably 0.5-50.
In addition, since copper of Cu(I) is superior in antimicrobial properties compared to copper of Cu(II), in the antimicrobial member of the first present invention, by X-ray photoelectron spectroscopy, 925 to 955 eV 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 range of for 5 minutes When the ratio of (Cu(I)/Cu(II)) is 1.0 to 4.0, the antimicrobial member has more excellent antimicrobial properties.

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.

As application examples of the antimicrobial member of the present invention, an embodiment of a handle is shown in FIG. 4, an armrest of a chair is shown in FIG. 5, and a table edge is shown in FIG. Note that the present invention is not limited to these descriptions, and any design modified appropriately by a person skilled in the art is also included in the scope of the present invention as long as it has the features of the present invention.

The handle of the present invention will be described below.
The handle of the present invention is a handle whose surface is made of polypropylene resin, and is formed by fixing a cured binder containing an antimicrobial component to the surface of the polypropylene resin constituting the handle, and the cured binder has an island shape. It is dispersed in the substrate surface and fixed to the substrate surface, or the substrate surface is provided with a region in which the binder cured product is formed and a region in which the binder cured product is not formed. and
Here, a handle is a knob attached to furniture, utensils, etc. for grasping by hand.

FIG. 4(a) is a cross-sectional view schematically showing an embodiment of the handle of the present invention, and FIG. 4(b) is a perspective view of the handle shown in FIG. 4(a).
In the handle embodiment of FIG. 4, the handle 40 has a handle portion 41 secured by a screw 43 . The handle portion 41 is made of polypropylene resin, and a hardened binder 42 containing an antimicrobial component is adhered to the surface thereof to impart antimicrobial properties.
Since the handle 41 of the handle 40 is provided with antimicrobial properties, it is possible to inactivate microorganisms such as viruses adhering to the handle 41. of microorganisms can be prevented from being infected. In addition, even if a person carrying a microorganism such as a virus touches the handle 41, the microorganism such as the virus can be deactivated. Contagion can be prevented. In addition, since the binder hardened material 42 containing the antimicrobial component has excellent adhesion to the handle portion 41, it does not come off even if it is touched by human hands one after another and even if it is wiped off.

The armrest of the chair of the present invention will be described below.
The chair armrest of the present invention is a chair armrest having a surface made of polypropylene resin, wherein a hardened binder containing an antimicrobial component is fixedly formed on the surface of the polypropylene resin constituting the armrest of the chair, and the binder The cured product is dispersed in islands and adhered to the surface of the base material, or is provided on the surface of the base material in a mixture of regions where the cured binder is formed and regions where the cured binder is not formed. It is characterized by being made.
Here, the armrest of the chair refers to a portion provided on the side of the chair, etc., on which the hand or elbow can be rested.

FIG. 5(a) is a perspective view schematically showing one embodiment of the armrest of the chair of the present invention, and FIG. 5(b) is the armrest A of the chair of the present invention shown in FIG. 5(a). -A sectional view.
In the chair arm embodiment of FIG. 5, the chair 50 is comprised of a back 55, a seat 56, four legs 53 and a pair of armrests 54, the chair 50 comprising a back 55 and a seat 56. is covered with a cushion material 51 . The armrests 54 are provided on top of the chair legs 53 connected to the seat 56 .
The armrest 54 has a surface made of polypropylene resin, on which a hardened binder 52 containing an antimicrobial component is fixed to provide antimicrobial properties.
Since the surface of the armrest 54 has an antimicrobial property, it is possible to inactivate microorganisms such as viruses adhering to the armrest 54, so that a person who touches the armrest 54 is prevented from being infected with microorganisms such as viruses. can be prevented. In addition, even if a person carrying a microorganism such as a virus touches the armrest 54, the microorganism such as the virus can be deactivated, and the next person who touches the armrest 54 can be prevented from being infected with the microorganism such as the virus. can be prevented. In addition, the hardened binder 52 containing the antimicrobial component has excellent adhesion to the armrest 54, so even if it is touched by human hands or elbows one after another, it will not come off even if it is wiped off.

The table edge of the present invention will be described below.
The table edge of the present invention is a table edge whose surface is made of polypropylene resin, and is formed by fixing and forming a binder hardened material containing an antimicrobial component on the surface of the polypropylene resin constituting the table edge, and the binder hardened material is , dispersed in the form of islands and fixed to the surface of the base material, or provided on the surface of the base material in a mixture of regions where the cured binder is formed and regions where the cured binder is not formed. It is characterized by
Here, the table edge is a portion that imparts cushioning properties and wear resistance to the side surface of the table and protects the table from impact and friction.

FIG. 6(a) is a perspective view schematically showing one embodiment of the table edge of the present invention, and FIG. 6(b) is a side view of the table edge of the present invention shown in FIG. 6(a). be.
In the table edge embodiment of FIG. 6, a table leg 63 is connected to a top plate 61 of a table 60 having a table edge (side) 61a. A table edge 61a of a top plate 61 of the table 60 has a surface made of polypropylene resin, and a hardened binder 62 having antimicrobial activity is adhered to the surface to impart antimicrobial properties.
Since the surface of the table edge 61a is imparted with an antimicrobial property, it is possible to inactivate microorganisms such as viruses adhering to the table edge 61a. can be prevented. In addition, even if a person carrying microorganisms such as viruses touches the table edge 61a on the side of the top plate 61, the binder hardened material 62 containing the antimicrobial component can deactivate the microorganisms such as viruses, and then the table can be cleaned. It is possible to prevent a person who touches the edge 61a from being infected with a microorganism such as a virus. In addition, since the cured binder 62 containing the antimicrobial component has excellent adhesion to the table edge, even if it is touched by human hands one after another, it will not come off even if it is wiped off.

(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 stirred using a magnetic stirrer. , and stirred at 600 rpm for 15 minutes to prepare an aqueous solution of copper acetate. The UV curable resin liquid is obtained by mixing a photo-radical polymerizable acrylate resin (UCECOAT7200 manufactured by Daicel-Ornex), a photopolymerization initiator (Omnirad500 manufactured by IGM) and (Omnirad184 manufactured by IGM) at a weight ratio of 97:2:1. It was prepared by stirring at 8000 rpm for 30 minutes using a homogenizer. The 1.75 wt % aqueous copper acetate solution and the 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 of 1-hydroxy-cyclohexyl-phenyl-ketone and benzophenone. This photopolymerization initiator is insoluble in water and exhibits reducing power when exposed to ultraviolet rays.

(2) Then, on a 300 mm x 300 mm polypropylene resin plate (manufactured by Sekisui Seizo Polysame) at a jetting speed of 1.2 g/min, it corresponds to 16.7 g / m ² in a state containing a dispersion medium. Using a spray gun (LPH-50, manufactured by Anest Iwata), the antimicrobial composition is sprayed in a mist state at an air pressure of 0.1 MPa and a stroke speed of 30 cm / sec, and droplets of the antimicrobial composition are applied to the surface of the polypropylene resin plate. attached to.

(3) After that, the polypropylene resin plate is 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). Thus, an antimicrobial member was obtained in which a cured binder containing a copper compound was fixedly formed on the surface of the polypropylene resin plate in which a part of the surface was exposed.

(Example 2)
The antimicrobial member obtained in Example 1 was wiped 11,000 times at a pressure of 150 Pa and a speed of 7.5 cm / sec using a microfiber cloth impregnated with tap water. It is used as an antimicrobial member.

(Comparative example)
After obtaining an antimicrobial composition in the same manner as in Example 1, a 300 mm × 300 mm polypropylene resin plate (manufactured by Sekisui Seizo Co., Ltd., Polytheme) was coated with the antimicrobial composition on the entire surface of the plate with a bar coater. An antimicrobial component was obtained.

(Evaluation of the shape of the antimicrobial member and the dispersion state of the cured binder)
A photograph of the obtained antimicrobial member was taken with an optical microscope (Microscope VHX-5000 manufactured by Keyence Corporation). 3 is an optical micrograph showing the antimicrobial member obtained in Example 1. FIG. It can be seen that the binder cured product is fixedly formed on the surface of the polypropylene resin plate which is the substrate so that a part of the surface is exposed. FIG. 3 shows a mixture of areas where the cured binder is formed and areas where the cured binder is not formed.

(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 1 and 2, JIS Z 2801 Antibacterial processed products-Antibacterial test method/Antibacterial effect 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) For the antimicrobial members obtained in Examples 1 and 2, the antimicrobial members were cut into squares of 50 mm square to prepare test samples. 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 10-fold dilution of a 108 PFU/mL stock with purified water was 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 member (polypropylene resin plate) obtained in Examples 1 and 2 was cut into a 50 mm square to prepare a test sample. 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. 1/500NB culture medium was used.
(2) As a control sample, a 50 mm square polyethylene film was prepared and inoculated with the test fungus 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 = (U _t - U ₀ ) - (A _t - U ₀ ) = U _t - A _t
R: Antibacterial activity value U ₀ : Average value of logarithm value of viable count immediately after inoculation of unprocessed test piece U _t : Average value of logarithm value of viable count of unprocessed test piece after 24 hours At _t : Antibacterial Average value of the logarithmic value of the number of viable bacteria after 24 hours of the processed test piece 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 member (polypropylene resin plate) obtained in Examples 1 and 2 was cut into a 50 mm square to prepare a test sample. 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 the spore suspension was evenly inoculated, 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.
A _a = (LogC _t −LogC ₀ )−(LogT _t −LogT ₀ )
A _a : Antifungal activity value LogC ₀ : Common logarithm value of arithmetic mean of ATP amount of 3 control specimens immediately after inoculation LogC _t : Arithmetic mean of ATP amount of 3 control specimens after culture LogT ₀ : Common logarithm value of arithmetic mean of ATP amount of 3 test materials immediately after inoculation LogT _t : Arithmetic mean of ATP amount of 3 test materials 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.

In the present invention, the antiviral activity value, the antibacterial activity value, and the antifungal activity value can all be maintained within a practical range even by wiping. In general, when a film-like cured binder is used, the adhesion between the surface of the polypropylene resin plate and the cured resin is poor. However, the antimicrobial member of the present invention does not exhibit such a decrease in antimicrobial activity even when wiped off, and an antimicrobial member having excellent durability can be obtained. In particular, the antiviral performance and antifungal performance are hardly degraded, and the durability of the antiviral and antifungal properties is excellent. In addition, since antimicrobial activity can be imparted simply by spraying, no special equipment is required and on-site construction can be realized at low cost.

In addition, when the antimicrobial members obtained in Example 1 and Comparative Example were heated to 70° C. with a halogen lamp and returned to room temperature, the antimicrobial member of Example 1 showed warpage in the polypropylene plate, No other changes were observed, but in the antimicrobial member of the comparative example, swelling was confirmed in the cured binder containing the antimicrobial component. It is presumed that thermal deformation of the polypropylene resin causes stress at the interface with the cured binder containing the antimicrobial component, resulting in blistering. On the other hand, in Example 1, since the cured binder containing the antimicrobial component adheres to the polypropylene resin layer in a discontinuous state, it is considered that stress concentration does not occur at the interface. As described above, the present invention can solve the problem that the cured binder containing the antimicrobial component peels off and falls off due to thermal deformation that tends to occur in polypropylene, resulting in a decrease in antimicrobial activity.

10, 20 Antimicrobial members 11, 21 Base material 12 Film formation region 13 Film non-formation region 22, 42, 52, 62 Binder hardened material 40 Handle 41 Handle 43 Screw 50 Chair 51 Cushion material 53 Leg 54 Armrest 55 Back 56 seat 60 table 61 table top 61a table edge 63 table leg

Claims (5)

Spray droplets of an antiviral composition that contains an organic binder and a copper compound and does not contain titanium oxide on the surface of a base material made of polypropylene resin and cure it,
By forming a cured binder containing an antiviral component on the surface of the base material, the cured binder is dispersed in islands and adhered to the surface of the base material, or the cured binder is formed on the surface of the base material. A method for producing an antiviral member, characterized in that a region having a substance formed thereon and a region having no cured binder formed thereon are mixedly provided. 2. The method for manufacturing an antiviral member according to claim 1 , wherein the organic binder is at least one selected from the group consisting of thermosetting resins and electromagnetic wave curing resins. A handle whose surface is made of polypropylene resin, and droplets of an antiviral composition containing an organic binder and a copper compound and not containing titanium oxide are sprayed onto the surface of the polypropylene resin constituting the handle, and then cured. Then, by fixing and forming a binder cured product containing an antiviral component, the binder cured product is dispersed in islands and adhered to the surface of the polypropylene resin that constitutes the handle, or the handle is composed. A method for producing a handle, characterized in that a region in which the cured binder is formed and a region in which the cured binder is not formed are mixedly provided on the surface of the polypropylene resin. An armrest of a chair whose surface is made of polypropylene resin, and droplets of an antiviral composition containing an organic binder and a copper compound and not containing titanium oxide are sprayed on the surface of the polypropylene resin constituting the armrest of the chair. By curing this to form a cured binder containing an antiviral component, the cured binder is dispersed in islands and adhered to the surface of the polypropylene resin that constitutes the armrest of the chair. Alternatively, an armrest of a chair, wherein a region in which the cured binder is formed and a region in which the cured binder is not formed are mixedly provided on the surface of the polypropylene resin constituting the armrest of the chair. manufacturing method. A table edge whose surface is made of polypropylene resin, and droplets of an antiviral composition that contains an organic binder and a copper compound and does not contain titanium oxide are sprayed on the surface of the polypropylene resin that constitutes the table edge. is cured and a cured binder containing an antiviral component is fixedly formed, so that the cured binder is dispersed in islands and fixed to the surface of the polypropylene resin that constitutes the table edge, or A method for manufacturing a table edge, characterized in that a region in which the cured binder is formed and a region in which the cured binder is not formed are mixedly provided on the surface of the polypropylene resin constituting the table edge.

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