Antiviral Materials

Abstract

To provide an antiviral member capable of efficiently deactivating virus dispensing with an excess antiviral agent.SOLUTION: The antiviral member is formed with a filmy resin layer containing a plurality of particulate antiviral agents having no photocatalytic function on a substrate surface where at least a part of the particulate antiviral agents is exposed from the resin layer, and an average value of distances between gravity centers of neighboring antiviral agents is 3-30 μm in a plane view of the antiviral member.SELECTED DRAWING: Figure 2

Description

[Technical field]

[0001] The present invention relates to an antiviral material. [Background technology]

[0002] In recent years, so-called "pandemics," in which infectious diseases transmitted by various pathogenic microorganisms spread rapidly in a short period of time, have become a problem, and deaths due to viral infections such as SARS (Severe Acute Respiratory Syndrome), norovirus, and avian influenza have been reported.

[0003] Accordingly, active development of antiviral agents that exhibit antiviral activity against various viruses is underway, and in fact, various components are coated with resins containing antiviral agents made of metals such as Pd or organic compounds that have antiviral activity, and components are manufactured that contain materials carrying antiviral agents.

[0004] Patent Document 1 discloses an antiviral decorative board comprising a substrate, a surface resin layer laminated on one or both sides of the substrate, and an antiviral functional layer disposed on the surface resin layer and containing inorganic antiviral particles, wherein the ratio of the film thickness of the antiviral functional layer to the average particle size of the inorganic antiviral particles is 0.3 to 1.1. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] JP2019-25918A Summary of the Invention [Problem to be solved by the invention]

[0006] However, Patent Document 1 does not disclose whether viruses can be inactivated by arranging antiviral particles at a certain density, and there have been cases where the antiviral effect was insufficient due to the arrangement of an excessive amount of antiviral agent or, conversely, a small amount of antiviral agent.

[0007] An object of the present invention is to provide an antiviral member in which the arrangement density of antiviral particles is adjusted so that a sufficient antiviral effect can be obtained using a minimum amount of antiviral agent. [Means for solving the problem]

[0008] As a result of intensive research, the present inventors found that the antiviral performance is maximized by adjusting the average value of the distance between the centers of gravity of adjacent antiviral agents to 3 to 30 µm, and completed the present invention.

[0009] That is, in the present invention, a film-like resin layer containing a plurality of granular antiviral agents having no photocatalytic function is formed on the surface of a substrate, at least a portion of the granular antiviral agents is exposed from the resin layer, and when viewed in plan, the average value of the distance between the centers of gravity of adjacent antiviral agents is 3.7 The antiviral material is characterized in that the thickness is between 100 μm and 30 μm. The antiviral agent is an imidazole-based antiviral agent or an antiviral component which is copper iodide.

[0010] In the anti-viral member of the present invention, a film-like resin layer made of at least one resin selected from a (meth)acrylate-based resin and a polysiloxane-based resin can be used as the film-like resin layer.

[0011] In the antiviral member of the present invention, an organic antiviral agent and / or an inorganic antiviral agent can be used as the antiviral agent as long as it does not have a photocatalytic function and is granular. The reason why it needs to be granular is that by mixing it with a resin, such as at least one resin selected from a (meth)acrylic resin and a polysiloxane resin, and forming it into a film, it can be easily exposed from the resin surface and easily come into contact with viruses.

[0012] In the antiviral member of the present invention, the antiviral agent does not have a photocatalytic function, and therefore the resin layer is less likely to deteriorate compared to when the antiviral agent has a photocatalytic function.

[0013] In the present invention, the distance between the centers of gravity is measured as follows. First, the surface of the antiviral member is photographed in a planar view under magnification with an electron microscope, and the photographed image is binarized. Next, three distances between the center of gravity of one granular antiviral agent in the image and the centers of gravity of multiple antiviral agents present around that antiviral agent are selected, from the shortest to the longest. Such measurements of the three distances between the centers of gravity of the granular antiviral agents are performed for all antiviral agents in the photographed image, and the average value is calculated. FIG. 1 is an electron microscope photograph of an antiviral member. FIG. 2 shows the state in which FIG. 1 is binarized to measure the distance between the centers of gravity of the antiviral agents.

[0014] ImageJ, an open source and public domain image processing software, was used for binarization, identification of the centroids of antiviral agents, and measurement of the distance between the centroids of adjacent antiviral agents.

[0015] By adjusting the average value of the distance between the centers of gravity of the adjacent antiviral agents to 3 to 30 μm, it is possible to prevent the content of the antiviral agent from becoming excessive, and by trapping the virus between the granular antiviral agent and increasing the probability of contact between the virus and the antiviral agent, it is possible to effectively inactivate the virus.

[0016] It is more desirable to adjust the average distance between the centers of gravity of the adjacent antiviral agents to be between 4 and 30 μm.

[0017] The average value of the distances between the centers of gravity of the adjacent antiviral agents can be adjusted by the amount of the antiviral agent dispersed in the resin.

[0018] In the present invention, the resin layer portion having antiviral properties may be made into a film. Specifically, the antiviral film may be made of a membranous resin layer containing a plurality of granular antiviral agents having no photocatalytic function, at least a portion of the granular antiviral agents being exposed from the resin layer, and the average value of the distance between the centers of gravity of adjacent antiviral agents is 3 to 30 μm when the antiviral member is viewed in plan.

[0019] The film is used by being attached to a substrate. It is preferable to provide a pressure-sensitive adhesive layer or an adhesive layer on the surface that contacts the substrate. A release sheet may be laminated on the pressure-sensitive adhesive layer or the adhesive layer.

[0020] In the antiviral member of the present invention, the antiviral agent is required to be an organic antiviral agent having no photocatalytic function and / or an inorganic antiviral agent having no photocatalytic function.

[0021] In the present invention, even if the oxidizing power is not as high as that of a photocatalyst, the virus can be reliably inactivated by increasing the probability of contact with the antiviral agent.

[0022] In the antiviral member of the present invention, it is preferable that the antiviral agent does not contain copper ions or copper compounds. If copper ions or copper compounds are contained, the resin layer is likely to be discolored, and the design properties of the resin layer may be reduced.

[0023] The antiviral agent in the present invention is desirably at least one selected from the group consisting of metal compounds having no photocatalytic function and zeolites ion-exchanged with metal ions.

[0024] The metal oxide may not contain copper ions or copper compounds. Since most copper ions and copper compounds are colored, when the cured product of the ultraviolet curable resin is formed into a film, the color of the substrate surface is impaired. As the antiviral agent, inorganic phosphate compounds, inorganic silicic acid compounds, silver ion-substituted zeolites, etc., which have antiviral functions, are suitable. In addition, if the color of the substrate surface is not affected even if copper ions or copper compounds are contained, the antiviral agent may contain a copper compound. Specifically, copper oxide, copper iodide, cuprous oxide, copper hydroxide, etc. can be used.

[0025] Examples of the metal compounds include metal oxides, inorganic phosphate compounds, and inorganic silicic acid compounds. Examples of the metal oxides include zinc oxide, silver oxide, and lead oxide. Examples of the inorganic phosphate compounds include inorganic phosphate compounds of titanium group elements such as zinc phosphate, zirconium phosphate, hafnium phosphate, and titanium phosphate, inorganic phosphate compounds such as aluminum phosphate and hydroxyapatite (phosphate mineral); and inorganic silicic acid compounds such as magnesium silicate, silica gel, aluminosilicate, sepiolite (hydrated magnesium silicate), montmorillonite (silicate mineral), and zeolite (aluminosilicate). As an inorganic antiviral agent, silver supported on silica has an antibacterial effect, but the surface area is small and silica itself does not have antiviral properties, so silver-supported silica does not function as an antiviral agent. On the other hand, zeolite has a large surface area and has an antiviral function, so zeolite substituted with silver ions is more preferable than silver-supported silica.

[0026] In addition, the organic antiviral agent is preferably at least one selected from the group consisting of triazine, azole, sulfonic acid surfactant, and bis-type quaternary ammonium salt. Examples of the organic antiviral agent include azoles such as imidazole, triazole, thiazole, and benzimidazole, triazine, chlorophenesin, thymol, salicylic acid and derivatives thereof, benzoic acid, sodium benzoate, paraoxybenzoic acid ester, sorbic acid, potassium sorbate, zinc pyrithione, bis-type pyridinium salt, bis-type quinolinium salt, and bis-type thiazolium salt. These organic compounds are granular at about 25°C, which is the temperature at which they are used.

[0027] In the antiviral material of the present invention, a (meth)acrylate resin can be used as the resin. The (meth)acrylate resin of the present invention is preferably made of a polyfunctional (meth)acrylate having three or more acryloyl groups. This is because the polymer chains of such (meth)acrylates form a strong network, and the polymer chains have high hardness and excellent abrasion resistance.

[0028] In the antiviral member of the present invention, the film-like resin layer may contain a leveling agent. As the leveling agent, a silicone-based leveling agent, particularly a non-volatile silicone, can be suitably used. Being non-volatile, the leveling effect is high and the finger slipperiness is also excellent. Examples of the non-volatile silicone include polyalkylsiloxane, polyarylsiloxane, polyalkylarylsiloxane, polysiloxane having an amino functional substituent, polyethersiloxane copolymer, and mixtures thereof. The amount of the non-volatile silicone added is preferably 0.002 to 0.007 parts by weight of solid content relative to 100 parts by weight of the solid content of the total (meth)acrylate.

[0029] The (meth)acrylate resin used in the antiviral material of the present invention is preferably a polyfunctional (meth)acrylate. In particular, a polyfunctional (meth)acrylate having three or more, preferably five or more, acryloyl groups in the molecule has the role of improving hardness. Specific examples of such polyfunctional (meth)acrylates include dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, alkyl-modified dipentaerythritol penta(meth)acrylate, caprolactone-modified dipentaerythritol hexa(meth)acrylate, and mixtures of two or more of these.

[0030] In the present invention, a polyfunctional urethane (meth)acrylate resin may be used as the (meth)acrylate resin. Polyfunctional urethane (meth)acrylate resins have high hardness and improved toughness, so they are less susceptible to wear and cracking, and even under wear conditions, the granular antiviral agent does not fall off, and the antiviral performance does not deteriorate over time.

[0031] In the present invention, the polyfunctional urethane (meth)acrylate resin is desirably composed of a polyfunctional urethane (meth)acrylate oligomer, and the polyfunctional urethane (meth)acrylate oligomer desirably has three or more (meth)acryloyl groups and is composed of a polyfunctional (meth)acrylate monomer and / or a polyfunctional acrylate oligomer having a hydroxyl group, and an isocyanate monomer or an organic polyisocyanate.

[0032] Examples of the isocyanate monomer include tolylene diisocyanate, diphenylmethane diisocyanate, xylylene diisocyanate, isophorone diisocyanate, and hexamethylene diisocyanate. Examples of the organic polyisocyanate include adduct type, isocyanurate type, and biuret type polyisocyanates synthesized from the isocyanate monomer.

[0033] Examples of polyfunctional acrylate monomers and / or oligomers having three or more (meth)acryloyl groups and hydroxyl groups include dipentaerythritol triacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, etc. These polyfunctional acrylate monomers and / or oligomers can form polyfunctional urethane (meth)acrylate oligomers with many crosslinking points by bonding with isocyanate monomers or organic polyisocyanates, and the cured product can realize three-dimensional crosslinking and has excellent hardness and toughness. The number of acryloyl groups is particularly preferably 5 or more.

[0034] The resin constituting the film-like resin layer in the present invention is preferably a polysiloxane-based resin. The polysiloxane-based resin that can be used in the present invention is a resin having a polysiloxane structure as the main chain.

[0035] There are no particular limitations on the method for producing polysiloxane resins, but the most well-known method is to produce polysiloxane resins by dehydration condensation and polymerization of chloroalkylsilanes using acids or bases as catalysts, as described in "Organic Chemistry of Siloxanes and Silanols" in the Journal of the Society of Organic Synthesis, Vol. 58, No. 10 (2000).

[0036] In addition to these methods, for example, a silicone resin having a polysiloxane structure as the main chain, reactive curing groups at the terminals, and capable of being cured by water may be polymerized using a catalyst described below to produce a polysiloxane-based resin. The reactive curing group is a functional group having a structure that generates a silanol group by reacting with an active hydrogen group-containing compound such as water. Depending on the type of protective group to be eliminated, there are de-alcohol type, de-oxime type, de-acetic acid type, de-amide type, de-acetone type, etc.

[0037] Examples of the curing catalyst for silicone resin include organic tin, inorganic tin, titanium catalyst, bismuth catalyst, metal complex, platinum catalyst, basic compound, organic phosphorus oxide, etc. Specific examples of organic tin include dibutyltin dilaurate, dioctyltin dimaleate, dibutyltin phthalate, stannous octylate, dibutyltin diacetate, and reaction products of dibutyltin salt and ethyl orthosilicate.

[0038] The resin constituting the film-like resin layer of the present invention may be a (meth)acrylate-based resin and a polysiloxane-based resin.

[0039] In the antiviral member of the present invention, the thickness of the resin layer containing the antiviral agent is desirably 0.1 μm to 20 μm.

[0040] In the anti-viral member of the present invention, the film-like resin layer may contain a (meth)acrylate having a phosphate group, and specific examples include 2-(meth)acryloyloxyethyl-dihydrophosphate, di-(2-(meth)acryloyloxy)hydrogen phosphate, ethylene oxide-modified phosphate dimethacrylate, etc. It is presumed that the presence of the phosphate group improves adhesion to metals and ceramics (including glass).

[0041] The method for producing an antiviral member of the present invention includes a resin curing step of coating a surface of a substrate with an antiviral composition comprising an uncured resin containing a granular antiviral agent having no photocatalytic function, for example, at least one resin selected from uncured (meth)acrylate resins and polysiloxane resins, in the form of a film, and then curing the resin to form a resin layer.

[0042] Alternatively, the method includes a resin curing step in which an antiviral composition made of an uncured resin, for example at least one resin selected from an uncured (meth)acrylate resin and a polysiloxane resin, is coated on the surface of a substrate in the form of a film, a granular antiviral agent having no photocatalytic function is adhered onto the uncured resin, and the resin is cured to form a resin layer.

[0043] In the method for producing an antiviral member of the present invention, it is preferable that the antiviral composition does not contain an organic solvent.

[0044] In this case, the antiviral composition can be cured by ultraviolet light or heat without drying, and the solvent, which is harmful to the human body, does not volatilize.

[0045] In addition, in the method for producing an antiviral material of the present invention, it is preferable that the antiviral composition does not contain water, because holes or air bubbles are likely to form in the cured film of the antiviral composition, and the strength of the cured film is also likely to decrease.

[0046] Alternatively, a resin layer can be formed by laminating a sheet obtained by forming an antiviral composition containing an uncured resin into a film and drying it to a so-called B-stage state on a substrate. [Brief description of the drawings]

[0047] [Figure 1] FIG. 1 is an electron microscope photograph (plan view) of the surface of an antiviral component according to Example 1 of the present invention. [Diagram 2] Figure 2 shows three adjacent granular antiviral agents selected based on the shortest distance between their centers of gravity, represented as lines connecting the centers of gravity. [Diagram 3] FIG. 3 is a histogram of the distance between the centers of gravity of antiviral agents represented by the line segments in FIG. [Figure 4] FIG. 4 shows three adjacent granular antiviral agents on the surface of the antiviral material according to Example 4 of the present invention, selected from those with the shortest distance between their centers of gravity, represented as line segments connecting the centers of gravity. [Diagram 5] FIG. 5 is a histogram of the distance between the centers of gravity of antiviral agents represented by the line segments in FIG. [Figure 6] FIG. 6 is a schematic cross-sectional view of the antiviral film of the present invention. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0048] The antiviral component of the present invention is characterized in that a film-like resin layer containing a plurality of granular antiviral agents without photocatalytic function is formed on the surface of a substrate, at least a portion of the granular antiviral agents is exposed from the resin layer, and when the antiviral component is viewed in a plan view, the average value of the distance between the centers of gravity of adjacent antiviral agents is 3 to 30 µm.

[0049] It is further desirable that the average distance between the centers of gravity of adjacent antiviral agents is from 4 to 30 μm.

[0050] In the present invention, the resin layer portion having antiviral properties may be made into a film. Specifically, the antiviral film may be made of a membranous resin layer containing a plurality of granular antiviral agents having no photocatalytic function, at least a portion of the granular antiviral agents being exposed from the resin layer, and the average value of the distance between the centers of gravity of adjacent antiviral agents is 3 to 30 μm when the antiviral member is viewed in plan.

[0051] The film is used by being attached to a substrate. It is preferable to provide a pressure-sensitive adhesive layer or an adhesive layer on the surface that contacts the substrate. A release sheet may be laminated on the pressure-sensitive adhesive layer or the adhesive layer.

[0052] The anti-viral member containing the virus member of the present invention will be described below with reference to the drawings. Figure 1 is a cross-sectional view that shows a schematic diagram of one example of the anti-viral member containing the virus member of the present invention.

[0053] In the antiviral member of the present invention, the material of the substrate is not particularly limited, and examples thereof include metals, ceramics such as glass, resins, woven fibers, and wood.

[0054] Furthermore, in the antiviral member of the present invention, the substrate may be a film, a sheet, a cloth, an interior material for the inside of a building, a wall material, wallpaper, window glass, a door, office equipment, furniture, etc., and it is particularly desirable for the substrate to be a member fixed to real estate.

[0055] In the anti-viral member of the present invention, a film-like resin layer made of at least one resin selected from a (meth)acrylate-based resin and a polysiloxane-based resin is used as the film-like resin layer, and a granular anti-viral agent is impregnated in this resin layer.

[0056] In the antiviral member of the present invention, the antiviral agent does not need to have a photocatalytic function and may be in a granular form. As the antiviral agent, an organic antiviral agent and / or an inorganic antiviral agent may be used. The reason that the agent needs to be in a granular form is that the distance between the centers of gravity of the antiviral agent particles can be controlled.

[0057] In the antiviral member of the present invention, the antiviral agent does not have a photocatalytic function, and therefore the resin layer is less likely to deteriorate compared to when the antiviral agent has a photocatalytic function.

[0058] In the antiviral member of the present invention, the antiviral agent is preferably an organic antiviral agent having no photocatalytic function and / or an inorganic antiviral agent having no photocatalytic function.

[0059] In the antiviral member of the present invention, it is preferable that the antiviral agent does not contain copper ions or copper compounds. If copper ions or copper compounds are contained, the resin layer is likely to be discolored, and the design properties of the resin layer may be reduced.

[0060] The inorganic antiviral agent is desirably at least one selected from the group consisting of metal compounds having no photocatalytic function and zeolites substituted with metal ions.

[0061] The metal oxide may not contain copper ions or copper compounds. Since most copper ions and copper compounds are colored, when the cured product of the ultraviolet curable resin is formed into a film, the color of the substrate surface is impaired. As the antiviral agent, inorganic phosphate compounds, inorganic silicic acid compounds, silver ion-substituted zeolites, and the like having antiviral functions are suitable.

[0062] In addition, if the color of the substrate surface is not affected even if copper ions or copper compounds are contained, the antiviral agent may contain a copper compound. Specifically, copper oxide, copper iodide, cuprous oxide, copper hydroxide, etc. can be used. Copper iodide is a white powder, is stable against oxidation, and can maintain the state of copper (I) for a long time even in an oxidizing atmosphere.

[0063] Examples of the metal compound include metal oxides, inorganic phosphate compounds, and inorganic silicic acid compounds. Examples of the metal oxide include zinc oxide, silver oxide, and lead oxide. Examples of the inorganic phosphate compound include zinc phosphate, titanium group element phosphate compounds such as zirconium phosphate, hafnium phosphate, and titanium phosphate, inorganic phosphate compounds such as aluminum phosphate and hydroxyapatite (phosphate mineral); inorganic silicic acid compounds such as magnesium silicate, silica gel, aluminosilicate, sepiolite (hydrated magnesium silicate), montmorillonite (silicate mineral), and zeolite (aluminosilicate). As an inorganic antiviral agent, silver supported on silica has an antibacterial effect, but the surface area is small and silica itself does not have antiviral properties, so silver-supported silica does not function as an antiviral agent. On the other hand, zeolite has a large surface area and has an antiviral function, so zeolite substituted with silver ions is more preferable than silver-supported silica.

[0064] The organic antiviral agent is preferably at least one selected from the group consisting of triazines, azoles, sulfonic acid surfactants, and bis-type quaternary ammonium salts.

[0065] Examples of organic antiviral agents include azoles such as imidazole, triazole, thiazole, and benzimidazole, triazine, chlorophenesin, thymol, salicylic acid and derivatives thereof, benzoic acid, sodium benzoate, paraoxybenzoic acid esters, sorbic acid, potassium sorbate, zinc pyrithione, bis-pyridinium salts, bis-quinolinium salts, bis-thiazolium salts, etc. These organic compounds are granular at about 25° C., which is the usage temperature.

[0066] Next, the film-like resin layer made of at least one resin selected from (meth)acrylate-based resins and polysiloxane-based resins in the anti-viral material of the present invention will be described.

[0067] Regarding the resin layer of the present invention, when a (meth)acrylate resin is used, an antiviral composition containing an uncured (meth)acrylate monomer / oligomer, a photopolymerization initiator, various additives, and an antiviral agent is used to form a film-like coating on the surface of the substrate, and then ultraviolet light is applied, whereby the photopolymerization initiator undergoes reactions such as cleavage reactions, hydrogen abstraction reactions, and electron transfer, and the photoradical molecules, photocation molecules, photoanion molecules, and the like thus generated attack the monomers and oligomers that constitute the uncured ultraviolet-curable resin, causing a polymerization reaction or crosslinking reaction of the monomers and oligomers to proceed, and a cured product of (meth)acrylate containing the antiviral agent is formed.

[0068] The (meth)acrylate resin used in the antiviral material of the present invention is preferably a polyfunctional (meth)acrylate. In particular, a polyfunctional (meth)acrylate having five or more acryloyl groups in the molecule serves to improve hardness. Specific examples of such polyfunctional (meth)acrylates include dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, alkyl-modified dipentaerythritol penta(meth)acrylate, caprolactone-modified dipentaerythritol hexa(meth)acrylate, and mixtures of two or more of these.

[0069] In the present invention, a polyfunctional urethane (meth)acrylate resin may be used as the (meth)acrylate resin. Polyfunctional urethane (meth)acrylate resins have high hardness and improved toughness, so they are less susceptible to wear and cracking, and even under wear conditions, the granular antiviral agent does not fall off, and the antiviral performance does not deteriorate over time.

[0070] In the present invention, the polyfunctional urethane (meth)acrylate resin is desirably composed of a polyfunctional urethane (meth)acrylate oligomer, and the polyfunctional urethane (meth)acrylate oligomer desirably has three or more (meth)acryloyl groups and is composed of a polyfunctional (meth)acrylate monomer and / or a polyfunctional acrylate oligomer having a hydroxyl group, and an isocyanate monomer or an organic polyisocyanate.

[0071] Examples of the isocyanate monomer include tolylene diisocyanate, diphenylmethane diisocyanate, xylylene diisocyanate, isophorone diisocyanate, and hexamethylene diisocyanate. Examples of the organic polyisocyanate include adduct type, isocyanurate type, and biuret type polyisocyanates synthesized from the isocyanate monomer.

[0072] Examples of polyfunctional acrylate monomers and / or oligomers having three or more (meth)acryloyl groups and hydroxyl groups include dipentaerythritol triacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, etc. These polyfunctional acrylate monomers and / or oligomers can form polyfunctional urethane (meth)acrylate oligomers with many crosslinking points by bonding their hydroxyl groups with isocyanate monomers or organic polyisocyanates, and the cured product can realize three-dimensional crosslinking and has excellent hardness and toughness. Five or more acryloyl groups are particularly preferable.

[0073] In addition, a polysiloxane-based resin can be obtained by subjecting an alkylchlorosilane, which is an uncured monomer of a polysiloxane-based resin, to a hydrolysis and polymerization reaction in the presence of an acid or a base. Also, a polysiloxane-based resin can be obtained by using a silicone resin that has a polysiloxane structure as the main chain, reactive curing groups at the terminals, and can be cured by water, and polymerizing it with a catalyst.

[0074] The resin constituting the film-like resin layer in the present invention is preferably a polysiloxane-based resin. The polysiloxane-based resin that can be used in the present invention is a resin having a polysiloxane structure as the main chain.

[0075] There are no particular limitations on the method for producing polysiloxane resins, but the most well-known method is to produce polysiloxane resins by dehydration condensation and polymerization of chloroalkylsilanes using acids or bases as catalysts, as described in "Organic Chemistry of Siloxanes and Silanols" in the Journal of the Society of Organic Synthesis, Vol. 58, No. 10 (2000).

[0076] In addition to these methods, for example, a silicone resin having a polysiloxane structure as the main chain, reactive curing groups at the terminals, and capable of being cured by water may be polymerized using a catalyst described below to produce a polysiloxane-based resin. The reactive curing group is a functional group having a structure that generates a silanol group by reacting with an active hydrogen group-containing compound such as water. Depending on the type of protective group to be eliminated, there are de-alcohol type, de-oxime type, de-acetic acid type, de-amide type, de-acetone type, etc.

[0077] Examples of the curing catalyst for silicone resin include organic tin, inorganic tin, titanium catalyst, bismuth catalyst, metal complex, platinum catalyst, basic compound, organic phosphorus oxide, etc. Specific examples of organic tin include dibutyltin dilaurate, dioctyltin dimaleate, dibutyltin phthalate, stannous octylate, dibutyltin diacetate, and reaction products of dibutyltin salt and ethyl orthosilicate.

[0078] The resin constituting the film-like resin layer of the present invention may be a (meth)acrylate-based resin and a polysiloxane-based resin.

[0079] In the antiviral member of the present invention, the thickness of the resin layer containing the antiviral agent is desirably 0.1 μm to 20 μm.

[0080] In the antiviral member of the present invention, the resin layer may contain a (meth)acrylate having a phosphate group, and specific examples include 2-(meth)acryloyloxyethyl-dihydrophosphate, di-(2-(meth)acryloyloxy)hydrogen phosphate, ethylene oxide-modified phosphate dimethacrylate, etc. It is presumed that the presence of the phosphate group improves adhesion to metals and ceramics (including glass).

[0081] The antiviral material of the present invention preferably contains at least one (meth)acrylate selected from the group consisting of methyl (meth)acrylate, dimethylol-tricyclodecane diacrylate, and cyclohexyl methacrylate, and a photopolymerization initiator, because these resins can reduce the viscosity of the acrylate resin before curing.

[0082] The (meth)acrylate resin of the present invention is preferably made of a polyfunctional (meth)acrylate having 3 or more, preferably 5 or more, acryloyl groups. This is because such (meth)acrylates have polymer chains that form a strong network, and have high hardness and excellent abrasion resistance. For this reason, the antiviral agent does not fall off even under severe abrasion conditions such as trampling and rubbing with shoes or rotating brushes used in machine cleaning, and the antiviral performance is not easily deteriorated over time.

[0083] In the antiviral member of the present invention, a leveling agent may be contained in the resin. As the leveling agent, a silicone-based leveling agent, particularly a non-volatile silicone, can be suitably used. Being non-volatile, the leveling effect is high and the finger slipperiness is also excellent. Examples of the non-volatile silicone include polyalkylsiloxane, polyarylsiloxane, polyalkylarylsiloxane, polysiloxane having an amino functional substituent, polyethersiloxane copolymer, and mixtures thereof. The amount of the non-volatile silicone added is preferably 0.002 to 0.007 parts by weight of solid content relative to 100 parts by weight of the solid content of the total (meth)acrylate.

[0084] The antiviral member of the present invention can impart antiviral functionality to, for example, interior materials, wall materials, window glass, doors, kitchen utensils, etc. used inside buildings, office equipment, furniture, etc., and decorative panels used for various applications, without changing the pattern, color, design, color tone, etc. formed on the surface.

[0085] Next, a method for producing the above-mentioned antiviral member will be described.

[0086] (1) Antiviral composition preparation process When producing the antiviral member of the present invention, first, an antiviral composition is prepared containing a granular antiviral agent having no photocatalytic function, an uncured resin, for example, at least one resin selected from uncured (meth)acrylate resins and polysiloxane resins, and, if necessary, a dispersion medium and a photopolymerization initiator. The average particle size of the granular antiviral agent in the antiviral composition is desirably 0.01 to 50 μm.

[0087] The antiviral agent in the antiviral composition is preferably an organic antiviral agent having no photocatalytic function and / or an inorganic antiviral agent having no photocatalytic function.

[0088] It is desirable that the antiviral agent in the antiviral composition does not contain copper ions or copper compounds, because if copper ions or copper compounds are contained, they are likely to be discolored, and the design properties of the resin layer may be reduced.

[0089] The inorganic antiviral agent in the antiviral composition is desirably at least one selected from the group consisting of metal compounds having no photocatalytic function and zeolites substituted with metal ions.

[0090] The metal oxide may not contain copper ions or copper compounds. Since most copper ions and copper compounds are colored, when the cured product of the ultraviolet curable resin is formed into a film, the color of the substrate surface is impaired. As the antiviral agent, inorganic phosphate compounds, inorganic silicic acid compounds, silver ion-substituted zeolites, and the like having antiviral functions are suitable.

[0091] In addition, if the color of the substrate surface is not affected even if copper ions or copper compounds are contained, the antiviral agent may contain a copper compound. Specifically, copper oxide, copper iodide, cuprous oxide, copper hydroxide, etc. can be used. Copper iodide is a white powder, is stable against oxidation, and can maintain the state of copper (I) for a long time even in an oxidizing atmosphere.

[0092] Examples of the metal compound include metal oxides, inorganic phosphate compounds, and inorganic silicic acid compounds. Examples of the metal oxide include zinc oxide, silver oxide, and lead oxide. Examples of the inorganic phosphate compound include zinc phosphate, titanium group element phosphate compounds such as zirconium phosphate, hafnium phosphate, and titanium phosphate, inorganic phosphate compounds such as aluminum phosphate and hydroxyapatite (phosphate mineral); inorganic silicic acid compounds such as magnesium silicate, silica gel, aluminosilicate, sepiolite (hydrated magnesium silicate), montmorillonite (silicate mineral), and zeolite (aluminosilicate). As an inorganic antiviral agent, silver supported on silica has an antibacterial effect, but the surface area is small and silica itself does not have antiviral properties, so silver-supported silica does not function as an antiviral agent. On the other hand, zeolite has a large surface area and has an antiviral function, so zeolite substituted with silver ions is more preferable than silver-supported silica.

[0093] The organic antiviral agent in the antiviral composition is desirably at least one selected from the group consisting of triazines, azoles, sulfonic acid surfactants, and bis-type quaternary ammonium salts.

[0094] Examples of organic antiviral agents include azoles such as imidazole, triazole, thiazole, and benzimidazole, triazine, chlorophenesin, thymol, salicylic acid and derivatives thereof, benzoic acid, sodium benzoate, paraoxybenzoic acid esters, sorbic acid, potassium sorbate, zinc pyrithione, bis-pyridinium salts, bis-quinolinium salts, bis-thiazolium salts, etc. These organic compounds are granular at about 25° C., which is the usage temperature.

[0095] The (meth)acrylate resin in the antiviral composition is preferably a polyfunctional (meth)acrylate. In particular, a polyfunctional (meth)acrylate having five or more acryloyl groups in the molecule has the role of improving hardness. Specific examples of such polyfunctional (meth)acrylates include dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, alkyl-modified dipentaerythritol penta(meth)acrylate, caprolactone-modified dipentaerythritol hexa(meth)acrylate, and mixtures of two or more of these.

[0096] In the present invention, a polyfunctional urethane (meth)acrylate resin may be used as the (meth)acrylate resin. Polyfunctional urethane (meth)acrylate resins have high hardness and improved toughness, so they are less susceptible to wear and cracking, and even under wear conditions, the granular antiviral agent does not fall off, and the antiviral performance does not deteriorate over time.

[0097] The polyfunctional urethane (meth)acrylate resin is desirably composed of a polyfunctional urethane (meth)acrylate oligomer, and the polyfunctional urethane (meth)acrylate oligomer desirably has three or more (meth)acryloyl groups and is composed of a polyfunctional (meth)acrylate monomer and / or a polyfunctional acrylate oligomer having a hydroxyl group, and an isocyanate monomer or an organic polyisocyanate.

[0098] Examples of the isocyanate monomer include tolylene diisocyanate, diphenylmethane diisocyanate, xylylene diisocyanate, isophorone diisocyanate, and hexamethylene diisocyanate. Examples of the organic polyisocyanate include adduct type, isocyanurate type, and biuret type polyisocyanates synthesized from the isocyanate monomer.

[0099] Examples of polyfunctional acrylate monomers and / or oligomers having three or more (meth)acryloyl groups and hydroxyl groups include dipentaerythritol triacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, etc. These polyfunctional acrylate monomers and / or oligomers can form polyfunctional urethane (meth)acrylate oligomers with many crosslinking points by bonding with isocyanate monomers or organic polyisocyanates, and the cured product can realize three-dimensional crosslinking and has excellent hardness and toughness. The number of acryloyl groups is particularly preferably 5 or more.

[0100] The polysiloxane resin in the antiviral composition can be prepared by subjecting an alkylchlorosilane, which is an uncured monomer of the polysiloxane resin, to a hydrolysis and polymerization reaction in the presence of an acid or a base, or by using a silicone resin that has a polysiloxane structure as the main chain, reactive curing groups at the terminals, and can be cured by water, and polymerizing it with a catalyst to prepare a polysiloxane resin.

[0101] There are no particular limitations on the method for producing polysiloxane resins, but the most well-known method is to produce polysiloxane resins by dehydration condensation and polymerization of chloroalkylsilanes using acids or bases as catalysts, as described in "Organic Chemistry of Siloxanes and Silanols" in the Journal of the Society of Organic Synthesis, Vol. 58, No. 10 (2000).

[0102] In addition to these methods, for example, a silicone resin having a polysiloxane structure as the main chain, reactive curing groups at the terminals, and capable of being cured by water may be polymerized using a catalyst described below to produce a polysiloxane-based resin. The reactive curing group is a functional group having a structure that generates a silanol group by reacting with an active hydrogen group-containing compound such as water. Depending on the type of protective group to be eliminated, there are de-alcohol type, de-oxime type, de-acetic acid type, de-amide type, de-acetone type, etc.

[0103] Examples of the curing catalyst for silicone resin include organic tin, inorganic tin, titanium catalyst, bismuth catalyst, metal complex, platinum catalyst, basic compound, organic phosphorus oxide, etc. Specific examples of organic tin include dibutyltin dilaurate, dioctyltin dimaleate, dibutyltin phthalate, stannous octylate, dibutyltin diacetate, and reaction products of dibutyltin salt and ethyl orthosilicate.

[0104] The resin constituting the film-like resin layer of the present invention may be a (meth)acrylate-based resin and a polysiloxane-based resin.

[0105] When a metal or ceramic is used as the substrate for the antiviral member of the present invention, the uncured acrylate resin may further contain a (meth)acrylate compound having a phosphate group.

[0106] The type of dispersion medium in the antiviral composition is not particularly limited, but alcohols or water can be used when stability is taken into consideration. Examples of alcohols include methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, and sec-butyl alcohol, in consideration of lowering viscosity. Among these alcohols, methyl alcohol and ethyl alcohol, which are less likely to increase in viscosity, are preferable, and a mixture of alcohol and water is preferable. Organic solvents such as methyl ethyl ketone and ethyl acetate may also be used.

[0107] In addition, if water is used as a dispersion medium, the (meth)acrylate and photopolymerization initiator will become an emulsion, which will cause the problem of not being able to form a uniform film when applied, so it is not desirable to use water to emulsify the (meth)acrylate, photopolymerization initiator, etc.

[0108] Moreover, the most desirable form for preparing the antiviral composition is to prepare the antiviral composition without using a dispersion medium, that is, without using a solvent.

[0109] When the antiviral composition is prepared without a solvent, the (meth)acrylate monomer / oligomer can be cured in a short time by irradiating ultraviolet light after application without performing a drying process for drying the dispersion medium. In addition, when an organic solvent is used as the dispersion medium, the organic solvent volatilizes during application and after curing of the antiviral composition, which may adversely affect the health of workers and people living in the space where the antiviral member is placed. Therefore, it is desirable to use a solvent-free composition from the health perspective.

[0110] In order to reduce the viscosity of the antiviral composition, it is desirable to add at least one (meth)acrylate selected from the group consisting of methyl (meth)acrylate, dimethylol-tricyclodecane diacrylate, and cyclohexyl methacrylate.

[0111] The antiviral composition preferably contains methyl methacrylate (MMA) as a viscosity modifier, and the viscosity of the antiviral composition is preferably adjusted to less than 10 mPa·s / 25° C. The content of MMA in the total composition is preferably 50 to 70% by weight.

[0112] In addition, the antiviral composition of the present invention and the curing thereof may contain dimethylol-tricyclodecane diacrylate as a difunctional (meth)acrylate and cyclohexyl methacrylate as a monofunctional (meth)acrylate, which can reduce the viscosity of the antiviral composition and can also reduce the curing shrinkage after curing.

[0113] Specifically, the photopolymerization initiator in the antiviral composition is preferably at least one selected from the group consisting of alkylphenones, acylphosphine oxides, intramolecular hydrogen abstraction types, and oxime esters.

[0114] Examples of alkylphenone-based photopolymerization initiators 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-morpholinyl)phenyl]-1-butanone, and the like.

[0115] Examples of the acylphosphine oxide photopolymerization initiator include 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, and the like.

[0116] Examples of intramolecular hydrogen abstraction type photopolymerization initiators include phenylglyoxylic acid methyl ester, oxyphenylsuccinate, 2-[2-oxo-2-phenylacetoxyethoxy]ethyl ester, and a mixture of oxyphenylacetic acid and 2-(2-hydroxyethoxy)ethyl ester.

[0117] Examples of oxime ester photopolymerization initiators include 1,2-octanedione, 1-[4-(phenylthio)-, 2-(O-benzoyloxime)], ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-, 1-(O-acetyloxime), and the like.

[0118] The content of the antiviral agent in the antiviral composition is preferably 2 to 30% by weight, the content of the uncured (meth)acrylate resin and / or polysiloxane resin is preferably 15 to 60% by weight, and, if a dispersion medium is required, the content of the dispersion medium is preferably 1 to 80% by weight.

[0119] The antiviral composition may contain ultraviolet absorbers, antioxidants, light stabilizers, adhesion promoters, rheology modifiers, leveling agents, defoamers, etc., as necessary. As the leveling agent, a silicone-based leveling agent, particularly a non-volatile silicone, can be suitably used. By being non-volatile, the leveling effect is high and the finger slipperiness is also excellent. Examples of non-volatile silicones include polyalkylsiloxanes, polyarylsiloxanes, polyalkylarylsiloxanes, polysiloxanes with amino functional substituents, polyethersiloxane copolymers, and mixtures thereof. The amount of non-volatile silicone added is preferably 0.002 to 0.007 parts by weight of solid content relative to 100 parts by weight of the solid content of the total (meth)acrylate.

[0120] (2) Coating process Next, the surface of the substrate is coated with the antiviral composition in the form of a film.

[0121] As the application method, for example, the antiviral composition can be applied to the surface of the substrate using a sponge roller, a brush, a mop, a squeegee, or the like.

[0122] Examples of the substrate include metal, ceramics such as glass, resin, woven fiber, wood, etc. When a resin is used, it is preferable that the substrate is in the form of a film or sheet. When the substrate is in the form of a film, it is preferable that an adhesive layer is provided on the side opposite to the side on which the antiviral agent is provided.

[0123] The antiviral composition can also be applied to a film substrate, dried to remove the dispersion medium, and used to produce a transfer film of a B-stage resin film, which can then be heat-pressed onto the substrate to form a resin layer.

[0124] Alternatively, the antiviral composition can be applied to a film substrate, dried to remove the dispersion medium, and the resulting B-stage resin film can be cured by heat curing or exposure to ultraviolet light or the like to produce a film, and this film can be attached to the substrate via a pressure-sensitive adhesive or bonding agent to form a resin layer.

[0125] (3) Curing process In the curing step, the uncured resin in the antiviral composition is cured to form a film-like resin layer.

[0126] The method for curing the resin should desirably be selected appropriately depending on the type of resin. For example, in the case of an uncured polyfunctional (meth)acrylate resin, ultraviolet irradiation or heating may be used, while in the case of a polysiloxane resin, heating, hydrolysis reaction, or contact with air having a humidity of 20% to 100% may be used.

[0127] When curing the resin by ultraviolet irradiation, the ultraviolet irradiation conditions are 1 to 300 mW / cm 2 , preferably 1 to 800 seconds.

[0128] When the resin is cured by heating, it is preferable to heat the resin at a temperature of 80°C to 180°C.

[0129] Furthermore, when hydrolysis polymerization is carried out using a chloroalkylsilane as a raw material, it is desirable to carry out the reaction in the presence of an acid or a base such as hydrochloric acid or sodium hydroxide.

[0130] Furthermore, when a silicone resin that has reactive curing groups at its terminals and can be cured by water is converted into a polysiloxane resin using a catalyst, it is desirable to bring the resin into contact with air with a humidity of 20% to 100%, so that the reactive curing groups at the terminals react with the water in the air and the polymerization reaction proceeds.

[0131] (Other processes) When the antiviral composition contains a dispersion medium, the antiviral composition is applied and then dried to evaporate and remove the dispersion medium, thereby temporarily fixing the antiviral composition to the surface of the substrate, and the granular antiviral agent can be exposed from the surface of the antiviral composition due to drying shrinkage of the antiviral composition.

[0132] Drying conditions are preferably 60 to 100° C. and 0.5 to 5.0 minutes.

[0133] Alternatively, as described above, the antiviral composition can be applied to a base film such as polyethylene terephthalate, and then dried to produce a transfer film of a resin film containing an antiviral agent. The transfer film can be placed so that the film of the antiviral composition is in contact with the base material, and after pressure is applied, the base film can be peeled off to cure the uncured resin. In this case, it is desirable to first place a granular antiviral agent on a base film such as polyethylene terephthalate, and then apply a film of the antiviral composition thereon to produce a transfer film of a resin film. EXAMPLES

[0134] Example 1 (1) An imidazole antimicrobial agent (Nippon Soda Co., Ltd., product name: Biocut BM100F) is pulverized in a ball mill to adjust the average particle size to 8.5 μm. (2) 250 parts by weight of MMA (methyl methacrylate) and a mixture of dipentaerythritol pentaacrylate and hexaacrylate (trade name: KAYARAD) as a polyfunctional (meth)acrylate having five or more acryloyl groups in the molecule. 100 parts by weight of DPHA (manufactured by Nippon Kayaku Co., Ltd., solid content 100%, penta ratio approximately 40%), 80 parts by weight of dimethylol-tricyclodecane diacrylate (trade name: Light Acrylate DCP-A, manufactured by Kyoeisha Chemical Co., Ltd., viscosity 130 to 170 mPa·s / 25°C) as a bifunctional (meth)acrylate, 20 parts by weight of cyclohexyl methacrylate (trade name: Light Ester CH, manufactured by Kyoeisha Chemical Co., Ltd.) as a monofunctional (meth)acrylate, 13.5 parts by weight of 1-hydroxy-cyclohexyl-phenyl ketone (trade name: Irgacure184, manufactured by BASF, solid content 100%) as a photopolymerization initiator, and 1.35 parts by weight of a solution of polyester modified polydimethylsiloxane having an acrylic group (trade name: BYK-UV3570, manufactured by Big Chemie Japan Co., Ltd.) as a leveling agent are mixed to obtain a solventless ultraviolet curable resin composition made of a (meth)acrylic resin.

[0135] Next, 15 parts by weight of an imidazole-based antimicrobial agent (antiviral agent) having an average particle size of 8.5 μm is added to 100 parts by weight of the solventless ultraviolet curable resin composition, and the mixture is kneaded with a triple roller to obtain an antiviral composition.

[0136] The obtained antiviral composition is coated on a white glossy melamine decorative board having a size of 500 mm x 500 mm using a rubber squeegee to a film thickness of 3 μm.

[0137] After this, an ultraviolet ray irradiation device (MP02 manufactured by COATTEC) was used, and the irradiation was performed at 30 mW / cm 2 By irradiating the white melamine decorative board with ultraviolet light for 80 seconds at an irradiation intensity of 100 nm, an anti-viral member according to Example 1 is obtained in which a film of a cured product made of an acrylic resin containing an imidazole anti-viral agent is formed on the surface of the white melamine decorative board as a substrate.

[0138] Example 2 The procedure is basically the same as in Example 1, but 5 parts by weight of an imidazole-based antimicrobial agent (antiviral agent) with an average particle size of 8.5 μm is added to 100 parts by weight of the solventless ultraviolet curable resin composition, and the mixture is kneaded with a triple roller to obtain an antiviral composition.

[0139] Example 3 The procedure is basically the same as in Example 1, but 30 parts by weight of an imidazole-based antimicrobial agent (antiviral agent) with an average particle size of 8.5 μm is added to 100 parts by weight of the solventless ultraviolet curable resin composition, and the mixture is kneaded with a triple roller to obtain an antiviral composition.

[0140] Example 4 (1) Commercially available cuprous iodide (CuI) powder was dispersed in ethanol, and then crushed and dispersed in a ball mill to obtain a cuprous iodide slurry with an average particle size of 1.2 μm. (2) 250 parts by weight of MMA (methyl methacrylate) and a mixture of dipentaerythritol pentaacrylate and hexaacrylate (trade name: KAYARAD) as a polyfunctional (meth)acrylate having five or more acryloyl groups in the molecule. 100 parts by weight of DPHA (manufactured by Nippon Kayaku Co., Ltd., solid content 100%, penta ratio approximately 40%), 80 parts by weight of dimethylol-tricyclodecane diacrylate (trade name: Light Acrylate DCP-A, manufactured by Kyoeisha Chemical Co., Ltd., viscosity 130 to 170 mPa·s / 25°C) as a bifunctional (meth)acrylate, 20 parts by weight of cyclohexyl methacrylate (trade name: Light Ester CH, manufactured by Kyoeisha Chemical Co., Ltd.) as a monofunctional (meth)acrylate, 13.5 parts by weight of 1-hydroxy-cyclohexyl-phenyl ketone (trade name: Irgacure184, manufactured by BASF, solid content 100%) as a photopolymerization initiator, and 1.35 parts by weight of a solution of polyester modified polydimethylsiloxane having an acrylic group (trade name: BYK-UV3570, manufactured by Big Chemie Japan Co., Ltd.) as a leveling agent are mixed to obtain a solventless ultraviolet curable resin composition made of a (meth)acrylic resin. (3) Next, 30 parts by weight of an antimicrobial (antiviral) agent slurry made of copper iodide having an average particle size of 1.2 μm is added to 100 parts by weight of the solventless ultraviolet curable resin composition, and the mixture is kneaded with a triple roller to obtain an antiviral composition. (4) The antiviral composition of (3) was applied to a 500 mm x 500 mm polyethylene terephthalate film sprayed with silicone oil as a release agent, and the composition was then exposed to ultraviolet light at 30 mW / cm using an ultraviolet irradiator (MP02 manufactured by COATTEC). 2 The antiviral film is then exposed to ultraviolet light at an irradiation intensity of 1000 nm for 80 seconds to produce an antiviral film having a thickness of 3 μm. (5) After a silicone-based adhesive is applied onto the antiviral film, the polyethylene terephthalate film is peeled off and the antiviral film is attached so that the adhesive layer is in contact with the surface of the black decorative board, thereby obtaining an antiviral member. (6) The antiviral film is manufactured by applying a silicone adhesive onto the antiviral film, laminating a Teflon sheet (release sheet), and then peeling off the polyethylene terephthalate film. This type of antiviral film can be attached to components that require antiviral properties by peeling off the release sheet at the construction site.

[0141] Comparative Example 1 The procedure is basically the same as in Example 1, but 1 part by weight of an imidazole-based antimicrobial agent (antiviral agent) with an average particle size of 8.5 μm is added to 100 parts by weight of the solventless ultraviolet curable resin composition, and the mixture is kneaded with a triple roller to obtain an antiviral composition.

[0142] Comparative Example 2 The procedure is basically the same as in Example 1, but 40 parts by weight of an imidazole-based antimicrobial agent (antiviral agent) with an average particle size of 8.5 μm is added to 100 parts by weight of the solventless ultraviolet curable resin composition, and the mixture is kneaded with a triple roller to obtain an antiviral composition.

[0143] (Antiviral evaluation using feline calicivirus) The antiviral test is carried out as follows. In order to evaluate the antiviral properties of the antiviral members obtained in each Example and Comparative Example, a modified method of JIS Z 2801 Antibacterial processed products - Antibacterial test method, antibacterial effect was used. The modification is to change "inoculation of test bacteria liquid" to "inoculation of test virus". All modifications due to the use of viruses are based on JIS L 1922 Antiviral test method for textile products. The measurement results are expressed as feline calicivirus inactivation level, which is the concentration of feline calicivirus that has lost the ability to infect CRFK cells, based on JIS L 1922 Appendix B for the antiviral members obtained in each Example and Comparative Example. Here, the concentration of the virus inactivated against CRFK cells (virus inactivation level) is used as an index of the virus concentration, and the antiviral activity value is calculated based on this virus inactivation level.

[0144] The procedure will be described in detail below. (1) The antiviral members according to each of the Examples and Comparative Examples were cut into squares measuring 50 mm on each side to prepare test samples. The test samples were placed in sterilized plastic petri dishes and then soaked in a test virus liquid (>10 7 The test virus solution is 10 8 A 10-fold dilution of the PFU / mL stock with purified water was used.

[0145] (2) As a control sample, a 50 mm square polyethylene film was prepared and inoculated with the virus liquid in the same manner as the test sample.

[0146] (3) The inoculated virus solution is left to react for 24 hours at 10°C without placing a film over it.

[0147] (4) Immediately after inoculation, add 10 mL of SCDLP medium and wash off the virus solution. Calculate the virus infectivity value according to JIS L 1922 Appendix B.

[0148] (5) Calculate the antiviral activity value using the following formula. Mv = Log(Vb / Vc) Mv: Antiviral activity value Log(Vb): Logarithmic value of infection value after a specified time reaction of polyethylene film Log(Vc): Logarithmic value of infection value after a given time reaction of the test sample Reference standards JIS L 1922, JIS Z 2801 The measurement was performed by plaque measurement. The test virus used is Feline calcivirus; Strain: F-9 ATCC VR-782.

[0149] Using the test samples of each Example and Comparative Example, the antiviral activity value was calculated in the same manner as in the above "Antiviral Activity Evaluation Using Feline Calicivirus." The results are shown in Table 1.

[0150] (Average distance between centers of gravity of antiviral agents) The surface of the antiviral member is photographed in plan view with an electron microscope (see FIG. 1, magnified 300 times), and the photographed image is binarized using an image processing software called ImageJ. ImageJ is an image processing software that can be downloaded from https: / / imagej.nih.gov / ij / . Next, three distances between the center of gravity of one granular antiviral agent in the binarized image and the centers of gravity of multiple antiviral agents present around the antiviral agent are selected from the shortest to the longest (see FIG. 2 and FIG. 4, line segments are the distances between the three centers of gravity). The three distances between the granular antiviral agents are measured for all antiviral agents in the photographed image. Histograms of the distances between the centers of gravity measured in this way are shown in FIG. 3 and FIG. 5. The average value of the distances between the centers of gravity of the antiviral agents is calculated to be 12.9 μm in the case of Example 1. Also, in the case of Example 4, it is 3.7 μm.

[0151] Table 1 shows the average value of the distance between the centers of gravity of the antiviral agents and the measurement results of the antiviral activity for Examples 1 to 4 and Comparative Examples 1 and 2. It can be seen that the antiviral activity is particularly high when the average value of the distance between the centers of gravity of the antiviral agents is 3 to 30 μm.

[0152] [Table 1]

[0153] The above results show that by adjusting the distance between the centers of gravity of the antiviral agent, high antiviral activity can be obtained, and an antiviral member can be obtained that can efficiently inactivate viruses without using an excessive amount of the antiviral agent.

Claims

1. An antiviral member comprising a film-like resin layer containing a plurality of granular antiviral agents having no photocatalytic function formed on a substrate surface, at least parts of the granular antiviral agents being exposed from the resin layer, and an average value of the distance between centers of gravity between adjacent antiviral agents being 4 to 30 µm in plan view, wherein the antiviral agent is an imidazole-based antiviral agent not containing silver ions.

2. The anti-viral member according to claim 1, wherein the granular anti-viral agent has an average particle size of 0.01 to 50 μm.

3. The anti-virus member according to claim 1 or 2, wherein the film-like resin layer contains at least one resin selected from the group consisting of (meth)acrylate-based resins and polysiloxane-based resins.

4. The anti-viral member according to any one of claims 1 to 3, wherein the film-like resin layer contains a leveling agent.

5. The anti-viral member according to any one of claims 1 to 4, wherein the film-like resin layer contains a (meth)acrylate having a phosphate group.

6. The anti-viral member according to claim 3 or 5, wherein the (meth)acrylate resin is a polyfunctional urethane (meth)acrylate resin.

7. The anti-viral member according to any one of claims 1 to 6, wherein the substrate is in the form of a film or a sheet.

8. The anti-viral member according to claim 7 , wherein the film- or sheet-like substrate has a pressure-sensitive adhesive layer provided on a surface opposite to the surface on which the anti-viral agent is disposed.

9. An antiviral film comprising a membranous resin layer containing a plurality of granular antiviral agents having no photocatalytic function, at least a portion of the granular antiviral agents being exposed from the resin layer, and in a planar view, the average value of the distance between the centers of gravity of adjacent antiviral agents is 4 to 30 µm, and the antiviral agent is an imidazole-based antiviral agent not containing silver ions.

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