Antiviral hardened material

Abstract

To provide a cured product that is applicable to any substrate and can express excellent antiviral properties.SOLUTION: An antiviral cured product is a cured product of a composition containing a polyfunctional methacryl monomer or oligomer having three or more functional groups. It is used to express antiviral properties by irradiation with 0.15 mW / cm2 or more of ultraviolet rays at a wavelength of 350 nm or less. Such a cured product can express excellent antiviral properties.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a cured product capable of exhibiting antiviral properties. [Background technology]

[0002] In response to the recent COVID-19 pandemic and other factors, technological developments have been attempted to improve the hygiene of various products, components, and commercial materials surrounding our living environments. For example, JP 2020-510734 A (Patent Document 1) reports a photocurable polymer film that exhibits antibacterial properties when irradiated with light in the visible light range. Specifically, it reports that a coating composition (see Claim 1, etc.) containing a (meth)acrylate monomer or oligomer containing an alkylene oxide having 1 to 10 carbon atoms, a photosensitizer, and a photoinitiator is applied to a substrate, followed by photocuring to produce a polymer film (see paragraphs 0044, 0047, 0091, etc.). When the polymer film is irradiated with light in the visible light range, the photosensitizer absorbs the visible light, generating active oxygen species or free radicals, thereby imparting antibacterial properties to the film (see paragraphs 0004, 0030, Table 1, etc.). [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Special Publication No. 2020-510734 Summary of the Invention [Problem to be solved by the invention]

[0004] The present inventors have now discovered a novel structure capable of exhibiting antiviral properties. Specifically, they confirmed that good antiviral properties can be obtained by irradiating a cured product of a composition containing a certain type of polymerizable monomer or oligomer with ultraviolet light having a wavelength of 350 nm or less. Specifically, they irradiated the cured product with ultraviolet light having a wavelength of 350 nm or less at 0.15 mW / cm. 2It was discovered that there are chemical species that generate radicals when irradiated with the above-mentioned light receiving amount, and that the radicals generated by these chemical species exhibit good antiviral properties. Furthermore, it was discovered that the chemical species that generates radicals present in the cured product is a polyfunctional (meth)acrylic monomer or oligomer having three or more functional groups contained in the composition. The present invention is based on this discovery.

[0005] Therefore, an object of the present invention is to provide a cured product that can exhibit good antiviral properties. [Means for solving the problem]

[0006] The antiviral cured product according to the present invention is A cured product of a composition containing a polyfunctional (meth)acrylic monomer or oligomer having three or more functional groups, which is exposed to ultraviolet light with a wavelength of 350 nm or less at 0.15 mW / cm 2 The antiviral activity is exhibited by irradiating the antiviral agent with the above-mentioned amount of received light. [Effects of the Invention]

[0007] According to the present invention, a cured product capable of exhibiting good antiviral properties is provided. DETAILED DESCRIPTION OF THE INVENTION

[0008] Cured product according to the present invention The cured product according to the present invention that can exhibit antiviral properties (hereinafter, sometimes referred to as "antiviral cured product") can exhibit antiviral properties when irradiated with ultraviolet light having a wavelength of 350 nm or less. The antiviral cured product according to the present invention is a cured product of a composition containing a compound that generates radicals when irradiated with ultraviolet light having a wavelength of 350 nm or less, specifically, a polyfunctional (meth)acrylic monomer or oligomer having three or more functional groups. The antiviral cured product according to the present invention can exhibit antiviral properties when irradiated with ultraviolet light having a wavelength of 350 nm or less at a wavelength of 0.15 mW / cm. 2The cured product is a compound that generates radicals when irradiated with an amount of light received of 0.15 mW / cm or more, preferably a composition containing a polyfunctional (meth)acrylic monomer or oligomer having three or more functional groups. 2 In the present invention, "ultraviolet rays with a wavelength of 350 nm or less are irradiated at 0.15 mW / cm 2 or more to exhibit antiviral properties. 2 "Irradiate with an amount of light received of 0.15 mW / cm or more" means that the cured product is irradiated with ultraviolet light of a wavelength of 350 nm or less, and the cured product is 2 This means that the composition is exposed to ultraviolet light with a wavelength of 350 nm or less in an amount of light equal to or greater than this amount. Note that the "cured product of the composition" refers to a product obtained by curing the composition.

[0009] Antiviral activity In the present invention, the mechanism by which antiviral activity is exhibited is believed to be as follows: That is, a cured product of a composition containing a compound that generates radicals when irradiated with ultraviolet light having a wavelength of 350 nm or less, preferably a polyfunctional (meth)acrylic monomer or oligomer having three or more functional groups (hereinafter sometimes referred to as the "cured product of the present invention" or simply the "cured product") is irradiated with ultraviolet light having a wavelength of 350 nm or less at 0.15 mW / cm. 2 By irradiating the cured product with the above-mentioned light receiving amount, radicals are generated in the cured product, originating from the polyfunctional (meth)acrylic monomer or oligomer having three or more functional groups, for example, due to the bonding or dissociation of some of the double bonds. When these radicals are present on the surface of the cured product, viruses adhering to the surface of the cured product come into contact with the radicals, and the viruses are inactivated by the oxidizing action of the radicals. In this way, the cured product according to the present invention can exhibit good antiviral properties. Note that the above-mentioned mechanism of antiviral activity is hypothetical, and the present invention is in no way limited by this hypothesis.

[0010] In the present invention, the antiviral property of the cured product according to the present invention means that the antiviral activity value determined by the following test method in accordance with JIS R1756 (2020) in a dark place is 2 or more.

[0011] Antiviral Test Method An antiviral test is carried out in accordance with JIS R1756 (2020) in a dark place, and the antiviral activity value (V) in a dark place is calculated using the following formula (1). Antiviral activity value: V=Log 10 (UV / TV) Equation (1) TV: Bacteriophage infectivity titer (pfu) 24 hours after instillation of bacteriophage UV: Bacteriophage infectivity (pfu) immediately after dropping the bacteriophage liquid

[0012] The cured product according to the present invention can exhibit antiviral properties such that the antiviral activity value V calculated by the above formula (1) is at least 2. In general, when the antiviral activity value V is at least 2, it is evaluated as having good antiviral properties.

[0013] Furthermore, the reduction rate of infectious viruses after 24 hours can be calculated using the TV and UV in the above formula (1) according to the following formula (2). Reduction rate (%)=(UV-TV) / UV×100 Formula (2) The infectious virus reduction rate calculated by the above formula (2) is also used as an index representing the antiviral properties of the cured product according to the present invention, similar to the antiviral activity value V.

[0014] The cured product of the present invention can exhibit antiviral properties with an infectious virus reduction rate of 99% or more as calculated by the above (2). In general, a reduction rate of infectious viruses of 99% or more is considered to have good antiviral properties.

[0015] In the present invention, "ultraviolet rays with a wavelength of 350 nm or less" includes all ultraviolet rays with a wavelength of 350 nm or less. Therefore, without being limited by the origin of the ultraviolet rays, it includes ultraviolet rays irradiated from the sun outdoors, ultraviolet rays irradiated from the sun indoors in everyday living environments, and ultraviolet rays irradiated from light sources other than the sun. It is said that sunlight contains about 5% ultraviolet rays, of which ultraviolet rays with a wavelength of 350 nm or less account for about 20%. The ultraviolet rays irradiated from the sun indoors in everyday living environments refer, for example, to ultraviolet rays irradiated from the sun that are transmitted through window glass or the like and irradiated indoors. The received light intensity of ultraviolet rays with a wavelength of 350 nm or less originating from sunlight irradiated indoors is 0.4 mW / cm. 2 More than 1.5mW / cm 2 Light sources other than the sun include low-pressure mercury lamps (germicidal lamps), high-pressure mercury lamps, ultra-high-pressure mercury lamps, xenon lamps, gallium lamps, metal halide lamps, ultraviolet lasers, and deep ultraviolet LED lamps. In the present invention, the received light intensity of ultraviolet light with a wavelength of 350 nm or less irradiated onto the cured product is 0.15 mW / cm. 2 It is preferable that the received light amount of ultraviolet light having a wavelength of 350 nm or less irradiated onto the cured product is 40 mJ / cm or more. As already explained, the received light amount of ultraviolet light having a wavelength of 350 nm or less irradiated onto the cured product means the amount of ultraviolet light having a wavelength of 350 nm or less received by the cured product. The received light amount is preferably measured using a Hamamatsu Photonics H9958 measuring instrument. In the present invention, the integrated received light amount due to irradiation with ultraviolet light having a wavelength of 350 nm or less is 40 mJ / cm or more. 2 More than 135 mJ / cm is preferable. 2 It is more preferable that the ultraviolet ray intensity is 0.15 mW / cm or more. This allows for the development of good antiviral properties. Hereinafter, "ultraviolet rays with a wavelength of 350 nm or less" will be referred to as "specific ultraviolet rays" and "0.15 mW / cm" will be referred to as "specific ultraviolet rays." 2 "Amount of received light greater than or equal to this" is sometimes called "specific amount of received light."

[0016] In the present invention, "ultraviolet rays with a wavelength of 350 nm or less are irradiated at 0.15 mW / cm 2The phrase "is used after being irradiated with an amount of UV light not less than the specified amount of UV light received to develop antiviral properties" means the following: Assuming that the antiviral properties developed when a cured product according to the present invention is irradiated once (once) with UV light of 350 nm or less at the specified amount of UV light received, the term refers to a cured product of a composition containing a compound that generates radicals when irradiated with UV light at the specified amount of UV light received, preferably a polyfunctional (meth)acrylic monomer or oligomer having three or more functional groups, being irradiated with UV light at the specified amount of UV light received as needed, that is, to the extent that antiviral properties are developed. In other words, irradiation with UV light at the specified amount of UV light received is not necessarily required when carrying out the present invention. For example, if a cured product that was placed in an environment where it could be irradiated with UV light at the specified amount of UV light received at some point in the past (a cured product that was actively or passively irradiated with UV light at the specified amount of UV light received) still maintains (sustains) the desired antiviral properties when used, irradiation with UV light at the specified amount of UV light is not necessarily required. On the other hand, in the above examples, if the desired antiviral properties are not maintained or there is a possibility that they will be maintained during use, the cured product can be irradiated with specific ultraviolet light at a specific light-receiving intensity, thereby restoring the antiviral properties. In other words, in the present invention, the need for irradiation with specific ultraviolet light at a specific light-receiving intensity can be determined appropriately, taking into account the environment in which the cured product is placed, the conditions of use, and the time over which the cured product can exhibit antiviral properties (the lifespan of the antiviral properties in the cured product). This is expected to enable the cured product of the present invention to semi-permanently maintain the expression of antiviral properties. Hereinafter, irradiation with specific ultraviolet light at a specific light-receiving intensity may be abbreviated simply as "irradiating specific ultraviolet light" or "irradiating specific ultraviolet light."

[0017] Durable antiviral properties When exposed to a specific amount of ultraviolet light with a wavelength of 350 nm or less, the antiviral cured product of the present invention can maintain good antiviral properties, with an antiviral activity value V of 2 or more, for approximately two weeks under normal environmental and static conditions. As described above, in the present invention, whether or not irradiation with ultraviolet light having a wavelength of 350 nm or less at a specific light receiving dose is necessary can be determined appropriately depending on the use and purpose of the cured product of the present invention. For example, the specific ultraviolet light can be irradiated again to restore the antiviral activity before the antiviral activity is lost after about two weeks. In other words, after irradiating with the specific ultraviolet light once, re-irradiation with the specific ultraviolet light can be carried out as appropriate within a range in which the desired antiviral activity can be sustained, for example, once a week. Furthermore, irradiation with the specific ultraviolet light can be carried out continuously or intermittently.

[0018] hydrophilic The antiviral cured product of the present invention preferably has hydrophilicity. This hydrophilicity can be expressed as an index of the static contact angle with water. The static contact angle with water of the antiviral cured product of the present invention can be measured, for example, using a FACE contact angle meter CA-X150 (Kyowa Interface Science Co., Ltd.) by dropping a 2 μL water droplet onto the antiviral cured product at room temperature and measuring the static contact angle after 20 seconds using the θ / 2 method. The water contact angle of the antiviral cured product of the present invention is preferably 40 degrees or less. When water adheres to the surface of a cured product having such a water contact angle, a rolling-up effect is achieved, resulting in a surface that is resistant to dirt adhesion. Because the antiviral cured product of the present invention also has such hydrophilicity, it is advantageous when applied to the surface of wet items.

[0019] Purpose The antiviral cured product according to the present invention can be applied to the surfaces of various articles. Preferably, it can be applied to the surfaces of wet-related articles that require high hygiene. In the present invention, wet-related articles refer to components used in toilets, bathrooms, kitchens, vanities, etc., and examples include bathroom wall materials, bathroom floor materials, bathroom counters, bathtubs, bathtub rims, bathroom window materials, bathroom door materials, shower booth wall materials, washbasin mirrors, vanities, washbasins, kitchen counters, kitchen doors, storage shelves, storage boards, toilet bowls, toilet seats, warm-water washing toilet seats and their cleaning nozzles, drains, faucets, range hood materials, etc., but are not limited to these.

[0020] The composition of the present invention and the method for producing the cured product thereof will now be described. composition In the present invention, the composition contains at least a compound that generates radicals upon irradiation with specific ultraviolet light. In the present invention, the compound that generates radicals upon irradiation with specific ultraviolet light is a polyfunctional (meth)acrylic monomer or oligomer having three or more functional groups. By including a polyfunctional (meth)acrylic monomer or oligomer having three or more functional groups in the composition, radicals can be efficiently generated by irradiation with specific ultraviolet light on a cured product of the composition, preferably on the surface of the cured product. Furthermore, by including a polyfunctional (meth)acrylic monomer or oligomer having three or more functional groups in the composition, durability can be imparted to the cured product of the composition. This durability is advantageous when the antiviral cured product of the present invention is applied to the surface of a wet area.

[0021] In the present invention, the composition preferably contains 25 to 99.9 wt % of a polyfunctional (meth)acrylic monomer or oligomer having three or more functional groups, and more preferably 40 to 99 wt % of a polyfunctional (meth)acrylic monomer or oligomer having three or more functional groups, which can further enhance the antiviral properties and durability of the cured product according to the present invention and can also impart strength to the cured product.

[0022] In the present invention, the functional group is preferably an ethylenically unsaturated group. The ethylenically unsaturated group is preferably a vinyl group, an acryloyl group, or a methacryloyl group, more preferably an acryloyl group or a methacryloyl group. The acryloyl group or methacryloyl group is likely to generate radicals upon irradiation with specific ultraviolet rays, and as a result, the cured product according to the present invention is likely to exhibit antiviral properties. In this specification, the term "(meth)acrylic monomer or oligomer" is synonymous with the term "(meth)acrylate monomer or oligomer."

[0023] Examples of the (meth)acrylic monomer (oligomer) having three or more functional groups include ethoxylated isocyanuric acid triacrylate, ε-caprolactone-modified tris-(2-acryloxyethyl)isocyanurate, pentaerythritol triacrylate, trimethylolpropane triacrylate, ditrimethylolpropane trimethacrylate, ethoxylated glycerin triacrylate, ethoxylated pentaerythritol tetraacrylate, ditrimethylolpropane tetraacrylate, pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, dipentaerythritol pentaacrylate, trimethylolpropane triacrylate, polyethylene glycol diacrylate, polyethylene glycol dimethacrylate, polypropylene glycol diacrylate, polytetramethylene glycol diacrylate, glycerin triacrylate ethoxylate, and dipentaerythritol polyacrylate.

[0024] Radical scavengers containing phenol groups In the present invention, the composition preferably further contains a radical scavenger having a phenol group. By including a radical scavenger containing a phenol group in the composition, when a cured product of the composition is irradiated with specific ultraviolet light, the scavenger captures radicals generated within the cured product, preferably on the surface of the cured product, and the radicals can remain on the surface of the cured product. Specifically, when a cured product of the composition is irradiated with specific ultraviolet light, a radical (·) generated in the cured product originating from a polyfunctional (meth)acrylic monomer or oligomer having three or more functional groups abstracts the phenolic hydrogen (-OH) of the radical scavenger, forming a stable radical (-O·). The presence of the radical scavenger on the surface of the cured product, which has captured the radical and is in a stable state, allows viruses attached to the surface of the cured product to come into contact with the radicals, more reliably inactivating the viruses and maintaining antiviral activity for a long period of time. In this way, when the cured product of the present invention is used after being irradiated with specific ultraviolet rays, it is possible to exhibit better antiviral properties for a long period of time due to the oxidizing action of both radicals that are generated from a radical-generating compound, preferably a polyfunctional (meth)acrylic monomer or oligomer having three or more functional groups, and that exist on the surface of the cured product in a mobile state, and radicals that exist on the surface of the cured product in a fixed state after being captured by a radical scavenger.

[0025] In the present invention, the radical scavenger having a phenol group is not particularly limited as long as it is a compound having radical scavenging ability. For example, 4-methoxyphenol (MEHQ), 3,6-dihydroxybenzonorbornane, 2,5-bis(1,1,3,3-tetramethylbutyl)hydroquinone, 2,2'-methylenebis(6-cyclohexyl-p-cresol), 4,4'-butylidenebis(6-tert-butyl-m-cresol), hydroquinone, 2,6-di-tert-butyl-p-cresol, tert-butylhydroquinone, 6-tert-butyl-2,4-xylenol, 4-tert-butylpyrocatechol, 2,6-di-tert-butylphenol, etc. can be used.

[0026] In the present invention, the composition preferably contains 10 ppm to 10,000 ppm of a radical scavenger having a phenol group. By including 10 ppm or more of the radical scavenger, it is possible to stabilize the radical-generating compound, preferably a polyfunctional (meth)acrylic monomer or oligomer having three or more functional groups, thereby enabling the production of a cured product with excellent antiviral properties and durability. By including 10,000 ppm or less of the radical scavenger, it is possible to suppress a decrease in the curing reactivity of the composition when irradiated with specific ultraviolet light, and it is also possible to suppress discoloration of the composition and its cured product. Suppressing discoloration of the cured product is advantageous in that it allows the appearance or design of an article to which the cured product of the present invention is applied to its surface to be maintained.

[0027] Other ingredients Compound (a) containing a sulfonic acid group In the present invention, the cured product of the present invention preferably contains sulfonic acid groups at least on the surface. By containing sulfonic acid groups on the surface of the cured product, the cured product can exhibit hydrophilicity in addition to antiviral properties, as described above. Having hydrophilicity, for example, when the cured product of the present invention is applied to the surface of a wet item, is advantageous in that it improves drainage and drying properties, making it possible to prevent the adhesion of stains such as water stains due to residual water, and further prevents the adhesion of oil. According to a preferred embodiment of the present invention, the cured product of the present invention contains sulfonic acid groups on its surface. According to a more preferred embodiment of the present invention, the cured product of the present invention contains more sulfonic acid groups on the surface than in its interior. In other words, it is preferable that the sulfonic acid groups segregate on the surface of the cured product of the present invention.

[0028] As described below, the cured product of the present invention can be obtained as follows: First, a composition is applied to a substrate, and the (wet) coating of the composition applied to the substrate is dried to obtain a (dried) coating. The (dried) coating of the composition is then cured to obtain a cured film of the composition. Herein, the dried (wet) coating, i.e., the (dry) coating, is also referred to as an "uncured film" because it is subsequently cured. As described above, the segregation of sulfonic acid groups on the surface of the cured product of the present invention is believed to be achieved by, but is not limited to, the following process. By drying the (wet) coating of the composition, i.e., by volatilizing the solvent and, optionally, the volatile compound (b) (details of which will be described later) contained in the (wet) coating along with compound (a), compound (a), which was uniformly dispersed in the composition, segregates to the surface of the uncured film as the drying (volatilization) progresses, taking advantage of the polarity difference and compatibility with the volatile compound (b). This is achieved by curing the uncured film while the drying of the (wet) coating is almost complete and the state in which compound (a) is most effectively segregated onto the surface of the uncured film is maintained.

[0029] In the present invention, the type of compound that provides sulfonic acid groups to the cured product is not particularly limited. For example, the composition before curing may contain a compound having a sulfonic acid group. Examples of such compounds include compounds having a sulfonic acid group and at least one ethylenically unsaturated group in the molecule. Specific examples include sodium or potassium salts of 2-((meth)acryloyloxy)ethanesulfonic acid, 3-((meth)acryloyloxy)propane-1-sulfonic acid, and acrylamido-tertiary-butylsulfonic acid. Preferred are linear alkylsulfonic acids having a (meth)acryloyloxy group and their salts, such as 2-((meth)acryloyloxy)ethanesulfonic acid and potassium 3-((meth)acryloyloxy)propane-1-sulfonate (potassium 3-sulfopropyl methacrylate). Further, examples of compounds having a sulfonic acid group and at least one ethylenically unsaturated group in the molecule include methacrylic sulfonic acid, sodium or potassium salt of p-styrenesulfonic acid, alkylsulfosuccinic acid alkenyl ether salt, polyoxyethylene (meth)acrylate sulfate ester salt, alkylsulfosuccinic acid alkenyl ester salt, glycerol-1-allyl-3-alkylphenyl-2-polyoxyethylene sulfate, etc. The above-mentioned sulfonic acid group-containing compound (a) has sufficient reactivity with the polyfunctional (meth)acrylic monomer or oligomer having three or more functional groups as already explained, and can impart high durability to the cured product according to the present invention.

[0030] Volatile compounds (b) In the present invention, the cured product of the present invention preferably contains a volatile compound (b) having a smaller molecular weight than the sulfonic acid group-containing compound (a) and a hydrophilic group in the molecule. Here, the volatile compound refers to a compound having a boiling point of 280°C or less, more preferably 260°C or less. The hydrophilic group in the volatile compound (b) is preferably a hydroxyl group or a carboxyl group. In one embodiment of the present invention in which the cured product contains the volatile compound (b), for example, the composition before curing may contain the volatile compound (b). Examples of such volatile compounds (b) include volatile compounds having a smaller molecular weight than the sulfonic acid group-containing compound (a) and having one ethylenically unsaturated group and a hydrophilic group in the molecule. Specific examples include hydroxymethyl (meth)acrylate, hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate and structural isomers thereof, hydroxybutyl (meth)acrylate and structural isomers thereof, tetrahydrofurfuryl (meth)acrylate, (meth)acryloylmorpholine, N-vinylformamide, (meth)acrylic acid, etc. Among these, hydroxymethyl (meth)acrylate, hydroxyethyl (meth)acrylate, and (meth)acrylic acid are preferred as the volatile compound (b) from the viewpoint of compatibility with the compound (a).

[0031] The cured product of the present invention can be obtained by applying the composition to a substrate, drying the (wet) coating on the substrate, and curing the uncured film. In this process, the sulfonic acid group-containing compound (a) and the volatile compound (b) are sufficiently compatible with each other. When the (wet) coating of the composition is dried by heating, compound (b) segregates to the surface of the uncured film together with compound (a), allowing compound (a) to be uniformly distributed on the surface of the uncured film. Furthermore, when the uncured film is cured, the volatile compound (b) remaining in the uncured film can easily polymerize with the polyfunctional (meth)acrylic monomer or oligomer having three or more functional groups and the sulfonic acid group-containing compound (a), which is believed to further increase the strength of the cured film.

[0032] The molecular weight of the volatile compound (b) is not particularly limited as long as it is smaller than the molecular weight of the compound (a), but is preferably 500 or less. By ensuring that the molecular weight of the volatile compound (b) is 500 or less, the volatile compound (b) can be efficiently volatilized when the (wet) coating of the composition is dried. Furthermore, as the volatile compound (b) is volatilized together with the solvent components described below, phase separation is thought to occur between the sulfonic acid group-containing compound (a), which is compatibilized by the inclusion of the volatile compound (b), and the polyfunctional (meth)acrylic monomer or oligomer having three or more functional groups. This phase separation is thought to promote segregation of the sulfonic acid group-containing compound (a) to the surface of the uncured film. The molecular weight of the volatile compound (b) is more preferably 100 to 200. This allows the compound (b) to volatilize without reducing the strength of the cured product when the uncured film of the composition is cured (polymerized).

[0033] In the present invention, the molar ratio of the amount of volatile compound (b) to the sum of the amounts of polyfunctional (meth)acrylic monomers or oligomers having three or more functional groups, compound (a) containing sulfonic acid groups, and volatile compound (b) is preferably greater than 0.5 and less than 0.99. When the molar ratio of compound (b) is greater than 0.5, sufficient moisture resistance can be achieved, while when the molar ratio is less than 0.99, the compatibility between compound (a) and compound (b) increases, allowing compound (a) to segregate on the surface of the cured product, which is believed to result in sufficient hydrophilicity being imparted to the cured product.

[0034] The molar ratio of the amount of compound (b) is more preferably greater than 0.5 and less than 0.8. This makes it possible to suppress a decrease in the durability of the cured product due to an increase in the ratio of compound (b) to the polyfunctional (meth)acrylic monomer or oligomer having three or more functional groups in the composition. The molar ratio of compound (b) to the polyfunctional (meth)acrylic monomer or oligomer having three or more functional groups (molar ratio: former / latter) is preferably 1.1 or greater and 2.5 or less. This makes it possible to obtain a cured product with high durability.

[0035] solvent In the present invention, the composition preferably contains a solvent to improve the wettability of the composition to the substrate and adjust the viscosity of the composition. Examples of such solvents include, but are not limited to, alcohols such as methanol, ethanol, IPA (isopropanol), and n-butanol, cellosolves such as methoxyethanol and methoxypropanol, ketones such as acetone, N,N'-dimethylformamide (DMF), and water, from the viewpoint of compatibility with other compounds contained in the composition. A mixture of multiple solvents may be used as needed.

[0036] polymerization initiator In the present invention, as described below, when an uncured film of the composition is cured (polymerized) by heat, the composition may contain a known radical polymerization initiator, curing catalyst, polymerization accelerator, etc. Furthermore, when an uncured film of the composition is cured (polymerized) by radiation, for example, active energy rays such as ultraviolet rays or visible light, the composition may contain a known photopolymerization initiator. An example of the photopolymerization initiator is Omnirad500 manufactured by IGM.

[0037] Method for producing a cured product according to the present invention The cured product according to the present invention can be produced, for example, as follows.

[0038] Preparing the substrate First, a substrate to which the composition is to be applied is prepared. In the present invention, the substrate is not particularly limited as long as it is a material to which the composition can be applied. From the viewpoint of the use of the cured product according to the present invention, the substrate is preferably a wet-related component that is used in an environment where it is periodically exposed to water and requires hygiene. Examples of wet-related components include, but are not limited to, bathroom wall materials, bathroom floor materials, bathroom counters, bathtubs, bathtub rims, bathroom window materials, bathroom door materials, shower booth wall materials, washbasin mirrors, vanity units, washbasins, kitchen counters, kitchen doors, storage shelves, storage boards, toilet bowls, toilet seats, warm-water washing toilet seats and their washing nozzles, drains, faucets, and range hood materials. In terms of materials, the substrate is not particularly limited, and examples thereof include metal, glass, resin, paper, and wood materials. Among these, a resin material is preferable. Examples of the resin material include thermosetting resins and thermoplastic resins. As the thermosetting resin, one or more types selected from urea resin, melamine resin, phenolic resin, unsaturated polyester resin, epoxy resin, and silicone resin can be used. The thermoplastic resin may be one or more selected from polypropylene resin (PP), polyethylene resin (PE), polyacetal resin (POM), polybutylene terephthalate resin (PBT), polyvinyl chloride resin (PVC), polystyrene resin (PS), acrylonitrile-butadiene-styrene copolymer resin (ABS), polyphenylene sulfide resin (PPS), polyethylene terephthalate resin (PET), polymethyl methacrylate resin (PMMA), polyamide resin (PA), polyether ether ketone resin (PEEK), polytrimethylene terephthalate resin (PTT), polycarbonate resin (PC), and polytetrafluoroethylene (PTFE) (tetrafluoroethylene resin). In the present invention, a thermoplastic resin is preferably used as the resin. More preferably, the resin is one or more selected from PP, PE, POM, PBT, PVC, ABS, PPS, PET, PMMA, PA, and PC. Among these, one or more selected from PP, POM, PBT, ABS, and PMMA are even more preferred. When the substrate is an acrylic resin material, the composition to be applied to the substrate contains a polyfunctional (meth)acrylic monomer or oligomer having three or more functional groups, so that the substrate made of, for example, an acrylic resin material has good affinity (for example, adhesion) with the composition or the coated product thereof.

[0039] Coating process The composition is then applied onto a substrate to form a (wet) coating of the composition. In the present invention, the composition can be applied to a substrate by any known method, such as brush coating, spray coating, dip coating, spin coating, or curtain coating.

[0040] Drying process Next, the (wet) coating formed on the substrate is dried to obtain an uncured film. At this time, it is sufficient to dry the (wet) coating, and if necessary, drying may be performed by heating. By (heating) drying, the solvent and volatile compound (b) contained in the (wet) coating are volatilized. In this process, as the solvent and volatile compound (b) volatilize from the (wet) coating (in other words, following the migration of the solvent and volatile compound (b) to the surface of the uncured film), compound (a), which was uniformly dispersed in the (wet) coating before (heating) drying, is thought to segregate to the surface of the uncured film by taking advantage of differences in polarity and compatibility with volatile compound (b).

[0041] Heat drying can be performed using known methods such as drying with infrared rays or hot air. The heating temperature is usually from room temperature to 200°C, preferably from 35°C to 150°C, and more preferably from 40°C to 100°C. The drying time can be determined appropriately within a range that allows sufficient volatilization of the solvent and volatile compound (b), and can be determined depending on the material and size of the member to which the composition is applied. For example, the drying time can be within 30 minutes, preferably within 20 minutes, and more preferably within 15 minutes.

[0042] Curing process The uncured film is then cured, i.e., the polyfunctional (meth)acrylic monomer or oligomer having three or more functional groups, the compound (a) containing a sulfonic acid group, and optionally the remaining volatile compound (b) are copolymerized. The curing of the uncured film is preferably carried out while the solvent and volatile compound (b) are sufficiently volatilized by the (heat) drying step and the state in which the compound (a) having sulfonic acid groups is segregated to the surface of the uncured film is maintained to the maximum extent. This is believed to ensure that the cured product of the present invention has sulfonic acid groups segregated to its surface. As a result, the antiviral cured product of the present invention is believed to be able to exhibit sufficient hydrophilicity. Even if volatile compound (b) remains in the uncured film, compound (b) can easily polymerize with polyfunctional (meth)acrylic monomers or oligomers having three or more functional groups and compound (a) containing a sulfonic acid group when the uncured film is cured, which is thought to make it possible to further increase the strength of the cured film.

[0043] As a method for curing the uncured film, known methods for polymerizing a compound containing an ethylenically unsaturated group, such as heat curing, active energy ray curing, or a combination thereof, can be used.

[0044] When polymerization curing is performed by thermal curing, a known polymerization initiator can be used. Furthermore, as the heating method, a known method of heating with infrared rays, hot air, or the like can be used, similar to the drying process of the (wet) coated material described above. In the case of thermal curing, the drying process and curing process of the (wet) coated material can be performed simultaneously in one process.

[0045] When polymerization and curing are carried out using active energy rays, examples of the radiation include visible light of 400 to 800 nm, ultraviolet light of 400 nm or less, and electron beams. However, ultraviolet light is preferred because it allows polymerization to be carried out easily and in a short time. When curing is carried out using ultraviolet light, a known photopolymerization initiator is used. The photopolymerization initiator is added in an amount of 0.01 to 20 mass% and preferably 1 to 10 mass% of the mass of the polymerizable compound contained in the composition. Examples of ultraviolet light sources include ultraviolet light such as low-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, xenon lamps, gallium lamps, metal halide lamps, ultraviolet lasers, deep ultraviolet LED lamps, and sunlight. The irradiation atmosphere may be air or an inert gas such as nitrogen or argon.

[0046] The thickness of the cured product of the present invention produced as described above may be appropriately determined depending on the intended use and within a range in which the effects of the present invention can be achieved. For example, the thickness is preferably in the range of 0.1 μm to 300 μm, more preferably in the range of 1 to 100 μm, and even more preferably in the range of 1 to 20 μm. According to a preferred embodiment of the present invention, the cured product according to the present invention is a membrane-like material. In the present invention, the term "membrane-like material" is synonymous with "sheet-like material" or "film-like material."

[0047] Between the above-mentioned steps, there may be a transfer step in which the substrate is transferred by a belt conveyer or the like, or a waiting step required for transferring to each step.

[0048] Antiviral materials According to one aspect of the present invention, there is provided an antiviral member comprising a substrate and the above-described antiviral cured product formed on the surface of the substrate.

[0049] Antiviral expression or maintenance systems One aspect of the present invention provides a system for developing or maintaining antiviral properties, comprising the above-described antiviral material and irradiation means capable of irradiating with ultraviolet light having a wavelength of 350 nm or less. In this system, the antiviral properties of the antiviral material can be developed or maintained by irradiating the antiviral material with ultraviolet light having a wavelength of 350 nm or less.

[0050] The irradiation means capable of irradiating ultraviolet light with a wavelength of 350 nm or less is not particularly limited as long as it is capable of irradiating ultraviolet light with a wavelength of 350 nm or less. Specifically, the ultraviolet light irradiated by the irradiation means includes ultraviolet light irradiated from the sun outdoors, ultraviolet light irradiated from the sun indoors in everyday life environments, and ultraviolet light irradiated from light sources other than the sun. Examples of irradiation means other than the sun, i.e., light sources other than the sun, include low-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, xenon lamps, gallium lamps, metal halide lamps, ultraviolet lasers, and deep ultraviolet LED lamps.

[0051] Water-related systems According to one aspect of the present invention, there is provided a plumbing system comprising the above-described antiviral expression or maintenance system. [Example]

[0052] The present invention will be specifically described based on the following examples, but the present invention is not limited to these examples.

[0053] Preparation of the composition Composition 1 Composition 1 was prepared by stirring a solution containing 7 g (12.2 mmol) of dipentaerythritol hexaacrylate containing 500 ppm of 4-methoxyphenol (MEHQ) as a radical scavenger, 0.14 g of Omnirad500 as a photopolymerization initiator, and 15 g of methoxyethanol as a solvent with a stirrer for 60 minutes. The photopolymerization initiator Omnirad500 is a mixture of 1-hydroxycyclohexylphenyl ketone and benzophenone in a weight ratio of 1:1.

[0054] Composition 2 0.08 g (0.32 mmol) of potassium 3-sulfopropyl methacrylate was dissolved in 0.5 g of water, and then 3.5 g (6.1 mmol) of dipentaerythritol hexaacrylate containing 500 ppm of 4-methoxyphenol (MEHQ) as a radical scavenger, 3.5 g (7.7 mmol) of trimethylolpropane triacrylate containing 100 ppm of 4-methoxyphenol (MEHQ) as a radical scavenger, 0.4 g (3.1 mmol) of hydroxymethyl methacrylate, 0.14 g of Omnirad500 as a photopolymerization initiator, and 15 g of methoxyethanol as a solvent were added, and the mixture was stirred with a stirrer for 60 minutes to prepare Composition 2.

[0055] Composition 3 0.08 g (0.32 mmol) of potassium 3-sulfopropyl methacrylate was dissolved in 0.5 g of water, and then 7 g (12.2 mmol) of dipentaerythritol hexaacrylate containing 500 ppm of 4-methoxyphenol (MEHQ) as a radical scavenger, 0.4 g (3.1 mmol) of hydroxymethyl methacrylate, 0.14 g of Omnirad500 as a photopolymerization initiator, and 15 g of methoxyethanol as a solvent were added, and the mixture was stirred with a stirrer for 60 minutes to prepare composition 3.

[0056] Preparation of cured film samples Preparing the substrate An acrylic plate (Acrylite EX (registered trademark) manufactured by Mitsubishi Chemical) (size: 100 × 100 × 2 mm) mainly composed of polymethyl methacrylate (PMMA) was prepared as the substrate. The water contact angle of this substrate was approximately 70°. The method for measuring the water contact angle will be described later.

[0057] Applying the composition to a substrate Compositions 1 to 3 were applied to the substrate by spray coating.

[0058] Drying The substrate on which the (wet) coating of the composition was formed was immediately placed in a hot air drying oven (DKN402 manufactured by Yamato Scientific Co., Ltd.) and heated at a drying temperature of 70°C for 10 minutes to volatilize the solvent.

[0059] hardening The substrate on which the uncured film was formed was removed from the hot air drying oven, and the uncured film was exposed to an integrated light intensity of 1000 mJ / cm 2 The substrate was irradiated with ultraviolet light (ANUP4154 manufactured by Panasonic Electric Works Co., Ltd.) In this way, cured film samples 1 to 7 and 9 to 15 each having a thickness of about 10 μm were formed on the surface of the substrate. Sample 8 is the same substrate as above.

[0060] evaluation The prepared samples 1 to 15 were evaluated as follows.

[0061] antiviral <Light source> The following light sources were prepared. The spectra of each light source were evaluated using a fiber multichannel spectrometer, Flame (detection wavelength: 200-400 nm; manufactured by Ocean Photonics, Inc.), and it was confirmed that germicidal lamps, high-pressure mercury lamps, sunlight, and fluorescent lamps contained ultraviolet light with wavelengths of 350 nm or less. Germicidal lamp (low-pressure mercury lamp): Toshiba GL15 germicidal lamp, central wavelength 254 nm, light intensity 0.15 mW / cm 2 (Measurement equipment: Hamamatsu Photonics H9535-254, measuring the amount of light received at a wavelength of 254 nm) High-pressure mercury lamp: Panasonic, ANUP54, central wavelength 254 nm, 313 nm, 365 nm, 405 nm, etc. (average central wavelength approx. 334 nm), light receiving power 125 mW / cm 2 (Measurement equipment: Hamamatsu Photonics H9958, measuring the amount of light received at a wavelength of 365 nm) · Sunlight: Center wavelength over 200nm, received light amount 0.9mW / cm 2 (Measurement equipment: Hamamatsu Photonics H9958, measuring the amount of light received at a wavelength of 365 nm) Fluorescent lamp: Toshiba Lightech, FHF32EX-NH, central wavelengths 313 nm, 365 nm, and over 405 nm (average central wavelength 361 nm), light receiving power 0.004 mW / cm 2 (Measurement equipment: Hamamatsu Photonics H9958, measuring the amount of light received at a wavelength of 365 nm) LED-1: Iwasaki Electric, LHPUV385, central wavelength 365nm, light receiving power 25.8mW / cm 2 (Measurement equipment: Hamamatsu Photonics H9958, measuring the amount of light received at a wavelength of 365 nm) LED-2: Iwasaki Electric, LHPUV365, central wavelength 385nm, light receiving power 60.2mW / cm 2 (Measurement equipment: Hamamatsu Photonics H9958, measuring the amount of light received at a wavelength of 365 nm) Black light: Spectronics Corporation, Mini MAX Series Model UV-5A, center wavelength 365 nm, light receiving power 0.45 mW / cm 2 (Measurement equipment: Hamamatsu Photonics H9958, measuring the amount of light received at a wavelength of 365 nm)

[0062] <Light irradiation> Each of Samples 1 to 15 was irradiated with light using a light source shown in Table 1 for a period of time shown in Table 1. Thereafter, each sample was allowed to stand for the period of time shown in Table 1. In the "resting time after light irradiation" section of Table 1, a simple time such as "1 hour" means that the sample was rested in a dark place for that time at room temperature after light irradiation. Also, "hot water 50°C x 15 minutes" means that the sample was rested in a dark place for 15 minutes with the entire film immersed in hot water at 50°C.

[0063] <Method for evaluating antiviral activity> Samples 1 to 15 were irradiated with light as described above and then allowed to stand for a predetermined period of time, and the antiviral activity was evaluated by the following method. The antiviral activity was evaluated in accordance with JIS R1756 (2020) in the dark. Specifically, an antiviral test was conducted using bacteriophage Qβ, and the antiviral activity value (V) in the dark was calculated using the following formula (1). Antiviral activity value: V=Log 10 (UV / TV) Equation (1) TV: Bacteriophage infectivity titer (pfu) 24 hours after instillation of bacteriophage UV: Bacteriophage infectivity (pfu) immediately after dropping the bacteriophage liquid In the present invention, when the antiviral activity value is V≧2, the sample is determined to exhibit good antiviral properties. In addition, the reduction rate of infectious virus after 24 hours was calculated using the following formula (2). Reduction rate (%)=(UV-TV) / UV×100 Formula (2) The antiviral activity values and infectious virus reduction rates of Samples 1 to 15 are shown in Table 1.

[0064] Samples 1 to 7, which are cured films of compositions containing polyfunctional acrylic monomers having three or more functional groups, were irradiated with ultraviolet light of 350 nm or less at 0.15 mW / cm 2 When irradiated with the light intensity of 1000 or more, the antiviral activity value V was greater than 2, and the reduction rate of infectious viruses was greater than 99%, confirming that good antiviral properties were exhibited. In contrast, sample 8, which is a cured film of a composition containing an acrylic monomer having only one functional group, was exposed to ultraviolet light with a wavelength of 350 nm or less at 0.15 mW / cm 2 Even when irradiated with this amount of light, the antiviral activity value V was less than 2, and the reduction rate of infectious viruses was only about 84%, so sufficient antiviral activity was not exhibited. Furthermore, even in the case of Samples 9 to 13, which are cured films of compositions containing a polyfunctional acrylic monomer having three or more functional groups, when no light irradiation was performed or when light with a wavelength exceeding 350 nm was irradiated, the irradiance was 0.15 mW / cm 2 When irradiated with light at an amount of received light of less than 1000 kJ / s, the antiviral activity value V was less than 2, and the reduction rate of infectious viruses was also smaller than that of samples 1 to 7, so sufficient antiviral activity was not exhibited.

[0065] As already explained, the expression of the antiviral activity of the present invention is limited. Therefore, samples 14 and 15, which are cured films of a composition containing a polyfunctional acrylic monomer having three or more functional groups, were irradiated with ultraviolet light of 350 nm or less at 0.15 mW / cm. 2 It was confirmed that even when irradiated with the light intensity of 1000, the antiviral activity value V or the reduction rate of infectious viruses was lowered if the sample was left to stand for a long period (2 weeks) after light irradiation or placed in a harsh environment (immersed in 50°C hot water for 1 hour). However, in the present invention, when or before it becomes difficult to maintain (sustain) the expression of the desired antiviral activity, the cured film of the present invention is irradiated with ultraviolet light having a wavelength of 350 nm or less at 0.15 mW / cm 2It is possible to restore the antiviral properties by irradiating the antiviral film with the above-mentioned amount of received light again. In other words, the antiviral film of the present invention can be appropriately irradiated with ultraviolet light of wavelengths of 350 nm or less at 0.15 mW / cm2 in consideration of the conditions of use, environment, etc. 2 By irradiating with the above amount of received light, it is possible to maintain good antiviral activity.

[0066] water contact angle The static contact angles of Samples 1 to 15 with respect to water were measured. Specifically, a FACE contact angle meter CA-X150 (Kyowa Interface Science Co., Ltd.) was used to drop a 2 μL water droplet onto the sample at room temperature, and the static contact angle after 20 seconds was measured by the θ / 2 method. The sample was washed with distilled water, dried, and then measurements were taken at three points, and the average value was used as the contact angle. The water contact angles of Samples 1 to 15 were as shown in Table 1.

[0067] Durability 1 Samples 1 to 15 were immersed in a 5 wt % aqueous solution of sodium hydroxide for 48 hours, then thoroughly rinsed with running water, dried, and visually evaluated for appearance. The evaluation criteria were as follows: ○: No change in appearance ×: There is a change in appearance

[0068] Durability 2 20 g of detergent containing an abrasive (Lion Bath Look Cleaning) was dropped onto Samples 1 to 15, and the samples were rubbed 100 times with a resin brush (TOTO EKL0034) under a load of 3 kg. Then, hydrophilicity evaluation (Evaluation 3) was performed. The obtained water contact angles were evaluated according to the following criteria. ○: The water contact angle is 45° or less, and the difference in the water contact angle before and after rubbing is less than 10° △: The water contact angle is 45° or less, and the difference in the water contact angle before and after rubbing is 10° or more ×: Water contact angle is 45° or more The results are shown in Table 1.

[0069]

Table 1

Claims

1. A cured product of a composition comprising a polyfunctional (meth)acrylic monomer or oligomer having three or more (meth)acryloyl groups and a radical scavenger having a hydroxyphenyl group, The cured product can be exposed to ultraviolet light with a wavelength of 350 nm or less at a rate of 0.15 mW / cm ２ By irradiating the material with the above-mentioned amount of received light, the material exhibits antiviral properties, and in the absence of the irradiation, the exhibited antiviral properties are maintained for a finite period of time. The composition contains 40% by weight or more and 99% by weight or less of the polyfunctional (meth)acrylic monomer or oligomer having three or more (meth)acryloyl groups.

2. The integrated amount of ultraviolet light received with a wavelength of 350 nm or less is 40 mJ / cm ２ The cured product according to claim 1 .

3. The cured product according to claim 1 or 2, wherein the composition contains the radical scavenger in an amount of 10 ppm or more and 10,000 ppm or less.

4. The antiviral cured product according to any one of claims 1 to 3, wherein when it becomes difficult or there is a possibility that the expressed antiviral activity will not be maintained, or when the expressed antiviral activity has decreased, the antiviral cured product can be used by irradiating it again to restore the antiviral activity.

5. The cured product according to any one of claims 1 to 4, which contains sulfonic acid groups at least on the surface.

6. The cured product according to any one of claims 1 to 5, wherein the surface has a water contact angle of 40 degrees or less.

7. An antiviral member comprising: a substrate; and the cured product according to any one of claims 1 to 6 formed on the surface of the substrate.

8. An antiviral activity development or maintenance device comprising the antiviral member according to claim 7 and irradiation means capable of irradiating ultraviolet light having a wavelength of 350 nm or less, an apparatus, characterized in that the antiviral member is able to exhibit or maintain antiviral properties by irradiating the antiviral member with ultraviolet light having a wavelength of 350 nm or less from the irradiation means.

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