Antiviral article and antiviral resin composition

Abstract

Provided is an antiviral article in which discoloration caused by light is inhibited. An antiviral article is an article having a cured product layer, the cured product layer including a cured product of a curable resin composition, an antiviral agent supported on a carrier or containing silver ions, and a light stabilizer, and including one or more hindered amine-based compounds selected from an NH-type hindered amine-based compound and an NR-type hindered amine-based compound as the light stabilizer. The antiviral article is preferably one in which the cured product layer is provided on a substrate.

Description

Technical Field

[0001] This invention relates to antiviral articles and antiviral resin compositions. Background Technology

[0002] From a hygiene perspective, antibacterial treatment has traditionally involved coating surfaces of objects that people touch, such as building interiors, vehicle interiors, office automation equipment, and touch panels, with antibacterial compositions.

[0003] Patent documents 1 to 3 have been proposed, for example, regarding compositions or articles with antimicrobial properties.

[0004] However, for viruses such as influenza viruses, antibacterial properties alone are insufficient. That is, for the antibacterial compositions or articles of Patent Documents 1-3, there are cases where antiviral properties are not met.

[0005] On the other hand, patent documents 4-5 have been proposed regarding compositions or articles with antiviral properties.

[0006] Existing technical documents

[0007] Patent documents

[0008] Patent Document 1: Japanese Patent Application Publication No. 63-265958

[0009] Patent Document 2: Japanese Patent No. 3551201

[0010] Patent Document 3: Japanese Patent No. 4840048

[0011] Patent Document 4: Japanese Patent No. 6145758

[0012] Patent Document 5: Japanese Patent No. 6229429 Summary of the Invention

[0013] The problem that the invention aims to solve

[0014] The antiviral resin composition in Patent Document 4 contains cuprous oxide particles, etc. Therefore, it is impossible to prevent the color (reddish-brown) hue originating from cuprous oxide.

[0015] Patent Document 5 describes an antiviral interior decorative sheet made by combining silver-based or zinc-based inorganic additives in the resin coating on the outermost surface of the decorative sheet.

[0016] In the additives described in Patent Document 5, the latter zinc-based inorganic additives pose health problems when ingested in large quantities.

[0017] On the other hand, in Patent Document 5, the silver-based inorganic additive is expensive but does not pose any health problems. However, when the amount of silver-based inorganic additive is increased to exhibit antiviral properties, a problem arises where it discolors to brown due to light (visible light, ultraviolet light). Patent Document 5 does not conduct any research on the discoloration problem caused by the increased amount of silver-based inorganic additive.

[0018] The objective of this invention is to suppress light-induced discoloration of silver-based antiviral articles and antiviral resin compositions.

[0019] Methods for solving problems

[0020] In order to solve the above problems, the present invention provides the following [1] to [2].

[0021] [1] An antiviral article having a cured layer comprising a cured resin composition, an antiviral agent supported on or containing silver ions, and a light stabilizer, and comprising one or more hindered amine compounds selected from NH-type hindered amine compounds and NR-type hindered amine compounds as the light stabilizer.

[0022] [2] An antiviral resin composition comprising a curable resin composition, an antiviral agent supported on or containing silver ions on a carrier, and a light stabilizer, wherein the light stabilizer comprises one or more hindered amine compounds selected from NH-type hindered amine compounds and NR-type hindered amine compounds.

[0023] Invention Effects

[0024] According to the present invention, it is possible to provide antiviral articles and antiviral resin compositions that inhibit the discoloration of silver-based antiviral agents caused by light (visible light, ultraviolet light). Attached Figure Description

[0025] Figure 1 This is a cross-sectional view illustrating one embodiment of the antiviral article of the present invention.

[0026] Figure 2 This is a cross-sectional view illustrating another embodiment of the antiviral article of the present invention.

[0027] Figure 3 This is a cross-sectional view illustrating another embodiment of the antiviral article of the present invention. Detailed Implementation

[0028] [Antiviral items]

[0029] The antiviral article of the present invention is an article having a cured layer, wherein the cured layer comprises a cured resin composition, an antiviral agent supported on a carrier or containing silver ions, and a light stabilizer, and comprises one or more hindered amine compounds selected from NH-type hindered amine compounds and NR-type hindered amine compounds as the light stabilizer.

[0030] Generally speaking, even articles made of the same materials and layers may exhibit varying degrees of "antiviral" efficacy and "antibacterial" and "antifungal" efficacy depending on different conditions. These conditions include the type of virus, the type of bacteria, the type of mold, and environmental conditions. Therefore, the antiviral article of the present invention can also be used for both antiviral and antibacterial purposes, depending on the type of bacteria, environmental conditions, and the required level of antibacterial activity. It should be noted that mold is a type of fungus; therefore, the antiviral article of the present invention can also be used for antifungal purposes, depending on the type of mold, environmental conditions, and the required level of antifungal activity.

[0031] Figure 1 (A)~(E) Figure 2 (A)~(D) and Figure 3 This is a cross-sectional view showing a representative embodiment of the antiviral article 100 of the present invention.

[0032] Figure 1 (A)~(E) Figure 2 (A)~(D) and Figure 3 The antiviral article 100 has a cured layer 10, which comprises a cured resin composition 11 and an antiviral agent 12 supported on or containing silver ions. It should be noted that... Figure 1 (A)~(E) Figure 2 (A)~(D) and Figure 3 The solidified layer 10 of the antiviral article 100 contains "one or more hindered amine compounds selected from NH-type hindered amine compounds and NR-type hindered amine compounds (not shown)".

[0033] Figure 1 The antiviral items 100 of (A) to (E) are formed from a single layer of solidified layer 10.

[0034] Figure 1 In the solidified layer 10 of (A), the antiviral agent 12 is contained throughout the solidified layer 10 in both the thickness direction (Z-axis direction of the figure) and the in-plane direction (directions in the XY plane of the figure). Figure 1In the solidified layer 10 of (B), an antiviral agent 12 is contained on the surface side (upper side of the figure) of the solidified layer 10. Figure 1 In the cured layer 10 of (C), an antiviral agent 12 is contained on the surface side (upper side of the figure) and the back side (lower side of the figure) of the cured layer 10. Figure 1 In the cured layer 10 of (D), an antiviral agent 12 is contained in a portion of the surface side (upper side of the figure) of the cured layer 10 in the in-plane direction. Figure 1 In the cured layer 10 of (E), a portion of the surface side (upper side of the figure) and a portion of the back side (lower side of the figure) of the cured layer 10 contain antiviral agent 12.

[0035] like Figure 1 As shown in (A) to (E), the location of the antiviral agent 12 within the solidified layer 10 is not particularly limited. However, from the viewpoint of improving antiviral activity, it is preferable that the antiviral agent 12 is present on the side that comes into contact with the human.

[0036] like Figure 1 The antiviral articles 100 consisting of a single layer of cured layer 10 (A) to (E) can be obtained, for example, by manufacturing a laminate formed by forming a cured layer 10 on a substrate with release properties, and then peeling the substrate with release properties from the laminate.

[0037] Figure 2 The antiviral articles 100 of (A) to (D) are formed by having a cured layer 10 on a substrate 20.

[0038] Figure 2 (A) The antiviral article 100 has a cured layer 10 on the entire surface of one side of the substrate 20. Figure 2 (B) The antiviral article 100 has a cured layer 10 on the entire surface of both sides of the substrate 20. Figure 2 (C) The antiviral article 100 has a cured layer 10 in a portion of one side of the substrate 20 (Z-axis direction + side in the figure). Figure 2 (D) The antiviral article 100 has a cured layer 10 in a portion of one side (Z-axis direction + side in the figure) and a portion of the other side (Z-axis direction - side in the figure) of the substrate 20.

[0039] like Figure 2 As shown in (A) to (D), the cured layer 10 can be formed on the entire surface of the substrate 20, or it can be formed on a portion of the substrate 20. Additionally, as... Figure 2 As shown in (A) to (D), the cured layer 10 may be formed on only one side of the substrate 20 or on both sides of the substrate 20.

[0040] Figure 3 The antiviral article 100 is formed by having a cured layer 10 on a three-dimensional substrate 20. It should be noted that... Figure 3 The three-dimensional base material 20 is used as the door handle. Figure 3 Its cross-sectional view is shown in the figure.

[0041] <Cure of the curable resin composition>

[0042] The cured layer comprises a cured product of the curable resin composition. In this specification, "cured product of the curable resin composition" may be referred to simply as "cured product".

[0043] The cured product of the curable resin composition primarily functions as a binder resin. By including this cured product, the antiviral articles exhibit good scratch resistance, making it easy to maintain antiviral properties for a long time.

[0044] Examples of cured products of curable resin compositions include cured products of thermosetting resin compositions or cured products of ionizing radiation-curable resin compositions. From the viewpoint of scratch resistance and production efficiency, cured products of ionizing radiation-curable resin compositions are preferred.

[0045] A thermosetting resin composition is a composition that contains at least a thermosetting resin and is a resin composition that is cured by heating.

[0046] Examples of thermosetting resins include acrylic resins, urethane resins, phenolic resins, urea-melamine resins, epoxy resins, unsaturated polyester resins, and silicone resins. In addition to these thermosetting resins, curing agents and curing catalysts may be added to the thermosetting resin composition as needed.

[0047] Regarding ionizing radiation-curable resin compositions, electron beam-curable resin compositions and ultraviolet (UV)-curable resin compositions are representative examples. Among these, electron beam-curable resin compositions are preferred from the viewpoint that they do not require polymerization initiators, thus producing less odor and being less prone to staining. Furthermore, when the cured layer contains a UV absorber (described later), electron beam-curable resin compositions are also preferred because they easily increase the crosslinking density of the cured layer and readily improve scratch resistance and stain resistance.

[0048] Ionizing radiation curable resin compositions are compositions containing compounds having ionizing radiation curable functional groups (hereinafter also referred to as "ionizing radiation curable compounds").

[0049] The term "ionizing radiation curable functional group" refers to a group that undergoes cross-linking and curing through irradiation with ionizing radiation. Preferred examples include functional groups with olefinic double bonds, such as (meth)acryloyl, vinyl, and allyl. Other examples of ionizing radiation curable functional groups include epoxy and oxocyclobutyl groups.

[0050] It should be noted that in this specification, the term "(meth)acryloyl" refers to acryloyl or methacryloyl. Additionally, in this specification, the term "(meth)acrylate" refers to acrylate or methacrylate.

[0051] In addition, ionizing radiation refers to radiation in electromagnetic waves or charged particle beams that contains energy quanta capable of polymerizing or cross-linking molecules. It can usually be ultraviolet (UV) or electron beam (EB). In addition, it also includes electromagnetic waves such as X-rays and gamma rays, as well as charged particle beams such as alpha rays and ion rays.

[0052] Specifically, for compounds that cure under ionizing radiation, appropriate selections can be made from polymeric monomers and polymeric oligomers (sometimes referred to as polymeric prepolymers) that have been conventionally used as resins that cure under ionizing radiation.

[0053] Regarding ionizing radiation-curable compounds, compounds having two or more olefinic unsaturated bond groups are more preferred, and polyfunctional (meth)acrylate compounds having two or more olefinic unsaturated bond groups are even more preferred. As polyfunctional (meth)acrylate compounds, either monomers or oligomers can be used.

[0054] As oligomers of multifunctional (meth)acrylate compounds, in order to achieve good scratch resistance, processability, and antiviral performance in the resulting articles, the weight-average molecular weight is preferably 1,000 or more and 10,000 or less, more preferably 2,000 or more and 6,000 or less. Furthermore, the number of functional groups per molecule of the oligomer is preferably 2 or more and 10 or less, more preferably 2 or more and 6 or less.

[0055] Among multifunctional (meth)acrylate compounds, examples of difunctional (meth)acrylate monomers include ethylene glycol di(meth)acrylate, bisphenol A tetraethoxydiacrylate, bisphenol A tetrapropoxydiacrylate, and 1,6-hexanediol diacrylate.

[0056] Examples of (meth)acrylate monomers with three or more functions include trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate, dipentaerythritol tetra(meth)acrylate, and isocyanuric acid modified tri(meth)acrylate.

[0057] Examples of multifunctional (meth)acrylate oligomers include urethane (meth)acrylates, epoxy (meth)acrylates, polyester (meth)acrylates, polyether (meth)acrylates, and other acrylate polymers.

[0058] Carbamate (meth)acrylates can be obtained, for example, by reacting polyols and organic diisocyanates with hydroxy (meth)acrylates.

[0059] Preferred epoxy (meth)acrylates are (meth)acrylates obtained by reacting trifunctional or higher aromatic epoxy resins, alicyclic epoxy resins, and aliphatic epoxy resins with (meth)acrylate; (meth)acrylates obtained by reacting difunctional or higher aromatic epoxy resins, alicyclic epoxy resins, and aliphatic epoxy resins with polybasic acids and (meth)acrylate; and (meth)acrylates obtained by reacting difunctional or higher aromatic epoxy resins, alicyclic epoxy resins, and aliphatic epoxy resins with phenols and (meth)acrylate.

[0060] The above-mentioned ionizing radiation curable resins can be used alone or in combination of two or more.

[0061] When the ionizing radiation curing compound is an ultraviolet curing compound, the ionizing radiation curing resin composition preferably contains additives such as photopolymerization initiators and photopolymerization accelerators.

[0062] As photopolymerization initiators, one or more can be selected from acetophenone, benzophenone, α-hydroxyalkyl phenyl ketone, michaelone, benzoin, benzoyl dimethyl ketal, benzoylbenzoate, α-acyl oxime ester, thioxanone, etc.

[0063] In addition, photopolymerization accelerators are substances that can reduce polymerization hindrance caused by air during curing and thus increase the curing speed. Examples include one or more selected from p-dimethylaminobenzoate isoamyl ester, p-dimethylaminobenzoate ethyl ester, etc.

[0064] The content of cured product in the curable resin composition is preferably 50% by mass or more, more preferably 70% by mass or more, further preferably 90% by mass or more, and most preferably 100% by mass, relative to the total amount of adhesive resin.

[0065] <Antiviral agents loaded with or containing silver ions on a carrier>

[0066] The solidified layer contains an antiviral agent supported on or containing silver ions. In this specification, "antiviral agent supported on or containing silver ions" may be simply referred to as "antiviral agent".

[0067] To improve antiviral properties, such as Figure 1 As shown in (A) to (E), at least a portion of the antiviral agent 12 preferably protrudes from the solidified layer 10.

[0068] As a carrier, inorganic compounds such as zeolite, apatite, glass, zirconium phosphate, and titanium phosphate are preferred, among which porous inorganic compounds are preferred.

[0069] Zeolites are aluminosilicates of alkali metals or alkaline earth metals, and can be either natural or synthetic. Furthermore, zeolites are classified according to their crystal structure into type A, octahedral zeolite (type X, type Y), mordenite, clinoptilolite, etc., and any of these can be used.

[0070] Apatite is a general term for minerals with the composition shown in the following formula.

[0071] M 10 (ZO4)3X2

[0072] In the above formula, M represents Ca, Ba, Mg, Na, K, Fe, and Al, etc.; Z represents P, S, Si, and As, etc.; and X represents F, Cl, O, and OH, etc. As a representative example corresponding to the above formula, fluorapatite (Ca...) can be cited. 10 (PO4)6F2”, Hydroxyapatite “Ca” 10 (PO4)6(OH)2.

[0073] Examples of glass include soda glass, borosilicate glass, lead glass, aluminosilicate glass, borosilicate glass, and phosphate glass.

[0074] As a method for loading or containing silver ions onto a carrier, various known methods can be appropriately selected, taking into account the type and form of the curable resin composition, processing conditions, required antiviral properties, and other factors. Here, "containing silver ions" means maintaining silver ions or substances capable of generating silver ions in the carrier in a certain way. Furthermore, "substances capable of generating silver ions" refers, for example, substances that generate silver ions through dissolution in water, or substances that generate silver ions through external factors or time.

[0075] Specific methods of loading or containing silver compounds include: loading through physical adsorption or chemical adsorption; loading through ion exchange reaction; loading through a binder; containing silver compounds by injecting them into a support; and loading or containing silver compounds by forming a thin layer of silver compounds on the surface of a support through thin film formation methods such as vapor deposition, dissolution reaction, or sputtering.

[0076] Antiviral agents are preferably in particle form.

[0077] The shape of antiviral agent particles can be spheres, ellipsoids, polyhedra, scales, etc., with no particular restrictions.

[0078] The average particle size of the antiviral agent is preferably 0.1 to 10.0 μm, more preferably 0.5 to 5.0 μm, and even more preferably 1.0 to 4.0 μm.

[0079] By setting the average particle size to 0.1 μm or more, the stability of the ink for the cured layer can be easily obtained. In addition, by setting the average particle size to 10.0 μm or less, it is easy to suppress poor appearance, reduced scratch resistance and stain resistance, and whitening of the coating film caused by excessive protrusion of antiviral agents from the surface of the cured layer. Furthermore, it is easy to suppress wear of components of the coating apparatus (coating rollers, doctor blades, etc.).

[0080] When the average particle size of the antiviral agent is defined as D and the thickness of the solidified layer is defined as T, D / T is preferably 1.0 or less, more preferably 0.7 or less, and even more preferably 0.4 or less.

[0081] By setting D / T to below 1.0, it is possible to easily suppress the reduction in stain resistance and whitening of the coating film caused by excessive protrusion of the antiviral agent from the surface of the cured layer, and thus easily suppress the wear of components of the coating device (coating rollers, doctor blades, etc.).

[0082] There is no particular restriction on the lower limit of D / T, which is usually above 0.01, and preferably above 0.05.

[0083] In this specification, average particle size refers to the particle size measured as the mass average value d50 in particle size distribution determination using laser diffraction.

[0084] The amount of silver ions in the antiviral agent is preferably 0.1 to 30.0 parts by mass relative to 100 parts by mass of the carrier, more preferably 0.5 to 25.0 parts by mass, and even more preferably 1.0 to 20.0 parts by mass. Here, "amount of silver ions" refers to both the silver ions carried and the silver ions contained therein.

[0085] By setting the amount of silver ions to 0.1 parts by mass or more, it is easier to achieve good antiviral properties. Furthermore, by setting the amount of silver ions to 30.0 parts by mass or less, it is easier to suppress light-induced discoloration.

[0086] The lower limit of the content of antiviral agent relative to 100 parts by weight of the solidified material is preferably 0.1 parts by weight or more, more preferably 0.5 parts by weight or more, and even more preferably 1.0 parts by weight or more. The upper limit of the content of antiviral agent is preferably 20.0 parts by weight or less, more preferably 17.0 parts by weight or less, more preferably 15.0 parts by weight or less, more preferably 10.0 parts by weight or less, and even more preferably 5.0 parts by weight or less.

[0087] By setting the content of the antiviral agent to 0.1 parts by weight or more, it is easy to achieve good antiviral properties.

[0088] By setting the antiviral agent content to 20.0 parts by weight or less, it is easier to suppress light-induced discoloration. Furthermore, by setting the antiviral agent content to 20.0 parts by weight or less, it is possible to suppress the reduction in coating properties such as film strength and scratch resistance. Moreover, by setting the antiviral agent content to 20.0 parts by weight or less, it is easier to suppress the reduction in stain resistance and whitening of the coating caused by excessive protrusion of the antiviral agent from the surface of the cured layer, and thus, it is easier to suppress wear on components of the coating apparatus (coating rollers, doctor blades, etc.).

[0089] It should be noted that when the adhesive resin is a cured product of a curable resin composition, the content of the antiviral agent is preferably set to be relatively high within the above-mentioned range.

[0090] <Light stabilizers>

[0091] The cured layer further comprises a light stabilizer, and further comprises one or more hindered amine compounds selected from NH-type hindered amine compounds and NR-type hindered amine compounds as light stabilizers. Without the presence of one or more hindered amine compounds selected from NH-type hindered amine compounds and NR-type hindered amine compounds as light stabilizers, it is impossible to suppress light-induced discoloration of the antiviral article.

[0092] Hindered amine compounds are substances that contain a 2,2,6,6-tetramethylpiperidine skeleton within their molecules.

[0093] Hindered amine compounds include NH-type, NR-type, and NOR-type hindered amine compounds. In this invention, it is necessary to include one or more hindered amine compounds selected from NH-type and NR-type hindered amine compounds. It is believed that the reason for inhibiting discoloration with one or more hindered amine compounds selected from NH-type and NR-type hindered amine compounds is that NH-type and NR-type hindered amine compounds readily form complexes with silver ions.

[0094] Furthermore, among NH-type hindered amine compounds and NR-type hindered amine compounds, NR-type hindered amine compounds are preferred. That is, the cured layer preferably contains one or more hindered amine compounds selected from NR-type hindered amine compounds.

[0095] The so-called NH-type hindered amine compounds are substances in which the hydrogen atoms bonded to the nitrogen atom in the 2,2,6,6-tetramethylpiperidine skeleton are still hydrogen atoms.

[0096] Specific examples of hindered amine compounds of the NH type include bis(2,2,6,6-tetramethyl-4-piperidinyl) sebacate.

[0097] The term "NR-type hindered amine compound" refers to a substance in which the hydrogen atom bonded to the nitrogen atom in the 2,2,6,6-tetramethylpiperidine skeleton is replaced by an alkyl group. The alkyl group preferably has 1 to 12 carbon atoms, more preferably 1 (the alkyl group being methyl).

[0098] Specific examples of hindered amine compounds of the NR type include 2-[[3,5-bis(1,1-dimethylethyl)-4-hydroxyphenyl]methyl]-2-butylmalonic acid bis[1,2,2,6,6-pentamethyl-4-piperidinyl] ester, sebacate bis(1,2,2,6,6-pentamethyl-4-piperidinyl) ester, sebacate 1-methyl-10-(1,2,2,6,6-pentamethyl-4-piperidinyl) ester, methacrylate 1,2,2,6,6-pentamethyl-4-piperidinyl ester, etc.

[0099] NOR-type hindered amine compounds refer to those in which the hydrogen atom bonded to the nitrogen atom in the 2,2,6,6-tetramethylpiperidine skeleton is replaced by an OR atom. 1 or OCOR 2 The substance. It should be noted that R 1 and R 2 It is an alkyl and / or cycloalkyl group, preferably an alkyl and / or cycloalkyl group having 5 to 12 carbon atoms.

[0100] The base dissociation constant (pkb) of the NH-type hindered amine compound and the NR-type hindered amine compound is preferably 8.5 or less, more preferably 7.0 or less, and even more preferably 6.0 or less. If the pkb of the NH-type hindered amine compound and the NR-type hindered amine compound is 8.5 or less, discoloration can be suppressed more easily.

[0101] There is no particular limitation on the lower limit of pkb for NH-type hindered amine compounds and NR-type hindered amine compounds, but it is preferably 4.0 or higher, and more preferably 4.5 or higher.

[0102] NH-type hindered amine compounds and NR-type hindered amine compounds may or may not have olefinic double bonds that enable polymerization with curable resin compositions.

[0103] From the viewpoint of facilitating good solubility of the NH-type hindered amine compounds in inks for cured layers, the molecular weight of the NH-type hindered amine compounds and NR-type hindered amine compounds is preferably 1000 or less, more preferably 800 or less, and even more preferably 700 or less. Good solubility of the NH-type hindered amine compounds and NR-type hindered amine compounds in inks for cured layers allows them to diffuse throughout the cured layer, thus more easily suppressing discoloration; this is preferable in this respect.

[0104] There is no particular limitation on the lower limit of the molecular weight of NH-type hindered amine compounds and NR-type hindered amine compounds, which is usually 200 or more, preferably 215 or more, and more preferably 230 or more.

[0105] Relative to 100 parts by weight of the antiviral agent, the content of NH-type hindered amine compounds and NR-type hindered amine compounds is preferably 20 to 1000 parts by weight, more preferably 30 to 500 parts by weight, and even more preferably 50 to 200 parts by weight. When two or more NH-type hindered amine compounds and NR-type hindered amine compounds are included, the above content refers to the total amount of the two or more NH-type hindered amine compounds and NR-type hindered amine compounds.

[0106] By setting the content of NH-type hindered amine compounds and NR-type hindered amine compounds to 20 parts by mass or more, discoloration can be easily suppressed. Furthermore, by setting the content of NH-type hindered amine compounds and NR-type hindered amine compounds to 1000 parts by mass or less, the reduction in crosslinking density of the cured resin composition, as well as the reduction in the scratch resistance and stain resistance of the cured layer, can be easily suppressed.

[0107] Other light stabilizers

[0108] The cured layer may also contain other light stabilizers to a extent that does not impair the effects of the present invention. Examples of other light stabilizers include NOR-type hindered amine compounds, aromatic compounds, amine compounds, organic acid compounds, and catechin compounds.

[0109] It should be noted that light stabilizers other than NH-type hindered amine compounds and NR-type hindered amine compounds are difficult to suppress discoloration. Therefore, it is preferable that the cured layer contains substantially no other light stabilizers (light stabilizers other than NH-type hindered amine compounds and NR-type hindered amine compounds). "Substantially not containing" means that, relative to the total solid components of the cured layer, the content of other light stabilizers is 0.1% by mass or less, preferably 0.01% by mass or less, and more preferably 0.001% by mass or less.

[0110] Antioxidants

[0111] The cured layer preferably further contains an antioxidant.

[0112] Examples of antioxidants include phenolic, sulfur-based, and phosphorus-based antioxidants, with phosphorus-based antioxidants being preferred. Including phosphorus-based antioxidants in the cured layer makes it easier to suppress photodiscoloration. Phosphorus-based antioxidants are particularly preferred in their ability to easily suppress photodiscoloration in the antiviral resin composition. By suppressing photodiscoloration in the antiviral resin composition, the processability of the antiviral resin composition can be improved. It is believed that phosphorus-based antioxidants can easily suppress the deterioration of silver ions because they can readily capture photo-generated free radicals.

[0113] Phosphorus-based antioxidants

[0114] Examples of phosphorus-based antioxidants include compounds having a phosphorous acid structure as shown in formula (1), compounds having a phosphonic acid structure as shown in formula (2), compounds having a hypophosphonic acid structure as shown in formula (3), and compounds having a phosphine oxide structure as shown in formula (4). Among these, compounds having a phosphorous acid structure as shown in formula (1) are preferred as they readily exhibit the effect of inhibiting light-induced discoloration in antiviral resin compositions. Furthermore, among compounds having a phosphorous acid structure as shown in formula (1), compounds having a general formula (1-2-1) are more preferred.

[0115] One or more phosphorus-based antioxidants can be used.

[0116] [Chemical Formula 1]

[0117]

[0118] Examples of compounds having the phosphorous acid structure shown in formula (1) include those represented by general formulas (1-1) to (1-3). Among general formulas (1-1) to (1-3), compounds of general formulas (1-1) and (1-2) are preferred in that they exhibit good solubility in inks for cured layers. By ensuring good solubility of the phosphorus-based antioxidant in inks for cured layers, the phosphorus-based antioxidant diffuses throughout the cured layer, making it easier to suppress discoloration, which is preferable in this respect.

[0119] [Chemical Formula 2]

[0120]

[0121] In general formula (1-1), R 11 R 12 and R 13Each group independently represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group, an aralkyl group, or a hydrocarbon group that may contain heteroatoms; these may have substituents. Additionally, groups selected from R... 11 R 12 and R 13 Two of them can bond together to form a ring.

[0122] From the perspective of further suppressing color change, R is preferred. 11 R 12 and R 13 At least one of them is a straight-chain alkyl group. The straight-chain alkyl group preferably has 6 to 18 carbon atoms, more preferably 8 to 15, and even more preferably 8 to 10. In R 11 R 12 and R 13 If at least one of them is a straight-chain alkyl group, the remaining R 11 R 12 and R 13 Phenyl is preferred.

[0123] Furthermore, from the perspectives of improving solubility and further suppressing discoloration, R is preferred. 11 R 12 and R 13 Non-bonded (preferably selected from R) 11 R 12 and R 13 (Two unbonded elements in the ring).

[0124] Specific examples of phosphorus-based antioxidants of general formula (1-1) are shown in the following formulas (1-1-1) to (1-1-3).

[0125] [Chemical Formula 3]

[0126]

[0127] In general formula (1-2), R 23 It can be a hydrocarbon group that contains heteroatoms, and may further have substituents. Additionally, R... 21 R 22 R 24 and R 25 Each group can be independently a hydrogen atom, a halogen atom, an alkyl group, an aryl group, an aralkyl group, or a hydrocarbon group that may contain heteroatoms, and may further have substituents. Additionally, R... 21 With R 22 They can bond together to form rings. Additionally, R 24 With R 25 They can bond together to form a ring.

[0128] From the perspective of further suppressing color change, R is preferred. 21 R 22 R24 and R 25 At least one of the components is a straight-chain alkyl group, more preferably all of them are straight-chain alkyl groups. The number of carbon atoms in the straight-chain alkyl group is preferably 6 to 18, more preferably 12 to 15. Furthermore, from the viewpoints of improving solubility and further suppressing discoloration, R is preferred. 21 R 22 R 24 and R 25 Non-bonded (preferably R) 21 R 22 R 24 and R 25 (They do not bond with each other to form a ring).

[0129] The following are specific examples of phosphorus-based antioxidants of general formula (1-2). In the following general formula (1-2-1), R independently represents a straight-chain alkyl group having 12 to 15 carbon atoms.

[0130] [Chemical Formula 4]

[0131]

[0132] In general formula (1-3), R 32 It can be a hydrocarbon group that contains heteroatoms, and may further have substituents. R 31 and R 33 Each of the following is independently a hydrogen atom, a halogen atom, an alkyl group, an aryl group, an aralkyl group, or a hydrocarbon group that may contain heteroatoms, and may further have substituents.

[0133] Phosphorus-based antioxidants may have olefinic double bonds capable of polymerizing with the curing resin composition, but are preferably free of such bonds. It is believed that by eliminating olefinic double bonds in phosphorus-based antioxidants that enable polymerization with the curing resin composition, the freedom of movement of the phosphorus-based antioxidants within the cured layer is increased, allowing the phosphorus-based antioxidants to diffuse throughout the entire cured layer and easily suppressing discoloration.

[0134] From the viewpoint of ensuring good solubility in inks used in cured layers, the molecular weight of phosphorus-based antioxidants is preferably 1500 or less, more preferably 1300 or less, and even more preferably 1200 or less. There is no particular limitation on the lower limit of the molecular weight of phosphorus-based antioxidants; it is generally 270 or more, preferably 300 or more, and more preferably 330 or more.

[0135] The lower limit of the content of phosphorus-based antioxidant relative to 100 parts by weight of antiviral agent is preferably 1 part by weight or more, more preferably 3 parts by weight or more, more preferably 5 parts by weight or more, more preferably 10 parts by weight or more, more preferably 15 parts by weight or more, more preferably 20 parts by weight or more, and the upper limit of the content of phosphorus-based antioxidant is preferably 1000 parts by weight or less, more preferably 800 parts by weight or less, more preferably 600 parts by weight or less, more preferably 400 parts by weight or less, more preferably 200 parts by weight or less, more preferably 100 parts by weight or less, more preferably 70 parts by weight or less.

[0136] By ensuring that the content of the phosphorus-based antioxidant is 1 part by mass or more, discoloration can be easily suppressed. Furthermore, by ensuring that the content of the phosphorus-based antioxidant is 1000 parts by mass or less, the reduction in crosslinking density of the cured resin composition, as well as the reduction in the scratch resistance and stain resistance of the cured layer, can be easily suppressed.

[0137] <UV absorber>

[0138] From a weather resistance perspective, the cured layer preferably further includes an ultraviolet absorber.

[0139] Examples of UV absorbers include benzotriazole-based, benzophenone-based, and triazine-based UV absorbers, with triazine-based UV absorbers being preferred. One or more UV absorbers may be used.

[0140] Furthermore, among triazine-based UV absorbers, hydroxyphenyl triazine-based UV absorbers are more preferably formed by attaching at least one organic group selected from hydroxyphenyl, alkoxyphenyl, and organic groups containing these groups to the triazine ring, and even more preferably hydroxyphenyl triazine-based UV absorbers represented by the following general formula (A). Because of their branched structure, hydroxyphenyl triazine-based UV absorbers are expected to be less prone to leaching from the cured layer, thus providing superior weather resistance over a longer period.

[0141] In addition, UV absorbers having olefinic double bonds such as (meth)acryloyl, vinyl, or allyl are preferred in terms of easily suppressing exudation.

[0142] [Chemical Formula 5]

[0143]

[0144] In general formula (A), R 11 R is a divalent organic group. 12 -C(=O)OR 15 The ester group shown, R 13 R 14 and R 15 Each is an independent monovalent organic group, n11 and n 12 Each is an integer from 1 to 5, independent of the others.

[0145] As R 11 The divalent organic group can be an aliphatic hydrocarbon group such as alkylene or alkenylene. From the viewpoint of weather resistance, alkylene is preferred, and its carbon number is preferably 1 or more and 20 or less, more preferably 1 or more and 12 or less, further preferably 1 or more and 8 or less, and particularly preferably 1 or more and 4 or less. The alkylene or alkenylene group can be any of linear, branched, or cyclic, with linear or branched forms being preferred.

[0146] Examples of alkylene groups having 1 or more carbon atoms and 20 or fewer include methylene, 1,1-ethylene, 1,2-ethylene, 1,3-propylene, 1,2-propylene, 2,2-propylene, and various other propylene groups (hereinafter, "various" refers to groups including straight-chain, branched, and their isomers), various butylene, various pentylene, various hexylene, various heptylene, various octylene, various nonylene, various decylene, various undecylene, various dodecylene, various tridecylene, various tetradecylene, various pentadecylene, various hexadecylene, various heptadecanylene, various octadecylene, various nonadecanylene, and various eicosylene.

[0147] As R 13 and R 14 The monovalent organic group can be alkyl, alkenyl, cycloalkyl, aryl, or aralkyl, with aryl and aralkyl aromatic hydrocarbon groups being preferred, and aryl being the most preferred. Among them, as R... 13 and R 14 The monovalent organic group, preferably phenyl.

[0148] As an aryl group, aryl groups with 6 or more but 20 or fewer carbon atoms are preferred, more preferably 6 or more but 12 or fewer carbon atoms are preferred, and even more preferably 6 or more but 10 or fewer carbon atoms are preferred. Examples include phenyl, various methylphenyl, various ethylphenyl, various dimethylphenyl, various propylphenyl, various trimethylphenyl, various butylphenyl, and various naphthyl groups. As an aralkyl group, aralkyl groups with 7 or more but 20 or fewer carbon atoms are preferred, more preferably 7 or more but 12 or fewer carbon atoms are preferred, and even more preferably 7 or more but 10 or fewer carbon atoms are preferred. Examples include benzyl, phenethyl, various phenylpropyl, various phenylbutyl, various methylbenzyl, various ethylbenzyl, various propylbenzyl, various butylbenzyl, and various hexylbenzyl groups.

[0149] As R 15 The monovalent organic group can be alkyl, alkenyl, cycloalkyl, aryl, or aralkyl, with aliphatic hydrocarbon groups such as alkyl and alkenyl being preferred, and alkyl being more preferred. That is, as R... 12Preferably, alkyl ester group or alkenyl ester group, more preferably alkyl ester group.

[0150] As an alkyl group, it is preferred to have 1 or more carbon atoms and 20 or fewer, more preferably 2 or more carbon atoms and 16 or fewer, and even more preferably 6 or more carbon atoms and 12 or fewer. Examples include methyl, ethyl, various propyl, various butyl, various pentyl, various hexyl, various octyl, various nonyl, various decyl, various undecyl, various dodecyl, various tridecyl, various tetradecyl, various pentadecyl, various hexadecyl, various heptadecanyl, various octadecyl, various nonadecanyl, and various eicosyl.

[0151] As an alkenyl group, alkenyl groups with 2 or more carbon atoms and 20 or less are preferred, more preferably 3 or more carbon atoms and 16 or less, and even more preferably 6 or more carbon atoms and 12 or less. Examples include vinyl, various propenyl, various butenyl, various pentenyl, various hexenyl, various octenyl, various nonenyl, various decenyl, various undecenyl, various dodecenyl, various thirteen-carbon alkenyl, various fourteen-carbon alkenyl, various fiveteen-carbon alkenyl, various sixteen-carbon alkenyl, various seventeen-carbon alkenyl, various eighteen-carbon alkenyl, various nineteen-carbon alkenyl, and various icosyl alkenyl.

[0152] As a hydroxyphenyl triazine compound represented by general formula (A), more specifically, R is preferred. 11 Alkylene with 1 or more carbon atoms and less than 20 carbon atoms, R 12 and R 15 alkyl ester groups with 1 or more and 20 or fewer alkyl carbons, R 13 and R 14 It is an aryl group with 6 or more carbon atoms and less than 20 carbon atoms, and n 11 and n 12 A hydroxyphenyltriazine compound with a concentration of 1, more preferably R 11 Alkylene with 1 or more carbon atoms and less than 12 carbon atoms, R 12 and R 15 Alkyl ester group with 2 or more but less than 16 carbon atoms, R 13 and R 14 It is an aryl group with 6 or more carbon atoms and less than 12 carbon atoms, and n 11 and n 12 A hydroxyphenyltriazine compound with a concentration of 1, further preferably R 11 Alkylene with 1 or more carbon atoms and less than 8 carbon atoms, R 12 and R 15 Alkyl ester group with 6 or more but less than 12 carbon atoms, R 13 and R 14 It is an aryl group with 6 or more carbon atoms and less than 10 carbon atoms, and n 11 and n 12 Hydroxyphenyl triazine compounds with a concentration of 1, particularly preferred by R 11Alkylene with 1 or more carbon atoms and less than 4 carbon atoms, R 12 and R 15 alkyl ester group with 8 carbon atoms, R 13 and R 14 It is a phenyl group, and n 11 and n 12 A hydroxyphenyltriazine compound with a concentration of 1.

[0153] The content of ultraviolet absorber is preferably 0.2 to 10.0 parts by weight relative to 100 parts by weight of the cured product, more preferably 0.5 to 5.0 parts by weight, and even more preferably 1.0 to 4.0 parts by weight.

[0154] The cured layer may contain extender pigments. Extender pigments can be used, for example, to adjust the design of antiviral items.

[0155] Examples of extender pigments include inorganic particles such as silicon dioxide, aluminum oxide, calcium carbonate, aluminum silicate, and barium sulfate, and organic particles such as polyethylene, urethane resin, polycarbonate, and polyamide (nylon).

[0156] The shape of the extender pigment is not particularly limited, but polyhedral, spherical, or flake-like shapes are preferred. Furthermore, the average particle size of the extender pigment is typically around 1–10 μm, preferably 3–8 μm.

[0157] Furthermore, the cured layer can contain colorants to achieve the desired hue, brightness, and saturation, as needed. As the colorant, an appropriate selection can be made from the same colorants used in the coloring layers and pattern layers described below. By using colorants to color the cured layer with appropriate colors (hue, brightness, and saturation), the design appearance can be improved. Alternatively, coloring can reduce the noticeable discoloration of the cured layer due to light, etc., and, combined with the discoloration reduction effect brought about by the addition of light stabilizers, can further enhance the discoloration reduction effect of the cured layer.

[0158] <Thickness>

[0159] From the perspective of balancing processing characteristics and scratch resistance, the thickness of the cured layer can be set to, for example, more than 1.0 μm and less than 10,000 μm.

[0160] In the case of antiviral articles consisting of a single layer of solidified material, the thickness of the solidified material layer is preferably set to be relatively thick.

[0161] On the other hand, when a cured layer is formed by coating a substrate, considering factors such as the substrate bearing the self-support and durability against external forces, the saturation of antiviral effects at a certain thickness, and the reduced adaptability to post-processing and increased material costs as the cured layer thickness increases, the thickness of the cured layer is preferably set to a thin film. Specifically, from the viewpoint of balancing processing characteristics and scratch resistance, the thickness of the cured layer is preferably 1.5 μm or more and 30 μm or less, more preferably 2 μm or more and 20 μm or less, and even more preferably 3 μm or more and 15 μm or less.

[0162] <Formation Method>

[0163] A cured layer can be formed, for example, by applying ink to a substrate containing a material constituting the cured layer (a hindered amine compound selected from NH-type hindered amine compounds and NR-type hindered amine compounds, a curable resin composition, an antiviral agent, etc.), and a solvent added as needed, followed by drying and curing. Alternatively, a cured layer can be formed by applying ink to a substrate with a release ductility, drying, and curing, and then transferring the cured layer to other substrates.

[0164] <Layered Structure>

[0165] The antiviral article of the present invention can be a single layer of solidified material, or it can have layers other than solidified material.

[0166] Antiviral articles consisting of a single layer of cured material can be obtained, for example, by creating a laminate by forming a cured material layer on a substrate with a release property, and then peeling the substrate with a release property from the laminate.

[0167] Other than the cured layer in antiviral articles, the layers include a substrate, a primer layer, a decorative layer, a transparent resin layer, and an adhesive layer. Examples of the layered structure of antiviral articles include (1) to (12) below. In (1) to (12) below, " / " indicates the interface between the layers.

[0168] It should be noted that, in addition to the solidified layer, layers in antiviral articles may include: magnetic layers for magnetic recording purposes; copper wires for circuits and currents, or conductive layers that function as electromagnetic wave shielding layers; gas barrier layers to inhibit the transmission of gases such as water vapor and oxygen; light reflective layers that reflect visible light with high reflectivity; anti-reflective layers to inhibit the reflection of visible light; and other functional layers. These functional layers may be formed in any part of the layered structure described in (1) to (12) below, depending on the function of each layer.

[0169] (1) Cured layer

[0170] (2) Substrate / Current Layer

[0171] (3) Substrate / primer layer / cured layer

[0172] (4) Substrate / Decorative Layer / Current Layer

[0173] (5) Substrate / Transparent Resin Layer / Currently Cured Layer

[0174] (6) Substrate / Adhesive layer / Transparent resin layer / Currently cured layer

[0175] (7) Substrate / Adhesive layer / Decorative layer / Transparent resin layer / Currently cured layer

[0176] (8) Substrate / Decorative layer / Adhesive layer / Transparent resin layer / Currently cured layer

[0177] (9) Substrate / Transparent Resin Layer / Primer Layer / Cure Layer

[0178] (10) Substrate / Adhesive layer / Transparent resin layer / Primer layer / Cure layer

[0179] (11) Substrate / Adhesive layer / Decorative layer / Transparent resin layer / Primer layer / Cure layer

[0180] (12) Substrate / Decorative layer / Adhesive layer / Transparent resin layer / Primer layer / Cure layer

[0181] From a treatment point of view, antiviral articles preferably have a curing layer on the substrate.

[0182] Substrate

[0183] The form of the substrate can include flat substrates such as films, sheets and plates, as well as three-dimensional substrates such as polyhedra, polygonal prisms, cylinders, spheres and ellipsoids of revolution, without any particular limitation.

[0184] It should be noted that, regarding films, sheets, and plates, they are mostly referred to as films, sheets, and plates in order of thickness from thinnest to thickest. However, in this instruction manual, unless otherwise specified, these three will not be distinguished.

[0185] Materials that can be used as the base material include resins, metals, non-metallic inorganic materials, fibrous materials, and wood-based materials, which can be selected appropriately according to the application.

[0186] The substrate can be a single layer or a substrate obtained by stacking two or more layers containing the above-mentioned materials. When the substrate is a laminate of two or more layers, it is preferable to stack two or more layers of different materials so that the properties of each layer are complementary. Examples of substrates formed by stacking two or more layers include A to J below. It should be noted that " / " indicates the interface between the layers.

[0187] (A) Resin / Wood-based materials

[0188] (B) Resin / Metal

[0189] (C) Resin / Fibrous Materials

[0190] (D) Resin / Non-metallic Inorganic Materials

[0191] (E) Resin 1 / Resin 2

[0192] (F) Metal / Wood-based materials

[0193] (G) Metallic / Nonmetallic Inorganic Materials

[0194] (H) Metal / Fibrous Materials

[0195] (I) Metal 1 / Metal 2

[0196] (J) Nonmetallic Inorganic Materials / Fibrous Materials

[0197] In E above, resin 1 and resin 2 represent resins of different types (for example, resin 1 is an olefin resin and resin 2 is an acrylic resin). Additionally, in H above, metal 1 and metal 2 represent metals of different types (for example, metal 1 is copper and metal 2 is chromium).

[0198] In addition, when the substrate is a laminate such as A to J described above, a layer (adhesive layer, etc.) for strengthening adhesion may be provided between the constituent layers of the laminate.

[0199] Resins used as base materials include resins composed of various synthetic or natural resins. Thermoplastic resins and curable resins can be used as synthetic resins.

[0200] Examples of thermoplastic resins include: polyethylene, polypropylene, polymethylpentene, ionomers, and various olefin-based thermoplastic elastomers; vinyl chloride resins such as polyvinyl chloride, polyvinylidene chloride, and vinyl chloride-vinyl acetate copolymer, which contain appropriate amounts of plasticizers as needed; polyester resins such as polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, ethylene glycol-terephthalic acid-isophthalic acid copolymer, and polyester-based thermoplastic elastomers; acrylic resins such as poly(methyl)acrylate, poly(ethyl)acrylate, poly(butyl)acrylate, and (methyl)acrylate-(butyl)acrylate copolymer; polyamide resins represented by nylon 6 or nylon 66; cellulose resins such as cellulose triacetate, cellophane, and celluloid; and polystyrene, acrylonitrile-styrene copolymer, and acrylonitrile-butadiene-styrene copolymer (AB). Styrene-based resins such as S); polyvinyl alcohol, ethylene-vinyl acetate copolymer, ethylene-vinyl alcohol copolymer, polycarbonate resin, polyarylate resin and polyimide resin, etc.

[0201] Examples of curable resins include thermosetting resins and ionizing radiation-cured resins, as exemplified in the cured layer.

[0202] Examples of natural resins include natural rubber, rosin, and amber.

[0203] Examples of metals that can be used as substrates include aluminum alloys such as aluminum or duralumin, iron or carbon steel, iron alloys such as stainless steel, copper or brass, copper alloys such as bronze, gold, silver, chromium, nickel, cobalt, tin, and titanium. Additionally, materials obtained by plating or similar processes on these metals can also be used as substrates.

[0204] Non-metallic inorganic materials used as substrates include, for example, materials such as: cement, ALC (lightweight aerated concrete), gypsum, calcium silicate, wood chip cement and other non-ceramic kiln materials, ceramic kiln materials such as ceramics, earthenware, glass, enamel and other ceramic kiln materials, limestone (including marble), granite, and andesite and other natural stones.

[0205] Examples of fibrous materials used as substrates include: tissue paper, kraft paper, premium paper, washi paper, titanium paper, cotton linter paper, tracing paper, paraffin paper, parchment paper, cellophane, wallpaper backing paper, cardboard paper, and gypsum board base paper; and woven or nonwoven fabrics containing polyester resin fibers, acrylic resin fibers, natural fibers such as silk, kapok, and hemp (protein-based or cellulose-based), glass fibers, and carbon fibers. To improve the inter-fiber or interlayer strength between the paper substrate and the paper, and to prevent pilling, resins such as acrylic resins, styrene-butadiene rubber, melamine resin, and urethane resins may be added to these papers (either through resin impregnation after papermaking or by filling during papermaking). Examples of resin-added papers include inter-paper reinforced paper and resin-impregnated paper.

[0206] In addition, as an example of a substrate made by layering resin layers on fibrous materials, wallpaper backing paper commonly used in the building materials industry is made by layering resin layers such as vinyl chloride resin layers, olefin resin layers, and acrylic resin layers on its surface.

[0207] There are no particular restrictions on the shape and size of the substrate; it can be selected appropriately based on the application, desired performance, and processing adaptability.

[0208] When the substrate is a flat sheet, film, or plate, the substrate has a thickness in terms of representative dimensions in the design of the article. There are no particular limitations on this thickness; generally, from the viewpoints of manufacturing adaptability, mechanical strength, operability, and economy, it can be set to approximately 10 μm or more and 10 cm or less. In the case of films or sheets, a thickness of approximately 20 μm or more and 500 μm or less is typically chosen; in the case of plates, a thickness of approximately 1 mm or more and 2 cm or less is typically chosen.

[0209] Regarding the substrate, in order to improve the adhesion to other layers constituting the antiviral article, or the adhesion to components laminated with the antiviral article, one or both sides of the substrate may be subjected to physical surface treatments such as oxidation or embossing, or chemical surface treatments.

[0210] Examples of oxidation methods include corona discharge treatment, chromium oxidation treatment, flame treatment, hot air treatment, and ozone-ultraviolet treatment. Examples of surface treatments include sandblasting and solvent treatment. These surface treatments are selected appropriately according to the type of substrate, but generally, considering the surface treatment effect and operability, corona discharge treatment is preferred.

[0211] Primer layer

[0212] Antiviral articles preferably have a primer layer that contacts the substrate side of the cured layer. The primer layer improves the adhesion between the substrate and the cured layer, making it easy to ensure good long-term interlayer adhesion (so-called weather resistance) when exposed to ultraviolet light, and also making it easy to achieve good scratch resistance.

[0213] It should be noted that examples of antiviral items being exposed to ultraviolet light include: places exposed to sunlight containing the ultraviolet spectrum, such as near windows; the interiors of kitchens, refrigerators, and cabinets equipped with germicidal mercury lamps; and outdoor areas directly exposed to sunlight. Examples of the installation, construction, or use of antiviral items include these examples.

[0214] The primer layer is mainly composed of adhesive resin, and may also contain additives such as ultraviolet absorbers and light stabilizers as needed.

[0215] Examples of suitable adhesive resins include urethane resins, acrylic polyol resins, acrylic resins, ester resins, amide resins, butyral resins, styrene resins, urethane-acrylic acid copolymers, polycarbonate-based urethane-acrylic acid copolymers (derived from polymers (polycarbonate polyols) having carbonate bonds in the polymer backbone and two or more hydroxyl groups at the ends and side chains), vinyl chloride-vinyl acetate copolymer resins, vinyl chloride-vinyl acetate-acrylic acid copolymer resins, chlorinated propylene resins, nitrocellulose resins (nitrocellulose), and cellulose acetate resins. These resins can be used individually or in combination. Furthermore, the adhesive resin can be a resin obtained by adding isocyanate-based curing agents, epoxy-based curing agents, or other curing agents to these resins and then cross-linking and curing them. Among these, resins obtained by cross-linking and curing polyol resins such as acrylic polyol resins using isocyanate-based curing agents are preferred, and resins obtained by cross-linking and curing acrylic polyol resins using isocyanate-based curing agents are more preferred.

[0216] To further improve weather resistance, the primer layer preferably contains UV absorbers and / or light stabilizers. Commonly used UV absorbers and light stabilizers can be used.

[0217] The thickness of the primer layer is preferably 0.01 μm or more and 10 μm or less, more preferably 0.7 μm or more and 8 μm or less, and even more preferably 1.0 μm or more and 6 μm or less.

[0218] It should be noted that, for the purpose of improving adhesion to the substrate, antiviral articles may have a back primer layer on the side of the substrate opposite to the cured layer.

[0219] Furthermore, for the purpose of adhesion to the substrate, antiviral articles may have an adhesive layer on the side of the substrate opposite to the cured layer. It should be noted that it is preferable to form a peelable release liner on the side of the adhesive layer opposite to the substrate.

[0220] Transparent resin layer

[0221] From the perspective of improving strength, antiviral articles can have a transparent resin layer between the substrate and the cured layer. In particular, when the substrate is a resin substrate, a transparent resin layer is preferred.

[0222] In the case of antiviral articles having a primer layer, the transparent resin layer is preferably located between the substrate and the primer layer. Furthermore, in the case of antiviral articles having a decorative layer, from the viewpoint of protecting the decorative layer, the transparent resin layer is preferably located between the decorative layer and the cured layer.

[0223] Examples of resins constituting the transparent resin layer include polyolefin resins, polyester resins, polycarbonate resins, acrylonitrile-butadiene-styrene resins (hereinafter also referred to as "ABS resins"), acrylic resins, and vinyl chloride resins. Among these, polyolefin resins are preferred from the viewpoint of processing adaptability. Furthermore, two or more of these exemplified resins can be layered or mixed for use.

[0224] From the viewpoint of processing adaptability, the content of polyolefin resin in the transparent resin layer is preferably 50% by mass or more, more preferably 70% by mass or more, and even more preferably 90% by mass or more, relative to the total resin composition of the transparent resin layer.

[0225] Examples of polyolefin resins used as transparent resin layers include polyethylene (low-density, medium-density, and high-density), polypropylene, polymethylpentene, polybutene, ethylene-propylene copolymer, propylene-butene copolymer, ethylene-vinyl acetate copolymer, ethylene-acrylic acid copolymer, and ethylene-propylene-butene copolymer. Among these, polyethylene (low-density, medium-density, and high-density), polypropylene, ethylene-propylene copolymer, and propylene-butene copolymer are preferred, and polypropylene is more preferred.

[0226] Transparent resin layers may contain additives such as UV absorbers, light stabilizers, and colorants.

[0227] From the viewpoint of balancing scratch resistance, processing adaptability and weather resistance, the thickness of the transparent resin layer is preferably 20 μm or more and 150 μm or less, more preferably 40 μm or more and 120 μm or less, and even more preferably 60 μm or more and 100 μm or less.

[0228] Decorative Layer

[0229] From a design perspective, antiviral items are preferably designed with decorative layers on any part of the item.

[0230] From the viewpoint of improving the weather resistance of the decorative layer, the area where the decorative layer is formed is preferably on the side closer to the substrate. For example, in the case of an antiviral article having a primer layer, the decorative layer is preferably located between the substrate and the primer layer. Furthermore, in the case of an antiviral article having a transparent resin layer, the decorative layer is preferably located between the substrate and the transparent resin layer.

[0231] The decorative layer can be formed on the entire surface of the antiviral article, or it can be formed only in certain areas. It should be noted that when the decorative layer covers the outer surface of the cured layer, in order not to hinder the performance of the antiviral properties, it is preferable to form the decorative layer only in certain areas.

[0232] Examples of decorative layers include: coloring layers formed by coating the entire surface with ink; patterned layers formed by printing ink in a patterned manner; metallic films; and so on.

[0233] Examples of patterns (textures) created by decorative layers include: wood grain such as annual rings and conduit grooves on wood panels; stone grain on marble, granite, and other stone slabs; fabric grain on cloth surfaces; leather grain on leather surfaces; tile patterns including seams; brick patterns including seams; sand grain; pear grain; patterns formed by arranging multiple concave and convex sections extending in mutually parallel directions (so-called "myriad-line concave-convex patterns" or "light-carved patterns"); abstract patterns such as geometric patterns, text, graphics, water droplets, and floral designs; etc.

[0234] As inks used for coloring and patterning layers, inks can be obtained by appropriately mixing pigments, dyes and other colorants, extender pigments, solvents, stabilizers, plasticizers, catalysts, curing agents, ultraviolet absorbers, light stabilizers and other substances into a binder resin.

[0235] There are no particular limitations on the adhesive resins used for the coloring and patterning layers. Examples include urethane resins, acrylic polyol resins, acrylic resins, ester resins, amide resins, butyral resins, styrene resins, urethane-acrylic acid copolymers, vinyl chloride-vinyl acetate copolymer resins, vinyl chloride-vinyl acetate-acrylic acid copolymer resins, chloropropylene resins, nitrocellulose resins, and cellulose acetate resins. Additionally, various types of resins can be used, such as one-component curing resins and two-component curing resins containing isocyanate compounds or similar curing agents.

[0236] As a coloring agent, there are no particular limitations. Examples include: inorganic pigments such as carbon black, iron black, titanium dioxide, antimony white, chrome yellow, titanium yellow, red lead, cadmium red, ultramarine, and cobalt blue; organic pigments or dyes such as quinacridone red, isoindolineone yellow, nickel azo complex, phthalocyanine blue, and azomethyl alkali azo black; metallic pigments containing flake-like foils such as aluminum and brass; pearlescent pigments containing flake-like foils such as titanium dioxide coated with mica and basic lead carbonate; etc.

[0237] The content of colorant is preferably 5 parts by mass or more and 90 parts by mass or less, more preferably 15 parts by mass or more and 80 parts by mass or less, and even more preferably 30 parts by mass or more and 70 parts by mass or less, relative to 100 parts by mass of the resin constituting the coloring layer and the pattern layer.

[0238] The coloring layer and pattern layer may contain additives such as ultraviolet absorbers, light stabilizers, and colorants.

[0239] The thickness of the coloring layer and the pattern layer can be appropriately selected according to the desired pattern. From the viewpoint of covering the background color of the object to be adhered and improving the design, it is preferably 0.5 μm or more and 20 μm or less, more preferably 1 μm or more and 10 μm or less, and even more preferably 2 μm or more and 5 μm or less.

[0240] Examples of metallic thin films include: thin films of elemental metals such as gold, silver, copper, tin, iron, indium, nickel, chromium, and cobalt; thin films of alloys containing two or more of the above-mentioned metals; and so on. Examples of alloys include brass, bronze, and stainless steel.

[0241] The thickness of the metal thin film can be set to about 0.1 μm to 1 μm.

[0242] Adhesive layer

[0243] Antiviral items may have an adhesive layer.

[0244] For example, in the case of antiviral articles having a transparent resin layer, it is preferable to form an adhesive layer between the substrate and the transparent resin layer to improve the adhesion between the two layers.

[0245] It should be noted that when a decorative layer is further provided between the substrate and the transparent resin layer, the positional relationship between the adhesive layer and the decorative layer is not particularly limited. Specifically, the decorative layer, adhesive layer, and transparent resin layer can be provided sequentially from the side closest to the substrate, or sequentially from the side closest to the substrate layer.

[0246] In addition, as described above, when the substrate is a laminate with two or more layers, an adhesive layer may be provided between the layers constituting the substrate.

[0247] The adhesive layer can be composed of adhesives such as urethane-based adhesives, acrylic-based adhesives, epoxy-based adhesives, and rubber-based adhesives. Among these adhesives, urethane-based adhesives are preferred in terms of adhesive strength.

[0248] Examples of urethane-based adhesives include adhesives obtained using two-component curing urethane resins containing various polyol compounds such as polyether polyols, polyester polyols, and acrylic polyols, as well as curing agents such as isocyanate compounds.

[0249] The thickness of the adhesive layer is preferably 0.1 μm or more and 30 μm or less, more preferably 1 μm or more and 15 μm or less, and even more preferably 2 μm or more and 10 μm or less.

[0250] The aforementioned decorative layer, adhesive layer, and primer layer can be formed, for example, by applying a coating liquid containing the composition forming each layer using known methods such as gravure printing, bar coating, roller coating, reverse roller coating, or comma coating, and then drying and curing it as needed.

[0251] <Shaping Processing>

[0252] Antiviral items can be given the desired textured or embossed shape (also known as embossed pattern) through shaping processes such as embossing.

[0253] In the case of embossing, for example, the antiviral article can be heated to a temperature preferably above 80°C and below 260°C, more preferably above 85°C and below 200°C, and even more preferably above 100°C and below 180°C, and the embossing plate can be pressed onto the antiviral article to perform the embossing process. The part where the embossing plate is pressed is preferably located on the side of the cured layer of the antiviral article.

[0254] <Antibacterial activity value>

[0255] The antiviral activity value of the antiviral article of the present invention, as determined by the method described below, is preferably greater than 0.0. To exhibit sufficient antiviral performance, an antiviral activity value of 1.0 or higher is more preferred, and even more preferably 2.0 or higher. The method described below is in accordance with ISO 21702.

[0256] Methods for Determining Antiviral Activity Value

[0257] Add 0.4 ml of virus solution to a 5 cm square test piece (processed and unprocessed antiviral product) and coat it with a 4 cm square membrane. Let the test piece stand at 25°C for 24 hours. After standing, wash off the virus from the test piece and recover it, and determine the virus infection value. Calculate the antiviral activity value using the following formula (1).

[0258] R = Ut - At (1)

[0259] R: Antiviral activity value

[0260] Ut: Virus infection value (PFU / cm³) of unprocessed product after standing for 24 hours. 2 The average of the common logarithms of )

[0261] At: Viral infection value (PFU / cm³) of antiviral processed products after standing for 24 hours. 2 The average of the common logarithms of )

[0262] <Application>

[0263] The antiviral article of the present invention can be used for a variety of purposes. As specific uses, the following uses (1) to (12) can be cited.

[0264] It should be noted that, when using the antiviral article of the present invention as various surface materials as described below, a known adhesive layer may be placed between the surface material and the adherend, which becomes the object of the laminated surface material, as needed. Examples of usable adhesives include: thermosetting adhesives that bond by heating and melting followed by cooling and curing; thermosetting adhesives that bond by utilizing a heated polymerization or crosslinking reaction; ionizing radiation curing adhesives that bond by undergoing a polymerization or crosslinking reaction under ionizing radiation such as ultraviolet light and electron beams; and adhesives that utilize the adhesiveness of the adhesive itself and bond only by applying pressure.

[0265] (1) Surface materials of interior parts such as walls, floors, and ceilings of buildings such as residences, offices, shops, hospitals, and clinics.

[0266] (2) Surface materials of the exterior parts of buildings such as residences, offices, shops, hospitals, clinics, etc., including walls, roofs, eaves, and rainproof window frames.

[0267] (3) Surface materials of windows, window frames, door leaves, door frames and other doors and windows (internal or external parts); surface materials of door and window accessories (handles, etc.); surface materials of door and window clamps.

[0268] (4) Surface materials of building components such as handrails, retaining walls, crown ornaments, thresholds, lintels, and beams.

[0269] (5) Surface materials of outdoor (exterior) parts such as columns or handrails of walls, doors, and balconies.

[0270] (6) Surface materials of furniture such as cabinets, tables, chairs, sideboards, and kitchen sinks; surface materials of furniture accessories (handles, etc.); surface materials of furniture clamps.

[0271] (7) Surface materials of the housings of various household appliances such as television receivers, radio receivers, refrigerators, microwave ovens, washing machines, electric fans, and air conditioners; surface materials of accessories of household appliances (handles, switches, touch panels, etc.); surface materials of clamps of household appliances.

[0272] (8) Surface materials of OA equipment such as electronic copiers, fax machines, printers, personal computers and other electronic computing devices; surface materials of the housings of various OA equipment such as ATMs of banks, post offices and other financial institutions; surface materials of various OA equipment accessories (keyboards, touch panels, etc.); surface materials of various OA equipment fixtures.

[0273] (9) Surface materials of interior or exterior parts (walls, floors, ceilings, handrails, pillars, control panels, poles, steering wheels, steering wheels, steering wheels, and other control equipment) of vehicles such as automobiles, railway vehicles, ships, and airplanes.

[0274] (10) Partitions of various buildings; shields or curtains used to prevent droplet infection of viruses in windows of shops, offices, government agencies, accounting settlement places, etc.; face protection such as protective face shields and protective glasses; or the surface materials of these.

[0275] (11) Commercial documents such as bills; passbooks; cash cards, credit cards, loyalty cards and other cards issued by financial institutions; or the surface material of these.

[0276] (12) Bottles of glass, resin, etc.; metal cans; resin retort containers, etc.; packaging materials of various pipes, etc.; or surface materials of these.

[0277] [Antibacterial Resin Composition]

[0278] The antiviral resin composition of the present invention comprises a curable resin composition, an antiviral agent supported on or containing silver ions on a carrier, and a light stabilizer, and comprises one or more hindered amine compounds selected from NH-type hindered amine compounds and NR-type hindered amine compounds as the light stabilizer.

[0279] The embodiments of the "cured resin composition", "antiviral agent supported on or containing silver ions" and "NH-type hindered amine compound and NR-type hindered amine compound" in the antiviral resin composition of the present invention are the same as those of the "cured resin composition", "antiviral agent supported on or containing silver ions" and "NH-type hindered amine compound and NR-type hindered amine compound" in the antiviral articles of the present invention described above.

[0280] The antiviral resin composition of the present invention may contain antioxidants and ultraviolet absorbers, etc., as needed.

[0281] The embodiments of the "antioxidant" and "ultraviolet absorber" in the antiviral resin composition of the present invention are the same as the embodiments of the "antioxidant" and "ultraviolet absorber" in the antiviral articles of the present invention described above.

[0282] Solvent

[0283] The antiviral resin composition of the present invention preferably contains a solvent.

[0284] Solvents can include, for example, ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone (MIBK), cyclohexanone, etc.), ethers (dioxane, tetrahydrofuran, etc.), aliphatic hydrocarbons (hexane, etc.), alicyclic hydrocarbons (cyclohexane, etc.), aromatic hydrocarbons (toluene, xylene, etc.), carbon halogens (dichloromethane, dichloroethane, etc.), esters (methyl acetate, ethyl acetate, butyl acetate, etc.), alcohols (isopropanol, butanol, cyclohexanol, etc.), cellosols (methyl cellosol, ethyl cellosol, etc.), glycol ethers (propylene glycol monomethyl ether acetate, etc.), cellosol acetates, sulfoxides (dimethyl sulfoxide, etc.), amides (dimethylformamide, dimethylacetamide, etc.), and mixtures thereof.

[0285] The solvent content is preferably 10 to 60% by mass of the total amount of the antiviral resin composition (ink for cured layer), more preferably 30 to 50% by mass.

[0286] Example

[0287] The invention will now be described in further detail through examples, but the invention is not limited to these examples in any way.

[0288] 1. Production and evaluation of antiviral products

[0289] -Crafting Antiviral Items-

[0290] [Example 1]

[0291] Ink a (antiviral resin composition a) for preparing the cured layer of Example 1, which is prepared by mixing and stirring the following components.

[0292] <Ink for Cured Layer (Antiviral Resin Composition (a)>

[0293] · 100 parts by weight of ionizing radiation curable resin composition

[0294] (Trifunctional urethane acrylate oligomer with a weight average molecular weight of 4000)

[0295] • 3 parts by weight of antiviral agent containing silver ions in the carrier

[0296] (Product number "PG711" manufactured by Koa Glass, with glass substrate and an average particle size of 3μm)

[0297] · NR-type hindered amine compounds, 2 parts by mass

[0298] (BASF product number "Tinuvin 144")

[0299] · 2 parts by weight of ultraviolet absorber

[0300] (Hydroxyphenyltriazine, TINUVIN479, manufactured by BASF)

[0301] • Extender pigment (amorphous silica) 16 parts by weight

[0302] (Average particle size: 10 μm)

[0303] · Solvent 50 parts by weight

[0304] (ethyl acetate)

[0305] Next, using gravure printing, a decorative layer containing a two-component curable acrylic-urethane resin and a colorant is applied to one side of a substrate (a 60μm thick polypropylene resin sheet containing titanium oxide) that has undergone double-sided corona discharge treatment, and then dried to form a 3μm thick wood grain decorative layer.

[0306] Next, an adhesive layer with a thickness of 3 μm containing a urethane resin adhesive is formed on the decorative layer. Then, a polypropylene resin is heated and melted and extruded onto the adhesive layer using a T-die extruder to form a transparent resin layer with a thickness of 80 μm.

[0307] Next, after performing corona discharge treatment on the surface of the transparent resin layer, the primer layer with the following composition is applied onto the transparent resin layer using gravure printing and then dried to form a primer layer with a thickness of 2μm.

[0308] Next, the cured layer was coated onto the primer layer using a roller coating method with ink a (antiviral resin composition a) to form an uncured cured layer. After drying at 60°C for 1 minute, it was irradiated with an electron beam (accelerating voltage: 175kV, 5Mrad (50kGy)) to crosslink and cure the curable resin composition (ionizing radiation curable resin composition), forming a cured layer with a thickness of 15μm, thus obtaining the antiviral article of Example 1. It should be noted that the cured layer ink a (antiviral resin composition a) was coated onto the primer layer immediately after preparation.

[0309] <Ink for primer layer>

[0310] 100 parts by weight of a mixture of urethane-acrylic acid copolymer and acrylic polyol

[0311] 5 parts by weight of hexamethylene diisocyanate

[0312] [Example 2]

[0313] The curing layer ink b (antiviral resin composition b) of Example 2 was prepared by changing the NR-type hindered amine compound of curing layer ink a (antiviral resin composition a) to an NR-type hindered amine compound (BASF product number "Tinuvin 765").

[0314] Next, the ink a (antiviral resin composition a) for the cured layer was changed to ink b (antiviral resin composition b) for the cured layer. Otherwise, the same procedure as in Example 1 was followed to obtain the antiviral article of Example 2.

[0315] [Example 3]

[0316] The curing layer ink c (antiviral resin composition c) of Example 3 was prepared by changing the NR-type hindered amine compound of the curing layer ink a (antiviral resin composition a) to an NR-type hindered amine compound (product number "LS3410" of Japan Emulsifier Co., Ltd.; a compound having an olefinic double bond that can polymerize with the curing resin composition).

[0317] Next, the ink a (antiviral resin composition a) for the cured layer was changed to ink c (antiviral resin composition c) for the cured layer. Otherwise, the same procedure as in Example 1 was followed to obtain the antiviral article of Example 3.

[0318] [Example 4]

[0319] The ink d for the cured layer of Example 4 (antiviral resin composition d) was prepared by changing the NR-type hindered amine compound of the cured layer ink a (antiviral resin composition a) to an NH-type hindered amine compound (BASF product number "Tinuvin 7 70DF").

[0320] Next, the ink a (antiviral resin composition a) for the cured layer was changed to ink d (antiviral resin composition d) for the cured layer. Otherwise, the same procedure as in Example 1 was followed to obtain the antiviral article of Example 4.

[0321] [Example 5]

[0322] The cured layer ink e (antiviral resin composition e) of Example 5 was prepared by adding 1 part by weight of a phosphorus-based antioxidant (the phosphorus-based antioxidant of Formula 1-1-1 above) to the cured layer ink a (antiviral resin composition a).

[0323] Next, the ink a (antiviral resin composition a) for the cured layer was changed to ink e (antiviral resin composition e) for the cured layer. Otherwise, the same procedure as in Example 1 was followed to obtain the antiviral article of Example 5.

[0324] [Example 6]

[0325] The cured layer ink f (antiviral resin composition f) of Example 6 was prepared by changing the NR-type hindered amine compound of cured layer ink a (antiviral resin composition a) to an NR-type hindered amine compound (product number "LS3410" from Nippon Emulsifier Co., Ltd.; a compound having an olefinic double bond that can polymerize with the cured resin composition), and by changing the amount added from 2 parts by mass to 5 parts by mass. The amount of hindered amine compound added to the cured layer ink c of Example 3 was increased.

[0326] Next, the ink a (antiviral resin composition a) for the cured layer was changed to ink f (antiviral resin composition f) for the cured layer. Otherwise, the same procedure as in Example 1 was followed to obtain the antiviral article of Example 6.

[0327] [Example 7]

[0328] In the cured layer ink a (antiviral resin composition a), the antiviral agent was changed to "SCE Environmental Science Co., Ltd. product number 'NEOSINTOL AV-18F', an antiviral agent supported on a carrier or containing silver ions, with an average particle size of 3.0 μm", the amount added was changed from 3 parts by mass to 0.5 parts by mass, and the NR-type hindered amine compound was changed to NR-type hindered amine compound (Japan Emulsifier Co., Ltd. product number "LS3410"; a compound having an olefinic double bond that can polymerize with the curable resin composition). This resulted in the cured layer ink g (antiviral resin composition g) of Example 7.

[0329] Next, the ink a (antiviral resin composition a) for the cured layer was changed to ink g (antiviral resin composition g) for the cured layer. Otherwise, the same procedure as in Example 1 was followed to obtain the antiviral article of Example 7.

[0330] [Example 8]

[0331] In the cured layer ink a (antiviral resin composition a), the antiviral agent was changed to "SCE Environmental Science Co., Ltd. product number 'NEOSINTOL AV-18F', an antiviral agent supported on a carrier or containing silver ions, with an average particle size of 3.0 μm," and the addition amount was changed from 3 parts by mass to 0.5 parts by mass. Furthermore, the NR-type hindered amine compound was changed to NR-type hindered amine compound (Japan Emulsifier Co., Ltd. product number "LS3410"; a compound having an olefinic double bond that can polymerize with the cured resin composition), and the addition amount was changed from 2 parts by mass to 5 parts by mass, resulting in the cured layer ink h (antiviral resin composition h) of Example 8. The addition amount of the hindered amine compound in the cured layer ink g of Example 7 was increased.

[0332] Next, the ink a (antiviral resin composition a) for the cured layer was changed to ink h (antiviral resin composition h) for the cured layer. Otherwise, the same procedure as in Example 1 was followed to obtain the antiviral article of Example 8.

[0333] [Comparative Example 1]

[0334] Comparative Example 1 prepared a cured layer ink i (antiviral resin composition i) by removing NR-type hindered amine compounds from cured layer ink a (antiviral resin composition a).

[0335] Next, the ink a (antiviral resin composition a) for the cured layer was changed to ink i (antiviral resin composition i) for the cured layer. Otherwise, the same procedure as in Example 1 was followed to obtain the antiviral article of Comparative Example 1.

[0336] [Comparative Example 2]

[0337] Comparative Example 2 prepared an ink j (antiviral resin composition j) for curing layer by changing the NR-type hindered amine compound of the cured layer ink a (antiviral resin composition a) to a NOR-type hindered amine compound (BASF product number "Tinuvin123").

[0338] Next, the ink a (antiviral resin composition a) for the cured layer was changed to ink j (antiviral resin composition j) for the cured layer. Otherwise, the same procedure as in Example 1 was followed to obtain the antiviral article of Comparative Example 2.

[0339] [Comparative Example 3]

[0340] Comparative Example 3 prepared an ink k (antiviral resin composition k) for curing layer by changing the NR-type hindered amine compound of the cured layer ink a (antiviral resin composition a) to a NOR-type hindered amine compound (BASF product number "Tinuvin152").

[0341] Next, the ink a (antiviral resin composition a) for the cured layer was changed to ink k (antiviral resin composition k) for the cured layer. Otherwise, the same procedure as in Example 1 was followed to obtain the antiviral article of Comparative Example 3.

[0342] Evaluation of the discoloration of an antiviral product -

[0343] Regarding the antiviral articles of the Examples and Comparative Examples, L was measured immediately after manufacturing. * a * b * The measurement atmosphere was set at 23℃±5℃ and 40~65%RH. The measuring apparatus used was a spectrophotometer ("Spectrolino" model, manufactured by GretagMacbeth).

[0344] Next, for the antiviral articles of the examples and comparative examples, a weathering acceleration test using a metal halide lamp (MWOM) will be conducted for two cycles (48 hours). This test involves irradiation with ultraviolet light for 20 hours under the following irradiation conditions, followed by condensation for 4 hours under the following condensation conditions; this process is considered one cycle, and the test is repeated. Then, the L after the weathering acceleration test will be measured. * a * b * value.

[0345] Then, the color difference (ΔE) is calculated based on the measured values ​​immediately after manufacturing and the measured values ​​after the accelerated weathering test. * ab). The results are shown in Table 1.

[0346] The measured value immediately after manufacturing is set as L. *1 a *1 and b *1 The measured value after the weathering resistance test will be set as L. *2 a *2 and b *2 At that time, color difference (ΔE) * (ab) can be calculated using the following mathematical formula.

[0347] ΔE * ab = [(L] *2 -L *1 ) 2 +(a *2 -a *1 )2 +(b *2 -a *2 ) 2 ] 1 / 2

[0348] <Experimental Apparatus>

[0349] The product name "Daipla Metal Weather" is manufactured by DAIPLA WINTES.

[0350] <Irradiation conditions>

[0351] Illuminance: 65mW / cm 2 Black panel temperature: 63℃, tank humidity: 50%RH, time: 20 hours

[0352] <Condensation Conditions>

[0353] Illuminance: 0 mW / cm 2 Humidity inside the tank: 98% RH; Time: 4 hours

[0354] -Antiviral activity value-

[0355] According to the "Method for Determination of Antiviral Activity Value" in the main text of the instruction manual, the antiviral activity value of the antiviral articles in the examples and comparative examples was determined. The antiviral activity value was measured for influenza virus and feline calicivirus.

[0356] [Table 1]

[0357] Table 1

[0358]

[0359] As shown in Table 1, it can be confirmed that the antiviral articles of the embodiments can inhibit discoloration.

[0360] Furthermore, as shown in Table 1, it can be confirmed that the antiviral articles of the embodiments exhibit good antiviral activity. It should be noted that hindered amine compounds are not considered to affect the antiviral activity value.

[0361] 2. Preparation or fabrication of antiviral resin compositions, and evaluation thereof.

[0362] -Preparation or fabrication of antiviral resin compositions-

[0363] As reference examples 1 to 4, the above-mentioned antiviral resin compositions a, e, i, and j were prepared.

[0364] Furthermore, the antiviral resin composition 1 of Reference Example 5 was prepared by removing the NR-type hindered amine compound from the cured layer ink a (antiviral resin composition a) and replacing it with 1 part by mass of a phosphorus-based antioxidant (the phosphorus-based antioxidant of Formula 1-1-1 above).

[0365] Furthermore, the antiviral resin composition m of Reference Example 6 was prepared by removing the NR-type hindered amine compound from the cured layer ink a (antiviral resin composition a) and replacing it with 1 part by mass of a phosphorus-based antioxidant (the phosphorus-based antioxidant of Formula 1-2-1 above).

[0366] Evaluation of discoloration of an antiviral resin composition -

[0367] In a room where external light was blocked, 30g of the antiviral resin composition of the reference example was placed in a glass bottle (manufactured by AS ONE, product number: Laboran Screw tube 50ml), and the cap was closed to prepare an evaluation sample. At this stage, no difference was found in the color of the antiviral resin composition in the sample compared to the composition without antiviral agent (the composition of the reference example after removing the antiviral agent from the antiviral resin composition); both were white.

[0368] Next, the samples were placed on a table and left indoors under fluorescent lighting for 24 hours. The color of the antiviral resin composition within the samples was then visually evaluated. The brightness of the fluorescent lamp on the table was set to the range of 500–1000 lux. The results are shown in Table 2.

[0369] [Table 2]

[0370] Table 2

[0371]

[0372] The results in Table 2 confirm that by including a phosphorus-based antioxidant in the antiviral resin composition, light-induced discoloration of the antiviral resin composition in its current state can be suppressed (compositions e, l, and m contain phosphorus-based antioxidants). This result indicates that antiviral resin compositions containing a phosphorus-based antioxidant, in addition to one or more hindered amine compounds selected from NH-type and NR-type hindered amine compounds, exhibit good processability without requiring storage in the dark. It should be noted that the results of Examples 1-8 in Table 1 show that even if the antiviral resin composition does not contain a phosphorus-based antioxidant, discoloration can be suppressed as long as a cured layer is formed from the composition before extensive light exposure. Therefore, including a phosphorus-based antioxidant is a preferred embodiment of the present invention.

[0373] Explanation of reference numerals in the attached figures

[0374] 100: Antiviral items

[0375] 10: Cured layer

[0376] 11: Cured product of a curable resin composition

[0377] 12: Antiviral agents loaded on or containing silver ions.

[0378] 20: Substrate.

Claims

1. An antiviral product having a solidified layer, The cured layer comprises a cured resin composition, an antiviral agent supported on a carrier or containing silver ions, a light stabilizer, and a hydroxyphenyltriazine-based ultraviolet absorber, and includes an NR-type hindered amine compound with a molecular weight of 200 to 1000 as the light stabilizer. When the average particle size of the antiviral agent is defined as D, and the thickness of the solidified layer is defined as T, D / T is 0.7 or less. Relative to 100 parts by weight of the solidified product, the antiviral article contains 0.1 to 20.0 parts by weight of the antiviral agent. Relative to 100 parts by weight of the antiviral agent, the antiviral article comprises 20 to 1000 parts by weight of the NR-type hindered amine compound. The amount of silver ions in the antiviral agent is 0.1 to 30.0 parts by mass relative to 100 parts by mass of the carrier.

2. The antiviral article according to claim 1, wherein, The average particle size of the antiviral agent is 0.1 μm to 10.0 μm.

3. The antiviral article according to claim 1 or 2, wherein at least a portion of the antiviral agent protrudes from the surface of the cured layer.

4. The antiviral article according to claim 1, wherein, The NR-type hindered amine compound is formed by replacing the hydrogen atom bonded to the nitrogen atom in the 2,2,6,6-tetramethylpiperidine skeleton with an alkyl group, wherein the alkyl group has 1 to 12 carbon atoms.

5. The antiviral article according to claim 1, wherein, The cured layer also contains antioxidants.

6. The antiviral article according to claim 5, wherein, The antioxidant is a compound having a phosphorous acid structure as shown in the following general formula (1). 。 7. The antiviral article according to claim 5 or 6, wherein, The antioxidant is a compound represented by the following general formula (1-2-1). ， In the formula, R independently represents a straight-chain alkyl group with 12 to 15 carbon atoms.

8. The antiviral article according to claim 1 or 2, wherein it is formed having the cured layer on a substrate.

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