Antiviral adhesive sheet and article with antiviral adhesive sheet

Abstract

To provide an antiviral adhesive sheet that does not cause a deterioration of the design of an article and has stable adhesion to the article.SOLUTION: An antiviral adhesive sheet comprises a laminate comprising a surface protective layer containing a binder component and an antiviral agent, an optically transparent substrate layer and an adhesive layer in the stated order, the optically transparent substrate layer being a polypropylene resin substrate, the antiviral agent being an organic antiviral agent.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] The present disclosure relates to an antiviral adhesive sheet and an article with the antiviral adhesive sheet. [Background technology]

[0002] From the viewpoint of hygiene, antibacterial treatment has conventionally been carried out by applying an antibacterial composition to the surfaces of objects that people touch, such as interior materials for buildings, interior materials for vehicles, office automation equipment, and touch panels.

[0003] Antibacterial compositions have been proposed, for example, in Patent Documents 1 and 2. However, merely having antibacterial properties is not enough against viruses such as influenza viruses and the novel coronavirus. That is, the antibacterial compositions of Patent Documents 1 and 2 sometimes failed to provide satisfactory antiviral properties.

[0004] On the other hand, Patent Documents 3 and 4 have proposed antiviral sheets. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] Japanese Patent Application Publication No. 63-265958 [Patent Document 2] Patent No. 3551201 [Patent Document 3] Patent No. 6145758 [Patent Document 4] Patent No. 6229429 DISCLOSURE OF THE INVENTION [Problem to be solved by the invention]

[0006] Due to the influence of the new coronavirus, antiviral sheets are sometimes attached to various items. When an antiviral sheet is attached to an article, air bubbles may become trapped between the article and the antiviral sheet. Furthermore, after the antiviral sheet is attached to the article, gas may be generated from the article, creating air bubbles between the article and the antiviral sheet. Air bubbles between the article and the antiviral sheet may reduce the design of the article. However, the antiviral sheets in Patent Documents 3 and 4 do not address the issue of air bubbles reducing the design of the article.

[0007] Furthermore, some antiviral agents are colored from the early stages or become colored over time. The antiviral agent of Patent Document 3 contains cuprous oxide particles and has a color derived from the reddish-brown color of cuprous oxide. Among the antiviral agents of Patent Document 4, the silver-based antiviral agent discolors to brown when exposed to light such as visible light and ultraviolet light. As such, the antiviral sheets of Patent Documents 3 and 4 do not consider at all the degradation of the design of the article due to the color of the antiviral agent.

[0008] Furthermore, antiviral sheets are required to have stable adhesion to various articles, but the antiviral sheets of Patent Documents 3 and 4 do not consider adhesion to articles at all.

[0009] The present disclosure has been made in view of the above-mentioned problems, and aims to provide an antiviral adhesive sheet that suppresses a decrease in the design quality of an article and has stable adhesion to the article. Another aim of the present disclosure is to provide an article with an antiviral adhesive sheet that suppresses a decrease in the design quality of the article and has stable adhesion to the antiviral adhesive sheet. [Means for solving the problem]

[0010] In order to solve the above problems, the present disclosure provides the following [1] and [2]. [1] An antiviral pressure-sensitive adhesive sheet comprising a laminate having, in this order, a surface protective layer containing a binder component and an antiviral agent, a light-transmitting substrate layer, and a pressure-sensitive adhesive layer, the light-transmitting substrate layer contains a polypropylene-based resin substrate, An antiviral adhesive sheet, wherein the antiviral agent is an organic antiviral agent. [2] An article with an antiviral adhesive sheet, comprising the antiviral adhesive sheet according to [1] attached to an article. [Effects of the Invention]

[0011] The antiviral adhesive sheet of the present disclosure can suppress deterioration in the design of an article and can provide stable adhesion to the article. Furthermore, an article equipped with the antiviral adhesive sheet of the present disclosure can suppress deterioration in the design of the article and can provide stable adhesion between the article and the antiviral adhesive sheet. [Brief explanation of the drawings]

[0012] [Figure 1] FIG. 1 is a cross-sectional view showing one embodiment of an antiviral adhesive sheet of the present disclosure. [Figure 2] FIG. 2 is a cross-sectional view showing another embodiment of the antiviral adhesive sheet of the present disclosure. [Figure 3] FIG. 2 is a cross-sectional view showing another embodiment of the antiviral adhesive sheet of the present disclosure. [Figure 4] FIG. 10 is a plan view illustrating an embodiment of a groove in a pressure-sensitive adhesive layer having a groove. DETAILED DESCRIPTION OF THE INVENTION

[0013] The present disclosure will be described in detail below.

[0014] [Antiviral adhesive sheet] The antiviral adhesive sheet of the present disclosure is an antiviral adhesive sheet including a laminate having, in this order, a surface protective layer containing a binder component and an antiviral agent, a light-transmitting base layer, and a pressure-sensitive adhesive layer, wherein the light-transmitting base layer is a polypropylene-based resin base, and the antiviral agent is an organic antiviral agent.

[0015] 1 to 3 are cross-sectional views showing one embodiment of an antiviral adhesive sheet according to the present disclosure. The antiviral adhesive sheet 100 in FIGS. 1 to 3 includes a laminate 10 having a surface protective layer 30, a light-transmitting base layer 20, and a pressure-sensitive adhesive layer 40, in this order. In FIGS. 1 to 3, the surface protective layer 30 includes a binder component 31 and an antiviral agent 32. In FIGS. 1 to 3, the antiviral adhesive sheet 100 further includes a separator 50. In FIGS. 1 to 3, the separator 50 is located on the opposite side of the pressure-sensitive adhesive layer 40 from the light-transmitting base layer 20.

[0016] When the viral adhesive sheet of the present disclosure simultaneously exhibits antibacterial and antifungal properties in addition to exhibiting antiviral properties, it can also be used as an antibacterial sheet and an antifungal sheet. Generally, even for sheets made of the same material and layer structure, the correlation between their exhibited "antiviral," "antibacterial," and "antifungal" properties may be effective or ineffective depending on the type of virus, bacteria, or mold in question; the environmental conditions; the required level of antiviral, antibacterial, or antifungal properties; etc. For this reason, the antiviral adhesive sheet of the present disclosure may be applicable not only to antiviral applications but also to antibacterial applications, depending on the type of bacteria, environmental conditions, and the required level of antibacterial properties. Note that, because mold is a type of fungus, the antiviral adhesive sheet of the present disclosure may also be applicable to antifungal applications, depending on the type of mold, environmental conditions, and the required level of antifungal properties.

[0017] In the present disclosure, "antiviral" means that the antiviral activity value measured by the following method is greater than 0.0. The antiviral pressure-sensitive adhesive sheet of the present disclosure preferably has an antiviral activity value of 1.0 or greater, and more preferably 2.0 or greater. The following method complies with ISO 21702.

[0018] <Method for measuring antiviral activity> Prepare 5cm square test pieces for the antiviral treated and untreated products. Drop 0.4ml of virus fluid onto the surface protective layer side of the test piece and cover with a 4cm square film. Leave this test piece at rest for 24 hours in an environment of 25°C and 90% RH. After leaving it at rest, wash off and recover the virus fluid dropped onto the test piece, and measure the virus infectivity. Calculate the antiviral activity value using the following formula (1): R=Ut-At (1) R: Antiviral activity value Ut: Virus infectivity (PFU / cm) after leaving the unprocessed product for 24 hours 2 ) the average of the base 10 logarithms At: Viral infectivity (PFU / cm) of antiviral processed product after leaving it for 24 hours 2 ) the average of the base 10 logarithms

[0019] <Laminate> The antiviral pressure-sensitive adhesive sheet of the present disclosure includes a laminate having, in this order, a surface protective layer, a light-transmitting substrate layer, and a pressure-sensitive adhesive layer.

[0020] The surface protection layer forms one surface of the laminate, and the pressure-sensitive adhesive layer forms the other surface of the laminate. The laminate may have a functional layer between the surface protective layer and the light-transmitting substrate layer and / or between the light-transmitting substrate layer and the pressure-sensitive adhesive layer. Examples of the functional layer include a primer layer.

[0021] Specific examples of the layer structure of the laminate include the following (1) and (2). (1) A laminate having a surface protective layer, a light-transmitting substrate layer, and a pressure-sensitive adhesive layer in this order. (2) A laminate having a surface protective layer, a primer layer, a light-transmitting substrate layer, and a pressure-sensitive adhesive layer in this order.

[0022] In the antiviral pressure-sensitive adhesive sheet of the present disclosure, the haze value of the laminate measured in accordance with JIS K7136:2000 is preferably 40% or more, more preferably 50% or more, and even more preferably 55% or more. Increasing the haze value of the laminate makes it easier to identify the location where the antiviral pressure-sensitive adhesive sheet is attached. Furthermore, when the pressure-sensitive adhesive layer is a porous layer, increasing the haze value of the laminate makes it difficult to visually detect thickness variations in the porous pressure-sensitive adhesive layer, which is preferable in terms of improving the appearance. On the other hand, if the haze value of the laminate is too high, the design applied to the article may become difficult to see. Therefore, the haze value of the laminate is preferably 90% or less, more preferably 75% or less, and even more preferably 65% ​​or less.

[0023] In the configuration requirements shown in this specification, when multiple upper limit options and multiple lower limit options are shown for each of the numerical values, one selected from the upper limit options and one selected from the lower limit options can be combined. For example, in the case of the haze value of the above laminate, 40% or more and 90% or less, 40% or more and 75% or less, 40% or more and 65% or less, 50% or more and 90% or less, Examples of embodiments include numerical ranges of 50% to 75%, 50% to 65%, 55% to 90%, 55% to 75%, and 55% to 65%.

[0024] In order to improve the visibility of the article, the laminate preferably has a total light transmittance measured in accordance with JIS K7361-1:1997 of 80% or more, more preferably 85% or more, and even more preferably 90% or more.

[0025] The laminate has an oxygen permeability of 50cc / m as measured in accordance with JIS K7126-2:2006. 2 ·day·atm or more is preferable, and 75cc / m 2 ·day·atm or more is more preferable, and 100cc / m 2It is more preferable that the oxygen permeability is 1·day·atm or more. In this specification, the conditions for measuring the oxygen permeability are a temperature of 23°C and a relative humidity of 90%. The oxygen permeability can be measured, for example, by an oxygen permeability measuring device (trade name: OX-TRAN) manufactured by MOCON (MOCON method). By setting the oxygen permeability within the above range, air bubbles between the article and the antiviral pressure-sensitive adhesive sheet can be easily removed. The upper limit of the oxygen permeability of the laminate is not particularly limited, but is preferably 2000 cc / m 2 ·day·atm or less is preferable.

[0026] 《Light-transparent base material layer》 The light-transmitting substrate layer serves as a support for the surface protective layer and the pressure-sensitive adhesive layer. The antiviral pressure-sensitive adhesive sheet of the present disclosure uses a substrate layer containing a polypropylene-based resin substrate as the light-transmitting substrate layer.

[0027] The light-transmitting substrate layer may contain two or more resin substrates such as polypropylene-based resin substrates, but preferably contains only one resin substrate to increase gas permeability, i.e., the light-transmitting substrate layer preferably contains only one polypropylene-based resin substrate as the resin substrate. The light-transmitting substrate layer may have a layer other than the polypropylene-based resin substrate. For example, the light-transmitting substrate layer may have a resin layer on the polypropylene-based resin substrate. The resin layer has a role of adjusting haze, for example.

[0028] Polypropylene-based resin substrates are highly permeable to gas. Therefore, even if air bubbles are introduced when the antiviral pressure-sensitive adhesive sheet is attached to an article, or if bubbles are generated due to gas being generated from the article after the antiviral sheet is attached to the article, the air bubbles can be easily removed. Therefore, polypropylene-based resin substrates can easily prevent deterioration of the design of the article. Furthermore, because polypropylene-based resin substrates have good shape conformability, they can provide stable adhesion to articles with curved or uneven surfaces.

[0029] The gas permeability of the polypropylene-based resin substrate can be adjusted by the blending of the resin, the crystallinity of the resin, the particles in the substrate, the thickness of the substrate, and the like.

[0030] The polypropylene resin may be a homopolymer of propylene or a copolymer of propylene and another comonomer copolymerizable with propylene (for example, an α-olefin such as ethylene, 1-butene, 1-hexene, or 1-octene; vinyl acetate, vinyl alcohol, etc.). These polypropylenes may be used alone or in combination of two or more.

[0031] When a propylene homopolymer is used as the resin constituting the polypropylene-based resin substrate, the higher the crystallinity of the polymer, the lower the gas permeability tends to be, and the lower the crystallinity of the polymer, the higher the gas permeability tends to be. When the thickness of the polypropylene-based resin substrate is within the range described below, the crystallinity of the polymer is preferably 30% or more, more preferably 40% or more, and the upper limit is preferably 80% or less, more preferably 70% or less. When a propylene homopolymer is used as the resin constituting the polypropylene-based resin substrate, the gas permeability of the polymer can also be adjusted by adjusting the mass ratio of isotactic polypropylene to atactic polypropylene. Generally, the gas permeability of the polymer decreases when isotactic polypropylene is added compared to when the proportion of atactic polypropylene in polypropylene is 100 mass%.

[0032] The polypropylene-based resin substrate may contain particles. When the polypropylene-based resin substrate contains particles, the gas permeability of the polypropylene-based resin substrate can be easily increased. Furthermore, when the polypropylene-based resin substrate contains particles, the internal haze of the polypropylene-based resin substrate can be easily increased. Note that if the particle content is too high, the polypropylene-based resin substrate may become embrittled.

[0033] The polypropylene-based resin substrate may contain additives such as an ultraviolet absorber, a light stabilizer, an antioxidant, and an antistatic agent.

[0034] The thickness of the polypropylene-based resin substrate is preferably 5 μm or more, more preferably 20 μm or more, and even more preferably 50 μm or more in order to improve strength and handleability and increase the haze value of the laminate, and is preferably 250 μm or less, more preferably 200 μm or less, and even more preferably 150 μm or less in order to improve shape conformability and facilitate high gas permeability.

[0035] As described above, the light-transmitting substrate layer may have a resin layer on a polypropylene-based resin substrate. The resin layer has a role of adjusting haze, for example. The resin layer preferably contains a binder resin and particles.

[0036] Examples of the binder resin of the resin layer include resins similar to those exemplified as binder resins of the primer layer described below. The particles in the resin layer may be general-purpose organic particles or general-purpose inorganic particles. To increase the internal haze of the resin layer, the particles preferably have a refractive index significantly different from that of the binder resin. The average particle size of the particles is preferably 0.1 μm or more and 5.0 μm or less, more preferably 0.2 μm or more and 3.0 μm or less. The content of the particles relative to the binder resin may be adjusted appropriately taking into consideration the desired internal haze and coating strength of the resin layer.

[0037] The thickness of the resin 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.

[0038] In order to improve the visibility of the article, the light-transmitting substrate layer preferably has a total light transmittance measured in accordance with JIS K7361-1:1997 of 80% or more, more preferably 85% or more, and even more preferably 90% or more.

[0039] In this specification, the total light transmittance, internal haze value, and haze can be calculated, for example, as follows. (1) A sample is cut from a defect-free portion of the antiviral pressure-sensitive adhesive sheet, or from a defect-free portion of a laminate made up of layers other than the pressure-sensitive adhesive layer. (2) Measure the total light transmittance, internal haze value, and haze at 20 points on the sample. The average values ​​of the 20 measurements are used as the total light transmittance, internal haze value, and haze of each sample.

[0040] The polypropylene resin base material has an oxygen permeability of 100cc / m, measured in accordance with JIS K7126-2:2006. 2 ·day·atm or more is preferable, and 150cc / m 2 ·day·atm or more is more preferable, and 200cc / m 2 It is even more preferable that it is 1000 kJ / day atm or higher. By setting the oxygen permeability within the above range, air bubbles between the article and the antiviral pressure-sensitive adhesive sheet can be easily removed. The upper limit of the oxygen permeability of the polypropylene-based resin substrate is not particularly limited, but is preferably 2500 cc / m 2 ·day·atm or less is preferable.

[0041] In order to improve adhesion between the polypropylene-based resin substrate and a layer that comes into contact with the polypropylene-based resin substrate, one or both surfaces of the polypropylene-based resin substrate may be subjected to an easy-adhesion treatment by physical or chemical treatment, or an easy-adhesion layer may be provided.

[0042] 《Surface protective layer》 The surface protective layer contains a binder component and an antiviral agent. The surface protective layer may be formed on the entire surface of the light-transmitting base layer, or may be formed on only a part of the surface. The surface protective layer preferably accounts for 80% or more of the surface area of ​​the light-transmitting base layer, more preferably 90% or more, and most preferably 100%.

[0043] To enhance the antiviral properties, it is preferable that at least a part of the antiviral agent protrudes from the surface of the surface protective layer opposite the light-transmitting base layer (hereinafter referred to as the "surface of the surface protective layer"), as shown in Figures 1 to 3. The distribution of the antiviral agent in the thickness direction of the surface protective layer may be unevenly distributed on the surface of the surface protective layer as shown in FIGS. 1 to 3 , or may be dispersed approximately uniformly in the thickness direction of the surface protective layer, or may be distributed so that the concentration of the antiviral agent increases from the light-transmitting base material layer side toward the surface of the surface protective layer. In the in-plane direction of the surface protective layer, the antiviral agent is preferably distributed throughout the entire surface protective layer. The distribution state in the in-plane direction may be such that there are regions where the antiviral agent is densely concentrated and regions where the antiviral agent is sparsely distributed, but it is preferable that the antiviral agent is distributed approximately uniformly.

[0044] The thickness of the surface protective layer is preferably from 1 μm to 100 μm in consideration of scratch resistance, processability, ease of application to an article, etc. The thickness of the surface protective layer is more preferably from 2 μm to 50 μm, even more preferably from 3 μm to 30 μm, and particularly preferably from 5 μm to 20 μm.

[0045] -Binder component- The binder component is preferably a resin in order to improve processability. Examples of resins used as binder components include thermoplastic resins and cured products of curable resin compositions. Among resins, cured products of curable resin compositions are preferred in order to improve scratch resistance. In this specification, the term "cured product of a curable resin composition" may be abbreviated as "cured product."

[0046] Examples of the cured product of the curable resin composition include a cured product of a thermosetting resin composition or a cured product of an ionizing radiation-curable resin composition. In order to improve the durability of the antiviral activity and production efficiency, a cured product of an ionizing radiation-curable resin composition is preferred.

[0047] A thermosetting resin composition is a composition containing at least a thermosetting resin, and is a resin composition that cures when heated. 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, a curing agent, a curing catalyst, and the like are added to the thermosetting resin composition as needed.

[0048] An ionizing radiation-curable resin composition is a composition containing a compound having an ionizing radiation-curable functional group (hereinafter also referred to as an "ionizing radiation-curable compound"). Representative examples of ionizing radiation-curable resin compositions include electron beam-curable resin compositions and ultraviolet light-curable resin compositions. Among these, electron beam-curable resin compositions are preferred because of their advantages such as high scratch resistance, little odor because no polymerization initiator is required, and resistance to coloration.

[0049] The ionizing radiation-curable functional group is a group that crosslinks and cures upon irradiation with ionizing radiation, and preferred examples thereof include functional groups having an ethylenic double bond such as a (meth)acryloyl group, a vinyl group, and an allyl group. Further examples of the ionizing radiation-curable functional group include an epoxy group and an oxetanyl group. In this specification, the term "(meth)acryloyl group" refers to an acryloyl group or a methcroyl group, and the term "(meth)acrylate" refers to an acrylate or a methacrylate.

[0050] Ionizing radiation refers to electromagnetic waves or charged particle beams that have an energy quantum capable of polymerizing or crosslinking molecules. Ionizing radiation typically includes ultraviolet (UV) rays or electron beams (EB), but also includes other electromagnetic waves such as X-rays and gamma rays, as well as charged particle beams such as alpha rays and ion beams.

[0051] The ionizing radiation-curable compound can be appropriately selected from polymerizable monomers and polymerizable oligomers that have conventionally been used as ionizing radiation-curable resins. The ionizing radiation-curable compound is preferably a compound having two or more ethylenically unsaturated bond groups, and more preferably a polyfunctional (meth)acrylate compound having two or more ethylenically unsaturated bond groups. Either a monomer or an oligomer can be used as the polyfunctional (meth)acrylate compound. Among these, it is preferable to use an oligomer, considering its excellent mechanical properties, flexibility, suitability for application, and the like. In addition to the oligomer, a monomer can also be added to adjust the viscosity.

[0052] For the purpose of achieving scratch resistance, processability, and antiviral properties, the oligomer of the polyfunctional (meth)acrylate compound preferably has a weight-average molecular weight of 1,000 to 10,000, more preferably 2,000 to 6,000. The number of functional groups per oligomer molecule is preferably 2 to 10, more preferably 2 to 6. Among the polyfunctional (meth)acrylate compounds, examples of bifunctional (meth)acrylate monomers include ethylene glycol di(meth)acrylate, bisphenol A tetraethoxydiacrylate, bisphenol A tetrapropoxydiacrylate, and 1,6-hexanediol diacrylate.

[0053] Examples of trifunctional or higher (meth)acrylate monomers 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.

[0054] Examples of the polyfunctional (meth)acrylate oligomer include acrylate polymers such as urethane (meth)acrylate, epoxy (meth)acrylate, polyester (meth)acrylate, and polyether (meth)acrylate. Among these, urethane (meth)acrylate oligomers are preferred for reasons such as ensuring coating film hardness and toughness. The urethane (meth)acrylate oligomer preferably contains a caprolactone-modified urethane (meth)acrylate oligomer. By including a caprolactone-modified urethane (meth)acrylate oligomer, flexibility can be imparted while ensuring coating film hardness and toughness, making it easier to improve processability. The proportion of the caprolactone-modified urethane (meth)acrylate oligomer in the urethane (meth)acrylate oligomer is preferably 10% by mass or more and 90% by mass or less, and more preferably 20% by mass or more and 80% by mass or less. Urethane (meth)acrylates can be obtained, for example, by reacting a polyhydric alcohol and an organic diisocyanate with a hydroxy (meth)acrylate.

[0055] The above ionizing radiation curable compounds can be used alone or in combination of two or more.

[0056] When the ionizing radiation curable compound is an ultraviolet ray curable compound, the ionizing radiation curable resin composition preferably contains additives such as a photopolymerization initiator and a photopolymerization accelerator. The photopolymerization initiator may be one or more selected from acetophenone, benzophenone, α-hydroxyalkylphenone, Michler's ketone, benzoin, benzil dimethyl ketal, benzoyl benzoate, α-acyloxime ester, thioxanthones, and the like. The photopolymerization accelerator can reduce polymerization inhibition caused by air during curing and increase the curing rate, and examples thereof include one or more selected from p-dimethylaminobenzoic acid isoamyl ester, p-dimethylaminobenzoic acid ethyl ester, etc.

[0057] The content of the cured product of the curable resin composition is preferably 50% by mass or more, more preferably 70% by mass or more, even more preferably 90% by mass or more, and most preferably 100% by mass, based on the total amount of the binder component.

[0058] -Antiviral agent- The antiviral pressure-sensitive adhesive sheet of the present disclosure uses an organic antiviral agent as the antiviral agent. The organic antiviral agent can suppress discoloration at an early stage and discoloration over time, making it easier to suppress deterioration of the design of the article. The organic antiviral agent may be used alone or in combination of two or more types.

[0059] Examples of organic antiviral agents include one or more selected from the following (1) to (3). These organic antiviral agents are preferably present in the form of particles in the surface protective layer in order to improve the gas permeability in the surface protective layer and to facilitate increasing the haze value. The shape of the particles is not particularly limited, and examples include spheres, ellipsoids, polyhedrons, and scales. (1) Antiviral agents containing imidazole compounds (2) Antiviral agent containing a styrene polymer derivative compound and an unsaturated carboxylic acid derivative compound (3) Antiviral agents containing styrene resin

[0060] (1) Antiviral agents containing imidazole compounds The imidazole compound is a compound containing an imidazole skeleton as a molecular structural unit. In the present disclosure, among various imidazole compounds, it is preferable to use one that maintains the particle shape within the surface protective layer. As an imidazole compound that easily maintains the particle shape, one that is poorly soluble in water and organic solvents is preferred, and examples thereof include methyl benzimidazol-2-ylcarbamate (also known as carbendazim) and polymerized imidazole compounds. However, care must be taken because even methyl benzimidazol-2-ylcarbamate (also known as carbendazim) and polymerized imidazole compounds may dissolve in certain solvents. For example, for methyl benzimidazol-2-ylcarbamate (also known as carbendazim), it is preferable to use methyl ethyl ketone, ethyl acetate, or the like as a solvent.

[0061] (2) Antiviral agent containing a styrene polymer derivative compound and an unsaturated carboxylic acid derivative compound In the present disclosure, the "antiviral agent comprising a styrene polymer derivative compound and an unsaturated carboxylic acid derivative compound" may be an "antiviral agent comprising a styrene polymer derivative compound and an unsaturated carboxylic acid derivative compound," or may be a "mixture of an antiviral agent comprising a styrene polymer derivative compound and an antiviral agent comprising an unsaturated carboxylic acid derivative compound," or a combination thereof. The constituent components of the styrene polymer derivative compound and the unsaturated carboxylic acid derivative compound preferably have at least one structure selected from the group consisting of styrene, sodium sulfonate, acrylic acid, maleic acid, and fumaric acid, and more preferably have both at least one structure of styrene and sodium sulfonate and at least one structure selected from the group consisting of acrylic acid, maleic acid, and fumaric acid.

[0062] The content ratio of the styrene polymer derivative compound to the unsaturated carboxylic acid derivative compound in the antiviral agent is not limited, but the mass ratio is preferably 30:70 to 70:30, and more preferably 40:60 to 60:40. By achieving this mass ratio, antiviral activity can be more easily exerted against both enveloped and non-enveloped viruses. Note that, when antiviral activity is to be exerted only against enveloped viruses, it is sufficient to contain only the styrene polymer derivative compound.

[0063] The reason why an antiviral agent containing a styrene polymer derivative compound and an unsaturated carboxylic acid derivative compound exhibits antiviral activity is thought to be as follows, although it is not limited to the mechanism speculated below. Influenza viruses invade host cells by binding to sugar chain receptors (the sugar chain ends in neuraminic acid) on the surface of the host cells, but copolymers containing styrene sulfonate have ionic groups similar to those of neuraminic acid, and therefore bind to and capture the viruses instead of the host cells, thereby preventing the viruses from binding to the host cell receptors and exerting their antiviral effects.In addition, unsaturated carboxylic acid derivative compounds generate hydroxyl groups (OH-) when they come into contact with water, and these hydroxyl groups are thought to exert their antiviral effects.

[0064] (3) Antiviral agents containing styrene resin The antiviral agent containing a styrene resin is an antiviral agent that does not contain the unsaturated carboxylic acid derivative compound.

[0065] In the present disclosure, the antiviral agent is preferably in the form of particles. The average particle size of the antiviral agent is preferably 1 μm or more and 10 μm or less, more preferably 2 μm or more and 9 μm or less, and even more preferably 3 μm or more and 7 μm or less. By making the average particle size 1 μm or more, it is possible to improve the stability of the ink for the surface protective layer, to increase the haze value of the surface protective layer, and to increase the gas permeability of the surface protective layer. An average particle size of 10 μm or less can help prevent the antiviral agent from excessively protruding from the surface of the surface protective layer, which can help prevent deterioration in the appearance, scratch resistance, and contamination resistance of the antiviral pressure-sensitive adhesive sheet, as well as help prevent wear on coating device components such as the coating roll and doctor blade. In this specification, the average particle size refers to the mass average value d50 measured in particle size distribution measurement by laser light diffraction method.

[0066] When the average particle size of the antiviral agent is defined as D and the thickness of the surface protective layer is defined as T, D / T is preferably 1.0 or less, more preferably 0.8 or less, and even more preferably 0.6 or less. Setting D / T to 1.0 or less makes it easier to prevent the antiviral agent from excessively protruding from the surface of the surface protective layer. The lower limit of D / T is not particularly limited, but is usually 0.01 or more, and preferably 0.05 or more.

[0067] With regard to the content of the antiviral agent in the surface protective layer, relative to 100 parts by mass of the binder component, the lower limit is preferably 0.5 parts by mass or more, more preferably 1.0 part by mass or more, and more preferably 2.0 parts by mass or more, and the upper limit is preferably 20.0 parts by mass or less, more preferably 15.0 parts by mass or less, more preferably 10.0 parts by mass or less, more preferably 7.5 parts by mass or less, and more preferably 5.0 parts by mass or less. By setting the content of the antiviral agent to 0.5 parts by mass or more, it is possible to easily achieve the desired antiviral performance and increase the haze value of the surface protective layer, and it is also possible to easily increase the gas permeability of the surface protective layer. By setting the content of the antiviral agent to 20.0 parts by mass or less, deterioration in coating film physical properties such as coating film strength and scratch resistance can be easily suppressed, and wear of coating device components such as a coating roll and a doctor blade can be easily suppressed.

[0068] -Other ingredients- The surface protective layer may contain additives such as antioxidants, light stabilizers, ultraviolet absorbers, anti-wear agents, and surface conditioners, as long as the effects of the present disclosure are not impaired.

[0069] Examples of the antioxidant include phenol-based antioxidants, sulfur-based antioxidants, phosphorus-based antioxidants, and amine-based antioxidants. The content of the antioxidant is preferably 0.1 parts by mass or more and 10.0 parts by mass or less, and more preferably 0.5 parts by mass or more and 5.0 parts by mass or less, relative to 100 parts by mass of the binder component. The light stabilizer may be a hindered amine compound, and the content of the light stabilizer is preferably 0.1 parts by mass or more and 10.0 parts by mass or less, and more preferably 1.0 parts by mass or more and 5.0 parts by mass or less, relative to 100 parts by mass of the binder component. Examples of the ultraviolet absorber include benzotriazole-based ultraviolet absorbers, benzophenone-based ultraviolet absorbers, and triazine-based ultraviolet absorbers, with triazine-based ultraviolet absorbers being preferred. The content of the ultraviolet absorber is preferably 0.1 parts by mass or more and 20.0 parts by mass or less, and more preferably 0.5 parts by mass or more and 15.0 parts by mass or less, relative to 100 parts by mass of the binder component. Examples of the anti-wear agent include nanometer-sized particles such as silica and alumina. The average primary particle size of the anti-wear agent is preferably 10 nm or more, and the upper limit is preferably 700 nm or less to improve transparency. The content of the anti-wear agent is preferably 0.1 to 30.0 parts by mass, more preferably 0.3 to 10.0 parts by mass, per 100 parts by mass of the binder component. Examples of the surface conditioner include silicone-based surface conditioners. The content of the surface conditioner is preferably 0.1 parts by mass or more and 10.0 parts by mass or less, and more preferably 0.3 parts by mass or more and 5.0 parts by mass or less, relative to 100 parts by mass of the binder component.

[0070] <<Adhesive layer>> The pressure-sensitive adhesive layer can be formed from a general-purpose pressure-sensitive adhesive resin composition. The pressure-sensitive adhesive layer may be exemplified by the following embodiments (1) to (3). (1) A pressure-sensitive adhesive layer having a substantially flat surface opposite to the light-transmitting base layer. (2) A pressure-sensitive adhesive layer having a groove on the surface opposite to the light-transmitting base layer. (3) Porous adhesive layer

[0071] (1) A pressure-sensitive adhesive layer having a substantially flat surface opposite to the light-transmitting base layer. The antiviral adhesive sheet in Fig. 1 has the adhesive layer of embodiment (1). The adhesive layer of embodiment (1) can be formed, for example, by applying an adhesive resin composition to the surface of the light-transmitting base layer opposite the surface protective layer, drying the composition, and then laminating a separator with a flat surface. The adhesive resin composition preferably contains, for example, a resin having adhesive properties, and further contains, as necessary, a salt, a solvent, and an additive. Embodiments of the adhesive resin composition will be described later. The pressure-sensitive adhesive layer of the embodiment (1) can more easily prevent a decrease in the visibility of the design of the article.

[0072] In embodiment (1), the thickness of the adhesive layer is preferably 5 μm or more and 100 μm or less, more preferably 10 μm or more and 75 μm or less, even more preferably 15 μm or more and 50 μm or less, and even more preferably 15 μm or more and 25 μm or less. By making the thickness of the adhesive layer 5 μm or more, it is possible to easily increase adhesion to an article, and by making the thickness of the adhesive layer 100 μm or less, it is possible to easily prevent a decrease in workability due to an increase in the total thickness of the antiviral adhesive sheet and to easily increase the gas permeability of the antiviral adhesive sheet.

[0073] In the embodiment (1), the surface opposite to the light-transmitting substrate layer being substantially flat means that the arithmetic mean roughness Ra measured in accordance with JIS B0601:2001 with a cutoff value of 0.25 mm is 0.10 μm or less. Ra is preferably 0.05 μm or less.

[0074] (2) A pressure-sensitive adhesive layer having a groove on the surface opposite to the light-transmitting base layer. The antiviral adhesive sheet of Fig. 2 has a pressure-sensitive adhesive layer according to embodiment (2). The pressure-sensitive adhesive layer according to embodiment (2) can be formed, for example, by applying an adhesive resin composition to the surface of a light-transmitting substrate layer opposite the surface protective layer, drying the composition, and then laminating a separator having convex portions on the surface. The pressure-sensitive adhesive layer according to embodiment (2) can also be formed by applying an adhesive resin composition to a separator having convex portions on the surface, drying the composition, and then laminating a light-transmitting substrate layer to the pressure-sensitive adhesive layer. That is, a shape complementary to the shape of the convex portions of the separator can be formed in the pressure-sensitive adhesive layer, forming a pressure-sensitive adhesive layer having grooves. The adhesive resin composition preferably contains, for example, a resin having adhesive properties, and further contains, as necessary, a salt, a solvent, and an additive. Embodiments of the adhesive resin composition will be described later. In the adhesive layer of embodiment (2), gas escapes through the grooves, making it easy to remove air bubbles after alignment, and shortening the application time.

[0075] In embodiment (2), the thickness of the pressure-sensitive adhesive layer is preferably 15 μm or more and 120 μm or less, more preferably 25 μm or more and 100 μm or less, and even more preferably 30 μm or more and 80 μm or less. By making the thickness of the adhesive layer 15 μm or more, it becomes easier to form grooves and increase adhesion to the article, while by making the thickness of the adhesive layer 120 μm or less, it becomes easier to prevent a decrease in workability due to an increase in the total thickness of the antiviral adhesive sheet.

[0076] In the embodiment (2), the grooves are preferably formed across the adhesive layer to facilitate gas escape. Figures 4(a) and (b) show embodiments of groove patterns. The diagonal lines in the figures indicate groove patterns. The groove pattern is not limited to the patterns in the embodiments of Figures 4(a) and (b), as long as it allows gas to escape easily.

[0077] The width of the groove is not particularly limited, but is preferably 0.05 mm or more and 1 mm or less. The depth of the groove is not particularly limited, but is preferably 2% to 50% of the thickness of the adhesive layer. The ratio of the area of ​​the grooves to the total area of ​​the adhesive layer is not particularly limited, but is preferably 10% or more and 75% or less.

[0078] (3) Porous adhesive layer The antiviral adhesive sheet of FIG. 3 has an adhesive layer of embodiment (3). The pressure-sensitive adhesive layer of embodiment (3) allows gas to escape through the holes, making it easy to remove air bubbles after alignment and shortening the application time. In addition, the pressure-sensitive adhesive layer of embodiment (3) can easily increase the haze value of the laminate.

[0079] The porous adhesive layer is a layer that is composed of pores and a resin portion formed by the adhesive that forms the adhesive layer. Pores in the pressure-sensitive adhesive layer may have, for example, the following forms: (i) spherical pores 41 and (ii) concave openings 42, as shown in Fig. 3. The pores in Fig. 3 are a combination of (i) spherical pores 41 and (ii) concave openings 42. The (ii) concave openings 42 are formed on the surface of the pressure-sensitive adhesive layer, i.e., at the interface between the light-transmitting base layer and the pressure-sensitive adhesive layer, and at the interface between the pressure-sensitive adhesive layer and the separator. The pressure-sensitive adhesive layer having the above-described configuration is prone to thickness unevenness, but by increasing the haze value of the laminate, thickness unevenness of the pressure-sensitive adhesive layer can be made less visible, making it easier to improve the appearance.

[0080] The porous pressure-sensitive adhesive layer can be formed, for example, from a pressure-sensitive adhesive resin composition containing bubbles. When the pressure-sensitive adhesive layer is formed from a pressure-sensitive adhesive resin composition containing bubbles, the (i) spherical pores are formed when the bubbles remain as pores, and the (ii) concave openings are formed when the bubbles present on one surface of the pressure-sensitive adhesive layer and its vicinity, and on the other surface of the pressure-sensitive adhesive layer and its vicinity, burst. In Fig. 3, the surface of one side of the pressure-sensitive adhesive layer and its vicinity means the interface between the light-transmitting substrate layer 20 and the pressure-sensitive adhesive layer 40 and its vicinity. In Fig. 3, the surface of the other side of the pressure-sensitive adhesive layer and its vicinity means the interface between the pressure-sensitive adhesive layer 40 and the separator 50 and its vicinity. In the pressure-sensitive adhesive sheet of the present disclosure, the pores preferably have the above-mentioned (ii) concave openings, which can more easily prevent air bubbles from being mixed in when the antiviral pressure-sensitive adhesive sheet is attached.

[0081] (ii) The recessed openings are preferably evenly distributed on the surface of the pressure-sensitive adhesive layer facing the light-transmitting base layer and on the other surface of the pressure-sensitive adhesive layer. Having the recessed openings evenly distributed on both surfaces can more easily prevent air bubbles from being mixed in when the antiviral pressure-sensitive adhesive sheet is attached. Furthermore, having the recessed openings evenly distributed on both surfaces can make thickness variations in the porous pressure-sensitive adhesive layer less noticeable.

[0082] Regarding the above item (ii) that the recessed openings are evenly distributed, more specifically, it is preferable that the following conditions be satisfied. The average diameter of the concave openings on the surface of the pressure-sensitive adhesive layer on the side of the light-transmitting base layer is defined as D ave 1. The average diameter of the concave openings on the surface of the other side of the adhesive layer is D ave 2, it is preferable that the following condition (1) is satisfied. |D ave 1-D ave 2| / D ave 2≦0.5 (1) Regarding condition (1), |D ave 1-D ave 2| / D aveIt is more preferable that |D ave 1-D ave 2| / D ave It is more preferable that 2≦0.15.

[0083] When the pores in the pressure-sensitive adhesive layer have the above-mentioned (i) spherical pores, the average diameter D of the spherical pores ave 3 preferably satisfies the following condition (2). D ave 1≦D ave 3≦D ave 2 or D ave 2≦D ave 3≦D ave 1(2)

[0084] Regarding the above conditions (1) and (2), the average diameter of the openings, etc., D ave 1. D ave 2 and D ave It is practically impossible to obtain the average for all concave openings and spherical voids in the measurement of 3. Therefore, in this specification, the diameters of three concave openings and three spherical voids are measured in descending order of diameter within an observation area of ​​1500 μm × 1100 μm, and the average value is used as the average diameter of each opening.

[0085] When the (ii) concave openings among the pores in the PSA layer satisfy condition (1), the physical properties of the PSA layer can be made more uniform, which makes it easier to achieve more uniform adhesiveness over the entire surface of the PSA layer, thereby facilitating better workability when attaching the antiviral PSA sheet to an article. Furthermore, among the pores in the pressure-sensitive adhesive layer, (i) spherical pores satisfying condition (2) also make the physical properties of the pressure-sensitive adhesive layer more uniform, as with condition (1), and therefore facilitate improved workability when attaching the antiviral pressure-sensitive adhesive sheet to an article.

[0086] The average diameters of the (i) spherical pores and (ii) recessed openings are not particularly limited as long as they satisfy the above conditions (1) and (2), and although it is difficult to generalize because they vary depending on the thickness of the pressure-sensitive adhesive layer, they are usually 1 μm or more and 300 μm or less. In consideration of improving workability, the lower limit is preferably 3 μm or more, more preferably 5 μm or more, and even more preferably 10 μm or more, and the upper limit is preferably 250 μm or less, more preferably 200 μm or less, and even more preferably 100 μm or less.

[0087] In consideration of improving workability, the density of the porous adhesive layer is preferably 0.1 g / cm as the lower limit. 3 More preferably, 0.2 g / cm 3 More preferably, 0.3 g / cm 3 The upper limit is preferably 0.8 g / cm 3 or less, more preferably 0.7 g / cm 3 More preferably 0.6 g / cm or less 3 The following is the result.

[0088] The adhesion weight of the porous adhesive layer is 13 g / m 2 More than 70g / m 2 Preferably, it is 15 g / m or less. 2 More than 60g / m 2 More preferably, it is 20 g / m or less. 2 More than 50g / m 2 It is more preferable that the adhesion amount of the pressure-sensitive adhesive layer is as follows: In this specification, the adhesion amount of the pressure-sensitive adhesive layer means the adhesion amount of the solid content. The adhesion weight of the porous adhesive layer is 13 g / m 2 By setting the adhesion amount of the pressure-sensitive adhesive layer at 13 g / m or more, it is possible to easily increase the haze value of the laminate and also to easily increase the adhesion to the article. 2 By doing so, it becomes easier to form the recessed opening (ii) above. The adhesion weight of the porous adhesive layer is 70g / m 2 By setting the thickness to the following value, it becomes easier to suppress a decrease in workability due to an increase in the total thickness of the antiviral pressure-sensitive adhesive sheet.

[0089] -Adhesive resin composition- The resin composition used to form the pressure-sensitive adhesive layer (sometimes referred to herein as "adhesive resin composition") preferably contains, for example, a resin having adhesive properties, and further contains a salt, a solvent, and / or an additive as necessary. For a porous pressure-sensitive adhesive layer, an adhesive resin composition containing bubbles is preferred.

[0090] Examples of adhesive resins include various rubber-based resins such as urethane rubber, styrene butadiene polymer (styrene butadiene rubber), polyisoprene, natural rubber, acrylonitrile butadiene rubber, ethylene propylene rubber (EPR), ethylene propylene diene terpolymer rubber (EPDM), polynorbornene, polybutadiene, nitrile rubber, chloroprene rubber, butyl rubber, halogenated butyl rubber, ethylene-vinyl acetate rubber (EVA), silicone rubber, fluororubber, ethylene acrylic rubber, polyester elastomer, epichlorohydrin rubber, and polysulfide rubber; various adhesive resins such as acrylic polymer, polyurethane, chlorinated polyethylene, polyethylene, polystyrene, polyimide, polyvinyl chloride, and polypropylene; and various thermoplastic elastomers such as polyolefin, polyurethane, polyester, polyamide, and polystyrene. Resin compositions containing these resins may be cured products of the resin compositions. The cured products of the resin compositions may be one-component cured products or two-component cured products. Among these resins, acrylic resins with good weather resistance are preferred. That is, the pressure-sensitive adhesive layer preferably contains an acrylic resin composition, more preferably a cured product of the acrylic resin composition. The cured product of the acrylic resin composition may be a one-component cured product or a two-component cured product.

[0091] The weight-average molecular weight of the adhesive resin is preferably 250,000 or more, more preferably 260,000 or more, and even more preferably 270,000 or more, and is preferably 12,000,000 or less, more preferably 10,000,000 or less, and even more preferably 8,000,000 or less as the lower limit. When the weight-average molecular weight of the resin is within the above range, it is easy to obtain appropriate adhesion. Furthermore, when the weight-average molecular weight of the resin is within the above range, it is easy to form a porous adhesive layer. The weight average molecular weight in this specification is an average molecular weight measured by GPC analysis and converted into standard polystyrene.

[0092] As the salt, various salts such as inorganic salts and organic salts can be used. Preferred examples of inorganic salts include sulfates, sulfites, carbonates, hydrogencarbonates, nitrates, nitrites, chlorates, hypochlorites, chlorites, perchlorates, permanganates, chromates, phosphates, hydrogenphosphates, chlorides, bromides, and iodides of metals such as sodium, magnesium, aluminum, potassium, calcium, iron, nickel, copper, zinc, silver, lead, tin, and barium; and also ammonium sulfate, ammonium carbonate, ammonium hydrogencarbonate, ammonium nitrate, ammonium chloride, and potassium aluminum sulfate (alum).

[0093] Examples of organic salts include C1-18 carboxylic acid salts such as formates, acetates, propanoates, butanoates, and pentanoates of metals such as sodium, magnesium, aluminum, potassium, calcium, iron, nickel, copper, zinc, silver, lead, tin, and barium; and ammonium salts of C1-18 carboxylic acids. In addition to the above, examples of the organic salt include ammonium-based, pyridinium-based, imidazolium-based, pyrrolidinium-based, choline-based, phosphonium-based, sulfonium-based, and pyrazolium-based ionic liquids.

[0094] In the adhesive resin composition, the salt content per 100 parts by mass of the adhesive resin is preferably 1 part by mass or more, more preferably 1.3 parts by mass or more, even more preferably 3 parts by mass or more, even more preferably 5 parts by mass or more, and particularly preferably 6.0 parts by mass or more, and the upper limit is preferably 80 parts by mass or less, more preferably 50 parts by mass or less, even more preferably 25 parts by mass or less, even more preferably 20 parts by mass or less, and particularly preferably 10 parts by mass or less.

[0095] The adhesive composition may contain a solvent in consideration of ease of application, that is, ease of forming an adhesive layer. The solvent may be either water or an organic solvent.

[0096] The content of the solvent in the adhesive resin composition is preferably 10% by mass or more, more preferably 20% by mass or more, even more preferably 30% by mass or more, and even more preferably 40% by mass or more, relative to the total amount of the adhesive resin and solvent, and the upper limit is preferably 80% by mass or less, more preferably 70% by mass or less, and even more preferably 60% by mass or less.

[0097] Other additives can be appropriately selected and used depending on the desired performance, and examples thereof include surfactants, foam stabilizers, foaming agents (foaming agents), foaming aids, foam stabilizers, antifoam agents (foam suppressors, foam breakers), emulsifiers, dispersants, wetting agents, propellants, thickeners, curing agents, crosslinking agents, polymerization initiators, colorants (pigments, dyes), plasticizers, adhesives, fillers, antifouling agents, viscoelasticity modifiers, rust inhibitors, slip agents, driers, stabilizers, ultraviolet absorbers, antibacterial agents, antifungal agents, and flame retardants. When a porous adhesive layer is to be formed, it is preferable to use a surfactant, a foam stabilizer, a foaming agent (foaming agent), a foaming assistant, or a foam stabilizer so that the adhesive resin composition can easily contain bubbles.

[0098] The content of other additives can be set appropriately depending on the desired performance and is not particularly limited, but is preferably 0.1 parts by mass or more, more preferably 0.5 parts by mass or more, relative to 100 parts by mass of the adhesive resin, and the upper limit is preferably 10 parts by mass or less, more preferably 8.5 parts by mass or less, even more preferably 5 parts by mass or less, and even more preferably 1.9 parts by mass or less.

[0099] As described above, the adhesive resin composition for forming the porous adhesive layer is preferably an adhesive resin composition containing bubbles. The method for obtaining a composition containing bubbles is not particularly limited, but can be, for example, as follows. First, the adhesive resin and solvent are used to prepare a form such as a colloid, suspension, sol, or emulsion, and then a salt and, if necessary, additives are added to prepare a stock solution. By stirring the stock solution while supplying nitrogen gas, bubbles can be incorporated into the stock solution, and an adhesive resin composition containing bubbles can be prepared.

[0100] When nitrogen gas is supplied, the density of the bubble-containing adhesive resin composition can be adjusted by adjusting the amount of nitrogen gas supplied, and by adjusting the density of the bubble-containing adhesive resin composition, the adhesive layer formed using the composition can more easily satisfy the above-mentioned pore shape, density, etc.

[0101] The density of the adhesive resin composition containing bubbles is preferably 0.1 g / cm 3 More preferably, 0.2 g / cm 3 More preferably, 0.3 g / cm 3 The upper limit is preferably 0.8 g / cm 3 or less, more preferably 0.7 g / cm 3 More preferably 0.6 g / cm or less 3 The following is the result.

[0102] The pressure-sensitive adhesive layer may contain additives such as a light stabilizer and an ultraviolet absorber.

[0103] <Primer layer> The antiviral pressure-sensitive adhesive sheet may have a primer layer to improve interlayer adhesion. The primer layer can be formed, for example, between the light-transmitting substrate layer and the surface protective layer.

[0104] The primer layer preferably contains a binder resin. Examples of binder resins include one or more selected from urethane resins, acrylic polyol resins, acrylic resins, ester resins, amide resins, butyral resins, styrene resins, urethane-acrylic copolymers, polycarbonate-based urethane-acrylic copolymers (urethane-acrylic copolymers derived from polymers having carbonate bonds in the polymer main chain and two or more hydroxyl groups), vinyl chloride-vinyl acetate copolymer resins, vinyl chloride-vinyl acetate-acrylic copolymer resins, chlorinated propylene resins, nitrocellulose resins, and cellulose acetate resins. The binder resin may be a resin obtained by crosslinking and curing the above-mentioned resins with a curing agent such as an isocyanate-based curing agent or an epoxy-based curing agent. Among these, a polyol-based resin such as an acrylic polyol resin crosslinked and cured with an isocyanate-based curing agent is preferred, and an acrylic polyol resin crosslinked and cured with an isocyanate-based curing agent is more preferred.

[0105] The primer layer preferably contains an ultraviolet absorber and / or a light stabilizer to further improve weather resistance. General-purpose ultraviolet absorbers and light stabilizers can be used.

[0106] 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.

[0107] Among the layers constituting the laminate, a laminate obtained by laminating layers other than the pressure-sensitive adhesive layer preferably has an internal haze value of 50% or more, more preferably 60% or more. When the pressure-sensitive adhesive layer is a porous layer, by setting the internal haze value within the above range, thickness unevenness of the porous pressure-sensitive adhesive layer can be made less visible. In order to improve the visibility of the article, the internal haze is preferably 80% or less, and more preferably 70% or less. The internal haze value can be measured by, for example, laminating a transparent substrate on the front and back surfaces of a laminate obtained by laminating layers other than the pressure-sensitive adhesive layer among the layers constituting the laminate, thereby filling in the surface irregularities on the front and back surfaces.

[0108] <separator> The antiviral adhesive sheet preferably has a separator on the laminate, with the adhesive layer and the separator being in contact with each other. By having the separator in the antiviral adhesive sheet, the handleability of the antiviral adhesive sheet can be improved.

[0109] The material of the separator is not particularly limited, but may be a plastic film such as polyethylene terephthalate, paper, or nonwoven fabric. The thickness of the separator is preferably 10 μm or more and 200 μm or less, and more preferably 50 μm or more and 150 μm or less. When the thickness of the separator is in this range, workability when peeling off the separator can be improved. The separator may have a surface that has been subjected to a release treatment with a release agent such as a silicone-based release agent.

[0110] The antiviral adhesive sheet of the present disclosure may have a protective film having low adhesiveness on the surface protective layer opposite the light-transmitting base layer. The protective film serves to protect the surface protective layer during distribution of the antiviral adhesive sheet. The protective film is peeled off from the surface protective layer before and after the antiviral adhesive sheet is attached to an article.

[0111] <Application> The antiviral pressure-sensitive adhesive sheet of the present disclosure can be used in the following applications (1) to (12). (1) Surface materials for interior walls, floors, ceilings, etc. of buildings such as houses, offices, stores, hospitals, and clinics. (2) Surface materials for exterior parts such as exterior walls, roofs, eaves ceilings, door pockets, etc. of buildings such as houses, offices, stores, hospitals, and clinics. (3) Surface materials for building fixtures such as windows, window frames, doors, and door frames (interior or exterior parts); surface materials for fixture accessories (handles, etc.); surface materials for building fixture jigs. (4) Surface materials for fixtures such as handrails, waist walls, moldings, thresholds, lintels, and top boards. (5) Surface materials for outdoor (exterior) parts such as fences, gates, drying rack pillars and handrails. (6) Surface materials for furniture such as chests of drawers, desks, chairs, cupboards, kitchen sinks, etc.; surface materials for furniture accessories (handles, etc.); surface materials for furniture fixtures. (7) Surface materials for the housings of various home appliances such as television receivers, radio receivers, refrigerators, microwave ovens, washing machines, electric fans, and air conditioners; surface materials for accessories of home appliances (handles, switches, touch panels, etc.); surface materials for fixtures of home appliances. (8) Surface materials for office automation equipment such as electronic copying machines, facsimiles, printers, personal computers, and other computing equipment; surface materials for the housings of various office automation equipment such as ATM machines at financial institutions such as banks and post offices; surface materials for accessories of various office automation equipment (keyboards, touch panels, etc.); surface materials for jigs of various office automation equipment. (9) Surface materials for the interior or exterior parts (walls, floors, ceilings, handrails, supports, control panels, levers, handles, steering wheels, and other control equipment) of vehicles such as automobiles, railway cars, ships, and aircraft. (10) Partitions in various buildings; shielding plates or curtains to prevent droplet infection of viruses at counters, accounting counters, etc. of stores, offices, government offices, etc.; face protection equipment such as protective masks (face guards) and protective glasses (goggles); or surface materials for these. (11) Business forms such as slips; bankbooks; cards such as cash cards, credit cards, and point cards of financial institutions; or the surface materials of these. (12) Glass, resin, etc. bottles; metal cans; resin soft packaging materials such as resin retort containers; packaging materials such as various tubes; or the surface materials of these.

[0112] [Items with antiviral adhesive sheets] An article with an antiviral adhesive sheet according to the present disclosure is formed by attaching the above-described antiviral adhesive sheet according to the present disclosure onto an article.

[0113] Examples of the article include the articles exemplified for use with the antiviral adhesive sheet. An article with an antiviral adhesive sheet according to the present disclosure preferably contains a resin. Articles containing a resin may release gas over time. The antiviral adhesive sheet constituting the article with an antiviral adhesive sheet according to the present disclosure has a light-transmitting substrate layer made of a polypropylene resin substrate, and therefore has good gas permeability. Therefore, even if gas is generated from the article over time, accumulation of air bubbles between the article and the antiviral adhesive sheet can be suppressed, making it easier to suppress deterioration of the design of the article.

[0114] The present disclosure provides, for example, the following [1] to

[12] . [1] An antiviral pressure-sensitive adhesive sheet comprising a laminate having, in this order, a surface protective layer containing a binder component and an antiviral agent, a light-transmitting substrate layer, and a pressure-sensitive adhesive layer, the light-transmitting substrate layer contains a polypropylene-based resin substrate, An antiviral adhesive sheet, wherein the antiviral agent is an organic antiviral agent. [2] The antiviral adhesive sheet according to [1], wherein the content of the antiviral agent per 100 parts by mass of the binder component is 0.5 parts by mass or more and 20.0 parts by mass or less. [3] The antiviral adhesive sheet according to [1] or [2], wherein the average particle size of the antiviral agent is 1 μm or more and 10 μm or less. [4] The antiviral pressure-sensitive adhesive sheet according to any one of [1] to [3], wherein the organic antiviral agent is one or more selected from the following (1) to (3): (1) Antiviral agents containing imidazole compounds (2) Antiviral agent containing a styrene polymer derivative compound and an unsaturated carboxylic acid derivative compound (3) Antiviral agents containing styrene resin [5] The antiviral pressure-sensitive adhesive sheet according to any one of [1] to [4], wherein the polypropylene resin substrate has a thickness of 5 μm or more and 250 μm or less. [6] The antiviral pressure-sensitive adhesive sheet according to any one of [1] to [5], wherein the pressure-sensitive adhesive layer has a substantially flat surface opposite to the light-transmitting base layer. [7] The antiviral pressure-sensitive adhesive sheet according to any one of [1] to [5], wherein the pressure-sensitive adhesive layer has a groove on the surface opposite to the light-transmitting base layer. [8] The antiviral adhesive sheet according to any one of [1] to [5], wherein the adhesive layer is a porous layer. [9] The antiviral pressure-sensitive adhesive sheet according to any one of [1] to [8], wherein the laminate has a total light transmittance of 80% or more as measured in accordance with JIS K7361-1:1997.

[10] The antiviral pressure-sensitive adhesive sheet according to any one of [1] to [9], which has a separator on the laminate, and the pressure-sensitive adhesive layer and the separator are in contact with each other.

[11] An article with an antiviral adhesive sheet, comprising the antiviral adhesive sheet according to any one of [1] to

[10] attached to an article.

[12] An article with the antiviral adhesive sheet according to

[11] , wherein the article contains a resin. [Example]

[0115] Next, the present disclosure will be described in more detail by way of examples, but the present disclosure is not limited to these examples in any way.

[0116] 1. Evaluation The antiviral adhesive sheets of the Examples and Comparative Examples were subjected to the following measurements and evaluations. The measurements and evaluations were carried out in an atmosphere with a temperature of 23°C ± 5°C and a relative humidity of 40% to 65%. The results are shown in Table 1.

[0117] 1-1. Suppression of bubbles caused by outgassing from the substrate The separator was removed from the antiviral adhesive sheets of the Examples and Comparative Examples and attached to a 2 mm thick transparent acrylic plate (50 mm long x 50 mm wide) to obtain an article with an antiviral adhesive sheet. The articles with the antiviral adhesive sheet were left in a 60°C environment for 48 hours, and then visually evaluated by a healthy person in their 30s in a bright room environment according to the following criteria. A: No air bubbles were observed between the acrylic plate and the adhesive layer. C: Air bubbles can be seen between the acrylic plate and the adhesive layer.

[0118] 1-2.Discoloration over time The total light transmittance of the antiviral adhesive sheets of the Examples and Comparative Examples was measured immediately after production. The measurement was performed in an atmosphere with a temperature of 23°C ± 5°C and a relative humidity of 40% to 65%. The measurement device used was a direct-reading haze meter manufactured by Toyo Seiki Seisakusho. Next, the antiviral adhesive sheets of the examples and comparative examples were left in an environment of 40°C and 90% relative humidity for one week, and then the total light transmittance was measured. When the antiviral adhesive sheet discolors, the transmittance at specific wavelengths decreases, and therefore the total light transmittance also decreases. Therefore, discoloration over time can be evaluated based on the total light transmittance. The difference between the measured value immediately after production and the measured value after leaving it for one week was rated as "A" if it was 0% or more but less than 0.5%, "B" if the difference was 0.5% or more but less than 1%, and "C" if the difference was 1% or more.

[0119] 1-3. Visibility of the lower part The separator was peeled off from the antiviral adhesive sheets of the Examples and Comparative Examples, and the sheets were attached to a wood-grain pattern decorative sheet, taking care not to trap any large air bubbles. Immediately after attachment, a healthy person in their 30s visually evaluated the sheets in a brightly lit room according to the following criteria. A: The wood grain pattern is clearly visible. B: The wood grain pattern is slightly blurred but still visible. C: The wood grain pattern is barely visible.

[0120] 1-4. Adhesion The separator was removed from the antiviral adhesive sheets of the Examples and Comparative Examples and attached to a 40 mm diameter vinyl chloride rod to obtain an article with an antiviral adhesive sheet. The articles with the antiviral adhesive sheet were left in an environment of 23°C ± 5°C and a relative humidity of 40% to 65% for 48 hours, and then visually evaluated by a healthy person in their 30s in a bright room according to the following criteria. A: The stick and the antiviral adhesive sheet are in good contact. C: Part of the antiviral adhesive sheet is floating from the stick.

[0121] 1-5. Haze value and total light transmittance The haze value and total light transmittance of the laminate constituting the antiviral pressure-sensitive adhesive sheet of each of the examples and comparative examples were measured using a direct-reading haze meter manufactured by Toyo Seiki Seisakusho, Ltd.

[0122] 1-6. Antiviral activity value The antiviral activity values ​​of the antiviral adhesive sheets of the examples were measured according to the "Method for measuring antiviral activity value" in the main text of the specification. The antiviral activity values ​​were measured against influenza virus. Antiviral activity values ​​of 2 or more were rated "A," and antiviral activity values ​​of less than 2 were rated "C."

[0123] 2. Material Preparation An ink for a surface protective layer and a composition for a pressure-sensitive adhesive layer having the following compositions were prepared. <Surface protection layer ink 1> Multifunctional urethane acrylate oligomer 70 parts by mass Bifunctional urethane acrylate oligomer 30 parts by mass Antiviral agent 3 parts by weight (Antiviral agent containing the following particles A1 and A2 in a mass ratio of 1:1, average particle diameter 5 μm) (Particle A1: Particles containing a styrene polymer derivative compound, a polystyrene sulfonic acid derivative manufactured by Shima Trading Co., Ltd., product name "VERSA-TL3") (Particles A2: particles containing an unsaturated carboxylic acid derivative compound, particles formed by drying BYK's solvent-based unsaturated polycarboxylic acid polymer, product name "BYK-P104") Solvent (ethyl acetate) 40 parts by weight

[0124] <Surface protection layer ink 2> Multifunctional urethane acrylate oligomer 70 parts by mass Bifunctional urethane acrylate oligomer 30 parts by mass Antiviral agent 3 parts by weight (An inorganic antiviral agent containing silver ions in the carrier, product number "PG711" manufactured by Koa Glass Co., Ltd., the carrier is glass, average particle size 3 μm) Solvent (ethyl acetate) 40 parts by weight

[0125] <Adhesive resin composition 1> Acrylic adhesive (product name "RC-910W" manufactured by Nichiei Shinka Co., Ltd.)

[0126] <Adhesive resin composition 2> Acrylic adhesive (product name "RC-915" manufactured by Nichiei Shinka Co., Ltd.)

[0127] <Preparation of Adhesive Resin Composition 3 (Adhesive Resin Composition Containing Bubbles)> An acrylic one-component curing adhesive (trade name "Powertight WQ-1000" manufactured by Kansai Paint Co., Ltd.) was stirred with a stirrer to prepare an adhesive resin composition containing bubbles. The density of the obtained adhesive resin composition containing bubbles was 0.4 g / cm. 3 It was.

[0128] 3. Preparation of antiviral adhesive sheets [Example 1] The ink 1 for surface protection layer was applied by roll coating to one side of a light-transmitting substrate layer (a substrate layer having a particle-containing resin layer on one side of an 80 μm-thick polypropylene resin substrate) and dried at 60°C for 1 minute. The resin component was then cured by irradiating with an electron beam (accelerating voltage: 175 kV, 5 Mrad (50 kGy)) to form a 10 μm-thick surface protection layer. Next, adhesive resin composition 1 was applied to the surface of the light-transmitting base layer opposite to the surface on which the surface protective layer was formed, and dried to form a 20 μm-thick adhesive layer. In this way, a laminate having the surface protective layer, light-transmitting base layer, and adhesive layer in this order was obtained. Next, a separator (a polyethylene terephthalate film with a thickness of 75 μm) was laminated onto the surface of the laminate facing the pressure-sensitive adhesive layer, thereby obtaining the antiviral pressure-sensitive adhesive sheet of Example 1. In the antiviral pressure-sensitive adhesive sheet of Example 1, the surface of the pressure-sensitive adhesive layer opposite the light-transmitting base layer is approximately flat.

[0129] [Example 2] A surface protective layer was formed in the same manner as in Example 1 using the same light-transmitting substrate layer as in Example 1. Next, adhesive resin composition 2 was applied to the surface of the light-transmitting base layer opposite to the surface on which the surface protective layer was formed, and dried to form a 35 μm-thick adhesive layer. In this way, a laminate having the surface protective layer, light-transmitting base layer, and adhesive layer in this order was obtained. Next, a paper separator having convex portions on its surface was laminated onto the surface of the laminate facing the adhesive layer, to obtain an antiviral adhesive sheet of Example 2. The antiviral adhesive sheet of Example 2 has grooves on the surface of the adhesive layer opposite the light-transmitting base layer.

[0130] [Example 3] A surface protective layer was formed in the same manner as in Example 1 using the same light-transmitting substrate layer as in Example 1. Next, the bubble-containing adhesive resin composition 3 was applied to the surface of the light-transmitting base layer opposite to the surface on which the surface protective layer was formed, and dried at 100°C for 2 minutes to form a porous adhesive layer. The adhesion amount of the adhesive layer after drying was 30 g / m 2 The density of the formed adhesive layer was 0.4 g / cm 3 In this way, a laminate having the surface protective layer, the light-transmitting substrate layer, and the pressure-sensitive adhesive layer in this order was obtained. Next, a separator (a polyethylene terephthalate film with a thickness of 75 μm) was laminated onto the surface of the laminate facing the adhesive layer, thereby obtaining an antiviral adhesive sheet of Example 3. In the antiviral adhesive sheet of Example 3, the adhesive layer is a porous layer.

[0131] [Comparative Example 1] An antiviral adhesive sheet of Comparative Example 1 was obtained in the same manner as in Example 1, except that the light-transmitting base layer was changed to the light-transmitting base layer described below and Ink 1 for surface protective layer was changed to Ink 2 for surface protective layer. Light-transmitting substrate layer of Comparative Example 1: a single layer of polyethylene terephthalate substrate having a thickness of 75 μm.

[0132] Comparative Example 2 An antiviral adhesive sheet of Comparative Example 2 was obtained in the same manner as in Example 2, except that the light-transmitting base layer was changed to the light-transmitting base layer used in Comparative Example 1 and the ink 1 for surface protective layer was changed to the ink 2 for surface protective layer.

[0133] Comparative Example 3 An antiviral pressure-sensitive adhesive sheet of Comparative Example 3 was obtained in the same manner as in Example 2, except that the light-transmitting base layer was changed to the light-transmitting base layer used in Comparative Example 1.

[0134] Comparative Example 4 An antiviral adhesive sheet of Comparative Example 4 was obtained in the same manner as in Example 1, except that Ink 1 for surface protective layer was changed to Ink 2 for surface protective layer.

[0135] [Table 1]

[0136] As shown in Table 1, the antiviral adhesive sheets of Examples 1 to 3 did not show any bubbles due to outgassing and were able to suppress discoloration over time, demonstrating that they could suppress deterioration in the design of articles. Furthermore, the antiviral adhesive sheets of Examples 1 to 3 were confirmed to have stable adhesion to articles. [Explanation of symbols]

[0137] 10: Laminate 20: Light-transparent base material layer 30: Surface protective layer 31: Binder component 32: Antiviral agent 40: Adhesive layer 41: Pore (spherical hole) 42: Pore (concave opening) 50: Separator 100: Antiviral adhesive sheet

Claims

1. An antiviral pressure-sensitive adhesive sheet comprising a laminate having, in this order, a surface protective layer containing a binder component and an antiviral agent, a light-transmitting base layer, and a pressure-sensitive adhesive layer, the light-transmitting substrate layer contains a polypropylene-based resin substrate, the pressure-sensitive adhesive layer is a porous layer, An antiviral adhesive sheet, wherein the antiviral agent is an organic antiviral agent.

2. 2. The antiviral pressure-sensitive adhesive sheet according to claim 1, wherein a content of the antiviral agent relative to 100 parts by mass of the binder component is 0.5 parts by mass or more and 20.0 parts by mass or less.

3. The antiviral pressure-sensitive adhesive sheet according to claim 1 or 2, wherein the average particle size of the antiviral agent is 1 μm or more and 10 μm or less.

4. The antiviral pressure-sensitive adhesive sheet according to any one of claims 1 to 3, wherein the organic antiviral agent is one or more selected from the following (1) to (3): (1) Antiviral agent containing an imidazole compound (2) Antiviral agent containing a styrene polymer derivative compound and an unsaturated carboxylic acid derivative compound (3) Antiviral agents containing styrene resins

5. The antiviral pressure-sensitive adhesive sheet according to any one of claims 1 to 4, wherein the polypropylene resin substrate has a thickness of 5 µm or more and 250 µm or less.

6. The antiviral pressure-sensitive adhesive sheet according to any one of claims 1 to 5, wherein the laminate has a total light transmittance of 80% or more as measured in accordance with JIS K7361-1:1997.

7. The antiviral pressure-sensitive adhesive sheet according to any one of claims 1 to 6, further comprising a separator on the laminate, the pressure-sensitive adhesive layer being in contact with the separator.

8. An article with an antiviral adhesive sheet, comprising the antiviral adhesive sheet according to any one of claims 1 to 7 attached to an article.

9. The article with the antiviral adhesive sheet according to claim 8 , wherein the article contains a resin.

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