JP2024034272A - Antiviral sheet-like article - Google Patents

Abstract

To provide an antiviral sheet-like article that has enhanced antiviral properties without compromising its aesthetic quality.SOLUTION: The present invention provides an antiviral sheet-like article comprising at least a substrate layer and a surface-treated layer, where the surface-treated layer comprises a resin component, an antiviral agent composed of an inorganic filler with a sulfonic acid-based surfactant carried thereon, and a nonionic surfactant.SELECTED DRAWING: None

Description

The present invention relates to an antiviral sheet material having excellent antiviral properties and appearance.

Until now, viral diseases caused by severe respiratory tract infection (SARS) virus, avian influenza virus, foot-and-mouth disease virus, new type influenza virus, etc. have become social problems one after another. Recently, the new coronavirus has been raging around the world, and antiviral properties are expected not only to be prepared for a pandemic (explosion of infection) caused by the virus, but also for interior materials, construction materials, and daily necessities. It's coming.

In particular, sheet-like materials with antiviral properties are in high demand because they can be applied to various daily necessities, buildings, vehicles, etc. There are two known methods of imparting antiviral properties to sheet materials: one is to knead an antiviral agent directly into the sheet material, and the other is to apply a paint containing an antiviral agent to the surface of the sheet material. ing. When directly incorporating an antiviral agent, there are problems such as increased cost and decreased productivity. On the other hand, when applying a paint containing an antiviral agent, such problems can be reduced.
Patent Document 1 discloses a decorative sheet for interior use having antiviral properties in which a silver-based inorganic additive or a zinc-based inorganic additive is blended into a coating resin for resurfacing the decorative sheet.

Japanese Patent Application Publication No. 2015-80887

Coating agents containing antiviral agents containing such metals may react with the resin components in the coating agent or the components of the substrate when applied to the substrate, resulting in discoloration. The appearance of the product could be damaged. In particular, construction materials and daily necessities often have a design on their surfaces, and it is required to provide antiviral properties without impairing the design.

The present invention solves the above problems, and aims to provide an antiviral sheet material that has excellent antiviral properties and does not impair its appearance.

The means used by the present invention to solve the above problems includes at least a base material layer and a surface treatment layer, and the surface treatment layer is an inorganic filler on which a resin component and a sulfonic acid surfactant are supported. This is an antiviral sheet-like material containing an antiviral agent consisting of the following and a nonionic surfactant.
Furthermore, the inorganic filler is calcium carbonate or talc that has not been hydrophobically treated, or the resin component is made of an acrylic resin or a vinyl chloride resin, or the sulfonic acid surfactant and the inorganic filler are combined. The weight ratio is 1:20 to 1:1, or the content of the antiviral agent in the surface treatment layer is 1 to 80% by weight, or the content of the nonionic surfactant in the surface treatment layer. It is an antiviral sheet material having an amount of 1 to 40% by weight.

According to the present invention, a sheet-like product with excellent antiviral properties and excellent appearance can be obtained.

The present invention will be explained in detail below.
The antiviral sheet material of the present invention has a base material layer and a surface treatment layer, and the surface treatment layer contains a resin component, an antiviral agent, and a nonionic surfactant. The antiviral agent consists of an inorganic filler carrying a sulfonic acid surfactant.

The surface treatment layer is formed by applying a surface treatment agent to the surface of the sheet-like base layer. It is preferable that the surface treatment agent contains a resin component, an antiviral agent, and a nonionic surfactant in advance. In addition to the above-mentioned main components, a solvent such as an organic solvent or water is added to the surface treatment agent. In preparing the surface treatment agent, an antiviral agent and a nonionic surfactant can be added to a general treatment agent consisting of a resin component and a solvent. Since the antiviral sheet material of the present invention can be used for interior materials, etc., an aqueous resin emulsion using water as a solvent can be suitably used as a treatment agent in consideration of reducing VOC (volatile organic compounds). Note that the sulfonic acid surfactant contained in antiviral agents is anionic, so when using an aqueous emulsion, using an anionic surfactant will stabilize the emulsion, and it will be applied to the base layer and the surface. This is preferable because a surface treated layer with excellent appearance can be obtained when forming the treated layer.

Examples of the resin component of the surface treatment layer include silicone compounds, fluorine compounds, urethane compounds, acrylic compounds, vinyl chloride compounds, etc. Copolymers or mixtures of two or more of these compounds may also be used. In particular, acrylic compounds are preferred.

The antiviral agent used in the present invention is composed of an inorganic filler on which a sulfonic acid surfactant is supported in advance. Here, "supported" refers to a state in which the sulfonic acid surfactant is fixed on the surface of the inorganic filler. By using an antiviral agent made of an inorganic filler supporting a sulfonic acid surfactant, it is possible to obtain a surface treatment layer with a uniform thickness and excellent appearance.

Examples of the sulfonic acid surfactants used in the antiviral agent of the present invention include alkylbenzenesulfonic acid compounds, alkyldiphenyl ether disulfonic acid compounds, alkylnaphthalene sulfonic acid compounds, alkyl sulfate ester compounds, and polyoxyethylene alkyl sulfate esters. and naphthalenesulfonic acid-formalin condensate-based compounds. Among these, alkylbenzenesulfonic acid compounds, alkyldiphenyl ether disulfonic acid compounds, and alkylnaphthalenesulfonic acid compounds are preferred from the viewpoint of excellent antiviral properties, and alkylbenzenesulfonic acid compounds are particularly preferred because of their excellent antiviral properties.

In sulfonic acid-based surfactants, it is assumed that the sulfonic acid group has a high affinity with, for example, influenza virus neuraimidase, and can exhibit an inhibitory effect. Furthermore, the structure of the functional group has an influence on the approach to neureimidase, and it is thought that a structure that is not bulky and is not susceptible to steric hindrance is important. In this respect, alkylbenzenesulfonic acid surfactants are suitable, and dodecylbenzenesulfonic acid is particularly preferred.
Furthermore, the above-mentioned sulfonic acid surfactants include alkali metal salts such as sodium salts and potassium salts, alkaline earth metal salts such as calcium and barium, and the like. Alkali metal salts are preferred because of their excellent antiviral properties, and sodium dodecylbenzenesulfonate is more preferred.
Further, a plurality of sulfonic acid surfactants may be used as long as the antiviral properties are not inhibited.

Examples of inorganic fillers used in the antiviral agent of the present invention include silica, calcium carbonate, talc, mica, and clay. These inorganic fillers, which are generally used as additives for resins, rubbers, etc., are sometimes subjected to hydrophobic treatment in order to improve their miscibility with resins, rubbers, and other additives. In the present invention, when using an aqueous resin emulsion as a surface treatment agent for forming a surface treatment layer, it is preferable to use an inorganic filler that has not been hydrophobically treated in view of miscibility with the aqueous resin emulsion.

The method for supporting the sulfonic acid surfactant on the inorganic filler is not particularly limited and any known method can be used, such as a method in which an aqueous solution of the sulfonic acid surfactant is sprayed onto the inorganic filler and dried. Examples include a method in which an inorganic filler is added and mixed with an aqueous solution of a sulfonic acid surfactant, water is removed and dried, and the remaining solid content is ground with a known grinder such as a ball mill.

The proportion of the sulfonic acid surfactant supported on the inorganic filler is preferably 1:20 to 1:1 as a weight ratio of the sulfonic acid surfactant to the inorganic filler. If the ratio of sulfonic acid surfactant is less than 1:20, it is necessary to add a large amount of antiviral agent in order to develop antiviral properties, making it difficult to obtain a uniform surface treatment layer with excellent appearance. If the ratio of the sulfonic acid surfactant is more than 1:1, the antiviral agent will become lumpy due to the hygroscopicity of the sulfonic acid surfactant, causing poor dispersion in the surface treatment layer, resulting in poor antiviral properties. May affect the appearance of the sheet.

The content of the antiviral agent in the surface treatment layer is preferably 1 to 80% by weight. If it is less than 1% by weight, antiviral properties are poor, and if it is more than 80% by weight, the appearance of the surface treatment layer may deteriorate. In view of the relationship between antiviral properties and the appearance of the surface treated layer, a more preferable amount of the antiviral agent added to the surface treated layer is 10 to 60% by weight. The amount of the sulfonic acid surfactant in the surface treatment layer is preferably 0.5% by weight or more, more preferably 1.0% by weight or more.

The surface treatment layer contains a nonionic surfactant, thereby making it possible to obtain a surface treatment layer with a uniform thickness and excellent appearance. Nonionic surfactants include ester-based, ether-based, ester-ether-based, alkanolamide-based, and acetylene-based surfactants, among which acetylene-based surfactants are particularly preferred.

The content of the nonionic surfactant in the surface treatment layer is preferably 1 to 40% by weight. If it is less than 1% by weight, the appearance of the surface treatment layer may deteriorate, and if it is more than 40% by weight, the antiviral properties may become poor. In view of the relationship between antiviral properties and the appearance of the surface treatment layer, the amount of nonionic surfactant added to the surface treatment layer is preferably 5 to 30% by weight.

The surface treatment layer may contain leveling agents, film-forming aids, wetting agents, thickeners, thinners, ultraviolet absorbers, light stabilizers, ultraviolet shielding agents, antistatic agents, as long as they do not impede the purpose of the present invention. Flame retardants, fluorescent agents, crosslinking agents, antibacterial agents, antifungal agents, flame retardants, flame retardants, pH adjusters, etc. can be used as appropriate.

For the base material layer, polyolefin resins such as polyethylene and polypropylene, polyester resins such as polyethylene terephthalate and modified polyester, polyvinyl chloride, ethylene-vinyl chloride, propylene-vinyl chloride copolymer, and vinyl chloride-vinyl acetate copolymer are used. Sheets made of synthetic resins such as polyvinyl chloride resins such as polyvinyl chloride-vinylidene chloride copolymers, acrylic resins, and polyurethane resins, and sheet-like materials such as paper, woven fabrics, and non-woven fabrics can be used.
Furthermore, it may be a multilayer structure in which layers made of one or more of the above materials are laminated, and layers such as various resin foam layers, design layers such as printed layers and colored layers can be provided to suit the intended use and required physical properties. An antiviral sheet-like product can be obtained. Here, the design layer may be any layer other than the exemplified printed layer and colored layer as long as it is visually aesthetically pleasing.

It is preferable to select the resin component of the surface treatment layer depending on the material used for the base layer. The resin component of the surface treatment layer is preferably selected in consideration of adhesion to the base layer and durability. Here, when the base material layer is composed of a polyvinyl chloride resin, it is preferable to use an acrylic resin or a vinyl chloride resin as the resin component of the surface treatment layer.

The antiviral sheet material of the present invention is obtained by forming a surface treatment layer by applying a surface treatment agent to the surface of a sheet-like base material layer. The surface treatment agent preferably contains a resin component, an antiviral agent, and a nonionic surfactant in advance, and is obtained by stirring these with a mixer or the like. A known technique can be used to apply the surface treatment agent to the base layer, and the surface treatment layer must be obtained by drying and solidifying the surface treatment agent after application. Conditions for drying and solidifying include, for example, heating in an oven or the like at a temperature of 100 to 150° C. for 0 to 60 seconds.

The coating amount of the surface treatment agent is preferably 0.5 g/m ² to 10 g/m ² in a dry state. If it is less than 0.5 g/m ² , sufficient antiviral properties may not be obtained. Moreover, if it exceeds 10 g/m ² , the design of the base material layer may be impaired.

Although the antiviral sheet material of the present invention is expected to have antiviral effects against various viruses, it exhibits particularly high antiviral properties against enveloped viruses. Examples of enveloped viruses include influenza viruses such as avian influenza virus, human influenza virus, and swine influenza virus, hepatitis B virus, hepatitis C virus, human immunodeficiency virus, varicella zoster virus, herpes simplex virus, and human herpes virus. Viruses include mumps virus, respiratory syncytial virus, and Ebola virus.

The antiviral sheet material of the present invention can be used, for example, in construction materials, daily necessities, protective clothing, masks, filters, and the like.

The present invention will be explained in more detail with reference to Examples, but the present invention is not limited to these Examples.

The specific substance names of each compounding agent for the treatment layer used in Examples and Comparative Examples are as follows.
A. Antiviral agent・A-1
Sulfonic acid surfactant: Inorganic filler (heavy calcium carbonate (no hydrophobic treatment) trade name: Whiten 305, manufactured by Shiraishi Calcium) is added to a 50% aqueous solution of sulfonic acid surfactant (sodium alkylbenzene sulfonate). A composition in which the filler was added at a weight ratio of 1:1 and stirred, then the water was evaporated and the remaining solid content was ground and supported in a mortar - A-2
Sulfonic acid surfactant: Inorganic filler (heavy calcium carbonate (no hydrophobic treatment) trade name: Whiten 305, manufactured by Shiraishi Calcium) is added to a 50% aqueous solution of sulfonic acid surfactant (sodium alkylbenzene sulfonate). A composition in which the filler was added at a weight ratio of 1:5 and stirred, then the water was evaporated and the remaining solid content was ground and supported in a mortar - A-3
Sulfonic acid surfactant: Inorganic filler (heavy calcium carbonate (no hydrophobic treatment) trade name: Whiten 305, manufactured by Shiraishi Calcium) is added to a 50% aqueous solution of sulfonic acid surfactant (sodium alkylbenzene sulfonate). A composition in which the filler was added at a weight ratio of 1:20 and stirred, then the water was evaporated and the remaining solid content was ground and supported in a mortar - A-4
Add an inorganic filler (talc (no hydrophobic treatment), trade name: Micro Ace K-1, manufactured by Nippon Talc) to a 50% aqueous solution of a sulfonic acid surfactant (sodium alkylbenzenesulfonate) as a sulfonic acid surfactant: inorganic filling. Composition A-5 in which the material is added at a weight ratio of 1:5 and stirred, then the water is evaporated and the remaining solid content is ground and supported in a mortar.
A sulfonic acid surfactant (sodium alkylbenzene sulfonate) and an inorganic filler (heavy calcium carbonate (no hydrophobic treatment), trade name: Whiten 305, manufactured by Shiraishi Calcium) are combined into a sulfonic acid surfactant: inorganic filler = Mixture A-6 mixed at a weight ratio of 1:5
Silver-based inorganic antiviral agent B. Processing agent/B-1
Water-based resin emulsion (acrylic) Solid content 19%
(Product name: Viniblan (registered trademark) 840B, manufactured by Nissin Chemical Industry)
・B-2
Water-based resin emulsion (PVC type) Solid content 13%
(Product name: Viniblan (registered trademark) 871-8, manufactured by Nissin Chemical Industry)
C. Nonionic surfactant・C-1
Acetylene surfactant 90% active ingredient
・C-2
Ester surfactant 100% active ingredient

A method for producing sheet-like products in Examples and Comparative Examples will be described.
In Examples 1 to 10 and Comparative Examples 1 to 5, the antiviral agent (A), treatment agent (B), and nonionic surfactant (C) listed in Table 1 or Table 2 were used in Table 1 or Table 2, respectively. The ingredients were added to the blending ratio shown in Table 2 and mixed for 3 minutes using a stirrer at a rotation speed of 500 rpm to prepare a surface treatment agent.
Next, the prepared surface treatment agent was mixed with 100 parts by weight of polyvinyl chloride resin for paste, 50 parts by weight of phthalic acid plasticizer, 4 parts by weight of Ba-Zn stabilizer, 6 parts of azodicarbonamide foaming agent, and 100 parts by weight of calcium carbonate. A polyvinyl chloride resin sheet consisting of parts by weight was coated using a gravure printing machine in a dry state to a coating amount of 5 g/m ² . Thereafter, the mixture was heated and foamed in a gear oven at 225° C. for 30 seconds to obtain a sheet-like product.

<Exterior>
The appearance of the surface (surface treatment layer side) of the sheet-like article was visually evaluated.
○: No chipping of the surface treatment layer.
Δ: Slight chipping of the surface treatment layer occurs.
x: Chips in the surface treatment layer clearly occur.

<Color tone>
Immediately after heating and foaming, the color tone of the surface (surface treated layer side) of the sheet material was visually evaluated.
○: No discoloration.
Δ: Slight discoloration occurs.
×: Discoloration clearly occurs.

<Antiviral properties>
Avian influenza virus A/whistling swan/Shimane/499/83 (H5N3) strain was used as the test virus. (hereinafter referred to as H5N3 strain).
A test virus solution was prepared by diluting the H5N3 strain with sterile phosphate buffered saline (PBS; pH 7.2) to 1.0×10 ⁶ EID ₅₀ /0.1 mL.
Place the 5 cm x 5 cm sheet-like material prepared in the Examples and Comparative Examples listed in Tables 1 and 2 in a petri dish, place 0.22 ml of the test virus solution on the surface of the sheet-like material, and place the 4 cm x 4 cm sheet-like material on top of it. The petri dish was covered with a polyethylene film, and the petri dish was placed in an incubator set at 20° C. for 1 hour. After 24 hours, the virus solution on the surface of the sheet was collected, serially diluted 10 times with the above PBS, and 0.1 mL of the diluted virus solution was inoculated into the chorioallantoic cavity of a 10-day-old embryonated chicken egg using a syringe needle. did.
After inoculation, embryonated chicken eggs were cultured at 37°C for 2 days, and the presence or absence of virus proliferation in the chorioallantoic cavity was determined by a hemagglutination test, and the virus titer (log ₁₀ EID ₅₀ /0.1ml) was determined by the method of Reed & Muench. was calculated.
The lower the virus titer, the stronger the antiviral properties of the sheet material.
○: Virus titer is less than 0.5, high antiviral effect △: Virus titer is 0.5 or more, less than 3.0, has antiviral effect ×: Virus titer is 3.0 or more, low antiviral effect

Comparing Examples 4 and 7 with Comparative Example 1, and Example 8 with Comparative Example 2, it can be seen that chipping of the surface treatment layer is suppressed by using the nonionic surfactant. Furthermore, it can be seen that by using an acetylene surfactant as the nonionic surfactant, the appearance is more excellent without changing the color tone.
Comparing Examples 1 to 10 and Comparative Example 3, it can be seen that the use of an antiviral agent made of an inorganic filler supporting a sulfonic acid surfactant resulted in an excellent appearance.
Comparing Examples 1 to 10 and Comparative Example 5, it can be seen that the use of an antiviral agent made of an inorganic filler supporting a sulfonic acid surfactant results in no discoloration and excellent appearance.

According to the present invention, it is possible to provide a sheet-like material with an excellent appearance that quickly reduces the virus titer of the virus it comes into contact with and inactivates the virus, so it is suitable for various daily necessities, buildings, vehicles, etc. It is especially suitable for places where many people gather at once and the risk of virus infection is high, such as hospitals, offices, old-age buildings, public facilities such as schools, buses, and trains.

Claims (6)

It has at least a base material layer and a surface treatment layer, and the surface treatment layer includes an antiviral agent made of a resin component and an inorganic filler carrying a sulfonic acid surfactant, and a nonionic surfactant. An antiviral sheet material characterized by: The antiviral sheet material according to claim 1, wherein the inorganic filler is calcium carbonate or talc that has not been hydrophobically treated. 2. The antiviral sheet material according to claim 1, wherein the resin component comprises an acrylic resin or a vinyl chloride resin. The antiviral sheet material according to claim 1, wherein the weight ratio of the sulfonic acid surfactant to the inorganic filler is 1:20 to 1:1. The antiviral sheet material according to claim 1, wherein the content of the antiviral agent in the surface treatment layer is 1 to 80% by weight. The antiviral sheet material according to claim 1, wherein the content of the nonionic surfactant in the surface treatment layer is 1 to 40% by weight.