JP7737698B2 - Antiviral article and manufacturing method thereof - Google Patents

Description

The present invention relates to an antiviral article and a method for manufacturing the same, and more specifically to an antiviral article with excellent antiviral durability and a method for manufacturing the same.

It has been known that some quaternary ammonium salts can be used as antiviral agents against enveloped viruses. A method for immobilizing such quaternary ammonium salts on the surface of an article has been proposed, in which a silane coupling agent is used as a binder (see Patent Document 1).

International Publication No. 2010/073825

However, in masks using antiviral articles manufactured using the antiviral agent immobilization method described in Patent Document 1, the antiviral durability of masks that are washed and reused is only about 50 washes, which poses the problem that the durability of the antiviral properties is insufficient to meet the improved performance requirements of such masks.

However, in order to improve the durability of the antiviral properties, the inventors used a thermosetting resin instead of a silane coupling agent to bind a quaternary ammonium salt to the surface of a fiber assembly. However, contrary to expectations, they discovered that this resulted in the article no longer exhibiting antiviral properties.

The present invention was made in consideration of these issues and technical knowledge of the prior art, and aims to provide an antiviral article with excellent antiviral durability and a method for manufacturing the same.

As a result of extensive research into achieving the above-mentioned objectives, the inventors discovered that the above-mentioned objectives can be achieved by partially exposing the quaternary ammonium salt on the surface of a coating layer that is disposed on the surface of a substrate and contains a resin and a quaternary ammonium salt, and thus completed the present invention.

That is, the antiviral article of the present invention comprises a substrate and a coating layer that coats the surface of the substrate. The substrate is partially exposed on the surface of the coating layer, and the coating layer contains a resin and a quaternary ammonium salt. The quaternary ammonium salt is partially exposed on the surface of the coating layer.

The method for producing an antiviral article of the present invention is the same as the method for producing an antiviral article of the present invention described above, and includes the following first and second steps. The first step is a step of forming a coating layer containing a resin and a quaternary ammonium salt on the surface of a substrate. The second step is carried out after the first step and is a step of removing the resin on the surface of the coating layer by polishing or dissolving, thereby partially exposing the quaternary ammonium salt on the surface of the coating layer.

According to the present invention, the quaternary ammonium salt is partially exposed on the surface of a coating layer that is disposed on the surface of a substrate and contains a resin and a quaternary ammonium salt, thereby providing an antiviral article with excellent antiviral durability and a method for manufacturing the same.

1 is a schematic cross-sectional view showing the configuration of a first embodiment of an antiviral article of the present invention. 2 is a schematic cross-sectional view showing an enlarged view of a portion of the coating layer shown in FIG. 1 surrounded by line II. FIG. 1 is a schematic cross-sectional view showing the configuration of a second embodiment of the antiviral article of the present invention. FIG. 2 is an explanatory diagram schematically showing a polishing procedure in the first embodiment of the method for producing an antiviral article of the present invention.

Below, several embodiments of the antiviral article and its manufacturing method of the present invention will be described in detail with reference to the drawings.

[Antiviral products]
First, the antiviral article of the present invention will be described. Fig. 1 is a schematic cross-sectional view showing the configuration of a first embodiment of the antiviral article of the present invention. Fig. 2 is a schematic cross-sectional view showing an enlarged view of the portion of the coating layer surrounded by line II shown in Fig. 1.

As shown in Figure 1, the antiviral article 1 of this embodiment includes a substrate 3 and a coating layer 5 that coats the surface of the substrate 3. In the illustrated example, rubber is used as the substrate 3. Furthermore, as shown in Figure 2, the coating layer 5 contains a resin 7 and a quaternary ammonium salt 9 held in the resin 7. Furthermore, the quaternary ammonium salt 9 is partially exposed on the surface of the coating layer 5.

The antiviral article of this embodiment is disposed on the surface of a substrate, and the quaternary ammonium salt is partially exposed on the surface of the coating layer containing a resin and a quaternary ammonium salt, so it is believed to have excellent durability of antiviral properties.

In particular, artificial leather to which such an antiviral article is applied is thought to have excellent antiviral durability against washing. Furthermore, in the antiviral article of the present embodiment, the substrate is partially exposed on the surface of the coating layer .

Furthermore, such antiviral articles have the secondary advantage that they may further have at least one of shape stability, deodorizing properties, and antibacterial properties.

Each component is explained in more detail below.

The substrate 3 preferably includes, for example, wallpaper, rubber, coatings, films, tapes, resins, paper, fibers, and fiber aggregates. Among these, rubber, coatings, films, and tapes are exposed to the surface of the coating layer , which facilitates the generation of static charges, such as negative ions, that would otherwise be inhibited by the resin of the coating layer , and is thought to significantly increase their ability to adsorb viruses. Similarly, fiber aggregates are also exposed to the surface of the coating layer , which facilitates the generation of static charges, such as negative ions, that would otherwise be inhibited by the resin of the coating layer , and is thought to significantly increase their ability to adsorb viruses.

Examples of wallpaper include resin wallpaper used in buildings, Japanese paper wallpaper, and diatomaceous earth wallpaper. Examples of rubber include rubber used in building fixtures and transportation machinery, and rubber used in kitchenware, office equipment, furniture, etc. Examples of coatings include coatings formed on products used in building fixtures and transportation machinery, and coatings formed on kitchenware, office equipment, furniture, etc. Examples of films include films used in building fixtures and transportation machinery, and films used in kitchenware, office equipment, furniture, etc. Examples of tapes include tapes used in kitchenware, office equipment, furniture, etc. Examples of resins include resins used in building fixtures and transportation machinery, and resins used in kitchenware, office equipment, furniture, etc. Examples of paper materials include paper such as newspaper rolls, printing and communication paper, packaging paper, sanitary paper, and miscellaneous paper, as well as paperboard such as cardboard, paperboard for paper containers, building material paper, paper tube paper, wrap, and other paperboard. Examples of fibers include carbon fiber, aramid fiber, and glass fiber. These fibers may be formed into fiber assemblies. Fiber assemblies preferably include, for example, twisted yarns, nonwoven fabrics, woven fabrics, and knitted fabrics.

Among these, it is more preferable to use woven fabric as the fiber assembly, as this is an example of an antiviral article that can be easily applied to masks that can be washed and reused.

Although not particularly limited, examples of materials for the fiber assembly include synthetic fibers, semi-synthetic fibers, and natural fibers.

The fiber assembly preferably contains, for example, cotton fibers, hemp fibers, wool fibers, silk fibers, rayon fibers, acetate fibers, polyester fibers, polyamide fibers, polyvinyl alcohol fibers, polyvinylidene chloride fibers, polyolefin fibers, polyurethane fibers, polytetrafluoroethylene fibers, and carbon fibers. Furthermore, any combination of two or more of these fibers can also be used.

Although not particularly limited, preferred synthetic fibers include polyester fibers such as polyethylene terephthalate fibers, polypropylene terephthalate fibers, polybutylene terephthalate fibers, and polyhexamethylene terephthalate fibers, polyamide fibers such as nylon 6 fibers and nylon 6,6 fibers, polyacrylic fibers, polypropylene fibers, polyvinyl chloride fibers, and polyvinyl alcohol fibers.

Although not particularly limited, it is preferable to use semi-synthetic fibers such as acetate fibers and rayon fibers.

Although not particularly limited, among natural fibers, preferred fibers include wool, silk, cotton, and hemp.

Among these, it is more preferable to use a woven fabric that combines cotton fibers and polyester fibers as the fiber assembly, as static electricity is more likely to occur between the two types of fibers, making them more likely to adsorb viruses.

The resin 7 used as the binder for binding the quaternary ammonium salt can be, for example, a thermoplastic resin, a thermosetting resin, an ultraviolet-curable resin, or a two-component room-temperature curable resin. However, a thermosetting resin is preferred. Examples of suitable thermoplastic resins include acrylic resin, vinyl acetate resin, polyethylene resin, polystyrene resin, polyvinyl chloride resin, polypropylene resin, polymethyl methacrylate resin, acrylonitrile butadiene styrene resin, butadiene resin latex, polycarbonate resin, polyacetal resin, nylon resin, polyester resins such as polyethylene terephthalate and polybutylene terephthalate, polyphenylene oxide resin, polyphenylene sulfide resin, polysulfone resin, polyethersulfone resin, polyetheretherketone resin, polyarylsulfone resin, polyimide resin, polyaminobismaleimide resin, polyamideimide resin, polyetherimide resin, bismaleimide triazine resin, polymethylpentene resin, fluorinated resin, olefin-vinyl alcohol copolymer resin, polyurethane resin, and polyarylate resin. These can be used alone or in any combination of two or more. Thermosetting resins preferably include, for example, alkyd resins, melamine resins, phenolic resins, unsaturated polyesters, diallyl phthalate resins, epoxy resins, silicone resins, and urea resins. These can also be used alone or in any combination of two or more.

Among these, it is more preferable to use melamine resin as the thermosetting resin, from the viewpoint of improving the water resistance and weather resistance of the antiviral article.

As the quaternary ammonium salt 9, any conventionally known quaternary ammonium salt that exhibits antiviral properties against enveloped viruses can be used.

Quaternary ammonium salts are known as a type of surfactant. Furthermore, mixed solutions of cationic and anionic surfactants are known to form various molecular aggregates, even in more dilute systems than general surfactant solutions. In particular, vesicles, which have attracted attention as such molecular aggregates, are bag-like self-assemblies in which amphiphilic molecules that possess both hydrophilic and hydrophobic properties are closely aligned in water, forming a lipid bilayer. Furthermore, when forming such molecular aggregates, it is also known that it is preferable that the molar ratio when mixing these two types of surfactants is not nearly equimolar.

For example, when producing antiviral functional fibers with washing durability using an anionic antibacterial finishing agent, which is an anionic surfactant, it is necessary to add a binder to improve washing durability. Furthermore, to further improve durability, it is necessary to increase the amount of resin used as the binder or the amount of crosslinking agent added to the resin. However, this can impair the soft texture of the textile product and increase costs.

On the other hand, when manufacturing antiviral functional fibers with wash durability using two types of agents, for example, a cationic antibacterial finishing agent (Nickanon RB), which is a cationic surfactant, and an anionic antibacterial finishing agent, which is an anionic surfactant, the bond between these molecular assemblies and the binder becomes strong. Here, Nikanon RB contains a quaternary ammonium salt. Therefore, the amount of resin used as the binder for binding the quaternary ammonium salt to the substrate can be reduced. As a result, the soft texture of the textile product can be maintained while reducing costs.

Furthermore, a cationic surfactant, cationic antibacterial finishing agent (Niccanon RB), is diluted with an anionic surfactant, anionic antibacterial finishing agent, and then a binder is added to the mixture. The resulting binder mixture containing a quaternary ammonium salt is then applied to fibers, firmly binding the quaternary ammonium salt to the fibers. While a single binder may be used, using multiple binders can more firmly bind the quaternary ammonium salt to the fibers. While not particularly limited, a combination of an acrylic emulsion and a nonionic crosslinking agent is preferred as the resin functioning as the binder. Note that "acrylic emulsion" refers to an emulsion containing finely divided acrylic polymers. A typical example is a self-crosslinking acrylic ester copolymer emulsion that appears as a milky white emulsion (a milky white liquid). It is also preferred to mix the cationic surfactant and anionic surfactant in a molar ratio that deviates from an equimolar mixture.

Until now, it has been considered difficult to use a binder to bind quaternary ammonium salts to fibers such as polyester or nylon to turn them into wash-resistant antiviral functional fibers. However, as described above, by using a mixture of cationic surfactants, anionic surfactants, and binders, it is possible to turn fibers such as polyester and nylon into antiviral functional fibers.

Although not particularly limited, for example, from the viewpoint of further improving the durability of the antiviral property of the antiviral article, the quaternary ammonium salt is preferably present in a dispersed state in the coating layer .

Although not particularly limited, it is preferable that the content of the quaternary ammonium salt relative to the fiber assembly be 0.5 to 3.0% o.w.f. (on the weight of fiber). If the content of the quaternary ammonium salt relative to the fiber assembly is less than 0.5% o.w.f., the washing durability of the antiviral article may decrease. On the other hand, if the content of the quaternary ammonium salt relative to the fiber assembly exceeds 3.0% o.w.f., the soft texture of the textile product after processing may be impaired.

Examples of rubber products to which the antiviral article of the present invention can be applied include toys, play equipment, sporting goods, condoms, etc.

Examples of painted products to which the antiviral article of the present invention can be applied include articles painted with water-based paint, oil-based paint, acrylic paint, furniture/floor paint, etc.

Examples of film products to which the antiviral article of the present invention can be applied include protective films for keyboards, protective films for elevator buttons, protective films for desks, touch panel films for smartphones and tablet computers, touch panel films for medical devices and public facilities, panel films for various digital signage, face shields, window films, and touch panel films for automotive in-vehicle displays.

Examples of tape products to which the antiviral article of the present invention can be applied include gymnasium line tape, medical protective tape, and contact infection prevention tapes (doorknobs, staircase handrails, bathroom handrails, toilet handrails, etc.) used in buildings and offices, stores and commercial facilities, schools and educational facilities, hospitals and medical facilities, nursing homes, and sports and recreation facilities.

Examples of resin products to which the antiviral article of the present invention can be applied include toys, play equipment, and sporting goods.

Examples of paper products to which the antiviral article of the present invention can be applied include cardboard, magazines, newspapers, etc.

Fibers to which the antiviral article of the present invention can be applied include those used in fiber-reinforced plastics, such as carbon fiber, aramid fiber, and glass fiber.

Examples of textile products to which the antiviral article of the present invention can be applied include clothing, nursing care products, miscellaneous goods, interior goods, and bedding.

Clothing items include, for example, outdoor wear, sportswear, home wear, relaxation wear, pajamas, sleepwear, underwear, office wear, work clothes, food service uniforms, nursing uniforms, patient wear, care wear, school uniforms, and kitchen wear.

Examples of nursing care products include supports, corsets, rehabilitation shoes, underwear, diaper covers, and small items.

Examples of miscellaneous items include aprons, towels, gloves, scarves, socks, hats, shoes, sandals, bags, umbrellas, etc.

Examples of interior goods include curtains, carpets, mats, kotatsu covers, sofa covers, cushion covers, sofa coverings, toilet seat covers, toilet seat mats, tablecloths, etc.

Bedding products include, for example, futon cover fabrics, futon batting, blankets, blanket cover fabrics, pillow fillings, sheets, waterproof sheets, futon covers, pillowcases, etc.

Figure 3 is a schematic cross-sectional view showing the configuration of a second embodiment of the antiviral article of the present invention. The enlarged schematic cross-sectional view of the area surrounded by line II in Figure 3 is similar to Figure 2.

As shown in FIG. 3, the antiviral article 1A of this embodiment includes a substrate 3 and a coating layer 5 that coats the surface of the substrate 3. In the illustrated example, a woven fabric, which is an example of a fiber assembly, is used as the substrate 3. Furthermore, as shown in FIG. 2, the coating layer 5 contains a resin 7 and a quaternary ammonium salt 9 held in the resin 7. Furthermore, the quaternary ammonium salt 9 is partially exposed on the surface of the coating layer 5. In the illustrated example, a thermosetting resin is used as the resin 7.

As described above, the antiviral article of this embodiment is disposed on the surface of a fiber assembly, and the quaternary ammonium salt is partially exposed on the surface of the coating layer containing a thermosetting resin and a quaternary ammonium salt. This is thought to result in excellent durability of the antiviral properties.

In particular, a mask incorporating such an antiviral article is believed to have excellent antiviral washing durability. Furthermore, in the antiviral article of this embodiment, it is preferable that the fiber aggregate is partially exposed on the surface of the coating layer . As described above, the fiber aggregate is exposed on the surface of the coating layer , which is thought to facilitate the generation of static electricity, such as negative ions, in the fiber aggregate that had been prevented from being generated by the thermosetting resin of the coating layer , and thus greatly increase the ability to adsorb viruses. Note that each component has been described in detail above, so redundant description will be omitted.

[Method for manufacturing antiviral articles]
Next, a method for producing an antiviral article of the present invention will be described. The method for producing an antiviral article of the present invention is one embodiment of the method for producing an antiviral article of the present invention described above. Therefore, the antiviral article of the present invention is not limited to those obtained by the method for producing an antiviral article of the present invention.

A first embodiment of the method for producing an antiviral article of the present invention includes the following first and second steps.
The first step is a step of forming a coating layer containing a resin and a quaternary ammonium salt on the surface of a substrate.
The second step is carried out after the first step, and is a step in which the resin on the surface of the coating layer is removed by polishing or dissolving, thereby partially exposing the quaternary ammonium salt on the surface of the coating layer.

Figure 4 is an explanatory diagram schematically illustrating the polishing procedure in the first embodiment of the method for manufacturing an antiviral article of the present invention. (A) in the figure shows the state before polishing, and (B) in the figure shows the state after polishing. As shown in Figures 4(A) and (B), in the second step, the resin 7 in the polished portion 11 on the surface of the coating layer 5 is removed by polishing, partially exposing the quaternary ammonium salt 9 on the surface of the coating layer 5.

Although not shown, in the first embodiment of the method for producing an antiviral article of the present invention, the resin in the dissolving portion (corresponding to the polishing portion in FIG. 4 ) on the surface of the coating layer before dissolution may be removed by dissolution, thereby partially exposing the quaternary ammonium salt on the surface of the coating layer.

The method for manufacturing an antiviral article of this embodiment is capable of partially exposing the quaternary ammonium salt on the surface of a coating layer that is disposed on the surface of a substrate and contains a resin and a quaternary ammonium salt, and is therefore believed to be capable of producing an antiviral article with excellent antiviral durability.

In particular, masks using the antiviral article obtained in this way are thought to have excellent antiviral durability against washing.

An additional benefit of the antiviral article obtained in this manner is that it may further possess at least one of shape stability, deodorizing properties, and antibacterial properties.

Each step is explained in more detail below.

In the first step, for example, a substrate (preferably a fiber assembly) is first contacted with and impregnated with a quaternary ammonium salt-containing liquid as an antiviral agent to obtain a substrate (preferably a fiber assembly) containing the quaternary ammonium salt-containing liquid. The substrate (preferably the fiber assembly) is then dried to obtain a substrate (preferably a fiber assembly) containing the quaternary ammonium salt-containing liquid. Next, the quaternary ammonium salt-containing substrate (preferably the fiber assembly) is contacted with and impregnated with a resin (preferably a thermosetting resin) raw material-containing liquid as an adhesive to obtain a substrate (preferably a fiber assembly) containing the resin (preferably a thermosetting resin) raw material-containing liquid and the quaternary ammonium salt-containing substrate. The resin (preferably a thermosetting resin) raw material-containing liquid and the quaternary ammonium salt-containing substrate (preferably the fiber assembly) are then heated to form a coating layer containing the resin (preferably a thermosetting resin) and the quaternary ammonium salt on the surface of the substrate (preferably the fiber assembly). From the viewpoint of being able to firmly adhere the quaternary ammonium salt to the substrate (preferably the fiber assembly), this type of first step is preferred.

In the first step, for example, a substrate (preferably a fiber assembly) is contacted and impregnated with a quaternary ammonium salt-containing liquid and a resin (preferably a thermosetting resin) raw material-containing liquid in this order, or a mixture of a quaternary ammonium salt-containing liquid and a resin (preferably a thermosetting resin) raw material-containing liquid is contacted and impregnated to obtain a substrate (preferably a fiber assembly) containing a quaternary ammonium salt-containing liquid/resin (preferably a thermosetting resin) raw material-containing liquid, and then the substrate (preferably a fiber assembly) containing the quaternary ammonium salt-containing liquid/resin (preferably a thermosetting resin) raw material-containing liquid is heated to form a coating layer containing a resin (preferably a thermosetting resin) and a quaternary ammonium salt on the surface of the substrate (preferably a fiber assembly). From the viewpoint of easily exposing the quaternary ammonium salt to the surface of the coating layer and easily allowing the quaternary ammonium salt to exist in a dispersed state in the coating layer , it is preferable to carry out such a first step.

Although not particularly limited, the solvent used for the quaternary ammonium salt and resin (preferably thermosetting resin) raw material is preferably a solvent that dissolves the quaternary ammonium salt and resin (preferably thermosetting resin) raw material. However, this is not a limitation, and a solvent that forms an emulsion can also be used. Furthermore, although not particularly limited, examples of solvents used for the quaternary ammonium salt and resin (preferably thermosetting resin) raw material include alcohols such as water, methanol, ethanol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, and sec-butyl alcohol.

Among these, from the viewpoint of preventing the viscosity of the quaternary ammonium salt-containing liquid or the resin (preferably thermosetting resin) raw material-containing liquid from becoming too high, the solvents used for the quaternary ammonium salt and the resin (preferably thermosetting resin) raw material are preferably methanol and ethanol, and mixtures of water with alcohols such as methanol and ethanol are also preferred.

Furthermore, when forming a coating layer , instead of the resin raw material-containing liquid as the adhesive described above, for example, solvent-based lacquer paints, water-based emulsion paints, thermoplastic powder paints, and other paints that form a coating film by drying and curing without a chemical reaction, such as solvent-based lacquer paints applied to a substrate, water-based emulsion paints, and thermoplastic powder paints, or paints that form a coating film by drying and curing with a chemical reaction, such as drying oil-based alkyd paints, unsaturated polyester paints, ultraviolet-curable paints, ambient-drying epoxy paints, ambient-drying urethane paints, thermosetting liquid paints, and thermosetting powder paints, can be used. For example, a quaternary ammonium salt may be mixed into such paints in advance. Examples of resins contained in adhesives and paints include the thermoplastic resins and thermosetting resins described above. Furthermore, adhesives and paints may be one-component or two-component. Commercially available adhesives and paints can be used as the adhesives and paints, respectively.

Although not particularly limited, when the substrate is a fiber assembly, the drying conditions described above are preferably 90 to 150°C and 30 seconds to 5 minutes. If the drying temperature is below 90°C, the washing durability of the antiviral article may decrease. On the other hand, if the drying temperature exceeds 150°C, the quaternary ammonium salt, which is the antiviral agent, may deteriorate.

Although not particularly limited, when the substrate is a fiber aggregate, the heating conditions described above are preferably 120 to 200°C and 30 seconds to 10 minutes. When heating in this manner, it is also preferable to apply pressure similar to that used when ironing clothing, for example, using a roller.

In one example of the second step, the resin (preferably a thermosetting resin) on the surface of the coating layer obtained in the first step is removed in a dry state by grinding with a grindstone, sandpaper, or the like, exposing the quaternary ammonium salt on the surface of the coating layer, thereby obtaining an antiviral article.

In another example of the second step, the resin (preferably a thermosetting resin) on the surface of the coating layer obtained in the first step is removed by polishing with a grindstone, sandpaper, or the like, in a wet state by wetting the coating layer with water, an aqueous hypochlorous acid solution, or the like, in other words, by wet sanding, to expose the quaternary ammonium salt on the surface of the coating layer, thereby obtaining an antiviral article.

In yet another example of the second step, the resin (preferably a thermosetting resin) on the surface of the coating layer obtained in the first step is removed by polishing in a dry state by rubbing it against, for example, the resin (preferably a thermosetting resin) on the surface of another coating layer obtained in the first step, exposing the quaternary ammonium salt on the surface of the coating layer and obtaining an antiviral article.

In yet another example of the second step, the resin (preferably a thermosetting resin) on the surface of the coating layer obtained in the first step is removed by polishing, in a wet state obtained by wetting the coating layer with water, an aqueous hypochlorous acid solution, or the like, by rubbing it against, for example, a resin (preferably a thermosetting resin) on the surface of another coating layer obtained in the first step, in other words, by water sanding, to expose the quaternary ammonium salt on the surface of the coating layer, thereby obtaining an antiviral article.

Although not particularly limited, the conditions for the above-mentioned polishing are preferably such that a pressure of about 5 to 50 kgf per 1 ^m2 is applied, the sliding speed of the grindstone, sandpaper, and other coating layer is about 0.5 to 5 m/s, and the rubbing time is about 0.5 seconds to 5 minutes.

Although not particularly limited, it is preferable that the temperature of the coating layer during the above-mentioned polishing be equal to or lower than the glass transition temperature of the resin contained in the coating layer so that the coating layer is not heated by heat generated by friction and the adhesion of the coating layer is not significantly reduced.

Rather than removing the resin (preferably a thermosetting resin) on the surface of the coating layer obtained in the first step by polishing in a dry state, polishing the coating layer in a wet state with water, an aqueous hypochlorous acid solution, or the like, in other words removing it by wet sanding, has the advantage that the shape and structure of the substrate (preferably a fiber aggregate) can be maintained and the durability of the antiviral properties can be further improved.

The resin (preferably a thermosetting resin) on the surface of the coating layer of the article obtained in step 1 is removed by polishing the coating layer in a wet state with water, a hypochlorous acid aqueous solution, or the like, in other words, by wet sanding, rather than by polishing in a dry state, which allows the shape and structure of the substrate (preferably a fiber aggregate) to be maintained. Furthermore, if the fiber aggregate is formed from two types of fibers that are prone to static electricity, static electricity will occur between the two types of fibers, allowing the substrate to maintain a shape and structure that is prone to adsorb viruses. This has the advantage of further improving the durability of the antiviral properties.

Although the thermosetting resin may contain formalin, the thermosetting resin on the surface of the coating layer obtained in the first step can be removed by polishing the coating layer with a grindstone or sandpaper while moistening the coating layer with an acid or alkali, particularly an aqueous solution of hypochlorous acid, or by polishing the coating layer by rubbing it against the thermosetting resin on the surface of the coating layer of another article obtained in the first step, in other words, by water sanding. This has the advantage that the formalin can be removed.

Among the examples of the second step described above, it is preferable to remove the thermosetting resin on the surface of the coating layer obtained in the first step by rubbing the coating layer in a wet state with water, a hypochlorous acid aqueous solution, or the like against the thermosetting resin on the surface of the coating layer of another article obtained in the first step, for example, by polishing, in other words, by water grinding.

In another example of the second step, the resin (preferably a thermosetting resin) on the surface of the coating layer obtained in the first step is dissolved with a solvent, the dissolved portion is then removed, and the quaternary ammonium salt is then exposed on the surface of the coating layer to obtain an antiviral article.

The solvent used to dissolve the resin can be appropriately selected from conventionally known solvents depending on the type of resin contained in the coating layer .

Although not particularly limited, it is preferable that the temperature of the coating layer during the above-mentioned dissolution be equal to or lower than the glass transition temperature of the resin contained in the coating layer so that the coating layer is not heated by the reaction heat generated by the dissolution and the adhesion of the coating layer is not significantly reduced.

The present invention will be explained in more detail below using examples, but the present invention is not limited to these examples.

Example 1
A fiber assembly (plain woven fabric, 40% polyester, 60% cotton) was contacted with a mixed liquid (Nikkanon RB (manufactured by Nicca Chemical Co., Ltd.)) containing a quaternary ammonium salt as an antiviral agent and a thermosetting resin raw material-containing liquid as an adhesive for 0.5 seconds so that the quaternary ammonium salt was carried at 2.0% o.w.f. relative to the fiber assembly, yielding a fiber assembly containing the quaternary ammonium salt-containing liquid and the thermosetting resin raw material-containing liquid. This was then wrung out using a padder to a wringing rate of 100%, and then heated at 120°C for 5 minutes to form a coating layer containing the thermosetting resin and the quaternary ammonium salt on the surface of the fiber assembly. Hereinafter, this will be referred to as "Article 1."

Thereafter, the thermosetting resin on the surface of the coating layer of the obtained article 1 was removed by polishing, in a wet state moistened with an aqueous hypochlorous acid solution, by rubbing the other coating layer against the thermosetting resin on the surface of the other coating layer at a sliding speed of 1 m/s for 1 second while applying a pressure of 10 kgf per ¹ m2, in other words, by water sanding, to partially expose the quaternary ammonium salt on the surface of the coating layer, thereby obtaining the antiviral article of this example.

Example 2
A fiber assembly (woven fabric, 40% polyester, 60% cotton) was contacted with an antiviral processing solution containing 5 parts by weight of a cationic quaternary ammonium salt (Niccanon RB (manufactured by Nicca Chemical Co., Ltd.)) as an antiviral agent, 5 parts by weight of an anionic quaternary ammonium salt, 5 parts by weight of an acrylic emulsion as a binder, 2 parts by weight of a nonionic crosslinking agent as a binder aid, and 80 parts by weight of water for 0.5 seconds so that the quaternary ammonium salt was carried at 2.0% o.w.f. relative to the fiber assembly. This produced a fiber assembly containing the antiviral processing solution. This was then wrung out at a wringing rate of 100% using a padder and then heated at 120°C for 5 minutes to form a coating layer containing a resin and a quaternary ammonium salt on the surface of the fiber assembly. This product will be referred to as "Article 2" hereinafter.

Thereafter, the resin on the surface of the coating layer of the obtained article 2 was wetted with an aqueous hypochlorous acid solution and polished by rubbing it against the thermosetting resin on the surface of another coating layer at a sliding speed of 1 m/s for 1 second while applying a pressure of 10 kgf per 1 m2 ^, in other words, by water sanding, to remove the resin, and the quaternary ammonium salt was partially exposed on the surface of the coating layer, thereby obtaining the antiviral article of this example.

(Comparative Example 1)
Article 1 (unpolished article) obtained in Example 1 was used as the article of this example.

[Performance evaluation]
(Antiviral test)
The antiviral articles and products of each example were evaluated in accordance with the method described in the 2014 edition of ISO 18184. The following two types of viruses were tested.
Influenza A virus (H3N2) (ATCC VR-1679)
Feline calicivirus (F-9) (ATCC VR-782)

(Washing method)
The fabric was washed 150 times using the standard washing method (method described in 1995 edition of JIS L0217 103) in accordance with the "Washing Method for SEK Mark Textile Products" (revised April 1, 2014, document number JEC326) issued by the Product Certification Department of the Japan Textile Evaluation Technology Council, a general incorporated foundation, and then hung to dry.

It was found that the antiviral articles of Examples 1 and 2 within the scope of the present invention exhibited excellent antiviral properties even when the articles were unwashed or washed 150 times.
Furthermore, the reason why the antiviral article of the present invention exhibits excellent antiviral properties is thought to be not only because the quaternary ammonium salt is exposed on the surface of the coating layer , but also because removing the thermosetting resin on the surface of the coating layer by polishing facilitates the generation of ions in the fiber assembly, which had been prevented from being generated by the thermosetting resin of the coating layer, thereby greatly increasing the ability to adsorb viruses.
On the other hand, it was found that the article of Comparative Example 1, which is not in accordance with the present invention, did not exhibit antiviral properties.

Example 3
A fiber assembly (woven fabric, 40% polyester, 60% cotton) was contacted with an antiviral processing solution containing 10 parts by mass of a cationic quaternary ammonium salt (Niccanon RB (manufactured by Nicca Chemical Co., Ltd.)) as an antiviral agent, 5 parts by mass of an acrylic emulsion as a binder, 2 parts by mass of a nonionic crosslinking agent as a binder aid, and 80 parts by mass of water for 0.5 seconds so that the quaternary ammonium salt was carried at 2.0% o.w.f. relative to the fiber assembly. This produced a fiber assembly containing the antiviral processing solution. This was then wrung out at a wringing rate of 100% using a padder and then heated at 120°C for 5 minutes to form a coating layer containing a resin and a quaternary ammonium salt on the surface of the fiber assembly. This will be referred to as "Article 3" below.

Thereafter, the resin on the surface of the coating layer of the obtained article 3 was wetted with an aqueous hypochlorous acid solution and rubbed against the thermosetting resin on the surface of another coating layer at a sliding speed of 1 m/s for 1 second while applying a pressure of 10 kgf per 1 ^m2 , in other words, by water polishing, to remove the resin, and the quaternary ammonium salt was partially exposed on the surface of the coating layer, thereby obtaining the antiviral article of this example.

Example 4
A fiber assembly (woven fabric, 40% polyester, 60% cotton) was contacted for 0.5 seconds with an antiviral processing solution containing 2.5 parts by mass of a cationic quaternary ammonium salt (Niccanon RB (manufactured by Nicca Chemical Co., Ltd.)) as an antiviral agent, 2.5 parts by mass of an anionic quaternary ammonium salt, 2.5 parts by mass of an acrylic emulsion as a binder, 1 part by mass of a nonionic crosslinking agent as a binder aid, and 80 parts by mass of water, as in Example 4, to obtain a fiber assembly containing the antiviral processing solution. This was then wrung out using a padder to a wringing rate of 100% and then heated at 120°C for 5 minutes to form a coating layer containing a resin and a quaternary ammonium salt on the surface of the fiber assembly. Hereinafter, this will be referred to as "Article 4."

Thereafter, the resin on the surface of the coating layer of the obtained article 4 was wetted with an aqueous hypochlorous acid solution and rubbed against the thermosetting resin on the surface of another coating layer at a sliding speed of 1 m/s for 1 second while applying a pressure of 10 kgf per 1 ^m2 , in other words, by water polishing, to remove the resin, and the quaternary ammonium salt was partially exposed on the surface of the coating layer, thereby obtaining the antiviral article of this example.

(Comparative Example 2)
Article 4 (unpolished article) obtained in Example 4 was used as the article of this example.

[Performance evaluation]
(Antiviral test)
The antiviral articles and articles of each example were evaluated in accordance with the antiviral test method for textile products (JIS L1922:2016 plaque measurement method). Some of the test conditions and the results obtained are shown in Tables 1 and 2.

Tables 1 and 2 show that the antiviral articles of Examples 3 and 4, which fall within the scope of the present invention, also exhibit excellent antiviral properties. Furthermore, the results of the antiviral articles of Examples 3 and 4 show that Example 4, in which the blending ratio of the binder and other materials was reduced by 50%, also exhibits excellent antiviral properties. In other words, it was found that the amount of resin used as the binder can be reduced when binding a quaternary ammonium salt to a substrate such as polyester. Furthermore, it was found that the reduction in the amount of resin used allows the soft texture of textile products to be maintained while also reducing costs.
On the other hand, it was found that the article of Comparative Example 2, which is not in accordance with the present invention, did not exhibit antiviral properties.

The present invention has been described above using a few embodiments and examples, but the present invention is not limited to these and various modifications are possible within the scope of the present invention.

REFERENCE SIGNS LIST 1, 1A Antiviral article 3 Substrate 5 Coating layer 7 Resin 9 Quaternary ammonium salt 11 Polished portion

Claims (11)

A substrate and a coating layer that coats the surface of the substrate,
the substrate is partially exposed on a surface of the coating layer,
the coating layer contains a resin and a quaternary ammonium salt,
An antiviral article, characterized in that the quaternary ammonium salt is partially exposed on the surface of the coating layer . the substrate is a fiber assembly,
2. The antiviral article according to claim 1, wherein the resin is a thermosetting resin. The antiviral article according to claim 2, characterized in that the fiber assembly comprises twisted yarn, nonwoven fabric, woven fabric, or knitted fabric. The antiviral article according to claim 2 or 3, characterized in that the fiber assembly contains at least one fiber selected from the group consisting of cotton fibers, hemp fibers, wool fibers, silk fibers, rayon fibers, acetate fibers, polyester fibers, polyamide fibers, polyvinyl alcohol fibers, polyvinylidene chloride fibers, polyolefin fibers, polyurethane fibers, polytetrafluoroethylene fibers, and carbon fibers. An antiviral article according to any one of claims 2 to 4, characterized in that the fiber assembly contains cotton fibers and polyester fibers. The antiviral article described in any one of claims 2 to 5, characterized in that the thermosetting resin contains at least one selected from the group consisting of melamine resin, phenolic resin, unsaturated polyester, diallyl phthalate resin, epoxy resin, silicone resin, and urea resin. The antiviral article described in any one of claims 2 to 6, characterized in that the content of the quaternary ammonium salt relative to the fiber aggregate is 0.5 to 3.0% o.w.f. (on the weight of fiber). 8. The antiviral article according to claim 1, wherein the quaternary ammonium salt is present in a dispersed state in the coating layer . An antiviral article according to any one of claims 1 to 8, characterized in that the resin contains anions. A method for producing an antiviral article according to any one of claims 1 to 9, comprising:
a first step of forming a coating layer containing a resin and a quaternary ammonium salt on the surface of a substrate;
a second step, which is carried out after the first step, of removing the resin on the surface of the coating layer by polishing or dissolving it to partially expose the quaternary ammonium salt on the surface of the coating layer. the substrate is a fiber assembly,
the resin is a thermosetting resin,
The method for producing an antiviral article according to claim 10, characterized in that the removal of the resin in the second step is carried out by polishing the coating layer with a grindstone or sandpaper in a wet state in which the coating layer is moistened with water or an aqueous hypochlorous acid solution.