JP2022041998A - Antiviral article and method for producing the same - Google Patents

Abstract

To provide an antiviral article which is excellent in antiviral durability, and a method for producing the same.SOLUTION: An antiviral article includes a base material, and a coating layer coating the surface of the base material. The coating layer contains a resin, and a quaternary ammonium salt. The quaternary ammonium salt is partially exposed to the surface of the coating layer. A method for producing an antiviral article includes: a first step of forming a coating layer containing a resin and a quaternary ammonium salt on a surface of a base material; and a second step of removing the resin on the surface of the coating layer by polishing or dissolving, and partially exposing the quaternary ammonium salt to the surface of the coating layer, after the first step.SELECTED DRAWING: Figure 2

Description

The present invention relates to an antiviral article and a method for producing the same, and more particularly to an antiviral article having excellent antiviral durability and a method for producing the same.

Conventionally, it is known that a part of a quaternary ammonium salt can be used as an antiviral agent against a virus having an envelope. As a method for immobilizing such a quaternary ammonium salt on the surface of an article, an antiviral agent immobilization method using a silane coupling agent as a binder has been proposed (see Patent Document 1).

International Publication No. 2010/0738225

However, in the case of a mask to which an antiviral article manufactured by using an antiviral agent immobilization method as described in Patent Document 1 is applied, the antiviral washing durability in a mask that is washed and reused. However, there is a problem that the antiviral durability is not sufficient for the improvement of the required performance in such a mask.

On the other hand, in order to improve the antiviral durability, the present inventor used a thermosetting resin instead of the silane coupling agent to bind the quaternary ammonium salt to the surface of the fiber aggregate. As a result, we obtained the technical knowledge that the article does not show antiviral properties unexpectedly.

The present invention has been made in view of the problems and technical knowledge of such prior art, and an object of the present invention is to provide an antiviral article having excellent antiviral durability and a method for producing the same. ..

As a result of diligent studies to achieve the above object, the present inventor has placed the quaternary ammonium salt on the surface of the base material and partially puts the quaternary ammonium salt on the surface of the coating layer containing the resin and the quaternary ammonium salt. It has been found that the above object can be achieved by exposing it to, and the present invention has been completed.

That is, the antiviral article of the present invention includes a base material and a coating layer that covers the surface of the base material. 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.

Further, the method for producing an antiviral article of the present invention is the above-mentioned method for producing an antiviral article of the present invention, and has 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 the base material. The second step, which is performed after the first step, is a step of removing the resin on the surface of the coating layer by polishing or dissolving, and partially exposing the quaternary ammonium salt to the surface of the coating layer.

According to the present invention, the quaternary ammonium salt is partially exposed on the surface of the coating layer which is arranged on the surface of the base material and contains the resin and the quaternary ammonium salt. It is possible to provide an antiviral article having excellent properties and a method for producing the same.

It is a schematic sectional drawing which shows the structure of 1st Embodiment of the antiviral article of this invention. FIG. 3 is a schematic cross-sectional view showing an enlarged portion of the covering layer shown in FIG. 1 surrounded by line II. It is a schematic sectional drawing which shows the structure of the 2nd Embodiment of the antiviral article of this invention. It is explanatory drawing which shows typically the procedure of polishing in 1st Embodiment of the manufacturing method of the antiviral article of this invention.

Hereinafter, some embodiments of the antiviral article of the present invention and the method for producing the same will be described in detail with reference to the drawings.

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

As shown in FIG. 1, the antiviral article 1 of the present embodiment includes a base material 3 and a coating layer 5 that covers the surface of the base material 3. In the illustrated example, rubber is applied as the base material 3. Further, as shown in FIG. 2, the coating layer 5 contains the resin 7 and the quaternary ammonium salt 9 held by the resin 7. Further, the quaternary ammonium salt 9 is partially exposed on the surface of the coating layer 5.

The antiviral article of the present embodiment is placed on the surface of the substrate, and the quaternary ammonium salt is partially exposed on the surface of the coating layer containing the resin and the quaternary ammonium salt. It is considered to have excellent viral durability.

In particular, artificial leather to which such an antiviral article is applied is considered to have excellent antiviral washing durability. Further, in the antiviral article of the present embodiment, it is preferable that the base material is partially exposed on the surface of the coating layer.

Further, such an antiviral article has a secondary advantage that it may be further provided with at least one of morphological stability, deodorant property and antibacterial property.

Hereinafter, each component will be described in more detail.

The base material 3 preferably contains, for example, wallpaper, rubber, a coating film, a film, a tape, a resin, a paper material, a fiber, and a fiber aggregate. Among them, in rubber, coating film, film and tape, these charges, for example, negative ions, which were prevented from being generated by the resin of the coating film layer due to being exposed on the surface of the coating film layer, It is thought that the outbreak will be easier and the ability to adsorb the virus will be greatly increased. Further, also in the fiber aggregate, since it is exposed on the surface of the coating layer, it becomes easy to generate a charge, for example, a negative ion in the fiber aggregate which was prevented from being generated by the resin of the coating layer. , It is thought that the ability to adsorb viruses is greatly increased.

Examples of the wallpaper include resin wallpaper used for buildings, Japanese paper / paper wallpaper, and diatomaceous earth wallpaper. Examples of the rubber include rubber used for fittings and transportation machinery of buildings, rubber used for kitchen utensils, office equipment, furniture and the like. Examples of the coating film include coating films formed on products used as fittings for buildings and transportation machinery, kitchen utensils, office equipment, furniture and the like. Examples of the film include a film used for fittings of buildings and transportation machinery, a film used for kitchen utensils, office equipment, furniture and the like. Examples of the tape include tapes used for kitchen utensils, office equipment, furniture and the like. Examples of the resin include resins used for fittings and transportation machinery of buildings, and resins used for kitchen utensils, office equipment, furniture and the like. Examples of paper materials include newspaper rolls, printing / information papers, wrapping papers, sanitary papers, miscellaneous papers, cardboard base papers, paperboards for paper containers, building material base papers, paper tube base papers, wamps, and other paperboards such as paperboards. be able to. Examples of the fiber include carbon fiber, aramid fiber, glass fiber and the like. These fibers may be fiber aggregates. The fiber aggregate preferably includes, for example, plying, non-woven fabric, woven fabric, and knitted fabric.

Among them, it is more preferable to use a woven fabric as a fiber aggregate from the viewpoint that it can be easily applied to a mask that is washed and reused, which is an application example of an antiviral article.

The material of the fiber aggregate is not particularly limited, and examples thereof include synthetic fibers, semi-synthetic fibers, and natural fibers.

The fiber aggregate includes, for example, cotton fiber, linen fiber, wool fiber, silk fiber, rayon fiber, acetate fiber, polyester fiber, polyamide fiber, polyvinyl alcohol fiber, polyvinylidene chloride fiber, polyolefin fiber, polyurethane fiber, polytetrafluoroethylene. It is preferable to contain fibers and carbon fibers. Furthermore, two or more of these can be used in any combination.

Although not particularly limited, among the synthetic fibers, for example, polyester fibers such as polyethylene terephthalate fiber, polypropylene terephthalate fiber, polybutylene terephthalate fiber, polyhexamethylene terephthalate fiber, polyamide fiber such as nylon 6 fiber and nylon 6,6 fiber, and poly. It preferably contains acrylic fiber, polypropylene fiber, polyvinyl chloride fiber, and polyvinyl alcohol fiber.

Although not particularly limited, it is preferable to include, for example, acetate fiber and rayon fiber among the semi-synthetic fibers.

Although not particularly limited, it is preferable to include wool fiber, silk fiber, cotton fiber and hemp among natural fibers.

Among them, from the viewpoint that static electricity is likely to occur between the two types of fibers and viruses are easily adsorbed, it is more preferable to use a woven fabric in which cotton fibers and polyester fibers are combined as a fiber aggregate.

As the resin 7 as a binder for binding the quaternary ammonium salt, for example, any of a thermoplastic resin, a thermosetting resin, an ultraviolet curable resin, and a two-component mixed room temperature curable resin can be used. However, it is more preferable to use a thermosetting resin. The thermoplastic resin is, for example, 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. Polyester resin such as resin, polyethylene terephthalate, polybutylene terephthalate, polyphenylene oxide resin, polyphenylene sulfide resin, polysulphon resin, polytatetel sulphon resin, polyether ether ketone resin, polyallyl sulfone resin, polyimide resin, polyaminobismaleimide resin, polyamide It is preferable to include an imide resin, a polyetherimide resin, a bismaleimide triazine resin, a polymethylpentene resin, a fluororesin, an olefin / vinyl alcohol copolymer resin, a polyurethane resin, and a polyallylate resin. In addition, these can be used alone or in any combination of two or more. The thermosetting resin preferably contains, for example, an alkyd resin, a melamine resin, a phenol resin, an unsaturated polyester, a diallyl phthalate resin, an epoxy resin, a silicone resin, and a urea resin. Further, these can also be used alone or in any combination of two or more.

Among them, it is more preferable to use a melamine resin as a thermosetting resin from the viewpoint that the water resistance and weather resistance of the antiviral article can be improved.

As the quaternary ammonium salt 9, a conventionally known quaternary ammonium salt showing antiviral property against an enveloped virus can be used.

Quaternary ammonium salts are known as a type of surfactant. Further, it is known that a mixed solution of a cationic surfactant and an anionic surfactant forms various molecular aggregates even in a system diluted as compared with a general surfactant solution. In particular, the vesicle, which is attracting attention as such a molecular assembly, is a bag-shaped self-assembly in which amphipathic molecules having hydrophilicity and hydrophobicity are lined up without gaps in water to form a lipid bilayer. It is also known that when forming such a molecular aggregate, it is preferable that the molar ratio when mixing these two types of surfactants is not close to equimolar.

For example, when an anionic antibacterial processing agent, which is an anionic surfactant, is used to produce an antiviral functional fiber having washing durability, it is necessary to add a binder in order to increase the washing durability. Then, in order to further improve the durability, it is necessary to increase the amount of the resin used as the binder and the amount of the cross-linking agent added to the resin. However, this can impair the soft texture of the textile product and increase costs.

On the other hand, for example, an antiviral function having washing durability by using two kinds of a cationic antibacterial processing agent (Nikkanon RB) which is a cationic surfactant and an anionic antibacterial processing agent which is an anionic surfactant. When producing fibers, the bond between these molecular aggregates and the binder becomes strong. Here, Nikkanon RB contains a quaternary ammonium salt. Therefore, the amount of the resin used as a binder for binding the quaternary ammonium salt to the base material can be reduced. As a result, the flexible texture of the textile product can be maintained and the cost can be reduced.

Further, a cationic antibacterial processing agent (Nikkanon RB), which is a cationic surfactant, and a diluted anionic antibacterial processing agent, which is an anionic surfactant, are added and mixed, and then the mixture is mixed. When the binder is added and the obtained binder mixture containing the quaternary ammonium salt is coated on the fiber, the quaternary ammonium salt can be firmly bonded to the fiber. At this time, one type of binder may be used, but if a plurality of types of binders are used, the quaternary ammonium salt can be firmly bonded to the fibers. Although not particularly limited, it is preferable to combine an acrylic emulsion and a nonionic cross-linking agent as a resin that functions as a binder. The "acrylic emulsion" is an emulsion containing fine-grained acrylic polymers. As a typical example, a self-crosslinking acrylic acid ester copolymer emulsion having a composition and a milky white emulsion (milky white liquid) having an appearance can be mentioned. Further, it is preferable to mix the cationic surfactant and the anionic surfactant at a molar ratio deviated from the equimolar mixture.

Until now, it has been considered difficult to bind a quaternary ammonium salt to a fiber such as polyester or nylon using a binder to obtain an antiviral functional fiber having washing durability. As described above, fibers such as polyester and nylon can be used as antiviral functional fibers by using a mixture of a cationic surfactant, an anionic surfactant and a binder.

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

Although not particularly limited, for example, the content of the quaternary ammonium salt in the fiber aggregate is 0.5 to 3.0% o. w. f. (On the weight of fiber) is preferable. The content of the quaternary ammonium salt in the fiber aggregate is 0.5% o. w. f. If it is less than, the washing durability of the antiviral article may be reduced. On the other hand, the content of the quaternary ammonium salt in the fiber aggregate is 3.0% o. w. f. If it exceeds, the soft texture of the processed textile product may be impaired.

Examples of rubber products to which the antiviral article of the present invention is applied include toys, play equipment, sports equipment, condoms and the like.

Examples of the coated product to which the antiviral article of the present invention is applied include articles coated with water-based paint, oil-based paint, acrylic paint, furniture / floor paint and the like.

Film products to which the antiviral article of the present invention is applied include, for example, 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 of various digital signage, face shields, window films, in-vehicle display touch panel films for automobiles, and the like.

Examples of tape products to which the antiviral article of the present invention is applied include gymnasium line tapes, medical protective tapes, buildings / offices, stores / commercial facilities, schools / educational facilities, hospitals / medical facilities, nursing care facilities, and exercise.・ Tapes for preventing contact infections in amusement facilities, etc. (door knobs, stair railings, washroom railings, toilet railings, etc.) can be mentioned.

Examples of the resin product to which the antiviral article of the present invention is applied include toys, play equipment, sports equipment and the like.

Examples of paper products to which the antiviral article of the present invention is applied include corrugated cardboard, magazines, newspapers and the like.

Examples of the fiber to which the antiviral article of the present invention is applied include carbon fiber, aramid fiber, glass fiber and the like applied to fiber reinforced plastic.

Examples of textile products to which the anti-virus article of the present invention is applied include clothing products, nursing care products, miscellaneous goods products, interior products, bedding products and the like.

Clothing items include, for example, outing clothing, sportswear, homewear, relaxing wear, pajamas, sleeping clothes, underwear, office wear, work clothes, food white coats, nursing white coats, patient clothes, nursing clothes, student clothes, kitchen clothes, etc. Can be mentioned.

Examples of nursing care products include supporters, corsets, rehabilitation shoes, underwear, diaper covers, accessories and the like.

Examples of miscellaneous goods include aprons, towels, gloves, mufflers, socks, hats, shoes, sandals, bags, umbrellas and the like.

Examples of interior goods include curtains, rugs, mats, kotatsu covers, sofa covers, cushion covers, sofa side fabrics, toilet seat covers, toilet seat mats, tablecloths and the like.

Examples of bedding products include side fabrics for duvets, cotton padding for duvets, blankets, side fabrics for blankets, pillow fillers, sheets, waterproof sheets, duvet covers, pillowcases and the like.

FIG. 3 is a schematic cross-sectional view showing the configuration of a second embodiment of the antiviral article of the present invention. The schematic cross-sectional view shown by enlarging the portion surrounded by the line II in FIG. 3 is the same as that in FIG.

As shown in FIG. 3, the antiviral article 1A of the present embodiment includes a base material 3 and a coating layer 5 that covers the surface of the base material 3. In the illustrated example, the woven fabric, which is an example of the fiber aggregate, is applied as the base material 3. Further, as shown in FIG. 2, the coating layer 5 contains the resin 7 and the quaternary ammonium salt 9 held by the resin 7. Further, the quaternary ammonium salt 9 is partially exposed on the surface of the coating layer 5. In the illustrated example, a thermosetting resin is applied as the resin 7.

As described above, the antiviral article of the present embodiment is arranged on the surface of the fiber aggregate, and the quaternary ammonium salt is partially on the surface of the coating layer containing the thermosetting resin and the quaternary ammonium salt. Since it is exposed, it is considered to have excellent antiviral durability.

In particular, a mask to which such an antiviral article is applied is considered to have excellent antiviral washing durability. Further, in the antiviral article of the present embodiment, it is preferable that the fiber aggregate is partially exposed on the surface of the coating layer. As described above, since the fiber aggregate is exposed on the surface of the coating layer, charging in the fiber aggregate, for example, generation of negative ions, which was prevented from being generated by the thermosetting resin of the coating layer, is generated. It will be easier and the ability to adsorb the virus will be greatly increased. Since the detailed description of each component has been described above, duplicate description will be omitted.

[Manufacturing method of antiviral articles]
Next, a method for producing the antiviral article of the present invention will be described. The method for producing an antiviral article of the present invention is an embodiment of the above-mentioned method for producing an antiviral article of the present invention. Therefore, the antiviral article of the present invention is not limited to that obtained by the method for producing the antiviral article of the present invention.

The 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 the base material.
The second step, which is performed after the first step, is a step of removing the resin on the surface of the coating layer by polishing or dissolving, and partially exposing the quaternary ammonium salt to the surface of the coating layer.

FIG. 4 is an explanatory diagram schematically showing the procedure of polishing in the first embodiment of the method for producing an antiviral article of the present invention. In the figure (A), the state before polishing is shown, and in the figure (B), the state after polishing is shown. As shown in FIGS. 4A and 4B, in the second step, the resin 7 of the polished portion 11 on the surface of the coating layer 5 is removed by polishing, and the quaternary ammonium salt 9 is removed from the coating layer 5. Partially exposed to the surface.

Although not shown, in the first embodiment of the method for producing an antiviral article of the present invention, the resin of the dissolved portion (corresponding to the polished portion in FIG. 4) on the surface of the coating layer before dissolution is used. It may be removed by dissolution and the quaternary ammonium salt may be partially exposed on the surface of the coating layer.

In the method for producing an antiviral article of the present embodiment, the quaternary ammonium salt may be partially exposed on the surface of a coating layer containing a resin and a quaternary ammonium salt, which is arranged on the surface of a substrate. Therefore, it is considered that an antiviral article having excellent antiviral durability can be obtained.

In particular, the mask to which the antiviral article thus obtained is applied is considered to be excellent in antiviral washing durability.

Further, the antiviral article thus obtained has a secondary advantage that it may be further provided with at least one of morphological stability, deodorant property and antibacterial property.

Hereinafter, each step will be described in more detail.

In the first step, for example, first, a base material (preferably a fiber aggregate) is contacted with a quaternary ammonium salt-containing liquid as an antiviral agent and impregnated to impregnate the base material (preferably a quaternary ammonium salt-containing liquid-containing base material). A quaternary ammonium salt-containing liquid-containing substrate (preferably a fiber aggregate) is then dried to obtain a quaternary ammonium salt-containing substrate (preferably a fiber aggregate). .. Next, a quaternary ammonium salt-containing base material (preferably a fiber aggregate) is impregnated with a resin (preferably a thermosetting resin) raw material-containing liquid as an adhesive to impregnate the resin (preferably a thermosetting resin). ) Raw material-containing liquid / quaternary ammonium salt-containing base material (preferably fiber aggregate), then resin (preferably thermosetting resin) raw material-containing liquid / quaternary ammonium salt-containing base material (preferably fiber) It is preferable to heat the aggregate) to form a coating layer containing a resin (preferably a thermosetting resin) and a quaternary ammonium salt on the surface of the base material (preferably a fiber aggregate). From the viewpoint that the quaternary ammonium salt can be firmly adhered to the substrate (preferably the fiber aggregate), it is preferable to carry out such a first step.

Further, in the first step, for example, the base material (preferably a fiber aggregate) is impregnated with a quaternary ammonium salt-containing liquid and a resin (preferably thermosetting resin) raw material-containing liquid in this order. A mixture of a quaternary ammonium salt-containing liquid and a resin (preferably thermosetting resin) raw material-containing liquid is contacted and impregnated to impregnate the quaternary ammonium salt-containing liquid / resin (preferably thermosetting resin) raw material-containing liquid. A quaternary ammonium salt-containing liquid / resin (preferably a thermosetting resin) raw material-containing liquid-containing base material (preferably a fiber aggregate) is heated to obtain a contained base material (preferably a fiber aggregate). It is preferable to form a coating layer containing a resin (preferably a thermosetting resin) and a quaternary ammonium salt on the surface of the base material (preferably a fiber aggregate). From the viewpoint that the quaternary ammonium salt is easily exposed on the surface of the coating layer and the quaternary ammonium salt is easily present in a dispersed state in the coating layer, it is preferable to carry out such a first step.

Here, although not particularly limited, the solvent applied to the quaternary ammonium salt and resin (preferably thermosetting resin) raw material is a solvent for dissolving the quaternary ammonium salt and resin (preferably thermosetting resin) raw material. Is preferable. However, the present invention is not limited to this, and a solvent that becomes an emulsion state can also be applied. Further, although not particularly limited, the solvent applied to the quaternary ammonium salt and the resin (preferably thermocurable resin) raw material includes, for example, water, methanol, ethanol, n-propyl alcohol, isopropyl alcohol, and n-butyl alcohol. , Isobutyl alcohol, sec-butyl alcohol and other alcohols can be mentioned.

Among them, from the viewpoint that the viscosity of the quaternary ammonium salt-containing liquid or resin (preferably thermocurable resin) raw material-containing liquid is unlikely to increase, the quaternary ammonium salt or resin (preferably thermocurable resin) raw material. The solvent applied to is preferably methanol or ethanol, and a mixed solution of alcohol such as methanol or ethanol and water is also preferable.

Further, when forming the coating layer, instead of the resin raw material-containing liquid as the adhesive material described above, for example, a chemical reaction of a solvent-based lacquer paint, a water-based emulsion paint, a thermoplastic powder paint or the like to be coated on a base material is used. Paints that form a coating film by drying and curing without the need for, dry oil type alkyd paint, unsaturated polyester paint, ultraviolet curable paint, normal dry epoxy paint, normal dry urethane paint, thermosetting liquid paint, thermosetting type A paint such as a powder paint that forms a coating film by drying and curing accompanied by a chemical reaction can be used. For example, such a paint may be mixed with a quaternary ammonium salt in advance. Examples of the resin contained in the adhesive or the paint include the above-mentioned thermoplastic resin and thermosetting resin. Further, the adhesive or the paint may be a one-component type or a two-component type. As the adhesive and the paint, commercially available adhesives and paints can be used, respectively.

Although not particularly limited, when the base material is a fiber aggregate, the above-mentioned drying conditions are preferably 90 to 150 ° C. for about 30 seconds to 5 minutes. If the drying temperature is less than 90 ° C., the washing durability of the antiviral article may decrease. On the other hand, if the drying temperature exceeds 150 ° C., deterioration of the quaternary ammonium salt, which is an antiviral agent, may occur.

Although not particularly limited, when the base material is a fiber aggregate, the above-mentioned heating conditions are preferably 120 to 200 ° C. and 30 seconds to 10 minutes. At the time of such heating, it is preferable to further pressurize the clothes to the same degree as when ironing the clothes, and for example, it is preferable to pressurize with a roller.

In an 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, etc. in a dry state, and quaternary ammonium is used. The salt is exposed on the surface of the coating layer to obtain 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 moistened with water, a hypochlorite aqueous solution, or the like in a wet state. Then, it is removed by polishing with a grindstone or sandpaper, in other words, by water polishing, and the quaternary ammonium salt is exposed on the surface of the coating layer to obtain an antiviral article.

In still 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 used in a dry state, for example, another coating layer obtained in the first step. It is removed by polishing by rubbing with a resin (preferably a thermosetting resin) on the surface of the coating layer, and a quaternary ammonium salt is exposed on the surface of the coating layer to obtain an antiviral article.

In still another example of the second step, the surface resin (preferably a thermosetting resin) of the coating layer obtained in the first step is moistened with water, a hypochlorite aqueous solution, or the like to moisten the coating layer. In this state, polishing by rubbing with, for example, a resin (preferably a thermosetting resin) on the surface of another coating layer obtained in the first step, in other words, removing by water polishing, and coating with a quaternary ammonium salt. Exposure to the surface of the layer gives an antiviral article.

Although not particularly limited, the above-mentioned polishing conditions are such that the sliding speed of the grindstone, sandpaper, and another coating layer is about 0.5 to 5 m / s while applying a pressing force of about 5 to 50 kgf per 1 m ² . It is preferable to perform polishing with a rubbing time of about 0.5 seconds to 5 minutes.

Although not particularly limited, the temperature of the coating layer in the above-mentioned polishing is set to 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. It is preferable to do so.

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, the coating layer is moistened with water, a hypochlorite aqueous solution, or the like in a wet state. Polishing with water, in other words, removing by water polishing has the advantage that the shape and structure of the base material (preferably fiber aggregate) can be maintained and the durability of antiviral property can be further improved.

Rather than removing the resin (preferably a thermosetting resin) on the surface of the coating layer of the article obtained in the first step by polishing in a dry state, the coating layer was moistened with water, an aqueous hypochlorous acid solution, or the like. The shape and structure of the base material (preferably fiber aggregates) can be maintained by polishing in a wet state, in other words, removing by water polishing. When the fiber aggregate is formed of two types of fibers in which static electricity is likely to occur, static electricity is generated between the two types of fibers, and the shape and structure in which the virus is easily adsorbed can be maintained. As a result, there is an advantage that the durability of antiviral property can be further improved.

The thermosetting resin may contain formalin, but the thermosetting resin on the surface of the coating layer obtained in the first step is coated with an acid or an alkali, particularly a hypochlorite aqueous solution. In a moistened state, polishing with a grindstone or sandpaper, or polishing by rubbing with a thermosetting resin on the surface of the coating layer of another article obtained in the first step, in other words, by water polishing. By removing it, there is an advantage that formalin can be removed.

In the above-mentioned example of the second step, the thermosetting resin on the surface of the coating layer obtained in the first step is moistened with water, a hypochlorite aqueous solution, or the like in a wet state, and the first step is performed. For example, it is preferable to remove it by polishing by rubbing it with a thermosetting resin on the surface of the coating layer of another article, in other words, by water polishing.

Further, 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, and then the dissolved portion is removed. Later, the quaternary ammonium salt is exposed to the surface of the coating layer to obtain an antiviral article.

Further, the solvent used for dissolving the resin can be appropriately selected from conventionally known solvents according to the type of the resin contained in the coating layer.

Although not particularly limited, the temperature of the coating layer in the above-mentioned melting is 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 due to the dissolution and the adhesion of the coating layer is not significantly deteriorated. Is preferable.

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

(Example 1)
A mixed solution containing a fiber aggregate (plain woven cloth, 40% polyester, 60% cotton) containing a quaternary ammonium salt as an antiviral agent and a thermosetting resin raw material-containing liquid as an adhesive (Nikkanon RB (Nichika Kagaku)). Quaternary ammonium salt was added to the fiber aggregate in 2.0% o. w. f. Contact was carried out for 0.5 seconds so as to support the mixture to obtain a quaternary ammonium salt-containing liquid / thermosetting resin raw material-containing liquid-containing fiber aggregate, which was then squeezed with a padder at a drawing ratio of 100%, and then at 120 ° C. A coating layer containing a thermosetting resin and a quaternary ammonium salt was formed on the surface of the fiber aggregate. Hereinafter, this is referred to as "article 1".

After that, the thermosetting resin on the surface of the coating layer of the obtained article 1 was moistened with a hypochlorite aqueous solution in a wet state, and the thermosetting resin on the surface of another coating layer and 10 kgf per 1 m ² were used. Polishing by rubbing another coating layer at a sliding speed of 1 m / s for 1 second while applying pressure, in other words, removing by water polishing, and partially applying a quaternary ammonium salt to the surface of the coating layer. Exposure was obtained to obtain the antiviral article of this example.

(Example 2)
5 parts by mass of cationic quaternary ammonium salt (Nikkanon RB (manufactured by Nikka Kagaku Co., Ltd.)) using fiber aggregate (woven cloth, 40% polyester, 60% cotton) as an antiviral agent, anionic quaternary ammonium An antiviral processing liquid containing 5 parts by mass of salt, 5 parts by mass of an acrylic emulsion as a binder, 2 parts by mass of a nonionic cross-linking agent as a binder aid, and 80 parts by mass of water, with respect to the fiber aggregate. The quaternary ammonium salt is 2.0% o. w. f. The fibers were contacted for 0.5 seconds so as to be carried to obtain an antiviral processing liquid-containing fiber aggregate, which was then squeezed with a padder at a drawing ratio of 100%, and then heated at 120 ° C. for 5 minutes to obtain the fiber aggregate. A coating layer containing a resin and a quaternary ammonium salt was formed on the surface of the above. Hereinafter, this is referred to as "article 2".

After that, in a wet state where the resin on the surface of the coating layer of the obtained article 2 was moistened with an aqueous hypochlorite solution, a pressure of 10 kgf per 1 m ² was applied to the thermosetting resin on the surface of another coating layer. While adding, polishing by rubbing another coating layer at a sliding speed of 1 m / s for 1 second, in other words, removing by water polishing, and partially exposing the quaternary ammonium salt to the surface of the coating layer. , The antiviral article of this example was obtained.

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

[Performance evaluation]
(Antiviral test)
The antiviral articles and articles of each example were evaluated according to the method described in the 2014 version of ISO18184. There are two types of viruses to be tested.
-Influenza A virus (H3N2) (ATCC VR-1679)
・ Feline calicivirus (F-9) (ATCC VR-782)

(Washing method)
Standard washing method (1995 version JIS L0217 103 method) in accordance with "Washing method for SEK mark textile products" (revised April 1, 2014, document number JEC326) issued by the Product Certification Department of the Textile Evaluation Technology Council. It was washed 150 times using the method described), and then hung and dried.

It was found that the antiviral articles of Examples 1 and 2 belonging to the scope of the present invention show excellent antiviral properties regardless of whether the product is unwashed or washed 150 times.
Further, the antiviral article of the present invention exhibits excellent antiviral properties not only because the quaternary ammonium salt is exposed on the surface of the coating layer, but also because the thermosetting resin on the surface of the coating layer is removed by polishing. It is also considered that this facilitates the generation of ions in the fiber aggregate, which was inhibited from being generated by the thermosetting resin of the coating layer, and greatly increases the ability to adsorb the virus.
On the other hand, it was found that the article of Comparative Example 1 outside the present invention did not show antiviral properties.

(Example 3)
10 parts by mass of cationic quaternary ammonium salt (Nikkanon RB (manufactured by Nikka Kagaku Co., Ltd.)) as an antiviral agent, acrylic as a binder, using a fiber aggregate (woven cloth, 40% polyester, 60% cotton). An antiviral processing solution containing 5 parts by mass of a system emulsion, 2 parts by mass of a nonionic cross-linking agent as a binder aid, and 80 parts by mass of water contains 2.0% of a quaternary ammonium salt with respect to the fiber aggregate. o. w. f. The fibers were contacted for 0.5 seconds so as to be carried to obtain an antiviral processing liquid-containing fiber aggregate, which was then squeezed with a padder at a drawing ratio of 100%, and then heated at 120 ° C. for 5 minutes to obtain the fiber aggregate. A coating layer containing a resin and a quaternary ammonium salt was formed on the surface of the above. Hereinafter, this is referred to as "article 3".

After that, in a wet state where the resin on the surface of the coating layer of the obtained article 3 was moistened with an aqueous hypochlorite solution, a pressure of 10 kgf per 1 m ² was applied to the thermosetting resin on the surface of another coating layer. While adding, polishing by rubbing another coating layer at a sliding speed of 1 m / s for 1 second, in other words, removing by water polishing, and partially exposing the quaternary ammonium salt to the surface of the coating layer. , The antiviral article of this example was obtained.

(Example 4)
2.5 parts by mass of cationic quaternary ammonium salt (Nikkanon RB (manufactured by Nikka Kagaku Co., Ltd.)) using fiber aggregate (woven cloth, 40% polyester, 60% cotton) as an antiviral agent, anionic quaternary ammonium salt An antiviral processing liquid containing 2.5 parts by mass of a quaternary ammonium salt, 2.5 parts by mass of an acrylic emulsion as a binder, 1 part by mass of a nonionic cross-linking agent as a binder aid, and 80 parts by mass of water. , Contact for 0.5 seconds in the same manner as in Example 4 to obtain an antiviral processing liquid-containing fiber aggregate, which is then squeezed with a padder at a drawing ratio of 100%, and then heated at 120 ° C. for 5 minutes. A coating layer containing a resin and a quaternary ammonium salt was formed on the surface of the fiber aggregate. Hereinafter, this is referred to as "article 4".

After that, in a wet state where the resin on the surface of the coating layer of the obtained article 4 was moistened with an aqueous hypochlorite solution, a pressure of 10 kgf per 1 m ² was applied to the thermosetting resin on the surface of another coating layer. While adding, polishing by rubbing another coating layer at a sliding speed of 1 m / s for 1 second, in other words, removing by water polishing, and partially exposing the quaternary ammonium salt to the surface of the coating layer. , The antiviral article of this example was obtained.

(Comparative Example 2)
The 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 according to the antiviral test method (JIS L1922: 2016 plaque measurement method) for textile products. Tables 1 and 2 show some of the test conditions and the results obtained.

From Tables 1 and 2, it was found that the antiviral articles of Examples 3 and 4 belonging to the scope of the present invention also show excellent antiviral properties. Furthermore, from the results of the antiviral articles of Examples 3 and 4, it was found that even in Example 4 in which the blending ratio of the binder and the like was reduced by 50%, excellent antiviral properties were exhibited. That is, it was found that the amount of the resin used as the binder can be reduced when the quaternary ammonium salt is bound to the base material such as polyester. Furthermore, it was found that the amount of resin used can be reduced, so that the flexible texture of the textile product can be maintained and the cost can be reduced.
On the other hand, it was found that the article of Comparative Example 2 outside the present invention did not show antiviral properties.

Although the present invention has been described above with reference to some embodiments and examples, the present invention is not limited thereto, and various modifications can be made within the scope of the gist of the present invention.

1,1A Antiviral article 3 Base material 5 Coating layer 7 Resin 9 Quaternary ammonium salt 11 Polished part

Claims (10)

A base material and a coating layer covering the surface of the base material are provided.
The coating layer contains a resin and a quaternary ammonium salt.
The quaternary ammonium salt is an antiviral article characterized in that it is partially exposed on the surface of the coating layer. The base material is a fiber aggregate and
The antiviral article according to claim 1, wherein the resin is a thermosetting resin. The antiviral article according to claim 2, wherein the fiber aggregate includes a twisted yarn, a non-woven fabric, a woven fabric, or a knitted fabric. The fiber aggregates are cotton fiber, linen fiber, wool fiber, silk fiber, rayon fiber, acetate fiber, polyester fiber, polyamide fiber, polyvinyl alcohol fiber, polyvinylidene chloride fiber, polyolefin fiber, polyurethane fiber, polytetrafluoroethylene fiber. The antiviral article according to claim 2 or 3, which comprises at least one selected from the group consisting of carbon fibers and carbon fibers. The antiviral article according to any one of claims 2 to 4, wherein the fiber aggregate contains cotton fibers and polyester fibers. 2. The thermosetting resin is characterized by comprising at least one selected from the group consisting of a melamine resin, a phenol resin, an unsaturated polyester, a diallyl phthalate resin, an epoxy resin, a silicone resin and a urea resin. The antiviral article according to any one of 5. The content of the quaternary ammonium salt with respect to the fiber aggregate is 0.5 to 3.0% o. w. f. The antiviral article according to any one of claims 2 to 6, wherein the antiviral article is (On the weight of fiber). The antiviral article according to any one of claims 1 to 7, wherein the quaternary ammonium salt is present in a dispersed state in the coating layer. The method for producing an antiviral article according to any one of claims 1 to 8.
The first step of forming a coating layer containing a resin and a quaternary ammonium salt on the surface of a base material, and
Having a second step performed after the first step, in which the resin on the surface of the coating layer is removed by polishing or dissolution and the quaternary ammonium salt is partially exposed on the surface of the coating layer. A method for producing an antiviral article. The base material is a fiber aggregate and
The resin is a thermosetting resin and is
The method for producing an antiviral article according to claim 9, wherein the removal of the resin in the second step is performed by removal of the resin by polishing.

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