JP2016102072A - Surface treatment agent having anti-viral property, and anti-viral sheet shaped product coated with surface treatment agent - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide: a surface treatment agent that has an anti-viral property as well as does not impair the appearance of an object body to be coated when used for the coating, and that is excellent in anti-viral property and has a transparency; and an object body coated with the same, especially an anti-viral sheet shaped product such as a sheet and a film or the like.SOLUTION: Provided are: an anti-viral surface treatment agent obtained by adding a sulfonic acid-based surfactant to an anionic aqueous resin emulsion; and an anti-viral sheet shaped product in which at least one surface of a sheet shaped product is coated with said anti-viral surface treatment agent.SELECTED DRAWING: None

Description

  The present invention relates to a surface treatment agent having antiviral properties and an antiviral sheet-like material coated with the surface treatment agent.

Viral diseases such as severe respiratory infection (SARS) virus, avian influenza virus, foot-and-mouth disease virus, and new influenza virus are becoming social problems one after another.
Originally, the host range of viruses is limited, and it is normal that only mammals infect mammals and only birds infect birds. However, since avian influenza virus is a virus with a wide host range that can infect not only birds but also mammals, it may infect humans. In recent years, H5N1 avian influenza virus has spread in Asia and Europe, and there is concern about the emergence of highly toxic influenza mutated based on it. Recently, highly resistant noroviruses and Ebola viruses with high mortality rates when infected are becoming more and more prominent. They are not only prepared for pandemic (infection explosion) caused by viruses, but also resistant to building materials such as interior materials and everyday items. Viral products are expected.

  As a method for easily imparting antiviral properties to various building materials and daily products, there is a method of applying a paint to which an inorganic filler is added. Patent Document 1 discloses calcium and / or magnesium oxides and / or An antiviral coating composition containing an antiviral component containing a hydroxide and a coating resin component is disclosed. And it is preferable that content of the antiviral component with respect to a coating resin component (solid content) is 50-500 mass%, and if it is less than 50 mass%, antiviral expression will become difficult. . Therefore, when calcium oxide, calcium hydroxide, or the like is used as an antiviral component, it is necessary to add a relatively large amount of these inorganic fillers for antiviral expression.

JP 2007-106876 A

  As described above, a coating containing an inorganic filler needs to be added with a relatively large amount of antiviral components for the development of antiviral properties, and this coating is an inorganic filling that is an added antiviral component. Depending on the material, the transparency may be reduced and the material may become opaque. Thus, when the transparency of a coating material falls, the external appearance of the construction material etc. which are to-be-coated bodies will be impaired. In particular, building materials and everyday items often have design properties on their surfaces, and it is required to impart antiviral properties without harming their design properties.

  The present invention solves the above-mentioned problems, has antiviral properties and does not impair the appearance of the coated object when applied, and has excellent antiviral properties and transparency. An object of the present invention is to provide an antiviral sheet-like material such as a sheet or film.

  The means used by the present invention to solve the above-mentioned problems is to provide an antiviral surface treatment agent in which a sulfonic acid surfactant is added to an aqueous resin emulsion. Furthermore, it is preferable to use an antiviral surface treatment agent containing 1 to 10% by weight of a sulfonic acid surfactant relative to the total of the solid content of the aqueous resin emulsion and the sulfonic acid surfactant. The aqueous resin emulsion may be an anionic resin emulsion, or a water-insoluble filler may be contained in the solid content of the aqueous resin emulsion. Moreover, it is an antiviral sheet-like material in which the antiviral surface treatment agent described above is applied to at least one surface of the sheet-like material.

  According to the present invention, an antiviral surface treatment agent having excellent antiviral properties can be obtained. Moreover, the antiviral surface treatment agent in which the film | membrane applied to the to-be-coated body has transparency can be obtained. Furthermore, by applying to a sheet material, a sheet material having antiviral properties and transparency can be obtained.

Hereinafter, the present invention will be described in detail.
The aqueous resin emulsion of the present invention is a product in which a resin as a dispersoid is dispersed in water as a dispersion medium. Here, the water as the dispersion medium may contain a hydrophilic solvent such as alcohol. As a method of dispersing the resin in water, there are a forced emulsification type using a surfactant as an emulsifier and a self-emulsification type in which a hydrophilic group is introduced into the resin. In the present invention, both forced emulsification type and self-emulsification type can be used.

  Further, there are a colloidal dispersion type in which dispersed resin particles are in the colloid range and an emulsion type in which dispersed resin particles are beyond the colloid range. The aqueous resin emulsion of the present invention includes both. The emulsion type is preferred from the viewpoint of imparting stain resistance by increasing the molecular weight of the resin and reducing VOC due to low solvent content.

  Here, a sulfonic acid surfactant is added to the aqueous resin emulsion, but the sulfonic acid surfactant is anionic. Accordingly, the aqueous resin emulsion is also preferably anionic. If the aqueous resin emulsion is anionic, a stable dispersed antiviral surface treatment agent can be obtained even if an anionic surfactant is added. On the other hand, when a cationic aqueous resin emulsion is used, the emulsion may be destroyed by the addition of an anionic sulfonic acid surfactant. Therefore, it is preferable to use an anionic aqueous resin emulsion because a more stable antiviral surface treatment agent can be obtained.

  Commonly used resins such as acrylics, urethanes, acrylic urethanes, styrene acrylics, polycarbonates, epoxys, EVAs, vinyl acetates, vinyl chlorides, etc. as resins used in aqueous resin emulsions Can be used. You may mix and use these resin.

Examples of the sulfonic acid surfactant used in the present invention include alkylbenzene sulfonic acid compounds, alkyl diphenyl ether disulfonic acid compounds, alkyl naphthalene sulfonic acid compounds, alkyl sulfate esters, polyoxyethylene alkyl sulfate esters, naphthalene sulfones. Examples include acid formalin condensate compounds. Of these, alkylbenzenesulfonic acid compounds, alkyldiphenyl ether disulfonic acid compounds, and alkylnaphthalenesulfonic acid compounds are preferable from the viewpoint of excellent antiviral properties, and alkylbenzenesulfonic acid compounds that are particularly excellent in antiviral properties are more preferable.
In the sulfonic acid surfactant used in the present invention, it is assumed that the sulfonic acid group has a high affinity with, for example, influenza virus neuramidase and can exhibit an inhibitory action. In addition, the structure of the functional group has an influence on the approach to the neuraimidase, and it is considered that a structure that is not bulky and hardly receives steric hindrance is important. In that respect, alkylbenzene sulfonic acid surfactants are preferred, and dodecylbenzene sulfonic acid is particularly preferred.
Furthermore, examples of the sulfonic acid surfactant include alkali metal salts such as sodium salt and potassium salt, alkaline earth metal salts such as calcium and barium, and the like. An alkali metal salt is preferable in terms of excellent antiviral properties, and sodium dodecylbenzenesulfonate (DBS) is more preferable.
Further, a plurality of sulfonic acid surfactants may be added as long as antiviral properties are not inhibited, and addition of other types of surfactants is not limited.

  The content of the sulfonic acid surfactant is preferably 1 to 10% by weight, more preferably 3 to 7% by weight, based on the total of the solid content of the aqueous resin emulsion and the sulfonic acid surfactant. If it is less than 1% by weight, the antiviral property is poor, and if it exceeds 10% by weight, the stain resistance may be poor.

  Further, a filler insoluble in water which is a medium of the aqueous resin emulsion can be added. Here, the medium is not limited to water but may be a mixture of water and a hydrophilic solvent. That is, a filler that is insoluble in the aqueous medium of the aqueous resin emulsion can be added. By adding a filler insoluble in water, a high antiviral effect can be expected even when the amount of the sulfonic acid surfactant added is low. As such a water-insoluble filler, organic and inorganic fillers can be used. Various resin pellets and cross-linked resins are used as organic fillers that are insoluble in water. In particular, an acrylic cross-linked resin can be preferably used. Examples of the inorganic filler include silica, calcium carbonate, talc, mica and clay. Silica is preferred from the viewpoint of transparency and matting properties.

  The filler content relative to the solid content of the aqueous resin emulsion is preferably 1 to 10% by weight, and more preferably 3 to 7% by weight. That is, it is preferable that the content of the filler with respect to the solid content of the aqueous resin emulsion containing the filler is the above weight percent. By containing the filler, the antiviral property is improved, but when the amount of the filler added is increased, the stain resistance and transparency are lowered.

The reason why antiviral properties are improved by containing a water-insoluble filler is currently assumed as follows. When an antiviral surface treatment agent containing a filler is applied, a film of an aqueous resin emulsion is formed on the surface of the object to be coated. Fine irregularities are formed on the surface of the film by the contained filler. The contact area between the film and the virus increases due to the minute irregularities on the film surface. In addition, the virus is adsorbed on the filler present on the surface of the membrane, and the contact opportunity between the sulfonic acid surfactant and the virus increases.
Therefore, the water-insoluble filler of the present invention may be any substance that is dispersed in an aqueous medium that is a medium of an aqueous resin emulsion and exists as particles when a film is formed on the surface of the object to be coated.

In the present invention, the water-insoluble filler is contained in the solid content of the aqueous resin emulsion, and the amount of the sulfonic acid surfactant added is defined relative to the solid content of the aqueous resin emulsion. In addition, the water-based resin emulsion includes an antifoaming agent, a leveling agent, a film-forming aid, a wetting agent, a thickening agent, a thinning agent, an ultraviolet absorber, a light stabilizer, an ultraviolet shielding agent, an antistatic agent, a flame retardant, A fluorescent agent, an antibacterial agent, an antifungal agent, a flame retardant, a flame retardant, a pH adjuster, and the like may be added, and the solid content of the aqueous resin emulsion is included including these solid contents.
Further, the antiviral surface treatment agent of the present invention includes an antifoaming material, a leveling agent, a film-forming aid, a wetting agent, a thickening agent, a thickening agent, an ultraviolet absorber, a light stabilizer, an ultraviolet shielding agent, a charging agent. An inhibitor, a flame retardant, a fluorescent agent, a crosslinking agent, an antibacterial agent, an antifungal agent, a flame retardant, a flame retardant, a pH adjuster, and the like can be used as appropriate.

  The antiviral surface treatment agent of the present invention can be applied to the surface of various articles. For example, it can be used for building materials, daily necessities, furniture, protective clothing, masks, filters, and the like. Here, it is preferable to apply an antiviral surface treatment agent to a sheet-like material such as a film, a sheet, and leather because it can be used for various purposes.

There are no particular restrictions on the sheet-like material, but polyolefin resins such as polyethylene and polypropylene, polyester resins such as polyethylene terephthalate and modified polyester, polyvinyl chloride, ethylene-vinyl chloride, propylene-vinyl chloride copolymer, chloride Use materials such as polyvinyl chloride resin such as vinyl-vinyl acetate copolymer, vinyl chloride-vinylidene chloride copolymer, synthetic resin sheet such as acrylic resin, polyurethane resin, paper, woven fabric, non-woven fabric, etc. Can do.
Furthermore, it is good also as a multilayer which laminated | stacked the layer which consists of one or more types of the said sheet-like material, and the use used and the physical property requested | required by providing layers, such as various resin foam layers, design layers, such as a printing layer and a colored layer. The sheet-like material according to can be obtained. Here, the design layer may be a layer that causes an aesthetic appearance through vision in addition to the printed layer and the colored layer exemplified.

  It is preferable to select the composition of the aqueous resin emulsion according to the material used for the object to be coated such as a sheet-like material. The aqueous resin emulsion is preferably selected in consideration of adhesion to the body to be coated and durability. Here, in the case where the object to be coated such as a sheet-like material is composed of a polyvinyl chloride resin, it is preferable to use urethane-based, acrylic-based, urethane-acrylic-based resin, or a mixture thereof as the resin of the aqueous resin emulsion.

  In addition, it is preferable to impart antiviral properties to the object to be coated with the antiviral surface treatment agent of the present invention, and it is expected to improve the antiviral effect sustainability together with the antiviral surface treatment agent layer. it can. Therefore, when making a to-be-coated body into a sheet-like thing, it is preferable to provide the layer which has antiviral property in a sheet-like thing. And when forming the layer which has antiviral property with resin, the antiviral agent which has antiviral property can be added to resin.

  For example, when the sheet is made of a vinyl chloride resin sheet, a sulfonic acid surfactant is preferably used as the antiviral agent. Specifically, alkyl sulfate surfactants, alkylbenzene sulfonate surfactants, alkyl naphthalene sulfonate surfactants, alkyl diphenyl ether disulfonate surfactants, polyoxyethylene alkyl sulfate surfactants, naphthalene Examples include sulfonic acid formalin condensate. Alkylbenzene sulfonic acid surfactants are preferred because of their high antiviral effect, and dodecylbenzene sulfonic acid surfactants are more preferred. Furthermore, as the sulfonic acid surfactant, alkali metal salts such as sodium salt and potassium salt, and alkaline earth metal salts such as calcium and barium can be suitably used.

  The content of the sulfonic acid surfactant in the polyvinyl chloride resin constituting the polyvinyl chloride resin sheet is preferably 0.1 to 10 parts by weight with respect to 100 parts by weight of the polyvinyl chloride resin. In addition, since the addition of a sulfonic acid surfactant may cause coloration, a vinyl chloride resin for paste to which a sulfonic acid surfactant has been added in advance in the production stage is used as a polyvinyl chloride resin. By using as a part or all, coloring can be eliminated.

  The antiviral sheet material of the present invention is obtained by applying the antiviral surface treatment agent of the present invention to the surface of a sheet material. The antiviral surface treatment agent is obtained by stirring an aqueous resin emulsion and a sulfonic acid surfactant with a mixer or the like. Further, it is necessary to dry and solidify the antiviral surface treatment agent after coating. Examples of the conditions for drying and solidifying include a method of heating at a temperature of 100 to 150 ° C. for 3 to 5 minutes using an oven or the like.

  As a film thickness of coating, 1-100 micrometers is preferable and 5-50 micrometers is more preferable. If it is less than 1 μm, the antiviral effect tends to be lost due to wear, and if it is thicker than 100 μm, it may partially foam during drying to impair the appearance.

  In order to stir the aqueous resin emulsion and the sulfonic acid surfactant, a dissolver mixer, a butterfly mixer, a universal stirrer, or the like can be used.

  Knife coating, gravure coating, roll coating, bar coating, die coating, etc. can be used to apply the antiviral surface treatment agent to the sheet.

  In order to dry and solidify the antiviral surface treatment agent after coating, a hot air drying furnace, a far infrared drying furnace, or the like can be used.

  An aperture can be formed on the upper surface of the surface layer of the antiviral sheet by embossing or the like. It is possible to increase the design variations by forming the aperture.

  The antiviral surface treatment agent of the present invention is expected to have an antiviral effect in various viruses, but expresses high antiviral properties particularly against viruses having an envelope. Examples of viruses having an envelope include Ifluenza viruses such as avian influenza virus, human influenza virus and swine influenza virus, hepatitis B virus, hepatitis C virus, human immunodeficiency virus, varicella-zoster virus, herpes simplex virus, human Examples include herpes virus, mumps virus, RS virus, and Ebola virus.

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

Specific substance names of each compounding agent used in Examples and Comparative Examples are as follows.
Aqueous resin emulsion A-1: Urethane-based treatment agent (anionic) 33 wt% solid content 3 wt% in silica solid content
(Brand name; Daipla Coat (registered trademark) WF, manufactured by Dainichi Seika Kogyo)
Aqueous resin emulsion A-2: Urethane-based treatment agent (anionic) Solid content 30% by weight
(Product name: RS-2014, manufactured by Tokushiki)
Aqueous resin emulsion A-3: Urethane-based treatment agent (anionic) 30% by weight of solid content 3.6% by weight in silica solid content
(Product name: RS-2014, manufactured by Tokushiki)
Aqueous resin emulsion A-4: Acrylic treatment agent (anionic) Solid content 25.8% by weight
(Product name: Peorium (registered trademark), manufactured by Konishi)
Sulfonic acid surfactant B-1: Alkylbenzenesulfonic acid Na purity 65%
(Product name: Neoperex (registered trademark) G-65, manufactured by Kao Corporation)
Cationic surfactant C-1: quaternary ammonium salt, purity 50%
(Product name: ARCARD CB-50, manufactured by Lion)
Cationic surfactant C-2: quaternary ammonium salt purity 95%
(Product name: Arcade 210-80E, manufactured by Lion)
Firing dolomite D-1:
(Product name: Barriere P-2, manufactured by Mochigase)
Crosslinking agent E-1:
(Product name: Carbodilite (registered trademark) E-01, manufactured by Nisshinbo Chemical Co., Ltd.)

  The formulations of Examples and Comparative Examples shown in Table 1 were mixed for 2 minutes at 1000 rpm using a universal stirrer to prepare an antiviral surface treatment agent. And this antiviral surface treating agent was apply | coated to the soft PVC sheet with a base fabric with a bar coater as a sheet-like material. Next, it was dried in an oven at 130 ° C. for 4 minutes to solidify the antiviral treatment agent to obtain an antiviral sheet. The film thickness of the antiviral surface treatment agent was 30 μm.

<Emulsion stability>
The stability of the emulsion after mixing the surface treatment agents prepared in the examples and comparative examples shown in Table 1 was evaluated.

○: Stable after standing for 1 day.
Δ: Stable for 1 hour immediately after mixing.
X: The emulsion is broken immediately after mixing and the solid content is aggregated.

<Antiviral properties>
The avian influenza virus A / whisling swan / Shimane / 499/83 (H5N3) strain was used as a test virus. (Hereinafter referred to as H5N3 strain).
The test virus solution was prepared by diluting the H5N3 strain with sterile phosphate buffered saline (PBS; pH 7.2) to 1.0 × 10 ⁶ EID ₅₀ /0.1 mL.

  Place the sheet-like material 5 cm × 5 cm prepared in the examples and comparative examples shown in Table 1 on a petri dish, place 0.22 ml of the test virus solution on the surface of the sheet-like material, and place a 4 cm × 4 cm polyethylene film thereon. Covered, covered the petri dish, and allowed to stand for 1 hour in an incubator set at 20 ° C. One hour later, the virus solution on the surface of the sheet was collected, diluted 10-fold with PBS, and 0.1 mL of the diluted virus solution was inoculated into the chorioallantoic cavity of 10-day-old chicken eggs using an injection needle. did.

After inoculation, the embryonated chicken eggs were cultured at 37 ° C. for 2 days, and then the presence or absence of virus growth in the chorioallantoic cavity was determined by the hemagglutination test, and the virus titer (log ₁₀ EID ₅₀ /0.1 ml) was determined by the method of Reed & Muench. Was calculated.
In addition, the virus titer (log ₁₀ EID ₅₀ /0.1 ml) of the test virus solution before the test (before contact with the sheet-like material) was calculated as a blank according to the above procedure, and the antiviral property of the sheet-like material was determined before the test. Evaluation was made by subtracting the virus titer of the virus solution one hour after contacting the sheet-like material from the virus titer of the virus solution. The larger this difference, the stronger the antiviral properties of the sheet.

○: The difference between the virus titer (before the test) and the virus titer (after 1 hour) is 3 or more High antiviral effect △: The difference between the virus titer (before the test) and the virus titer (after 1 hour) is 1 Less than 3 Has antiviral effect ×: Difference between virus titer (before test) and virus titer (after 1 hour) is less than 1 Antiviral effect is low

<Transparency>
The transparency of the sheet-like materials produced in the examples and comparative examples described in Table 1 was evaluated visually.

○: Transparent.
Δ: A level that is slightly transparent but has no problem in use.
X: Opaque.

<Contamination resistance>
Put six standard rubber blocks in the Snell Capsule Tester described in JIS K 3920, set the surface layer of the sheet-like material in contact with the rubber block, and rotate 5 minutes in the normal direction and 5 minutes in the reverse direction at 50 rpm. After rotating the cycle, the sheet-like material was taken out and the degree of adhesion of the heel mark was observed to evaluate the dirtiness. Further, the cleaning property was evaluated from the degree of adhesion of the heel mark after the contaminated surface was wiped with a dry cloth. Contamination resistance was evaluated from both aspects of dirtiness and cleanability.

Dirtiness I: Almost no adhesion (Slight adhesion is recognized)
II: Adherence but not noticeable III: Adherence

Cleanability I: Dirt can be removed (dirt is not noticeable after cleaning)
II: Some dirt is difficult to remove (there is noticeable dirt after cleaning)
III: Many stains are difficult to remove

When Examples 1-7 are compared with Comparative Examples 1 and 5, it can be seen that antiviral properties are imparted by containing a sulfonate surfactant.
When Examples 1-7 are compared with Comparative Examples 2 and 3, it can be seen that the emulsion is stable by using the sulfonate surfactant.
When Examples 1-7 are compared with Comparative Example 4, it can be seen that the use of a sulfonate surfactant has transparency and excellent appearance.

  According to the present invention, since it is possible to provide a sheet-like product having an excellent appearance that rapidly inactivates the virus by rapidly reducing the virus titer of the contacted virus, it is suitable for various daily goods, buildings, vehicles, and the like. . In particular, it is suitable for places where many people gather at once, such as hospitals, offices, old buildings, public facilities such as schools, buses, trains, and the like, where there is a high risk of virus infection.

Claims (5)

  An antiviral surface treatment agent comprising a sulfonic acid surfactant added to an aqueous resin emulsion.   2. The antiviral surface treatment agent according to claim 1, wherein the sulfonic acid surfactant is contained in an amount of 1 to 10% by weight based on the total of the solid content of the aqueous resin emulsion and the sulfonic acid surfactant.   The antiviral surface treatment agent according to claim 1 or 2, wherein the aqueous resin emulsion is an anionic resin emulsion.   The antiviral surface treating agent according to any one of claims 1 to 3, wherein a filler insoluble in water is contained in the solid content of the aqueous resin emulsion.   The antiviral sheet-like material by which the antiviral surface treating agent of any one of Claims 1-4 is apply | coated to the at least single side | surface of a sheet-like material.