阅读说明：本技术 抗病毒剂、涂料组合物、树脂组合物及抗病毒制品 (Antiviral agent, coating composition, resin composition, and antiviral product ) 是由 杉浦晃治 于 2017-02-02 设计创作，主要内容包括：本发明涉及一种抗病毒剂、涂料组合物、树脂组合物及抗病毒制品。所述抗病毒剂含有酸性点浓度大于0.005mmol/g的无机固体酸。无机固体酸优选含有无机磷酸化合物、无机硅酸化合物或无机氧化物。无机固体酸中的酸性点的酸强度(pKa)优选为3.3以下。(The present invention relates to an antiviral agent, a coating composition, a resin composition and an antiviral product. The antiviral agent contains inorganic solid acid with acid spot concentration greater than 0.005 mmol/g. The inorganic solid acid preferably contains an inorganic phosphoric acid compound, an inorganic silicic acid compound or an inorganic oxide. The acid strength (pKa) of the acid sites in the inorganic solid acid is preferably 3.3 or less.)

1. An antiviral agent characterized by containing an inorganic solid acid having an acid site concentration of more than 0.005 mmol/g.

2. The antiviral agent according to claim 1, wherein the acid strength (pKa) of an acid site in the inorganic solid acid is 3.3 or less.

3. The antiviral agent according to claim 1 or 2, wherein the inorganic solid acid comprises an inorganic phosphoric acid compound, an inorganic silicic acid compound or an inorganic oxide.

4. The antiviral agent according to claim 1 or 2, which contains at least 1 selected from the group consisting of silver, copper, and a compound thereof.

5. A coating composition comprising the antiviral agent according to any one of claims 1 to 4.

6. A resin composition containing the antiviral agent according to any one of claims 1 to 4.

7. An antiviral agent comprising the antiviral agent according to any one of claims 1 to 4.

Technical Field

The present invention relates to an antiviral agent containing an inorganic solid acid, a coating composition containing the antiviral agent, a resin composition, and an antiviral article. The antiviral agent of the present invention can be applied to a fiber product such as clothing, bedding, and a mask, a filter for air cleaners, air conditioners, and the like, an indoor product such as a curtain, a carpet, and furniture, an automobile interior material, and the like, by spray processing or coating processing, or by spreading processing on a surface layer of a building material such as a wall paper, a floor material, and the like, to provide an effect of reducing viral activity.

Background

In recent years, demands for a sanitary and safe living environment have been increasing in the background of MERS (middle east respiratory syndrome), influenza epidemics, and the like, and development of various antiviral agents and antiviral products has been studied.

For coronaviruses, ethanol, sodium hypochlorite, iodoform, peracetic acid, formaldehyde, glutaraldehyde, and ethylene oxide gas have been reported to be effective as disinfectants. Further, 1-amantadine hydrochloride, thiosemicarbazide, arabinoside, nucleoside, 2, 3-dideoxynucleoside, pyrophosphate derivative, and the like are known as antiviral agents. However, drugs having these antiviral properties have only temporary effects and also have a problem of heat resistance, and therefore their sustained effects on antiviral preparations cannot be expected.

Patent document 1 discloses an inorganic antiviral agent composition containing an inorganic peroxide, tetraacetylethylenediamine, and an alkali metal salt of an inorganic acid and/or an alkaline earth metal salt of an inorganic acid. However, since such inorganic antiviral agents are of the inorganic peroxide type, they also have problems in durability, processability, and the like.

Products containing these conventional antiviral agents also have a problem of skin irritation when they are in direct contact with the human body.

In contrast, patent document 2 discloses a composition containingInorganic oxide fine particles having an average particle diameter of 500nm or less and containing a specific metal component, patent document 3 discloses a composition containing copper and titanium, and patent document 4 discloses a composition containing a specific BET surface area of 5 to 100m²An antibacterial and antiviral composition comprising cuprous oxide particles and a saccharide having an aldehyde group.

Documents of the prior art

Patent document

Patent document 1: japanese unexamined patent application publication No. 2001-72519

Patent document 2: japanese laid-open patent publication No. 2003-221304

Patent document 3: japanese unexamined patent application publication No. 2010-168578

Patent document 4: japanese patent laid-open publication No. 2011-153163

Disclosure of Invention

Problems to be solved by the invention

However, these copper compounds are easily oxidized in the air to divalent copper compounds, resulting in a decrease in antiviral effect. Further, when these inorganic antiviral agents are used alone, although antiviral effects can be confirmed, when they are kneaded and processed into a resin, sufficient antiviral effects may not be exhibited. Further, most of the copper compounds listed in patent documents 3 and 4 are originally colored, and when they are kneaded and processed into a resin, the resin is deteriorated due to copper ions, and therefore, discoloration and odor of the resin processed product sometimes occur, and the use and processing conditions are limited.

The purpose of the present invention is to provide an antiviral agent having excellent antiviral properties, for example, an antiviral agent which does not undergo deterioration due to melt kneading with a resin, has excellent heat resistance and processability, and maintains an effect of inactivating viruses. Another object of the present invention is to provide a coating composition, a resin composition, and an antiviral product, each of which is provided with a coating film or the like that does not come off when an antiviral agent comes into contact with water or the like.

Means for solving the problems

The present inventors have conducted intensive studies to solve the above problems, and as a result, have found that an inorganic solid acid having a specific concentration of acid sites (acid sites) exhibits high antiviral activity, and have completed the present invention. The present invention relates to an antiviral agent containing an inorganic solid acid having an acid site concentration of more than 0.005mmol/g, a coating composition, a resin composition and an antiviral article containing the same.

Effects of the invention

The antiviral agent of the present invention not only exhibits a higher antiviral activity than conventional antiviral agents, but also has heat resistance because it is an inorganic substance. Further, since it can be made light-colored, it is suitable for production of a coating composition, production of a resin composition, and the like, which is less colored and discolored, has excellent workability, and is provided with a coating film or the like which is not peeled off by contact with water or the like.

Further, the antiviral product of the present invention containing the antiviral agent of the present invention, for example, a resin molded product, an article having a coating film containing an antiviral agent, and the like, not only exhibit high antiviral activity, but also have excellent durability because the antiviral agent contained therein does not fall off or flow out with water.

Detailed Description

The present invention is as follows.

(1) An antiviral agent comprising an inorganic solid acid having an acid site concentration of greater than 0.005 mmol/g.

(2) The antiviral agent according to item (1), wherein the inorganic solid acid has an acid strength (pKa) at an acid site of 3.3 or less.

(3) The antiviral agent according to (1) or (2), wherein the inorganic solid acid comprises an inorganic phosphoric acid compound, an inorganic silicic acid compound or an inorganic oxide.

(4) The antiviral agent according to any one of (1) to (3) above, which comprises at least 1 selected from the group consisting of silver, copper and a compound thereof.

(5) A coating composition comprising the antiviral agent according to any one of (1) to (4) above.

(6) A resin composition comprising the antiviral agent according to any one of (1) to (4) above.

(7) An antiviral agent comprising the antiviral agent according to any one of (1) to (4) above.

In the present invention, the inorganic solid acid is a substance having an acid point on the surface of the inorganic solid. The acidic point is a position indicating a property of giving a proton to the base or a property of receiving an electron pair from the base. The number of the acid sites can be expressed in terms of acid site concentration, and the number of the acid sites or acid sites on the surface of the solid is usually expressed as the number or moles per unit weight or unit surface area of the solid.

In the inorganic solid acid contained in the antiviral agent of the present invention, the concentration of the acid sites on the surface of the inorganic solid (acid site concentration) is more than 0.005mmol/g in order to exhibit an effect of inactivating viruses (hereinafter referred to as "antiviral effect") appropriately.

Since the higher the acid point concentration is, the higher the antiviral effect is, there is no upper limit to the acid point concentration of the inorganic solid acid. However, an inorganic solid acid having an acid site concentration of more than 10mmol/g is generally unknown, and therefore, the upper limit is generally 10 mmol/g.

The concentration of the acid sites in the present invention is preferably 0.008mmol/g or more, more preferably 0.01mmol/g or more. In particular, an inorganic solid acid having an acid site concentration of 0.01mmol/g or more has an excellent antiviral effect and shows a high effect on various viruses.

As described above, the antiviral agent of the present invention can exhibit an antiviral effect at an acid site of the surface of an inorganic solid acid having an acid site concentration of more than 0.005 mmol/g.

Generally, viruses propagate through six stages of (1) adsorption to the cell surface, (2) invasion into the cell, (3) uncoating, (4) synthesis of parts, (5) assembly of parts, and (6) release from infected cells. It is presumed that the inorganic solid acid exhibits an antiviral effect by inactivating adsorption of viruses on the cell surface, which are in contact with acidic points on the surface of the inorganic solid.

The acid point concentration can be determined by measuring the amount of alkali that reacts with the powder (inorganic solid acid).

The acid site concentration can be measured in the liquid phase or the gas phase. As a method of measuring with a liquid phase, a titration method is known. As a method for measuring by gas phase, a gas chemisorption method is known in which the difference between the adsorption/desorption amount of He gas and hydrogen gas and the adsorption/desorption amount of an alkaline gas is measured.

Since the reaction of the antiviral agent of the present invention with viruses is a liquid-mediated reaction, the determination of the concentration of the acid site is suitably carried out by a liquid phase titration method.

Specific methods for measuring the acid point concentration of the inorganic solid acid by the titration method using a liquid phase are as follows.

The inorganic solid acid dispersed in the nonpolar solvent was titrated with n-butylamine, and the end point of the titration was confirmed by discoloration of the acid-base transition indicator. The indicator before reaction is in the basic form and in the form of its conjugate acid when it is adsorbed onto the inorganic solid acid. The acid point concentration thereof was determined by the titration amount of n-butylamine required to return from the color of the conjugate acid type to the color of the base type. The 1 acidic point of the solid corresponds to 1 molecule of n-butylamine. Since the titration base must displace the indicator that reacts with the acid site of the solid, it is more basic than the indicator.

General titration method when an indicator is added to an acid/benzene dispersion of an inorganic solid, the indicator exhibits an acidic color due to the acidity of the solid, and is preferably maintained for a sufficient time until the reaction is completed. Then, n-butylamine was added dropwise, and the acid spot concentration was calculated from the amount of n-butylamine when the indicator color returned to a basic color, which was the original color.

The specific procedure for measuring the acid point concentration of the inorganic solid acid is as follows.

(1) A20 mL sample bottle was charged with 10mL of benzene and 0.5g of an inorganic solid acid, and stirred to disperse the inorganic solid acid. For example, 20 pieces of the mixed dispersion are prepared.

(2) To each sample bottle, N-butylamine was added at a predetermined concentration of 0.1N while changing the amount of addition, and the mixture was stirred by a shaker to prepare 20 kinds of mixed solutions.

(3) After 24 hours, 0.5mL of a 0.1% indicator methyl red solution was added to each mixture, and the indicator was observed for color change.

(4) The amount of n-butylamine added which was the largest in the amount of n-butylamine in which indicator discoloration was not observed was expressed as the amount of base to be reacted with acid sites as the acid site concentration (mmol/g).

The inorganic solid acid is preferably an inorganic compound having a structure in which a substituent having a proton donating property or a proton accepting property is disposed on a surface with which the virus comes into contact. Specific examples of the inorganic solid acid include inorganic phosphoric acid compounds such as phosphoric acid compounds of titanium group elements such as zirconium phosphate, hafnium phosphate, and titanium phosphate, aluminum phosphate, and hydroxyapatite (phosphate minerals); inorganic silicic acid compounds such as magnesium silicate, silica gel, aluminosilicate, sepiolite (hydrous magnesium silicate), montmorillonite (silicate mineral), and zeolite (aluminosilicate); and inorganic oxides having an acid point concentration of 0.005mmol/g or more such as alumina, titania and hydrous titania. Among these, α -type or γ -type zirconium phosphate, α -type or γ -type titanium phosphate, amorphous magnesium silicate, activated titanium oxide, and the like, have an acid site concentration of more than 0.005mmol/g, and are preferable as inorganic solid acids contained in the antiviral agent of the present invention.

In the inorganic solid acid, the acid points on the surface of the inorganic solid have strength. That is, in addition to the high concentration of the acid sites of the inorganic solid acid itself, if the strength of each acid site is high, a high antiviral effect can be obtained. Therefore, the inorganic solid acid contained in the antiviral agent of the present invention is preferably high in the acid point strength. The strength of the acid site can be expressed by pKa as acid strength.

The acid strength of the inorganic solid acid in the present invention is preferably 3.3 or less in pKa, more preferably 1.5 or less in pKa, and further preferably 0.8 or less.

When the acid strength of the acid site is small, that is, when the pKa is high, the ability to inactivate viruses tends to decrease, and when the pKa is 0.8 or less, particularly excellent antiviral performance can be obtained.

The lower the pKa, the stronger the property of giving a proton to the base or the property of receiving an electron pair from the base, that is, the stronger the acid strength, and the stronger the acid strength, the higher the ability to inactivate viruses.

The acid strength of the inorganic solid acid in the present invention refers to the ability of the acid points on the surface of the inorganic solid acid to impart protons to the base or to receive electron pairs from the base. The acid strength (pKa) of the inorganic solid acid can be measured as the ability to convert the basic form into the conjugated acid form using various acid-base conversion indicators for which the pKa is known. When the base type is changed to the conjugate acid type, the change can be discriminated by the color change of the acid-base transition indicator.

Examples of the acid-base conversion indicator (pKa value) that can be used for measuring the acid strength include methyl red (+4.8), 4-phenylazo-1-naphthylamine (+4.0), dimethyl yellow (+3.3), 2-amino-5-azotoluene (+2.0), 4-phenylazo-diphenylamine (+1.5), 4-dimethylaminoazo-1-naphthalene (+1.2), crystal violet (+0.8), p-nitrophenylazo-p' -nitro-diphenylamine (+0.43), disuccinoylacetone (-3.0), benzaldehyde acetophenone (-5.6), and anthraquinone (-8.2).

Examples of the method for measuring the acid strength (pKa) of the inorganic solid acid using the acid-base transition indicator described above are shown below.

(1) A test tube was charged with 2mL of benzene and 0.1g of an inorganic solid acid, and stirred to disperse the inorganic solid acid. Only the kind of the acid-base change indicator of the dispersion liquid was tested.

(2) To the dispersion, about 2 drops of 0.1% benzene solution (0.1% ethanol solution instead of benzene solution) of each acid-base conversion indicator was added, and the mixture was mixed by gentle shaking to observe the change in color.

(3) The acid strength (pKa) of the inorganic solid acid is less than the strongest acid strength (i.e., lowest pKa value) at which the indicator discoloration is confirmed, and is greater than the weakest acid strength (i.e., highest pKa value) at which the indicator discoloration is not confirmed. Therefore, the pKa values of the inorganic solid acids were labeled (the highest pKa value for which no discoloration was observed) to (the lowest pKa value for which discoloration was observed). In addition, the case where there is no suitable indicator showing the lower limit is set to "the lowest pKa value at which discoloration is confirmed or less", and the case where there is no suitable indicator showing the upper limit is set to "the highest pKa value at which discoloration is not confirmed".

The antiviral agents of the present invention may contain silver or copper or both. The antiviral agent of the present invention may be either an antiviral agent containing an inorganic solid acid having silver ions (silver atoms) or copper ions (copper atoms) in the structure or a mixture of silver or copper or a compound thereof and an inorganic solid acid containing no silver and copper. An antiviral agent containing silver or copper has an excellent antiviral effect. The total content of silver, copper, or a compound thereof in such an antiviral agent is preferably 0.1% by mass or more, more preferably 0.3% by mass or more, and still more preferably 1% by mass or more. Examples of the inorganic solid acid having a structure containing silver ions (silver atoms) or copper ions (copper atoms) include silver zirconium phosphate and copper zirconium phosphate.

The antiviral agent of the present invention is preferably in the form of powder in order to be suitably processed into various materials and forms. The powdery antiviral agent is suitable for the preparation of a coating composition having excellent dispersibility and containing the antiviral agent and a binder, the preparation of a resin composition for obtaining a resin molded article having excellent dispersibility and containing the antiviral agent and a molding resin, and the like.

The average particle size of the powdery antiviral agent is preferably 0.01 to 50 μm, and more preferably 0.1 to 20 μm. The powder having an average particle diameter of 0.01 μm or more has an advantage of being less likely to aggregate and thus being easy to handle. Further, since the coating composition containing the powder having an average particle diameter of 50 μm or less has good dispersibility, the texture of the coated fiber is not impaired when the coating composition is applied to the surface of the fiber, and the fiber is not easily broken when the fiber is produced by spinning from the resin composition.

The average particle diameter is a median diameter analyzed on a volume basis, which can be measured by a laser diffraction particle size distribution analyzer or the like.

The color of the antiviral agent of the present invention is not limited, and white or a light color with high brightness is preferable in order to be suitable for processing into various materials and forms. The luminance is preferably 80 or more, more preferably 85 or more, and further preferably 95 or more, in the case of the value of L when measured by color difference meter.

The antiviral agent of the present invention can easily exhibit an antiviral effect by maintaining a certain amount of moisture.

The water content in the antiviral agent is preferably 0.5% by mass or more, more preferably 1% by mass or more, and still more preferably 3% by mass or more. In addition, the inorganic solid acid having hygroscopicity retains moisture in the inorganic solid acid even when mixed with other materials or the humidity of the atmosphere changes, and thus, the antiviral agent itself has an advantage in having moisture necessary for virus inactivation.

In general, in the measurement of antiviral effects, a method of measuring the amount of virus (infection value) by utilizing a cell modification phenomenon in which the shape of a cell infected with virus is changed is employed.

Examples of the method for measuring the infection value include a plaque number measuring method and a 50% tissue culture infection amount (TCID)₅₀) Assay and 50% viral titer (EID)₅₀) And (4) measuring.

The antiviral effect can be evaluated as an antiviral activity value obtained by the following formula (1). In the formula (1), the initial viral infection value is the amount of virus in the virus solution immediately after inoculation for evaluation, and the residual viral infection value is the amount of virus after a certain period of contact with the antiviral sample. The higher the value of the antiviral activity value, the higher the antiviral effect, preferably 2 or more, more preferably 3 or more.

Antiviral activity value ═ Log (initial viral infection value) -Log (residual viral infection value) (1)

The form of use of the antiviral agent of the present invention is not particularly limited, and the antiviral agent may be used alone, or may be mixed with other components or compounded with other materials as appropriate depending on the use.

The powdered antiviral agent can be prepared in various forms of use, for example, as a powder-containing dispersion, powder-containing particles, powder-containing paint, powder-containing fiber, powder-containing paper, powder-containing plastic, powder-containing film, powder-containing aerosol, and the like. Further, various additives such as a deodorant, an antibacterial agent, an antifungal agent, a flameproofing agent, an anticorrosive agent, and a fertilizer may be used in combination as required; materials for building materials, etc.

In addition, viruses in living spaces can be inactivated by adding the antiviral agent of the present invention to resin, paper, plastic, rubber, glass, metal, concrete, wood, paint, fiber, leather, stone, or the like, which is a material that may come into contact with humans.

The antiviral agent of the present invention is preferably used in the form of a coating composition containing the antiviral agent. The coating composition of the present invention is a composition containing the antiviral agent of the present invention, and if necessary, a binder, a dispersant, and the like. The coating composition of the present invention may also contain additives. In the case of using the coating composition of the present invention, it may be diluted with a solvent or water before being applied to articles of various shapes.

The concentration of the antiviral agent in the coating composition is preferably 0.5 to 50% by mass, more preferably 1 to 30% by mass, from the viewpoint of ease of dispersion and good storage stability. Generally, the antiviral effect is exhibited by bringing an antiviral agent into contact with viruses on the surface of antiviral articles having various shapes, and the mode of fixing an antiviral agent on the surface of an antiviral article using the coating composition of the present invention is preferable because a large effect can be obtained with a small amount of antiviral agent.

As the binder which can be used in the coating composition of the present invention, natural resins, natural resin derivatives, phenol resins, xylene resins, urea resins, melamine resins, ketone resins, coumarone-indene resins, petroleum resins, terpene resins, cyclized rubbers, chlorinated rubbers, alkyd resins, polyamide resins, polyvinyl chloride, acrylic resins, vinyl chloride-vinyl acetate copolymer resins, polyvinyl acetate, polyvinyl alcohol, polyvinyl butyral, chlorinated polypropylene, styrene resins, epoxy resins, polyurethane resins, cellulose derivatives and the like can be cited. Among them, polyurethane resins, acrylic resins, polyvinyl chloride, and vinyl chloride-vinyl acetate copolymer resins are preferable, and among them, latex type resins are preferable because of low pollution and easy handling.

The dispersant usable in the coating composition of the present invention is not particularly limited as long as it can uniformly disperse the antiviral agent of the present invention in the coating composition. Examples of the dispersant include polymeric dispersants such as polycarboxylic acids, polyethylene glycols, polyethers and polyalkylene polyamines, surface active agent dispersants such as alkylsulfonic acids, quaternary ammonium salts, higher alcohol alkylene oxides, polyol esters and alkyl polyamines, inorganic dispersants such as polyphosphates, and water, alcohol solutions, lime, soda ash, sodium silicate, starch, glue, gelatin and tannin.

Examples of the additive which can be used in the coating composition of the present invention include pigments such as zinc oxide and titanium oxide, dyes, antioxidants, light stabilizers, flame retardants, antistatic agents, foaming agents, impact strength enhancers, lubricants such as glass fibers and metal soaps, thickeners, moisture inhibitors and extenders, coupling agents, nucleating agents, fluidity improvers, deodorants, wood flour, antifungal agents, antibacterial agents, antifouling agents, rust inhibitors, metal powders, ultraviolet absorbers, and ultraviolet blockers. In addition, the antiviral effect can be improved by using an organic antiviral agent or the like in combination.

The coating composition of the present invention is useful for forming a coating film having an antiviral effect on the surface of an article containing an inorganic material or an organic material.

The coating composition of the present invention is mainly used for processing into fibers or fiber products (woven fabrics, nonwoven fabrics, knitted fabrics, etc.).

As a method of coating the fiber or the fiber product, a method of coating, dipping, or spraying the coating composition as it is or a liquid diluted with a solvent or the like on the fiber or the fiber product can be exemplified. The fibers are not particularly limited, and examples thereof include natural fibers such as cotton, silk and wool; synthetic fibers such as polyester, nylon (polyamide-based synthetic fibers), and acrylonitrile; semi-synthetic fibers such as triacetate and diacetate; regenerated fibers such as viscose rayon, and the like. Further, the composite fiber may contain 2 or more of these fibers. In the case of the nonwoven fabric, a nonwoven fabric containing polyethylene fibers, polypropylene fibers, or the like can be prepared.

The method for producing an antiviral product from the coating composition is not particularly limited, and when any coating method such as dipping treatment, printing treatment, spray coating treatment or the like is employed, it is also necessary to dry the coating film after the coating composition is applied. The drying method may be any of natural drying, hot air drying, vacuum drying, and the like, and is preferably a method by heating. The drying is preferably carried out at 40 to 250 ℃ and more preferably 50 to 180 ℃ for preferably 1 minute to 5 hours and more preferably 5 minutes to 3 hours. Thus, the antiviral agent can be immobilized on the fiber or the fiber product.

In the case of using the coating composition of the present invention, the amount of spreading of the antiviral agent on the fiber or the fiber product is 1m relative to the surface area of the fiber or the fiber product from the viewpoint that the antiviral effect can be suitably exhibited²Preferably 0.05g or more. The spreading amount is preferably 10g/m from the viewpoint of suppressing deterioration of physical properties, texture and the like of the obtained antiviral product²The amount of the surfactant is more preferably 0.3 to 5g/m²。

When the coating composition of the present invention is applied to an article such as a fiber or a fiber product, if the coating composition is strongly acidic, it may corrode a metal of a production facility, or cause deterioration of a treatment liquid and deterioration of stability. On the other hand, when the coating composition is strongly alkaline, the inorganic solid acid is sometimes neutralized and the antiviral effect is reduced. Therefore, the pH of the coating composition of the present invention is preferably 3 to 9, and more preferably 5 to 8.

The pKa of the inorganic solid acid greatly affects factors that determine the pH of the coating composition, and in addition, the concentration of the acid point, the solubility of the antiviral agent when dissolved in the medium, the hydrophilicity, and the like also affect the pH.

The coating composition of the present invention may also be used as a coating.

Examples of the resin component for coating include oils and fats such as soybean oil, linseed oil, safflower oil and castor oil, natural resins such as rosin, copal resin and shellac, processed resins such as chroman resin and petroleum resin, synthetic resins such as alkyd resin, acrylic resin, epoxy resin and urethane resin, vinyl chloride resin, silicone resin and fluorine-based resin, rubber derivatives such as chlorinated rubber and cyclized rubber, cellulose derivatives such as nitrocellulose (lacquer) and acetyl cellulose.

The coating composition may further contain additives and solvents such as pigments, UV curing agents, plasticizers, dispersants, anti-settling agents, emulsifiers, thickeners, defoaming agents, antifungal agents, preservatives, scale inhibitors, drying agents, anti-sagging agents, matting agents, antistatic agents, conductive agents, flame retardants, and anti-graffiti agents, which are contained in conventionally known coating compositions.

Examples of the pigment include colorants such as (white) titanium, (black) carbon, (brown) iron oxide, (vermilion) chrome vermilion, (blue) prussian blue, (yellow) yellow lead, and (red) iron oxide, pigments such as calcium carbonate, talc, and barite powder, rust-preventive pigments such as red lead, zinc monoxide, and hydrazine lead, and functional pigments such as aluminum powder and zinc sulfide (fluorescent pigment).

Examples of the solvent include water, alcohols, diluents such as diluents for paints, and diluents for polyurethane resins.

In the case of producing an antiviral article using a coating material as the coating composition of the present invention, the coating material is applied as it is or a liquid coating material diluted with a solvent or the like to a substrate or the like by a brush coating method, a roll coating method, a spray coating (mist) method, a blade coating method or the like, and dried as necessary. The content of the antiviral agent contained in the coating film was 1m relative to the surface area of the substrate²Preferably 0.05g or more. After the coating, the obtained coating film is cured by irradiation with radiation such as UV.

Examples of the base material include plastic molded articles such as polyethylene, polypropylene, polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, polyester, polycarbonate, acrylic resin, polystyrene, polyacrylonitrile, ABS resin, MBS resin, polyamide resin, cellophane and the like, joint agents such as modified silicone and polyurethane, metals, alloys, kiln siding, porcelain, stoneware, pottery, glazed tile, marble, granite, glass and the like.

In the coating material as the coating composition of the present invention, from the viewpoint that the antiviral effect can be suitably exhibited by the coating film containing the antiviral agent, the lower limit of the content of the antiviral agent is preferably 10% by mass when the total amount of the antiviral agent and the solid component such as the resin component is 100% by mass. The upper limit is preferably 50% by mass for economic reasons, the physical properties of the substrate to be coated, the quality of the antiviral product to be obtained, and the like, and the physical properties, functions, and the like of the coating material are not significantly impaired. The content of the antiviral agent is particularly preferably 20 to 40% by mass.

The resin composition of the present invention contains a resin and the antiviral agent of the present invention.

The kind of resin that can be used in the resin composition is not limited, and may be any of natural resins, synthetic resins, and semi-synthetic resins, and may be any of thermoplastic resins and thermosetting resins.

Specific examples of the resin include molding or fiber resins such AS olefin resins (polyethylene, polypropylene, etc.), vinyl chloride, ABS resins, AS resins, MBS resins, nylon resins (polyamide-based synthetic resins), polyesters (PET, PBT, etc.), polyvinylidene chloride, polystyrene, polyacetal, polycarbonate, acrylic resins, fluorine-based resins, polyurethane elastomers, polyester elastomers, melamine, urea resins, tetrafluoroethylene resins, unsaturated polyester resins, rayon, acetate, polyvinyl alcohol, cuprammonium fibers (キュプラ), triacetate, and vinylene resins, rubber-like resins such as natural rubber, silicone rubber, styrene-butadiene rubber, ethylene-propylene rubber, fluorine-based rubber, nitrile rubber, chlorosulfonated polyethylene rubber, butadiene rubber, synthetic natural rubber, butyl rubber, urethane rubber, and acrylic rubber.

The resin composition of the present invention may contain an additive. Examples of the additives include pigments such as zinc oxide and titanium oxide, dyes, antioxidants, light stabilizers, flame retardants, antistatic agents, foaming agents, impact strength enhancers, lubricants such as glass fibers and metal soaps, moisture-proofing agents, extenders, coupling agents, nucleating agents, fluidity improvers, deodorants, wood flour, mildewcides, antifouling agents, rust inhibitors, metal powders, ultraviolet absorbers, and ultraviolet blockers. They are all preferably used.

The method for producing the resin composition of the present invention is not particularly limited, and a conventionally known method can be used, and for example, in the case of producing a thermoplastic resin composition, the resin composition can be produced by kneading a raw material mixture containing a resin and an antiviral agent. When a modified resin or an antiviral agent having a specific functional group or the like on the surface is used, for example, the following methods are exemplified: (1) a method of directly mixing a granular resin or a powdery resin with a mixer using an additive to which an antiviral agent and a resin are easily attached and/or a dispersant for improving dispersibility of the antiviral agent, (2) a method of mixing the components as described in (1) above, molding the mixture into granules by an extrusion molding machine, and then blending the molded product into the granular resin, (3) a method of dispersing and mixing an antiviral agent in wax or the like, molding the mixture into granules, and then blending the granular molded product into the granular resin, and (4) a method of dispersing and mixing an antiviral agent in a high-viscosity liquid such as a polyol to prepare a paste composition, and then blending the paste composition into the granular resin.

The antiviral agent of the present invention is an article containing the above-mentioned antiviral agent of the present invention.

Examples of the antiviral product of the present invention include: a product obtained by molding the resin composition of the present invention into a predetermined shape; and products obtained by applying the coating composition of the present invention to a predetermined portion of a substrate and then drying the coating film to form a thin film.

When the resin composition of the present invention is used for molding, a known molding technique and a known machine can be used depending on the properties of the resin. The shape of the molded article may be a block, sponge, film, sheet, filament, tube, or a composite thereof.

The antiviral product obtained by applying the coating composition of the present invention includes an article having a coating film containing an antiviral agent on at least a part of the surface of a substrate such as a fiber, a fiber product (woven fabric, nonwoven fabric, woven fabric, or the like), or a film.

Examples of uses of antiviral products requiring virus reduction include indoor products, bedding products, filters, furniture products, interior products, fiber products, house building products, paper products, toys, leather products, and toiletry products. More specifically, there are room supplies such as carpets, curtains, wall papers, tatami mats, barrier papers, bed wax, calendars, bed supplies such as futons, beds, sheets, pillows, pillow cases, and the like, filters such as air cleaners, air conditioners, furniture such as sofas and chairs, car supplies such as children's seats and seat mats, dust bags for electric vacuum cleaners, clothing products, masks, cloth dolls, kitchen supplies, and the like, but the present invention is not limited thereto.

When the antiviral agent of the present invention is incorporated into a nonaqueous coating composition, a resin composition, or the like to prepare an antiviral product, the antiviral agent incorporated into the antiviral product may come into contact with another product to corrode a metal portion of the other product or discolor a resin portion. For example, the inventors have confirmed through experiments with aqueous dispersion that such a disadvantage can be suppressed by setting the pH of the coating composition in a predetermined range.

In the test of the aqueous dispersion, it is a simple method to disperse the antiviral agent in water and measure the pH. For example, the antiviral agent is dispersed in deionized water to 5% by mass, and the pH after stirring with a stirrer at 25 ℃ for 5 minutes is measured using a glass electrode pH meter. The pH at this time is preferably 3 to 9, more preferably 5 to 8. Antiviral products containing an antiviral agent in which the pH of the aqueous dispersion is within the above range are less likely to cause corrosion of metals and discoloration of resins, and therefore are preferably used in coating compositions, paints, resin compositions, and the like.

Examples

The present invention will be described more specifically with reference to the following examples, but the present invention is not limited to these examples. In this specification, "%" represents mass%.

In the examples and comparative examples, measurement of physical properties and evaluation of heat resistance of an antiviral agent, production and evaluation of a coating composition containing an antiviral agent, and production and evaluation of a resin composition containing an antiviral agent were carried out.

The method for measuring the acid point concentration of the inorganic solid acid powder constituting the antiviral agent is as follows. 0.5g of each inorganic solid acid powder was put into each of 20mL sample bottles, 10mL of benzene was added thereto, and the mixture was gently shaken and mixed. Subsequently, 0.1N N-butylamine was added to each sample bottle while changing the amount of the solution to prepare 20 kinds of mixed solutions, and the mixed solutions were stirred with a shaker. After 24 hours, 0.5mL of a 0.1% methyl red solution diluted with benzene was added to each mixture, and the discoloration of methyl red was visually observed. The amount of n-butylamine added which was the largest in the amount of n-butylamine in which no methyl red discoloration was observed was defined as the amount of base which reacted with acid sites, i.e., the acid site concentration (mmol/g).

The method for measuring the acid strength of the inorganic solid acid powder constituting the antiviral agent is as follows. A sample (0.1 g) was collected in a test tube, 2 drops of a 0.1% benzene solution (2 mL of benzene and the following indicator) were added thereto, and the mixture was mixed with gentle shaking to observe the change in color. When crystal violet is used, a 0.1% ethanol solution is used. The acid strength is considered to be not more than the strongest acid strength (lowest pKa value) at which the indicator is confirmed to be discolored and more than the weakest acid strength (highest pKa) at which the indicator is not discolored, and therefore this range is recorded as a pKa value. The indicators are methyl red (pKa ═ 4.8), 4-phenylazo-1-naphthylamine (pKa ═ 4.0), dimethyl yellow (pKa ═ 3.3), 4-phenylazo-diphenylamine (pKa ═ 1.5), crystal violet (pKa ═ 0.8), disuccinamide acylacetone (pKa ═ -3.0), benzaldehyde acetophenone (pKa ═ 5.6) and anthraquinone (pKa ═ 8.2).

The average particle diameter of the inorganic solid acid powder constituting the antiviral agent is a volume-based median diameter (μm) measured by a laser diffraction particle size distribution analyzer.

The method for measuring the water content of the inorganic solid acid powder constituting the antiviral agent is as follows. About 5g of the sample was weighed in an aluminum cup with a constant amount of 1 hour at 250 ℃ in a dryer, dried at 250 ℃ for 2 hours, and weighed again, and the value obtained by dividing the loss by drying (the amount of reduction) by the mass before drying was expressed in% as the water content of the inorganic solid acid powder.

The antiviral effect of antiviral agents was evaluated as follows. Adding refined water into antiviral agent, adjusting the concentration of inorganic solid acid powder to 0.5mg/mL, adding virus infection value of 2 × 10 to 900 μ L of the solution⁴PFU/mL of influenza A virus solution (100. mu.L) was allowed to stand at 25 ℃ for 2 hours. Then, the mixed solution was collected, and the collected solution was supplied to a plaque number measuring method to measure a viral infection value. In addition, the virus infection value was also measured for the mixed solution before standing for 2 hours.

The antiviral effect was determined from these virus infection values, and the case where the virus infection value after standing for 2 hours was equal to or less than the detection limit was set to "+", the case where the antiviral activity value after standing for 2 hours (i.e., the calculated value of Log (virus infection value immediately after inoculation) -Log (virus infection value after 2 hours)) was decreased by 1 or more was set to "+", and the cases other than "+" and "+" after standing for 2 hours were set to "-".

Evaluation of "1" of the coating composition was performed by evaluating the antiviral effect of an antiviral article (antiviral processing cloth) obtained by dip-coating the composition on a polyester cloth. 0.4g of antiviral processing cloth before or after washing is dipped and inoculated with virus with the infection value of 2 multiplied by 10⁴PFU/mL of influenza A virus solution (0.2 mL) was allowed to stand at 25 ℃ for 2 hours. Then, the virus solution was collected, and the collected solution was subjected to plaque number measurement to measure the viral infection value. In addition, the virus infection value was also measured for the contact solution before standing for 2 hours.

The antiviral effect was evaluated by the antiviral activity value obtained by the following formula.

Antiviral activity value ═ Log (viral infection value immediately after inoculation) -Log (viral infection value after 2 hours)

The coating composition was further evaluated by evaluating the antiviral effect of an antiviral article (antiviral processed film) obtained by coating the composition on a polyester film. The virus infection value of 2X 10 is dropped on the surface of an antiviral processing membrane with the size of 5cm X5 cm⁴PFU/mL of influenza A virus solution 0.4mL, and then the liquid portion was covered with a polyethylene film of 4cm by 4cm in size. After standing at 25 ℃ for 2 hours, the virus solution dropped on the surface of the antiviral processing film was collected, and the collected solution was subjected to plaque number measurement to measure the viral infection value. In addition, the virus infection value was also measured for the contact solution before standing for 2 hours.

The antiviral effect was evaluated by the antiviral activity value obtained by the following formula.

Antiviral activity value ═ Log (viral infection value immediately after inoculation) -Log (viral infection value after 2 hours)

Resin group containing antiviral agentThe evaluation of the compound was carried out by evaluating the antiviral effect of the antiviral fiber obtained by spinning the composition. 0.4g of antiviral fiber was dipped and inoculated with a virus infection value of 2X 10⁴PFU/mL of influenza A virus solution (0.2 mL) was allowed to stand at 25 ℃ for 2 hours. Then, the virus solution was collected, and the collected solution was subjected to plaque number measurement to measure the viral infection value. In addition, the virus infection value was also measured for the contact solution before standing for 2 hours.

The antiviral effect was evaluated by the antiviral activity value obtained by the following formula.

Antiviral activity value ═ Log (viral infection value immediately after inoculation) -Log (viral infection value after 2 hours)

1. Production and evaluation of antiviral Agents

Example 1 (amorphous magnesium silicate)

Sulfuric acid, magnesium sulfate and water glass were used as raw materials, and they were mixed and reacted. Then, the obtained precipitate was filtered, washed with water, dried and pulverized to obtain white amorphous magnesium Silicate (SiO)₂1.3) — MgO. The obtained amorphous magnesium silicate powder was used as an antiviral agent (V1), and the color L value, average particle diameter, water content, acid strength, and acid point concentration were measured to evaluate antiviral effects. The results are shown in Table 1.

Example 2 (alpha type zirconium phosphate)

A15% aqueous solution of zirconium oxychloride was added to a 75% aqueous solution of phosphoric acid, and the mixture was aged at 100 ℃ for 12 hours. Then, the obtained precipitate was filtered, washed with water, dried and disintegrated to obtain white α -type zirconium phosphate powder. The obtained α -type zirconium phosphate powder was used as an antiviral agent (V2), and the color L value, average particle diameter, water content, acid strength, and acid point concentration were measured to evaluate antiviral effect. The results are shown in Table 1.

Example 3 (alpha type zirconium silver phosphate)

A15% aqueous solution of zirconium oxychloride was added to a 75% aqueous solution of phosphoric acid, and the mixture was aged at 100 ℃ for 12 hours. Then, the obtained precipitate was washed with water and recovered. Subsequently, the precipitate was stirred in an aqueous silver nitrate solution at 100 ℃ for 2 hours. Then, the obtained precipitate was filtered, washed with water, dried and disintegrated to obtain white α -type silver zirconium phosphate powder containing 4.2% silver. The obtained α -type silver zirconium phosphate powder was used as an antiviral agent (V3), and the color L value, average particle diameter, water content, acid strength, and acid point concentration were measured to evaluate antiviral effect. The results are shown in Table 1.

Example 4 (alpha type zirconium copper phosphate)

A15% aqueous solution of zirconium oxychloride was added to a 75% aqueous solution of phosphoric acid, and the mixture was aged at 100 ℃ for 12 hours. Then, the obtained precipitate was washed with water and recovered. Subsequently, the precipitate was stirred in an aqueous copper sulfate solution at 100 ℃ for 2 hours. Then, the obtained precipitate was filtered, washed with water, dried and disintegrated to obtain a water-colored α -type copper zirconium phosphate powder containing 2.8% copper. The obtained α -type zirconium copper phosphate powder was used as an antiviral agent (V4), and the color L value, average particle diameter, water content, acid strength, and acid point concentration were measured to evaluate antiviral effect. The results are shown in Table 1.

Example 5 (gamma-type zirconium phosphate)

An aqueous solution of zirconium carbonate was added to a 75% aqueous solution of phosphoric acid, and the mixture was heated under reflux at 98 ℃ for 24 hours. Then, the obtained precipitate was filtered, washed with water, dried and disintegrated to obtain white γ -type zirconium phosphate powder. The obtained γ -form zirconium phosphate powder was used as an antiviral agent (V5), and the color L value, average particle diameter, water content, acid strength, and acid point concentration were measured to evaluate antiviral effect. The results are shown in Table 1.

Example 6 (activated titanium oxide)

Titanyl sulfate and oxalic acid were used as raw materials, and they were mixed and reacted. Subsequently, the obtained precipitate was filtered and dried, and subjected to calcination treatment at 500 ℃. Then, the resultant was pulverized to obtain white activated titanium oxide powder. The obtained titanium oxide powder was used as an antiviral agent (V6), and the color L value, average particle diameter, water content, acid strength, and acid point concentration were measured to evaluate antiviral effects. The results are shown in Table 1.

Comparative example 1 (crystalline magnesium silicate)

Sulfuric acid, magnesium sulfate and water glass are used as raw materials, and then they are mixedMixing and reacting. Then, the obtained precipitate is filtered, washed with water, hydrothermally treated, dried and pulverized to obtain crystalline magnesium Silicate (SiO)₂1.3) — MgO. The obtained crystalline magnesium silicate powder was used as an antiviral agent (V7), and the antiviral effect was evaluated by measuring the color L value, the average particle diameter, the water content, the acid strength, and the acid point concentration. The results are shown in Table 1.

Comparative example 2 (crystalline aluminum silicate silver copper)

Sodium hydroxide and sodium silicate were added to aluminum hydroxide and aged at 100 ℃ for 6 hours. Then, the obtained precipitate was washed with water and recovered. Subsequently, the precipitate was added to an aqueous solution of silver nitrate and copper nitrate, and stirred at 100 ℃ for 2 hours. The resulting precipitate was then filtered, washed with water, dried and crushed to give a crystalline aluminum silicate silver copper powder containing 2.2% silver and 6.2% copper. The obtained crystalline aluminum-silver-copper silicate powder was used as an antiviral agent (V8), and the average particle size, water content, acid strength, and acid point concentration were measured to evaluate antiviral effects. The results are shown in Table 1.

Comparative example 3(NASICON type zirconium phosphate)

Oxalic acid and a 75% aqueous solution of phosphoric acid were added to the aqueous solution of zirconium oxychloride. Subsequently, the pH of the mixture was adjusted to 2.7 with caustic soda, and the mixture was refluxed at 98 ℃ for 12 hours. Then, the obtained precipitate was filtered, washed with water, dried and disintegrated to obtain NASICON-type zirconium phosphate powder. The NASICON-type zirconium phosphate powder obtained was used as an antiviral agent (V9), and the antiviral effect was evaluated by measuring the average particle size, the water content, the acid strength, and the acid point concentration. The results are shown in Table 1.

Comparative example 4 (titanium oxide)

As the antiviral agent (V10), titanium oxide "MC-50" (trade name) powder manufactured by Shidaisie industries, Ltd. The average particle diameter and acid strength of the powder were measured to evaluate antiviral effect. The results are shown in Table 1.

Comparative example 5 (activated alumina)

As an antiviral agent (V11), powder of activated alumina "GNDY-2" (trade name) manufactured by Shuizzio chemical Co., Ltd was used. The average particle diameter and acid strength of the powder were measured to evaluate antiviral effect.

The results are shown in Table 1.

As is clear from Table 1, examples 1 to 6 using antiviral agents (V1) to (V6) containing an inorganic solid acid having an acid site concentration of more than 0.005mmol/g exhibited excellent antiviral activity.

On the other hand, comparative examples 1 to 5 using an antiviral agent containing an inorganic solid acid having an acid site concentration of 0.005mmol/g or less showed no antiviral activity.

In conclusion, antiviral agents containing inorganic solid acids having an acid site concentration of more than 0.005mmol/g have been shown to be effective.

2. Production and evaluation of coating composition (1)

Example 7

An antiviral agent (V1) containing amorphous magnesium silicate of example 1 and a urethane latex binder containing 30% nonvolatile components (hereinafter, referred to as "NV 30") were mixed in a solid content mass ratio of 1: 1, a coating composition (C1) was produced.

Next, the resultant coating composition (C1) was dipped in 185g/m²The polyester cloth of (4) was coated so that the spreading amount of the antiviral agent (V1) was 3g/m²And dried at 105 c to produce an antiviral processing cloth.

The antiviral effect was evaluated on the antiviral processed fabric and the antiviral processed fabric washed 3 times by JIS L0217103. The results are shown in Table 2.

Example 8

A coating composition (C2) was produced in the same manner as in example 7, except that an antiviral agent (V2) containing α -type zirconium phosphate in example 2 was used instead of the antiviral agent (V1). Then, an antiviral processed fabric was produced using the coating composition (C2), and antiviral effects were evaluated. The results are shown in Table 2.

Example 9

A coating composition (C3) was produced in the same manner as in example 7, except that an antiviral agent (V3) containing α -type silver zirconium phosphate of example 3 was used instead of the antiviral agent (V1). Then, an antiviral processed fabric was produced using the coating composition (C3), and antiviral effects were evaluated. The results are shown in Table 2.

Example 10

A coating composition (C4) was produced in the same manner as in example 7, except that an antiviral agent (V4) containing α -type zirconium copper phosphate of example 4 was used instead of the antiviral agent (V1). Then, an antiviral processed fabric was produced using the coating composition (C4), and antiviral effects were evaluated. The results are shown in Table 2.

Example 11

A coating composition (C5) was produced in the same manner as in example 7, except that an antiviral agent (V5) containing γ -type zirconium phosphate of example 5 was used instead of the antiviral agent (V1). Then, an antiviral processed fabric was produced using the coating composition (C5), and antiviral effects were evaluated. The results are shown in Table 2.

Example 12

A coating composition (C6) was produced in the same manner as in example 7, except that an antiviral agent (V6) containing the activated titanium oxide of example 6 was used instead of the antiviral agent (V1). Then, an antiviral processed fabric was produced using the coating composition (C6), and antiviral effects were evaluated. The results are shown in Table 2.

Comparative example 6

A coating composition (C7) was produced in the same manner as in example 7, except that an antiviral agent (V7) containing crystalline magnesium silicate of comparative example 1 was used instead of the antiviral agent (V1). Then, an antiviral processed fabric was produced using the coating composition (C7), and antiviral effects were evaluated. The results are shown in Table 2.

Comparative example 7

A coating composition (C8) was produced in the same manner as in example 7, except that an antiviral agent (V8) containing crystalline silver aluminum silicate copper of comparative example 2 was used instead of the antiviral agent (V1). Then, an antiviral processed fabric was produced using the coating composition (C8), and antiviral effects were evaluated. The results are shown in Table 2.

Comparative example 8

A coating composition (C9) was prepared in the same manner as in example 7, except that dodecylbenzyldimethylammonium chloride (quaternary ammonium salt) was used instead of the antiviral agent (V1). Then, an antiviral processed fabric was produced using the coating composition (C9), and antiviral effects were evaluated. The results are shown in Table 2.

Comparative example 9

The antiviral effect was evaluated on the raw polyester fabric. The results are shown in Table 2.

[ Table 2]

As is clear from Table 2, the anti-viral processed fabrics of examples 7 to 12 showed higher anti-viral activity values than the polyester fabric of comparative example 9, and thus the coating composition was effective. In addition, the antiviral processed cloths washed 3 times with these cloths also showed high antiviral activity values, indicating that the antiviral agent in the coating film was not easily eluted with water.

On the other hand, the antiviral processed cloths of comparative examples 6 and 7 were low in antiviral activity value both in the case of not washing and after washing 3 times, and the formed coating film showed no antiviral effect. In addition, comparative example 8 showed an antiviral activity value without washing, and therefore, although the formed coating film showed an antiviral effect, the antiviral activity value after 3 times of washing was very small, and it is considered that the antiviral agent in the coating composition was eluted by water.

3. Production and evaluation of coating composition (2)

Example 13

The above-described urethane latex binder containing the α -type silver zirconium phosphate of example 3 (V3) and NV30 was mixed until the solid content mass ratio was 1: 1, a coating composition (C11) was produced. Next, the coating composition (C11) was coated on a polyester film and air-dried so that the spreading amount of the antiviral agent (V3) was 0.5g/m²Thereby obtaining an antiviral processing film. Then, the anti-viral processed membrane was assayed for its anti-virus activityAnd (4) the activity value of the virus. The results are shown in Table 3.

Comparative example 10

A coating composition (C12) was obtained in the same manner as in example 13, except that an antiviral agent (V8) containing crystalline silver aluminum silicate copper of comparative example 2 was used instead of the antiviral agent (V3). Then, an antiviral processed film was produced using the coating composition (C12). Then, the antiviral activity value of the antiviral processing membrane was measured. The results are shown in Table 3.

Comparative example 11

A coating composition (C13) was obtained in the same manner as in example 13, except that an antiviral agent (V10) containing titanium oxide of comparative example 4 was used instead of the antiviral agent (V3). Then, an antiviral processed film was produced using the coating composition (C13). Then, the antiviral activity value of the antiviral processing membrane was measured. The results are shown in Table 3.

Comparative example 12

A coating composition (C14) was obtained in the same manner as in example 13, except that an antiviral agent (V11) containing activated alumina of comparative example 5 was used instead of the antiviral agent (V3). Then, an antiviral processed film was produced using the coating composition (C14). Then, the antiviral activity value of the antiviral processing membrane was measured. The results are shown in Table 3.

Comparative example 13

The urethane latex adhesive was coated on a polyester film and air-dried so that the spreading amount of the urethane resin was 1g/m²Thereby producing a film having a coating film containing a urethane resin. Then, the antiviral activity value was measured. The results are shown in Table 3.

[ Table 3]

As is clear from table 3, the antiviral activity value of the antiviral processed film of example 13 showed a value greater than 4.4, and the coating composition containing the antiviral agent of the present invention was suitable for forming a coating film exhibiting an antiviral effect.

On the other hand, the antiviral activity values of the antiviral processing films of comparative examples 10 to 12 were less than 0.3, and the antiviral effect was found to be insufficient.

4. Production and evaluation of resin composition

Example 14

An antiviral agent (V2) containing α -type zirconium phosphate of example 2 was blended at a ratio of 20% with a polyester resin "MA 2101" manufactured by mitsubishi レイヨン, and kneaded at a temperature of 290 ℃ using a twin-screw extruder to prepare a master batch in the form of pellets. Subsequently, this master batch was mixed with the above polyester resin to produce a resin composition containing 3% of α -type zirconium phosphate (R1). Then, the obtained resin composition (R1) was melt-spun to produce a 36f multifilament yarn at 290 ℃. The filaments were then drawn to produce 2 denier antiviral processed fibers as antiviral articles. Then, the antiviral activity value of the antiviral processed fiber was measured. The results are shown in Table 4.

Example 15

A master batch was prepared in the same manner as in example 14, except that an antiviral agent (V3) containing α -type silver zirconium phosphate of example 3 was used instead of the antiviral agent (V2). Subsequently, a resin composition (R2) containing 2% of an antiviral agent (V3) was obtained in the same manner as above. Then, using this resin composition (R2), 2 denier antiviral processed fiber was produced as an antiviral article. Then, the antiviral activity value of the antiviral processed fiber was measured. The results are shown in Table 4.

Comparative example 14

A master batch was prepared in the same manner as in example 14, except that an antiviral agent (V9) containing NASICON-type silver zirconium phosphate of comparative example 3 was used instead of the antiviral agent (V2). Subsequently, a resin composition (R3) containing 3% of an antiviral agent (V9) was obtained in the same manner as above. Then, using this resin composition (R3), a processed fiber of 2 denier was produced. Then, the antiviral activity value of the processed fiber was measured. The results are shown in Table 4.

Comparative example 15

Spinning was performed using only the above polyester resin to obtain a2 denier fiber. Then, the antiviral activity value of the fiber was measured. The results are shown in Table 4.

[ Table 4]

As is clear from table 4, the antiviral processed fibers of examples 14 and 15 had an excellent antiviral activity value of 3.0 or more, and therefore, the resin composition of the present invention obtained an antiviral product exhibiting an antiviral effect. Further, it is found that the antiviral agent of the present invention is excellent in heat resistance and processability because the resin composition is melt-spun.

5. Heat resistance test of antiviral agent

Example 16

The antiviral agent (V2) containing the α -type zirconium phosphate powder of example 2 was heated at 350 ℃ for 1 hour using an electric furnace. And cooling to room temperature. The heat-treated product was evaluated for antiviral effect by measuring color L value, average particle diameter, water content, acid strength and acid point concentration. The results are shown in Table 5.

Example 17

The antiviral agent (V3) containing the α -type silver zirconium phosphate powder of example 3 was heated at 350 ℃ for 1 hour using an electric furnace. And cooling to room temperature. The heat-treated product was evaluated for antiviral effect by measuring color L value, average particle diameter, water content, acid strength and acid point concentration. The results are shown in Table 5.

As is clear from table 5, even when α -type zirconium phosphate and α -type silver zirconium phosphate were heated at 350 ℃, the antiviral activity was exhibited with almost no change in physical properties other than the water content, and the heat resistance was excellent.

As is clear from the above examples, the antiviral agent, the coating composition and the resin composition of the present invention exhibit excellent antiviral effects. The antiviral agent of the present invention was also shown to have excellent processability and heat resistance.

Industrial applicability

When the antiviral agent of the present invention is used for a material related to human living space such as a fiber product or a building material, influenza virus and the like can be inactivated. Furthermore, the coating composition or resin composition containing the antiviral agent of the present invention is suitable for the production of fiber products such as clothing, bedding, masks, etc., filters for air cleaners, air conditioners, etc., interior products such as wall papers, curtains, carpets, furniture, etc., interior materials for automobiles, building materials, etc.