TWI735447B - Anti-virus material, and anti-viral material-containing anti-virus product - Google Patents

Abstract

In the past, various technologies for eliminating a virus or inhibiting replication of a virus have been proposed.  Such proposals, for examples, includes a proposal of using silver, a proposal of using a quaternary ammonium, a proposal of using a metal hydroxyl pyrithione, a proposal of using a sulfonic acid group and so on.  However, these proposals may not be satisfied in performance for solving problems such as discoloration, heat resistance, anti-virus and others. In view of this status, the present invention is completed accordingly.  The purpose of the present invention is to provide: an anti-virus material which has no problem of discoloration due to silver, but having excellent heat resistance, and high antiviral properties for a wide range of virus patterns, and to provide an anti-viral material-containing anti-virus product. The solution according to the present invention is an anti-viral material comprising a polymer having a H-type carboxyl group and H-type sulfonic acid group, or a mixture of a polymer having H-type carboxyl group, and a polymer having a H-type sulfonic acid group.

Description

Antiviral materials and antiviral products containing the materials

The present invention relates to antiviral materials with antiviral properties and antiviral products containing the materials.

Viral infection is not limited to direct contact with virus-containing droplets (sneezes, etc.) released by a virus-infected person, but also occurs when it comes into contact with clothing or towels that the virus-infected person has touched (indirect). Contact). For example, although masks are generally used as a means to prevent virus infection, once the time of use increases, the virus forms a concentrated state in the filtering part of the mask, so when the mask is taken off, the virus will become It will attach to the hand, and then through the towel or clothing touched by the hand, the virus attaches to the towel or clothing. Then, when a third party touches the virus attachment location on the towel or clothes, the virus will attach to the hand and cause a secondary infection.

In view of such problems, various proposals related to technologies for extinguishing viruses or inhibiting the proliferation of viruses have been proposed. For example, it is known: technology using silver (Patent Documents 1 and 2), technology using quaternary ammonium (Patent Documents 3 and 4), technology using metal pyrithione (Patent Documents 5 and 6), using sulfonic acid Basic technology (Patent Document 7); however, it is not necessarily satisfactory in terms of discoloration, heat resistance, and antiviral performance. Especially In terms of anti-viral performance, the current situation is: because viruses have various forms, it is impossible to obtain materials with sufficient anti-viral performance for a wide range of virus forms.

【Advanced Technical Literature】 【Patent Literature】

【Patent Document 1】International Publication No. 2005/083171 Brief Booklet

[Patent Document 2] Japanese Patent Laid-Open No. 11-19238

[Patent Document 3] JP 2008-115506 A

[Patent Document 4] JP 2001-303372 A

[Patent Document 5] JP 2006-9232 No.

[Patent Document 6] JP 2005-281951 A

[Patent Document 7] JP 2015-034291 No.

The present invention was created by the inventor in view of the above-mentioned current situation, and its purpose is to provide: an antiviral material that has no discoloration caused by silver, has excellent heat resistance, and has effective antiviral properties against a wide range of virus forms, And an antiviral product containing the material.

In order to achieve the above-mentioned purpose, the inventors deliberately reviewed the results and developed a polymer having H-type carboxyl group and H-type sulfonic acid group, or polymer having H-type carboxyl group, and polymer having H-type sulfonic acid group. The mixture of substances can make the virus more than sulfonic or carboxyl groups The price of infectivity is reduced, the antiviral performance is multiplied, there is no problem of discoloration, and the heat resistance is excellent, and the present invention has been completed.

That is, the present invention was achieved by the following means.

(1) An antiviral material containing a polymer having an H-type carboxyl group and an H-sulfonic acid group, or a mixture of a polymer having an H-type carboxyl group, and a polymer having an H-sulfonic acid group.

(2) The antiviral material as described in (1), characterized by having 1-13 mmol/g H-type carboxyl group and 0.2-8 mmol/g H-type sulfonic acid group.

(3) The antiviral material as described in (1) or (2), characterized in that: a mixture of a polymer having an H-type carboxyl group and a polymer having an H-type sulfonic acid group is A polymer having an H-type sulfonic acid group is attached to the polymer.

(4) The antiviral material as described in (1) or (2), characterized in that: a mixture of a polymer having an H-type carboxyl group and a polymer having an H-type sulfonic acid group is based on a polymer having an H-type carboxyl group The inside of the polymer is compounded with a polymer having an H-type sulfonic acid group.

(5) The antiviral material as described in any one of (1) to (4), characterized in that the polymer system having an H-type carboxyl group has 2 or more nitrogen per molecule for the acrylic fiber The nitrogen-containing compound is cross-linked and hydrolyzed.

(6) The antiviral material as described in any one of (1) to (5), which is characterized in that it is in the form of fibers, particles, or dispersions.

(7) A product with antiviral properties, characterized in that it contains the antiviral material as described in any one of (1) to (6).

The antiviral material of the present invention has excellent virus infectivity price reduction performance for various types of viruses. In addition, because it can be made into dry powder, water-dispersed milk In the form of liquid, organic solvent dispersion, fiber, etc., it can be easily applied to products in various applications and fields, and can impart antiviral properties.

"The form used to implement the invention"

The antiviral material of the present invention is a material containing a polymer having both H-type carboxyl group and H-type sulfonic acid group, or a polymer having H-type carboxyl group and polymer having H-type sulfonic acid group Mixture of things. In the present invention, although it is important that the type of the carboxyl group and the sulfonic acid group be H type to exhibit excellent antiviral performance, it may coexist with the metal base type carboxyl group or sulfonic acid group. In this article, the so-called H-type carboxyl group and H-type sulfonic acid group respectively represent _{functional groups with COOH and SO 3} H; the so-called metal base type represents that the H part of their functional groups is replaced by metal ions. Things.

In order to achieve a level with practical effects, relative to the weight of the antiviral material of the present invention, the amount of H-type carboxyl groups is preferably 1 mmol/g or more; more preferably 2 mmol/g or more; more preferably 3 mmol/g or more . In addition, in order to achieve a level with practical antiviral effect, it is desirable that the amount of H-type sulfonic acid group is preferably 0.2 mmol/g or more relative to the weight of the antiviral material; more preferably 0.5 mmol/g or more ; More preferably, it is 1 mmol/g or more.

In addition, the upper limit of the H-type carboxyl group and the H-type sulfonic acid group is not particularly limited. However, when considering that the content of the functional group of one of them is slightly too much, the content of the functional group of the other may be When the lower limit is not met and the polymer is obtained from a general monomer, the upper limit of the H-type carboxyl group in the present invention is preferably 13 mmol/g, and the upper limit of the H-type sulfonic acid group is preferably 8 mmol/g. Furthermore, when the antiviral material of the present invention has a certain shape such as fiber shape or particle shape, when the amount of H-type carboxyl group or H-type sulfonic acid group increases, it will be eluted or eluted when contacted with water. There may be insufficient strength due to swelling. In order to avoid this situation, the Hope: the amount of H-type carboxyl groups is preferably 10 mmol/g or less, more preferably 8 mmol/g or less; the amount of H-sulfonic acid groups is preferably 6 mmol/g or less, more preferably 4 mmol/g or less.

The polymer having H-type carboxyl group and H-type sulfonic acid group used in the present invention is a high-molecular polymer containing both of H-type carboxyl group and H-type sulfonic acid group in one molecule. The type of polymer is not particularly limited, and it may be any of addition polymerization polymer and addition condensation polymerization polymer; examples of the former, for example, may be polyolefin or ethylene-based polymerization. Examples of the latter, for example, for example, it may be a polyether-based polymer, a polyester-based polymer, a polyamide-based polymer, a polyurethane-based polymer, etc. Among these, from the viewpoint that the types of monomers are abundant and characteristics other than the antiviral performance can be easily adjusted, the more suitable one is an ethylene-based polymer.

The method for producing such a polymer having H-type carboxyl group and H-type sulfonic acid group is not particularly limited. For example, it may be a combination of a monomer having H-type carboxyl group and H-type sulfonic acid group. A method of copolymerizing monomers with acid groups; a method of introducing H-type carboxyl groups or H-type sulfonic acid groups by chemically modifying polymers; or a method of polymerizing polymers with H-type carboxyl groups or H-type sulfonic acid groups Methods of branch polymerization of monomers, etc.

In the copolymerization method and the branch polymerization method, the monomer having an H-type carboxyl group, for example, may be acrylic acid, methacrylic acid, maleic acid, itaconic acid, or the like. In addition, the monomer having H-type sulfonic acid group, for example, it may be vinyl sulfonic acid, p-styrene sulfonic acid, acrylamide-t-butyl sulfonic acid, methallyl sulfonic acid Wait.

In addition, the above-mentioned chemical modification method, if it is a chemical modification treatment, for example, for example, after obtaining a polymer made of a monomer having a functional group such as an available carboxyl group, A method of modifying a basic or H-type carboxyl group by hydrolysis, and in the case of a basic-type carboxyl group, it is converted into an H-type carboxyl group with an ion exchange resin or the like. Examples of monomers that can be used in this method, for example, for example, acrylonitrile, methacrylonitrile Such as nitrile monomers; methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate , N-octyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, hydroxyethyl (meth)acrylate and other (meth)acrylic acid derivatives; maleic anhydride, itaconic anhydride Anhydrides such as (meth)acrylamide, dimethyl (meth)acrylate, monoethyl (meth)acrylate, Nt-butyl (meth)acrylate, and other amide compounds Wait. In addition, the so-called "(meth)acryl group" is used as a term meaning both "acryl group" and "methacryl group".

In addition to this, it is also possible to use a polymer having an oxidizable polar group such as a double bond, a halogen group, a hydroxyl group, an aldehyde group, etc., to introduce an H-type carboxyl group through an oxidation reaction. For this oxidation reaction, a commonly used oxidation reaction can be used.

The method of introducing H-type sulfonic acid groups by chemical modification, for example, permanganate is used to oxidize polymers with equivalent functional groups of mercaptan, disulfide, or sulfinic acid Methods.

(甲基)丙烯酸酯、二乙二醇二(甲基)丙烯酸酯、三乙二醇二(甲基)丙烯酸酯、三羥甲基丙烷三(甲基)丙烯酸酯、亞甲基雙丙烯酸醯胺等之交聯性乙烯化合物。 It is possible to produce polymers with H-type carboxyl groups and H-type sulfonic acid groups by combining the above-mentioned methods alone or appropriately. However, it is not only the above-mentioned monomers, but can also be copolymerized with them in the polymer. The other monomers are copolymerized together. Such other monomers, for example, can be halogenated vinyl compounds such as chlorinated vinyl, brominated vinyl, and fluorinated vinyl; among vinylidene chloride, vinylidene bromide, vinylidene fluoride, etc. Vinylene monomers; acrylates such as methyl acrylate, ethyl acrylate, butyl acrylate, octyl acrylate, methoxyethyl acrylate, phenyl acrylate, cyclohexyl acrylate, etc.; methyl methacrylate, methyl methacrylate Methacrylates such as ethyl acrylate, butyl methacrylate, octyl methacrylate, phenyl methacrylate, cyclohexyl methacrylate, etc.; methyl ketene, ethyl ketene, phenyl vinyl Unsaturated ketones such as ketones, methyl isobutenyl ketones, methyl isopropenyl ketones; vinyl formate, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl benzoate, vinyl monochloroacetate, Vinyl esters such as dichloro vinyl acetate, trichloro vinyl acetate, monofluoro vinyl acetate, difluoro vinyl acetate, trifluoro vinyl acetate, etc.; methyl vinyl ether, ethyl vinyl ether, etc. Vinyl ethers; Acrylic amides and their alkyl substitutions; Styrene, methyl styrene, chlorostyrene, etc., and their alkyl or halogen substitutions; Allyl alcohols and their esters or ethers ; Vinylimines such as N-vinylphthalimide, N-vinyl succinimide, etc.; Vinylpyridine, vinylimidazole, dimethylaminoethyl methacrylate, N-vinylpyrrolidone, N-vinyl Basic vinyl compounds such as carbazole and vinyl pyridine; unsaturated aldehydes such as acrolein and methacrolein; glycidyl methacrylate, N-hydroxymethacrylate, methacrylic acid Hydroxyethyl, triallyl isocyanurate, triallyl cyanurate, divinylbenzene, ethylene glycol

(Meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, methylene diacrylate Cross-linkable vinyl compounds such as amines.

Among the mixtures of polymers having H-type carboxyl groups and polymers having H-sulfonic acid groups (hereinafter, also referred to as polymer mixtures) used in the present invention, polymers having H-type carboxyl groups and polymers having H The sulfonic acid-based polymer can be prepared by the above-mentioned "copolymerization method", "chemical modification method" and "branch polymerization method" to meet the needs of the target product.

In addition, the mixed state in the polymer mixture used in the present invention, for example, may be a state in which a polymer having an H-type sulfonic acid group is attached to the surface of a polymer having an H-type carboxyl group ( Hereinafter, referred to as adhesion type); a state in which a polymer having an H-type sulfonic acid group is also compounded inside the polymer having an H-type carboxyl group (hereinafter referred to as an internal compound type); and, for example, a polymer having an H-type carboxyl group A state in which a polymer and a polymer having an H-type sulfonic acid group are uniformly mixed (hereinafter referred to as a homogeneous type), etc.

The adhesion-type manufacturing method, for example, may be a method of immersing fibers or particles formed from a polymer having H-type carboxyl groups in a solution or dispersion of a polymer having H-type sulfonic acid groups; Or in fibers formed from polymers with H-type carboxyl groups or A method of polymerizing monomers having H-type sulfonic acid groups in the presence of particles, etc. The internal composite type manufacturing method, for example, can be a solution of a monomer having an H-type sulfonic acid group to swell fibers or particles formed from a polymer having an H-type carboxyl group, and the The method of polymerizing the monomer in this case, etc. A homogeneous manufacturing method, for example, can be carried out after dissolving their polymers in a good solvent common to polymers having H-type carboxyl groups and polymers having H-type sulfonic acid groups. The method of removing the solvent, etc.

The antiviral material of the present invention, such as the above-mentioned polymer having H-type carboxyl group and H-type sulfonic acid group, or a mixture of polymer having H-type carboxyl group and polymer having H-type sulfonic acid group, can be It is formed only from their polymers or polymer mixtures, and can also contain other polymers or additives.

In addition, the shape of the antiviral material of the present invention may be, for example, a fiber shape, a particle shape, a film shape, an arbitrary three-dimensional shape, a dispersion shape, a solution shape, etc., for example. The method of obtaining these shapes, for example, can be appropriately adopted: a method of manufacturing using raw materials having the shape; a method of forming processing by spinning, pelletizing, injection molding, coating, etc.; by suspension polymerization , Emulsion polymerization, solution polymerization, etc. and directly prepared methods, etc.

As a representative example of the antiviral material of the present invention described above, for example, the acrylic fiber can be cross-linked and hydrolyzed through a nitrogen-containing compound having a nitrogen number of 2 or more per molecule. In the presence of a polymer having H-type carboxyl groups in a fiber shape, monomers having H-type sulfonic acid groups are polymerized to compound the polymer having H-type sulfonic acid groups to obtain an internal composite type antiviral material . Hereinafter, the manufacturing method will be described.

The acrylonitrile-based fiber of the raw material fiber is a fiber formed of an acrylonitrile-based polymer containing 40% by weight or more, preferably an acrylonitrile-based polymer containing 50% by weight or more. Therefore, in addition to the acrylonitrile single polymer, the acrylonitrile-based polymer may also be a copolymer of acrylonitrile and other monomers. The other monomers in the copolymer are not specifically limited, but And, for example, it may be halogenated vinyl and halogenated vinylidene; (meth)acrylate; sulfonic acid group-containing monomers such as methallylsulfonic acid, p-styrenesulfonic acid, and their salts ; (Meth) acrylic acid, itaconic acid and other carboxylic acid groups containing monomers and their salts; acrylic acid amide, styrene, vinyl acetate and so on.

The manufacturing method of such an acrylic fiber is not limited, and a well-known method can be used suitably. In addition, the form of the acrylic fiber may be any form of short fiber, tow, silk, woven fabric, non-woven fabric, etc.; it does not matter even if it is a semi-finished product or waste fiber in the middle of a manufacturing process.

For such an acrylic fiber, crosslinking treatment is performed with a nitrogen-containing compound having a nitrogen number of 2 or more per molecule. Through this cross-linking treatment, the nitrile group in the acrylic fiber reacts with a nitrogen-containing compound having a nitrogen number of 2 or more per molecule to form a cross-linked structure, and the nitrogen content in the fiber also increases. Examples of nitrogen-containing compounds with a nitrogen number of 2 or more per molecule that can be used in the cross-linking treatment, for example, can be hydrazine compounds such as hydrogenated hydrazine, hydrazine sulfate, hydrazine hydrochloride, etc.; or Compounds with multiple amine groups such as ethylenediamine, hexamethylenediamine, diethylenetriamine, triethylenetetramine, and polyethyleneimine. Among these, hydrazine-based compounds are preferred because they are easy to react and are also advantageous in terms of cost.

The cross-linking treatment conditions of nitrogen-containing compounds with a nitrogen number of 2 or more per molecule are from the viewpoint of swelling with a solution containing a monomer having an H-type sulfonic acid group and polymerizing it in this case Ideally, it is preferable to continuously swell moderately and maintain the fiber physical properties that can be handled without difficulty to form the conditions for cross-linking. Specifically, it is preferable that the water swelling degree of the fiber becomes 0.5~4.5g/g after the hydrolysis; the specific processing conditions in the case of using hydrazine compounds, the industrially preferable method is : In an aqueous solution with a hydrazine compound concentration of 5 to 80% by weight, at a temperature of 50 to 120°C, treat for 1 to 5 hours.

The fiber subjected to cross-linking treatment as described above is then subjected to hydrolysis treatment to chemically modify the nitrile group into a carboxyl group. The means of hydrolysis treatment, for example, can be, for example, the cross-linked fiber is immersed in an alkaline aqueous solution of alkali metal hydroxide, alkali metal carbonate, ammonium, etc., or nitric acid, sulfuric acid, hydrochloric acid, etc. It is a means of heat treatment in the state of its aqueous solution. The specific treatment conditions include appropriately setting various conditions such as the concentration of the treatment agent, the reaction temperature, and the reaction time in consideration of the amount of carboxyl groups retained by the antiviral material of the present invention finally obtained; however, the preferred means is 0.5-10% by weight; more preferably, it is 1 to 5% by weight in an aqueous solution of a treatment agent at a temperature of 50 to 120°C for 1 to 10 hours, because it is beneficial to industrial manufacturing and the fiber properties are also good. In addition, the hydrolysis treatment may also be performed at the same time as the above-mentioned crosslinking treatment.

The carboxyl group of the fiber subjected to the hydrolysis treatment as described above is a whole fiber having an H-type carboxyl group after the following acid treatment, that is, a polymer having an H-type carboxyl group in a fiber shape. In the hydrolysis treatment, when an alkaline aqueous solution of alkali metal hydroxide, alkali metal carbonate, ammonium, or the like is used, the generated carboxyl group forms a cation and ionic bond of alkali metal or the like. By acid treatment, this cation is replaced by hydrogen ion and the carboxyl group becomes COOH form. As far as this acid treatment method is concerned, it is suitable for a method in which the hydrolyzed fiber is immersed in an acidic aqueous solution such as hydrochloric acid, acetic acid, nitric acid, sulfuric acid, etc., and then dried.

In addition, for acrylic fibers, fibers obtained by crosslinking and hydrolyzing a nitrogen-containing compound having a nitrogen number of 2 or more per molecule can also be used conventionally known ones. For example, it can be used in JP-A-8- 246342, JP 8-325938, JP 11-081130, JP 2000-265365, etc.

Next, in the presence of the fiber containing the H-type carboxyl group obtained as described above, the monomer having the sulfonic acid group is polymerized.

The method of polymerizing a monomer having a sulfonic acid group, for example, may be, for example, immersing a fiber having the aforementioned carboxyl group (hereinafter, also referred to as a raw fiber) in: a pre-adjusted amount of the fiber having a sulfonic acid group A method of swelling and polymerizing monomers and a solution containing a polymerization initiator. In addition, the above-mentioned raw material fiber has a cross-linked structure with moderate hydrophilicity with a carboxyl group, and therefore has the characteristic of not being dissolved in a solution but swelling.

The single system with sulfonic acid group can use unsaturated hydrocarbon sulfonic acid such as ethylene sulfonic acid, p-styrene sulfonic acid, acrylamide t-butyl sulfonic acid, methallyl sulfonic acid and/or this And other salts, etc. In addition, the polymerization initiator may be, for example, hydrogen peroxide, ammonium persulfate, sodium persulfate, calcium persulfate, or the like.

The method of dipping into a solution containing a monomer having a sulfonic acid group and a polymerization initiator to swell it is not particularly limited to these. For example, it may be, for example, dissolving the monomer in water or organic A method of mixing the raw fibers in a solvent or a mixed solution of these, and then adding a polymerization initiator; or a method of mixing the raw fibers after the polymerization initiator is included in the monomer solution; dispersing the raw fibers in water, Or organic solvent, or their mixed solution, followed by a method of adding polymerization initiator and monomer.

In addition, the amount of the sulfonic acid group-containing monomer in the solution containing the sulfonic acid group-containing monomer and the polymerization initiator can be determined according to the amount of the sulfonic acid group in the finally obtained antiviral material of the present invention It is set within the above range. In addition, the addition amount of the polymerization initiator may cause insufficient polymerization when the addition amount is slightly small. In the case of hydrogen peroxide, it is preferable to add 0.01 to 50% by weight relative to the raw fiber.

The polymerization temperature is low-temperature polymerization. As the polymerization rate is slow, more polymers are compounded; on the other hand, when the polymerization rate is too slow, the polymers are not compounded with good efficiency. Therefore, it is preferably 40 to 80°C. In addition, the polymerization time can be based on the polymerization temperature, The monomer concentration is appropriately determined without limitation, but it is preferably about 2 hours to 20 hours industrially.

In addition, in the above-mentioned manufacturing method, although the carboxyl group and the sulfonic acid group are converted into the H-type in the middle of the process; however, it can also be performed after the composite of the polymer having the carboxyl group and the polymer having the sulfonic acid group is completed. Carry out the conversion to H-shape.

As described above, the anti-viral material of the present invention is not limited to the virus to be removed, and it can be applied to any one of a virus with an envelope and a virus without an envelope. The inactivation effect. The virus having an outer membrane, for example, may be herpes simplex virus, influenza virus, vaccinia virus, measles virus, or human immunodeficiency virus. In addition, a virus that does not have an outer membrane, for example, may be feline calicivirus, Norovirus, or the like. Among these, the antiviral material of the present invention shows an excellent inactivation effect against influenza virus and feline calicivirus.

The antiviral material of the present invention can be used in a wider range by including it in various products. There are almost no restrictions on the products that can contain the antiviral material of the present invention, and it may be contained in various ways in accordance with products that do not want to provide antiviral properties.

For example, as long as it is the antiviral material of the present invention in the shape of particles, for example, it may be a method of mixing fibers, paper, non-woven fabrics, fabrics, knitted fabrics, sheets, foams, etc. during the manufacturing process, Or the method of coating together with the bonding agent. Moreover, as long as it is in the form of a dispersion liquid or a liquid, it may be a method of impregnation and coating as it is. In addition, it may be mixed with paint for use, or it may be added to a spray agent. In the case where the base material of fibers, non-woven fabrics, woven fabrics, knitted fabrics, etc. has a cationic functional group, it is very suitable because it can prevent the antiviral material of the present invention from falling off the base material even if it is washed or the like.

When it is contained in the fiber, it is possible to use the so-called kneading method by adding the antiviral material of the present invention in the form of particles, dispersion or liquid to the spinning dope of the fiber, and mixing them for spinning. . The fiber to be mixed is not limited. For example, it can be nylon, vinylon, polyester, acrylic, polyolefin, polyurethane, rayon, and polinosic. Blended fiber (polynosic), Cupra fiber (CUPRA), cellulose fiber (LYOCELL), acetylated fiber, etc.

In addition, when it is contained in a resin molded body, a method of adding the antiviral material of the present invention to a resin composition, mixing it, and performing molding processing may also be adopted. The type of resin is not particularly limited. For example, it may be acrylic resin, epoxy resin, polyurethane resin, ABS resin, polymethacrylate resin, poly Chlorinated vinyl resins, etc.

In addition, as long as the antiviral material of the present invention in a fiber shape is formed into a fiber structure alone or in combination with other materials, it can be more useful. When combined with other materials, the use amount of the antiviral material of the present invention in the shape of a fiber is preferably 10% by weight or more, more preferably 30% by weight or more; it can also be practically effective in fiber structures. Anti-virus performance.

The appearance of this kind of fiber structure is: for example, silk, yarn (including wrapped yarn), filament, fabric, knitted fabric, non-woven fabric, paper, sheet, laminated body, cotton-like body (also including spherical , Lumps), etc., and also have outer coverings on them. The anti-viral material of the present invention in the structure contains a form that is substantially uniformly distributed by mixing with other materials; and in the case of a structure with a plurality of layers, for example, one kind is concentrated in any Layers (may be singular or plural), or one type of each layer distributed at a specific ratio, etc.

Therefore, there are countless types of such fiber structures that have combinations of the above-exemplified appearance forms and containing forms. The formation of all structures is determined by the investigation: the use of the final product Appearance (for example, seasonal, sporty, or used as underwear, middle clothes, outerwear, or curtains, bedspreads, bedding, cushions, insoles, etc.), required functions, and the use of such functions The method of administration of the antiviral material of the present invention and the like are appropriately determined.

Other materials that can be used in combination in the above-mentioned fiber structure are not particularly limited, and common natural fibers, organic fibers, semi-synthetic fibers, and synthetic fibers can be used; and inorganic fibers, glass fibers, etc. can be used according to the application. Specific examples, for example, may be cotton, hemp, silk, wool, nylon, rayon, polyester, acrylic fiber, etc.

Although the reason why the antiviral material of the present invention described above can find excellent antiviral performance has not yet been concluded, it is considered that its performance is higher than that of either the H-type carboxyl group and the H-type sulfonic acid group alone. It has also increased dramatically, so it is presumed that, for example, the functional group on one side is used to promote the adsorption of the virus, and the functional group on the other side is used to inactivate the virus, so efficient performance can be found!

[Examples]

Hereinafter, in order to make the present invention easy to understand, examples are illustrated. However, they are only illustrative after all, and the gist of the present invention is of course not limited thereby. In addition, in the examples, parts and percentages, as long as they are not specifically stated, are all based on weight.

<Measurement of antiviral performance of influenza virus>

The antiviral performance of influenza virus was evaluated by using influenza virus A (H1N1) PR8 strain with the 50% infectivity method (TCID ₅₀ ). With respect to a 40 mg dry sample, 200 μL of virus solution was added, and after shaking for 1 hour while maintaining at 28°C, centrifugation treatment (3000 rpm, 30 minutes) was performed. After centrifugation, the supernatant was diluted 10-fold in stages, and the TCID ₅₀ (50% infectivity value) was _{measured using MDCK cells to calculate the virus infectivity value log 10} (TCID ₅₀ /mL). In addition, for the blank group, the virus infectivity value was calculated by performing the same operation as described above without using the sample. Using the obtained virus infectivity value, the virus inactivation rate was calculated by the following formula. When the reduction value of the infectivity value is greater than 1, it means that the infectivity is reduced by 10 times.

Virus infectivity value reduction value = (viral infectivity value of the blank group-virus infectivity value of the sample)/(viral infectivity value of the blank group)

<Determination of Antiviral Performance of Feline Calicivirus>

In the aforementioned <Measurement of Antiviral Performance for Influenza Virus>, except for using feline calicivirus (F9 strain) instead of influenza virus and using CRFK cells instead of MDCK cells, the same evaluations were performed.

<Measurement of antiviral performance of herpes simplex virus>

In the above-mentioned <Measurement of Antiviral Performance of Influenza Virus>, herpes simplex virus was used instead of influenza virus, plaque method was used instead of 50% infectivity value method for evaluation, and Vero cells were used instead Except for MDCK cells, evaluations were performed in the same manner.

<Determination of Antiviral Performance of Vaccinia Virus>

In the above <Measurement of antiviral performance for influenza virus>, vaccinia virus was used instead of influenza virus, plaque method was used instead of 50% infectivity value method for evaluation, and Vero cells were used instead of MDCK cells. All were evaluated in the same way.

<Measurement of the antiviral performance of measles virus>

In the above-mentioned <Measurement of Antiviral Performance for Influenza Virus>, except that measles virus was used instead of influenza virus, and Vero cells were used instead of MDCK cells, they were all evaluated in the same way.

<Measurement of the amount of sulfonic acid group and carboxyl group (mmol/g)>

Approximately 1 g of a sufficiently dried sample (Xg) is accurately weighed, 200 mL of water is added to it, and then a titration curve is obtained by titration with a 0.1 mol/L sodium hydroxide aqueous solution according to a general method. Aqueous sodium hydroxide solution to obtain the consumption amount consumed from the sulfonic acid group titration curves (Ycm ^3), and the consumption of caustic soda solution (Zcm ³⁾ consumed by carboxy, sulfonic acid group is calculated by the following formula, and the amount of carboxyl group ( mmol/g).

Sulfonic acid group amount (mmol/g)=0.1Y/X

Amount of carboxyl group (mmol/g)=0.1Z/X

<Examples 1~6>

Add 20 parts of a monomer mixture composed of sodium p-styrene sulfonate, methacrylic acid and acrylonitrile to adjust the monomer mixing ratio in such a way that the amount of carboxyl groups and the amount of sulfonic acid groups as shown in Table 1 can be obtained. In an aqueous solution containing 80 parts of ammonium persulfate with a monomer ratio of 3.0% and sodium methyl bisulfite with a monomer ratio of 1.8%, put it into a polymerization tank with a stirrer, and then polymerize at 75°C for 20 minutes. The obtained dispersion-like polymer is ion-exchanged using a strongly acidic ion exchange resin to obtain a dispersion-like antiviral material having H-type carboxyl groups and H-type sulfonic acid groups. The antiviral performance was evaluated, and the results are shown in Table 1.

<Example 7>

A spinning dope formed by dissolving 10 parts of an acrylonitrile polymer composed of 90% acrylonitrile and 10% acrylic methyl in a 48% sodium thiocyanate aqueous solution of 90 parts, spinning and drawing according to the usual method Stretched and dried to obtain acrylic-based fibers of 1.7 detX. The acrylic fiber was added to a 15% hydrazine aqueous solution, and the hydrazine crosslinking reaction was performed at 110° C. for 4.5 hours. After the obtained crosslinked fiber was washed with water and dehydrated, it was further added to a 4.5% sodium hydroxide aqueous solution, and a hydrolysis reaction was carried out at 90°C for 2 hours. After washing with water and dehydrating, it is treated in an aqueous solution adjusted to pH 2.0 with hydrochloric acid to obtain supporting fiber A. The fiber was immersed in a 3.3% sodium p-styrene sulfonate aqueous solution adjusted to pH 2.0 by using 1 mol/L hydrochloric acid, and the bath ratio was 1:50. Next, a 2.16% aqueous solution containing hydrogen peroxide was added to the fiber, heated at 60°C for 6 hours, and washed with water. Then, after treatment with 4% nitric acid, it is washed with water. After repeating this nitric acid treatment and washing with water a total of 3 times, dehydration and drying were performed to obtain a fiber-shaped antiviral material. Table 1 shows the evaluation results of the antiviral performance of the obtained material.

<Example 8>

Add 20 parts of sodium p-styrene sulfonate to: 80 parts of an aqueous solution of ammonium persulfate with a monomer ratio of 3.0% and sodium methyl bisulfite with a monomer ratio of 1.8%. After being in the polymerization tank, polymerization was carried out at 75°C for 20 minutes. For the obtained dispersion-like polymer, ion exchange is performed using a strongly acidic ion exchange resin to obtain a dispersion-like polymer having an H-type sulfonic acid group. The supporting fiber A obtained in Example 7 was immersed in a dispersion-like polymer having such H-type sulfonic acid groups to obtain a fiber-shaped antiviral material. Table 1 shows the evaluation results of the antiviral performance of the obtained material.

<Comparative Example 1>

20 parts of a monomer mixture composed of sodium p-styrene sulfonate and acrylonitrile whose monomer mixing ratio is adjusted according to the amount of carboxyl groups and sulfonic acid groups as shown in Table 1 is added to 80 parts of the monomer mixture. The aqueous solution of ammonium persulfate with a monomer ratio of 3.0% and sodium methyl bisulfite with a monomer ratio of 1.8% was put into a polymerization tank with a stirrer, and then polymerized at 75°C for 20 minutes. The obtained dispersion-like polymer is ion-exchanged using a strongly acidic ion exchange resin to obtain a dispersion-like polymer having an H-type sulfonic acid group. Table 1 shows the evaluation results of the antiviral performance of the obtained polymer.

<Comparative Example 2>

In Example 1, except for not performing ion exchange with an ion exchange resin, the same operation was performed to obtain a polymer in the form of a dispersion liquid having an H-type carboxyl group and a sodium-type sulfonic acid group. Table 1 shows the evaluation results of the antiviral performance of the obtained polymer.

In Table 1, when comparing Example 1 with Comparative Examples 1 and 2, it can be understood that compared with the case where only one of the H-type carboxyl group or the H-type sulfonic acid group is present, the In the case of both types of sulfonic acid groups, the antiviral performance increases dramatically. In addition, it can be understood that: Examples 2-8 have good antiviral performance. In addition, since no silver compound is used as in the conventional technique, it can be confirmed that the color does not change even with time. In addition, in Table 1, the oblique line in the column of the reduction value of virus infectivity value indicates that the evaluation has not been performed.

In addition, when the antiviral material of Example 1 was placed at 105°C for 3 hours, and then the antiviral performance was evaluated, the reduction value of the virus infectivity value was 3.5 for feline calicivirus and 3.5 for influenza virus. Is 6.5. Therefore, even if the antiviral material of the present invention is heated, the antiviral performance will not decrease.

Claims (2)

A use for inhibiting virus proliferation, which is a mixture of fiber-shaped polymers containing H-type carboxyl groups and polymers having H-type sulfonic acid groups used to inhibit virus proliferation; wherein the aforementioned H-type carboxyl groups The polymer is obtained by cross-linking and hydrolyzing the acrylonitrile-based fiber with a nitrogen-containing compound having 2 or more nitrogen in one molecule; the aforementioned mixture is in the interior of the polymer having H-type carboxyl It is compounded with a polymer having H-type sulfonic acid groups; and the reduction value of the viral infectivity value for influenza virus of the aforementioned mixture is 3.0 or more, and the reduction value of virus infectivity value for feline calicivirus is 3.3 or more. The use for inhibiting the proliferation of viruses as described in claim 1, which has H-type carboxyl groups of 1 to 13 mmol/g and H-type sulfonic acid groups of 0.2 to 8 mmol/g.