JP2010018915A - Antiviral textile product - Google Patents

Abstract

The present invention provides an antiviral fiber product that is surely effective against viruses.
An antiviral fiber product comprising polyhexamethylene biguanide in natural fiber or synthetic fiber containing at least one compound selected from polyhexamethylene biguanide, a spreading agent and a binder. To manufacture.
[Selection figure] None

Description

  The present invention relates to a textile product having antiviral properties and a method for producing the same.

  Worldwide, there is a concern about the spread of viral diseases, and the risk of secondary infection with viruses in the medical field has become realistic. In order to prevent such secondary infection with viruses, as a textile product used in medical sites, food factories, livestock production sites, etc., it is antiviral in order to suppress virus transmission and transmission of viruses. It is required to use an antiviral fiber product to which is added. Such textile products have a wide variety of demands such as clothing, masks, curtains, towels and dust cloths.

  For example, Patent Document 1 describes an antibacterial cellulose claimed to have an effect on influenza virus. Patent Document 2 and Patent Document 3 describe antibacterial fibers using a polyhexamethylene biguanide compound of n = 4 to 7, and Patent Document 2 [0004] [0005] describes this as a california. It describes that it is used to inactivate viruses. Patent Document 4 describes in detail the antibacterial and antifungal properties of a fiber material using polyhexamethylene biguanide.

JP 2008-38293 A JP 2006-340949 A Japanese Patent Laid-Open No. 7-82665 Japanese Patent Laid-Open No. 61-63772

  However, there are many textile products that insist on antiviral effects such as anti-influenza virus characteristics, but many of them insist on antiviral effects with an anticipation as an extension of antibacterial effects. Many of them have not studied activity against viruses. Whether or not an antiviral agent actually has an effect on a virus is more difficult to verify than an effect on a fungus. This is because viruses and bacteria have completely different biological structures, and since many of the biological organs that act directly on bacteria are not present in viruses, they have a counteracting effect on bacteria and mold. But it often doesn't work against viruses. Moreover, even if the terminal group and the repeating unit of the compound are slightly different, whether or not to exert an inactivating effect on the virus is different. Therefore, just because there are antibacterial agents and antibacterial fiber products having antibacterial properties, those skilled in the art cannot directly convert them to antiviral agents or antiviral products, and strict verification is necessary. It cannot be diverted. That is, most of the textile products that claim antiviral properties alongside antibacterial properties and many of the literatures that refer to them are actually unclear whether or not they exhibit antiviral properties. Even if such a document is known, it is uncertain whether it exhibits antiviral properties, and thus it cannot be said that those skilled in the art can easily come up with antiviral fiber products.

  Although the antibacterial cellulose described in Patent Document 1 also claims an effect on influenza virus, it has not been verified that it is actually effective.

  Patent Document 2 and Patent Document 3 are examples using a polyhexamethylene biguanide compound of n = 4 to 7, but this also has no verification as to whether an actual antiviral effect is exerted against viruses. . In Patent Document 2, although a preferred pH is described in [0012] and examples are described, it is unclear what kind of virus was actually used and what kind of verification was performed. In other words, it merely claims that it has antiviral properties as an extension of antibacterial properties. Regarding the non-woven material of Patent Document 4, bacteria such as Pseudomonas aeruginosa and Escherichia coli are mainly studied in the examples, and verification of viruses such as influenza virus has not been performed.

  Then, this invention verifies that it can actually exhibit an effect with respect to a virus, and it aims at providing the textiles which show an effect with respect to viruses, such as influenza virus and norovirus, reliably.

  The present invention includes an antiviral imparting agent containing polyhexamethylene biguanide, or an antiviral imparting agent containing polyhexamethylene biguanide and one or more compounds selected from a spreading agent and a binder. It was verified by verifying that the textile product actually exerts an effect on viruses such as influenza virus, and showed that it can be used as an antiviral textile product.

  Even if polyhexamethylene biguanide alone is a natural fiber that has many functional groups with polarities such as hydroxyl groups, the fiber molecules and polyhexamethylene biguanide are fully compatible by hydrogen bonding, but nylon, polyester, etc. In the case of a synthetic fiber with relatively few polar functional groups, heat treatment using one or more compounds selected from a spreading agent and a binder is effective in blending the fiber with polyhexamethylene biguanide. Can increase the sustainability.

  If the target textile product has fewer functional groups than natural fibers such as cotton, and the polyhexamethylene biguanide is difficult to fit into the textile product, use a spreading agent and binder together with the polyhexamethylene biguanide. Increase sex. Among these, examples of the spreading agent include nonionic surfactants, polyvinyl alcohol, polyethylene glycol, polyvinyl acetate, polyhydric alcohol, and polysaccharides. Examples of the binder include melamine compounds, glyoxal compounds, urethane compounds, blocked isocyanate compounds, silicon compounds, acrylic resins, polyester resins, and acrylic resins having silicon. Among these, acrylic resins and polyester resins that do not release formaldehyde, and acrylic resins having silicon are particularly preferable.

  The antiviral fiber product using this polyhexamethylene biguanide reliably exhibits antiviral properties, particularly anti-influenza virus properties and anti-calicivirus properties.

  The present invention will be specifically described below. The present invention provides an antiviral property-imparting agent containing polyhexamethylene biguanide or an antiviral property-imparting agent containing polyhexamethylene biguanide and one or more compounds selected from a spreading agent and a binder. An antiviral fiber product and a method for producing the same.

  Specifically, the polyhexamethylene biguanide is a compound represented by the following chemical formula (1). Generally, it is distributed as a salt such as hydrochloride, and the salt may be used. Further, not only polyhexamethylene biguanide having a single polymerization degree n but also a mixture of polyhexamethylene biguanides having different polymerization degrees n may be used. However, in the case of a mixture, the number average value of the polymerization degree n is 10 to 13, and the main component of the mixture is preferably polyhexamethylene biguanide having a polymerization degree n of 8 to 16. In addition, a main component means here that 50 mol% or more is n = 8-16 among the polyhexamethylene biguanides to comprise.

  The spreading agent refers to a compound having a spreading effect that facilitates adhesion to fibers, and the binder refers to a compound having a bonding effect. These spreading agents and binders are used to improve the adhesion and bonding properties of polyhexamethylene biguanide to the resulting antiviral fiber product by blending the fiber product with polyhexamethylene biguanide. Among these, examples of the spreading agent include nonionic surfactants, polyvinyl alcohol, polyethylene glycol, polyvinyl acetate, polyhydric alcohol, and polysaccharides. As binders, melamine compounds, glyoxal compounds, urethane compounds, blocked isocyanate compounds, silicon compounds, acrylic resins, polyester resins, and acrylic resins containing silicon as organosiloxanes can be used. These may be used alone or in combination. Among these, a blocked isocyanate compound, a silicon compound, an acrylic resin, a polyester resin, and an acrylic resin containing silicon are preferable because they do not emit formaldehyde. Hereinafter, one or more compounds selected from a spreading agent and a binder are collectively referred to as “a spreading agent or the like”.

  Examples of the nonionic surfactant include polyoxyethylene alkyl ether, polyoxyethylene alkyl aryl ether, polyethylene oxide-polypropylene oxide block copolymer, polyoxyethylene sorbitan derivative, and the like.

  Examples of the polyhydric alcohol include glycerin, polyglycerin, and polyvinyl alcohol.

  Examples of the polysaccharide compounds include starch and carboxymethyl cellulose.

  The melamine compound is preferably a compound containing a triazine ring and having at least two reactive functional groups. As the reactive functional group, an amino group and an amide group are preferable, and an amide group is particularly preferable. Among such melamine compounds, compounds in which the hydrogen atom bonded to each nitrogen of the amino group and amide group is substituted with any of a methylol group, an ethylol group, and an N-methylolamide group are particularly preferable. used. In addition, about groups other than the reactive functional group of these melamine type compounds, you may be arbitrary functional groups, such as a hydrogen atom, a hydroxyl group, a phenyl group, an alkyl group, and an alkyl ester group.

  Examples of the glyoxal compound include glyoxal.

  Examples of the urethane compound include a compound obtained by reacting a compound having two or more active hydrogens reactive with an isocyanate group and polyisocyanate. Among these, examples of the compound having two or more active hydrogens include polyhydric alcohols, compounds having a carboxyl group and two hydroxyl groups, and polyamines. Examples of the polyisocyanate include aliphatic diisocyanate, alicyclic diisocyanate, and aromatic diisocyanate. Moreover, when it has an isocyanate group in the terminal of this urethane type compound, the compound which blocked a part of the isocyanate group with sodium bisulfite, methyl ethyl ketoxime, etc. can also be used.

  As the above blocked isocyanate compounds, sodium bisulfite, acetylacetone, ethyl acetoacetate, diethylmalonate, etc., react with isocyanate groups to form a stable compound temporarily, and then dissociate by heat treatment to produce isocyanate groups. A compound containing at least one blocked isocyanate group in the molecule, or at least one of these compounds is an acrylic or methacrylic compound, and a silicon-modified (meth) acrylic compound or fluorine-modified (meth) The compound obtained by making it react with an acryl-type compound is mentioned.

  As the silicon compound, a condensation-crosslinking resin classified into a silicone resin or a silicone varnish can be preferably used. This condensation-crosslinking resin can be obtained by polycondensing one or two or more silane compounds selected from silane compounds such as tetraethoxysilane and methyltrimethoxysilane.

  Examples of the acrylic resin include polymers of one or more monomers of (meth) acrylate monomers such as acrylic acid, methacrylic acid, methyl (meth) acrylate, and n-butyl (meth) acrylate, and ( A copolymer of a (meth) acrylic monomer and another copolymerizable vinyl monomer can be preferably used.

  Examples of the polyester resin include polyethylene terephthalate, polybutylene terephthalate, polyethylene isophthalate / terephthalate copolycondensate, and the like.

  Examples of the acrylic resin containing silicon include a polycondensate of a (meth) acrylic acid ester monomer and an organopolysiloxane compound.

  Among the above binders, the effect of improving the bonding property is to cause a cross-linking reaction like a melamine compound or a glyoxal compound to cause a chemical bond between the fiber product and the polyhexamethylene biguanide. Especially high. However, the binder that can be used in the present invention is not necessarily limited to a substance that causes chemical bonding. Polyhexamethylene biguanide is used by increasing the affinity between the polyhexamethylene biguanide and the fiber substrate. Any material that is not cross-linked as long as it is held on the surface of the textile can be used.

  Whether or not the antiviral property-imparting agent should contain a spreading agent or the like depends on the target textile product. Natural fibers such as cotton, silk, hemp, and wool, cellulose fibers such as rayon, semi-synthetic fibers such as cellulose acetate fibers, and fibers with a large number of functional groups that have polarity as a whole, such as cationic dimer polyesters with functional groups. In contrast, the polyhexamethylene biguanide exhibits sufficient affinity, and even when the antiviral fiber product is stored for a long period of time or repeatedly bent, the polyhexamethylene biguanide is less likely to fall off, It also exhibits high washing durability and maintains antiviral properties stably. However, most synthetic fibers such as polyester, polyamide, and polyacrylonitrile have less polar functional groups than the natural fibers described above, and the polyhexamethylene biguanide alone has insufficient affinity. For this reason, for textile products with relatively few polar functional groups, by adding the above-mentioned spreading agent or the like to the antiviral property-imparting agent, the textile product and polyhexamethylene biguanide are blended together to produce polyhexamethylene biguanide. Show the sustainability of the effect. In addition, the antiviral property-imparting agent containing the said spreading agent etc. is used also with respect to the natural fiber and semi-synthetic fiber which can fully exhibit the sustainability of the effect of polyhexamethylene biguanide without the said spreading agent etc. This is not hindered, and the sustainability of the effect of polyhexamethylene biguanide can be further improved as compared with the case of using the antiviral imparting agent not using the spreading agent.

  As a preferable method when an antiviral property-imparting agent containing polyhexamethylene biguanide or an antiviral property-imparting agent containing polyhexamethylene biguanide and a spreading agent is contained in a textile product, polyhexamethylene biguanide concentration Is preferably brought into contact with the fiber product as an aqueous solution of 0.1% by mass or more and 2% by mass or less. When the polyhexamethylene biguanide concentration is less than 0.1% by mass, the amount of adhesion is insufficient, and the antiviral properties of the resulting antiviral fiber product may be insufficient. On the other hand, when it exceeds 2 mass%, it may cause discoloration of the impregnated fiber product. In addition, said density | concentration is a density | concentration of polyhexamethylene biguanide itself, and when using salts, such as hydrochloride, it is a density | concentration which excluded the component originating in those acids. In addition, as a method of attaching such an aqueous solution to a textile product, immersion, spraying, application, and the like can be given.

  Moreover, when the said antiviral imparting agent has the said spreading agent etc., it is preferable when content of the said spreading agent etc. with respect to a polyhexamethylene biguanide shall be 100 to 5000 mass%. If the content of the spreading agent or the like is less than 100% by mass, the effect of improving the adhesion by the binder that improves the affinity with the fiber product is insufficient, and the resulting antiviral fiber product is polyhexamethylene biguanide. The possibility that the antiviral property is reduced or disappears due to detachment cannot be ignored. On the other hand, when it exceeds 5000 mass%, the texture of the obtained antiviral fiber product may be lowered.

  Regardless of the presence or absence of the spreading agent or the like, the antiviral fiber product according to the present invention is obtained by including the antiviral property-imparting agent in the fiber product. The method of including the antiviral property-imparting agent in the textile product is to impregnate or attach the antiviral property-imparting agent to fibers, and then heat-treat or dry-treat at 90 ° C. or more and 200 ° C. or less to produce fibers. A method of blending polyhexamethylene biguanide into a product is mentioned. If the temperature is lower than 90 ° C., the binder is not sufficiently solidified, so that the familiarity of the polyhexamethylene biguanide is not only insufficient, but the bond of the polyhexamethylene biguanide to the fiber is thin, and the working efficiency is remarkably lowered. On the other hand, if it exceeds 200 ° C., it causes discoloration of the fiber due to the drug, so-called fiber burn. Among these temperature ranges, 100 ° C. or higher is preferable, and 180 ° C. or lower is preferable.

  As described above, the fibers constituting the fiber product that can be used as the antiviral fiber product according to the present invention include natural fibers such as paper, cotton, hemp, silk, wool, and semisynthetic fibers such as regenerated cellulose. Synthetic fibers such as polyester, polyamide and polyacrylonitrile. Moreover, if it is the fiber generally used for a cloth, paper, and a filter, it can be used without a problem.

  Specific textile products include lab coats and aprons used by medical personnel, hospital clothes worn by hospital patients, work clothes used at livestock and food factories, hats, footwear such as shoes and sandals, and mouths. And masks covering the nose, curtains, nets such as bird nets, mats, filters for air purifiers and air conditioners, filters to prevent viruses contained in the air exhausted from sealed rooms, Towels, mops, towels, etc. Even if it is exposed to washing such as curtains and clothing, the polyhexamethylene biguanide is not easily dropped by itself if it is the above-mentioned natural fiber or the above-mentioned semi-synthetic fiber. Hold. Moreover, even if it is said synthetic fiber, sufficient durability is exhibited by using together with the said spreading agent. In addition, even if it is said natural fiber, the sustainability of a higher effect can be exhibited by using together with the said spreading agent.

  The antiviral fiber product according to the present invention surely exhibits anti-influenza virus properties and anti-feline calicivirus properties, among other antiviral properties. Note that feline calicivirus is a substitute virus for norovirus that cannot be artificially cultured, and the antiviral fiber product according to the present invention is considered to exhibit anti-calicivirus properties including anti-norovirus properties.

  Examples in which the antiviral fiber product according to the present invention is actually used against viruses to exhibit antiviral properties are shown below. The experimental analysis was requested from the Japan Food Analysis Center.

<Antiviral evaluation test against feline calicivirus>
As a polyhexamethylene biguanide, norovirus that cannot be artificially cultured using Osaka Kasei Co., Ltd. Markaside AV (average value of polymerization degree n in the above formula (1) is 12, the main component is n = 8-14, hydrochloride) The antiviral property against feline calicivirus, which is an alternative virus, was verified.

<How to wash>
It was carried out by home washing at 40 ° C. specified in JIS L0217-103.

Example 1a
A 100% cotton cloth is dipped in a 0.29% by mass aqueous solution of polyhexamethylene biguanide, squeezed to a moisture content of 70%, heat-treated at 120 ° C. for 30 seconds, and 0.20% owf of polyhexamethylene biguanide. A processed cotton fabric was obtained. This processed cotton fabric was washed 10 times.

(Example 1b)
A processed cotton fabric was obtained by the same procedure except that polyhexamethylene biguanide was changed to a 0.14% by mass aqueous solution in Example 1a.

(Comparative Example 1)
The cotton fabric used in Examples 1a and 1b was used without being impregnated with polyhexamethylene biguanide.

(Use agent for preparation of virus suspension)
Feline calicivirus vaccine strain (feline calicivirus) was used as the test virus, and CRFK cells manufactured by Dainippon Pharmaceutical Co., Ltd. were used as the cells used. As the cell growth medium, Eagle MEM (containing 0.06 mg / ml kanamycin) added with 10% by mass of fetal calf serum was used. As the cell maintenance medium, the above-mentioned Eagle MEM added with 2% by mass of fetal calf serum was used.

(Preparation of virus suspension)
Using the above cell growth medium, the used cells were cultured in a monolayer in a tissue culture flask. After monolayer culture, the cell growth medium was removed from the flask and inoculated with the test virus. Next, a cell maintenance medium was added and cultured in a carbon dioxide incubator (CO ₂ concentration: 5 mass%) at 37 ° C. ± 1 ° C. for 5 days. After culturing, the morphology of the cells was observed using an inverted phase contrast microscope, and it was confirmed that morphological changes (cytopathic effect) occurred in the cells. Next, the culture solution was centrifuged (3000 r / min, 10 minutes), and the resulting supernatant was diluted 10 times with purified water.

(Sample preparation)
Samples obtained in Examples 1a and 1b and Comparative Example 1 were cut into a size of 3 cm × 3 cm and subjected to high-pressure steam sterilization (121 ° C., 15 minutes) as samples.

(Test operation)
To the samples of the above Examples and Comparative Examples, 0.2 ml of the prepared virus suspension was dropped and stored at room temperature for 1 hour, and then the virus infectivity was measured. In parallel with this, the virus suspension of the sample stored for 1 hour in the same manner using the samples of Examples and Comparative Examples was washed out with 2 ml of cell maintenance medium to obtain a washing solution.

For the measurement of virus infectivity, cell growth medium was used, and the cells used were monolayer cultured in a tissue culture microplate (96 wells), then the cell growth medium was removed and 0.1 ml of cell maintenance medium was added. . Next, the sample washing solution and 0.1 ml of the diluted solution thereof were inoculated into 4 wells and cultured for 7 days in a 37 ° C. ± 1 ° C. carbon dioxide incubator (same as above). After culturing, the presence or absence of cell morphological change (cytopathic effect) is observed using an inverted phase contrast microscope, and the 50% tissue culture infectious dose (TCID ₅₀ ) is calculated by the Reed-Muench method. Converted to virus infectivity. The logarithmic values are shown in Table 1.

  All of Examples 1a and 1b showed a clear virus inactivation effect 1000 times or more as compared with the comparative example and the control. Moreover, even after 10 washings, Example 1a showed a good inactivation effect. The control body is a standard cotton cloth.

Claims (9)

  An antiviral fiber product containing a polyhexamethylene biguanide or an antiviral agent containing polyhexamethylene biguanide and one or more compounds selected from a spreading agent and a binder. The antiviral fiber product according to claim 1, wherein the polyhexamethylene biguanide is a compound represented by the following chemical formula (1) or a salt thereof.

  The spreading agent is made of one or more compounds selected from nonionic surfactants, polyvinyl alcohol, polyethylene glycol, polyvinyl acetate, polyhydric alcohols and polysaccharides, and the binder is a melamine compound, 3. A glyoxal compound, a urethane compound, a blocked isocyanate compound, a silicon compound, an acrylic resin, a polyester resin, and at least one compound selected from silicon-containing acrylic resins. Antiviral fiber product as described in 1.   The antiviral fiber product according to any one of claims 1 to 3, which has anti-influenza virus properties and anti-calicivirus properties.   The antiviral textile product according to any one of claims 1 to 4, wherein the textile product is one type selected from clothing, bedding, curtains, filters, hats, mats, nets, mops, and masks. .   An antiviral fiber product containing a polyhexamethylene biguanide or containing an antiviral property-imparting agent containing polyhexamethylene biguanide and one or more compounds selected from a spreading agent and a binder. Production method. An aqueous solution of an antiviral agent having a polyhexamethylene biguanide concentration of 0.1% by mass to 2% by mass, or
One or more compounds selected from a spreading agent and a binder having a polyhexamethylene biguanide concentration of 0.1% by mass or more and 2% by mass or less and 100% by mass or more and 5000% by mass or less with respect to the polyhexamethylene biguanide. An antiviral property that an aqueous solution of an antiviral property-imparting agent, which is an aqueous solution containing a polyhexamethylene biguanide, is attached to the fiber product by contacting the fiber product with a heat treatment at a temperature of 90 ° C. to 200 ° C. Manufacturing method of textile products.   An antiviral imparting agent containing polyhexamethylene biguanide or polyhexamethylene biguanide and a binder.   The antiviral property-imparting agent according to claim 8, which has anti-influenza virus properties and anti-calicivirus properties.