JP6475059B2 - Antiviral component - Google Patents

Description

  The present invention relates to an antiviral member having a free acidic functional group showing acidity introduced on the surface of a substrate.

  In recent years, deaths due to viral infections such as SARS (Severe Acute Respiratory Syndrome), Norovirus and avian influenza have been reported. In addition, norovirus and influenza infections in facilities such as hospitals and nursing homes are prevalent, and nosocomial infections caused by drug-resistant bacteria such as MRSA are prevalent, and immediate countermeasures are required. From these backgrounds, development of a member having a high inactivation function against viruses and bacteria is desired.

  In order to cope with such a situation, a technique for fixing inorganic fine particles having antiviral performance on a member surface has been developed (Patent Document 1).

International Publication No. 2011/040048

  However, when the inorganic fine particles are fixed on the surface of the member as in Patent Document 1, although the effect is high, there is a problem of dropping off. In addition, when the member has a complicated shape, there are problems such as difficulty in uniform processing and difficulty in processing the inner surface of a tube or the like.

  Accordingly, in order to solve the above problems, the present invention provides a novel antiviral member that is free from worries about dropping off and has few shape restrictions.

  That is, in the first invention, a substrate having at least a part of its surface made of a polymer, and an introduction amount of 0.03 meq / g or more and 3 meq / g or less are introduced into at least a part of the polymer of the substrate. It is an antiviral member characterized by having a free acidic functional group.

  The second invention is the antiviral member according to the first invention, wherein a free acidic functional group is introduced by a graft polymerization method.

  The third invention is the antiviral member according to the second invention, wherein the graft polymerization method is a radiation graft polymerization method.

  Furthermore, a fourth invention is characterized in that, in the first to third inventions, the free acidic functional group is selected from the group consisting of a sulfone group, a phosphate group, and a carboxy group. It is an antiviral member.

  Furthermore, a fifth invention is the antiviral member according to any one of the first to fourth inventions, wherein the substrate is a fiber structure.

  Furthermore, a sixth invention is the antiviral member according to any one of the first to fourth inventions, wherein the substrate is a resin molded body.

  Furthermore, a seventh invention is the antiviral member according to any one of the first to fourth inventions, wherein the substrate is a film or a sheet.

  According to the present invention, it is possible to provide a novel antiviral member that is free from fear of falling off and has few shape restrictions. By introducing a free acidic functional group showing acidity, the portion where the free acidic functional group is introduced, for example, the polymer surface of the substrate is made acidic, and as a result, the virus attached to the antiviral member is inactivated. can do.

  Hereinafter, embodiments of the present invention will be described in detail. An antiviral member according to an embodiment of the present invention includes a substrate and a free acidic functional group introduced into (at least a part of) a polymer constituting at least a part of the surface of the substrate. It is an antiviral member that inactivates viruses attached to (more specifically, the polymer portion of the substrate).

  The substrate of the antiviral member of this embodiment is a substrate that imparts antiviral properties. Although it does not specifically limit as a material used for the said base | substrate, It is preferable that at least one part of the surface is a polymer. In the case of a metal material such as aluminum or stainless steel, or an inorganic material such as glass or ceramic, if the polymer layer is formed on the surface by a coating film or the like, it can be used as the substrate of this embodiment. Examples of polymers include polyethylene, polypropylene, polystyrene, polycarbonate, polyester, polyamide, polyacetal, polyvinyl chloride, polyvinylidene chloride, polyvinylidene fluoride, polyacrylic acid, polymethyl methacrylate, polyurethane, ABS, SBC, latex, etc. Can be mentioned.

  The shape and form of the substrate used for the antiviral member of this embodiment are not particularly limited, and in addition to sheet-like materials such as woven fabrics, knitted fabrics, nonwoven fabrics, sheets, and films, resin products such as molded products can also be used. It is. Therefore, using the antiviral member of this embodiment, a mask, a cap (cap), a shoe cover, a curtain, a blind, an air conditioner filter, an air purifier filter, a vacuum cleaner filter, a ventilation fan filter, and a vehicle air conditioner Filters, air conditioning filters, ventilator filters, tubes, artificial noses, medical drapes (medical wraps, medical sheets), disposable gloves, medical gloves, wound covering materials, in-size drapes, surgical tapes, gauze , Wallpaper, clothing, bedding, nets for screen doors, nets for poultry houses, nets such as mosquito nets, and the like.

  Furthermore, you may make it the other member, for example, a film and a sheet | seat, be laminated | stacked on the antiviral member of this embodiment. For example, waterproofing can be imparted to the antiviral member by laminating a waterproof film or sheet. High-performance protective clothing, medical gloves, and hospitals that can prevent the transmission of viruses and blood by, for example, sewing and bonding the sheets using the waterproof sheet-like antiviral member. And sheets for nursing care can be configured.

  As the film or sheet to be laminated, a film having moisture permeability that shields water and allows air (humidity) to pass therethrough is preferably used so that the user can spend comfortably. Specifically, a commercially available product may be selected and used according to the purpose of use.

  Furthermore, an adhesive or the like can be laminated on the antiviral member of the present embodiment so that the user can arbitrarily adhere to a mask, wall or floor. Specifically, a virus inactivation mask can be obtained by attaching the antiviral member of the present embodiment to the surface of a hand-held mask.

  Moreover, the base | substrate which concerns on the antiviral member of this embodiment does not permeate | transmit air regardless of the structure which has air permeability, In other words, you may be provided with airtightness. Specifically, the substrate may be polyester, polyethylene, polypropylene, polyamide, polyvinyl chloride, polyvinylidene fluoride, polyvinyl alcohol, polyvinyl acetate, polyimide, polyamideimide, polytetrafluoroethylene, ethylene tetrafluoride-ethylene copolymer, etc. A sheet made of the above resin, a polycarbonate resin sheet / film, a vinyl chloride sheet, a fluororesin sheet, a polyethylene sheet, a silicone resin sheet, a nylon sheet, an ABS sheet, a urethane sheet, or a polymer sheet. The surface of the substrate may be painted or printed.

  Among the antiviral members of the present embodiment, members having airtightness include, for example, wallpaper, shower curtains, blinds, desk mats, food storage bags, food wrap films, keyboard covers, touch panels, touch panel covers, and medical drapes. , In-size drapes, interior materials for buildings such as hospitals, interior materials for trains and cars, seats for vehicles, covers for chairs and sofas, equipment for handling viruses, antifouling sheets for doors and floorboards, respirator masks, It can be used in various fields such as ventilator parts.

Next, the free acidic functional group that the antiviral member of this embodiment has will be described. The acidic functional group includes a strongly acidic free type that releases protons, and a neutral sodium type in which protons are replaced with sodium and neutralized with an aqueous sodium chloride solution or the like. The antiviral member of the present embodiment is characterized in that at least a part of the polymer is provided with a free acidic functional group that exhibits acidity. Further, at least a part of the polymer may be a part that can come into contact with the virus, and may be the surface of the polymer or the inside of the polymer.
In the antiviral member of this embodiment, by introducing a free acidic functional group showing acidity into the polymer, the surface or the inside of the polymer into which the free acidic functional group has been introduced becomes acidic, and as a result, adhered. It seems that the virus can be inactivated. Examples of the free acidic functional group include a sulfone group, a phosphate group, and a carboxy group, and any one or two or more of these can be introduced into the polymer.

  As a method for introducing these free acidic functional groups into the substrate (at least a part of the polymer), graft polymerization described later is preferably used. In order to make the surface or the inside of the polymer acidic, it is important to introduce a considerable amount (large amount) of acidic functional groups. For example, in the case of introducing a sulfone group, by simply contacting with sulfuric anhydride, concentrated sulfuric acid, chlorosulfonic acid, fuming sulfuric acid, sulfur trioxide, sulfamic acid, sodium sulfite, sodium bisulfite or a combination thereof, Although sulfone groups can be introduced on the surface of the substrate, the introduction amount is small, so it is difficult to achieve an acidic environment sufficient to inactivate the virus (if the introduction amount is increased by this method, the substrate will be colored). Or the strength is lost).

  In the present embodiment, the introduction amount of the acidic functional group to the polymer is preferably 0.03 meq / g or more and 3 meq / g or less, more preferably 0.1 meq / g or more and 3 meq / g or less. It can be. This is because when the introduction amount of the acidic functional group is less than 0.03 meq / g, the antiviral property is insufficient as compared with the range, and when it exceeds 3 meq / g, the strength of the substrate is compared with the range. This is because it deteriorates. The introduction amount [meq / g] of the acidic functional group is calculated by the following formula (1). The number of moles of acidic functional group introduced can be determined by neutralization titration. The weight of the polymer into which the functional group is introduced is the weight of the portion subjected to the introduction treatment of the free acidic functional group.

Introduction amount of acidic functional group (I _ex ) = n / S (1)
n: Number of moles of acidic functional group introduced into the polymer (mmol)
S: Weight of polymer into which functional group is introduced (g)

  Here, the graft polymerization method will be described. In the graft polymerization method, a radical is formed by irradiating the polymer portion of the substrate with radiation, etc., and a polymerizable monomer such as a vinyl monomer is grafted to the generated radical portion, and then a target functional group is formed. It is brought into contact with a substance to be contained (in this embodiment, a substance containing a free acidic functional group) and fixed. Since this method can introduce many functional functional groups into polymers having various shapes, it is a method used for separation functional materials and the like.

Examples of the method for generating radicals on the substrate (specifically, at least a part of the polymer portion) include a radiation irradiation method, an ultraviolet (UV) method, a corona discharge method, a plasma method, or a combination thereof. Can do.
The radiation irradiation method is a method of irradiating a substrate with radiation such as α rays, β rays, γ rays, and electron beams in an inert gas such as nitrogen, argon or helium gas. Alternatively, the substrate may be irradiated with radiation while the substrate is impregnated with an alcohol such as isopropyl alcohol (IPA).

The ultraviolet (UV) method is a method of irradiating a substrate with ultraviolet rays in the presence of a photoinitiator. In the ultraviolet irradiation method, similarly to the radiation irradiation method, the substrate may be irradiated with ultraviolet rays in an inert gas atmosphere or in a state where alcohol is impregnated with the substrate.
Photoinitiators include benzophenone and anthraquinone. There are a case where the energy of light absorbed by the photoinitiator moves to the polymer to create a radical, and a case where the photoinitiator radical abstracts the hydrogen of the polymer to create a radical in the polymer.

The corona discharge method is a method of irradiating a substrate with corona discharge.
The plasma method is a method of irradiating a substrate with plasma generated by glow discharge. In the plasma method, there are a method in which electrons in plasma form radicals in the polymer and a method in which radicals are reacted with oxygen to form peroxide radicals.
A feature of the UV method, plasma method, and corona discharge method is that radical generation is limited only to the vicinity of the surface of the substrate.

  Methods for generating radicals on the substrate include chemical initiator methods in addition to the above-described radiation irradiation method, ultraviolet method (UV method), corona discharge method, plasma method, and the like. Examples of the chemical initiator method include a chain transfer method, an emulsion polymerization method, and a cerium salt method. In the chain transfer method, peroxides such as benzoyl peroxide, azoisobutyronitrile (AIBN), and the like are used as chemical initiators.

  When graft polymerization is used in the production of the antiviral member of the present embodiment, depending on the purpose and application, as a radical generation method, a radiation irradiation method, a UV method, a plasma method, and a corona discharge method may be appropriately selected. Although it is good, the radiation irradiation method of irradiating α-rays, β-rays, γ-rays, or electron beams having a high energy amount is preferably used. The radiation irradiation method includes a simultaneous irradiation method and a pre-irradiation method. The simultaneous irradiation method is a method of irradiating in the presence of a polymer and a reactant, and the pre-irradiation method is also referred to as a trapping radical method. The characteristics of the radiation irradiation method are that it can be used for substrates of various shapes, that radicals can be generated inside the polymer, that more free acidic functional groups can be introduced, and that no initiator remains. Point and the point which can be mass-produced. Therefore, the radical polymerization method that can be used in this embodiment is preferably a radical polymerization method using radiation (radiation radical polymerization method).

  Regarding the radicals generated by the above radical generation method, for example, there are many reports in polyethylene, and alkyl, allyl, polyenyl, and peroxide radicals are generated by irradiation. Radicals are generated in the crystal part and the amorphous part, but in the amorphous part where the movement of the molecular chain is intense, it immediately disappears by a reaction such as recombination. Observed are radicals in the crystal part. Alkyl radicals are extremely reactive, move through the crystal part while extracting hydrogen, and are consumed by recombination (crosslinking), oxidation reaction, and graft reaction in the amorphous part.

  In this embodiment, when a free acidic functional group is introduced immediately after irradiation of the substrate, for example, within 1 to 2 minutes, the temperature at which the substrate is irradiated and the temperature at which the substrate is stored after irradiation. There are no particular restrictions on. However, when a free acidic functional group is introduced after a period of generation of radicals, it is desirable to perform irradiation and storage at a low temperature in order to preserve the radicals. If stored at a low temperature of about −5 ° C., a reaction using polymer radicals can be performed without any problem even after 20 days of irradiation.

  In the case of using the method of irradiating radiation when generating radicals on the base of the antiviral member of the present embodiment, the radiation irradiation dose is such that the amount of radical generation sufficient to introduce a free acidic functional group is sufficient. There is no particular limitation as long as it is an economical irradiation dose that is obtained and does not cause unnecessary crosslinking or partial decomposition. Since the radicals are uniformly generated and have little influence on the rigidity and chemical resistance of the substrate constituting the antiviral member of this embodiment, the radiation dose is preferably in the range of 1 kGy to 1000 kGy. It is more preferably in the range of ˜500 kGy, particularly preferably in the range of 10 kGy to 300 kGy.

  As described above, after generating radicals by irradiating the substrate surface with radiation, a monomer (polymerizable monomer) such as a vinyl monomer is brought into contact with the substrate surface, and the monomer is introduced as a polymer (graft chain) onto the substrate surface. Alternatively, radicals can be generated by irradiating the substrate surface with a monomer (polymerizable monomer) such as a vinyl monomer to generate radicals, and the monomer can be introduced into the substrate surface as a polymer (graft chain). it can. And the free type acidic functional group is introduce | transduced into each monomer which comprises a graft chain by making the introduced graft chain and the substance containing a free type acidic functional group contact. As a result, a polymer having a large number of free acidic functional groups produced by this graft polymerization method is introduced onto the surface of the substrate constituting the antiviral member of this embodiment.

  In this case, examples of the monomer (polymerizable monomer) used for the graft polymerization include acrylonitrile, acrolein, vinylpyridine, styrene, chloromethylstyrene, and glycidyl methacrylate. Examples of the substance having a free acidic functional group include acrylic acid and methacrylic acid that can introduce a carboxy group, and those that can introduce a sulfone group include sulfuric anhydride, concentrated sulfuric acid, and chlorosulfone. Examples include acid, fuming sulfuric acid, sulfur trioxide, sulfamic acid, and the like. When sodium styrene sulfonate, sodium methallyl sulfonate, sodium allyl sulfonate, sodium sulfite, sodium hydrogen sulfite or the like is used, a sodium-type acidic functional group is introduced. When sodium type acidic groups are introduced, free acidic functional groups can be obtained by substituting sodium ions and hydrogen ions in an acidic solution. For example, as a monomer, glycidyl methacrylate is introduced into a substrate (for example, a nonwoven fabric substrate) by radiation graft polymerization, and then a sulfonating agent such as sodium sulfite is reacted with an epoxy group of glycidyl methacrylate to introduce a sodium type sulfone group. After that, by immersing in hydrochloric acid or the like, an antiviral substrate into which a free acidic functional group has been introduced (for example, a nonwoven fabric) can be obtained.

  The virus that can be inactivated in the antiviral member of the present embodiment is not particularly limited, and various viruses can be inactivated regardless of the type of genome, the presence or absence of an envelope, and the like. For example, rhinovirus, poliovirus, foot-and-mouth disease virus, rotavirus, norovirus, enterovirus, hepatovirus, astrovirus, sapovirus, hepatitis E virus, type A, type B, type C influenza virus, parainfluenza virus, mumps virus (mumps) ) · Measles virus · Human metapneumo virus · RS virus · Nipah virus · Hendra virus · Yellow fever virus · Dengue virus · Japanese encephalitis virus · West Nile virus · Type B, hepatitis C virus · Eastern and western equine encephalitis virus · Onion Nyon virus, rubella virus, Lassa virus, Funin virus, Machupo virus, Guanarito virus, Sabia virus, Crimea congo hemorrhagic fever virus, snubber fever, hantavirus, shin Umbre virus, rabies virus, ebola virus, marburg virus, bat lyssa virus, human T cell leukemia virus, human immunodeficiency virus, human coronavirus, SARS coronavirus, human porvovirus, polyomavirus, human papillomavirus, adenovirus Examples include herpes virus, varicella-zoster rash virus, EB virus, cytomegalovirus, smallpox virus, monkeypox virus, cowpox virus, molasipox virus, and parapox virus.

  According to the antiviral member of the present embodiment as described above, it is possible to provide a novel antiviral member that is free from fear of falling off and has few shape restrictions. And according to the present embodiment, although the degree of the effect varies depending on the type and amount of the free acidic functional group to be introduced, the antiviral property with high immediate effect that can inactivate the virus in a very short time. The effect that a member can be provided is acquired.

  Next, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to only these examples.

<Production of bactericidal and antiviral components>
Hereinafter, an electron curtain type electron beam irradiation apparatus (CB250 / 15 / 180L manufactured by Iwasaki Electric Co., Ltd.) was used for the electron beam irradiation in the examples. Examples and comparative examples of antiviral members were produced as follows.

Example 1
A PP (polypropylene) -based meltblown nonwoven fabric (EM05010 manufactured by Toray Fine Chemical Co., Ltd.) was irradiated with an electron beam at an acceleration voltage of 200 kV at 20 Mrad in a nitrogen atmosphere. Next, the nonwoven fabric was immersed in a 10% glycidyl methacrylate solution, graft polymerization reaction was performed, and after sulfonation with an aqueous sodium hydrogen sulfite solution, free type sulfone groups were introduced by immersion in a hydrochloric acid solution. The obtained member was obtained. The amount of acidic functional group introduced into this sample was 0.6 meq / g.

(Example 2)
After irradiating the same nonwoven fabric as Example 1 with an electron beam, it was immersed in a 20% glycidyl methacrylate methanol solution and reacted at 40 ° C. for 5 hours. Then, after immersing in a mixed aqueous solution of sodium sulfite and isopropyl alcohol and reacting at 80 ° C. for 8 hours to effect sulfonation, a member into which a free sulfone group was introduced was obtained by immersion in a hydrochloric acid solution. . The amount of acidic functional group introduced into this sample was 2.4 meq / g.

(Example 3)
A PP (polypropylene) -based meltblown nonwoven fabric (EM05010 manufactured by Toray Fine Chemical Co., Ltd.) was irradiated with an electron beam at an acceleration voltage of 200 kV at 20 Mrad in a nitrogen atmosphere. Subsequently, this nonwoven fabric was immersed in a 50% aqueous acrylic acid solution, and a graft polymerization reaction was performed to carboxylate the substrate. At this time, 2.5% of a Mole salt was added to the aqueous acrylic acid solution to prevent the formation of a homopolymer. By washing, a member into which a free carboxy group was introduced was obtained. The amount of acidic functional group introduced into this sample was 0.9 meq / g.

Example 4
The same melt blown nonwoven fabric of PP (polypropylene) substrate as in Example 1 was irradiated with 5 Mrad of an electron beam at an acceleration voltage of 200 kV in a nitrogen atmosphere. The nonwoven fabric was then immersed in 0.5% fuming sulfuric acid at 60 ° C. for 15 minutes for sulfonation, and after washing, a member into which free sulfone groups were introduced was obtained. The amount of acidic functional group introduced into this sample was 0.05 meq / g.

(Comparative Example 1)
The same melt blown nonwoven fabric of PP (polypropylene) substrate as in Example 1 was irradiated with 5 Mrad of an electron beam at an acceleration voltage of 200 kV in a nitrogen atmosphere. Next, this nonwoven fabric was exposed to 30% fuming sulfuric acid for 1 hour under a nitrogen atmosphere to effect sulfonation to obtain a member into which free sulfone groups were introduced. The amount of acidic functional group introduced into this sample was 0.01 meq / g.

(Comparative Example 2)
The same melt blown nonwoven fabric of PP (polypropylene) substrate as in Example 1 was irradiated with 20 Mrad of an electron beam at an acceleration voltage of 200 kV in a nitrogen atmosphere. Next, this nonwoven fabric was immersed in a 10% glycidyl methacrylate solution, subjected to a graft polymerization reaction, further sulfonated with an aqueous sodium hydrogen sulfite solution, washed with water, and then a member into which a sodium type sulfone group was introduced was obtained. The amount of acidic functional group introduced into this sample was 0.9 meq / g.

<Evaluation of antiviral properties>
For the antiviral evaluation of each sample of Examples 1 to 4 and Comparative Examples 1 and 2, influenza virus (influenza A / Kitakyushu / 159/93 (H3N2)) cultured using MDCK cells was used. 100 μL of the virus suspension was dropped onto a plastic petri dish, each sample cut out 2 cm × 2 cm from the top was placed, the suspension was spread over the entire surface of the sample, and then allowed to act at room temperature for 5 minutes. After 5 minutes, 1900 μL of SCDLP medium was added, the virus was washed out by pipetting, and the supernatant was collected. Next, a 10-fold serial dilution series of the collected supernatant was prepared using cell culture medium (MEM). The recovered supernatant and 0.1 mL of each diluted solution were inoculated into a 6-well cell culture plate in which MDCK cells were cultured. After allowing to stand for 60 minutes to adsorb the virus to the cells, 0.7% agar medium was overlaid and cultured for 48 hours in a 34 ° C., 5% CO 2 incubator. Thereafter, formalin fixation and methylene blue staining were performed, the number of plaques formed was counted, and the virus infectivity (PFU / 0.1 mL, Log 10); (PFU: plaque-forming units) was calculated. The test results are shown in Table 1.

  From the above results, in Examples 1 to 3 in which a sufficient amount of sulfone group or carboxy group, which is a free acidic group showing acidity, was introduced by radiation graft polymerization, the detection limit was as low as 5 minutes in contact with the virus. A high antiviral effect of below the value was confirmed. Example 4 introduced with fuming sulfuric acid also showed a very high effect of 99.99% or more, but some coloring was seen in the nonwoven fabric. On the other hand, although Comparative Example 1 had some antiviral effect, a sufficient amount of sulfone group was not introduced compared to Example 1, so that a sufficient effect was not seen. Further, the neutralized sodium-type sulfone group of Comparative Example 2 showed no antiviral effect despite the introduction of a sufficient amount of functional groups by radiation graft polymerization. From these results, it was confirmed that various antiviral products can be provided by using the antiviral member of the present invention.

Claims (5)

A substrate having at least part of its surface made of a polymer;
A free acidic functional group introduced by a graft polymerization method at an introduction amount of 0.03 meq / g or more and 3 meq / g or less into at least a part of the polymer of the substrate ;
The antiviral member, wherein the free acidic functional group is a sulfone group or a carboxy group . The antiviral member according to claim 1 , wherein the graft polymerization method is a radiation graft polymerization method. The antiviral member according to claim 1 or 2 , wherein the substrate is a fiber structure. Antiviral member according to claim 1 or 2, wherein the substrate is a resin molding. The antiviral member according to claim 1 or 2 , wherein the substrate is a film or a sheet.