JP2016056481A - Antibacterial sheet and method for producing antibacterial sheet - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an antibacterial sheet having antibacterial action against more strains and a method for producing the same.SOLUTION: There are provided an antibacterial sheet in which antibacterial particles are carried on at least one of a surface or inside of fibers which constitutes a nonwoven fabric, and an antimicrobial sheet in which antibacterial particles are carried on at least one of a surface or inside of a nanofiber sheet composed of nano fibers having a fiber diameter of less than 1000 nm. There is also provided a method for producing an antimicrobial sheet including a step of spinning a mixed solution obtained by mixing a dispersion liquid in which antibacterial particles are dispersed with a polymer resin solution which constitutes the nano fibers dispersing antibacterial particles, by an electrospinning method to carry the antibacterial particles on at least one of a surface or inside of a nanofiber sheet composed of the nano fibers having a fiber diameter of less than 1000 nm.SELECTED DRAWING: None

Description

  The present invention relates to an antibacterial sheet carrying antibacterial particles and a method for producing the same.

  Conventionally, as a sheet having excellent antibacterial properties, for example, Patent Document 1 describes a superabsorbent antibacterial sheet in which a superabsorbent polymer layer is provided on one surface of a nonwoven fabric containing an inorganic antibacterial agent or between the nonwoven fabrics. In the antibacterial sheet described in Patent Document 1, antibacterial agents such as silver, copper, calcium, sulfur, and chlorine are used.

  Patent Document 2 describes an antibacterial sheet having a plant-derived water-soluble extract as an antibacterial agent. For the antibacterial sheet described in Patent Document 2, a fiber sheet in the form of a film or sheet composed of a woven fabric, a knitted fabric, a nonwoven fabric, or a pulp product such as paper is used.

  In addition, for example, the following techniques have been known as antibacterial agents having an antibacterial effect against bacteria such as Gram-positive bacteria.

  That is, Patent Document 3 describes an antibacterial agent containing cyanoacrylate polymer particles conjugated with an antibiotic as an active ingredient as an antibacterial agent for vancomycin-resistant gram-positive bacteria. The cyanoacrylate polymer particles are obtained by anionic polymerization of a cyanoacrylate monomer that is used, for example, as an adhesive for wound closure in the surgical field. Cyanoacrylate-based polymer particles are porous, and a desired substance can be conjugated inside. In the antibacterial agent of Patent Document 1, vancomycin-resistant enterococci (VRE) that has acquired resistance to various antibiotics by conjugating antibiotics to cyanoacrylate polymer particles and has become impossible to antibacterial by administration of the antibiotics. ), The antibacterial action of antibiotics was exerted, and the growth of VRE could be suppressed.

JP-A-9-143850 Japanese Patent Laid-Open No. 11-200245 International Publication No. 2008/126646

  In recent years, antibacterial sheets are increasingly required to meet diversifying needs, and it is required to develop products optimized for diversifying needs. Therefore, it is desirable that various antibacterial agents can be applied to fiber sheets and the like to produce antibacterial sheets that can be used for a wide range of purposes.

  Accordingly, an object of the present invention is to provide an antibacterial sheet having an antibacterial action against more bacterial species and a method for producing the same.

  The first characteristic configuration of the antibacterial sheet according to the present invention for achieving the above object is that the antibacterial particles are supported on at least one of the surface and the inside of the fiber constituting the nonwoven fabric.

According to this structure, the nonwoven fabric fiber sheet which can anticipate the antibacterial effect with respect to a desired microbe species can be produced. In addition, with the antibacterial sheet of this configuration, the antibacterial power can be easily controlled by the application amount (g / m ² ) of the antibacterial particles, so the application amount is appropriate depending on the product application and the target bacterial species. Can be adjusted. Therefore, the antibacterial sheet of the present invention can be used as a filter for a water purifier, in addition to sanitary materials such as floors and equipment wipers, air filters such as air conditioners, diapers, sanitary products and masks.

  The second characteristic configuration of the antibacterial sheet according to the present invention is that the antibacterial particles are supported on at least one of the surface and the inside of the nanofiber sheet composed of nanofibers having a fiber diameter of less than 1000 nanometers. is there.

  According to this structure, the nanofiber sheet | seat which can anticipate the antibacterial effect with respect to a desired microbe species can be produced. In addition, because of the characteristics of nanofibers with a very large specific surface area, the adsorption characteristics and adhesion characteristics are excellent, so that the effect of capturing a desired bacterial species is excellent, and the captured bacteria can be surely killed. Furthermore, a phenomenon called a slip flow effect occurs due to the characteristics of the nanofiber, and when a fine filter is produced using the nanofiber sheet, the influence on the flow velocity of the air passing through the filter can be reduced. Therefore, for example, when a mask is produced with a nanofiber sheet, a highly functional mask with less breathing can be produced.

In addition, with the antibacterial sheet of this configuration, the antibacterial power can be easily controlled by the application amount (g / m ² ) of the antibacterial particles, so the application amount is appropriate depending on the product application and the target bacterial species. Can be adjusted. Therefore, the antibacterial sheet of the present invention can be used as a filter for a water purifier, in addition to sanitary materials such as floors and equipment wipers, air filters such as air conditioners, diapers, sanitary products and masks.

  The third characteristic configuration of the antibacterial sheet according to the present invention is that the antibacterial particles are cyanoacrylate polymer particles.

  According to this configuration, for example, Gram-positive bacteria, which are bacteria that synthesize cell walls, such as Staphylococcus aureus (methicillin-resistant Staphylococcus aureus (MRSA)), enterococci (vancomycin-resistant enterococci (VRE)), streptococci (pneumococcus pneumoniae) Antibacterial effects against cocci, oral streptococci, pyogenes streptococci, peptostreptococcus bacteria, diphtheria, propionibacterium acnes, acid-fast bacteria (tuberculosis, non-tuberculous mycobacteria, etc.) However, it is not limited to these. Therefore, an antibacterial sheet having an antibacterial action against more bacterial species can be provided.

  It is considered that the cyanoacrylate polymer particles specifically adhere to the cell wall of Gram-positive bacteria and can be lysed by contacting the cyanoacrylate polymer particles with the peptidoglycan layer of Gram-positive bacteria.

  A fourth characteristic configuration of the antibacterial sheet according to the present invention is that the antibacterial particles are cyanoacrylate polymer particles containing an organic acid in at least one of conjugation or mixing.

  According to this configuration, in addition to the gram-positive bacteria described above, an antibacterial effect against, for example, gram-negative bacteria, which are bacteria that synthesize cell walls, such as Escherichia coli, Legionella, Pseudomonas aeruginosa, Salmonella, and Klebsiella pneumoniae can be expected. Therefore, an antibacterial sheet having an antibacterial action against more bacterial species can be provided.

  In this embodiment, the organic acid which is an antibacterial active ingredient acts on the outer membrane (capsular membrane) composed of lipopolysaccharide of Gram-negative bacterial cells, and the organic acid is contained in at least one form of conjugation or mixing It is considered that the particles were able to be lysed as a result of the particles breaking through the outer membrane and passing through and contacting the peptidoglycan layer inside the particles with the cyanoacrylate polymer particles.

  The characteristic means of the method for producing an antibacterial sheet according to the present invention is that the fiber diameter is obtained by spinning a mixture liquid in which antibacterial particles are dispersed and a polymer resin liquid constituting a nanofiber by an electrospinning method. It has the process of carrying | supporting on the surface of the nanofiber sheet comprised with the nanofiber below 1000 nanometer, and / or the inside.

  In the electrospinning method, a high voltage is applied between the capillary and the substrate, and the sample solution (polymer resin solution) is sprayed as a charged fiber from the nozzle at the tip of the capillary. The charged fibers emitted from the capillaries are drawn toward the substrate (electrode) in the electric field and are deposited on the substrate to form a thin fiber layer. The nanofibers thus formed can be formed into a nonwoven fabric to form a nanofiber sheet.

  According to this means, since the mixture liquid in which the dispersion liquid in which the antibacterial particles are dispersed and the polymer resin liquid constituting the nanofiber is spun by the electrospinning method, the nanofiber sheet composed of the nanofiber is formed. Antimicrobial particles can be carried on at least one of the surface and the inside.

  The characteristic constitution of the antibacterial nanofiber according to the present invention is that the antibacterial particles are supported on the surface of the nanofiber having a fiber diameter of less than 1000 nanometers.

  According to this configuration, since antibacterial particles can be supported on the surface of the nanofiber, an antibacterial nanofiber that can be expected to have an antibacterial effect against a desired bacterial species can be produced.

It is the photograph figure which observed the sample piece (polyester spunlace) considered that the antibacterial particle has adhered with the electron microscope. It is the graph which showed the result of having investigated the antimicrobial property after heating an antimicrobial sheet. It is the photograph figure which observed the nanofiber sheet considered that the antibacterial particle has adhered with the electron microscope. It is the photograph figure which observed the nanofiber sheet considered that the antibacterial particle has adhered with the electron microscope. It is the photograph figure which observed the sample piece which made the antibacterial particle adhere with the acrylic emulsion binder observed with the electron microscope.

Hereinafter, embodiments of the present invention will be described with reference to the drawings.
In the antibacterial sheet of the present invention, the antibacterial particles are supported on at least one of the surface and the inside of the fiber constituting the nonwoven fabric. Alternatively, in the antibacterial sheet of the present invention, the antibacterial particles are supported on at least one of the surface and the inside of the nanofiber sheet composed of nanofibers having a fiber diameter of less than 1000 nanometers.

  Antibacterial particles can contain cyanoacrylate polymer particles as an active ingredient. The cyanoacrylate polymer portion of the antibacterial particles is obtained by anionic polymerization of a cyanoacrylate monomer. The cyanoacrylate monomer used is preferably an alkyl cyanoacrylate monomer (the carbon number of the alkyl group is preferably 1 to 8), and is used as an adhesive for wound closure, particularly in the surgical field. It is preferable to use butyl cyanoacrylate represented by the formula.

  As the cyanoacrylate monomer, butyl cyanoacrylate such as isobutyl cyanoacrylate, n-butyl-2-cyanoacrylate, sec-butyl cyanoacrylate, tert-butyl cyanoacrylate, etc. can be used, and methyl cyanoacrylate, ethyl cyanoacrylate ( Other alkyl cyanoacrylates such as adhesive for false eyelashes) and propyl cyanoacrylate may be selected. In particular, isobutyl cyanoacrylate, n-butyl-2-cyanoacrylate, and ethyl cyanoacrylate are excellent in safety.

  In anionic polymerization, saccharides may be used for stabilizing the polymerization. That is, the “cyanoacrylate polymer particles” of the present invention include those containing a polymerization stabilizer such as a saccharide. The saccharide is not particularly limited, and may be any of a monosaccharide having a hydroxyl group, a disaccharide having a hydroxyl group, and a polysaccharide having a hydroxyl group, and is particularly preferably a polysaccharide. Examples of monosaccharides include glucose, mannose, ribose and fructose, and glucose is preferred. Examples of the disaccharide include maltose, trehalose, lactose and sucrose. As the polysaccharide, dextran, mannan, or the like used for the polymerization of conventionally known cyanoacrylate polymer particles can be used. These sugars may be either cyclic or chain-like, and when they are cyclic, they may be any one of pyranose type, furanose type and the like. In addition, there are various isomers of sugar, and any of them may be used. Usually, monosaccharides exist in a pyranose type or furanose type form, and disaccharides are those in which they are α-bonded or β-bonded, and sugars in such a normal form can be used as they are.

  Moreover, it can replace with the saccharide | sugar mentioned above and can use if it has the function of the polymerization stabilization of anionic polymerization, such as polyethyleneglycol and surfactant.

  The saccharides, polyethylene glycols and surfactants mentioned above can be used alone or in combination of two or more. Of the saccharides described above, dextran is preferable, and dextran is preferably dextran having a polymerization degree of about 10,000 to 500,000 in average molecular weight, but is not limited thereto.

The antibacterial particles may contain only cyanoacrylate polymer particles. However, since the cyanoacrylate polymer particles are porous, a desired substance can be conjugated inside. After forming the cyanoacrylate polymer particles, the desired substance may be conjugated to the inside of the cyanoacrylate polymer particles by immersing the cyanoacrylate polymer particles in an aqueous solution of the desired substance or adding the desired substance. The desired substance may be conjugated to the produced particles by performing the above-described anionic polymerization in the presence of the desired substance. As a desired substance, for example, in this embodiment, a case where an organic acid is conjugated to cyanoacrylate polymer particles will be described. Conjugation refers to a state in which a foreign substance is held in, for example, a hydrophilic molecule.
In addition, it is not limited to the aspect which conjugated an organic acid to a cyanoacrylate polymer particle like this embodiment, You may set it as the aspect which the cyanoacrylate polymer particle and the organic acid are mixing. The said mixing should just be an aspect with which the cyanoacrylate polymer particle and the organic acid coexist and are mixed.

  As the organic acid, glycolic acid, fumaric acid, citric acid, acetic acid, lactic acid and the like having antibacterial properties can be used. Among these organic acids, at least one or more can be selected and used. In particular, glycolic acid has the smallest molecular weight among organic acids and is excellent in permeability. These organic acids can be used as long as they have antibacterial properties.

  Water can be used as a solvent for the polymerization reaction. Purified water, ion-exchanged water, distilled water, pure water, tap water, ground water, etc. may be appropriately selected as the water depending on the product application having different required purity.

  When the organic acid is conjugated to the cyanoacrylate polymer particles, the antibacterial particles can be produced by performing anion polymerization of the cyanoacrylate monomer in the presence of the cyanoacrylate monomer, saccharide and organic acid. Specifically, the polymerization reaction is performed, for example, by dissolving a polymerization stabilizer such as an organic acid and a saccharide to be conjugated to water as a solvent, adding a cyanoacrylate monomer under stirring, and continuing stirring. be able to. Although reaction temperature is not specifically limited, It is good to carry out at room temperature. The reaction time varies depending on the pH of the reaction solution, the type of solvent, and the concentration of the polymerization stabilizer, and is not particularly limited because it may be appropriately selected depending on these factors, but is usually about 1 to 6 hours. It is.

  The concentration of the cyanoacrylate monomer in the polymerization reaction solution at the start of the reaction is not particularly limited, but is usually about 0.01 to 5%, preferably about 0.1 to 3%. The concentration of the organic acid in the polymerization reaction solution at the start of the reaction is not particularly limited, but is usually about 0.01 wt% to 10 wt%, preferably about 0.05 wt% to 5 wt%, more preferably 0.05 wt% to 3 wt%. It may be about%. The concentration of the saccharide in the polymerization reaction solution at the start of the reaction is not particularly limited, but is usually about 0.01 to 5%, preferably about 0.1 to 3%.

  By the polymerization reaction described above, the cyanoacrylate monomer is anionically polymerized to synthesize cyanoacrylate polymer particles (organic acid-conjugated particles) efficiently conjugated with an organic acid, thereby producing antibacterial particles. When two or more kinds of organic acids are allowed to coexist during anionic polymerization, antibacterial particles having organic acid-conjugated particles conjugated with two or more kinds of organic acids can be produced.