WO2017082117A1 - Sustained release antimicrobial agent and article - Google Patents

Sustained release antimicrobial agent and article Download PDF

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Publication number
WO2017082117A1
WO2017082117A1 PCT/JP2016/082419 JP2016082419W WO2017082117A1 WO 2017082117 A1 WO2017082117 A1 WO 2017082117A1 JP 2016082419 W JP2016082419 W JP 2016082419W WO 2017082117 A1 WO2017082117 A1 WO 2017082117A1
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Prior art keywords
metal particles
antibacterial
sustained
hydrophilic
release
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PCT/JP2016/082419
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French (fr)
Japanese (ja)
Inventor
吉田　育弘
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三菱電機株式会社
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Priority to JP2017550274A priority Critical patent/JPWO2017082117A1/en
Publication of WO2017082117A1 publication Critical patent/WO2017082117A1/en

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    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
    • A01N25/08—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing solids as carriers or diluents
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N59/00—Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
    • A01N59/16—Heavy metals; Compounds thereof
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N59/00—Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
    • A01N59/16—Heavy metals; Compounds thereof
    • A01N59/20—Copper
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D201/00—Coating compositions based on unspecified macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/14—Paints containing biocides, e.g. fungicides, insecticides or pesticides
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives

Definitions

  • the present invention relates to a sustained-release antibacterial agent and an article having a coating formed of the sustained-release antibacterial agent on the surface.
  • a method of forming a film having antibacterial or antifungal properties is preferably used because it is simple and can treat various articles.
  • Antibacterial properties can be imparted by adding an antibacterial agent to the coating. In such a coating, since the antibacterial agent is continuously released over time, the antibacterial property gradually decreases. In order to lengthen the period during which the antibacterial property can be exhibited, metal ions such as copper and silver that are effective in a small amount are often used.
  • a method using an inorganic layered compound or zeolite containing a metal ion is known.
  • Patent Document 1 describes a composition for producing an antibacterial hydrophilic coating that includes a hydrophilic polymer, a photoinitiator, particles containing metallic silver, and the like.
  • the present invention has been made to solve the above-described problems, and provides a sustained-release antibacterial agent capable of stably and slowly releasing antibacterial metal ions over a long period of time. With the goal.
  • the present invention is a sustained-release antibacterial agent comprising antibacterial metal particles, metal particles having a lower redox potential than the metal constituting the antibacterial metal particles, and a hydrophilic substrate,
  • the sustained-release antibacterial agent is characterized in that the metal particles having a low oxidation-reduction potential are contained in the range of 1 to 5 times the content of the antibacterial metal particles.
  • a sustained-release antibacterial agent capable of stably and slowly releasing antibacterial metal ions over a long period of time can be provided.
  • Embodiment 1 FIG.
  • the sustained-release antibacterial agent according to Embodiment 1 of the present invention includes antibacterial metal particles, metal particles having a redox potential lower than that of the metal constituting the antibacterial metal particles, a hydrophilic substrate, It contains.
  • FIG. 1 is a schematic diagram showing a process in which antibacterial metal particles are eluted over time in an antibacterial agent containing antibacterial metal particles and a hydrophilic substrate.
  • the antibacterial agent is in a state where the antibacterial metal particles 1 are dispersed in the hydrophilic substrate 2.
  • the antibacterial metal particles 1 react with various substances such as oxygen, water, carbonic acid, and nitric acid present in the environment, and thereby oxides, hydroxides, etc.
  • metal ions are generated and released from the antibacterial metal particles 1.
  • Metal ions form hydration and various ions that coexist or complex ions with the hydrophilic substrate 2.
  • the complex ions diffuse into the antibacterial agent, it is gradually released to the outside of the antibacterial agent and exhibits antibacterial properties.
  • the hydrophilic substrate 2 is a hydrophilic resin
  • the path through which the complex ions diffuse is a gap between molecular chains swollen with water
  • the hydrophilic substrate 2 is a hydrophilic inorganic substance. In some cases, the water is present in gaps or pores in the hydrophilic inorganic substance.
  • the amount of metal ions generated depends on the amount of antibacterial metal particles 1 added and the total surface area of the antibacterial metal particles 1, and the amount of metal ions generated is initially large, but is shown in FIG. Thus, since the particle size of the antibacterial metal particles 1 becomes smaller with the passage of time, the amount of metal ions generated is reduced, and the antibacterial property does not last for a long time. In addition, the antibacterial metal particle 1 existing in the vicinity of the surface of the antibacterial agent tends to have a small particle size.
  • FIG. 2 shows an antibacterial metal in a sustained-release antibacterial agent comprising antibacterial metal particles, metal particles having a lower redox potential than the redox electricity of the metal constituting the antibacterial metal particles, and a hydrophilic substrate. It is a schematic diagram which shows the process in which particle
  • the sustained-release antibacterial agent has antibacterial metal particles 1 and metal particles 3 having a low redox potential dispersed in a hydrophilic substrate 2, and a part of the antibacterial metal particles 1.
  • the metal particles 3 having a low oxidation-reduction potential are in contact with each other.
  • a conductive medium such as a water-containing material and dissolved oxygen is present
  • the metal with a low oxidation-reduction potential is oxidized first and oxidized. Oxidation of a metal having a high reduction potential is suppressed.
  • the antibacterial metal particles 1 that are not in contact with the metal particles 3 having a low redox potential are oxidized and eluted in the same manner as in FIG. The particle size becomes smaller.
  • the antibacterial metal particles 1 that are in contact with the metal particles 3 having a low redox potential are slow to be eluted.
  • the elution rate varies depending on the mass ratio of the antibacterial metal particles 1 in contact with the metal particles 3 with a low redox potential, and the amount of the metal particles 3 with low redox potential in contact with the antibacterial metal particles 1 If the amount is large, the effect of suppressing oxidation / elution is large, and the action period is also long.
  • generated from the antibacterial metal particle 1 may also be reduced on the surface of the metal particle 3 with a low oxidation-reduction potential and returned to a metal.
  • the oxidation of the antibacterial metal particle 1 is suppressed by the presence of the metal particle 3 having a low redox potential.
  • Some of the antibacterial metal particles 1 are oxidized from the initial stage depending on the surrounding environment, and some of the antibacterial metal particles 1 start to be oxidized after a long period of time as shown in FIG.
  • antibacterial property can be maintained for a long time by mixing the antibacterial metal particles 1 having different oxidation progresses.
  • the shape of the sustained-release antibacterial agent according to Embodiment 1 of the present invention is not particularly limited, but may be a film shape, a bulk shape, a fiber shape, a granular shape, or the like.
  • the use form of the sustained-release antibacterial agent is a method of coating various article surfaces as a coating film, a bulk or fibrous sustained-release antibacterial agent, a method of placing in contact with water, and a granular sustained-release antibacterial agent The method of mixing with water is mentioned.
  • the antibacterial metal particles 1 in the present invention silver, copper, nickel, chromium, cobalt, and the like can be used. From the viewpoint that no harmfulness to the human body is observed in normal use, the antibacterial metal particles 1 are made of silver and copper. It is preferably at least one selected from the group. These metals may be used alone or in combination of two or more, or may be used as an alloy. Even if the metal is harmful to human body, the antibacterial action of silver or copper can be amplified if it is added in a small amount within a range where the toxicity to silver or copper is not obvious.
  • the average particle diameter of the antibacterial metal particles 1 is preferably 0.1 ⁇ m or more and 200 ⁇ m or less, and more preferably 0.3 ⁇ m or more and 50 ⁇ m or less.
  • the average particle size of the antibacterial metal particles 1 is 0.1 ⁇ m or more, the antibacterial property can be maintained for a longer period.
  • the average particle size of the antibacterial metal particles 1 is 200 ⁇ m or less, oxidation / elution tends to proceed stably.
  • shape of the antibacterial metal particles 1 various shapes such as a lump shape, a plate shape, a needle shape, and a spherical shape can be used.
  • the shape of the antibacterial metal particles 1 may be porous such that fine particles are aggregated.
  • any metal having a lower oxidation-reduction potential than the metal constituting the antibacterial metal particle 1 can be used, but it is inexpensive and harmful to the human body.
  • At least one selected from the group consisting of aluminum and zinc from the viewpoint of low properties, formation of hydroxide and the like during oxidation, and little change in color tone and shape such as coloring and cloudiness as a sustained-release antibacterial agent Preferably it is a seed.
  • the average particle size of the metal particles 3 having a low oxidation-reduction potential is preferably 0.1 ⁇ m or more and 200 ⁇ m or less, and more preferably 0.3 ⁇ m or more and 100 ⁇ m or less.
  • the average particle size of the metal particles 3 having a low oxidation-reduction potential is 0.1 ⁇ m or more, the antibacterial property can be maintained for a longer period.
  • the average particle size of the metal particles 3 having a low oxidation-reduction potential is 200 ⁇ m or less, a sufficient contact point with the antibacterial metal particles 1 can be ensured, and the oxidation inhibiting action can be effectively exhibited.
  • the average particle size of the metal particles 3 having a low redox potential is preferably 0.2 to 3 times the average particle size of the antibacterial metal particles 1, and is 0.5 to 2 times the average particle size. More preferably.
  • the average particle size of the metal particles 3 having a low oxidation-reduction potential is 0.2 times or more than the average particle size of the antibacterial metal particles 1, the antioxidation effect of the antibacterial metal particles 1 can be maintained over a long period of time.
  • antibacterial metal ions can be appropriately diffused and gradually released, antibacterial properties can be sufficiently exhibited.
  • the average particle size of the metal particles 3 having a low redox potential is not more than 3 times the average particle size of the antibacterial metal particles 1, the oxidation of the metal particles 3 having a low redox potential proceeds appropriately. Since it is easy to ensure the number of antibacterial metal particles 1 that come into contact with the metal particles 3 having a low oxidation-reduction potential, the oxidation-inhibiting action can be improved.
  • Various shapes such as a lump shape, a plate shape, a needle shape, and a spherical shape can be used as the shape of the metal particles 3 having a low oxidation-reduction potential.
  • the shape of the metal particles 3 having a low oxidation-reduction potential may be porous such that fine particles are aggregated.
  • the average particle size of the antibacterial metal particles 1 and the metal particles 3 having a low redox potential means an average particle size measured by a Coulter method (for example, “Multisizer 4e” manufactured by Beckman Coulter, Inc.).
  • hydrophilic substrate 2 in the present invention examples include hydrophilic resins and hydrophilic inorganic substances.
  • hydrophilic resin a resin whose hydrophilicity is ensured by a hydroxyl group is preferable.
  • resins include polyvinyl alcohol, polyvinyl pyrrolidone, polyethylene glycol, polyacrylamide, polyacrylic acid, polymethacrylic acid or esters thereof, a mixture of these thermoplastic resins, amylose, amylopectin, glycogen, cellulose, chitin. , Polysaccharides such as agarose and carrageenan, and mixtures thereof.
  • Such a hydrophilic resin is easily dissolved or swollen in water when immersed in water.
  • the hydrophilic resin it is preferable to suppress dissolution and swelling by heating the hydrophilic resin, adding various crosslinking agents to the hydrophilic resin, or using these techniques in combination.
  • the crosslinking agent used here include zirconium chloride and polycarbodiimide.
  • the addition amount of the crosslinking agent may be appropriately adjusted within a range in which the swelling ratio of the hydrophilic resin can be suppressed to 50% or less, but is usually 0.1% by mass or more and 20% by mass with respect to the solid content of the hydrophilic resin. % Or less.
  • thermosetting resin such as melamine resin, novolak resin, urea resin, or a mixture thereof may be used.
  • those that have been given hydrophilicity by introducing hydrophilic substituents such as hydroxyl groups or mixing hydrophilic substances into resins that are generally poorly hydrophilic, such as polyolefins, polyurethanes, and epoxy resins. Is possible.
  • the hydrophilic substance used here include various inorganic particles such as silica, alumina, and clay in addition to the above-described hydrophilic resin. Since such a resin is less swelled by water, the antibacterial property can be maintained for a longer period of time.
  • the form using the hydrophilic resin as the hydrophilic substrate 2 as described above has an advantage that it is easy to form a sustained-release antibacterial agent thin film.
  • a hydrophilic substrate 2, antibacterial metal particles 1 and metal particles 3 having a low redox potential are added to a medium such as water or alcohol to form a coating liquid, which is applied and dried as necessary.
  • a film made of a releasable antibacterial agent can be formed. If a film made of a sustained-release antibacterial agent is formed, it is possible to easily impart antibacterial properties to various members and application ranges.
  • hydrophilic substrate 2 examples include hydraulic hydrophilic inorganic substances such as gypsum, cement and hydraulic lime, or hydrophilic inorganic substances obtained by curing inorganic particles such as silica and alumina by baking or adding a binder. It is done.
  • the hydrophilic inorganic material is used as the hydrophilic substrate 2, the antibacterial property can be maintained for a longer period since the alteration due to the metal ions hardly occurs.
  • the antibacterial metal particles 1 are 0.5% by mass or more and 5% by mass or less with respect to the hydrophilic substrate 2. It is preferable to contain in the range.
  • the hydrophilic base material 2 is a hydrophilic inorganic substance, it is preferable that the antibacterial metal particle 1 is contained in 0.5 to 30 mass% with respect to the hydrophilic base material 2.
  • the mass at this time is a dry mass for both the antibacterial metal particles 1 and the hydrophilic substrate 2, and it is preferable to use the mass after heat drying at 100 ° C.
  • the antibacterial metal ions are sufficiently released to the outside of the sustained-release antibacterial agent to exhibit good antibacterial properties.
  • the hydrophilic substrate 2 is a hydrophilic resin
  • the sustained-release antibacterial agent is difficult to break even if metal ions are eluted, The shape can be maintained over a long period of time.
  • the hydrophilic substrate 2 is a hydrophilic inorganic substance
  • the content of the antibacterial metal particles 1 is 30% by mass or less
  • the sustained-release antibacterial agent is difficult to break even if metal ions are eluted, The shape can be maintained over a long period of time.
  • the reason why the content of the antibacterial metal particles 1 can be increased as compared with the case where the hydrophilic substrate 2 is a hydrophilic resin is that the strength of the material itself is large, This is because a phenomenon in which the functional resin is easily deteriorated due to metal ions does not occur.
  • the metal particles 3 having a low oxidation-reduction potential must be contained in the range of 1 to 5 times the content (mass basis) of the antibacterial metal particles 1 described above, and 1.5 to 3 times. It is preferable to contain in the following ranges.
  • the content of the metal particles 3 having a low oxidation-reduction potential is 1 or more times the content of the antibacterial metal particles 1, the antibacterial metal particles 1 have a sufficient antioxidation effect. Can last.
  • the content of the metal particles 3 having a low redox potential is 5 times or less than the content of the antibacterial metal particles 1, the release of the antibacterial metal ions is not excessively suppressed.
  • the sustained-release antibacterial agent of the present invention can be produced by mixing the antibacterial metal particles 1 described above, the metal particles 3 having a low redox potential, and the hydrophilic substrate 2.
  • the sustained-release antibacterial agent obtained by mixing the antibacterial metal particle 1 and the metal particle 3 having a low redox potential in advance with a hydrophilic base material is in contact with the antibacterial metal particle 1 in contact. And since the quantity of the metal particle 3 with a low oxidation-reduction potential can be increased, antimicrobial property can be maintained over a longer period.
  • Solidification can be applied to the surface of an article, formed into a film by drying, or shaped by drying after being put into a mold.
  • powdered antibacterial metal particles 1 and metal particles 3 having a low redox potential are mixed with powdered hydrophilic base material 2 and stirred appropriately, and then powdered. There is a method of compressing the mixture with a press or the like. Further, the antibacterial metal particles 1 and the metal particles 3 having a low oxidation-reduction potential are added to and mixed with a liquid component such as water, and agglomerated with an aggregating agent.
  • the hydrophilic base material 2 is further added there, and the antimicrobial metal particle 1, the metal particle 3 with a low oxidation-reduction potential, and the dispersion liquid containing the hydrophilic base material 2 are prepared.
  • the sustained-release antibacterial agent of the present invention can also be obtained by coating this on the surface of the article and drying to form a coating, or by drying and shaping after charging into the mold.
  • the material of the article on which the coating comprising the sustained-release antibacterial agent of the present invention is formed is not particularly limited, and may be appropriately selected according to the type of the article requiring antibacterial and antifungal properties. it can.
  • the material of the article include metals such as aluminum and stainless steel, glass and plastic.
  • the thickness of the coating composed of the sustained-release antibacterial agent may be appropriately set according to the type of the article that requires antibacterial and antifungal properties, but is usually 12 ⁇ m or more and 3000 ⁇ m or less.
  • a film thickness of less than 12 ⁇ m is not preferable because metal particles contained in the film are reduced and sustained release over a long period of time may not be realized.
  • a film thickness exceeding 3000 ⁇ m is not preferable because it is difficult to form a film, or the formed film is easily cracked or easily peeled off.
  • the part where the film is formed in the article of the present invention is not limited, but mold, yeast, bacteria, and the like may be formed by wetting with water, flowing water, accumulating water, or condensation.
  • the site where the microorganisms are easy to grow is preferable.
  • preferable parts include a drain pan 12 installed below the heat exchanger 11 in the air conditioner 10 installed on the wall, a drain hose 13 connected to the drain pan 12 and the like as shown in FIG.
  • the drain water flow path can be mentioned.
  • a coating 14 made of the sustained-release antibacterial agent of the present invention is formed on the inner surface of the drain pan 12 and the inner surface of the drain hose 13.
  • Other parts include, for example, water droplet adhering parts and drainage channels of hand dryers, drainage channels of washing machines and clothes dryers, parts that get wet with water such as refrigerators, humidifiers, ventilators, dishwashers, water heaters, water A site where water flows, a site where water accumulates, a site where condensation occurs, and the like.
  • Example 1 Copper powder with an average particle size of 1.2 ⁇ m as antibacterial metal particles (1100Y manufactured by Mitsui Metal Mining Co., Ltd.) and aluminum powder with an average particle size of 2 ⁇ m as metal particles with low redox potential (manufactured by Toyo Aluminum Co., Ltd.) TFH-A02P) in ethanol at a mass ratio of 1: 2 and dried.
  • This powder was mixed with colloidal silica (Snowtex (registered trademark) PS-M, manufactured by Nissan Chemical Industries, Ltd.) as a hydrophilic substrate, 1.0 mass% copper powder, 2.0 mass% aluminum.
  • An aqueous dispersion containing powder and 8.0% by weight of colloidal silica was prepared. This was coated on a glass plate by spraying and dried at room temperature to form a coating having a thickness of 30 ⁇ m.
  • Example 1 A film having a thickness of 32 ⁇ m was formed in the same manner as in Example 1 except that no aluminum powder was used. Samples were prepared by exposing this to flowing water at room temperature for 7 days, 14 days, and 21 days. Antibacterial properties were evaluated in the same manner as in Example 1. The evaluation results are shown in Table 2.
  • Example 2 the antibacterial property of the film made of the antibacterial agent of Comparative Example 1 is lost only by being exposed to running water for a short time.
  • Example 1 in which aluminum powder was mixed, it can be seen that the antibacterial life is long.
  • Comparative Example 1 although the amount is smaller than that in Example 1, copper remains in the film as copper oxide or copper covered with copper oxide.
  • the cause of the loss of antibacterial properties is presumed that, in addition to the reduction of copper, copper is covered with a copper oxide film and has the effect of making it difficult to elute copper ions. It is considered that the mixing of the aluminum powder not only suppresses the oxidation elution rate of copper but also has an effect of suppressing the growth of the copper oxide film and maintaining the sustained release.
  • Example 2 The copper powder and aluminum powder were mixed in advance and dried, and the same as in Example 1 except that the aqueous dispersion was prepared by mixing copper powder, aluminum powder, and colloidal silica at a thickness of 31 ⁇ m. A film was formed. Samples were prepared by exposing this to flowing water at room temperature for 7 days, 14 days, and 21 days. Antibacterial properties were evaluated in the same manner as in Example 1. The evaluation results are shown in Table 3.
  • the antimicrobial agent film of Example 2 has a longer antimicrobial life than the antimicrobial agent film of Comparative Example 1. Moreover, although the film which consists of an antibacterial agent of Example 2 has the same composition as the film which consists of the antibacterial agent of Example 1, it has resulted in a short antibacterial life. From this, it can be seen that the antibacterial life is extended by previously mixing the antibacterial metal particles and the metal particles having a low redox potential.
  • Example 3 Copper atomized powder as an antibacterial metal particle is screened to a particle size of 45 ⁇ m (measured with Multisizer 4e manufactured by Beckman Coulter), and aluminum with an average particle size of about 60 ⁇ m as a metal particle having a low redox potential Powder (No. 18000 manufactured by Yamato Metal Powder Industry Co., Ltd.) was mixed with a 10% by mass aqueous solution of polyethylene glycol (average molecular weight 20000) as a hydrophilic substrate.
  • the copper atomized powder was contained in an amount of 3.0% by mass with respect to polyethylene glycol (solid content)
  • the aluminum powder was contained in an amount of 5.0% by mass with respect to polyethylene glycol (solid content).
  • aqueous dispersion was prepared by adding 0.5% by mass of zirconium chloride as a cross-linking agent to this mixed liquid with respect to polyethylene glycol (solid content). This was poured on a glass plate, dried, and heated at 100 ° C. for 15 minutes to form a coating having a thickness of 30 ⁇ m.
  • Example 1 A sample was prepared by exposing it to flowing water at room temperature for 7 days, 14 days, and 21 days. Antibacterial properties were evaluated in the same manner as in Example 1 (only Staphylococcus aureus). The evaluation results are shown in Table 4.
  • Example 3 except that the content of aluminum powder was changed to 1.5% by mass with respect to polyethylene glycol (solid content) (the content of aluminum powder was 0.5 times the content of copper atomized powder) A film having a thickness of 35 ⁇ m was formed in the same manner as described above. Samples were prepared by exposing this to flowing water at room temperature for 7 days and 14 days. Antibacterial properties were evaluated in the same manner as in Example 1 (only Staphylococcus aureus). The evaluation results are shown in Table 4.
  • the coating made of the antibacterial agent of Example 3 has long-term antibacterial properties.
  • the comparative example 2 in which the aluminum powder content is too small relative to the copper atomized powder content and the comparative example 3 in which the aluminum powder content is too large relative to the copper atomized powder content are inferior in antibacterial properties. I understand.
  • 1 antibacterial metal particles 1 hydrophilic substrate, 3 metal particles with low redox potential, 10 air conditioner, 11 heat exchanger, 12 drain pan, 13 drain hose, 14 coating.

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Abstract

This sustained release antimicrobial agent includes antimicrobial metal particles, metal particles having an oxidation-reduction potential that is lower than the oxidation-reduction potential of the metal that constitutes the antimicrobial metal particles, and a hydrophilic substrate, the metal particles having a low oxidation-reduction potential being included in a range of one to five times the amount of the antimicrobial metal particles. At least a portion of the antimicrobial metal particles is preferably in contact with at least a portion of the metal particles having a low oxidation-reduction potential. The antimicrobial metal particles are preferably at least one selected from the group consisting of silver and copper, and the metal particles having a low oxidation-reduction potential are preferably at least one selected from the group consisting of aluminum and zinc.

Description

徐放性抗菌剤及び物品Sustained release antibacterial agent and article
　本発明は、徐放性抗菌剤及びその徐放性抗菌剤からなる被膜が表面に形成された物品に関するものである。 The present invention relates to a sustained-release antibacterial agent and an article having a coating formed of the sustained-release antibacterial agent on the surface.
　物品に抗菌性あるいは抗かび性を付与する方法として、抗菌性あるいは抗かび性を有する被膜を形成する方法が、簡便であり且つ多様な物品を処理できるために好ましく用いられている。被膜に抗菌剤を含有させることで抗菌性を付与することができる。このような被膜では、時間の経過とともに抗菌剤が放出され続けるため、抗菌性が徐々に低下する。抗菌性を発揮できる期間を長くするために、微量で効果が得られる銅や銀などの金属イオンが利用されることが多い。無機層状化合物やゼオライト等に金属イオンを含有させたものを用いる方法が知られているが、金属の含有量を更に増やす方法として、金属銅や金属銀の粒子を添加する方法がある。例えば、特許文献１には、抗菌性親水性コーティングを作製するための配合物として、親水性ポリマー、光開始剤、金属銀を含む粒子等を含むものが記載されている。 As a method for imparting antibacterial or antifungal properties to an article, a method of forming a film having antibacterial or antifungal properties is preferably used because it is simple and can treat various articles. Antibacterial properties can be imparted by adding an antibacterial agent to the coating. In such a coating, since the antibacterial agent is continuously released over time, the antibacterial property gradually decreases. In order to lengthen the period during which the antibacterial property can be exhibited, metal ions such as copper and silver that are effective in a small amount are often used. A method using an inorganic layered compound or zeolite containing a metal ion is known. As a method of further increasing the metal content, there is a method of adding metallic copper or metallic silver particles. For example, Patent Document 1 describes a composition for producing an antibacterial hydrophilic coating that includes a hydrophilic polymer, a photoinitiator, particles containing metallic silver, and the like.
特表２０１０－５０３７３７号公報Special table 2010-503737
　抗菌性被膜が抗菌性を長期にわたって発揮するには、金属イオンが安定的に徐放される必要がある。しかしながら、特許文献１では、金属銀を含む粒子を添加しているため、錯化剤等を配合することにより銀イオンの放出を調節したとしても、徐放とともに金属銀を含む粒子の粒径が小さくなり、銀イオンの徐放速度が大きく変動してしまうという問題が生じる。
　従って、本発明は、上記のような問題点を解決するためになされたものであり、抗菌性の金属イオンを長期間にわたって安定的に徐放させることのできる徐放性抗菌剤を提供することを目的とする。 In order for the antibacterial coating to exhibit antibacterial properties over a long period of time, metal ions need to be stably and gradually released. However, in Patent Document 1, since particles containing metallic silver are added, even if the release of silver ions is adjusted by blending a complexing agent or the like, the particle size of the particles containing metallic silver is not limited to sustained release. There arises a problem that the rate of release of silver ions greatly fluctuates.
Accordingly, the present invention has been made to solve the above-described problems, and provides a sustained-release antibacterial agent capable of stably and slowly releasing antibacterial metal ions over a long period of time. With the goal.
　本発明は、抗菌性金属粒子と、該抗菌性金属粒子を構成する金属の酸化還元電位より酸化還元電位の低い金属粒子と、親水性基材とを含有する徐放性抗菌剤であって、該酸化還元電位の低い金属粒子が、該抗菌性金属粒子の含有量の１倍以上５倍以下の範囲で含有されることを特徴とする徐放性抗菌剤である。 The present invention is a sustained-release antibacterial agent comprising antibacterial metal particles, metal particles having a lower redox potential than the metal constituting the antibacterial metal particles, and a hydrophilic substrate, The sustained-release antibacterial agent is characterized in that the metal particles having a low oxidation-reduction potential are contained in the range of 1 to 5 times the content of the antibacterial metal particles.
　本発明によれば、抗菌性の金属イオンを長期間にわたって安定的に徐放させることのできる徐放性抗菌剤を提供することができる。 According to the present invention, a sustained-release antibacterial agent capable of stably and slowly releasing antibacterial metal ions over a long period of time can be provided.
抗菌性金属粒子と親水性基材とを含有する抗菌剤における抗菌性金属粒子の溶出過程を示す模式図である。It is a schematic diagram which shows the elution process of the antibacterial metal particle in the antibacterial agent containing an antibacterial metal particle and a hydrophilic base material. 本発明の徐放性抗菌剤における抗菌性金属粒子の溶出過程を示す模式図である。It is a schematic diagram which shows the elution process of the antibacterial metal particle in the sustained release antibacterial agent of this invention. 空気調和機において本発明の徐放性抗菌剤からなる被膜が形成された部位を説明するための模式図である。It is a schematic diagram for demonstrating the site | part in which the film which consists of a sustained release antibacterial agent of this invention was formed in an air conditioner.
　実施の形態１．
　本発明の実施の形態１に係る徐放性抗菌剤は、抗菌性金属粒子と、該抗菌性金属粒子を構成する金属の酸化還元電より酸化還元電位の低い金属粒子と、親水性基材とを含有するものである。 Embodiment 1 FIG.
The sustained-release antibacterial agent according to Embodiment 1 of the present invention includes antibacterial metal particles, metal particles having a redox potential lower than that of the metal constituting the antibacterial metal particles, a hydrophilic substrate, It contains.
　まず、抗菌性金属粒子と親水性基材とを含有し、酸化還元電位の低い金属粒子を含有しない抗菌剤において、抗菌性が長期に持続しない理由を図面を参照しながら説明する。図１は、抗菌性金属粒子と親水性基材とを含有する抗菌剤において、抗菌性金属粒子が経時で溶出する過程を示す模式図である。図１の（ａ）において、抗菌剤は、抗菌性金属粒子１が親水性基材２中に分散した状態となっている。抗菌剤が水に曝されたり、加湿されると、抗菌性金属粒子１は、環境中に存在する酸素、水、炭酸、硝酸等の各種の物質との反応により、酸化物、水酸化物等の各種の塩を生成する。これらの反応に伴い、抗菌性金属粒子１から金属イオンが生成し放出されることになる。金属イオンは、水和や共存する各種のイオンあるいは親水性基材２により錯イオンを形成する。その錯イオンが抗菌剤中に拡散することで抗菌剤の外部に徐放され抗菌性を発現する。ここで、錯イオンが拡散する経路は、親水性基材２が親水性樹脂である場合には、水で膨潤した分子鎖の隙間であり、一方、親水性基材２が親水性無機物である場合には、親水性無機物中の隙間や細孔中に存在する水である。金属イオンの生成量は、抗菌性金属粒子１の添加量及び抗菌性金属粒子１の表面積の総和に依存し、初期には金属イオンの生成量が多いが、図１の（ｂ）に示されるように、時間の経過とともに抗菌性金属粒子１の粒径が小さくなるため、金属イオンの生成量が少なくなり、抗菌性が長期に持続しない。なお、抗菌剤の表面近傍に存在する抗菌性金属粒子１は粒径が速く小さくなる傾向がある。 First, the reason why antibacterial property does not last for a long time in an antibacterial agent containing antibacterial metal particles and a hydrophilic base material and not containing metal particles having a low redox potential will be described with reference to the drawings. FIG. 1 is a schematic diagram showing a process in which antibacterial metal particles are eluted over time in an antibacterial agent containing antibacterial metal particles and a hydrophilic substrate. In FIG. 1A, the antibacterial agent is in a state where the antibacterial metal particles 1 are dispersed in the hydrophilic substrate 2. When the antibacterial agent is exposed to water or humidified, the antibacterial metal particles 1 react with various substances such as oxygen, water, carbonic acid, and nitric acid present in the environment, and thereby oxides, hydroxides, etc. To produce various salts. With these reactions, metal ions are generated and released from the antibacterial metal particles 1. Metal ions form hydration and various ions that coexist or complex ions with the hydrophilic substrate 2. When the complex ions diffuse into the antibacterial agent, it is gradually released to the outside of the antibacterial agent and exhibits antibacterial properties. Here, when the hydrophilic substrate 2 is a hydrophilic resin, the path through which the complex ions diffuse is a gap between molecular chains swollen with water, while the hydrophilic substrate 2 is a hydrophilic inorganic substance. In some cases, the water is present in gaps or pores in the hydrophilic inorganic substance. The amount of metal ions generated depends on the amount of antibacterial metal particles 1 added and the total surface area of the antibacterial metal particles 1, and the amount of metal ions generated is initially large, but is shown in FIG. Thus, since the particle size of the antibacterial metal particles 1 becomes smaller with the passage of time, the amount of metal ions generated is reduced, and the antibacterial property does not last for a long time. In addition, the antibacterial metal particle 1 existing in the vicinity of the surface of the antibacterial agent tends to have a small particle size.
　次に、本発明の実施の形態１に係る徐放性抗菌剤において、抗菌性が長期に持続する理由を図面を参照しながら説明する。図２は、抗菌性金属粒子と、抗菌性金属粒子を構成する金属の酸化還元電より酸化還元電位の低い金属粒子と、親水性基材とを含有する徐放性抗菌剤において、抗菌性金属粒子が経時で溶出する過程を示す模式図である。図２の（ａ）において、徐放性抗菌剤は、抗菌性金属粒子１及び酸化還元電位の低い金属粒子３が親水性基材２中に分散しており、抗菌性金属粒子１の一部と酸化還元電位の低い金属粒子３の一部とが接触した状態となっている。このように酸化還元電位の異なる異種金属粒子が接触した状態で、水分を含む素材などの導電性媒体に包まれ、溶存酸素が存在する場合、酸化還元電位の低い金属が先に酸化され、酸化還元電位の高い金属の酸化が抑制される。図２の（ｂ）に示されるように、酸化還元電位の低い金属粒子３と接触していない抗菌性金属粒子１は、図１の（ｂ）の場合と同様に酸化されて溶出するため、粒径が小さくなる。酸化還元電位の低い金属粒子３と接触している抗菌性金属粒子１は溶出が遅くなる。接触している抗菌性金属粒子１と酸化還元電位の低い金属粒子３との質量の比率により溶出速度は異なり、抗菌性金属粒子１に接触している酸化還元電位の低い金属粒子３の量が多ければ、酸化・溶出の抑制作用は大きく、作用期間も長い。また、抗菌性金属粒子１から生成した金属イオンは、酸化還元電位の低い金属粒子３の表面で還元され金属に戻る現象もある。このように酸化還元電位の低い金属粒子３が存在することで、抗菌性金属粒子１の酸化は抑制される。抗菌性金属粒子１は、その周囲環境により、初期から酸化されるものもあれば、図２の（ｃ）に示されるように長時間経過後に酸化が始まるものもある。このように酸化の進行が異なる抗菌性金属粒子１が混在することにより、抗菌性を長期にわたって持続させることができる。 Next, the reason why the antibacterial property of the sustained-release antibacterial agent according to Embodiment 1 of the present invention is maintained for a long time will be described with reference to the drawings. FIG. 2 shows an antibacterial metal in a sustained-release antibacterial agent comprising antibacterial metal particles, metal particles having a lower redox potential than the redox electricity of the metal constituting the antibacterial metal particles, and a hydrophilic substrate. It is a schematic diagram which shows the process in which particle | grains elute with time. In FIG. 2A, the sustained-release antibacterial agent has antibacterial metal particles 1 and metal particles 3 having a low redox potential dispersed in a hydrophilic substrate 2, and a part of the antibacterial metal particles 1. And a part of the metal particles 3 having a low oxidation-reduction potential are in contact with each other. When dissimilar metal particles having different oxidation-reduction potentials are in contact with each other and wrapped in a conductive medium such as a water-containing material and dissolved oxygen is present, the metal with a low oxidation-reduction potential is oxidized first and oxidized. Oxidation of a metal having a high reduction potential is suppressed. As shown in FIG. 2B, the antibacterial metal particles 1 that are not in contact with the metal particles 3 having a low redox potential are oxidized and eluted in the same manner as in FIG. The particle size becomes smaller. The antibacterial metal particles 1 that are in contact with the metal particles 3 having a low redox potential are slow to be eluted. The elution rate varies depending on the mass ratio of the antibacterial metal particles 1 in contact with the metal particles 3 with a low redox potential, and the amount of the metal particles 3 with low redox potential in contact with the antibacterial metal particles 1 If the amount is large, the effect of suppressing oxidation / elution is large, and the action period is also long. Moreover, the metal ion produced | generated from the antibacterial metal particle 1 may also be reduced on the surface of the metal particle 3 with a low oxidation-reduction potential and returned to a metal. Thus, the oxidation of the antibacterial metal particle 1 is suppressed by the presence of the metal particle 3 having a low redox potential. Some of the antibacterial metal particles 1 are oxidized from the initial stage depending on the surrounding environment, and some of the antibacterial metal particles 1 start to be oxidized after a long period of time as shown in FIG. Thus, antibacterial property can be maintained for a long time by mixing the antibacterial metal particles 1 having different oxidation progresses.
　本発明の実施の形態１に係る徐放性抗菌剤の形状は、特に限定されるものではないが、膜状、バルク形状、繊維状、粒状等であることができる。徐放性抗菌剤の使用形態は、塗布膜として各種物品表面を被覆する方法、バルクや繊維状の徐放性抗菌剤として水と接触する位置に設置する方法、粒状の徐放性抗菌剤として水に混合する方法等が挙げられる。 The shape of the sustained-release antibacterial agent according to Embodiment 1 of the present invention is not particularly limited, but may be a film shape, a bulk shape, a fiber shape, a granular shape, or the like. The use form of the sustained-release antibacterial agent is a method of coating various article surfaces as a coating film, a bulk or fibrous sustained-release antibacterial agent, a method of placing in contact with water, and a granular sustained-release antibacterial agent The method of mixing with water is mentioned.
　本発明における抗菌性金属粒子１としては、銀、銅、ニッケル、クロム、コバルト等を使用することができるが、通常の使用において人体に対する有害性が認められないという観点から、銀及び銅からなる群から選択される少なくとも１種であることが好ましい。これらの金属は、単独で使用してもよいし、２種以上を併用してもよいし、合金として使用してもよい。人体への有害性が懸念される金属であっても、銀や銅に対して有害性が顕在化しない範囲での少量添加であれば、銀や銅の抗菌作用を増幅させることができる。 As the antibacterial metal particles 1 in the present invention, silver, copper, nickel, chromium, cobalt, and the like can be used. From the viewpoint that no harmfulness to the human body is observed in normal use, the antibacterial metal particles 1 are made of silver and copper. It is preferably at least one selected from the group. These metals may be used alone or in combination of two or more, or may be used as an alloy. Even if the metal is harmful to human body, the antibacterial action of silver or copper can be amplified if it is added in a small amount within a range where the toxicity to silver or copper is not obvious.
　抗菌性金属粒子１の平均粒径は、０．１μｍ以上２００μｍ以下であることが好ましく、０．３μｍ以上５０μｍ以下であることが更に好ましい。抗菌性金属粒子１の平均粒径が０．１μｍ以上であると、抗菌性をより長期にわたって持続させることができる。一方、抗菌性金属粒子１の平均粒径が２００μｍ以下であると、酸化・溶出が安定的に進行し易くなる。
　抗菌性金属粒子１の形状は、塊状、板状、針状、球状等の各種のものが利用できる。抗菌性金属粒子１の形状は、微粒子が凝集しているような多孔質のものでもよい。 The average particle diameter of the antibacterial metal particles 1 is preferably 0.1 μm or more and 200 μm or less, and more preferably 0.3 μm or more and 50 μm or less. When the average particle size of the antibacterial metal particles 1 is 0.1 μm or more, the antibacterial property can be maintained for a longer period. On the other hand, when the average particle size of the antibacterial metal particles 1 is 200 μm or less, oxidation / elution tends to proceed stably.
As the shape of the antibacterial metal particles 1, various shapes such as a lump shape, a plate shape, a needle shape, and a spherical shape can be used. The shape of the antibacterial metal particles 1 may be porous such that fine particles are aggregated.
　本発明における酸化還元電位の低い金属粒子３としては、抗菌性金属粒子１を構成する金属の酸化還元電位より酸化還元電位が低い金属であれば使用することができるが、安価であり人体に対する有害性が低いこと、酸化時には水酸化物等を形成し、徐放性抗菌剤として着色や白濁等の色調変化や形状の変化が少ないという観点から、アルミニウム及び亜鉛からなる群から選択される少なくとも１種であることが好ましい。 As the metal particle 3 having a low oxidation-reduction potential in the present invention, any metal having a lower oxidation-reduction potential than the metal constituting the antibacterial metal particle 1 can be used, but it is inexpensive and harmful to the human body. At least one selected from the group consisting of aluminum and zinc from the viewpoint of low properties, formation of hydroxide and the like during oxidation, and little change in color tone and shape such as coloring and cloudiness as a sustained-release antibacterial agent Preferably it is a seed.
　酸化還元電位の低い金属粒子３の平均粒径は、０．１μｍ以上２００μｍ以下であることが好ましく、０．３μｍ以上１００μｍ以下であることが更に好ましい。酸化還元電位の低い金属粒子３の平均粒径が０．１μｍ以上であると、抗菌性をより長期にわたって持続させることができる。酸化還元電位の低い金属粒子３の平均粒径が２００μｍ以下であると、抗菌性金属粒子１との接触点を十分に確保することができ、酸化抑制作用を効果的に発揮することができる。また、酸化還元電位の低い金属粒子３の平均粒径は、抗菌性金属粒子１の平均粒径の０．２倍以上３倍以下であることが好ましく、０．５倍以上２倍以下であることが更に好ましい。酸化還元電位の低い金属粒子３の平均粒径が抗菌性金属粒子１の平均粒径の０．２倍以上であると、抗菌性金属粒子１の酸化抑制作用を長期間にわたって維持することができる上に、抗菌性の金属イオンを適度に拡散、徐放させることができるため、抗菌性を十分に発揮することができる。一方、酸化還元電位の低い金属粒子３の平均粒径が抗菌性金属粒子１の平均粒径の３倍以下であると、酸化還元電位の低い金属粒子３の酸化が適度に進行し、また、酸化還元電位の低い金属粒子３と接触する抗菌性金属粒子１の数を確保し易いため、酸化抑制作用を向上させることができる。
　酸化還元電位の低い金属粒子３の形状は、塊状、板状、針状、球状等の各種のものが利用できる。酸化還元電位の低い金属粒子３の形状は、微粒子が凝集しているような多孔質のものでもよい。 The average particle size of the metal particles 3 having a low oxidation-reduction potential is preferably 0.1 μm or more and 200 μm or less, and more preferably 0.3 μm or more and 100 μm or less. When the average particle size of the metal particles 3 having a low oxidation-reduction potential is 0.1 μm or more, the antibacterial property can be maintained for a longer period. When the average particle size of the metal particles 3 having a low oxidation-reduction potential is 200 μm or less, a sufficient contact point with the antibacterial metal particles 1 can be ensured, and the oxidation inhibiting action can be effectively exhibited. The average particle size of the metal particles 3 having a low redox potential is preferably 0.2 to 3 times the average particle size of the antibacterial metal particles 1, and is 0.5 to 2 times the average particle size. More preferably. When the average particle size of the metal particles 3 having a low oxidation-reduction potential is 0.2 times or more than the average particle size of the antibacterial metal particles 1, the antioxidation effect of the antibacterial metal particles 1 can be maintained over a long period of time. In addition, since antibacterial metal ions can be appropriately diffused and gradually released, antibacterial properties can be sufficiently exhibited. On the other hand, when the average particle size of the metal particles 3 having a low redox potential is not more than 3 times the average particle size of the antibacterial metal particles 1, the oxidation of the metal particles 3 having a low redox potential proceeds appropriately. Since it is easy to ensure the number of antibacterial metal particles 1 that come into contact with the metal particles 3 having a low oxidation-reduction potential, the oxidation-inhibiting action can be improved.
Various shapes such as a lump shape, a plate shape, a needle shape, and a spherical shape can be used as the shape of the metal particles 3 having a low oxidation-reduction potential. The shape of the metal particles 3 having a low oxidation-reduction potential may be porous such that fine particles are aggregated.
　なお、本発明において、抗菌性金属粒子１及び酸化還元電位の低い金属粒子３の平均粒径とは、コールター法（例えば、ベックマンコールター社製 Multisizer 4e）により測定された平均粒径を意味する。 In the present invention, the average particle size of the antibacterial metal particles 1 and the metal particles 3 having a low redox potential means an average particle size measured by a Coulter method (for example, “Multisizer 4e” manufactured by Beckman Coulter, Inc.).
　本発明における親水性基材２としては、親水性樹脂、親水性無機物等が挙げられる。親水性樹脂としては、水酸基により親水性が確保されている樹脂が好ましい。このような樹脂としては、ポリビニルアルコール、ポリビニルピロリドン、ポリエチレングリコール、ポリアクリルアミド、ポリアクリル酸やポリメタクリル酸あるいはそのエステル類、これらの熱可塑性樹脂の混合物、また、アミロース、アミロペクチン、グリコーゲン、セルロース、キチン、アガロース、カラギーナン等の多糖類やこれらの混合物等が挙げられる。このような親水性樹脂は、水に浸漬した場合、水に溶解したり膨潤したりし易い。親水性樹脂を加熱したり、親水性樹脂に各種の架橋剤を添加したり、あるいはこれらの手法を併用することにより、溶解や膨潤を抑制することが好ましい。水に溶解する樹脂をこれらの手法で不溶化し、膨潤率を５０％以下に抑えるような状態としたものは、金属イオンの良好な徐放性が得られ易い。ここで使用する架橋剤としては、例えば、塩化ジルコニウム、ポリカルボジイミド等が挙げられる。架橋剤の添加量は、親水性樹脂の膨潤率を５０％以下に抑えることができる範囲で適宜調整すればよいが、通常、親水性樹脂の固形分に対して０．１質量％以上２０質量％以下である。 Examples of the hydrophilic substrate 2 in the present invention include hydrophilic resins and hydrophilic inorganic substances. As the hydrophilic resin, a resin whose hydrophilicity is ensured by a hydroxyl group is preferable. Examples of such resins include polyvinyl alcohol, polyvinyl pyrrolidone, polyethylene glycol, polyacrylamide, polyacrylic acid, polymethacrylic acid or esters thereof, a mixture of these thermoplastic resins, amylose, amylopectin, glycogen, cellulose, chitin. , Polysaccharides such as agarose and carrageenan, and mixtures thereof. Such a hydrophilic resin is easily dissolved or swollen in water when immersed in water. It is preferable to suppress dissolution and swelling by heating the hydrophilic resin, adding various crosslinking agents to the hydrophilic resin, or using these techniques in combination. When a resin that dissolves in water is insolubilized by these methods and the swelling rate is suppressed to 50% or less, good sustained release of metal ions is easily obtained. Examples of the crosslinking agent used here include zirconium chloride and polycarbodiimide. The addition amount of the crosslinking agent may be appropriately adjusted within a range in which the swelling ratio of the hydrophilic resin can be suppressed to 50% or less, but is usually 0.1% by mass or more and 20% by mass with respect to the solid content of the hydrophilic resin. % Or less.
　親水性樹脂として、メラミン樹脂、ノボラック樹脂、尿素樹脂等の熱硬化性樹脂、これらの混合物を使用してもよい。また、ポリオレフィン、ポリウレタン、エポキシ樹脂等の一般的に親水性の乏しい樹脂に、水酸基等の親水性置換基を導入したり、親水性物質を混合したりすることにより親水性を付与したものも使用可能である。ここで使用する親水性物質としては、上述した親水性樹脂の他、シリカ、アルミナ、クレイ等の各種の無機粒子が挙げられる。このような樹脂は水による膨潤が少ないため、抗菌性をより長期にわたって持続させることができる。 As the hydrophilic resin, a thermosetting resin such as melamine resin, novolak resin, urea resin, or a mixture thereof may be used. Also used are those that have been given hydrophilicity by introducing hydrophilic substituents such as hydroxyl groups or mixing hydrophilic substances into resins that are generally poorly hydrophilic, such as polyolefins, polyurethanes, and epoxy resins. Is possible. Examples of the hydrophilic substance used here include various inorganic particles such as silica, alumina, and clay in addition to the above-described hydrophilic resin. Since such a resin is less swelled by water, the antibacterial property can be maintained for a longer period of time.
　上述したような親水性樹脂を親水性基材２として用いる形態は、徐放性抗菌剤の薄膜を形成し易いという利点がある。水、アルコール等の媒体に、親水性基材２、抗菌性金属粒子１及び酸化還元電位の低い金属粒子３を添加してコーティング液とし、これを塗布し、必要に応じて乾燥することにより徐放性抗菌剤からなる被膜を形成することができる。徐放性抗菌剤からなる被膜の形成であれば、多様な部材や適用範囲に対し、簡便に抗菌性を付与することが可能である。 The form using the hydrophilic resin as the hydrophilic substrate 2 as described above has an advantage that it is easy to form a sustained-release antibacterial agent thin film. A hydrophilic substrate 2, antibacterial metal particles 1 and metal particles 3 having a low redox potential are added to a medium such as water or alcohol to form a coating liquid, which is applied and dried as necessary. A film made of a releasable antibacterial agent can be formed. If a film made of a sustained-release antibacterial agent is formed, it is possible to easily impart antibacterial properties to various members and application ranges.
　また、親水性基材２としては、石膏、セメント、水硬性石灰等の水硬性の親水性無機物、あるいはシリカ、アルミナ等の無機粒子を焼成やバインダー添加により硬化させて得られる親水性無機物が挙げられる。親水性無機物を親水性基材２として用いる形態では、金属イオンによる変質が起こり難いため、抗菌性をより長期にわたって持続させることができる。 Examples of the hydrophilic substrate 2 include hydraulic hydrophilic inorganic substances such as gypsum, cement and hydraulic lime, or hydrophilic inorganic substances obtained by curing inorganic particles such as silica and alumina by baking or adding a binder. It is done. In the form in which the hydrophilic inorganic material is used as the hydrophilic substrate 2, the antibacterial property can be maintained for a longer period since the alteration due to the metal ions hardly occurs.
　親水性基材２が親水性樹脂である場合（親水性樹脂をベースとする場合を含む）、抗菌性金属粒子１は、親水性基材２に対して０．５質量％以上５質量％以下の範囲で含有されることが好ましい。また、親水性基材２が親水性無機物である場合、抗菌性金属粒子１は、親水性基材２に対して０．５質量％以上３０質量％以下の範囲で含有されることが好ましい。この時の質量は、抗菌性金属粒子１及び親水性基材２ともに乾燥質量であり、１００℃で加熱乾燥した後の質量を用いることが好ましい。抗菌性金属粒子１の含有量が０．５質量％以上であると、抗菌性の金属イオンが徐放性抗菌剤の外部に十分に徐放され良好な抗菌性を発現する。一方、親水性基材２が親水性樹脂である場合において、抗菌性金属粒子１の含有量が５質量％以下であると、金属イオンが溶出しても徐放性抗菌剤が壊れ難くなり、形状を長期にわたって維持することができる。また、親水性基材２が親水性無機物である場合において、抗菌性金属粒子１の含有量が３０質量％以下であると、金属イオンが溶出しても徐放性抗菌剤が壊れ難くなり、形状を長期にわたって維持することができる。更に、親水性基材２が親水性無機物である場合には、親水性樹脂である場合よりも抗菌性金属粒子１の含有量を多くすることができる理由は、材質自体の強度が大きく、親水性樹脂が金属イオンにより劣化して壊れ易くなるような現象が起こらないためである。 When the hydrophilic substrate 2 is a hydrophilic resin (including the case where the hydrophilic substrate is based on the hydrophilic resin), the antibacterial metal particles 1 are 0.5% by mass or more and 5% by mass or less with respect to the hydrophilic substrate 2. It is preferable to contain in the range. Moreover, when the hydrophilic base material 2 is a hydrophilic inorganic substance, it is preferable that the antibacterial metal particle 1 is contained in 0.5 to 30 mass% with respect to the hydrophilic base material 2. The mass at this time is a dry mass for both the antibacterial metal particles 1 and the hydrophilic substrate 2, and it is preferable to use the mass after heat drying at 100 ° C. When the content of the antibacterial metal particles 1 is 0.5% by mass or more, the antibacterial metal ions are sufficiently released to the outside of the sustained-release antibacterial agent to exhibit good antibacterial properties. On the other hand, when the hydrophilic substrate 2 is a hydrophilic resin, if the content of the antibacterial metal particles 1 is 5% by mass or less, the sustained-release antibacterial agent is difficult to break even if metal ions are eluted, The shape can be maintained over a long period of time. Further, when the hydrophilic substrate 2 is a hydrophilic inorganic substance, when the content of the antibacterial metal particles 1 is 30% by mass or less, the sustained-release antibacterial agent is difficult to break even if metal ions are eluted, The shape can be maintained over a long period of time. Furthermore, when the hydrophilic substrate 2 is a hydrophilic inorganic substance, the reason why the content of the antibacterial metal particles 1 can be increased as compared with the case where the hydrophilic substrate 2 is a hydrophilic resin is that the strength of the material itself is large, This is because a phenomenon in which the functional resin is easily deteriorated due to metal ions does not occur.
　酸化還元電位の低い金属粒子３は、上述した抗菌性金属粒子１の含有量（質量基準）の１倍以上５倍以下の範囲で含有されることが必要であり、１．５倍以上３倍以下の範囲で含有されることが好ましい。酸化還元電位の低い金属粒子３の含有量が抗菌性金属粒子１の含有量の１倍以上であると、抗菌性金属粒子１の酸化抑制作用が十分に得られるため、抗菌性をより長期にわたって持続させることができる。一方、酸化還元電位の低い金属粒子３の含有量が抗菌性金属粒子１の含有量の５倍以下であると、抗菌性の金属イオンの放出が過度に抑制されることがない。 The metal particles 3 having a low oxidation-reduction potential must be contained in the range of 1 to 5 times the content (mass basis) of the antibacterial metal particles 1 described above, and 1.5 to 3 times. It is preferable to contain in the following ranges. When the content of the metal particles 3 having a low oxidation-reduction potential is 1 or more times the content of the antibacterial metal particles 1, the antibacterial metal particles 1 have a sufficient antioxidation effect. Can last. On the other hand, when the content of the metal particles 3 having a low redox potential is 5 times or less than the content of the antibacterial metal particles 1, the release of the antibacterial metal ions is not excessively suppressed.
　本発明の徐放性抗菌剤は、上述した抗菌性金属粒子１、酸化還元電位の低い金属粒子３及び親水性基材２を混合することによって製造することができる。特に、抗菌性金属粒子１と酸化還元電位の低い金属粒子３とを予め混合したものを、親水性基材と混合して得られる徐放性抗菌剤では、接触している抗菌性金属粒子１及び酸化還元電位の低い金属粒子３の量を多くすることができるため、抗菌性をより長期にわたって持続させることができる。これは、抗菌性金属粒子１、酸化還元電位の低い金属粒子３及び親水性基材２を一度に混合する場合よりも、徐放性抗菌剤中で酸化還元電位の異なる異種金属粒子が接触している確率が高くなるためである。
　より具体的には、抗菌性金属粒子１と酸化還元電位の低い金属粒子３とを混合したものに、水、アルコール等の液体成分を少量添加して湿潤させた後、これを乾燥させ粉末化する。この粉末を、溶剤に溶解又は分散させた親水性基材２と混合し、これを乾燥して固体化することで本発明の徐放性抗菌剤を得ることができる。固体化は、物品表面への塗布、乾燥による被膜形成、あるいは型へ投入後の乾燥による賦型が可能である。賦型する他の方法として、抗菌性金属粒子１と酸化還元電位の低い金属粒子３とを粉末化したものを、粉末状の親水性基材２と混合して適度に撹拌した後、粉末状混合物をプレス機等で圧縮する方法がある。
　また、水等の液体成分に抗菌性金属粒子１及び酸化還元電位の低い金属粒子３を添加、混合し、凝集剤等により凝集させる。そこに親水性基材２を更に添加して、抗菌性金属粒子１、酸化還元電位の低い金属粒子３及び親水性基材２を含有する分散液を調製する。これを物品表面へ塗布、乾燥して被膜を形成したり、あるいは型へ投入後に乾燥して賦型することで本発明の徐放性抗菌剤を得ることもできる。 The sustained-release antibacterial agent of the present invention can be produced by mixing the antibacterial metal particles 1 described above, the metal particles 3 having a low redox potential, and the hydrophilic substrate 2. In particular, the sustained-release antibacterial agent obtained by mixing the antibacterial metal particle 1 and the metal particle 3 having a low redox potential in advance with a hydrophilic base material is in contact with the antibacterial metal particle 1 in contact. And since the quantity of the metal particle 3 with a low oxidation-reduction potential can be increased, antimicrobial property can be maintained over a longer period. This is because different types of metal particles having different oxidation-reduction potentials are in contact with each other in the sustained-release antibacterial agent, compared to the case where the antibacterial metal particles 1, the metal particles 3 having a low oxidation-reduction potential, and the hydrophilic substrate 2 are mixed at once. This is because there is a higher probability of being.
More specifically, a mixture of antibacterial metal particles 1 and metal particles 3 having a low redox potential is added with a small amount of liquid components such as water and alcohol, moistened, and then dried to be powdered. To do. The powder is mixed with the hydrophilic base material 2 dissolved or dispersed in a solvent, and dried to solidify it, whereby the sustained-release antibacterial agent of the present invention can be obtained. Solidification can be applied to the surface of an article, formed into a film by drying, or shaped by drying after being put into a mold. As another method of forming, powdered antibacterial metal particles 1 and metal particles 3 having a low redox potential are mixed with powdered hydrophilic base material 2 and stirred appropriately, and then powdered. There is a method of compressing the mixture with a press or the like.
Further, the antibacterial metal particles 1 and the metal particles 3 having a low oxidation-reduction potential are added to and mixed with a liquid component such as water, and agglomerated with an aggregating agent. The hydrophilic base material 2 is further added there, and the antimicrobial metal particle 1, the metal particle 3 with a low oxidation-reduction potential, and the dispersion liquid containing the hydrophilic base material 2 are prepared. The sustained-release antibacterial agent of the present invention can also be obtained by coating this on the surface of the article and drying to form a coating, or by drying and shaping after charging into the mold.
　本発明の徐放性抗菌剤からなる被膜が表面に形成される物品の素材としては、特に限定されず、抗菌性及び抗かび性が必要とされる物品の種類に応じて適宜選択することができる。物品の素材の例としては、アルミニウム、ステンレス等の金属、ガラス、プラスチック等が挙げられる。また、徐放性抗菌剤からなる被膜の厚さは、抗菌性及び抗かび性が必要とされる物品の種類に応じて適宜設定すればよいが、通常、１２μｍ以上３０００μｍ以下である。１２μｍ未満の膜厚では、膜中に含まれる金属粒子が少なくなり、長期にわたる徐放が実現できなくなることがあるため好ましくない。一方、３０００μｍを超える膜厚では、被膜形成が困難であったり、形成された被膜に亀裂が入ったり、剥離しやすかったりしやすくなるため好ましくない。 The material of the article on which the coating comprising the sustained-release antibacterial agent of the present invention is formed is not particularly limited, and may be appropriately selected according to the type of the article requiring antibacterial and antifungal properties. it can. Examples of the material of the article include metals such as aluminum and stainless steel, glass and plastic. Further, the thickness of the coating composed of the sustained-release antibacterial agent may be appropriately set according to the type of the article that requires antibacterial and antifungal properties, but is usually 12 μm or more and 3000 μm or less. A film thickness of less than 12 μm is not preferable because metal particles contained in the film are reduced and sustained release over a long period of time may not be realized. On the other hand, a film thickness exceeding 3000 μm is not preferable because it is difficult to form a film, or the formed film is easily cracked or easily peeled off.
　本発明の物品において被膜が形成される部位は、限定されるものではないが、水で濡れたり、水が流れたり、水が溜まったり、又は結露したりすることで、カビ、酵母、細菌などの微生物が生育しやすい部位が好ましい。好ましい部位の具体例としては、図３に示されるような、壁に設置された空気調和機１０内の熱交換器１１の下方に設置されたドレンパン１２、ドレンパン１２に接続されたドレンホース１３等のドレン水の流路を挙げることができる。図３では、ドレンパン１２の内面及びドレンホース１３の内面に、本発明の徐放性抗菌剤からなる被膜１４が形成されている。その他の部位としては、例えば、ハンドドライヤーの水滴付着部及び排水流路、洗濯機及び衣類乾燥機の排水流路、冷蔵庫、加湿器、換気扇、食器洗い機、給湯器等の水で濡れる部位、水が流れる部位、水が溜まる部位及び結露する部位等が挙げられる。これらの部位に被膜を形成することで、微生物の繁殖による変色、衛生性の低下及びスライム（微生物の塊）の発生を抑制することができる。 The part where the film is formed in the article of the present invention is not limited, but mold, yeast, bacteria, and the like may be formed by wetting with water, flowing water, accumulating water, or condensation. The site where the microorganisms are easy to grow is preferable. Specific examples of preferable parts include a drain pan 12 installed below the heat exchanger 11 in the air conditioner 10 installed on the wall, a drain hose 13 connected to the drain pan 12 and the like as shown in FIG. The drain water flow path can be mentioned. In FIG. 3, a coating 14 made of the sustained-release antibacterial agent of the present invention is formed on the inner surface of the drain pan 12 and the inner surface of the drain hose 13. Other parts include, for example, water droplet adhering parts and drainage channels of hand dryers, drainage channels of washing machines and clothes dryers, parts that get wet with water such as refrigerators, humidifiers, ventilators, dishwashers, water heaters, water A site where water flows, a site where water accumulates, a site where condensation occurs, and the like. By forming a film on these parts, discoloration due to the growth of microorganisms, deterioration of hygiene, and generation of slime (microorganism lump) can be suppressed.
〔実施例１〕
　抗菌性金属粒子としての、平均粒径１．２μｍの銅粉（三井金属鉱業株式会社製１１００Ｙ）と、酸化還元電位の低い金属粒子としての、平均粒径２μｍのアルミニウム粉（東洋アルミニウム株式会社製ＴＦＨ－Ａ０２Ｐ）とを、質量比１：２でエタノール中で混合し、乾燥した。この粉末を、親水性基材としての、コロイダルシリカ（日産化学工業株式会社製スノーテックス（登録商標）ＰＳ－Ｍ）と混合し、１．０質量％の銅粉、２．０質量％のアルミニウム粉及び８．０質量％のコロイダルシリカを含有する水分散液を調製した。これをガラス板上にスプレーにて塗布し、室温で乾燥することにより、厚さ３０μｍの被膜を形成した。 [Example 1]
Copper powder with an average particle size of 1.2 μm as antibacterial metal particles (1100Y manufactured by Mitsui Metal Mining Co., Ltd.) and aluminum powder with an average particle size of 2 μm as metal particles with low redox potential (manufactured by Toyo Aluminum Co., Ltd.) TFH-A02P) in ethanol at a mass ratio of 1: 2 and dried. This powder was mixed with colloidal silica (Snowtex (registered trademark) PS-M, manufactured by Nissan Chemical Industries, Ltd.) as a hydrophilic substrate, 1.0 mass% copper powder, 2.0 mass% aluminum. An aqueous dispersion containing powder and 8.0% by weight of colloidal silica was prepared. This was coated on a glass plate by spraying and dried at room temperature to form a coating having a thickness of 30 μm.
　これを、室温の流水中に７日間、１４日間及び２１日間曝したサンプルを作製し、ＪＩＳ　Ｚ　２８０１に準拠した抗菌性試験方法に従って抗菌活性値を求めた。抗菌活性値が２．０以上の場合を抗菌効果「有」とし、抗菌活性値が２．０未満の場合を抗菌効果「無」と評価した。評価結果を表１に示す。 Samples were exposed to running water at room temperature for 7 days, 14 days, and 21 days, and antibacterial activity values were determined according to an antibacterial test method based on JIS Z 2801. When the antibacterial activity value was 2.0 or more, the antibacterial effect was “present”, and when the antibacterial activity value was less than 2.0, the antibacterial effect was “no”. The evaluation results are shown in Table 1.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
　表１から分かるように、実施例１の抗菌剤からなる被膜は、流水に長時間曝されたにもかかわらず、抗菌性が維持されている。 As can be seen from Table 1, the antimicrobial properties of the coating film made of the antibacterial agent of Example 1 are maintained despite being exposed to running water for a long time.
〔比較例１〕
　アルミニウム粉を用いなかったこと以外は実施例１と同様にして、厚さ３２μｍの被膜を形成した。これを、室温の流水中に７日間、１４日間及び２１日間曝したサンプルを作製した。実施例１と同様にして抗菌性を評価した。評価結果を表２に示す。 [Comparative Example 1]
A film having a thickness of 32 μm was formed in the same manner as in Example 1 except that no aluminum powder was used. Samples were prepared by exposing this to flowing water at room temperature for 7 days, 14 days, and 21 days. Antibacterial properties were evaluated in the same manner as in Example 1. The evaluation results are shown in Table 2.
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
　表２から分かるように、比較例１の抗菌剤からなる被膜は、流水に短時間曝されただけで抗菌性が失われている。アルミニウム粉を混合した実施例１では、抗菌性の寿命が長くなっていることが分かる。比較例１においても、実施例１に比べて量は少ないが、銅は酸化銅あるいは酸化銅に覆われた銅として被膜中に残留している。抗菌性が失われた原因は、銅が少なくなったことの他、銅が酸化銅被膜に覆われ銅イオンを溶出しにくくなる効果もあることが推察される。アルミニウム粉の混合は、銅の酸化溶出速度を抑制するだけでなく、酸化銅被膜の成長を抑制し、徐放を維持させる効果もあると考えられる。 As can be seen from Table 2, the antibacterial property of the film made of the antibacterial agent of Comparative Example 1 is lost only by being exposed to running water for a short time. In Example 1 in which aluminum powder was mixed, it can be seen that the antibacterial life is long. Even in Comparative Example 1, although the amount is smaller than that in Example 1, copper remains in the film as copper oxide or copper covered with copper oxide. The cause of the loss of antibacterial properties is presumed that, in addition to the reduction of copper, copper is covered with a copper oxide film and has the effect of making it difficult to elute copper ions. It is considered that the mixing of the aluminum powder not only suppresses the oxidation elution rate of copper but also has an effect of suppressing the growth of the copper oxide film and maintaining the sustained release.
〔実施例２〕
　銅粉とアルミニウム粉とを予め混合、乾燥することなく、銅粉、アルミニウム粉及びコロイダルシリカを一度に混合して水分散液を調製したこと以外は実施例１と同様にして、厚さ３１μｍの被膜を形成した。これを、室温の流水中に７日間、１４日間及び２１日間曝したサンプルを作製した。実施例１と同様にして抗菌性を評価した。評価結果を表３に示す。 [Example 2]
The copper powder and aluminum powder were mixed in advance and dried, and the same as in Example 1 except that the aqueous dispersion was prepared by mixing copper powder, aluminum powder, and colloidal silica at a thickness of 31 μm. A film was formed. Samples were prepared by exposing this to flowing water at room temperature for 7 days, 14 days, and 21 days. Antibacterial properties were evaluated in the same manner as in Example 1. The evaluation results are shown in Table 3.
　表３から分かるように、実施例２の抗菌剤からなる被膜は、比較例１の抗菌剤からなる被膜と比べて、抗菌性の寿命が長くなっていることが分かる。また、実施例２の抗菌剤からなる被膜は、実施例１の抗菌剤からなる被膜と組成が同じであるにもかかわらず、抗菌性の寿命が短い結果となっている。このことから、抗菌性金属粒子と酸化還元電位の低い金属粒子とを予め混合することにより、抗菌性の寿命が延びることが分かる。 As can be seen from Table 3, it can be seen that the antimicrobial agent film of Example 2 has a longer antimicrobial life than the antimicrobial agent film of Comparative Example 1. Moreover, although the film which consists of an antibacterial agent of Example 2 has the same composition as the film which consists of the antibacterial agent of Example 1, it has resulted in a short antibacterial life. From this, it can be seen that the antibacterial life is extended by previously mixing the antibacterial metal particles and the metal particles having a low redox potential.
〔実施例３〕
　抗菌性金属粒子としての、銅のアトマイズ粉をふるい分けして粒径４５μｍ（ベックマンコールター社製 Multisizer 4eで測定）としたものと、酸化還元電位の低い金属粒子としての、平均粒径約６０μｍのアルミニウム粉（大和金属粉工業株式会社製Ｎｏ．１８０００）とを、親水性基材としてのポリエチレングリコール（平均分子量２００００）の１０質量％水溶液と混合した。この混合液において、銅のアトマイズ粉はポリエチレングリコール（固形分）に対して３．０質量％含有され、アルミニウム粉はポリエチレングリコール（固形分）に対して５．０質量％含有されていた。この混合液に架橋剤としての塩化ジルコニウムをポリエチレングリコール（固形分）に対して０．５質量％添加して水分散液を調製した。これをガラス板に掛け流した後、乾燥させ、１００℃で１５分間加熱することにより、厚さ３０μｍの被膜を形成した。 Example 3
Copper atomized powder as an antibacterial metal particle is screened to a particle size of 45 μm (measured with Multisizer 4e manufactured by Beckman Coulter), and aluminum with an average particle size of about 60 μm as a metal particle having a low redox potential Powder (No. 18000 manufactured by Yamato Metal Powder Industry Co., Ltd.) was mixed with a 10% by mass aqueous solution of polyethylene glycol (average molecular weight 20000) as a hydrophilic substrate. In this mixed solution, the copper atomized powder was contained in an amount of 3.0% by mass with respect to polyethylene glycol (solid content), and the aluminum powder was contained in an amount of 5.0% by mass with respect to polyethylene glycol (solid content). An aqueous dispersion was prepared by adding 0.5% by mass of zirconium chloride as a cross-linking agent to this mixed liquid with respect to polyethylene glycol (solid content). This was poured on a glass plate, dried, and heated at 100 ° C. for 15 minutes to form a coating having a thickness of 30 μm.
　これを、室温の流水中に７日間、１４日間及び２１日間曝したサンプルを作製した。実施例１と同様にして抗菌性を評価（黄色ぶどう球菌のみ）した。評価結果を表４に示す。 A sample was prepared by exposing it to flowing water at room temperature for 7 days, 14 days, and 21 days. Antibacterial properties were evaluated in the same manner as in Example 1 (only Staphylococcus aureus). The evaluation results are shown in Table 4.
〔比較例２〕
　アルミニウム粉の含有量をポリエチレングリコール（固形分）に対して１．５質量％に変更した（アルミニウム粉の含有量は、銅のアトマイズ粉の含有量の０．５倍）こと以外は実施例３と同様にして、厚さ３５μｍの被膜を形成した。これを、室温の流水中に７日間及び１４日間曝したサンプルを作製した。実施例１と同様にして抗菌性を評価（黄色ぶどう球菌のみ）した。評価結果を表４に示す。 [Comparative Example 2]
Example 3 except that the content of aluminum powder was changed to 1.5% by mass with respect to polyethylene glycol (solid content) (the content of aluminum powder was 0.5 times the content of copper atomized powder) A film having a thickness of 35 μm was formed in the same manner as described above. Samples were prepared by exposing this to flowing water at room temperature for 7 days and 14 days. Antibacterial properties were evaluated in the same manner as in Example 1 (only Staphylococcus aureus). The evaluation results are shown in Table 4.
〔比較例３〕
　アルミニウム粉の含有量をポリエチレングリコール（固形分）に対して２０質量％に変更した（アルミニウム粉の含有量は、銅のアトマイズ粉の含有量の６．７倍）こと以外は実施例３と同様にして、厚さ３０μｍの被膜を形成した。これを、室温の流水中に７日間曝したサンプルを作製した。実施例１と同様にして抗菌性を評価（黄色ぶどう球菌のみ）した。評価結果を表４に示す。 [Comparative Example 3]
The content of aluminum powder was changed to 20% by mass with respect to polyethylene glycol (solid content) (the content of aluminum powder was 6.7 times the content of copper atomized powder). Thus, a film having a thickness of 30 μm was formed. A sample was prepared by exposing it to running water at room temperature for 7 days. Antibacterial properties were evaluated in the same manner as in Example 1 (only Staphylococcus aureus). The evaluation results are shown in Table 4.
Figure JPOXMLDOC01-appb-T000004
Figure JPOXMLDOC01-appb-T000004
　表４から分かるように、実施例３の抗菌剤からなる被膜では、長期間の抗菌性が得られている。銅のアトマイズ粉の含有量に対してアルミニウム粉の含有量が少な過ぎる比較例２や銅のアトマイズ粉の含有量に対してアルミニウム粉の含有量が多過ぎる比較例３は、抗菌性が劣ることが分かる。 As can be seen from Table 4, the coating made of the antibacterial agent of Example 3 has long-term antibacterial properties. The comparative example 2 in which the aluminum powder content is too small relative to the copper atomized powder content and the comparative example 3 in which the aluminum powder content is too large relative to the copper atomized powder content are inferior in antibacterial properties. I understand.
　なお、本国際出願は、２０１５年１１月１２日に出願した日本国特許出願第２０１５－２２２１２２号に基づく優先権を主張するものであり、これらの日本国特許出願の全内容を本国際出願に援用する。 This international application claims priority based on Japanese Patent Application No. 2015-222122 filed on November 12, 2015, and the entire contents of these Japanese patent applications are incorporated herein by reference. Incorporate.
　１　抗菌性金属粒子、２　親水性基材、３　酸化還元電位の低い金属粒子、１０　空気調和機、１１　熱交換器、１２　ドレンパン、１３　ドレンホース、１４　被膜。 1 antibacterial metal particles, 2 hydrophilic substrate, 3 metal particles with low redox potential, 10 air conditioner, 11 heat exchanger, 12 drain pan, 13 drain hose, 14 coating.

Claims (7)

  1. 　抗菌性金属粒子と、該抗菌性金属粒子を構成する金属の酸化還元電位より酸化還元電位の低い金属粒子と、親水性基材とを含有する徐放性抗菌剤であって、該酸化還元電位の低い金属粒子が、該抗菌性金属粒子の含有量の１倍以上５倍以下の範囲で含有されることを特徴とする徐放性抗菌剤。 A sustained-release antibacterial agent comprising antibacterial metal particles, metal particles having a redox potential lower than the redox potential of the metal constituting the antibacterial metal particles, and a hydrophilic substrate, the redox potential The sustained-release antibacterial agent is characterized in that the metal particles having a low content are contained in the range of 1 to 5 times the content of the antibacterial metal particles.
  2. 　前記抗菌性金属粒子の少なくとも一部と前記酸化還元電位の低い金属粒子の少なくとも一部とが接触した状態であることを特徴とする請求項１に記載の徐放性抗菌剤。 The sustained-release antibacterial agent according to claim 1, wherein at least a part of the antibacterial metal particles and at least a part of the metal particles having a low redox potential are in contact with each other.
  3. 　前記抗菌性金属粒子が、銀及び銅からなる群から選択される少なくとも１種であり、且つ前記酸化還元電位の低い金属粒子が、アルミニウム及び亜鉛からなる群から選択される少なくとも１種であること特徴とする請求項１又は２に記載の徐放性抗菌剤。 The antibacterial metal particles are at least one selected from the group consisting of silver and copper, and the metal particles having a low redox potential are at least one selected from the group consisting of aluminum and zinc. The sustained-release antibacterial agent according to claim 1 or 2, characterized in.
  4. 　前記抗菌性金属粒子の平均粒径が、０．１μｍ以上２００μｍ以下であり、且つ前記酸化還元電位の低い金属粒子の平均粒径が、前記抗菌性金属粒子の平均粒径の０．２倍以上３倍以下であることを特徴とする請求項１～３の何れか一項に記載の徐放性抗菌剤。 The average particle size of the antibacterial metal particles is 0.1 μm or more and 200 μm or less, and the average particle size of the metal particles having a low redox potential is 0.2 times or more of the average particle size of the antibacterial metal particles. The sustained-release antibacterial agent according to any one of claims 1 to 3, which is 3 times or less.
  5. 　前記親水性基材が、親水性樹脂であり、前記抗菌性金属粒子が、前記親水性基材に対して０．５質量％以上５質量％以下の範囲で含有されることを特徴とする請求項１～４の何れか一項に記載の徐放性抗菌剤。 The hydrophilic substrate is a hydrophilic resin, and the antibacterial metal particles are contained in a range of 0.5% by mass to 5% by mass with respect to the hydrophilic substrate. Item 5. The sustained release antibacterial agent according to any one of Items 1 to 4.
  6. 　前記親水性基材が、親水性無機物であり、前記抗菌性金属粒子が、前記親水性基材に対して０．５質量％以上３０質量％以下の範囲で含有されることを特徴とする請求項１～４の何れか一項に記載の徐放性抗菌剤。 The hydrophilic substrate is a hydrophilic inorganic substance, and the antibacterial metal particles are contained in a range of 0.5% by mass to 30% by mass with respect to the hydrophilic substrate. Item 5. The sustained release antibacterial agent according to any one of Items 1 to 4.
  7. 　請求項１～６の何れか一項に記載の徐放性抗菌剤からなる被膜が表面に形成されていることを特徴とする物品。 An article characterized in that a film comprising the sustained-release antibacterial agent according to any one of claims 1 to 6 is formed on the surface.
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