WO2024168046A1

WO2024168046A1 - Antimicrobial textile, fiber, or yarn composition comprising a synergistic blend of components

Info

Publication number: WO2024168046A1
Application number: PCT/US2024/014819
Authority: WO
Inventors: Chenyu Wang; Vikram KANMUKHLA; Rachel SALVATORI
Original assignee: Cupron Inc
Current assignee: Cupron Inc
Priority date: 2023-02-08
Filing date: 2024-02-07
Publication date: 2024-08-15
Anticipated expiration: 2025-08-08
Also published as: WO2024168063A1; WO2024168052A1; IL322567A; EP4661676A1; EP4661670A1; WO2024168067A1; CN121152561A; CN120916642A; WO2024168041A2; EP4661669A2; IL322568A; WO2024182104A1; EP4662360A1; AU2024218475A1; WO2024168041A3

Abstract

The antimicrobial fibers, yarns, and textiles may include a mixture of at least one antimicrobial metal compound and at least one synergistic compound. For example, the antimicrobial fibers, yarns, and textiles may comprise at least one antimicrobial metal compound and a boric compound blended into a masterbatch, a mixture of powders, or a liquid dispersion. The c antimicrobial fibers, yarns, and textiles may further include at least one pH adjuvant that creates an acidic environment within or exterior to the composition. It has been surprisingly found that these components create a synergistic relationship within a composition that provides a more tailored antimicrobial polymeric composition or article.

Description

Title

ANTIMICROBIAL TEXTILE, FIBER, OR YARN COMPOSITION COMPRISING A SYNERGISTIC BLEND OF

COMPONENTS

FIELD OF THE INVENTION

Antimicrobial compositions and articles include, but are not limited to fibers, yarns, woven textiles, nonwoven textiles and articles, films, coatings, foams, masterbatches, powders, liquid dispersions, ointments, gels, aqueous dispersions, organic super-absorbent polymers, or other molded or extruded polymeric articles. Extruded polymeric articles may include antimicrobial, antiviral, or antifungal fibers, yarns, and textile fabrics, for example.

The antimicrobial, antiviral, or antifungal fibers, yarns, and textile fabrics may comprise a mixture of at least one antimicrobial metal compound and a synergistic compound. For example, in one embodiment, the antimicrobial, antiviral, or antifungal fibers, yarns, and textile fabrics may comprise particles comprising at least one antimicrobial metal compound and particles comprising a boric compound. The composition may further comprise at least one pH adjuvant that creates an acidic or basic environment within the composition. The inventors have surprisingly found that these components create a synergistic relationship within or on the article that provides a more tailored, lower cost, and/or higher efficacy antimicrobial polymeric article.

Methods of producing antimicrobial, antiviral, or antifungal fibers, yarns, and textile fabrics may comprise blending at least one antimicrobial metal compound, at least one boric compound, and, optionally, at least one pH adjuvant in thermoplastic resin to produce an antimicrobial, antiviral, and antifungal polymeric slurry that may be extruded or spun to produce the fibers and yarns.

BACKGROUND

Metal oxides or other antimicrobial metal compounds include, but are not limited to, copper oxide, copper iodides, copper carbonates, silver oxide, zinc oxide, silver chloride, zinc pyrithione, gold oxide, or combinations thereof. Such antimicrobial metal compounds have broad-spectrum antimicrobial properties and have demonstrated antifungal, antibacterial, and antiviral properties. Copper and its compounds can be found in articles, liquid coatings, and paints, plastic components, and polymeric material to impart durable and long-lasting antimicrobial activity to the different substrates.

There is a need for an antimicrobial, antiviral, and/or antifungal that is efficacious, processible, and has other advantageous properties for the production of antimicrobial compositions and articles.

BRIEF DESCRIPTION OF THE FIGURES

Figure 1 shows the effectiveness of polyester fabric samples comprising particles of copper oxide and particles of zinc borate versus untreated polyester fabric samples in preventing AN growth on the surface of the fabric samples; untreated PET fabric control before (Al) and after (Bl) 4-week incubation; Sample #4 before (A2) and after (B2) 4-week incubation; Sample #7 before (A3) and after (B3) 4-week incubation; Sample #8 before (A4) and after (B4) 4-week incubation; Sample #10 before (A5) and after (B5) 4-week incubation; Sample #11 before (A6) and after (B6) 4-week incubation; Sample #12 before (A7) and after (B7) 4-week incubation;

Figure 2 shows the effectiveness of polyester fabric samples comprising particles of copper oxide and particles of zinc borate versus untreated polyester fabric samples in preventing AN growth on the surfaces after 1-week incubation in SDB at 22 °C; and

Figure 3 shows the color stability comparing the prior art PET fabric sample containing (left) 1% copper oxide and (right) an embodiment of the PET fabric sample comprising 0.6% copper oxide, 0.6% zinc borate and 0.3% molybdenum oxide after being exposed to 10% H₂O₂ solution.

SUMMARY

Embodiments of an antimicrobial composition or article comprises a polymer, particles comprising water insoluble antimicrobial metal compound that release of antimicrobial ions upon contact with a fluid embedded in the polymer, particles comprising a boric compound embedded in the polymer. In additional embodiments, antimicrobial composition or article comprises a polymer, particles comprising water insoluble antimicrobial metal compound that release of antimicrobial ions upon contact with a fluid embedded in the polymer, particles comprising a boric compound embedded in the polymer, and particle comprising a pH adjuvant. An antimicrobial textile fabric for combating nosocomial and other infections may comprise antimicrobial polymeric fibers. In such embodiments, the antimicrobial polymeric fibers may comprise a polymer, particles comprising water insoluble antimicrobial metal compound that release antimicrobial ions upon contact with a fluid, and particles comprising boric compounds embedded in the polymer. The particles comprising the water insoluble antimicrobial metal compound and the boric that release antimicrobial ions upon contact with a fluid may be present in a concentration from an amount effective to control the microbes, virus, or fungus to less than 10 wt. %. For example, 17. An antimicrobial fiber, yarn, film, or textile may comprise a polymeric substrate fiber, particles comprising water insoluble metal compounds that release antimicrobial ions upon contact with a fluid in a concentration from 0.01 wt. % to 10 wt. % embedded in the polymer substrate; and particles comprising a boric compound in a concentration from 0.01 wt. % to 10 wt. % embedded in the polymer substrate.

The polymer may be at least one of natural fibers, synthetic cellulosic fibers, regenerated protein fibers, acrylic fibers, polyester fibers, nylon, polypropylene, polyethylene, polyethylene terephthalate, polyolefin fibers, polyurethane fibers, vinyl fibers, copolymers thereof, and blends thereof.

The particles comprising water-insoluble antimicrobial metal that release antimicrobial metal ions at a certain rate and produce some antimicrobial efficacy upon contact with a fluid, for example. The degree of antimicrobial efficacy may be a function of the antimicrobial agent, its concentration in the fiber, yarn, film, nonwoven, or textile article or composition, the environment that the antimicrobial article experiences, the physical and mechanical properties of the article, the inert ingredients in the article, the thickness of the fibers, and other factors. There may be a need or desire to modify this inherent antimicrobial efficacy, inherent antimicrobial durability, or the concentration of the antimicrobial compounds necessary to provide the desired antimicrobial efficacy and/or antimicrobial durability in some applications of the composition or article. A synergistic blend of the particles comprising water-insoluble antimicrobial metal, the particles comprising the boric compounds, and a pH adjuvant, can modify the release rate and efficacy of the antimicrobial article by providing a combination of antimicrobial metal ions, controlling the pH on the surface of the polymer when in contact with water, producing additional antimicrobial agents, and/or other chemical or mechanical modifications to the article. The term "textile" as used herein includes woven and nonwoven fabrics, textiles, or other articles.

In an embodiment, the antimicrobial metal compound is copper oxide. The water-insoluble copper oxide particles release at least one of Cu+ ions and Cu++ ions upon contact with a fluid and are embedded in the polymer, wherein a portion of the particles comprising the water-insoluble copper oxides are exposed and protruding from surfaces of the polymeric material. In such embodiments, the water insoluble copper compound may be in a concentration from 0.01 wt. % to 10 wt. % of the antimicrobial article or composition. The water insoluble antimicrobial metal compound in other embodiments may include, but are not limited to, copper oxide, copper chlorides, cuprous oxide, cupric oxide, copper iodides, copper carbonates, silver oxide, silver iodide, silver chlorides, zinc oxide, zinc chlorides, zinc pyrithione, gold oxide, or combinations thereof, for example. In another embodiment more advantageous for certain applications, copper oxide or other antimicrobial metal compounds may be in a concentration from 0.1 wt.% to 2 wt.% of the weight of the article or composition. In still other embodiment more advantageous for certain applications, copper oxide or other antimicrobial metal compounds may be in a concentration from 0.1 wt.% to 6.0 wt.% of the weight of the article or composition.

Embodiment may also comprise particles comprising at least one boric compound. The at least one boric compound may include, but is not limited to, metal borates, boric salts, boric acid, sodium borate, a compound that produces an antimicrobial metal ion and boric acid on contact with water, sodium borate, potassium borate, zinc borate, and combinations thereof. The boric compounds may be in a concentration from 0.05 wt.% to 15 wt. % of the antimicrobial composition or article.

The synergistic blend may also comprise particles comprising a pH adjuvant. The pH adjuvant may be in a concentration from 0.01 wt. % to 5.0 wt.% or, in a more specific embodiment, the pH adjuvant is in a concentration from 0.1 wt.% to 3 wt.%. In certain embodiments, the solid pH adjuvant particle is molybdenum oxide.

More specific embodiments of the antimicrobial fiber, yarns, or textiles may comprise a polymer, water insoluble antimicrobial metal particles that release of antimicrobial ions upon contact with a fluid in a concentration from 0.01 wt. % to 6.0 wt. % embedded in the polymer, a metal borate, and a pH adjuvant, wherein the pH adjuvant is embedded in the polymer and the pH adjuvant changes the pH on the surface of the polymer when in contact with water thereby adjusting a rate of release of the antimicrobial ions and controlling the decomposition of the metal borate. Such embodiments may further comprise particles comprising the boric compound in a concentration from 0.1 wt. % to 10 wt.% of the fiber, yarn, film, or textile, for example.

The antimicrobial article comprising the synergistic blend of components may include, but is not limited to, threads, nonwoven filters, nonwoven wound dressings, medical linens, bed sheets, films, pillow cases, fabric curtains, shower curtains, polymeric tubing, polyvinyl chloride tubing, polyvinyl chloride composites, upholstery fabric, carpet, carpet backing, mattress covers, mattress foam, other mattress components, fibers, nonwovens, a component of a bandage or other wound covering, foam, polyurethane foams, wall cladding, flooring, airline seat components, airline tray tables, public transportation components, doors, window frames, polymeric piping, filters, clothing, and solid surfaces, for example.

Unless otherwise defined, all terms (including technical and scientific terms) used herein have the same meaning as commonly understood by one having ordinary skill in the art to which this invention belongs. It will be further understood that terms, such as those defined in commonly used dictionaries, should be interpreted as having a meaning that is consistent with their meaning in the context of the relevant art and the present disclosure and will not be interpreted in an idealized or overly formal sense unless expressly so defined herein.

In describing the invention, it will be understood that a number of components, parts, techniques and steps are disclosed. Each of these has individual benefits and each can also be used in conjunction with one or more, or in some cases, all of the other disclosed embodiments and techniques. Accordingly, for the sake of clarity, this description will refrain from repeating every possible combination of the individual steps in an unnecessary fashion. Nevertheless, the specification and claims should be read with the understanding that such combinations are entirely within the scope of the invention and the claims.

DESCRIPTION

Antimicrobial compositions and articles comprise an antimicrobial agent that prevents or inhibits the growth of microbes on the composition or the article. Microbes may include bacteria, viruses, fungi, and algae, for example. The inventors have found that the efficacy, durability, zone of inhibition, processibility, and other antimicrobial properties of such articles may be improved by combining the antimicrobial agents with different components to produce a blend of synergistic compounds. The antimicrobial compositions and articles include antimicrobial fibers, yarns, and textiles.

An antimicrobial polymeric composition or article comprise synergistic compounds that increase the antimicrobial efficacy above the efficacy, durability, or other properties of the individual antimicrobial agents alone. The antimicrobial efficacy of an individual antimicrobial agent and the antimicrobial efficacy of the synergistic combination of a blend comprising the individual antimicrobial compound and a potentially synergistic compound may be measured by determining and comparing the zone of inhibition of the individual antimicrobial compounds and the blend or by other tests. A highly effective antimicrobial composition comprises at least one antimicrobial metal compound and at least one metal borate (hereinafter "synergistic antimicrobial composition"). It was surprisingly discovered that even though zinc borate has no significant inherent antimicrobial activity. In some embodiments, the antimicrobial efficacy of the synergistic antimicrobial composition is found to be greater than sum of its component's individual efficacy, though the synergistic compounds may improve other properties other than efficacy.

In one embodiment, the synergistic polymeric composition comprises a polymer, a plurality of antimicrobial metal compounds embedded in the polymer, boric compounds, and, optionally, a pH adjuvant that controls the pH of the polymeric composition when in contact with water.

Embodiments of the antimicrobial fibers, yarns, or textiles comprise a polymer substrate, a plurality of particles comprising at least one water insoluble antimicrobial metal compound that releases antimicrobial ions upon contact with water. Antimicrobial metal compounds include, but are not limited to, copper oxide, cuprous oxide, cupric oxide, copper iodides, copper carbonates, silver oxide, silver iodide, silver chloride, zinc oxide, zinc pyrithione, gold oxide, or combinations thereof, for example. In another embodiment, the particles may consist essentially of one antimicrobial metal compound selected from the group consisting of include, but are not limited to, copper oxide, cuprous oxide, cupric oxide, copper iodides, copper carbonates, silver oxide, silver chloride, silver iodide, zinc oxide, zinc pyrithione, gold oxide, or combinations thereof for example.

Embodiments of the antimicrobial fiber, yarn, film, or textile may comprise at least one particle comprising at least one water insoluble antimicrobial metal compound that releases antimicrobial ions upon contact with water and a particle comprising a boric compound. In some embodiments, the particle may comprise a combination of the water insoluble metal compounds that releases antimicrobial ions upon contact with water and a boric compound.

The antimicrobial metal compound and the boric compound may be present in any concentration from an effective amount to 20 wt% of the fiber, yarn, film, fabric, article, masterbatch, or dispersion. The synergistic compounds may be incorporated into polymeric fibers, yarns, and fabrics. The fabrics may be medical textiles such as sheets, room dividers, pillowcases, towels, wash cloths, shower curtains, bandages, woven or nonwoven components of wound dressings, and window curtains, patient gowns, scrubs, masks, and other medical textiles for combating nosocomial infections, for example.

An embodiment of an antimicrobial textile fabric comprises antimicrobial polymeric fibers or antimicrobial polymer yarns. The antimicrobial polymeric fibers or antimicrobial polymer yarns may comprise a polymer and particles comprising synergistic antimicrobial agents. The synergistic antimicrobial particles may comprise water insoluble antimicrobial metal compound that releases antimicrobial ions upon contact with a fluid embedded in the polymer and particles comprising boric compounds embedded in the polymer.

The polymer may be selected from acrylic fibers, nylon, polypropylene, polyethylene, polyethylene terephthalate, polyolefin fibers, polyurethane fibers, vinyl fibers, copolymers thereof, and blends thereof. The antimicrobial textile fabric may further comprise additional polymeric fibers. The additional polymeric fibers may comprise at least one of natural fibers, cotton fibers, wool fibers, hemp fibers, synthetic cellulosic fibers, regenerated protein fibers, acrylic fibers, nylon, polypropylene, polyethylene terephthalate, polyolefin fibers, polyurethane fibers, vinyl fibers, and blends thereof. The additional fibers may be antimicrobial fibers or not.

The particles comprising a boric compound embedded in the polymer and the particles comprising the antimicrobial metal compounds embedded in the polymer or polymer substrate may have a particle size distribution such that ninety percent of the particles are between 0.2 to 20 microns. In some further embodiments, the particles may have a particle size distribution such that ninety percent of the particles are between 1 to 10 microns. In some further embodiments, the particles may have a particle size distribution such that ninety percent of the particles are between 1 to 5 microns. In still further embodiments, the particles may have an average particle size between 2 to 4 microns.

Certain embodiments of antimicrobial fibers, yarns, or fabric comprise an antimicrobial metal compound embedded in a polymer, wherein the antimicrobial metal compound is in a concentration range from 0.02 wt.% to 10 wt. % of the weight of the fiber, yarn, film, or fabric or in a concentration range from 0.02 wt.% to 6 wt.%; or, in some embodiments, the concentration range may be from 0.05 wt.% to 2 wt.%.

In such embodiments of antimicrobial fibers, yarns, or fabric comprise a boric compound embedded in a polymer in a concentration range from 0.05 wt.% to 15 wt. %; or in a concentration range from 0.2 wt.% to 10 wt.%; or, in some embodiments, the concentration range may be from 0.2 wt.% to 5 wt.% in combination with the antimicrobial metal compound.

In further embodiments, the antimicrobial textile polymeric fibers, yarns, and fabrics may further comprise a pH adjuvant.

In a specific embodiment, the antimicrobial fibers, yarns, or fabric comprise particles comprising copper oxide and particles comprising zinc borate. In such an embodiment, the particles comprising water insoluble antimicrobial metal compound that release antimicrobial ions upon contact with a fluid is a particle comprising copper oxide and the particles comprising the boric compounds are particles comprising zinc borate.

Embodiments of an antimicrobial fiber, yarn, film, or textile may comprise a polymer or polymeric substrate comprising antimicrobial particles. The antimicrobial particles may comprise particles comprising water insoluble antimicrobial metal compound that release antimicrobial ions upon contact with a fluid embedded in the polymer substrate and boric compounds.

In certain embodiments, the polymer or polymeric substrate is at least one of polyester, nylon, polypropylene, polyethylene, polyurethane, and polyethylene terephthalate. In a specific embodiment, the particles comprising water insoluble antimicrobial metal compound that release antimicrobial ions upon contact with a fluid are copper oxide particles and the particles comprising a boric compound are particles comprising zinc borate.

Embodiments also comprise a method of producing antimicrobial fibers, yarns, or fabrics. For example, an embodiment of a method of producing the antimicrobial fibers or yarns comprises preparing a polymeric slurry comprising a plurality of antimicrobial particles in a polymeric resin comprising a thermoplastic polymer. The antimicrobial particles comprise particles comprising or consisting essentially of water insoluble antimicrobial metal compound that release antimicrobial ions upon contact with a fluid and particle comprising or consisting essentially of a boric compound. The method may further comprise extruding or spinning the polymeric slurry spinning the slurry to form a polymeric fiber, wherein the particles are incorporated or embedded in the polymer and wherein a portion of the particles in the polymer are exposed and protruding from the surface of the material or fiber and release antimicrobial metal ions when exposed to water or water vapor to provide the antimicrobial activity of the polymeric material.

An embodiment of the method may further comprise filtering the slurry to remove any particles over a desired particle size.

The polymeric slurry may comprise a polymer selected from polyester, polyethylene terephthalate, nylon, polyurethane, polyolefins, polypropylene, polyethylene, copolymers thereof, or combinations thereof. The particles comprising antimicrobial metal compounds and particles comprising boric compounds may be added to the polymer or polymeric reaction mixture as a powder comprising the antimicrobial metal compounds, powder comprising the boric compounds, a blend of such powders, a powder comprising particles comprising both the antimicrobial metal compound and the boric compound, or on or more masterbatch comprising particles comprising the antimicrobial metal compounds and particles comprising boric compounds. The masterbatch and powders may further comprise other processing agents.

A method of producing antimicrobial textile fabric comprising preparing antimicrobial textile fabric from polymeric fibers comprising water insoluble antimicrobial metal compound particles that release antimicrobial ions upon contact with a fluid in a concentration embedded in a polymer and boric acid particles or particles comprising a boric compound embedded in the polymer. The fibers may comprise blends of fibers. Further, the fabric (woven or nonwoven) may comprise fibers that do not comprise the synergistic blend of antimicrobial particles described herein.

The fiber, yarn, film, and fabric articles may include, but are not limited to, woven materials, nonwoven materials, air handling equipment and components, apparel (Uniforms, outerwear, gloves, aprons, coats, sportswear, sleepwear, stockings, socks, hosiery, caps, undergarments, linings, shoes, headwear), automotive liners , seat covering, roof liners, and surfaces, awnings, bags (including garment, garbage, bedding, vacuum), barrier fabrics and films bath fixtures and components, bedding (Blankets, mattresses, ticking, pads, sheets, pillow cases, fiberfill, pillows, sleeping bags), carpet and rug components and assembly, cleaning equipment (durable and disposable), cleaning supplies and tools, cloths and wipes, collection and storage container and equipment (including piping systems, silos, tanks, and processing vessels), conveyer belts, ear plugs, filters - gas and fluid, flooring materials and components, footwear and footwear components, furniture assemblies and components, furniture stuffing, gaskets, industrial equipment, insulation for wiring and cable, insulators and weather stripping, kitchen-Bath hardware and fixtures, liners, mats (exercise, kitchen, bath), packaging material, plumbing supplies and fixtures, protective covers (durable and disposable), rain and sun barriers (awnings, umbrellas, vehicle covers), refuse containers (baskets, cans, bags), respirator components, sports clothing and equipment, synthetic leather, tape - medical, industrial, commercial, tarpaulins and covers, tools, tubing, hoses, pipes and components, water containers, for example.

For example, an embodiment of the synergistic polymeric fibers, yarns, or texties may comprise a polymer, a plurality of copper compounds that release copper ions in the presence of water, zinc borate, and molybdenum oxide.

Proposed Theoretical Mechanism

Embodiments of the invention comprise a synergistic blend of compounds that produce an improved antimicrobial efficacy, improved color stability, improved processibility, or improve other properties to a polymeric article, film, fiber, yarn, film, or other molded or extruded polymeric article. An embodiment of an antimicrobial polymeric composition comprises synergistic blend of components, wherein the synergistic blend of components includes at least one antimicrobial metal compound, that, for example, increases the antimicrobial efficacy of the polymeric composition above the antimicrobial efficacy of a polymeric composition consisting essentially of the individual components alone. The individual antimicrobial efficacy of an individual antimicrobial compound and the antimicrobial efficacy of the synergistic combination of a blend comprising the individual antimicrobial compound and a potentially synergistic compounds may be measured by determining and comparing or the zone of inhibition of the individual antimicrobial compounds and the blend in the polymeric composition. The improvement in other properties may be similarly measured and compared.

The synergistic polymeric composition comprises a polymer, particles comprising a plurality of antimicrobial metal compounds embedded in the polymer and particles comprising a boric compound. The synergistic polymeric composition may comprise a metal borate and copper oxides, for example.

For example, an embodiment of the synergistic polymeric composition may comprise a polymer, a plurality of copper compounds that release copper ions in the presence of water and particles comprising zinc borate. Though not wishing to be limited by a disclosed mechanism, in such an embodiment, it is theorized that though the zinc borate (ZnB3O4(OH)3) is only sparingly incongruent soluble in water at room temperature and may reversibly hydrolyze to insoluble Zn(OH)2 and soluble H3BO3, a weak acid.

One of the synergistic compounds may dissolve incongruently. Many substances dissolve congruently (the composition of the solid and the dissolved solute stoichiometrically match). However, some substances may dissolve incongruently, whereby the composition of the solute in solution does not match that of the solid. This solubilization is accompanied by alteration of the "primary solid" particle and possibly formation of a secondary solid phase. In this embodiment, the ZnB3O4(OH)3 hydrolyzes to a secondary solid phase of insoluble Zn(OH)2 which may form an insoluble surface shell on the ZnB3O4 particle preventing or significantly reducing further solubilization and formation of the soluble orthoboric acid. The zinc borate, ZnB3O4(OH)3, also described as 2ZnO-3B2O3 3.5H2O, is sparingly soluble in water and hydrolyzes incongruently to soluble boric acid and insoluble zinc hydroxide. The produced boric acid is slightly acidic.

It is further theorized that the subsequently formed Zn(OH)2 may decompose according to the formula, Zn(OH)2 + 2H+

Zn2+ + 2H2O, in the presence of a moisture or pH adjuvant, for example. Such decomposition produces zinc ions which may further act as an antimicrobial ion. As can be seen in the zone of inhibition testing the copper oxide alone has some antimicrobial efficacy, zinc borate alone has no significant antimicrobial efficacy, and the combination of copper oxide and zinc borate does not have any synergistic antimicrobial effect.

Since the zinc borate hydrolyzes on the exposed outer portion of the particle to insoluble Zn(OH)2, it would be expected that there would be no further release of zinc ions. However, a desired concentration of pH adjuvant or water can control further decomposition of the insoluble Zn(OH)2 to further release the antimicrobial zinc ions. In this manner, the polymeric composition or article comprises a fast or slow release of antimicrobial metal ions. The metal ions in the metal oxide and the metal borate may be further chosen to provide antimicrobial efficacy by different mechanisms thereby killing a wider range of microbes or combining to kill microbes more effectively. In embodiments, the synergistic compounds may be chosen to affect or control the release of antimicrobial ions, antimicrobial efficacy, antimicrobial durability, color stabilization, or other properties.

POLYMERS

The antimicrobial article may comprise any polymer. The polymer may be a thermoplastic or thermoset polymer.

The polymer is one of polyvinyl chloride, polyolefins, polyethylene, polypropylene, polyethylene phthalate, polydienes, polybutadiene, polyesters, polystyrene, polystyrene acrylonitrile, acid polymers, nylon polymers, bakelite, polyolefins, polyethylene, polypropylene, polyallomer, polyacetal, polyamide, polyvinyl chloride, polyesters, polyethers, polyamides, polyacrylates, polymethacrylates, polyacrylics, acrylonitrile-butadiene-styrene, acrylonitrile styrene acrylate, nylons, polybutylene, polylactic acid, polyurethane, fluoropolymers (such as polytetrafluoroethylene), blended polymers thereof, or copolymers thereof.

In certain embodiments, the polymer is not a polyacid or an anionic polymer. For example, in such embodiments, the polymer does not comprise carboxylic acid or carboxylate moieties, sulfonic acids moieties (-SO3H), phosphonic acid moieties, or boronic acid moieties.

The thermoplastic resins may comprise any thermoplastic resin known in the art and appropriate for the envisioned application, for example, but without limitation, such thermoplastic resins may include olefins (such as low and high density polyethylene and polypropylene), dienes (such as polybutadiene and Neoprene elastomer), vinyl polymers (such as polystyrene, acrylics, and polyvinyl chloride), fluoropolymers (such as polytetrafluoroethylene) and heterochain polymers (such as polyamides, polyesters, polyurethanes, polyethers, polyacetals and polycarbonates). Thermoset resins include phenolic resins, amino resins, unsaturated polyester resins, epoxy resins, polyurethanes, and silicone polymers.

ANTIMICROBIAL PARTICLE

An antimicrobial metal compound may be any water insoluble metal compound that releases the antimicrobial ions when in contact with water. The antimicrobial metal particle comprises at least one of antimicrobial copper compounds, antimicrobial silver compounds, antimicrobial zinc compounds, and other antimicrobial metallic compounds. For example, the antimicrobial metal compounds include, but are not limited to, copper oxide, copper chlorides, cuprous oxide, cupric oxide, copper iodides, copper carbonates, silver oxide, silver chlorides, zinc oxide, zinc chlorides, zinc pyrithione, gold oxide, or combinations thereof, for example. In another embodiment, the particles may consist essentially of one antimicrobial metal compound selected from the group consisting of include, but are not limited to, copper oxide, cuprous oxide, cupric oxide, copper iodides, copper carbonates, silver oxide, zinc oxide, zinc pyrithione, gold oxide, or combinations thereof for example.

In certain embodiments, the antimicrobial compounds or particles may consist essentially of one of a copper oxide, cooper chlorides, cuprous oxide, cupric oxide, copper iodides, copper carbonates, silver oxide, silver chlorides, zinc oxide, zinc chlorides, zinc pyrithione, gold oxide, or combinations thereof, for example. In another embodiment, the particles may consist essentially of one antimicrobial metal compound selected from the group consisting of include, but are not limited to, copper oxide, cuprous oxide, cupric oxide, copper iodide, copper carbonate, silver oxide, zinc oxide, zinc pyrithione, gold oxide. The antimicrobial particle comprising the water insoluble metal compound may comprise functionality or coating. The functionality or coating may assist in the processing or final product properties, for example.

Metal oxide powders comprising at least one of water-insoluble copper oxide particles, silver oxide, zinc oxides may be particularly useful in embodiments of the antimicrobial compositions or articles. The antimicrobial particles may be antimicrobial particles consisting essentially of copper oxide, silver oxide, or zinc oxide, for example.

In some embodiments, the particles comprising or consisting essentially of antimicrobial metal compound particles are mechanically held in the polymer matrix, and not ionically bound, hydrogen bonded, coordination complexed, etc. to the polymer.

BORIC COMPOUNDS

The synergistic compound or a component of a synergistic blend of components may comprise a boric compound. The boric compound may include, but is not limited to, a metal borate, silver borate, copper borate, zinc borate, gold borate, sodium borate, calcium borate, potassium borate, boric salts, boric acid, a compound that produces boric acid and an antimicrobial metal ion on contact with water, and combinations thereof. For example, a metal borate decomposes to release an antimicrobial ion in the presence of the water or pH adjuvant, even though the metal borate has no significant inherent antimicrobial efficacy alone. In some embodiments, the boric compound or the particles comprising a boric compound may be replaced with another compound that synergistically interacts with water or the pH adjuvant and the antimicrobial metal compound to increase the efficacy of the polymeric article over the article comprising only an antimicrobial metal compound.

In one embodiment, the boric compound is a boric compound that dissolves incongruently in water. The boric compounds may be chosen to control antimicrobial efficacy, the durability of the antimicrobial efficacy, color stability, and/or processability of the polymer resin to produce the final product by spinning, drawing, extruding, or molding, for example. pH ADJUVANTS

The pH adjuvant is a compound that creates acidic environment upon contact with a fluid to facilitate the hydrolyzation of metal borate to release an antimicrobial metal ion and/or release of the metal ions from the antimicrobial composition. The pH adjuvant may decompose or dissociate to form an acidic environment. The pH adjuvant creates a microenvironment in response to an external stimulus to adjust the pH on the surface of the antimicrobial polymeric article. In some embodiments, the pH adjuvant has a decomposition temperature above the compounding and forming (extruding or molding) temperatures of the polymeric article. In other embodiments, the pH adjuvant may be formed from the decomposition of a compound due to exposure of the compound to elevated temperatures in the compounding, molding, extruding, or other processing step.

For example, molybdenum oxide decomposes into molybdic acid and hydronium ions when in contact with humidity or other source of water according to the following formula:

Other acids will also form hydronium ions that decompose the metal borate to boric acid and release metal ions. The hydronium ions may accelerate the ionization of the metal borate and antimicrobial metal compound to form a synergistic antimicrobial product with higher antimicrobial efficacy than the additive antimicrobial efficacy of the individual components.

In some embodiments, the pH adjuvant is in a concentration from 0.01 wt. % to 5.0 wt.%.

The pH adjuvant may be chosen to control antimicrobial efficacy, the durability of the antimicrobial efficacy, color stability, and/or processability of the polymer resin to produce the final product by spinning, drawing, extruding, or molding. Examples of pH adjuvants include but are not limited to, sulphur, acids including, but not limited to, citric acid, phosphoric acid, etc.; acidic salts including, but not limited to, NaH2PO4, ZnCI2, NH4CI, and acidic oxides including, but not limited to, MoO3, CrO3, Mn2O7, etc. Therefore, the pH adjuvant may be one of a compound that produces an acidic environment on contact with water, acidic oxide, acidic salt, molybdenum oxide, chromium oxide, chromium chloride, molybdenum chloride, and combinations thereof.

The acid dissociation constant, pKa, of an acid may be used to determine if the compound will create an appropriate acidic environment upon contact with moisture to sufficiently hydrolyze the metal borate and to accelerate the release of the antimicrobial metal ions (Cu+ ions and Cu++ ions from copper oxide, for example) for the desired properties of the polymeric product.

The polymeric article may further comprise a pH adjuvant package comprising one or more pH adjuvant. The pH adjuvant may comprise an acid and a buffer, for example. The buffer may be an acidic buffer or an alkaline buffer, for example. An acidic buffer may comprise weak acid and an acidic salt, for example. Similarly, an alkaline buffer may comprise a weak base and a basic salt, for example.

Methods of forming the antimicrobial polymeric compositions or articles include processing steps that include elevated temperatures for compounding, curing, melting, forming, or softening the polymer. In certain applications, the pH adjuvant has a decomposition temperature above these processing temperatures so all or a portion of the pH adjuvant does not decompose or dissociate during processing.

POWDER BLENDS

The method of forming the antimicrobial fibers, yarns, and textiles may comprise mixing an at least one antimicrobial powder comprising at least one of the particles comprising the antimicrobial metal compounds and the particles comprising the boric compounds with a polymeric resin to produce a polymeric slurry. The polymeric slurry may be further processed as known in the art to produce the fibers, yarns, and textiles. Embodiments of the antimicrobial powders may comprise a blend of synergistic antimicrobial powders. The synergistic powders may be individually blended into a polymer resin or an aqueous dispersion to produce an antimicrobial composition that may be further processed to form antimicrobial articles. For example, an embodiment of the synergistic antimicrobial powders may comprise particles comprising water insoluble metal compounds, and particles comprising boric compounds. The water insoluble antimicrobial powder may comprise a ratio of metal oxide particles to particles comprising boric compounds of between 20:1 to 1:10.

The synergistic antimicrobial powders may be added to the polymer to produce an antimicrobial polymer article comprising antimicrobial metal oxide in a concentration from 0.1 wt.% to 5 wt.%.

The particles comprising antimicrobial metal oxides may be particles comprising or consisting essentially of one or more of copper oxide, zinc oxide, silver oxide, gold oxide, or combinations thereof. The particles comprising boric compounds may be particles comprising zinc borate, particles comprising copper borate, particles comprising silver borate, particles comprising calcium borate, particles comprising sodium borate, or combinations thereof such particles or particles comprising one or more of the boric compounds, for example. In one embodiment, a blend of synergistic antimicrobial powders comprises particles comprising water insoluble antimicrobial copper oxide and particles comprising zinc borate.

In another embodiment, the blend of synergistic antimicrobial powders further comprises a pH adjuvant. Therefore, in one embodiment, the blend of synergistic antimicrobial powders may comprise particles comprising antimicrobial metal compound, particles comprising a boric compound, and particles comprising a pH adjuvant.

In specific embodiment, the blend of synergistic powders comprises copper oxide and zinc borate. In another embodiment, the blend of synergistic powders comprises copper oxide, molybdenum oxide, and zinc borate.

MASTERBATCH

The method of forming the antimicrobial fibers, yarns, and textiles may comprise mixing an at least one antimicrobial masterbatch comprising at least one of the particles comprising the antimicrobial metal compounds and the particles comprising the boric compounds with a polymeric resin to produce a polymeric slurry. An antimicrobial masterbatch may be blended with virgin polymer to add desired color or other properties to the virgin polymer prior to further processing to form antimicrobial polymeric articles, fibers, yarns, fabrics, or other articles. Methods and processes for producing an antimicrobial and/or antiviral polymeric masterbatch are known. The synergistic antimicrobial compounds described herein may be added to a virgin polymer (such as PET or a polyolefin) to produce the masterbatch and subsequently the masterbatch may be added to a virgin polymer to produce an antimicrobial polymeric resin.

The masterbatch may be extruded into pellets, chips, or formed into other particles for subsequent blending with the virgin polymer to add antimicrobial, antiviral, or antifungal properties to the polymeric materials.

Embodiments of the polymeric masterbatch for preparing antimicrobial polymer materials may comprise a thermoplastic or a thermoset polymer substrate, a blend of antimicrobial synergistic compounds comprising at least one of particles of water insoluble antimicrobial metal compounds (as described herein) and boric compounds (as described herein). The masterbatch may further comprise a polymeric wax, an agent for occupying the charge of the ionic copper oxide, processing aids, or other property modifying agents The antimicrobial synergistic compounds may further comprise particles comprising a pH adjuvant. A method of producing an antimicrobial article, fiber, yarn, film, textile, or other molded or extruded article, comprises adding a polymeric antimicrobial masterbatch comprising a thermoplastic resin, a blend of antimicrobial synergistic compounds comprising water insoluble particles of copper oxide and zinc borate to a thermoplastic polymeric resin and forming the antimicrobial article, film, fiber, yarn, film, and other molded or extruded articles.

A method of producing an antimicrobial article, fiber, yarn, film, or other molded or extruded article, comprises adding a first polymeric masterbatch comprising a thermoplastic resin, a blend of antimicrobial synergistic compounds comprising water insoluble particles of copper oxide, pH adjuvant, and zinc borate to a thermoplastic polymeric resin; adding a second masterbatch comprising at least one of the antimicrobial synergistic compounds comprising particles of water insoluble copper oxide, pH adjuvant, and zinc borate, wherein the second masterbatch comprises at least one of the synergistic compounds that is not included in the first polymeric masterbatch, and forming the antimicrobial article, film, fiber, yarn, film, and other molded or extruded article.

For example, the first polymeric masterbatch may consist essentially of particles of water insoluble copper oxide and particles of zinc borate and the second polymeric masterbatch may comprise the pH adjuvant such as molybdenum oxide.

Further embodiments of the polymeric masterbatch for preparing antimicrobial polymer materials may comprise a thermoplastic resin, particles of a blend of antimicrobial synergistic compounds comprising water insoluble metal compounds such as copper oxide, for example, and particles of a boric compound such as zinc borate, for example, a polymeric wax, and an agent for occupying the charge of the ionic copper oxide. The antimicrobial synergistic compounds may further comprise a pH adjuvant.

Antimicrobial, antifungal, and/or antiviral masterbatch allows a polymeric product producer to add antimicrobial and/or antiviral components economically to polymers during the manufacturing process. More particularly, the present invention relates to an improved process and masterbatch for preparing antimicrobial and antiviral polymeric materials having a multitude of antimicrobial uses.

Embodiments of the antimicrobial powders may comprise a blend of synergistic antimicrobial powders. The blend of synergistic powders may be blended into a polymer resin to produce an antimicrobial polymer that may be further processed to form antimicrobial articles. The water insoluble antimicrobial powder may comprise a ratio of metal oxide particles to particles comprising boric compounds of between 20:1 to 1:1. Any of the antimicrobial masterbatches described herein may comprise the blend of antimicrobial synergistic compounds or a subset of the blend of antimicrobial synergistic compounds in a concentration from 10 wt.% to 70 wt.%, for example.

The synergistic antimicrobial powders may be added to the polymeric resin to produce an antimicrobial polymer article comprising particles comprising antimicrobial metal oxide sin a concentration from 0.1 wt.% to 5 wt.%.

An embodiment of a first antimicrobial masterbatch may comprise antimicrobial particles comprising at least one water insoluble antimicrobial metal compound and at least one boric compound embedded in a polymer, wherein the antimicrobial masterbatch comprises antimicrobial particles in a concentration from 12 wt. % to 50 wt. %.

An embodiment of a second masterbatch may comprise molybdenum oxide particles, wherein the second masterbatch comprises molybdenum oxide particles in a concentration from 5 wt. % to 50 wt. %.

An embodiment of a third masterbatch may comprise a blend of particles comprising antimicrobial metal compounds, a boric compound, and a pH adjuvant, wherein the third masterbatch comprises the blend of particles in a concentration from 5 wt. % to 50 wt. %.

A method of producing an antimicrobial fiber, nonwoven, film, or other extruded or molded article, comprising compounding the first antimicrobial masterbatch with a polymer. The method may further comprise compounding the first antimicrobial masterbatch, the second masterbatch and the polymer to produce a polymeric article comprising a metal oxide, a metal borate, and molybdenum oxides.

EMBODIMENTS

Fabrics Performance Apparel

Performance apparel is designed to enhance the wearer's comfort and functionality during physical activities, such as sports, exercise, and occupational use. An embodiment may be designed as re-usable washable, re-usable non-washable or disposable apparel with inherent antimicrobial or material preservation protection. Embodiments of the performance apparel may comprise any of the fibers, yarns, and/or fabrics described herein.

The embodiment may be designed for or suitable for various performance applications (e.g. sports, medical procedure or medical care, first responders, technical military, aerospace applications, scientific labs) in which microbial management or material preservation is the or one of the enhanced performance objectives of the product. Surgical Masks

In one embodiment, a three-layer surgical mask is composed of a hydrophilic nonwoven polypropylene inner layer comprising between 0.5 wt % and 3.0 wt. % (for example, 1.5 wt. %) cuprous oxide and between 0.5 wt % and 3.0 wt. % (for example, 1.5 wt. %) zinc borate. The mask may further comprise a meltdown nonwoven polypropylene middle layer comprising between 0.5 wt % and 3.0 wt. % (for example, 1 wt. %) cuprous oxide and between 0.5 wt % and 3.0 wt. % (for example, 1 wt. %) zinc borate. Additionally, the surgical mask may comprise a hydrophobic nonwoven polypropylene outer layer comprising between 0.5 wt % and 3.0 wt. % (for example, 1.5 wt. %) cuprous oxide and between 0.5 wt % and 3.0 wt. % (for example, 1.5 wt. %) zinc borate. The average particle size of the particles in each layer may be between 1 to 5 pm for both cuprous oxide and zinc borate powders. Optionally, 0.1 wt. % to 0.5 wt. % pH adjuvant may be added to all the three layers.

The assembly of layers may be designed to retard transmission of pathogenic material or material degrading organisms across environments from the same by the managed deposition of metal ions in, on and around the microenvironment of the surface.

Wound Dressings

Wound dressings or medical devices are applied to a variety of human and animal wounds to facilitate healing and prevent infection. Embodiments of a wound dressing may comprise one or more layers designed to protect the wound site and enhance healing,

In one embodiment, a wound dressing may comprise an absorbent base layer and a hydrophobic top layer. The base layer may comprise a natural or synthetic polymer configured to be in contact with skin, a wound, a burn, a blister, abrasion, or other injury to a human or animal. The base layer may be a polymeric nonwoven material or comprise a cellulose based mesh fabric. To add antimicrobial and wound healing efficacy to the base layer, the base layer may comprise particles comprising a water insoluble antimicrobial metal particles that release antimicrobial ions and particles comprising a boric compound. The total concentration of the particles in the base layer may be in a concentration from 0.01 wt. % to 10.0 wt. % embedded in the polymer, for example. The concentration of the particles may be any concentration effective to provide an antimicrobial efficacy and/or therapeutic efficacy as described herein. For example, the base layer may comprise between 0.1 wt. %and 2.0 wt. % (such as 1 wt. %) of cuprous or cupric oxide and between 0.1 wt. % and 2.0 wt. % (such as 1 wt.%) of zinc borate. The thickness of the base layer may be between 3 to 5 mm. The top layer may comprise antimicrobial efficacy. For example, the top layer may be made of nonwoven polypropylene fabric impregnated with a concentration between 0.2 wt. % and 3.0 wt. % (such as 1.5 wt. %) particles of a metal compound such as cuprous oxide and a concentration between 0.2 wt. % and 3.0 wt. % (such as 1.5 wt. %) of a boric compound such as zinc borate. The average particles size of the particles incorporated into the top layer may be in the range of 1 to 5 pm for both cuprous oxide and zinc borate powders.

Optionally, the top layer may be covered with a semi-liquid or a viscous liquid layer to prevent tissue adhesion to the top layer. Examples of the semi-liquid and the viscous liquid include Vaseline, polymeric wax, grease, petrolatum, and hydrogels. The semi-liquid and the viscous liquid layer may or may not comprise antimicrobial efficacy. For example, the semi-liquid and the viscous liquid layer may be impregnated with a concentration between 0.1 wt. % and 1.0 wt. % (such as 0.5 wt. %) particles of a metal compound such as cuprous oxide and a concentration between 0.1 wt. % and 1.0 wt. % (such as 0.5 wt. %) of a boric compound, such as zinc borate. The average particles size of the particles incorporated into the semi-liquid and viscous liquid may be in the range of 1 to 10 pm for both cuprous oxide and zinc borate powders.

The assembly of layers designed to manage fluid and wound exudate in, on and around the wound site to manage anti-microbial burden and enhance wound healing from the managed deposition of metal ions in, on and around the microenvironment of the surface.

Filter Media, Structure and Assembly

Filter media is used to remove particle matters and contaminants from an gas or liquid stream. Antimicrobial filter media may also provide antimicrobial efficacy to the filter media. Embodiment could be a portion of a device, part, or product intended to play a role in the treatment, management, change, or modification of the gas, fluid, or semi-solid moving through it,

The embodiment may be designed re-usable and washable, re-usable and non-washable, or disposable with inherent antimicrobial or material preservation protection properties.

In one embodiment, a disposable nonwoven polymer (such as polypropylene) commercial or residential air conditioner filter media comprising between 0.5 wt. % to 1.5 wt. % antimicrobial metal compound (such as cuprous oxide) and 1 wt. % to 2 wt. % of boric compounds (such as zinc borate), and, optionally, a polymer wax. The filter may be a single layer filter for lower air flow resistance or a multiple layer filter for better filtration capability. The average particle size may be between 1 to 5 pm for both cuprous oxide and zinc borate powders. Optionally, the filter may also comprise 0.1 wt. % to 0.5 wt. % pH adjuvant may be added to the material.

The filter assembly of layers may be designed to retard transmission of pathogenic material or material degrading organisms across environments from the same by the managed deposition of metal ions in, on and around the microenvironment of the surface.

EXAMPLES

Zone of Inhibition (ZOI)

Materials. Cupron copper oxide (Cu2O) particles were supplied by Cupron, LLC. Antimony oxide (Antimony (III) oxide, Sb2O3, 99%), molybdenum oxide (molybdenum (VI) oxide, MoO3, 99.5%), sodium borate (sodium tetraborate, Na2B4O7, 99.5%), boric acid (H3BO3, 99.5%), zinc oxide (ZnO, 99.5%), sodium molybdate (sodium molybdate (VI) dihydrate, Na2MoO4-2H2O, 99%), calcium chloride (CaCI2, 97%) sodium citrate (Na3C6H5O7, lab grade), magnesium sulfate (magnesium sulfate, heptahydrate, MgSO4-7H2O, 99%), basic copper(ll) carbonate (BCC) were purchased from Fisher. Zinc chloride (ZnCI2, 98%) and zinc bromide (ZnBr2, 98%) were bought from Thermo Scientific. Zinc sulfate (zinc sulfate monohydrate, ZnSO4 H2O) was obtained from Alpha Chemicals. Zinc borate (Firebrake ZB) was provided by U.S. Borax. Microcrystalline cellulose powder was purchased from LFA Tablet Presses Store. Aspartic acid (98%) was purchased from Acros organics. Molybdic acid, Potassium borate, Chromium(lll) chloride, Chromium(VI) oxide, Molybdenum(V) chloride, Molybdenum disulfide, Chromium(lll) hydroxide were bought from Fisher. All the chemicals were used as received.

Sample preparation. Sample pellets were made from the chemical powders using an DABPRESS 4-ton hydraulic press. The weight percentage of each powder component is specified in Table 1 and 2. Microcrystalline cellulose powder (20 wt%) was added as a binding agent. The chemical powders were mixed by vortexing for 20 s to ensure mixing. Then, 0.2 g powder blend was added to each hole of a 12 holes aluminum tablet mold (hole diameter = 10 mm). The tablet mold was then pressed by using the hydraulic press to yield sample pellets.

Zone of Inhibition (ZOI). E. coli (ATCC 8739) were used for the ZOI tests. The cultures were streaked on Luria Agar (LB) plates and incubated overnight at 37 ⁹C. A single colony was used to inoculate 10 mL of nutrient broth (NB) and grown overnight at 37 ⁹C with rocking and a stock suspension of (~109) colony-forming units per milliliter (CFU/mL) was obtained. 50 pL of this stock suspension was spread homogeneously on a trypticase soy agar (TSA) plate (diameter 10 cm). Sample pellets ^triplicates) containing copper oxide and the adjuvants were then placed on the agar and incubated for 24 h at 37 °C. The diameter of the inhibition zones around the sample pellets were measured using a ruler and the results are summarized in Table 1 and 2.

Results. As a screening test, Cupron copper oxide particles and its blends with 14 different adjuvants were investigated in the ZOI study to explore the potential synergy for antimicrobial effectiveness. The results of this study are summarized in Table 1. The diameter of the ZOI for copper

Table 1. ZOI test results for the blends of copper oxide and various adjuvants against E. coli, after 24 h incubation at 37 °C. The mix ratio of copper oxide to adjuvant was 2 to 1. Cellulose was used a binder.

oxide alone was found to be 13 mm against E. coli after 24 h incubation at 37 °C. Significant increased ZOI dimension was observed when copper oxide was blended with molybdenum oxide, sodium borate, borate acid, zinc chloride, zinc bromide, zinc sulfate, calcium chloride, molybdic acid, potassium borate, chromium(lll) chloride, chromium(VI) oxide, molybdenum(V) chloride, and molybdenum disulfide, suggesting that these chemicals improved the antimicrobial effectiveness of copper oxide against E. coli. No effect on the ZOI diameter was found for antimony oxide, zinc borate, zinc oxide, sodium molybdate, sodium citrate, magnesium sulfate, aspartic acid, and chromium(lll) hydroxide. These results suggested that (1) molybdenum oxide, chromium(lll) chloride, chromium(VI) oxide and molybdenum(V) chloride may improve the copper ion release by reducing the environmental pH. (2) Zinc borate alone had no impact on the antimicrobial effectiveness of copper oxide. However, the hydrolyzation products of zinc borate in an acidic environment, including boric acid, zinc chloride, zinc bromide and zinc sulfate, improved the antimicrobial effectiveness of copper oxide significantly. (3) Sodium borate and potassium borate, as basic salts, improved the antimicrobial effectiveness of copper oxide, indicating that borate ion has synergistic effect with copper oxide that resulted in a greater antimicrobial effectiveness. Thus it is not necessary to reduce the pH in order to enhance the antimicrobial effectiveness of Cupron copper oxide. Beside the results discussed above, calcium chloride and molybdenum disulfide were also found to increase the diameter of ZOI when blended with copper oxide. Future studies are needed to find out the reason of this result.

The results described above suggested that the hydrolyzation products of zinc borate in acidic environments improved the antimicrobial effectiveness of copper oxide. It has been reported that molybdenum oxide reacts with water and reduces the environmental pH. Thus, the presence of molybdenum may create a desirable environment for the hydrolyzation of zinc borate, and hence a synergy on antimicrobial effectiveness may exist among copper oxide, molybdenum oxide and zinc borate. To validate this theory, the ZOI study shown in Table 2 was carried out. The diameter of the ZOI for was found to be 13 mm and 19 mm for copper oxide and molybdenum oxide respectively. No ZOI was observed for zinc borate. The blends of copper oxide and zinc borate had 12 to 13 mm ZOI with zinc borate content ranging from 20% to 70% (Table 2, Test # 4, 7, 10 and 13), indicating that zinc borate alone does not affect the antimicrobial effectiveness of copper oxide in this study. The ZOI for the blends of copper oxide and molybdenum oxide were larger than the that for copper oxide alone, and the ZOI dimension increased with increasing molybdenum oxide content (Table 2, Test # 5, 8, 11 and

Table 2. ZOI test results for the blends of copper oxide, zinc borate and molybdenum oxide against E. coli, after 24 h incubation at 37°C. Cellulose was used as a binder.

14). Remarkably, the largest ZOI was observed for the blends of copper oxide, molybdenum oxide and zinc borate, particularly for the blends with higher contents of molybdenum oxide and zinc borate (Table 2, Test # 9, 12 and 15). The result confirmed the synergistic effect among copper oxide, zinc borate and molybdenum oxide on the antimicrobial effectiveness against E. coli. To extend the field of application to the synergy described above, BCC was used as a

Table 3. ZOI test results for the blends of basic copper(ll) carbonate (BCC), antimony oxide, zinc borate and molybdenum oxide against E. coli, after 24 h incubation at 37°C. Cellulose was used as a binder.

replacement for copper oxide in the ZOI study. As shown in Table 3, BCC was blended with antimony oxide, zinc borate and molybdenum oxide and the diameter of ZOI for the blends was measured. The diameter of the ZOI for was found to be 12 mm for BCC alone. The blends of BCC and antimony or zinc borate had 11 mm ZOI (Table 3, Test # 2 and 3), indicating that zinc borate or antimony oxide does not affect the antimicrobial effectiveness of BCC in this study. The ZOI for the blends of copper oxide and molybdenum oxide were found to be much larger (20 mm, Table 3, Test # 4)) than the that for BCC alone (11 mm, Table 3, Test # 1). BCC was then blended with the mixture of antimony oxide and zinc borate (Table 3, test # 5), the mixture of antimony oxide and molybdenum oxide (Table 3, Test # 6) and the mixture of zinc borate and molybdenum oxide (Table 3, Test # 7). No noticeable changed of ZOI (11 mm) was observed for BCC after blended with antimony oxide and zinc borate. The blend of BCC with antimony oxide and molybdenum oxide had a ZOI diameter of 18 mm, which is larger than the ZOI diameter for BCC alone but smaller than the blend of BCC and molybdenum. This result suggested that the enlarged ZOI for the blend of BCC with antimony oxide and molybdenum is mainly attributed to the synergy between BCC and molybdenum, but the addition of antimony oxide had no significant synergistic effect with BCC or molybdenum for the antimicrobial effectiveness. The largest ZOI was observed for the blend of BCC with the mixture of zinc borate and molybdenum oxide (25 mm, Table 3, Test # 7), which indicated that zinc borate and molybdenum oxide could synergy with various copper compounds to result in a greater antimicrobial effectiveness. At last, BCC was blended with the mixture of antimony oxide, zinc borate and molybdenum oxide. The addition of antimony oxide slightly reduced the size of ZOI to 22 mm, indicating that antimony oxide does not improve the antimicrobial effect for copper compounds.

Fabric sample preparation

The compositions of the PET fibers embedded with copper oxide particles, zinc borate particles and molybdenum oxide particles are summarized in Table 4. The fibers were produced through melt extrusion. These fibers were brought together to from yarn. As the fibers were brought together to form the yarns they were air-cooled/quenched to solidify the yarns. The yarns were knitted into 4" wide sleeves using a Lawson knitter.

Anti-mold study 1

Experimental. To assess their performance against Aspergillus Niger (AN) mold spores, 2x2" samples of polyethylene terephthalate (PET) fabric

were carefully cut from Lawson sleeves.

These fabric samples curled along their length and formed stripe shape. Samples #4, 7, 8, 10, 11, 12 and the untreated PET control were involved in this test. Table 4. AN was inoculated on Trypticase soy agar (TSA) and was incubated at 37°C. After 2 weeks of growth, the spores were harvested by placing 15 mL DI water in the TSA plates and gently scraping the agar surface with a L-shaped cell spreader. The spore suspension was transferred to a test tube and diluted 10 times in sabouraud dextrose broth (SDB) to generate a stock suspension. The stock suspension (5pL) was inoculated on each TSA plate and was carefully spread on the entire surface. The PET fabric samples were placed on the inoculated TSA plates. 200 pL stock suspension was then carefully added on the fabric sample surfaces drop wisely. Efforts were made to ensure the uniform distribution of stock suspension distribute on the sample surfaces. The samples were inoculated at 37°C for 1 month to evaluate the fabric's effectiveness in inhibiting mold growth. After the incubation period, a rating scale between 0-4 determines the antifungal efficacy of tested materials. Ratings are described as below. 1 0 - No growth on the specimen

1 - Traces of growth on the specimen (less than 10 %)

2 - Light growth (10 to 30 %)

3 - Medium growth (30 to 60 %)

4 - Specimens completely covered with growth (60 %)

Results. The images of AN mold growth on PET sample Table 5. PET fabric sample surfaces before and after 4-week incubation are shown in Figure compositions and their antimold rate. 1. The compositions of the samples are specified in Table 4, and their corresponding anti-mold rates are summarized in Table 5. Figure 1 clearly demonstrates that the untreated PET control sample was heavily contaminated with AN mold after the 4-week incubation period (Figure 1, Al and Bl). The surface of the control sample was completely covered with black AN mold, thus warranting an anti-mold rate of 4 for the untreated PET control (Table 5). However, PET fabrics embedded with 1% copper oxide (Table 5, Sample #4) or 1% zinc borate (Table 5, Sample #7) exhibited improved anti-mold effectiveness. Although both Sample #4 and Sample #7 displayed noticeable mold growth on

their surfaces, it was significantly less compared to the untreated

control. (Figure 1, A2 and B2, A3 and B3) Therefore, an anti-mold rate of 2 was assigned to both Sample #4 and Sample #7 in Table 5. Sample #8, containing 0.5% copper oxide and 0.5% zinc borate, performed better than Sample #4 and Sample #8 in terms of mold resistance. As shown in Figure 1A4 and 1B4, Sample #8 did not completely stop the mold overgrowth, but it was barely noticeable after 4-week incubation was barely noticeable. As a result, an anti-mold rate of 1 was assigned to Sample #8. The introduction of molybdenum oxide further enhanced the anti-mold properties. Sample #10, comprising 0.1% copper oxide, 0.6% zinc borate, and 0.3% molybdenum oxide, performed similarly to Sample #8 (Figure 1, A5 and B5), achieved an anti-mold rate of 1. Furthermore, Sample #11 and Sample #12, which both contained zinc borate and molybdenum oxide but had a higher copper oxide content compared to Sample #10, attained an anti-mold rate of 0. Remarkably, there was no noticeable AN overgrowth observed on Sample #11 and #12 after the 4-week incubation period. (Figure 1, A6 and B6, A7 and B7) To summarize, the combination of zinc borate with copper oxide significantly improved the overall anti-mold properties of PET fabric samples. This was evident in the results, where the PET sample containing 0.5% copper oxide and 0.5% zinc borate outperformed the samples with either 1% copper oxide or 1% zinc borate alone in preventing AN mold overgrowth. These findings suggest a synergistic effect between copper oxide and zinc borate in inhibiting AN mold growth. Furthermore, the addition of molybdenum oxide further enhanced the resistance of the samples to mold growth. PET fabric samples with 0.3% molybdenum oxide, 0.6% zinc borate, and 0.3% or higher copper oxide were able to completely prevent AN mold overgrowth throughout the duration of the study.

In conclusion, incorporating zinc borate alongside copper oxide in PET fabric samples showed significant improvements in their anti-mold properties, and the inclusion of molybdenum oxide further enhanced their effectiveness in inhibiting mold growth. These findings highlight the potential of these additives in developing mold-resistant PET fabrics.

Anti-mold study 2

Experimental. 1" long samples of PET fabric were carefully cut from Lawson sleeves and were placed in 20 mL clear sample vials with caps. Samples #3, 5, 6, 9 in Table 4 and the untreated PET control were involved in this test. AN was inoculated in Sabouraud Dextrose Broth (SDB) and was incubated at 37°C. After 1 weeks of growth, the AN suspension was transferred to a test tube and diluted 10 times in sabouraud dextrose broth (SDB) to generate a stock suspension. The stock suspension (5mL) was carefully spread on the entire sample surface. The caps of the vials were loosely closed to allow air exchange. The samples were inoculated at 22°C for 1 week to evaluate the fabric's effectiveness in inhibiting AN mold growth.

Results. The effectiveness of PET fabric samples in preventing mold growth is illustrated in Figure 2. After a 1-week incubation at 22°C, notable mold growth was observed in several samples, including the untreated PET control, Samples #3, #5, and #6 (Figure 2). These samples also exhibited evidence of spore generation, indicated by the presence of black spots. This suggests that using copper oxide or zinc borate alone is insufficient to inhibit AN mold growth in the tested conditions, and in fact, copper oxide even seemed to encourage spore production while zinc borate only partially reduced it.

In contrast, Sample #9 showed only minor mold growth, with no black spore generation detected. This indicates that the combination of copper oxide and zinc borate in Sample #9 is more effective at preventing AN mold growth at 22°C than using either copper oxide or zinc borate in isolation. These findings align with the results from a previous anti-mold study (referred to as "anti-mold study 1" in the passage), indicating a consistent pattern of synergy between copper oxide and zinc borate in inhibiting AN mold growth.

In summary, the combination of copper oxide and zinc borate demonstrates superior anti-mold properties compared to using either substance alone. This suggests a synergistic effect between copper oxide and zinc borate, making them a promising choice for preventing AN mold growth in PET fabric samples at 22°C.

Ion release study

containing 0.6% zinc borate, 0.3% molybdenum oxide and various copper oxide content have 4.7, 11.6 and 15.9 ppm copper ion released from one gram of sample. Copper ion release rate increased with increasing copper oxide content. Additionally, Test Samples #1, #2, and #3, which contained only copper oxide, released copper ions at rates of 5.1, 9.8, and 10.6 ppm per gram of the sample. This finding demonstrated that the release rate of copper ions increased with higher copper oxide content, regardless of the presence of zinc borate or molybdenum oxide.

Interestingly, Sample #11, which contained 0.3% copper oxide along with zinc borate and molybdenum oxide, exhibited a copper ion release rate of 11.6 ppm per gram, which was 18% higher than that of Sample #2 containing the same amount of copper oxide but without zinc borate and molybdenum oxide. A similar trend was observed for samples with higher copper oxide content. For instance, Sample #12, which contained 0.6% copper oxide along with zinc borate and molybdenum oxide, had a copper ion release rate of 15.9 ppm per gram, which was 50% higher than that of Sample #3 with 10.6 ppm/g copper ion release rate. Except for the samples with 0.1% copper oxide, the addition of zinc borate and molybdenum oxide accelerated the release of copper ions in samples with 0.3% and 0.6% copper oxide. Overall, the results suggested that the presence of zinc borate and molybdenum oxide positively influenced the release of copper ions, leading to higher release rates compared to samples without these additives, especially at higher copper oxide concentrations.

Antimicrobial study 1

All polymeric samples were evaluated using ISO - 22196 test method for antimicrobial efficacy.

For antimicrobial efficacy testing, 1-inch x 1-inch samples were cut from the PET fabric Lawson sleeves.

The log Reduction values are calculated as per the calculations below:

Log Reduction = Log_w [CFU_COntroi at 2-hour] - Logio [CFU_Sam_Pie at 2-hour]

Results. Table 7 summarizes the antimicrobial effectiveness against E. coli under various test conditions. When incubated at 37°C and using a 5% nutrient broth (NB) in saline inoculation carrier, Sample #1 containing 0.1% copper oxide (without zinc borate or molybdenum) showed a 4.9 log reduction in E. coli bacteria. However, when 0.6% zinc borate and 0.3% molybdenum oxide were added to Sample #1 (creating Sample #10), the efficacy of the substrate increased to greater than 6.9 log reduction, an improvement of over 2.0 log reduction. Similar trends were observed for Sample #2 with 0.3% copper oxide, achieving a 6.7 log reduction, and Sample #11 with 0.3% copper oxide, 0.6% zinc borate, and 0.3% molybdenum oxide, demonstrating greater than 6.9 log reduction. Sample #3 and Sample #12 both achieved greater than 6.9 log reduction, which is the detection limit of this test. These results suggest that the presence of zinc borate and molybdenum oxide enhanced the antimicrobial effectiveness against E. coli at 37°C with a 5% NB in saline inoculation carrier, particularly at lower copper oxide concentrations.

When using a 5% trypticase soy broth (TSB) in saline inoculation carrier, Sample #1 with 0.1% copper oxide (without zinc borate or molybdenum) displayed a 1.6 log reduction against E. coli bacteria. However, upon adding 0.6% zinc borate and 0.3% molybdenum oxide to Sample #1 (creating Sample #10), the efficacy of the substrate increased to a 3.2 log reduction, an improvement of 1.6 log reduction. A similar trend was observed for Sample #2 with 0.3% copper oxide and Sample #3 with 0.6% copper oxide, achieving 3.3 and 6.2 log reductions, respectively. Additionally, Sample #11 and #12 with zinc borate and molybdenum oxide adjuvants demonstrated greater than 6.5 and 6.4 log reductions, respectively. Again, these results indicate that the presence of zinc borate and molybdenum oxide enhanced the antimicrobial effectiveness against E. coli at 37°C with a 5% NB in saline inoculation carrier.

To understand the influence of zinc Table 8. Antimicrobial effectiveness using various borate to antimicrobial effectiveness, pathogens at 21 °C in synthetic sweat. antimicrobial study was carried out on Samples #3, 5, and 9 at 21 C in synthetic sweat, which contains 0.5 g/L L- histidine:HCI:H₂O, 5 g/L NaCI, 2.2 g/L Na2PO4 12H₂O, and 15mL/L 0.1M NaOH. PH was adjusted to 5.5 with HCI before using. As shown in Table 8, all the test samples achieved greater than 3 log reduction for E. coli and greater than 5 log reduction for P.

aeruginosa. Negligible difference between

samples with copper oxide only (Samples #3 and 5) and samples with copper oxide and zinc borate was found for E. coli and P. aeruginosa. However, the addition of zinc borate appeared to reduce the antimicrobial efficacy against S. aureus under the same test condition. Sample #9 with 0.6% copper oxide and 0.6% zinc borate had 3.7 log reduced against S. aureus. This is 1 log lower than Sample #3 with 0.6% copper and 1.4 log lower than Sample #5 with 1.2% copper oxide. Further studies are required to understand why the antimicrobial efficacy was comprised by the addition of zinc borate.

In conclusion, the presence of zinc borate and molybdenum oxide adjuvants enhanced the antimicrobial effectiveness against E. coli at an elevated temperature of 37 °C, but the addition of zinc borate alone was not able to achieve the same effect at ambient temperature.

Antimicrobial study 2

Experimental. To determine the antimicrobial efficacy on different polymer substrates, PVC chip samples were prepared via injection moulding process. Sample compositions are specified in Table 9. Prior to experimentation, all test samples (1" x 1") were sterilized under UV in a biosafety safety cabinet for 1 h on each side. Test pathogen

was inoculated in growth medium and allowed to grow to saturation in an orbital shaker for 24 h at 37

°C. Afterwards, the pathogen suspension was diluted to ~1.0e8 CFU/mL in an inoculum carrier (IC) containing 5 wt.% M3 broth, 0.89 wt.% NaCI, and 0.05 wt.% triton. Two labeled petri dishes per sample with foam inserts were pretreated with 1.5 mL sterilized DI water. Then a PVC sample chip was placed on top of the pretreated foam. Twenty microliters of bacteria-containing IC were then pipetted onto the center of each test sample. A plastic coverslip (22 mm) was then placed on top and pressed gently to spread IC. The petri dishes were then covered and placed in an incubator for 2 h at 37 °C. After the incubation period, the petri dishes were removed and the test samples with coverslips were placed in individual 50 mL conical centrifuge tubes containing 17.5 mL of Letheen broth. The 50 mL conical centrifuge tubes were vortexed for 2 min and then solutions were serial diluted and plated on nutrient agar. Agar plates were then placed in an incubator for 24 h at 37 °C and then colonies were counted.

Results. As presented in Table 9, Sample #16, which included both copper oxide and zinc borate, demonstrated notable reductions: a 3.4 log reduction for E. coli, a 5 log reduction for S. aureus, and a 4.5 log reduction for P. aeruginosa. These outcomes surpass the performance of Sample #14 (containing only copper oxide) and Sample #15 (containing only zinc borate). The data suggest a synergistic antimicrobial effect when copper oxide and zinc borate are combined on the PVC substrate. Color shift

Color analysis was conducted using a Konica Minolta chroma meter CR-410, which was first calibrated

Table 10. Chroma meter results. on a completely white surface prior to

the measurements. The summarized results can be found in Table 10, with L*, a*, and b* representing the three values used to objectively measure color and calculate color variations. L* quantifies the degree of lightness on a scale from zero to 100, spanning from black to white, while a* and b* denote chromaticity without specific numerical boundaries. Negative a* values correspond to green hues, positive a* values indicate red hues, negative b* values signify blue hues, and positive b* values represent yellow hues. Delta (A) signifies the disparities between the tested surface and a pure white reference. AE* serves as a comprehensive measure of the overall difference between the tested surface and a pure white reference, calculated using the following equation:

AE* = ((AL*)² + (Aa*)² + (Ab*)²)^1/2

As shown in Table 10, Sample #9, which contains 0.6% copper oxide and 0.6% zinc borate, exhibits the highest brightness (L* ). Sample #12 displays the lowest a* and b* values, implying that the inclusion of 0.6% zinc borate and 0.3% molybdenum oxide effectively mitigated color shifts of copper oxide towards redness and yellowness. Moreover, when considering the overall color shift (AE*), it becomes evident that Samples #9 and #12 exhibit substantially lower values compared to Samples #3 and #5. This suggests that the introduction of zinc borate and molybdenum oxide has a significant impact in reducing the color shifts caused by the presence of copper oxide.

Color stability to oxidation

For the investigation of color stability in PET fabric samples, Sample #5 and Sample #12 from Table 4 were selected. The study aimed to assess the effects of a strong oxidizing agent on the color stability of these samples. Specifically, Sample #5 (1.2% copper oxide) and Sample #12 (0.6% copper oxide content with 0.6% zinc borate and 0.3% molybdenum oxide) were subjected to an aging process using 10% H₂O₂.

During the experiment, both Sample #1 and Sample #6 were boiled in 10% H2O2 for 3 minutes, followed by soaking in 10% H2O2 at 37 °C for 3 days. It was observed that both Sample #5 and Sample #12 experienced shrinkage during the boiling process. Before the aging process, Figure 3 shows that the as-received Sample #5 had a pinkish red color. However, after undergoing the aging process, the color of Sample #5 shifted to pinkish grey. On the other hand, there was no noticeable color shift observed for Sample #12 after the aging process. This suggests that the combining copper oxide with zinc borate and molybdenum oxide contributed to the improved color stability of the PET fabric, as it remained unaffected by the oxidizing agent.

Claims

1. An antimicrobial textile fabric for combating nosocomial and other infections, comprising: antimicrobial polymeric fibers , wherein the antimicrobial fibers comprise: a polymer; particles comprising water insoluble antimicrobial metal compound that release antimicrobial ions upon contact with a fluid; and particles comprising boric compounds embedded in the polymer.

2. The antimicrobial textile fabric of claim 1, wherein polymer is at least one of natural fibers, synthetic cellulosic fibers, regenerated protein fibers, acrylic fibers, polyester fibers, nylon, polypropylene, polyethylene terephthalate, polyolefin fibers, polyurethane fibers, vinyl fibers, and blends thereof.

3. The antimicrobial textile fabric of claim 1, wherein polymer is at least one of polyurethane, polyolefins, nylon, polypropylene, polyethylene and combinations thereof.

4. The antimicrobial textile fabric of claim 1, comprising particles comprising a pH adjuvant.

5. The antimicrobial textile fabric of claim 4, wherein the pH adjuvant is one of a compound that produces an acidic environment on contact with water, acidic oxide, acidic salt, molybdenum oxide, chromium oxide, chromium chloride, molybdenum chloride, and combinations thereof.

6 The antimicrobial textile fabric of claim 1, wherein the particles comprising the boric compound also produce an antimicrobial metal ion upon contact with water.

7. The antimicrobial textile fabric of claim 1, wherein the particles comprising the boric compound at least one of metal borate, boric acid, sodium borate, a compound that produces an antimicrobial metal ion and boric acid on contact with water, sodium borate, potassium borate, zinc borate, and combinations thereof.

8. The antimicrobial textile fabric of claim 1, wherein particles comprising the boric compound are zinc borate particles.

9. The antimicrobial textile fabric of claim 1, wherein the particles comprising water insoluble metal compounds that release antimicrobial ions upon contact with a fluid comprise at least one of copper oxide, copper chlorides, cuprous oxide, cupric oxide, copper iodides, copper carbonates, silver oxide, silver chlorides, zinc oxide, zinc chlorides, zinc pyrithione, gold oxide, or combinations thereof.

10. The antimicrobial textile fabric of claim 1, comprising particles comprising a pH adjuvant, wherein the particles comprising water insoluble metal compounds that release antimicrobial ions upon contact with a fluid is a copper oxide particles and the particles comprising the boric compounds are zinc borate particles.

11. The antimicrobial textile fabric of claim 10, the pH adjuvant is molybdenum oxide.

12. The antimicrobial textile fabric of claim 10, wherein the particles comprising water insoluble antimicrobial metal compound that release antimicrobial ions upon contact with a fluid are in a concentration from 0.01 wt. % to 5 wt. % embedded in the polymer; and the particles comprising boric compounds embedded in the polymer are in a concentration from 0.05 wt.% to 15 wt.%.

13. A method of producing antimicrobial textile fabric, comprising: preparing antimicrobial textile fabric from polymeric fibers comprising particles comprising water insoluble metal compounds that release antimicrobial ions upon contact with a fluid in a concentration embedded in a polymer and boric acid particles or particles comprising a boric compound embedded in the polymer.

14. The method of producing antimicrobial textile fabric of claim 13, wherein polymer is at least one of polyester, nylon, polypropylene, polyethylene.

15. The method of producing antimicrobial textile fabric of claim 13, wherein the polymeric fiber further comprises a pH adjuvant.

16. The method of producing antimicrobial textile fabric of claim 13, wherein the particles comprising water insoluble metal compounds are copper oxide particles and the particles.

17. An antimicrobial fiber, yarn, film, or textile, comprising: a polymeric substrate; particles comprising water insoluble metal compounds that release antimicrobial ions upon contact with a fluid in a concentration from 0.01 wt. % to 10 wt. % embedded in the polymer substrate; and particles comprising a boric compound embedded in the polymer substrate.

18. The antimicrobial fiber, yarn, film, or textile of claim 17, wherein polymer is at least one of natural fibers, synthetic cellulosic fibers, regenerated protein fibers, acrylic fibers, polyester fibers, nylon, polypropylene, polyethylene terephthalate, polyolefin fibers, polyurethane fibers, vinyl fibers, and blends thereof.

19. The antimicrobial fiber, yarn, film, or textile of claim 17, wherein polymer is at least one of nylon, polypropylene, polyethylene.

20. The antimicrobial fiber, yarn, film, or textile of claim 17, comprising a pH adjuvant, wherein the pH adjuvant is a compound that produces an acidic environment on contact with water.

21. The antimicrobial fiber, yarn, film, or textile of claim 20, wherein the compound that produces an acidic environment on contact with water is one of acidic oxide, acidic salt, molybdenum oxide, chromium oxide, chromium chloride, molybdenum chloride, and combinations thereof.

22. The antimicrobial fiber, yarn, film, or textile of claim 17, wherein the particles comprising a boric compounds embedded in the polymer are in a concentration from 0.05 wt.% to 15 wt.%.

23. The antimicrobial fiber, yarn, film, or textile of claim 17, wherein the particles comprising a boric compound is at least one of metal borate, sodium borate, a compound that produces an antimicrobial metal ion and boric acid on contact with water, sodium borate, potassium borate, zinc borate, and combinations thereof.

24. The antimicrobial fiber, yarn, film, or textile of claim 17, wherein particles comprising a boric compound are particles comprising zinc borate.

25. The antimicrobial fiber, yarn, film, or textile of claim 17, wherein the particles comprising water insoluble metal compounds that release antimicrobial ions upon contact with a fluid comprise at least one of copper oxide, copper chlorides, cuprous oxide, cupric oxide, copper iodides, copper carbonates, silver oxide, silver chlorides, zinc oxide, zinc chlorides, zinc pyrithione, gold oxide, or combinations thereof.

26. The antimicrobial fiber, yarn, film, or textile of claim 17, comprising the particles comprising a boric compound, wherein the particles comprising water insoluble metal compounds that release antimicrobial ions upon contact with a fluid is a copper oxide particles and the particles comprising a boric compound are zinc borate particles.

27. The antimicrobial fiber, yarn, film, or textile of claim 20, comprising molybdenum oxide.

28. A method of producing the antimicrobial fibers or yarns of claims 1 to 27, comprising: preparing a polymeric slurry comprising a plurality of antimicrobial particles in a polymeric resin, wherein the antimicrobial particles comprise water insoluble antimicrobial metal compound that release antimicrobial ions upon contact with a fluid and particles comprising a boric compound; filtering the slurry to remove any large particles that cause processing problems; and spinning the slurry to form a polymeric material wherein the particles are incorporated in the polymer, wherein a portion of the particles in the polymer are exposed and protruding from the surface of the material and release antimicrobial metal ions when exposed to water or water vapor to provide the antimicrobial activity of the polymeric material.