CN120916642A

CN120916642A - Antimicrobial molded polymer articles, extruded polymer articles, and film polymer articles containing synergistic component blends.

Info

Publication number: CN120916642A
Application number: CN202480020683.9A
Authority: CN
Inventors: 王晨宇; V·卡姆卡拉
Original assignee: Kopilong Performance Additive Co
Current assignee: Kopilong Performance Additive Co
Priority date: 2023-02-08
Filing date: 2024-02-07
Publication date: 2025-11-07
Also published as: WO2024168052A1; WO2024168041A2; WO2024182104A1; IL322568A; WO2024168063A1; AU2024218475A1; WO2024168067A1; IL322567A; CN121152561A; EP4661669A2; WO2024168046A1; EP4662360A1; WO2024168041A3; EP4661670A1; EP4661676A1

Abstract

The molded polymeric articles, extruded polymeric articles, and polymeric films or coatings comprise a mixture of at least one antimicrobial metal compound and at least one synergistic compound. For example, the molded polymeric article, the extruded polymeric article, and the polymeric film or the coating may comprise a mixture or liquid dispersion of at least one antimicrobial metal compound and a boron compound, powder, blended into a masterbatch. These polymeric articles may further comprise at least one pH adjuvant that creates an acidic environment inside or outside of the composition. It has surprisingly been found that these components create a synergistic relationship within the composition that provides a more tailored antimicrobial polymer composition or article.

Description

Antimicrobial molded polymeric articles, extruded polymeric articles, and film polymeric articles comprising synergistic component blends

Technical Field

Antibacterial articles and compositions include, but are not limited to, molded polymeric articles, extruded polymeric articles, and polymeric films or coatings. Molded polymeric articles, extruded polymeric articles, and polymeric films or coatings may be produced from thermoplastic polymers or thermosetting polymers. The antimicrobial molded polymeric articles, extruded polymeric articles, and polymeric films or coatings may comprise a mixture of at least one antimicrobial metal compound and a synergistic compound. For example, in one embodiment, the antimicrobial molded polymeric article, the extruded polymeric article, and the polymeric film or coating may comprise a polymeric substrate, particles comprising at least one antimicrobial metal compound, and particles comprising a boron compound. The composition may further comprise at least one pH adjuvant that creates an acidic environment within the composition. The inventors have surprisingly found that these components create a synergistic relationship within the composition that provides a more tailored, lower cost and/or higher efficacy antimicrobial polymer composition or article.

An embodiment of a method of producing a molded polymeric article, an extruded polymeric article, and a polymeric film or coating may comprise blending at least one antimicrobial metal compound, at least one boron compound, and optionally at least one pH adjuvant in a polymeric resin, extruding or molding the resin to produce an antimicrobial polymeric article. Another method comprises blending at least one antimicrobial metal compound, at least one boron compound, and optionally at least one pH adjuvant in the components of the polymerization reaction (such as monomers, oligomers, or other raw materials) and extruding or molding the reaction mixture as the crosslinking reaction occurs.

Background

The metal oxide or other antimicrobial metal compound includes, but is not limited to, copper oxide, copper iodide, copper carbonate, silver oxide, silver iodide, zinc oxide, silver chloride, zinc pyrithione, gold oxide, or combinations thereof. Such antibacterial metal compounds have broad-spectrum antibacterial properties and have been shown to have antifungal, antibacterial, and antiviral properties. Copper and its compounds may be present in articles, liquid coatings and paints, plastic components, and polymeric materials to impart durable and long-lasting antimicrobial activity to various substrates.

There is a need for an antibacterial, antiviral and/or antifungal agent that is effective, processable, and has other advantageous properties for the production of antibacterial compositions and articles.

Disclosure of Invention

The polymer may be extruded or molded to produce polymeric articles such as, but not limited to, molded polymeric articles, extruded polymeric articles, and polymeric films or coatings. Molding processes for producing polymeric articles include, but are not limited to, extrusion molding, compression molding, blow molding, injection molding, and rotational molding. Thermoplastic or thermoset polymers may be extruded or molded to produce antimicrobial polymeric articles.

Any of these processes and polymers may also be used to create antimicrobial molded polymeric articles. An embodiment of a method for preparing an antimicrobial molded polymeric article may include preparing a polymeric slurry including a plurality of antimicrobial particles in a polymeric resin. The particles may comprise water insoluble particles comprising an antimicrobial metal compound and particles comprising a boron compound that release antimicrobial ions upon contact with a fluid. The method includes molding the slurry to form a molded polymer article, wherein particles are incorporated into the molded polymer. A portion of the particles in the polymer may be exposed and protrude from the surface of the material and release antimicrobial metal ions upon exposure to water or water vapor, thereby providing antimicrobial activity and efficacy to the molded polymeric material.

Similarly, an embodiment of a method for extruding an antimicrobial polymeric material may include preparing a polymeric slurry comprising a plurality of antimicrobial particles in a polymeric resin, wherein the particles comprise particles of a water insoluble antimicrobial metal compound that release antimicrobial ions upon contact with a fluid and particles of a boron compound, and extruding 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 protrude from a surface of the material and release the antimicrobial metal ions upon exposure to water or water vapor, thereby providing antimicrobial activity of the polymeric material. Methods for extrusion, molding, and film production are known in the art and may be used to produce antibacterial, antifungal, or antiviral articles comprising the synergistic compounds described herein.

In further embodiments, the antimicrobial extruded or molded particles comprise a polymer (thermoset or thermoplastic), particles embedded in the polymer that release antimicrobial ions upon contact with a fluid comprising a water insoluble antimicrobial metal compound, particles embedded in the polymer comprising a boron compound, and optionally particles comprising a pH adjuvant.

For example, water insoluble antimicrobial metal particles release antimicrobial metal ions at a rate and produce a certain antimicrobial efficacy upon contact with a fluid. The degree of antimicrobial efficacy may vary with the antimicrobial agent, the concentration of the antimicrobial agent in the article or composition, the environment to which the antimicrobial article is subjected, the physical and mechanical properties of the article, the inert ingredients in the article, and other factors. Such inherent antimicrobial efficacy, inherent antimicrobial durability, or concentration of antimicrobial compound necessary to provide the desired antimicrobial efficacy and/or antimicrobial durability in some applications of the composition or article may be needed or desired to be altered. Synergistic blends of particles comprising water insoluble antimicrobial metals, particles comprising boron compounds, and optionally a pH adjuvant can alter the release rate and efficacy of the antimicrobial article by providing a combination of antimicrobial metal ions, controlling the pH on the polymer surface upon contact with water, creating additional antimicrobial agents, and/or other chemical or mechanical alterations made to the article.

In one 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 the fluid and are embedded in the polymer, wherein a portion of the particles comprising the water-insoluble copper oxide are exposed and protrude from the surface of the polymer material. In such embodiments, the concentration of the water-insoluble copper compound may be from 0.1wt.% to 45wt.% of the antimicrobial article or composition. The water insoluble antimicrobial metal compound may include, but is not limited to, for example, copper oxide, copper chloride, cuprous oxide, cupric iodide, cupric carbonate, silver oxide, silver iodide, silver chloride, zinc oxide, zinc chloride, zinc pyrithione, gold oxide, or combinations thereof. In another embodiment, which is more advantageous for certain applications, the concentration of copper oxide or other antimicrobial metal compound may be from 0.2wt.% to 20wt.% of the weight of the article or the composition. Other embodiments may be based on silver compounds such as silver oxide and silver iodide.

Embodiments may also include particles comprising at least one boron compound. The at least one boron compound includes, but is not limited to, metal borates, boric acid, sodium borates, compounds that produce antibacterial metal ions and boric acid when contacted with water, sodium borates, potassium borates, zinc borates, and combinations thereof. The concentration of the boron compound may be from 0.05wt.% to 45wt.% based on the weight of the antimicrobial composition or the article.

The synergistic blend may also comprise particles comprising a pH adjuvant. The concentration of the pH adjuvant may be 0.01wt.% to 6.0wt.%, or in a more specific embodiment, the concentration of the pH adjuvant is 0.02wt.% to 2wt.%. In certain embodiments, the solid pH adjuvant particles are molybdenum oxide.

Embodiments of the antimicrobial molded article, extruded polymeric article, or film may comprise a polymer, water insoluble antimicrobial metal particles that release antimicrobial ions upon contact with a fluid, the concentration of the water insoluble antimicrobial metal particles being from 0.01wt.% to 6.0wt.%, the water insoluble antimicrobial metal particles being embedded in the polymer, a metal borate, and optionally 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 upon contact with water, thereby adjusting the release rate of the antimicrobial ions and controlling the decomposition of the metal borate.

Antimicrobial molded polymeric articles, extruded polymeric articles, and polymeric films comprising the synergistic component blends may include, but are not limited to, personal hygiene containers (bedpans, cups, hand basins, trays), air handling devices and components, appliances, automotive interiors and surfaces, bags (including clothing bags, trash bags, bedding bags, vacuum bags), barrier fabrics, bathroom fixtures and components, buckets, building materials and components (e.g., residential siding and commercial siding), carpet and mat components and assemblies, cleaning devices (durable and disposable), cleaning articles and tools, collection and storage containers and devices (including piping, silos, tanks, and disposal containers), conveyor belts, earplugs, films for fabrics, flooring materials and components, footwear and footwear components, furniture assemblies and components, gaskets, grease traps, aerospace components and fabrics, hand dryers, insulators and windshields, kitchen hardware and fixtures, liners, packaging materials, piping and fixtures, protective covers (durable and disposable), rain and sunshades (sunshades, vehicle covers, bags, athletic tapes, medical tape, and equipment, medical tape, and articles, tapes, and articles of commerce tape, and articles of manufacture, and bags, and rain-wear tapes, etc., for example.

Unless otherwise defined, all terms (including technical and scientific terms) used herein have the same meaning as commonly understood by one of 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 this disclosure and will not be interpreted in an idealized or overly formal sense unless expressly so defined herein.

In describing the present invention, it should be understood that numerous components, portions, techniques and steps have been disclosed. Each of these components, portions, techniques, and steps have their own benefits, and each may also be used in combination with one or more, or in some cases all, of the other disclosed embodiments and techniques. Thus, for the sake of clarity, this specification will avoid that each and every possible combination of individual steps is repeated in an unnecessary fashion. However, the description and claims should be read with the understanding that such combinations are entirely within the scope of the invention and the claims.

Drawings

FIG. 1 shows the effectiveness of a polyester fabric sample comprising copper oxide particles and zinc borate particles in preventing AN growth on the surface of the fabric sample relative to AN untreated polyester fabric sample, untreated PET fabric controls before (A1) and after (B1) incubation for 4 weeks, samples No. 4 before (A2) and after (B2) incubation for 4 weeks, samples No. 7 before (A3) and after (B3) incubation for 4 weeks, samples No. 8 before (A4) and after (B4) incubation for 4 weeks, samples No. 10 before (A5) and after (B5) incubation for 4 weeks, samples No. 11 before (A6) and after (B6) incubation for 4 weeks, samples No. 12 before (A7) and after (B7) incubation for 4 weeks;

FIG. 2 shows the effectiveness of a polyester fabric sample comprising copper oxide particles and zinc borate particles in preventing AN growth on a surface after 1 week of incubation in SDB at 22 ℃ relative to AN untreated polyester fabric sample, and

Fig. 3 shows color stability comparing a prior art PET fabric sample containing (left) 1% copper oxide after exposure to a 10% H ₂O₂ solution with an example of (right) a PET fabric sample containing 0.6% copper oxide, 0.6% zinc borate, and 0.3% molybdenum oxide.

Detailed Description

Antimicrobial molded polymeric articles, extruded polymeric articles, and polymeric films include an antimicrobial agent that prevents or inhibits the growth of microorganisms on surfaces and the microenvironment of the composition or the article. Microorganisms may include, for example, bacteria, viruses, fungi, algae, and the like. The inventors have discovered that the efficacy, durability, inhibition zone, processability, and other antimicrobial properties of such articles can be improved by combining the antimicrobial agent with different components to create synergistic compound blends.

Antimicrobial molded polymeric articles, extruded polymeric articles, and polymeric films comprise synergistic compounds that increase antimicrobial efficacy over the efficacy, durability, or other characteristics of the antimicrobial agent alone. The antimicrobial efficacy of an individual antimicrobial agent can be measured by determining and comparing the zone of inhibition of the individual antimicrobial compound and the blend or by other tests, as well as the antimicrobial efficacy of a combination of a synergistic blend comprising the individual antimicrobial compound and potentially a synergistic compound. As used herein, the term "antibacterial" means an antibacterial, antifungal and/or antiviral agent.

In one embodiment, the synergistic polymer composition comprises a polymer, a plurality of antimicrobial metal compounds embedded in the polymer, a boron compound, and optionally a pH adjuvant to control the pH of the polymer composition upon contact with water.

Embodiments of antimicrobial molded polymeric articles, extruded polymeric articles, and polymeric films comprise at least one particle comprising at least one water insoluble antimicrobial metal compound that releases antimicrobial ions upon contact with water. Antibacterial metal compounds include, but are not limited to, for example, copper oxide, cuprous oxide, cupric iodide, cupric carbonate, silver oxide, silver iodide, silver chloride, zinc oxide, zinc pyrithione, gold oxide, or combinations thereof. In another embodiment, the particles may consist essentially of an antimicrobial metal compound selected from the group consisting of, for example, copper oxide, cuprous oxide, cupric iodide, cupric carbonate, silver oxide, silver iodide, silver chloride, zinc oxide, zinc pyrithione, gold oxide, or combinations thereof.

Embodiments of antimicrobial molded polymeric articles, extruded polymeric articles, and polymeric films may comprise at least one particle comprising at least one water insoluble antimicrobial metal compound that releases antimicrobial ions upon contact with water, and particles comprising a boron compound. Thus, embodiments may further comprise a polymeric substrate, a plurality of antimicrobial particles embedded in the polymeric substrate, wherein the particles comprise water insoluble particles comprising an antimicrobial metal compound that release antimicrobial ions upon contact with a fluid, and particles comprising a boron compound. A portion of the particles in the polymeric substrate are exposed and protrude from the surface of the material and release antimicrobial metal ions upon exposure to water or water vapor. Such antimicrobial molded polymeric articles may be, for example, irrigation emitters, furniture, a portion of furniture, or fixtures in a hospital. Typical polymers for the molding process include, but are not limited to, at least one of polyolefin, polyamide, polyester, polyethylene, high density polyethylene, ABS, or polypropylene.

For example, an embodiment of a synergistic polymer composition may comprise a polymer, a plurality of copper compounds that release copper ions in the presence of water, and zinc borate.

Highly effective antimicrobial compositions comprise at least one antimicrobial metal compound and at least one metal borate (hereinafter "synergistic antimicrobial composition"). It has surprisingly been found that zinc borate does not have significant inherent antimicrobial activity even so. In some embodiments, the antimicrobial efficacy of the synergistic antimicrobial composition is found to be greater than the sum of the individual efficacy of its components, but the synergistic compound may improve other characteristics in addition to efficacy.

Embodiments may also include a method of extruding an antimicrobial polymer resin to produce an antimicrobial extruded polymer article. A method for preparing an extruded antimicrobial polymeric article may include preparing a polymeric syrup including a plurality of antimicrobial particles in a polymeric resin. The particles comprise particles comprising a water insoluble antimicrobial metal compound and particles comprising a boron compound that release antimicrobial ions upon contact with a fluid, and extruding a polymer slurry to form a polymer material, wherein the particles are incorporated into the polymer. A portion of the particles in the polymer are exposed and protrude from the surface of the material and release antimicrobial metal ions upon exposure to water or water vapor, thereby providing antimicrobial activity of the polymer material. Examples of extruded articles include, but are not limited to, fibers, tubes, rods, masterbatch chips or particles, antimicrobial particles for filters or tiles, and films, for example. The various antimicrobial particles can be in any effective concentration that allows for extrusion of the article as well as for the antimicrobial, flame retardant, or other desired characteristics to be effective in the final product. For example, the concentration of the particles may range from 1wt.% to 45wt.% of the polymeric article. In an exemplary embodiment, the polymer resin may be one of polypropylene, polyethylene, polystyrene, and combinations thereof. Additional polymers may also be used in the molding or extrusion process described above. For example, the extruded article may be further comminuted into antimicrobial polymer particles. The particles may be used as a masterbatch or may be incorporated into roofing materials such as, but not limited to, tiles.

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

In a specific embodiment, the antimicrobial molded, extruded article or film comprises particles comprising copper oxide and particles comprising zinc borate. In this embodiment, the particles comprising a water-insoluble antimicrobial metal compound that release antimicrobial ions upon contact with the fluid are particles comprising copper oxide, and the particles comprising a boron compound are particles comprising zinc borate.

Filtering the slurry to remove any particles exceeding the desired particle size may be further included in any embodiment of the method.

The particles comprising an antimicrobial metal compound and the particles comprising a boron compound may be added to the polymer or polymer reaction mixture in the form of a powder comprising an antimicrobial metal compound, a powder comprising a boron compound, a blend of such powders, a powder comprising particles comprising both an antimicrobial metal compound and a boron compound, or one or more master batches comprising particles comprising an antimicrobial metal compound and particles comprising a boron compound. The master batch and powder may further comprise other treatments.

Theory mechanism is drawn up

Embodiments of the present invention include synergistic compound blends that result in increased antimicrobial efficacy, increased color stability, increased handleability, or improved polymer articles, films, fibers, yarns, or other characteristics of molded or extruded polymer articles. An embodiment of the antimicrobial polymer composition comprises a synergistic blend of components, wherein the synergistic blend of components comprises at least one antimicrobial metal compound, for example, that increases the antimicrobial efficacy of the polymer composition to that of a polymer composition consisting essentially of individual components. The individual antimicrobial efficacy of an individual antimicrobial compound and the antimicrobial efficacy of a synergistic blend combination comprising the individual antimicrobial compound and potentially synergistic compounds can be measured by determining and comparing the zone of inhibition of the individual antimicrobial compound and the blend in the polymer composition. Other characteristic improvements may be similarly measured and compared.

The synergistic polymer composition comprises a polymer, particles comprising a plurality of antimicrobial metal compounds embedded in the polymer, and particles comprising a boron compound. For example, the synergistic polymer composition may comprise a metal borate and a copper oxide.

For example, an embodiment of a synergistic polymer composition may comprise a polymer, a plurality of copper compounds that release copper ions in the presence of water, and particles comprising zinc borate. Although not wishing to be limited by the mechanism disclosed, in this example, it is speculated that zinc borate (ZnB ₃O₄(OH)₃) is non-uniformly soluble in water at room temperature and reversibly hydrolyzes to insoluble Zn (OH) ₂ and soluble H ₃BO₃ (weak acid).

One of the synergistic compounds may dissolve non-uniformly. Many substances dissolve consistently (the composition of the solid and dissolved solute are stoichiometrically matched). However, some substances may dissolve inconsistently, whereby the composition of the solute in the solution does not match the composition of the solid. This dissolution is accompanied by a change in the "first solid" particles and possibly the formation of a second solid phase. In this embodiment, znB ₃O₄(OH)₃ hydrolyzes to a second solid phase insoluble Zn (OH) ₂ that can form insoluble surface shells on ZnB ₃O₄ particles, thereby preventing or significantly reducing further dissolution and formation of soluble metaboric acid. Zinc borate ZnB ₃O₄(OH)₃ (also described as 2ZnO-3B ₂O₃ 3.5H₂ O) is rarely dissolved in water and is non-uniformly hydrolyzed to soluble boric acid and insoluble zinc hydroxide. The boric acid produced is slightly acidic.

It is further speculated that, according to the formula Zn (OH) ₂+2H⁺→Zn²⁺+2H₂ O, subsequently formed Zn (OH) ₂ may decompose in the presence of, for example, moisture or pH adjuvants. This decomposition produces zinc ions which may further act as antibacterial ions. As can be seen in the zone of inhibition test, the copper oxide alone has some antimicrobial efficacy, the 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 zinc borate hydrolyzes to insoluble Zn (OH) ₂ on the exposed outer surface of the particles, no further release of zinc ions would be expected. However, the desired concentration of pH adjuvant or water may control further decomposition of insoluble Zn (OH) ₂, thereby further releasing the antimicrobial zinc ions. In this way, the polymer composition or article comprises a fast or slow release of antimicrobial metal ions. The metal ions in the metal oxide and metal borate may be further selected to provide antimicrobial efficacy through different mechanisms, thereby killing a wider range of microorganisms or a combination thereof to more effectively kill microorganisms. In embodiments, synergistic compounds may be selected to affect or control the release of antimicrobial ions, antimicrobial efficacy, antimicrobial durability, color stabilization, or other characteristics.

Polymer

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

The polymer is one of polyvinyl chloride, polyolefin, polyethylene, polypropylene, polyethylene phthalate, polydiene, polybutadiene, polyester, polystyrene acrylonitrile, acid polymer, nylon polymer, bakelite, polyolefin, polyethylene, polypropylene, polyiso-isomer, polyacetal, polyamide, polyvinyl chloride, polyester, polyether, polyamide, polyacrylate, polymethacrylate, polyacrylate, acrylonitrile-butadiene-styrene, acrylonitrile styrene acrylate, nylon, polybutylene, polylactic acid, polyurethane, fluoropolymer (e.g., 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 contain carboxylic acid or carboxylic acid moieties, sulfonic acid moieties (-SO ₃ H), phosphonic acid moieties, or boric acid moieties.

The thermoplastic resin may comprise any thermoplastic resin known in the art and suitable for the contemplated application, for example, but not limited to, such thermoplastic polymers may include olefins (e.g., low and high density polyethylene and polypropylene), dienes (e.g., polybutadiene and Neoprene elastomers), vinyl polymers (e.g., polystyrene, acrylics, and polyvinylchloride), fluoropolymers (e.g., polytetrafluoroethylene), and hybrid polymers (e.g., polyamides, polyesters, polyurethanes, polyethers, polyacetals, and polycarbonates). Thermosetting resins include phenolic resins, amino resins, unsaturated polyester resins, epoxy resins, polyurethanes, and silicone polymers.

Antibacterial particles

The antimicrobial metal compound may be any water insoluble metal compound that releases antimicrobial ions upon contact with water. The antimicrobial metal particles comprise at least one of an antimicrobial copper compound, an antimicrobial silver compound, an antimicrobial zinc compound, and other antimicrobial metal compounds. For example, antimicrobial metal compounds include, but are not limited to, for example, copper oxide, copper chloride, cuprous oxide, cupric iodide, cupric carbonate, silver oxide, silver iodide, silver chloride, zinc oxide, zinc chloride, zinc pyrithione, gold oxide, or combinations thereof. In another embodiment, the particles may consist essentially of an antimicrobial metal compound selected from the group consisting of, but not limited to, copper oxide, cuprous oxide, cupric iodide, cupric carbonate, silver oxide, silver iodide, zinc oxide, zinc pyrithione, gold oxide, or combinations thereof, for example.

In certain embodiments, the antimicrobial compound or particle may consist essentially of one of, for example, copper oxide, copper chloride, cuprous oxide, cupric iodide, cupric carbonate, silver oxide, silver iodide, silver chloride, zinc oxide, zinc chloride, zinc pyrithione, gold oxide, or combinations thereof. In another embodiment, the particles may consist essentially of an antimicrobial metal compound selected from the group consisting of, but not limited to, copper oxide, cuprous oxide, cupric iodide, cupric carbonate, silver oxide, silver iodide, zinc oxide, zinc pyrithione, gold oxide. The antimicrobial particles comprising the water-insoluble metal compound may comprise functional groups or coatings. The functional groups or coating may contribute to, for example, handling characteristics or end product characteristics.

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

The molded article and the extruded article may comprise at least one water insoluble metal compound in a concentration of between 0.1wt.% and 45wt.% of the antimicrobial article or composition. The concentration depends on the use, handling and size of the article.

In some embodiments, particles comprising or consisting essentially of antimicrobial metal compound particles are mechanically held in the polymer matrix and do not ionically bind to the polymer, hydrogen bond, coordinate complex, and the like. The antimicrobial metal compound may be present in the antimicrobial molded article, extruded article, nonwoven fabric, or film at a concentration of 0.02wt.% to 10wt.%, in other embodiments, the concentration may be 0.02wt.% to 6wt.%, in other embodiments, the concentration may be 0.05wt.% to 2wt.%. The concentration of the antimicrobial metal compound in the article may be based on the desired antimicrobial efficacy, the physical size of the article, the composition of the polymeric substrate, the environment in which the article will be used, and other factors.

Boron compound

The synergistic compound or components of the synergistic component blend may comprise a boron compound. The boron compound may include, but is not limited to, metal borates, silver borates, copper borates, zinc borates, gold borates, sodium borates, calcium borates, potassium borates, boric acid, compounds that produce boric acid and antimicrobial metal ions upon contact with water, and combinations thereof. For example, metal borates decompose in the presence of water or pH adjuvants to release antimicrobial ions, even though the metal borates alone do not have significantly inherent antimicrobial efficacy. In some embodiments, the boron compound or particles comprising the boron compound may be replaced with another compound that synergistically interacts with water or a pH adjuvant and the antimicrobial metal compound to increase the efficacy of the polymeric article relative to an article comprising only the antimicrobial metal compound.

The boron compound and its concentration in the article may be selected to control the antimicrobial efficacy, durability of the antimicrobial efficacy, color stability, and/or processability of the polymer resin to produce a final product by, for example, spinning, stretching, extrusion, or molding. The molded article and the extruded article may comprise at least one boron compound in a concentration of between 0.1wt.% and 45wt.% of the antimicrobial article or composition. The concentration depends on the use, handling and size of the article.

The boron compound may be present in the antimicrobial molded article, extruded article, nonwoven fabric, or film at a concentration of 0.05wt.% to 15wt.%, in other embodiments, the concentration may be 0.2wt.% to 10wt.%, in other embodiments, the concentration may be 0.2wt.% to 5wt.%.

PH adjuvant

A pH adjuvant is a compound that creates an acidic environment upon contact with a fluid to promote hydrolysis of the metal borate salt, thereby releasing antimicrobial metal ions and/or releasing 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, thereby adjusting the pH on the surface of the antimicrobial polymeric article. In some embodiments, the pH adjuvant has a decomposition temperature that is higher than the compounding and shaping (extrusion or molding) temperature of the polymeric article. In other embodiments, the pH adjuvant may be formed by the compound decomposing during compounding, molding, extrusion, or other processing steps due to exposure of the compound to elevated temperatures.

For example, molybdenum oxide decomposes into molybdic acid and hydrogen cations upon contact with humidity or other water sources according to the following formula:

MoO₃+3H₂O→2H₃O++MoO₄ ^2-

other acids will also form hydrogen cations that decompose the metal borates to boric acid and release the metal ions. The hydrogen cations can accelerate ionization of the metal borates and antimicrobial metal compounds, thereby forming synergistic antimicrobial products having higher antimicrobial efficacy than the additive antimicrobial efficacy of the individual components.

In some embodiments, the concentration of the pH adjuvant is 0.01wt.% to 5.0wt.%.

The pH adjuvant may be selected to control the antimicrobial efficacy, durability of the antimicrobial efficacy, color stability, and/or processability of the polymer resin to produce a final product by spinning, stretching, extrusion, or molding. Examples of pH adjuvants include, but are not limited to, sulfur, acids including, but not limited to, citric acid, phosphoric acid, and the like, acidic salts including, but not limited to, naH ₂PO₄、ZnCl₂、NH₄ Cl, and acidic oxides including, but not limited to, moO ₃、CrO₃、Mn₂O₇, and the like. Thus, the pH adjuvant may be at least one of a compound, an acidic oxide, an acidic salt, molybdenum oxide, chromium chloride, molybdenum chloride, and combinations thereof that create an acidic environment upon contact with water.

The acid dissociation constant pKa of the acid can be used to determine whether the compound will create a suitably acidic environment upon contact with moisture to allow adequate hydrolysis of the metal borate and to accelerate the release of antimicrobial metal ions (e.g., cu+ ions and cu++ ions from copper oxide) to achieve the desired properties of the polymer product.

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

A method of forming an antimicrobial polymer composition or article includes a treatment step comprising increasing the temperature to compound, cure, melt, or soften the polymer. In certain applications, the pH adjuvant has a decomposition temperature that is higher than these treatment temperatures, so that all or a portion of the pH adjuvant does not decompose or dissociate during the treatment.

Powder blend

Embodiments of the antimicrobial powder may comprise synergistic antimicrobial powder blends. The synergistic powders may be blended separately into a polymer resin or aqueous dispersion to produce an antimicrobial composition that may be further processed to form an antimicrobial article. For example, embodiments of the synergistic antimicrobial powder may include particles comprising a water-insoluble metal compound and particles comprising a boron compound. The water-insoluble antimicrobial powder may comprise a ratio of metal oxide particles to particles comprising a boron compound of from 20:1 to 1:10.

Synergistic antimicrobial powders can be added to polymers to produce antimicrobial polymeric articles comprising antimicrobial metal oxides, including concentrations of 0.1wt.% to 5 wt.%.

The particles comprising the antimicrobial metal oxide 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 the boron compound may be, for example, particles comprising zinc borate, particles comprising copper borate, particles comprising silver borate, particles comprising calcium borate, particles comprising sodium borate or a combination of such particles or particles comprising one or more of the boron compounds. In one embodiment, the synergistic antimicrobial powder blend comprises particles comprising water insoluble antimicrobial copper oxide and particles comprising zinc borate.

In another embodiment, the synergistic antimicrobial powder blend further comprises a pH adjuvant. Thus, in one embodiment, the synergistic antimicrobial powder blend may comprise particles comprising an antimicrobial metal compound, particles comprising a boron compound, and particles comprising a pH adjuvant.

In a particular embodiment, the synergistic powder blend comprises copper oxide and zinc borate. In another embodiment, the synergistic powder blend comprises copper oxide, molybdenum oxide, and zinc borate.

Masterbatch

The antimicrobial master batch may be blended with the virgin polymer to add a desired color or other characteristic to the virgin polymer prior to further processing to form an antimicrobial article, film, fiber, yarn, or other molded or extruded article. Methods and processes for producing antimicrobial and/or antiviral polymer masterbatches. The synergistic antimicrobial compounds described herein can be added to the virgin polymer to produce a masterbatch, and the masterbatch can then be added to the virgin polymer to produce an antimicrobial polymer 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 material.

Embodiments of the polymer master batch for preparing the antimicrobial polymeric material may include a thermoplastic resin, an antimicrobial synergistic compound blend including water insoluble antimicrobial metal compound particles (as described herein) and a boron compound (as described herein). The masterbatch may further comprise a polymer wax, an agent for occupying the charge of the ionic copper oxide, a processing aid or other modifier. The antimicrobial synergistic compound may further comprise particles comprising a pH adjuvant.

A method of producing an antimicrobial article, film, fiber, yarn, or other molded or extruded article comprises adding a polymeric antimicrobial masterbatch to a thermoplastic polymer resin, the polymeric antimicrobial masterbatch comprising a thermoplastic resin, an antimicrobial synergistic compound blend comprising water insoluble copper oxide particles and zinc borate, and forming the antimicrobial article, film, fiber, yarn, and other molded or extruded articles.

A method of producing an antimicrobial article, film, fiber, yarn, or other molded or extruded article includes adding a first polymer masterbatch to a thermoplastic polymer resin, the first polymer masterbatch comprising a thermoplastic resin, an antimicrobial synergistic compound blend comprising water insoluble copper oxide particles, a pH adjuvant, and zinc borate, adding a second masterbatch comprising at least one of the antimicrobial synergistic compound comprising water insoluble copper oxide particles, a pH adjuvant, and zinc borate, wherein the second masterbatch comprises at least one of the first polymer masterbatch in the synergistic compound, and forming the antimicrobial article, film, fiber, yarn, and other molded or extruded article.

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

Additional embodiments of polymer masterbatches for preparing the antimicrobial polymeric material can include thermoplastic resins, antimicrobial synergistic compound blend particles including water insoluble metal compounds (e.g., copper oxides), and boron compound (e.g., zinc borate) particles, polymeric waxes, and agents for occupying the charge of the ionic copper oxides. The antimicrobial synergistic compound may further comprise a pH adjuvant.

The antimicrobial, antifungal and/or antiviral master batch allows the polymer product manufacturer to economically add antimicrobial and/or antiviral components to the polymer during the manufacturing process. More particularly, the present invention relates to an improved process and masterbatch for preparing antibacterial and antiviral polymeric materials having a variety of antibacterial uses.

Embodiments of the antimicrobial powder may comprise synergistic antimicrobial powder blends. The synergistic powder blend may be blended into a polymer resin to produce an antimicrobial polymer, which may be further processed to form an antimicrobial article. The water-insoluble antimicrobial powder may comprise a ratio of metal oxide particles to particles comprising a boron compound of from 20:1 to 1:1. Any antimicrobial master batch as described herein may comprise an antimicrobial synergistic compound blend or a subset of antimicrobial synergistic compound blends at a concentration of, for example, 10wt.% to 70 wt.%.

Synergistic antimicrobial powders may be added to the polymeric resin to produce an antimicrobial polymeric article comprising particles comprising an antimicrobial metal oxide at a concentration of, for example, 0.1wt.% to 5 wt.%.

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

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

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

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

Examples

Molded irrigation parts and assemblies:

Embodiments of molded (e.g., irrigation emitter) or extruded articles (irrigation tubing) may be part or assembly of a component or layer comprising one or more components or layers to effect fluid flow. For example, the article may be a component of an irrigation system. The components of the irrigation system may comprise any synergistic particle combination described herein. Copper ions from copper compounds (e.g., copper oxides) have been shown to prevent root intrusion into irrigation equipment.

In one embodiment, an irrigation device (e.g., a emitter head, an irrigation pipe, or a portion of an irrigation pipe) is constructed from a polymer (e.g., polyethylene) embedded with 5wt.% to 20wt.% (e.g., 10 wt.%) particles comprising an antimicrobial metal compound (e.g., cuprous oxide) and 5wt.% to 20wt.% (e.g., 10 wt.%) of a boron compound (e.g., zinc borate). Plasticizers may be incorporated to achieve the desired mechanical properties of the emitter head or tube. Optionally, 0.1wt.% to 1wt.% of a pH adjuvant may be added to the material. Zinc borate provides resistance to UV radiation, whereby additional UV stabilizers may not be needed. The types of irrigation devices encompass emitter heads, irrigation strips, pipes, tubes, connectors, etc. The average particle diameter of the particles of both the cuprous oxide powder and the zinc borate powder is in the range of 5 μm to 10 μm.

An assembly of layers designed to prevent the flow of fluid from being impeded by insect habitat, root penetration, organic matter, biofilm or plant material by the managed deposition of metal compounds in, on, around the microenvironment of the surface. The assembly will also function to inhibit the effects of insect degradation and UV light degradation on the delivery device.

Examples

Antibacterial ring (ZOI)

Cupron copper oxide (Cu ₂ O) particles are supplied by Cupron, inc. (Cupron, LLC). Antimony oxide (antimony (III) oxide, sb ₂O₃, 99%), molybdenum oxide (molybdenum (VI) oxide, moO ₃, 99.5%), sodium borate (sodium tetraborate, na ₂B₄O₇, 99.5%) Boric acid (H ₃BO₃, 99.5%), zinc oxide (ZnO, 99.5%), sodium molybdate (sodium molybdate dihydrate (VI), na ₂MoO₄·2H₂ O, 99%), calcium chloride (CaCl ₂, 97%), sodium citrate (Na ₃C₆H₅O₇, laboratory grade), magnesium sulfate (magnesium sulfate heptahydrate, mgSO ₄·7H₂ O, 99%), basic copper (II) carbonate (BCC). Zinc chloride (ZnCl ₂, 98%) and zinc bromide (ZnBr ₂, 98%) were purchased from sameidshuri technologies company (Thermo Scientific). Zinc sulfate (zinc sulfate monohydrate, znSO ₄·H₂ O) was purchased from alpha chemical company (ALPHA CHEMICALS). Zinc borate (fiberbrake ZB) is provided by american borax corporation (u.s. Box). Microcrystalline cellulose powder was purchased from LFA tablet press store (LFA Tablet Presses Store). Aspartic acid (98%) was purchased from the aclos organic company (Acros organics). Molybdic acid, potassium borate, chromium (III) chloride, chromium (VI) oxide, molybdenum (V) chloride, molybdenum disulfide, and chromium (III) hydroxide were purchased from feishier company. All chemicals were used as received.

Sample preparation sample pellets were prepared from the chemical powders using a DABPRESS ton hydraulic press. The weight percentages of each powder component are detailed in tables 1 and 2. Microcrystalline cellulose powder (20 wt%) was added as a binder. The chemical powders were mixed by vortexing for 20 seconds to ensure mixing. Then, 0.2g of the powder blend was added to each well of a 12-well aluminum flake mold (pore size=10 mm). The tablet die was then pressed by using a hydraulic press to obtain sample pellets.

Zone of inhibition (ZOI) escherichia coli (e.coli) (ATCC 8739) was used for ZOI testing. Cultures were streaked onto Luria agar (LB) plates and incubated overnight at 37 ℃. A single colony was used to inoculate 10mL of Nutrient Broth (NB) and the single colony was grown overnight at 37 ℃ with shaking and a stock suspension of colony forming units per milliliter (CFU/mL) was obtained (about 10 ⁹). mu.L of this stock suspension was spread homogeneously on a Trypsin Soybean Agar (TSA) plate (diameter 10 cm). Sample pellets (≡three) containing copper oxide and adjuvant were then placed on agar and incubated for 24 hours at 37 ℃. The diameter of the zone of inhibition surrounding the sample pellet was measured using a ruler and the results are summarized in tables 1 and 2.

As a screening test, cupron copper oxide particles and their blends with 14 different adjuvants were studied in a ZOI study to explore potential cooperativity for antibacterial effectiveness. The results of this study are summarized in table 1. After 24 hours of incubation at 37 ℃, the ZOI of copper oxide alone was found to be 13mm in diameter for e.

When copper oxide is blended with molybdenum oxide, sodium borate, boric acid, zinc chloride, zinc bromide, zinc sulfate, calcium chloride, molybdic acid, potassium borate, chromium (III) chloride, chromium (VI) oxide, molybdenum (V) chloride, and molybdenum disulfide, a significant increase in ZOI size is observed, indicating that these chemicals improve the antimicrobial effectiveness of copper oxide against e. Antimony oxide, zinc borate, zinc oxide, sodium molybdate, sodium citrate, magnesium sulfate, aspartic acid, and chromium (III) hydroxide had no effect on the ZOI diameter. These results indicate that (1) molybdenum oxide, chromium (III) chloride, chromium (VI) oxide, and molybdenum (V) chloride can improve copper ion release by lowering the environmental pH. (2) Zinc borate alone had no effect on the antimicrobial effectiveness of the copper oxide. However, the antibacterial effectiveness of copper oxides is significantly improved by the hydrolysis products of zinc borate in an acidic environment, including boric acid, zinc chloride, zinc bromide, and zinc sulfate. (3) Sodium borate and potassium borate as alkaline salts increase the antimicrobial effectiveness of copper oxides, indicating that borate ions have a synergistic effect with copper oxides that results in greater antimicrobial effectiveness. Thus, there is no need to lower the pH to enhance the antimicrobial effectiveness of Cupron copper oxide. In addition to the results discussed above, calcium chloride and molybdenum disulfide have also been found to increase the diameter of the ZOI when blended with copper oxide. Future studies need to be made to find the cause of this result.

The results described above indicate that hydrolysis products of zinc borate in an acidic environment increase the antimicrobial effectiveness of copper oxides. Molybdenum oxide is reported to interact with water and lower the ring pH. Thus, the presence of molybdenum may create the environment required for zinc borate hydrolysis, and thus there may be a synergy in terms of antimicrobial effectiveness between copper oxide, molybdenum oxide, and zinc borate. To verify this theory, a ZOI study shown in table 2 was performed. The ZOI diameters of copper oxide and molybdenum oxide were found to be 13mm and 19mm, respectively. No ZOI of zinc borate was observed. The ZOI of the blends of copper oxide with zinc borate was 12mm to 13mm with zinc borate content ranging from 20% to 70% (Table 2, no. 4, no. 7, no. 10 and No. 13 test), indicating that zinc borate alone did not affect the antimicrobial effectiveness of copper oxide in this study. The ZOI of the blends of copper oxide and molybdenum oxide was greater than that of copper oxide alone, and the ZOI size increased with increasing molybdenum oxide content (test nos. 2,5, 8, 11 and 14). Notably, copper oxide,

The ZOI of the blends of molybdenum oxide and zinc borate was greatest, especially for the blends where the content of molybdenum oxide and zinc borate was higher (table 2,9, 12 and 15 tests). The results confirm that there is a synergistic effect in the copper oxide, zinc borate and molybdenum oxide in terms of antibacterial effectiveness against escherichia coli.

To extend the field of synergistic application described above, BCC was used as copper oxide in the ZOI study

Instead of this. As shown in table 3, BCC was blended with antimony oxide, zinc borate and molybdenum oxide, and the ZOI diameter of the blend was measured. The ZOI of the BCC alone was found to be 12mm in diameter. The ZOI of the blends of BCC with antimony oxide or zinc borate was 11mm (Table 3, test No. 2 and test No. 3), indicating that zinc borate or antimony oxide did not affect the antibacterial effectiveness of the BCC in this study. The ZOI of the blend of copper oxide and molybdenum oxide (20 mm, table 3,4 test) was found to be much greater than the ZOI of the BCC alone (11 mm, table 3,1 test). BCC was then blended with a mixture of antimony oxide and zinc borate (test No. 3, 5), a mixture of antimony oxide and molybdenum oxide (test No. 3, 6), and a mixture of zinc borate and molybdenum oxide (test No. 3, 7). No significant change in ZOI of BCC (11 mm) was observed after blending with antimony oxide and zinc borate. The ZOI diameter of the blend of BCC with antimony oxide and molybdenum oxide was 18mm, which is larger than the ZOI diameter of the BCC alone, but smaller than the ZOI diameter of the blend of BCC with molybdenum oxide. This result shows that the extended ZOI of the blend of BCC with antimony oxide and molybdenum oxide is mainly due to the synergy between BCC and molybdenum oxide, but that the addition of antimony oxide does not have a significant synergy with BCC or molybdenum oxide for antimicrobial effectiveness. The maximum ZOI of the blend of BCC with a mixture of zinc borate and molybdenum oxide was observed (25 mm, test No. 3, 7), indicating that zinc borate and molybdenum oxide can synergistically with various copper compounds to produce greater antimicrobial effectiveness. Finally, the BCC is blended with a mixture of antimony oxide, zinc borate and molybdenum oxide. The addition of antimony oxide slightly reduced the size of the ZOI to 22mm, indicating that antimony oxide does not increase the antimicrobial effectiveness of the copper compound.

Fabric sample preparation

A 2x 2 "sample of polyethylene terephthalate (PET) fabric was cut.

These fabric samples were crimped along their length and formed into a strip shape. Samples No.4, no. 7, no. 8, no. 10, no. 11, no. 12 and untreated PET controls were involved in this test. Table 4. AN was inoculated on Tryptic Soy Agar (TSA) and incubated at 37 ℃. After 2 weeks of growth, spores were collected by placing 15mL DI water in TSA plates and gently scraping the agar surface with L-shaped cell-coated bars. Spore suspension was transferred to a tube and diluted 10-fold in sand dextrose broth (sabouraud dextrose broth, SDB) to produce a stock suspension. Stock suspension (5 μl) was inoculated onto each TSA plate and carefully spread over the entire surface. PET fabric samples were placed on inoculated TSA plates. Then 200 μl of the stock suspension was carefully added drop-wise onto the fabric sample surface. Efforts were made to ensure uniform distribution of the stock suspension over the sample surface. Samples were inoculated at 37 ℃ for 1 month to evaluate the effectiveness of the fabric in inhibiting mold growth. After the incubation period, a rating scale of 0-4 determines the antifungal efficacy of the tested materials. The assessment is described below.

0-No growth on sample

1-Sample with trace growth (less than 10%)

2-Few growths (10% to 30%)

3-Medium growth (30% to 60%)

4-Sample was completely covered with growth (60%)

The facets all exhibited perceptible mold growth, but significantly less than the untreated control. (fig. 1, a2 and B2, A3 and B3) thus, in table 5, both sample No. 4 and sample No. 7 are designated as mold resistance of 2. Sample No. 8, which contained 0.5% copper oxide and 0.5% zinc borate, exhibited superior mold resistance to samples No. 4 and 8. Sample No. 8 did not completely prevent mold overgrowth, but after 4 weeks incubation, the mold overgrowth was barely noticeable, as shown in A4 of fig. 1 and B4 of fig. 1. Thus, sample No. 8 was designated as an antimycotic rate of 1. The introduction of molybdenum oxide further enhances the antimycotic properties. Sample No. 10, which contained 0.1% copper oxide, 0.6% zinc borate, and 0.3% molybdenum oxide, performed similarly to sample No. 8 (fig. 1, a5, and B5), achieving an antimycotic rate of 1. In addition, sample No. 11 and sample No. 12, each containing zinc borate and molybdenum oxide, but having a higher copper oxide content than sample No. 10, gave an antimycotic rate of 0. Notably, no appreciable AN overgrowth was observed on sample 11 and sample 12 after the 4 week incubation period. (FIGS. 1, A6 and B6, A7 and B7)

In summary, the combination of zinc borate and copper oxide significantly improved the overall anti-mold properties of the PET fabric samples. This is evident in the results, where PET samples containing 0.5% copper oxide and 0.5% zinc borate exhibited better than samples with 1% copper oxide or 1% zinc borate alone in preventing excessive growth of AN mold. These findings indicate that copper oxide and zinc borate have a synergistic effect in inhibiting AN mould growth. Furthermore, the addition of molybdenum oxide further enhances the resistance of the sample to mold growth. PET fabric samples with 0.3% molybdenum oxide, 0.6% zinc borate and 0.3% or more copper oxide were able to completely prevent AN mold overgrowth throughout the study.

In summary, the incorporation of zinc borate and copper oxide in PET fabric samples showed a significant improvement 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 anti-mold PET fabrics.

Antimycotic study 2

Samples of 1 "long PET fabric were carefully cut from the lawson sleeve and the fibers were placed in 20mL clear sample bottles with caps. Samples No. 3, no. 5, no. 6, no. 9 in table 4 and untreated PET controls were involved in this test. AN was inoculated in a glucose-in-sand broth (SDB) and incubated at 37 ℃. After 1 week of growth, AN suspension was transferred to a tube and diluted 10-fold in Sand Dextrose Broth (SDB) to produce a stock suspension. Stock suspension (5 mL) was carefully spread over the whole sample surface. The cap of the vial is loosely closed to allow air exchange. Samples were inoculated at 22 ℃ for 1 week to evaluate the effectiveness of the fabric in inhibiting the growth of AN mold.

The effectiveness of the PET fabric samples in preventing mold growth is shown in FIG. 2. After incubation at 22 ℃ for 1 week, perceptible mold growth was observed in several samples, including untreated PET control, sample No. 3, sample No. 5, and sample No. 6 (fig. 2). These samples also showed signs of spore formation, as indicated by the presence of black spots. This suggests that under the conditions tested, the use of copper oxide or zinc borate alone is not sufficient to inhibit AN mould growth and indeed, copper oxide even appears to promote spore production, whereas zinc borate only partially reduces said spore production.

In contrast, sample No. 9 showed only slight mold growth, in which no black spore production was detected. This shows that the combination of copper oxide and zinc borate in sample No. 9 was more effective than using separate copper oxide or zinc borate in preventing growth of AN mold at 22 ℃.

These findings are consistent with the results of previous antimycotic studies (referred to in this paragraph as "antimycotic study 1"), which indicate 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 exhibits superior mold resistance properties compared to the use of either material alone. This suggests a synergy between copper oxide and zinc borate, which makes it AN ideal choice to prevent the growth of AN mold at 22 ℃ in PET polyester fabric samples.

As shown in table 6, test samples No. 10, no. 11 and No. 12, containing 0.6% zinc borate, 0.3% molybdenum oxide and various copper oxide contents, released copper ions from one gram of sample at 4.7ppm, 11.6ppm and 15.9ppm. The copper ion release rate increases with increasing copper oxide content. In addition, test samples No. 1, no. 2 and No. 3 containing only copper oxide released copper ions at release rates of 5.1ppm, 9.8ppm and 10.6ppm per gram of sample. This finding shows that the release rate of copper ions increases with higher copper oxide content, whether zinc borate or molybdenum oxide is present or not.

Interestingly, sample No. 11, which contained 0.3% copper oxide and zinc borate and molybdenum oxide, exhibited a copper ion release rate of 11.6ppm per gram, which was 18% higher than sample No. 2, which contained the same amount of copper oxide but without zinc borate and molybdenum oxide. Similar trends were also observed for samples with higher copper oxide content. For example, sample No. 12, which contained 0.6% copper oxide and zinc borate and molybdenum oxide, had a copper ion release rate of 15.9ppm per gram, which was 50% higher than sample No. 3, which had a copper ion release rate of 10.6 ppm/g. In addition to the sample with 0.1% copper oxide, the acceleration of the addition of zinc borate and molybdenum oxide has

Inch x 1 inch sample. The composition of the samples used in this study is shown in table 4. Samples No.1, no.2, no.3, no. 5, no. 9, no. 10, no. 11, and No. 12 were involved in the study. Untreated PET fabric samples were included as controls. The 1"x 1" samples were inoculated with pathogen suspension and covered with coverslips and incubated for a2 hour period. The incubation temperatures and incubation vehicles are summarized in tables 7 and 8. Immediately after the addition of bacteria, the bacteria were recovered from a set of samples by digestion to determine the number of bacteria added to the substrate. After a2 hour contact time, bacteria were recovered from the other set of samples by digestion. The recovered bacteria were counted by colony forming units using serial dilution method.

The log reduction value is calculated according to the following calculation formula:

Log reduction = Log ₁₀ [ CFU _Control]-Log₁₀ at 2 hours [ CFU _{Sample of} at 2 hours ]

Table 7 summarizes the antibacterial effectiveness against E.coli under various test conditions. Sample No. 1, containing 0.1% copper oxide (without zinc borate or molybdenum oxide), showed a log reduction of 4.9 for e.coli when incubated at 37 ℃ and with saline inoculation vehicle containing 5% Nutrient Broth (NB). However, when 0.6% zinc borate and 0.3% molybdenum oxide were added to sample No. 1 (resulting in sample No. 10), the efficacy of the substrate increased to a log reduction of greater than 6.9 and an improvement of log reduction of greater than 2.0. A similar trend was observed for sample No. 2 with a log reduction of 6.7 having 0.3% copper oxide and sample No. 11 with 0.3% copper oxide, 0.6% zinc borate and 0.3% molybdenum oxide, which showed a log reduction of greater than 6.9. Both sample No. 3 and sample No. 12 achieved log reductions of greater than 6.9, which is the limit of detection for this test. These results demonstrate that the presence of zinc borate and molybdenum oxide enhances antibacterial effectiveness against E.coli at 37℃in saline inoculation vehicle with 5% NB, especially at lower copper oxide concentrations.

Sample No. 1 with 0.1% copper oxide (without zinc borate or molybdenum oxide) exhibited a log reduction of 1.6 against e.coli bacteria when the vehicle was inoculated with saline containing 5% Trypsin Soybean Broth (TSB). However, when 0.6% zinc borate and 0.3% molybdenum oxide were added to sample No. 1 (resulting in sample No. 10), the efficacy of the substrate increased to a log reduction of 3.2 and an improvement of 1.6 log reduction. Similar trends were observed for sample No. 2 with 0.3% copper oxide and sample No. 3 with 0.6% copper oxide, which achieved log reductions of 3.3 and 6.2, respectively. In addition, samples No. 11 and No. 12 with zinc borate and molybdenum oxide adjuvants, respectively, exhibited log reductions greater than 6.5 and 6.4. Again, these results indicate that the presence of zinc borate and molybdenum oxide enhances the antibacterial effectiveness against e.coli at 37 ℃ with 5% NB in saline vaccinated vehicle.

To understand the effect of zinc borate on antibacterial effectiveness, antibacterial studies were performed on samples No. 3,5 and 9 in synthetic sweat containing 0.5 g/L-histidine: HCl: H ₂ O, 5g/L NaCl, 2.2g/L Na ₂PO₄·12H₂ O and 15 mL/L0.1M NaOH at 21 ℃. Before use, the pH was adjusted to 5.5 with HCl. As shown in table 8, all test samples achieved log reductions of greater than 3 for e.coli and 5 for pseudomonas aeruginosa. It was found that there was a negligible difference between the samples with only copper oxide (samples No. 3 and 5) and the samples with copper oxide and zinc borate for e.coli and pseudomonas aeruginosa. However, the process is not limited to the above-described process,

1.4Log lower. Further research is needed to understand why antibacterial efficacy is contained due to the addition of zinc borate.

In summary, the presence of zinc borate and molybdenum oxide adjuvants enhances the antibacterial effectiveness against escherichia coli at an elevated temperature of 37 ℃, but the addition of zinc borate alone does not achieve the same effect at ambient temperature.

Antimicrobial study 2

All test samples (1 "x 1") were sterilized under UV in a full cabinet for 1 hour on each side. The test pathogen was inoculated in a growth medium and allowed to grow to saturation in an orbital shaker at 37 ℃ for 24 hours. Thereafter, the pathogen suspension was diluted to about 1.0e8 CFU/mL in an Inoculum Carrier (IC) containing 5wt.% M3 broth, 0.89wt.% NaCl, and 0.05wt.% triton. Two labeled petri dishes per sample with foam insert were pre-treated with 1.5mL of sterilized DI water. The PVC sample crumb was then placed on the pretreated foam. Twenty-two microliters of bacteria-containing ICs were then pipetted into the center of each test sample. A plastic coverslip (22 mm) was then placed on top and pressed gently to coat the IC. The dishes were then covered and placed in an incubator for 2 hours at 37 ℃. After the incubation period, the petri dishes were removed and the test samples with coverslips were placed in a 50mL conical centrifuge tube containing 17.5mL of lethes broth. A 50mL conical centrifuge tube was vortexed for 2 minutes and then the solution was serially diluted and plated onto nutrient agar. The agar plates were then placed in an incubator at 37 ℃ for 24 hours, and colonies were then counted.

As presented in table 9, sample No. 16, which included both copper oxide and zinc borate, exhibited significant reductions in log reduction of 3.4 for escherichia coli, log reduction of 5 for staphylococcus aureus, and log reduction of 4.5 for pseudomonas aeruginosa. These results exceeded the performance of sample No. 14 (containing only copper oxide) and sample No. 15 (containing only zinc borate). The data indicate that there is a synergistic antimicrobial effect when copper oxide and zinc borate are combined on PVC substrates.

Color shift

Color analysis was performed using a Konica Minolta (Konica Minolta) chroma measurement instrument CR-410, first of all

Three values for objectively measuring color and calculating color change are represented, respectively. L quantifies the degree of brightness from black to white on a scale of 0 to 100, while a and b represent chromaticity without specific numerical limits. A negative a value corresponds to a green hue, a positive a value represents a red hue, a negative b value represents a blue hue, and a positive b value represents a yellow hue. Delta (Delta) represents the difference between the surface tested and a pure white reference. Δe acts as a comprehensive measure of the overall difference between the tested surface and the pure white reference calculated using the following equation:

ΔE*=((ΔL*)²+(Δa*)²+(Δb*)²)^1/2

As shown in table 10, sample No. 9, which contained 0.6% copper oxide and 0.6% zinc borate, exhibited the highest brightness (L). Sample No. 12 shows the lowest a and b values, meaning that including 0.6% zinc borate and 0.3% molybdenum oxide is effective to reduce the color shift of copper oxide to red and yellow. Furthermore, it became apparent that samples No. 9 and No. 12 exhibited significantly lower values than samples No. 3 and No. 5 when considering the overall color shift (Δe). This suggests that the introduction of zinc borate and molybdenum oxide has a significant impact in reducing the color shift due to the presence of copper oxide.

Color stability against oxidation

To study the color stability of PET fabric samples, sample No. 5 and sample No. 12 from table 4 were selected. The study was aimed at assessing the effect of strong oxidants on the color stability of these samples. Specifically, sample No. 5 (1.2% copper oxide) and sample No. 12 (0.6% copper oxide content and 0.6% zinc borate and 0.3% molybdenum oxide) were subjected to an aging process using 10% H ₂O₂.

During the experiment, both sample No.1 and sample No. 6 were boiled in 10% H ₂O₂ for 3 minutes, followed by soaking in 10% H ₂O₂ at 37 ℃ for 3 days. It was observed that both sample No. 5 and sample No. 12 underwent shrinkage during boiling. Prior to the aging process, FIG. 3 shows that sample No. 5, as received, has a pink hue. However, sample No. 5 was shifted to a pink color after undergoing the aging process. On the other hand, no noticeable color shift was observed for sample No. 12 after the aging process. This suggests that combining copper oxide with zinc borate and molybdenum oxide helps to improve the color stability of PET fabrics because it remains unaffected by the oxidizing agent.

Claims

1. A method for preparing antibacterial polymer materials, the method comprising:

A polymer slurry is prepared comprising a variety of antibacterial particles in a polymer resin, wherein the particles include water-insoluble particles comprising antibacterial metal compounds that release antibacterial ions upon contact with a fluid, and boric acid particles or particles comprising compounds that generate boric acid upon contact with water; and

The slurry is molded to form a molded polymer article, wherein the particles are incorporated into the polymer, and a portion of the particles in the polymer is exposed and protrudes from the surface of the material, and releases antimicrobial metal ions upon exposure to water or water vapor, thereby providing the polymer material with antimicrobial activity.

2. The method according to claim 1, wherein the size of the particles is between 1 micrometer and 20 micrometers.

3. The method of claim 1, wherein the particles are introduced into the slurry in an amount of 0.1 wt.% to 45 wt.% of the polymer by weight.

4. The method according to claim 1, wherein the polymer material is an irrigation emitter.

5. The method of claim 1, wherein the polymer material is part of the furniture.

6. The method of claim 1, wherein the polymer material is used for fixation in a hospital.

7. An antibacterial polymer article comprising:

Polymer substrate;

Multiple antibacterial particles are embedded in the polymer substrate, wherein the particles include water-insoluble particles comprising antibacterial metal compounds that release antibacterial ions upon contact with a fluid, and particles comprising boron compounds, wherein a portion of the particles in the polymer material is exposed and protrudes from the surface of the material, and releases antibacterial metal ions upon exposure to water or water vapor.

8. The article of claim 7, wherein at least 90% of the antibacterial particles have a particle size of 1 micrometer to 20 micrometers.

9. The article of claim 8, wherein the concentration of the antibacterial particles ranges from 0.25 wt.% to 45 wt.%.

10. A method for preparing an antibacterial polymer material, the method comprising:

Prepare a polymer slurry comprising a variety of antibacterial particles in a polymer resin, wherein the particles include particles comprising water-insoluble antibacterial metal compounds that release antibacterial ions upon contact with a fluid, and particles comprising boron compounds or particles comprising compounds that generate boric acid upon contact with water; and

The slurry is extruded to form a polymer material, wherein the particles are incorporated into the polymer, and a portion of the particles in the polymer is exposed and protrudes from the surface of the material, and releases antimicrobial metal ions upon exposure to water or water vapor, thereby providing the polymer material with antimicrobial activity.

11. The method of claim 10, wherein the size of the particles is between 1 micrometer and 20 micrometers.

12. The method of claim 10, wherein the particles are introduced into the slurry in an amount of 0.1 wt.% to 45 wt.% of the polymer by weight.

13. The method of claim 10, wherein the polymer material is an antibacterial polymer fiber.

14. The method of claim 13, further comprising stretching the antimicrobial polymer fiber.

15. The method of claim 10, further comprising spinning the antimicrobial polymer fiber into yarn.

16. The method of claim 10, wherein the polymer material is a pipe or conduit.

17. The method of claim 10, wherein the polymer material is a film.

18. The method of claim 10, further comprising crushing or pulverizing the polymer material to form polymer microparticles.

19. The method of claim 18, further comprising incorporating the polymer particles into roofing shingles.

20. The method of claim 18, wherein the concentration range of the plurality of antimicrobial particles is from 4 wt.% to 20 wt.% of the polymer microparticles.

21. The method of claim 18, wherein the polymer resin is one of polypropylene, polyethylene, polystyrene, and combinations thereof.

22. A method for preparing an antibacterial polymer material, the method comprising:

Preparation of polymer resins;

Multiple antibacterial particles are blended into the polymer resin to produce a polymer slurry, wherein the particles include water-insoluble particles comprising antibacterial metal compounds that release antibacterial ions upon contact with a fluid, and particles comprising boron compounds; and

The polymer slurry is placed in a mold to form a polymer article, wherein a portion of the particles in the polymer article are exposed and protrude from the surface of the polymer article, and release antimicrobial metal ions when exposed to water or water vapor.

23. The method of claim 22, wherein the water-insoluble particles comprising an antimicrobial metal compound that release antimicrobial ions upon contact with a fluid comprise copper oxide, and the boron compound comprises zinc borate.

24. The method of claim 22, wherein the polymer resin comprises at least one selected from polyolefin, polyamide, polyester, polyethylene, high-density polyethylene, ABS, or polypropylene.

25. An antibacterial product comprising:

The polymer is selected from polyethylene phthalate, polyolefins, polyethylene, polypropylene, polyvinyl chloride, polyurethane, polycarbonate, copolymers thereof, and blends thereof.

Particles comprising a water-insoluble antimicrobial metal compound that release antimicrobial ions upon contact with a fluid, the concentration of said particles being from 0.01 wt.% to 10 wt.%, said particles being embedded in said polymer; and

The polymer contains boron compound particles embedded in it, the concentration of which is from 0.05 wt.% to 15 wt.%.

26. The antimicrobial article of claim 25, wherein the article is one of a film, debris, tube, pipe, panel, and artificial leather.

27. The antimicrobial article of claim 25, wherein the article comprises one layer of a multilayer article.

28. The antimicrobial article of claim 27, wherein the article comprises at least one layer of foam.

29. The antimicrobial article according to claim 25, wherein the boron compound is a basic boron compound.

30. The antimicrobial article of claim 25, comprising a pH adjuvant.

31. The antimicrobial article of claim 30, wherein the pH adjuvant is one of the following: a compound that produces an acidic environment upon contact with water, an acidic oxide, an acidic salt, molybdenum oxide, chromium oxide, chromium chloride, molybdenum chloride, and combinations thereof.

32. The antimicrobial article of claim 25, wherein the particles comprising the boron compound also generate antimicrobial metal ions upon contact with water.

33. The antimicrobial article of claim 25, wherein the particles comprising the boron compound are at least one of the following: metal borates, boric acid, sodium borate, compounds that generate antimicrobial metal ions and boric acid upon contact with water, sodium borate, potassium borate, zinc borate, and combinations thereof.

34. The antimicrobial article according to claim 25, wherein the particles of the boron compound are zinc borate particles.

35. The antimicrobial article of claim 25, wherein the water-insoluble particles comprising an antimicrobial metal compound that release antimicrobial ions upon contact with a fluid comprise at least one of the following: copper oxide, copper carbonate, silver oxide, silver iodide, zinc oxide, copper iodide, zinc pyrithione, gold oxide, or a combination thereof.

36. The antimicrobial article of claim 25, wherein the water-insoluble particles comprising an antimicrobial metal compound that release antimicrobial ions upon contact with a fluid are copper oxide particles, and the particles comprising the boron compound are zinc borate particles.

37. The antimicrobial textile fabric according to claim 25, comprising molybdenum oxide.

38. A method for producing an antimicrobial article, the method comprising:

Prepare an antibacterial polymer resin, wherein the polymer resin comprises water-insoluble particles, including antibacterial metal compounds, embedded in the polymer that release antibacterial ions upon contact with a fluid, and boric acid particles or particles comprising compounds that generate boric acid upon contact with water; and

The polymer resin is extruded to form one of the following: films, tubes, pipes, polymer debris, and artificial leather.

39. The method of producing an antimicrobial article according to claim 38, wherein the polymer resin comprises a polymer selected from polyethylene phthalate, polyolefins, polyethylene, polypropylene, polyvinyl chloride, polyurethane, copolymers thereof, and blends thereof.

40. The method of producing an antimicrobial article according to claim 38, wherein the polymer resin comprises particles including a pH adjuvant.

41. The method for producing an antimicrobial article according to claim 38, wherein the water-insoluble particles comprising the antimicrobial metal compound are copper oxide particles and the particles.