HK1170549B - Antimicrobial textiles comprising peroxide - Google Patents

Description

Peroxide containing antimicrobial textiles

Technical Field

The present invention relates to an antimicrobial textile fabric having durable antimicrobial properties.

Background

Antimicrobial agents are chemical compositions used to prevent microbial contamination and deterioration of products, materials and systems. Particular fields of application for antibacterial agents and compositions are, for example, cosmetics, disinfectants, sanitizers, wood preservation, food, animal feed, cooling water, metal working fluids, hospital and medical uses, plastics and resins, petroleum, pulp and paper, textiles, latex, adhesives, leather and hide glue and paint pastes. There are many types of known disinfectants, such as those discussed in fourth edition "Disinfection, Sterilization and preservation", edited and partially written by professor Seymour S.Block, published by Lea & Febiger, Pa.1991. Certain peroxides, chlorine compounds, phenolic compounds, quaternary ammonium compounds and surfactants are known to have germicidal properties. In many cases, the rate of disinfection is relatively slow, and some compounds emit volatile organic compounds or persist in the environment.

In recent years, great attention has been paid to the potential hazards of bacterial contamination from daily contact. Significant examples of this concern include the fatal consequences of food poisoning caused by certain strains of escherichia coli (e.coli) found in not-yet-cooked beef, particularly in fast food restaurants; disease caused by salmonella contamination in uncooked and dirty poultry food; and diseases and skin infections caused by staphylococcus aureus, klebsiella pneumoniae, yeast, and other unicellular organisms. As consumers have gained increased attention in this area, manufacturers have begun introducing antimicrobial agents into various household products and articles. For example, certain brands of polypropylene cutting boards and liquid toilet soaps contain antibacterial compounds. Among such articles, the most popular antimicrobial agent is triclosan. While incorporation of such compounds in liquid or polymeric media is relatively simple, it has proven difficult to incorporate in other matrices, including on the surface of textiles and fibers.

There is a need for textile surfaces, especially garment materials and film surfaces, that provide effective, long lasting and long lasting antimicrobial properties over an extended period of time. It is extremely difficult to achieve such intended use with triclosan, especially when wash durability is necessary, as triclosan is easily washed off on any such surface. Furthermore, although triclosan has proven to be effective as an antimicrobial agent, exposure to this compound may cause irritation of the skin, which makes triclosan unsuitable for use in fibers, films, and textiles of clothing.

It is known in the art to treat textiles to render them antimicrobial against microorganisms that come into contact with the textiles. Such articles include articles formed from paper, fiber, knitted and non-knitted textiles, and fabric analogs designed for use in hospitals, food processing plants, laboratories, and other areas where it is necessary to maintain a sterile environment. A Recent review of antimicrobially treated Textiles is found in "Recent Advances in Antimicrobial Treatments of Textiles", Y.Gao and R.Cranston, Textile Research Journal, Vol.78(1), p60-72 (2008).

Antibacterial materials such as cloth, fibers, polymers, and even children's toys are becoming increasingly popular due to public concerns about epidemic diseases and pathogens. With respect to antimicrobial fabrics, the domestic and international markets have grown dramatically due to public vigilance of these potential threats (see, Center for Disease Control and preservation, Infection Control and Biosafety, Medical Data international. report # RP-701530, 1992, and a.j.rigby et al,Fiber Horizons12 months 1993, pages 42-460). Antimicrobial garments may be used in medical and other general applications, such as in surgeon gowns, hats, masks, patient drapes, bandages, towels, sheets, wipers and drapes of various sizes.

Although the demand for antimicrobial fibers is high, such fibers are difficult to obtain, particularly fibers that are effective against a broad spectrum of bacteria and are effective after multiple machine washes. In recent years, with the advance of new methods for incorporating antibiotics into polymers as bactericides, research and development of fibers having lasting functionality have been actively conducted.

Various types of antimicrobial agents have been applied to fibrous substrates. However, only a very small number of agents retain their bactericidal activity after repeated washing, do not cause environmental problems, do not have side effects on the substrate or its user, and are inexpensive to manufacture.

For example, U.S. patent 2,791,518 discloses a method of imparting antimicrobial properties to an article, such as a textile fabric, by immersing the article in a first aqueous solution containing a water-soluble basic nitrogen compound (ammonia) and a monovalent silver salt dissolved in the solution, and then in a second solution containing a second salt that is ion-exchangeable with the silver salt, thereby forming a precipitate of the monovalent silver salt on the article. The silver precipitate formed is poorly soluble in water and imparts antimicrobial properties to the article after treatment.

Similarly, U.S. patent 5,271,952 discloses a method of treating fibers to render the fibers conductive and antimicrobial, the method comprising immersing the fibers in a bath comprising an aqueous solution of a cupric ion source, a reducing agent, sodium thiosulfate, and a source of iodide ions, thereby absorbing copper iodide into the fibers. Similar techniques using copper compounds to render fibers conductive and antimicrobial are disclosed in U.S. Pat. Nos. 4,410,593 and 5,458,906.

Substances such as clostaurin, which can be grafted onto textiles for the purpose of imparting antimicrobial properties, have also been disclosed (Williams et al,C&EN9/6/1999, page 36; and us patent 6576154). However, the textile thus treated is washed for only 5 hours, the antibacterial property is drastically lowered, and it is unstable after a long-term exposure to ultraviolet rays.

Us patent 5,882,357 discloses a durable and renewable cellulosic material obtained using a chemical processing method. Cotton and polyester/cotton fabrics are treated with hydantoin derivatives and the treated fibers are washed with a chlorine-containing laundry bleach to impart germicidal properties. Chlorination of the amine and imine linkages in the hydantoin ring produces bactericidal N-halamine sites. When the site is exposed to the microorganism, the N-halamines revert back to their precursor form. The fibres can then be rendered bactericidal again by using chlorine-containing bleaching agents. The main advantages of the chlorine regeneration finishing process are its durability, convenience and economy. However, N-halamine chemistry is not suitable for colored fabrics. The use of chlorine bleach can discolor the fibers. Thus, in certain applications, non-bleaching regenerants are desirable, particularly for colored materials.

It is well known that hydrogen peroxide is a safe and effective topical disinfectant and antiseptic, and dilute solutions thereof are used to cleanse wounds. However, it is not substantive to fibrous materials and can be easily removed from the fabric or fabric component by a single wash.

Hydrogen peroxide is favored in many applications because of its decomposition products, water and oxygen are harmless and often have broad-spectrum antimicrobial activity. Hydrogen peroxide is effective against a variety of bacteria, molds, fungi, and viruses. Broad spectrum antimicrobial activity is important in the presence of pests, but the species of pest is unknown. Hydrogen peroxide is a well-known antimicrobial agent, and aqueous solutions thereof have been widely used to treat infections in topical treatments for humans and animals. The reagents may be used in the original form after suitable dilution, or may be obtained from solid compounds which form salts or addition compounds with hydrogen peroxide. Including sodium perborate, sodium carbonate peroxide, sodium peroxyphosphate, urea peroxide, potassium persulfate, and others. Upon addition of water, these compounds hydrolyze to hydrogen peroxide and the corresponding carrier salt. However, the main limitation of the commonly used aqueous hydrogen peroxide solutions is their poor storage stability, which is caused by their easy decomposition into gaseous oxygen and water at normal temperature and the transient contact of the active oxidizing agent with the affected tissue. In addition, when the composition is formed from an addition compound and hydrogen peroxide, it is often desirable to prepare the addition composition prior to incorporating it into the desired composition.

Us patent 6,962,608 discloses a method of making an antimicrobial fiber, the method comprising: (a) immersing the textile in an aqueous treatment solution containing an organic acid, wherein the organic acid has at least two carboxyl groups; and (b) treating the fibers with an oxidizing agent to produce peroxycarboxylic acid functionality, thereby producing an antimicrobial textile comprising an average weight percent of 6% organic acid, demonstrating a coliform reduction in excess of 99% (2-log) when unwashed. The percent level of this reduction gradually decreased with additional washing of the sample, eventually to 85% (< 1-log) after four washes.

Danna et al in us patent 4,199,322 and 4,172,841 disclose applying a solution comprising Zinc Acetate (ZA) or zinc acetate dihydrate and Hydrogen Peroxide (HP) to a textile fabric and then drying the treated textile fabric to obtain a product with antimicrobial properties. Preferably, acetic acid is added to maintain homogeneity of the solution (clear and no precipitate or coagulum). The Danna reference discloses that the solution for treating textiles ("aqueous reaction mixture") may contain 1% -30% zinc acetate, and preferably 1.5 to 10 moles of hydrogen peroxide per mole of zinc acetate. In all cases, the formulations disclosed in the Danna reference use zinc acetate, Zn (OAc)₂Or zinc acetate dihydrate as an active agent. In other words, the Danna reference teaches that acetate and zinc must be used in a 2:1 molar ratio. The molar ratio of acetate to zinc is even higher if the Danna reference also discloses that it is beneficial to add acetate in the form of acetic acid to the formulation. Even if the acetic acid produced by the reaction of zinc acetate and hydrogen peroxide is removed (evaporated) in the drying step, the Danna reference discloses that the reaction product "contains a significant proportion of acetyl groups". Any additional acetic acid intentionally added to the solution is also removed during the drying step. Excess hydrogen peroxide is also evaporated off during this step.

Danna et al disclose in U.S. patent 4,199,322 (column 63, line to column 3, line 15) ("Danna' 322") that describes the products of an antibacterial reaction. The reaction product has the general formula shown in formula 1 (below), wherein X ranges from 9 to 16 and Y ranges from 1 to 7. Simple calculations revealed a molar ratio of acetate to zinc in the Danna' 322 reaction product ranging from 2: 10 (for x 9 and y 1) to 2: 23 (for x 16 and y 7). Thus, there is typically a molar excess of zinc of 500% to over 1,000% relative to the acetate salt in the reaction product. Or in other words, in the final antimicrobial reaction product, there are only 1 to 2 acetate moieties to 10 zinc atoms.

AcO-(ZnO₂)_X-(ZnO)_Y-ZnOAc

General formula 1: (X ═ 9 to 16 and Y ═ 1 to 7)

Since the initial ratio of acetate to zinc in the zinc acetate starting material was 2:1, this means that up to a 20-fold excess of acetate was employed (not including any contribution of acetic acid intentionally added to the formulation). In other words, the reactants are enriched in acetate relative to zinc; whereas the product is rich in zinc relative to acetate. The excess acetate is removed as acetic acid during the drying process and is essentially wasted. Excessive consumption of reagents is expensive from a raw material perspective and also presents other problems. Acid mist is a health, safety and environmental hazard. Acetic acid is flammable and has a flash point of about 40 ℃. In addition, acid mist is an irritant, can damage the respiratory system, and can corrode equipment. Clearly, the method described in Danna' 322 has significant disadvantages.

Zinc acetate is readily soluble in water and separates into zinc ions and acetate ions in solution. Mixing sodium acetate and zinc chloride (ZnCl)₂) Rather than zinc acetate, in a 2:1 molar combination, the solution will produce substantially the same ratio of zinc ions to acetate ions, presumably to achieve a similar antimicrobial effect.

In addition, the Danna' 322 process produces a textile that requires a washing step to remove excess reaction products that impart an unpleasant vinegar-sour taste to the textile product. Residual acetic acid can also be detrimental to the fabric itself, causing degradation or discoloration. Residual acetic acid may also present health risks to users handling textiles, such as skin irritation. Organic acids such as acetic acid are also known as food sources for certain microorganisms. The requirement for a rinsing step according to the Danna' 322 procedure and method also adds significant cost to the textile processing. The Danna' 322 formulation must be dried prior to rinsing to set (or fix, or cure) the treatment. The treated textile material is then rinsed to remove acetic acid, which necessitates a second drying step, which significantly increases energy costs.

Danna' 322 discloses the use of a homogeneous solution, which does not contain a precipitate. This is achieved by adding acetic acid to the reaction mixture to prevent the formation of a precipitate of zinc acetate-peroxide complex. Contrary to the teachings of Danna' 322, the present invention uses a mixture of zinc and hydrogen peroxide in an aqueous carrier, which comprises a precipitate, or a particle suspension, or a colloid.

Zinc acetate dissolved in water produces a solution with a pH of 5 to 6 (Merck index, 10 th edition)1983, page 1455, entry # 9926). Thus, the formulation disclosed by Danna' 322 has an acidic pH even before the addition of acetic acid. The addition of acetic acid to the formulation allowed a further decrease in pH.

Zinc Peroxide can be synthesized by using Zinc acetate as a starting material (see "Synthesis of Stabilized nanoparticules of Zinc Peroxide", Rosenthal-Toib, etc.,Chemical Engineering Journal 136(2008) p 425-429); wherein a solution of zinc acetate and HP is treated with NaOH to raise the pH, and a precipitate is formed, collected, washed, and dried to obtain solid Zinc Peroxide (ZP). The product can be heat treated at 300 ℃ to obtain Zinc Oxide (ZO). If a stabilizer such as PEG200 is added to the ZA/HPP solution, the final ZP or ZO particles are smaller in size (nanoparticles). Similar to the Danna' 322 work, only stoichiometric zinc acetate (2: 1 Ac: Zn) was used as the precursorAnd (4) driving the body. It is speculated that the drying step will give off a considerable amount of acetic acid, since the precursor solution has substantially the same composition as the solution disclosed by Danna' 322.

The zinc acetate formulation reported by Danna' 322 made some improvement over earlier patents disclosed by Welch et al (us 4,115,422 and 4,174,418) which disclosed a similar system in which zirconium acetate was used instead of zinc acetate. In a later patent published by Vigo et al (us patent 5,656,037), magnesium acetate was used in place of zinc acetate or zirconium acetate to provide better temperature stability of the antimicrobial reaction product. However, these variations all use high concentrations of acetate in the treatment formulation and the finished textile product, and suffer from the same disadvantages described above.

Corey, in U.S. Pat. No. 5,152,966, discloses a nonwoven wet wipe impregnated with an aqueous solution of zinc peroxyacetate.

Brief introduction to the invention

The present invention relates to methods of making antimicrobial treatment formulations and adhesive compositions. The invention also relates to an antimicrobial treatment formulation comprising an acetate-free complex of a metal derivative and hydrogen peroxide, which hydrogen peroxide imparts a durable antimicrobial activity to textile fabrics after treatment of the textile fabrics with the treatment formulation. Typically, even 50 washes, a 3-log to 6-log reduction in bacteria was observed. In addition, textiles treated with the antimicrobial treatment formulations are environmentally friendly, wash durable, and antimicrobial. In addition, the antimicrobial treatment formulations can be used on white, colored, natural and synthetic fibers and combinations thereof.

The invention also relates to a method of preparing the antimicrobial treatment formulation and a method of treating a textile with the antimicrobial treatment formulation to impart durable antimicrobial activity to the textile. An antimicrobial treatment formulation is prepared using a metal derivative, hydrogen peroxide and a source of hydroxyl ions. The acetate-free treatment formulation may be an aqueous solution or a dispersion, suspension, coacervate, or emulsion in an aqueous carrier. The antimicrobial preparation is free of acetate, wherein the preparation contains acetic acid (CH3COOH) orAcetate (CH3 COO)^-) The amount of groups is low enough to avoid adverse effects due to the presence of acetic acid or acetate salts, including odors, fumes, degradation of materials or equipment, staining, toxicity, irritation, environmental hazards, or safety hazards.

The metal derivative may be in the form of a salt, ion or complex. Preferably a metal salt, ion or complex of magnesium, zinc, aluminum or zirconium. Most preferred are metal salts, ions or complexes of zinc. The metal derivatives are typically soluble salts of metal ions in which the negative charge counterion does not adversely affect, for example, the formation of acetate or acetic acid. Preference is given to metal salts with inorganic counterions, such as chlorides, bromides, nitrates or sulfates. In one aspect of the invention, the metal derivative is a mixture of chloride and nitrate. In a preferred embodiment of the invention, the metal derivative is composed of a mixture of zinc chloride and zinc nitrate.

The hydrogen peroxide used to prepare the antimicrobial treatment is typically an aqueous solution of peroxide. The weight percentage of hydrogen peroxide in the treatment formulation ranges from 0.2% to 50%, and preferably from 0.5% to 10%. Most preferably, the hydrogen peroxide is present in an amount of about 2 to 6% by weight.

Various sources of hydroxide ions may be used. Preferred sources of hydroxide ions include sodium hydroxide and potassium hydroxide. The hydroxide ion serves to neutralize the acidity of the metal derivative. To raise the pH of the mixture significantly, it may be necessary to add a significant amount of hydroxide, because the mixture generally has a high acidic buffering capacity (as described below). The addition of hydroxide also reduces the solubility of metal ions by the formation of metal hydroxide species. After treatment, the reduction in solubility results in better durability (wash firmness, or wash stability) of the final antimicrobial material. Textiles treated with the compositions have significant and durable antimicrobial activity.

The antimicrobial treatment formulation or complex of metal derivative and hydrogen peroxide can be applied to a substrate such as a textile using methods known in the art, including, but not limited to, spraying, dipping, injecting, brushing, filling, or rolling. Textiles treated with the antimicrobial treatment formulations of the present invention do not exhibit any significant objectionable odor (e.g., "vinegar" odor) after being sufficiently dried, nor do they contain residual volatile acids. When the antimicrobial treatment formulations and methods of the present invention are properly used, the treated textile does not suffer significant or objectionable fading, staining, or other undesirable aesthetic effects from the antimicrobial treatment, even if the textile is a colored or dyed textile. Textiles treated according to the methods described herein exhibit significant durable antimicrobial activity, and when tested according to the methods described herein, can result in up to a 6-log reduction of bacteria, including staphylococcus aureus, escherichia coli, and klebsiella pneumoniae.

The antimicrobial treatment formulation is a colloidal suspension of metal hydroxides, oxides, complexes, and/or peroxides. The suspension had a generally milky appearance and solid white particles were visually observed in the suspension. Direct use of the prepared colloidal suspensions may leave undesirable white residues or deposits on the fiber surfaces treated with the suspensions. This is most pronounced on dark fibers. These deposits can be eliminated by reducing the particle size by homogenization prior to application to the textile. It has been found that the suspension after passing through a mesh filter of about 200 micron nominal pore size does not produce any visible residue on the commonly dark or woven fabrics consisting of cotton, polyester, or mixtures thereof. Accordingly, one aspect of the invention is to homogenize the antimicrobial treatment formulation and pass it through a 200 micron pore size filter prior to use. Homogenization can be achieved by conventional homogenization equipment such as a stirrer, high shear homogenizer, colloid mill, or ultrasonic equipment.

An aspect of the present invention is that the antimicrobial treatment formulation of the present invention may further comprise EDTA, or a salt of EDTA, for chelating iron. The presence of dissolved iron can decompose hydrogen peroxide, thereby interfering with the formation of complexes of hydrogen peroxide, metal derivatives, and hydroxide ions. The preferred EDTA salt is EDTA tetrasodium salt. One of ordinary skill in the art will recognize that other chelating agents may also be used to chelate iron.

An aspect of the present invention is that the antimicrobial treatment formulation may further comprise a tonicity enhancing agent that is miscible, soluble, or dispersible in aqueous media and may be a component of the acetate-free complex of the present invention comprising a metal derivative and hydrogen peroxide. The durability enhancing agent can be a polymer and can be added to the treatment formulation as a suspension, emulsion, dispersion, or solution. The endurance enhancing agent may also be a long chain fatty acid, or a salt thereof. Typically, less than about 1% by weight of long chain fatty acids are incorporated into the antimicrobial treatment formulation. A preferred persistence enhancer is sodium stearate.

An aspect of the present invention is that additives such as uv protective agents, processing aids, softening agents, antistatic agents, colorants, dyes, indicators, drugs, oils, lubricating oils, microspheres, temporary visual indicators, nutrients, growth factors, vitamins, emollients, moisturizers, fragrances, perfumes, and the like may be incorporated into the antimicrobial treatment formulation. Antimicrobial treatment formulations may also be incorporated into the adhesive composition for treating the substrate and imparting durable antimicrobial activity to the substrate.

The formulations and methods of the present invention are applicable to a variety of textile materials, including natural and synthetic materials, and mixtures thereof. The formulations and methods of the present invention are also applicable to a variety of substrates, including woven, knitted, non-woven textiles, polymers, films, fibers, or magnetic tapes. Substrates treated with the materials and methods of the invention can include wound dressings, burn dressings, sanitary napkins, incontinence pads, tampons, dressings of intrinsic antimicrobial absorbency, diapers, toilet paper, sanitary wipes, sponges, cotton swabs, surgical gowns, isolation gowns, lab coats, gloves, surgical scrubs, head covers, hair covers, masks, sutures, floor mats, lamp covers, examination table linens, plaster liners, splint liners, padding, gauze, packaging, mattress covers, bedding, sheets, towels, clothing, undergarments, socks, shoe covers, automotive air filters, aircraft air filters, HVAC system air filters, military protective clothing, devices for biohazard or biowarfare agents, food packaging, meat packaging, fish packaging, food processing clothing, food preparation countertops, carpets, wood, lumber, wood, tampons, dressings of intrinsic antimicrobial absorbency, diapers, absorbent pads, All or a portion of paper and paper currency.

The test results of the examples described herein show that textiles treated with the antimicrobial treatment formulations of the present invention resist discoloration.

The antimicrobial treatment formulations and methods of the present invention can be used to make adhesives, pressure sensitive adhesives, coatings, latex paints, acrylic latex paints, varnishes, sealants, coatings, shellacs, caulks, or water-resistant coatings having antimicrobial properties. The acetate-free treatment formulations of the present invention can be used to make pressure-treated wood, gypsum wallboard, or other building materials to increase resistance to microbial attack and material degradation. The acetate-free antimicrobial treatment formulation of the present invention may also be used to make antimicrobial wound dressings.

The antimicrobial treatment formulations of the present invention may be used to neutralize, inactivate, or destroy certain chemical substances, such as chemical warfare agents used in protective gear. The antimicrobial treatment formulation may be applied to protective devices such as garments, gloves, masks, or drapes to provide protection from exposure to toxic or harmful chemicals.

It is an aspect of the present invention to provide an acetate-free and substantially peroxide-free aqueous binder composition comprising a metal derivative and a source of hydroxide ions which can then be combined with hydrogen peroxide and subsequently used to treat a substrate and impart durable antimicrobial activity to said substrate. The adhesive composition is similar to the components of other antimicrobial treatment formulations described herein; however, the hydrogen peroxide component of the adhesive composition is removed or substantially reduced. Such a composition contributes to improved stability. Safety and storage or transport problems are minimized due to the absence of oxidizing agents (hydrogen peroxide).

Definition of

"microorganism" or "microorganism" refers to any organism or combination of organisms, such as a pathogen, virus, protozoa, yeast, fungus, mold, or a spore formed from any of them.

"antimicrobial" refers to the property of a compound, composition, formulation, article, or material that kills or inhibits the growth of microorganisms, which is capable of killing, destroying, inactivating, or neutralizing the microorganisms; or preventing or slowing the growth, viability, or reproduction of microorganisms.

"substrate" refers to a surface or medium, such as a textile material. An antimicrobial agent, such as the acetate-free antimicrobial treatment formulation of the present invention, is applied, injected or otherwise attached thereto.

"surface" refers to the general outer surface of the matrix and also to the inner surface of the fibers, voids, pores within the matrix.

By "durable" is meant that the material or treated substrate retains antimicrobial activity after one or more washes or rinses, or that the antimicrobial activity remains effective for a substantial portion of the expected useful life of the treated substrate under normal use conditions.

"metal derivative" refers to an ion, salt, complex, hydrated ion, ionic complex, complex of an ion with hydrogen peroxide, metal hydroxide, metal oxide, or metal peroxide, or a mixture thereof, which is derived from one or more of the metal elements used in the present invention. Preferred for use in the present invention are metal derivatives of zinc, magnesium, or zirconium. For purposes of the present invention, alkali metals (lithium, sodium, potassium, rubidium, cesium, and francium) are not included in the definition of "metal"; however, these elements may also be present in the formulations described herein.

By "acetate-free" is meant that the molar concentration of acetic acid or acetate groups in the "acetate-free complex" or "acetate-free treatment formulation" is generally less than about 10% of the molar concentration of the metal derivative, and that no acid or salt containing acetate or other volatile carboxylic acid compound is added to or present in the formulation or complex prior to use at a level greater than about 10% of the molar concentration of the metal derivative. Acetate-free also means that the acetate content is below the threshold. At the threshold, no acetate or acetic acid odor could be detected during handling and drying.

Brief description of the drawings

Figure 1 shows the neutralization curve of a 100 gram solution containing zinc chloride (1 gram) and hydrogen peroxide (35%, 5.7 grams) with 4M sodium hydroxide. The figure shows that the pH of the solution rises sharply after the dropwise addition of 4mL of sodium hydroxide solution. Initially, the addition of a significant amount of hydroxide had little effect on the pH of the composition; however, the dropwise addition of the hydroxide can affect the efficacy of the treatment formulation by reducing the solubility of the metal complex. The curve shows that the degree of neutralization of the treatment formulation cannot be accurately shown by measuring the pH alone, since there is an important region in which the pH does not vary drastically with neutralization.

Detailed Description

We have demonstrated that textiles treated with the formulation disclosed by Danna' 322 have very long lasting antimicrobial efficacy after 50 washes. The method uses zinc acetate. However, we have found that acetate is not an essential ingredient for the treatment of antimicrobial textiles based on Hydrogen Peroxide (HP) metal complexes. One of ordinary skill in the art would predict that a simple modification to the Danna' 322 process using zinc chloride (for example) instead of zinc acetate would completely alleviate the problem of acetic acid mist release and acetate residue in the finished textile product. In fact, we have found that the zinc chloride formulation treated textile does not have any antimicrobial efficacy after only two washes. In a similar test, the textile treated with a solution consisting of 5% magnesium chloride hexahydrate and 8.8% HP (sample #012009a) showed antimicrobial efficacy; however, the antibacterial efficacy substantially disappeared after only two washes. These unexpected results appear to indicate that acetate ions are necessary to form wash stable antimicrobial textiles for textiles treated with zinc or magnesium ions and hydrogen peroxide solutions. However, we subsequently found a complete difference according to the present invention.

The aqueous zinc chloride solution is strongly acidic and has a pH of about 4 (Merck index, 10 th edition-c 1983, p. 1456, entry # 9932). Our experiments showed that the pH of an aqueous solution of 1% zinc chloride and 2% hydrogen peroxide measured approximately 4.5. The pH of a concentrated zinc nitrate solution (17% zinc content) from a commercial source (gold eagle) was about 1.0.

We have made experimental tests of how the lower acetate to zinc ratio affects the antimicrobial properties of the treated textile. Danna discloses a "baseline" with an Ac to Zn ratio of 2 to 1 in the treatment solution when no acetic acid is added to further dissolve the complex. We have found that when a mixture of sodium acetate and zinc chloride (with 2% HP) is used, the antimicrobial efficacy after washing is essentially zero in the absence of acetate. We have found that antimicrobial efficacy is still obtained after extensive washing when the molar concentration of acetate is greater than or equal to about 1/4 molar concentration of chloride (i.e., 2 moles of chloride and 0.5 moles of acetate). When the molarity of acetic acid was 1/10, which is the molarity of chloride, only a slight antibacterial efficacy after washing was observed.

We have found that the bulk of the solid product formed on drying of an acidic aqueous solution containing zinc, acetate and HP (as taught by Danna) is practically water soluble; however, only the insoluble components of the reaction product may be immobilized on the textile substrate to impart durable (wash-resistant) antimicrobial activity thereto. Such a prediction is reasonable.

Note that the results, observations and conclusions described above relate to the aqueous mixture of zinc chloride, acetate and hydrogen peroxide, and the acidic pH after preparation. No deliberate neutralization or adjustment of the pH, i.e. no addition of hydroxide or alkaline agent, is made and the pH of all solutions is generally from 4 to 5.5. In other words, when a mixture of zinc acetate and hydrogen peroxide is used to treat textiles, a long lasting antimicrobial efficacy is observed even without neutralization or pH adjustment; however, the possibility of generation of undesirable acetic acid mist is eliminated by simply replacing zinc chloride with zinc acetate, but the antibacterial effect is not maintained for a long time.

As mentioned above, acetic acid acts as a reagent and a reaction by-product, and its volatility is a problem. We have attempted to replace the acetic acid used in the prior formulation and Danna process with less volatile carboxylic acids such as citrate, tartrate, gluconate, benzoate, or succinate. However, we have found that substrates treated with these carboxylic acids instead of acetate do not exhibit long lasting antibacterial activity. On the other hand, several volatile carboxylic acids such as formate, and propionate impart long lasting antimicrobial activity to the material; however, the formation of acid mist is still a considerable problem with this method.

We believe that the species therein will be less soluble if the acidity of such solutions is fully or partially neutralized by the addition of a hydroxide source. The addition of a hydroxide source typically results in the formation of a precipitate; however, even with the addition of a large amount of hydroxide, no significant change in pH occurred (see fig. 1). The formation of insoluble species allows the treated substrate to retain higher antimicrobial activity and less of the antimicrobial precipitate to be dissolved in subsequent washes, meaning that the antimicrobial effect is longer lasting. The efficiency of the method is improved because the same level of antimicrobial activity can be obtained for a long period of time despite the use of low concentrations of the agent.

Furthermore, we have found that if the acidity of the treatment solution is fully or partially neutralized by the addition of a hydroxide source, the textile produced may also have significant long-lasting antimicrobial activity, even when all the acetate is removed from the solution. For example, an aqueous solution of 1 weight percent zinc chloride and 2% hydrogen peroxide was adjusted to a pH of 7.5 with 4M NaOH. The addition of NaOH (hydroxide ion source) resulted in the formation of a large amount of finely dispersed white precipitate. The precipitate is not prone to agglomeration or settling and is easily redispersed by gentle agitation, stirring, or mixing. The green dyed textile material was thoroughly wetted with this suspension and then the excess liquid was drained through a roller press to obtain a wet textile fabric with a weight gain of about 100%. The damp textile is then dried. Of course, since the treatment solution does not contain acetate, there is no acetic acid odor or smoke released during this process. The treated textile did not release any bad smell nor did it contain any acidic residue. The textile does not appear to be dyed, discolored or otherwise aesthetically undesirable. It was found that the treated textiles had a significant lasting antibacterial activity (6-log reduction of bacteria) even after 50 washes. This is a significant and beneficial improvement over the Danna method. The addition of the hydroxide also converts soluble metal species (such as zinc chloride or zinc nitrate) to insoluble species (such as zinc hydroxide), which increases the durability of the antimicrobial product because the insoluble species are more difficult to wash away.

In the experiments and examples described herein, the pH of an initially acidic aqueous solution containing zinc ions was raised to a specific level (i.e., pH 7.5) by the addition of NaOH. Although it has been found that the antimicrobial efficacy of the treated textile is increased by increasing the pH of the zinc and hydrogen peroxide treatment solutions, it is not clear whether this effect is caused by the pH. While we do not wish to be bound by any particular theory, we believe that the antimicrobial effect is enhanced by the zinc hydroxide or hydroxide-like complex formed by the reaction of hydrated zinc ions with hydroxide ions. The observed change in pH is merely an artifact that allows one to discern whether a sufficient amount of hydroxide has been added. As described above, the conversion of hydrated zinc chloride to hydrated zinc hydroxychloride (and complexes associated with HP) results in the formation of a visible precipitate. It is speculated that the solubility of these precipitates upon drying reactions produces an antimicrobially active residue that is less than the corresponding residue formed when the solution is not modified by the addition of a hydroxide source.

If NaOH is used to titrate the mixed aqueous solution of zinc chloride and HP, the pH and the amount of NaOH added form a sigmoidal curve, with the initial flat region indicating that the pH does not change significantly with the addition of base (hydroxide) (see FIG. 1). The pH sharply increases around the pH 6.0, and the pH decreases around pH 7.5 or higher. The initial flat line at low pH clearly indicates that the added hydroxide is reacting with hydrated zinc ions, zinc chloride complexes, and/or zinc hydroxide species-or their hydrogen peroxide equivalents-to form complexes with more zinc hydroxide-like characteristics. Although the pH of the solution is not initially affected by the added peroxide source, the acidity is still being neutralized. The acidic buffering capacity of the mixture is decreasing because the hydrated zinc ions are being converted to hydroxide species. The sharp rise in pH shown in figure 1 most likely indicates that the conversion is substantially complete. The zinc hydroxide species themselves are not as readily soluble as simple hydrated zinc ions and the treated matrix will have better durability when the precipitated material is not readily soluble, so we believe that the antimicrobial metal-hydrogen peroxide complex will retain better and have a longer lasting antimicrobial effect as the neutralization reaction proceeds.

Since the pH does not change significantly during the early stages of the reaction, pH is not a useful tool to detect the progress of the reaction at the initial stage of neutralization; however, the observation of a sudden jump in pH above 7.0 is a very useful indicator that the correct properties of the solution have been obtained for a long lasting antimicrobial efficacy when treating textile substrates. The midpoint of the titration (pH 7.5) shown in figure 1 roughly indicates the addition of 0.0140 moles of hydroxide ion to 0.0074 moles of zinc ion. Essentially, the ratio of hydroxide to zinc is 2: 1. It should be noted that the exact ratio may vary depending on whether other acidic species are present in the mixture. Although treatment solutions having a pH of 7.5 or higher may produce better long-lasting antimicrobial efficacy than less pH neutralized solutions, in practice it has been found that higher neutralization also produces more precipitate and is more difficult to apply to the substrate in a uniform manner. In addition, it has been found that the reactivity (i.e. instability) of hydrogen peroxide is increased at alkaline pH values. This shortens the effective storage time of the composition and can lead to adverse effects such as bleaching of the coloured substrate. In addition, increasing the degree of neutralization requires the addition of solids to the treatment formulation and may reduce the solubility of the dried material, since the neutralization by-product (sodium chloride) is highly water soluble. Thus, the optimum degree of neutralization in the practice of the invention is generally between 50% and 100% (where 100% is equivalent to the amount of hydroxide required to raise the pH to about 7.5).

One aspect of the invention is an acetate-free treatment formulation comprising a metal derivative and hydrogen peroxide for imparting durable antimicrobial efficacy to a substrate. The treatment formulation may comprise a solution, suspension, dispersion or colloid. Preferred metal derivatives are zinc derivatives. The zinc derivative may be in the form of hydrated zinc ions, ionic complexes of zinc ions, complexes of zinc ions with hydrogen peroxide, or zinc hydroxide species, or combinations thereof.

The source of the metal derivative for the antimicrobial treatment formulation is typically a soluble metal salt, wherein the negatively charged counterion portion of the salt does not have an adverse effect, such as the release of acid mist. Metal salts with inorganic counterions such as chloride, bromide, nitrate, or sulfate are preferred. In one aspect of the invention, the metal derivative used in the antimicrobial treatment formulation is a mixture of chloride and nitrate salts, whereby the mixture reduces the potential corrosivity of the chlorine-containing solution. In a preferred embodiment of the invention, the source of metal ions for the antimicrobial treatment formulation is a mixture of zinc chloride and zinc nitrate. The preferred molar ratio of zinc chloride to zinc nitrate is 1:2 to 2: 1. A more preferred molar ratio of zinc chloride to zinc nitrate is 1: 1. Reducing the amount of zinc chloride in the mixture to a molar ratio of zinc chloride to zinc nitrate of less than about 1:2 can result in the formation of thick colloidal precipitates that are difficult to use in treating textiles.

The treatment formulation may also comprise a source of hydroxide ions. In general, it is advisable, in order to obtain a treatment preparation which imparts a long-lasting antimicrobial activity to the substrate, to add at least 25% of hydroxide ions in order to raise the pH of the acetate-free mixture comprising metal derivative and hydrogen peroxide from the initial pH to 7.5. Preferably, in order to obtain a treatment formulation capable of imparting durable antimicrobial activity to a substrate, it is necessary to add hydroxide ions in an amount of 50% to 100% so that the pH of the acetate-free mixture comprising metal derivative and hydrogen peroxide is raised from the initial pH to 7.5. Preferably, in order to obtain a treatment formulation capable of imparting durable antimicrobial activity to a substrate, it is necessary to add hydroxide ions in an amount of 75% so that the pH of the acetate-free mixture comprising metal derivative and hydrogen peroxide is raised from the initial pH to 7.5.

In a preferred embodiment of the invention, the metal concentration in the acetate-free treatment formulation is at least 0.05% by weight. In a more preferred embodiment of the invention, the metal derivative is present in the substantially acetate-free treatment formulation at a concentration of at least 0.250% by weight. In a further preferred embodiment of the invention, the metal derivative is present in a concentration of at least 0.75% by weight. In a still further preferred embodiment of the invention, the metal derivative is present in the substantially acetate-free treatment formulation in a concentration of at least 1.5% by weight. In the most preferred embodiment of the invention, the metal derivative is present in the acetate-free treatment formulation at a concentration of at least 3.00% by weight. The recited concentrations refer only to the metallic portion of the element and do not include the weight of any associated counterion, ligand, or complex species. The specific preferred ranges in this paragraph are merely for optimization of antimicrobial efficacy. Those skilled in the art will recognize that higher concentrations may be more costly, or other factors may require the use of lower levels.

In a preferred embodiment of the invention, the molar ratio of hydrogen peroxide to zinc in the acetate-free treatment formulation is 1: 1. In a more preferred embodiment of the invention, the molar ratio of hydrogen peroxide to zinc in the acetate-free treatment formulation is 2: 1. In a further preferred embodiment of the invention, the molar ratio of hydrogen peroxide to zinc in the acetate-free treatment formulation is 3: 1. In the most preferred embodiment of the invention, the molar ratio of hydrogen peroxide to zinc in the acetate-free treatment formulation is 4: 1. The specific preferred ranges in this paragraph are merely for optimization of antimicrobial efficacy. Those skilled in the art will recognize that higher concentrations may be more costly, or other factors may require the use of lower levels.

One aspect of the invention is the use of an acetate-free treatment formulation prepared by combining a metal derivative, water, hydrogen peroxide, and (optionally) a source of peroxide ions, to impart a long-lasting antimicrobial efficacy to a substrate. The treatment formulation may comprise a solution, suspension, dispersion, or colloid. In a preferred embodiment of the invention, the hydroxide ion source is capable of providing 0.50 moles of hydroxide for each mole of zinc ions in the treatment formulation. In a more preferred embodiment of the invention, the hydroxide ion source is capable of providing 1.0 to 2.0 moles of hydroxide per mole of zinc ions in the treatment formulation. In the most preferred embodiment of the invention, the hydroxide ion source is capable of providing at least 1.5 moles of hydroxide per mole of zinc ions in the treatment formulation.

In the practice of the present invention, the source of hydroxide ions will be a reagent familiar to those skilled in the art. Preferred hydroxide ion sources in the practice of the present invention include sodium hydroxide and potassium hydroxide.

In one aspect of the invention, the acetate-free treatment formulation comprising a metal derivative and hydrogen peroxide also comprises a persistence enhancer that is miscible, soluble, or dispersible in an aqueous medium. The durability enhancing agent can be a polymer (such as polyvinyl alcohol, or a copolymer thereof) and can be added to the treatment formulation in the form of a suspension, emulsion, dispersion, or solution. The persistence enhancing agent may also be a long chain fatty acid, or a salt thereof. Preferred persistence enhancers are sodium or potassium salts of C12-C20 fatty acids. The most preferred persistence enhancer is sodium stearate. When sodium stearate is used as a persistence enhancer, its concentration in the treatment formulation is preferably at least 0.1% by weight. In a more preferred embodiment, the concentration of the sodium stearate persistence enhancer is at least 0.25%, and in a most preferred embodiment, the concentration of the sodium stearate persistence enhancer is at least 0.50%. In a preferred embodiment, sodium stearate is added to the treatment solution as an aqueous solution, wherein the concentration of sodium stearate is 1% to 10%, and the solution has a melting point of about 60 ℃. Before further homogenization, a liquid sodium stearate solution is preferably added for uniform mixing.

It is well known that hydrogen peroxide reacts spontaneously with dissolved iron (Fenton reaction). This reaction decomposes the hydrogen peroxide, and so the presence of dissolved iron will interfere with the formation of the antimicrobial composition. Iron chelation activity may be achieved with chelating agents such as EDTA (ethylene diamine tetraacetic acid). Accordingly, one aspect of the present invention is to add EDTA, or a sodium salt of EDTA, to the treatment solution in order to stabilize the hydrogen peroxide from decomposition by iron. During contact with the treatment equipment, the treatment solution may come into contact with the iron, or the iron may even be present in the treatment water used to prepare the treatment solution. The addition of chelating agents such as EDTA stabilizes the treatment solution during use and storage. Those skilled in the art recognize that other chelating agents may also be used to chelate iron. In a preferred embodiment of the invention, the treatment formulation comprises at least 0.01% by weight of EDTA. In the most preferred embodiment of the invention, the treatment formulation comprises at least 0.05% by weight EDTA.

Unexpectedly, aqueous suspensions containing large amounts of insoluble solids or visible precipitates can be uniformly applied to textile substrates without causing a degree of staining, fading, or other adverse aesthetic effects. Danna in the prior art indicates that the treatment solution must be kept acidic to prevent the formation of insoluble precipitates. Unfortunately, as noted above, the Danna approach can lead to a number of problems, such as the generation of acid mist, wasteful consumption of chemicals, and low efficacy (long lasting antimicrobial activity) at a particular treatment level (metal content). All of these problems are cost issues, making this technology commercially unattractive. The present invention overcomes these problems by eliminating the use of acetate salts.

The treatment formulation used to prepare the antimicrobial treatment product of the present invention is a colloidal suspension or dispersion of metal hydroxides, oxides and/or peroxides. These suspensions generally have a milky appearance, and solid white particles are visible in the suspension. Direct use of the prepared colloidal suspension may leave an undesirable white residue or deposit on the textile surface treated with the suspension. This is most evident on dark colored textiles. These deposits can be removed by homogenization to reduce particle size prior to application to the textile. It has been found that the suspension after passing through a mesh filter with a pore size of about 200 microns does not produce any visible residue on the commonly dark or woven fabrics consisting of cotton, polyester, or mixtures thereof. Thus, one aspect of the invention is to homogenize the formulation and pass it through a filter having a pore size of 200 microns prior to use. Homogenization can be accomplished by conventional homogenizing equipment such as a stirrer, high shear homogenizer, colloid mill, or ultrasonic equipment.

The advantages of the current improved methods and formulations for preparing antimicrobial textiles with good wash durability have been demonstrated in laboratory experiments and also in pilot production runs conducted at commercial textile manufacturing plants. The following example gives details of laboratory experiments and pilot plant runs. The results of the pilot production run confirm the laboratory findings that the wash durability of antimicrobial textiles can be improved by both the addition of hydroxide to neutralize the treatment solution and the removal of acetate and acetic acid from the treatment formulation, even in low concentration treatment solutions. It was also confirmed that as a result of these changes, the physical and aesthetic properties of the treated textile were also improved. This also achieves economic cost benefits because of the improved process and formulation, and also in part because of the lower overall amount of chemicals required, the fact that zinc chloride is less expensive than zinc acetate, and the elimination of expensive rinsing and additional drying steps. In addition, the improved process is clearly beneficial to control, environmental, health and safety issues.

One aspect of the invention is the production of antimicrobial textiles by treating substrates with the treatment formulations of the invention.

One aspect of the present invention is that the antimicrobial textile prepared using the materials and methods of the present invention is effective in reducing viable bacteria when about 0.5mL of an aqueous solution containing about 1,000,000 viable bacterial organisms is contacted with 3 square inches of the antimicrobial textile. In a preferred embodiment of the present invention, the materials and methods of the present invention reduce viable bacteria, thereby reducing the residual content by at least 1000 viable organisms (3-log reduction). In a more preferred embodiment of the invention, the viable bacteria are reduced to less than 100 residual viable organisms (4-log reduction). In a more preferred embodiment of the invention, the viable bacteria are reduced to less than 10 residual viable organisms (5-log reduction). In the most preferred embodiment of the invention, the viable bacteria are reduced to zero (6-log reduction, or total kill) residual viable organisms. In a preferred embodiment of the invention, said reduction of viable bacteria occurs within 24 hours. In a more preferred embodiment of the invention, said reduction of viable bacteria occurs in less than 10 hours. In a further preferred embodiment of the invention, said reduction of viable bacteria occurs in less than 4 hours. In a further preferred embodiment of the invention, said reduction of viable bacteria occurs in less than 2 hours. In a further preferred embodiment of the invention, the reduction of viable bacteria occurs in less than 1 hour. In the most preferred embodiment of the invention, said reduction of viable bacteria occurs in less than 30 minutes.

In embodiments of the present invention, the reduction of viable bacteria is observed on the treated substrate or antimicrobial textile prepared according to the present invention prior to rinsing, washing or washing.

In a preferred embodiment, the reduction of viable bacteria is observed after rinsing the treated substrate or antimicrobial textile. In a more preferred embodiment, the reduction in viable bacteria is observed after washing of the treated substrate or antimicrobial textile. In a more preferred embodiment, the reduction in viable bacteria is observed after 5 washes of the treated substrate or antimicrobial textile. In a more preferred embodiment, the reduction in viable bacteria is observed after 10 washes of the treated substrate or antimicrobial textile. In a more preferred embodiment, the reduction in viable bacteria is observed after 25 washes of the treated substrate or antimicrobial textile. In the most preferred embodiment, the reduction in viable bacteria is observed after 50 or more washes of the treated substrate or antimicrobial textile. In a preferred embodiment of the invention, the reduction of viable bacteria occurs upon washing with cold water (< 80 ° f). In a more preferred embodiment of the invention, the reduction in viable bacteria occurs upon washing with warm water (80 to 119 ° f). In the most preferred embodiment of the invention, the reduction in viable bacteria occurs upon washing with hot water (> 119 ° f).

A drying step is required in the practice of the present invention. After treatment with the antimicrobial treatment formulation, the textile substrate is dried. One aspect of the method of the present invention is that the substrate can be completely dried using any combination of temperature and time.

For example, "dry" as used herein refers to drying a substrate exposed to a treatment formulation to a constant weight. As used herein, "dry to constant weight" means dry to a point where continued application of the selected drying procedure does not result in any appreciable weight loss due to evaporation of moisture or other solvents.

Achieving constant weight is a useful tool to measure dryness; however, achieving constant weight is not a real factor in imparting antimicrobial properties to a substrate. The particular temperature and drying time required to achieve thorough drying will also depend on the particular substrate material, the initial humidity of the substrate, the weight and size of the substrate, the flow rate of gas used for the substrate during drying, and the humidity of the air or other medium in contact with the substrate, among other things. Any combination of drying equipment, drying methods, temperatures and drying times that will thoroughly dry the treated substrate is possible. As an example, the drying step may be performed in an oven (e.g., 2 hours 80 ℃), a high throughput oven (e.g., 30 seconds 140 ℃), a clothes dryer, a vacuum chamber, a dehumidifier, a dehydrator, or a lyophilizer (lyophilizer), depending on the specific characteristics of the particular application. Infrared heat, radiant heat, microwaves and hot air are all suitable drying methods for substrates that have been exposed to the treatment formulation. The upper drying temperature limit for a particular application generally depends on the degradation temperature of the particular substrate or peroxide. Other drying methods, such as supercritical fluid drying, can also be successfully used in the practice of the present invention. Freeze drying may also be used. It is generally preferred that the treated article is not exposed to excessive heat. The heat required to complete the drying effect in a reasonable time is a reasonable heat.

In one aspect of the invention, the substantially acetate-free treatment formulation is applied to the substrate using methods known in the art including, but not limited to, spraying, dipping, injecting, brushing, filling, or rolling.

Excess substantially acetate-free treatment formulation may be removed by suitable methods known in the art, such as rollers, clamps, presses, centrifugation, wringing, or suction, and the like, to control the amount of composition in the final treated material. Any mechanical action or force may be used; however, when the treatment formulation has been removed, the mechanical or mechanical forces are preferably homogeneous in order to achieve a homogeneous distribution of the remaining components in the loaded matrix. It should be noted that mechanical force is applied to remove excess treatment formulation prior to drying, as opposed to a drying procedure, which removes both the antimicrobial agent and the carrier solution, whereas a drying procedure removes the carrier solution by evaporation only, leaving the antimicrobial agent on the treated substrate.

Laboratory experiments have demonstrated that the formulations and methods of the present invention are suitable for use with a variety of textile materials, including natural and synthetic materials and mixtures thereof. Textile substrates comprising cotton, polyester, acrylic, nylon, and lycra have all been shown to have durable antimicrobial activity after treatment with the materials and methods of the present invention. The formulations and methods of the present invention are suitable for use with a variety of substrates, including fabrics, knits, and non-woven textiles.

It was found that antimicrobial textiles prepared using the acetate-free treatment formulations of the present invention containing metal derivatives and hydrogen peroxide are resistant to discoloration. It is known that some antimicrobial textile products, such as those treated with silver, quaternary ammonium compounds (quats), or polyhexamethylene biguanide (PHMB), fade more readily than untreated textiles during use or laundering (see, e.g., U.S. patent 5700742). For quaternary ammonium compounds or biguanides such as PHMB, the positive charge of the active agent tends to bind with the detergent, which in turn binds the soil or grease. Similarly, the electrostatic attraction of anionic species such as dyes to positively charged sites can lead to discoloration. For silver-based technologies, the active agent itself can cause discoloration, particularly upon aging, or after exposure to light. The antimicrobial textiles produced using the acetate-free treatment formulations of the present invention do not discolor by these mechanisms, as evidenced by the test results of the standard methods described herein.

The acetate-free treatment formulation of the invention comprising a metal derivative and hydrogen peroxide may be combined with an aqueous polymer emulsion that may be used as or in the preparation of a pressure-sensitive adhesive. According to the method of the invention, the combination can be applied to a substrate to produce a material having adhesive and antimicrobial properties. The adhesive may be used as a component of a self-adhesive article, such as a tape, label, bandage, wound dressing, or other article for quick and easy adhesion to a surface.

The acetate-free treatment formulation of the present invention comprising a metal derivative and hydrogen peroxide may be combined with an aqueous polymer emulsion or solution used as or to prepare a coating, latex paint, acrylic latex paint, varnish, paint, sealant, coating, shellac, caulking glue, or waterproof coating.

The acetate-free treatment formulation of the present invention comprising a metal derivative and hydrogen peroxide can be used to prepare pressure-treated wood that is resistant to microbial attack and degradation. The treatment solutions of the present invention are impregnated, injected, or infiltrated into wood (wood), wood (timber), or wood (lumber) material using methods familiar to those skilled in the art. This typically involves the use of negative pressure or vacuum to assist in the penetration of the antimicrobial composition into the wood.

The acetate-free treatment formulations of the present invention comprising a metal derivative and hydrogen peroxide may be used to prepare antimicrobial wound dressings by applying the compositions to a suitable substrate such as a knitted or non-knitted textile, gauze, bandage, sponge, or other absorbent material. Because wound dressing materials are typically discarded rather than washed after use, the amount of antimicrobial component required may be lower than for the apparel textiles described herein. Prior to use, the prepared wound dressing may be rinsed to remove soluble or leachable components, which may be transferred from the garment to the body and may have adverse effects such as cytotoxicity or delayed wound healing.

In one aspect of the inventive methods of the present application, substrates treated using the materials and methods of the present invention include wound dressings, burn dressings, sanitary napkins, incontinence pads, tampons, inherently antimicrobial absorbent dressings, diapers, toilet paper, sanitary wipes, sponges, cotton swabs, surgical gowns, isolation gowns, lab coats, gloves, surgical scrubs, head covers, hair covers, masks, sutures, floor mats, lamp covers, examination table cloths, plaster liners, splint liners, padding, gauze, packaging materials, mattress covers, bedding, beddings, towels, garments, undergarments, socks, shoe covers, automotive air filters, aircraft air filters, HVAC system air filters, military protective clothing, adhesives, tapes, labels, devices for preventing biohazards or biological warfare agents, food packaging materials, meat packaging materials, fish packaging materials, Food processing clothing, countertops for preparing food, carpets, wood, gypsum wallboard, paints, varnishes, caulking glues, pressure sensitive adhesives, protective or decorative coatings, paneling, masonry, grout, tile, water-repellent press-treated wood, cat or other animal litter or bedding, paper, or paper currency.

In one aspect of the invention, additives such as uv protectants, processing aids, softeners, antistatic agents, colorants, dyes, indicators, drugs, oils, lubricants, microspheres, temporary visual indicators, nutrients, growth factors, vitamins, emollients, moisturizers, fragrances, perfumes, and the like may be incorporated into the acetate-free treatment formulation.

In one aspect, the invention provides an acetate-free and substantially peroxide-free aqueous binder composition for hydrogen peroxide comprising a metal derivative and a source of hydroxide ions; wherein the binder can be combined with hydrogen peroxide and subsequently used to treat a substrate and impart a persistent antimicrobial activity to the substrate. The adhesive composition components are similar to the other acetate-free treatment formulations described herein; however, the hydrogen peroxide component of the composition is removed or substantially reduced. Such a composition has the following advantages due to the absence of oxidizing agent (hydrogen peroxide): increased stability, safety and minimized storage or transportation problems. The binder component may be produced in concentrated form. The binder is homogenized as part of the manufacturing process. The adhesive composition may be mixed with or diluted with hydrogen peroxide and the substrate treated according to the method of the invention to impart a long lasting antimicrobial activity to the substrate. The same preferred embodiments of the other aspects described herein are also applicable to the adhesive composition, including the use of zinc chloride and zinc nitrate, the amount of hydroxide source, the addition of components such as EDTA and/or fatty acid salts, softeners, and other additives. In other words, the adhesive composition may comprise any of the components described in the various aspects of the invention, except for the removal of hydrogen peroxide or its concentration is substantially reduced as compared to the acetate-free treatment formulations described herein. The binder may be prepared in concentrated form, preferably containing twice the concentration of the metal derivatives and other additives described in the preferred antimicrobial treatment solutions described herein; more preferably, four times the concentration of the metal derivative and other additives described in the preferred antimicrobial treatment solutions described herein; most preferably, at least four times the concentration of the metal derivative and other additives described in the preferred antimicrobial treatment solutions described herein is included. Optimal performance and long lasting antimicrobial efficacy is achieved if the desired amount of HP can be added to the concentrated binder and mixed thoroughly before diluting the binder or binder-HP mixture to the target use concentration. Therefore, it is preferable to add HP in a concentrated form (preferably a 35% HP solution, and more preferably a 50% or higher HP solution). Preferably, the HP is allowed to react with the concentrated binder for at least 20 minutes before dilution or use. More preferably, the HP is allowed to react with the concentrated binder for at least 60 minutes before dilution or use. Preferably, the mixture of concentrated binder and HP is continuously and thoroughly stirred, mixed, or agitated as the reaction proceeds prior to dilution or use. Preferably, the mixture of concentrated binder and HP is also homogenised prior to dilution or use.

In one aspect of the invention, the acetate-free and substantially peroxide-free aqueous binder composition may be applied to a substrate without the addition of any additional hydrogen peroxide, after which the treated substrate may be treated with hydrogen peroxide before or after drying to produce a treated substrate having antimicrobial properties.

Over time, and over extended periods of normal use, antimicrobial articles of the present invention prepared by treating substrates with compositions of the present invention may lose some of their antimicrobial efficacy due to excessive laundering or other factors. In one aspect of the invention, at least a portion of the lost antimicrobial efficacy may be restored by exposing the article to hydrogen peroxide, which reacts with and binds to the article, or at least restoring a portion of the original antimicrobial efficacy of the article. Accordingly, one aspect of the present invention provides a method of preparing antimicrobial articles having regenerative antimicrobial efficacy.

In one aspect of the invention, the antimicrobial components, formulations and compositions, and treated substrates, materials, or articles of the present invention can be used to neutralize, inactivate, or destroy certain chemical substances. The antimicrobial components, formulations and compositions of the present invention, as well as the treated substrates, materials, or articles, comprise a peroxide, and it is well known that peroxides, as oxidizing or oxidizing agents, can destroy, neutralize, or inactivate a variety of different chemical species, including converting toxic chemicals to less or non-toxic forms. For example, hydrogen peroxide is known to react rapidly with hydrogen sulfide (a toxic gas), converting it to non-toxic sulfur and sulfate salts (see, e.g., U.S. patent 4,574,076). Similarly, peroxides can be used to inactivate chemical warfare agents (U.S. patent 7,442,677). Thus, in one aspect of the invention, a textile or other substrate treated with a formulation or composition of the invention comprises a protective device (e.g., a garment, glove, mask, or drape) designed to protect a person or object from exposure to toxic or harmful chemicals.

The release of hydrogen sulfide into buildings made of contaminated gypsum board (wallboard) imported in china (Tim Padgett, "Is drawal the Next Chinese inport Scandal?TimeMarch 23, 2009). The compositions and methods of the present invention are useful for neutralizing volatile sulfides released in contaminated gypsum board. For example, contaminated gypsum board may be treated with an acetate-free composition comprising hydrogen peroxide as described herein. Alternatively, the acetate-free treatment formulation of the present invention comprising a metal derivative and hydrogen peroxide may be combined with an aqueous polymer emulsion or solution used as or in the manufacture of paints, latex paints, acrylic latex paints, lacquers, varnishes, sealants, coatings, shellacs, caulking, or waterproofing coatings and combinations for contaminated gypsum board to prevent or neutralize the release of toxic or corrosive volatile chemicals. Alternatively, the acetate-free treatment formulation of the present invention may be incorporated into gypsum wallboard during manufacture.

In view of the general disclosure provided above in this application, those skilled in the art will appreciate that these disclosures enable the inventive methods defined in the various aspects described in this application to be performed on embodiments of the inventive methods. However, the experimental details included are provided to ensure that the invention is fully described in writing, including the best mode thereof. It should be understood, however, that the scope of the present invention should not be interpreted in accordance with the particular embodiments provided, but rather should be understood with reference to the aspects described herein and to the full description of the inventive process which is presented in this application as a whole.

It is to be understood that the invention may be embodied in other specific forms. Moreover, while the forms of the invention herein shown and described constitute preferred embodiments of the invention, it is not intended to represent all possible forms of the invention. It is also understood that the words which have been used are words of description rather than limitation, and various changes may be made without departing from the spirit and scope of the invention as disclosed. The scope of the invention should not be limited to only the given embodiments.

Concentrations, sizes, amounts, and other numerical data may be presented herein in a range format. It is to be understood that such range format is used merely for convenience and brevity and should be interpreted flexibly to include not only the numerical values explicitly recited as the limits of the range, but also to include all the individual numerical values or sub-ranges encompassed within that range as if each numerical value and sub-range is explicitly recited. For example, a weight ratio range of about 1 wt% to about 20 wt% should be interpreted to include not only the explicitly defined limits of 1 wt% and about 20 wt%, but also include individual weights, such as 2 wt%, 11 wt%, 14 wt%, and sub-ranges, such as 10 wt% to 20 wt%, 5 wt% to 15 wt%, etc.

Examples

Example 1-production of pilot scale antimicrobial textiles at low pH with solutions of Zinc, acetate, chloride, acetic acid, and Hydrogen peroxide (comparative example)

This is a comparative example, essentially following the procedure of Danna et al (U.S. Pat. No. 4,199,322). These experiments were conducted at a commercial textile processing laboratory located in south carolina. The textile substrate is 100% cotton (5 oz/yd) dyed olive green²) The knitted sweater material is used for manufacturing military underwear. All batches included the addition of fabric softener (Acralube CP) at normal use levels (about 2%). Hydrogen peroxide (50% aqueous) and acetic acid (56%) were provided in situ from the textile processing laboratory. Zinc chloride and sodium acetate were supplied by SNF corporation (Riceboro, GA). Two separate batch runs were performed (high and low concentration treatment solutions). The treatment compositions are described in table 1.1. The percentage values represent the raw material addition amount for each component. For example, "6.32% hydrogen peroxide" refers to hydrogen peroxide solutionThe actual concentration of the liquor was 3.16%, as indicated in the table, since the purity of the raw material was 50.00%.

TABLE 1.1

Each ingredient was added to water in order (from right to left) to prepare a treatment solution. The mixture was prepared in a tank and poured directly into the pad tank. The pH of the solution used in run 1 was determined to be 4.7 and the pH of the solution used in run 2 was determined to be 5.7. The fabric was treated using a horizontal padding machine running a single chain structure. To wet the dry pad (the fabric placed is dry), the settings were adjusted to obtain a 95% by weight solution of the fabric. After filling, the filling material was passed through a 2-pass dryer at-300 ° f at a speed of-20 ypm to complete drying, as per the instructions for the same fabric without the antimicrobial finish. The dry fabric was left in the funnel overnight before compaction.

The observed data are as follows: the laboratory personnel indicated that the softness of the treated textile in both batches was acceptable, although not as good as the same textile without antimicrobial finish. An unpleasant acidic odor (described as "sour") was noted. The odor was considered by the manufacturer to be quite unpleasant and precluded the commercial viability of these formulations. Slight color shading was also noted on the original fabric, which was more evident after the dry cloth was stored overnight in the funnel. The fabric appearance was also mottled with distinct discolored discrete areas resembling bleaching spots-probably due to insufficiently dissolved sodium acetate reacting with the overnight fabric stacked in the funnel under hot storage conditions after drying. The fabric stored for several weeks did not wash or rinse, and its color further faded, continuing to emit an acetic acid odor. Workers in textile processing laboratories say that the discoloration and odor problems are each severe enough to preclude the feasibility of commercial production of these formulations and methods.

The materials of run 1 were washed in multiple cycles (cold water wash, five cycles followed by drying, tack-free detergent) according to the method described herein and then tested for antimicrobial efficacy. The material so produced, the material that has been washed 1 time, and the material that has been washed 4 times as described herein showed (total kill) of staphylococcus aureus in the test methods described herein. The material in run 1, which had been washed 10 or 25 times, showed a 4.7-log reduction in staphylococcus aureus. The material in run 1, which had been washed 50 times, showed a 2.4-log reduction in Staphylococcus aureus.

The materials of run 1 were washed for multiple cycles according to the methods described herein and then tested for antimicrobial efficacy. The material so produced, the material that has been washed 1 time, and the material that has been washed 4, 10 or 25 times as described herein show (total kill) klebsiella pneumoniae. The material that had been washed 50 times in run 1 showed a 0.8-log reduction in klebsiella pneumoniae.

The materials of run 1 were washed for multiple cycles according to the methods described herein and then tested for antimicrobial efficacy. The material so produced, the material that has been washed 1 time, and the material that has been washed 4, 10, or 25 times as described herein show (total kill) of e. The material in run 1 that had been washed 50 times showed zero reduction in E.coli.

The material in run 2 was washed for multiple cycles according to the method described herein and then tested for antimicrobial efficacy. The materials so produced, which are described in this application, the materials which have been washed 1 time, and the materials which have been washed 4 times, show total kill of staphylococcus aureus. The material in run 2, which had been washed 10 times, showed a 2.0-log reduction in Staphylococcus aureus. The material in run 2, which had been washed 20 or 50 times, showed a 0.5-log reduction in staphylococcus aureus.

The material in run 2 was washed for multiple cycles according to the method described herein and then tested for antimicrobial efficacy. The produced material, the material that has been washed 1 time, and the material that has been washed 4 or 10 times described herein show (total kill) klebsiella pneumoniae. The material in run 2 that had been washed 25 or 50 times showed zero reduction in staphylococcus aureus.

The material in run 2 was washed for multiple cycles according to the method described herein and then tested for antimicrobial efficacy. The material produced, which is described in the present application, and which has been washed 1 time, shows (total killing) of E.coli. The material in run 2 and the material that had been washed 4, 10 or 25 times showed zero reduction in E.coli.

EXAMPLE 2 production of pilot scale antimicrobial textiles Using solutions of Zinc chloride and Hydrogen peroxide with addition of hydroxide (acetate free)

The materials, equipment and methods followed example 1. However, the composition of the treatment solution is modified, with the exception of other details described below. The treatment formulation contained acetate or acetic acid and was adjusted to pH 7.5 with sodium hydroxide. The treatment compositions actually used are shown in table 2.1.

TABLE 2.1

(1) Comprising water contained in a NaOH solution for adjusting the pH

The treatment formulation was prepared by adding zinc chloride to water (an exotherm was observed), and hydrogen peroxide to an aqueous solution of zinc chloride. After the HP addition, the pH was adjusted before softener addition. To wet the dry pad (the fabric placed is dry), the settings were adjusted to obtain a 95% by weight solution of the fabric. .

Runs 3 and 4 of this example and runs 1 and 2 of example 1 used a wet hood dry (WOD) process in which the material entering the treatment solution was dry. The production process used by most textile mills is Wet On Wet (WOW). This is for economy and plant utilization efficiency: the wet hood dry process adds an extra drying step in the preparation (the resulting fabric after bleaching or dyeing wet-WOD requires an extra drying step before filling with the final agent). The treatment cost of the additional drying step is estimated to be at least $0.10/lb of fabric. This cost does not take into account the opportunity cost of using drying equipment with which other materials can be processed.

The WOW operation was performed using the composition in table 2.2 (operation 5).

TABLE 2.2

(1) Comprising water contained in a NaOH solution for adjusting the pH

The pH was again adjusted to 7.5 with NaOH. Note that incoming wet fabrics contain large amounts of water (i.e. 40-70%). The water dilutes the treatment formulation for the pad bath. Therefore, it is necessary to prepare higher concentrations of treatment formulations for wet fill while still keeping the total amount of chemicals applied to the fabric the same. The amount of the pad bath composition collected during wet-on-wet was 15%. For wet hood wet processing, a pre-dilution process is utilized, wherein a high concentration pad mix is prepared and initially mixed with water in the pad tank, and then the same higher concentration feed mix is added to compensate for the water that the wet fabric carries into the system. This process compensates for dilution of the pad bath, which often occurs in wet hood systems. For run 5, the solution was prepared to a 10% harvest specification instead of 15% due to the addition of two barrels of the mixture and one barrel of water in the pad tank.

The observed data are as follows: the products of runs 3-5 did not differ from the visual observations of the control fabric, which was prepared by adding the softener (without the antimicrobial agent). No off-flavor is present during the treatment or in the finished fabric. A slight gloss was noted on the fabric prepared by the Wet On Wet (WOW) method of run 5 with a small shade change line at the fold of the sample. The manufacturer has originally pointed out that the "hand" (the jargon used in the textile industry to measure softness) of the so dried sample is insufficient. However, after compaction, the hand of the sample was reported to be acceptable. After filling and drying, the sample was compressed. In many cases, the freshly dried sample is allowed to stand for a period of 1-3 days before compaction to allow rewetting in the air step and prevent dimensional distortion from occurring in the future. The air step "relaxes" the fabric. Compacting consists of passing the fabric through steam, then flattening the fabric by means of a roller, and then folding it: the folded fabric may be conveniently boxed and may be cut into the desired shape in a stacked folded configuration. This process is part of a common textile production procedure.

Chemical availability of run 4, ZnCl, relative to runs 1 and 2 (example 1)₂The reduction is 4 times, the acetic acid content is reduced by 100 percent, and the HP is reduced by 50 percent. A small amount of NaOH is required as an additional ingredient. Using the improved process and formulation of example 2 (relative to the prior art process of example 1), the estimated cost of chemicals is reduced by one-half to two-thirds. Furthermore, this process was found to be commercially viable, since all the disadvantages observed in example 1 were excluded.

The materials of runs 3, 4 and 5 of this example were washed (in cold water) for multiple cycles according to the method described herein and then tested for antimicrobial efficacy. For all three runs, the so produced samples as described herein and the washed samples or samples washed 10 or 25 times showed greater than 5.50log reduction of klebsiella pneumoniae and staphylococcus aureus (tested separately). These results clearly show that the formulations and methods of the current invention produce a long lasting antimicrobial efficacy which is a significant improvement over the prior art. For example, the material of run 4 of the present example exhibited superior antibacterial efficacy to the material of run 2 (comparative example 1) despite the fact that the concentrations of zinc chloride and hydrogen peroxide in run 4 were half those in run 2. In addition, operation 4 does not use acetate and acetic acid.

Example 3 production of pilot scale antimicrobial textiles Using mixtures of Zinc chloride, Zinc nitrate, Hydrogen peroxide, sodium hydroxide, EDTA and sodium stearate

The materials, equipment and methods followed example 1, but the components of the treatment solution were modified, with the exception of the other details described below. The treatment formulation contained no acetate or acetic acid. The amounts of each agent actually added to prepare the treatment formulations are shown in table 3.1. The composition was equilibrated with distilled water. The reagents (except for the softener) were combined and then homogenized in a large commercial mixer for about 5-10 minutes. About 3.5 gallons of mixture per batch was passed through a nylon screen with 200 micron pore size and then several batches were mixed to obtain a final working volume of about 20 gallons of treatment formulation. The desired amount of softener is then added. The wet pickup was measured to be 90% by weight. These experiments were conducted at a commercial textile processing laboratory located in south carolina. The textile substrates of runs 6, 7 and 8 were 100% cotton (-5 oz/yd) dyed olive green²) The knitted sweater material is used for manufacturing military underwear. For run 9, a black cotton/polyester blend material was used. All batches included the addition of fabric softener (Acralube CP) at normal use levels. Hydrogen peroxide (50% in water) was supplied in situ from the textile processing laboratory. Zinc chloride ("ZC", solid) and zinc nitrate ("ZN", solution, zinc content 17%) were supplied by SNF corporation (Riceboro, georgia). Sodium hydroxide (99%) was purchased from AAA Chemicals (Pasadena, TX). Sodium stearate ("NaSt", cat #269880010) was purchased from Acros Organics (New Jersey, USA). EDTA tetrasodium salt, dihydrate (cat #03695) was purchased from Fluka. The treatment formulation of run 6 was then diluted for runs 7, 8 and 9 as described in table 3.1. And additional softener is added to maintain the softener concentration constant. The pH of all four treatment formulations was between 4.8 and 5.0. Some foaming was observed, but homogenization was beneficial to the solution because the solution easily passed through a 200 micron filter. There was no noticeable spotting or discoloration on the treated material. After drying, the treated materials of runs 6, 7 and 8 were subjected to a "ball blast" test as well as the untreated fabric. All values were between 80-85 pounds, indicating no loss of material.

Table 3.1: composition of treatment solution (in weight%)

Note: 1-ZnCl₂；2-Zn(NO₃)₂；3-EDTA·4Na·2H₂O

The treated antimicrobial textiles were repeatedly washed in operations 6-9 in a laboratory using the methods described herein, and then subjected to microbiological tests to assess the durability of the antimicrobial treatment. The samples were washed in hot water using ATCC detergent, and dried after each wash cycle. After 15, 20 or 25 wash cycles, the samples were microbiologically tested using e.coli according to the methods described herein. The results are shown in Table 3.2.

Table 3.2: average reduction in antibacterial efficacy against E.coli after a specified number of wash cycles (Log ^* As a whole killer)

In addition, samples of the treated material of run 6 were sent to independent certification laboratories (precision testing laboratory (PTL) of nashville, tennessee and pharmamingked laboratory of marylata, georgia) to evaluate the durable antimicrobial efficacy after washing and to test a range of physical properties common to the textile industry by AATCC standard methods. The following results were obtained:

● yarn count of fabric (ASTM D3887): 32 (transverse), 38 (longitudinal)

● color fastness in washing (AATCC-61, 3A, 3 cycles): 4.5 stage

● color fastness to rubbing (AATCC 8): grade 5 (dry), grade 4.5 (wet)

● light color fastness (AATCC 16, opt.a, 40 hours): 4.5 stage

● burst strength (ASTM D3787): 69lbs

● labile sulfur (Fed Std.191-2020): by passing

●pH(AATCC 81)：6.3

● dimensional stability,%, AATCC 135, table 1(1, IV, Aii)5 cycles: 11.1 (transverse), -6.3 (longitudinal)

● evaluation of the antibacterial finishing of textile materials (AATCC 100), after 25 washes: 99.95% (SA #6538), > 99.94% (KP #4352), > 99.93% (EC #8739)

The treated textiles of this example were washed according to the methods described herein for multiple cycles and then tested for antimicrobial efficacy against various bacterial compositions after washing using the methods described herein. The results are shown in table 3.3:

table 3.3: antibacterial effect after multiple washing

Mean reduction of surviving bacteria Log: (^*Killing all together

EXAMPLE 4 preparation of antimicrobial adhesive articles

An acetate-free treatment formulation comprising a metal derivative and hydrogen peroxide is prepared. For example, any of the treatment formulations described in tables 2.1 and 2.2 of example 2 (see above) may be used. The treatment formulation is combined with an aqueous emulsion of a polymer suitable for use in preparing a pressure sensitive adhesive, such as the emulsions described in U.S. patent 4,892,905 or 5,276,084. The mixture is applied to a substrate, such as paper, or a polymeric film or tape, using methods known in the art, and then dried and cured in an oven. The resulting pressure sensitive adhesive is expected to have antimicrobial properties.

EXAMPLE 5 preparation of antibacterial paints and coatings

An acetate-free treatment formulation comprising a metal derivative and hydrogen peroxide was prepared substantially similar in composition to the treatment formulation in example 3, run 6, except that the solution did not contain a softening agent. The treatment formulation was mixed with several different commercially available coating materials. All mixtures contained 10% by weight of the acetate-free treatment formulation and 90% by weight of the commercial coating material. 3 commercial coating materials were used: colorado "Aqua-Plastic" water-based polyurethane coatings; colorlessness acrylic paints of coronado "Seal & Finish"; and Olympic white semi-gloss "kitchen & bath" 100% acrylic latex paint. The mixture was applied to a thin sheet of polyester film (5 mil coating thickness) using a BYK coating bar, dried, and then stored for approximately one week. The coated sample was found to adhere to the substrate and normal curing occurred. Antimicrobial efficacy was tested using ASTM method E2180-07 ("standard test method for determining the activity of antimicrobial agents incorporated into polymeric or hydrophobic materials", also known as the "agar syrup" test). After one night exposure to staphylococcus aureus, all three coatings "killed" all bacteria (> 4log reduction) compared to uncoated mylar film sheets.

Example 6: comparison of Corrosion resistance Performance of acetate-free treatment formulations comprising a Metal derivative and Hydrogen peroxide

A treatment formulation was prepared consisting of about 4% zinc chloride, 7% hydrogen peroxide, and about 75% total sodium hydroxide used to raise the pH of the treatment formulation to 7.5 (i.e., about 1.8%). And then divided into two parts. In one part, sufficient tetrasodium EDTA salt was added to produce a solution concentration of about 0.025% tetrasodium EDTA salt. About 10mL of treatment formulation was poured into each individual glass petri dish. One steel nail was placed in each solution. After a few minutes, corrosion of the steel nail was observed in the petri dish without EDTA addition, with signs of significant foaming, evolution of the characteristic rust colour in the released gas and solution and on the steel nail. In contrast, in the EDTA-containing dishes, there was little sign of corrosion. This indicates that EDTA has a positive effect on stabilizing the acetate-free treatment formulation comprising metal derivatives and hydrogen peroxide against decomposition caused by contact with iron. Stable solutions are expected to have significantly longer shelf lives and be less corrosive to equipment than unstable solutions.

Example 7: corrosion resistance of acetate-free treatment formulations comprising a metal derivative and hydrogen peroxide was compared as a function of the relative concentrations of nitrate and chloride ions

Several aqueous treatment formulations containing zinc nitrate and zinc chloride in varying proportions were prepared. The total concentration of zinc salts is equal to about 4% in all cases. Each solution also contained about 5% hydrogen peroxide, 0.33% sodium stearate, and 1.8% sodium hydroxide. Formulations were prepared by mixing the ingredients into water using a magnetically driven stirrer. The ratio of zinc chloride to zinc nitrate used is shown in table 6.1. Approximately 10mL of each solution was placed in a petri dish and one steel screw was placed in each solution. After about 10 minutes, the reactivity of the solution with the steel screws was visually evaluated, as shown in table 6.1. The results clearly show that the addition of nitrate reduces the reactivity of the acetate-free treatment formulation comprising the metal derivative and hydrogen peroxide with steel and stabilizes the treatment formulation against decomposition. A stable solution is expected to have a significantly longer shelf life than an unstable solution.

Table 7.1: effect of Zinc nitrate to Zinc chloride ratio on Steel Corrosion

Example 8: effect of homogenization on the appearance of textiles treated with an acetate-free treatment formulation comprising a metal derivative and hydrogen peroxide

An aqueous treatment formulation was prepared by mixing the ingredients in water using a magnetically driven stirrer, which essentially contained 4% zinc chloride, 5% hydrogen peroxide, 0.33% sodium stearate, and 1.8% sodium hydroxide. It was used to treat 100% cotton (-5 oz/yd) dyed olive green²) The knitted sweater material of (1) was dipped into the formulation and the fabric was passed through a series of driven rollers to drain excess liquid so that the wet pick-up of the treatment formulation (relative to dry fabric) was about 115 mass%. The fabric was dried in an oven at 80 ℃ for 30 minutes. Discoloration caused by the deposition of white residues embedded or attached to the treated fabric surface was clearly observed. The experiment was repeated using the same formulation that had passed through a plastic screen with an opening size of about 200 microns. The formulation was assisted in passing through the screen by pressing and scraping the screen with a rubber spatula, wherein the formulation contained a suspended white gel-like mass. The white discoloration of the dry fabric is significantly reduced and the appearance is significantly improved. The test was again performed using the same treatment formulation, which had been homogenized in a common kitchen blender for one minute. The treatment formulation passed easily through the screen without the aid of a spatula. The fabrics treated with this homogenized formulation did not show visible white deposits or discoloration after drying. The homogenized preparation had some white precipitate settled at the bottom of the storage vessel after several days of storage; however, it redisperses easily upon gentle shaking. The redispersed suspension was readily passed through a screen and used to treat fabrics. The resulting material did not show visible white deposits or discoloration after drying.

Example 9: effect of nitrate ion substitution for chloride ion on processability of Acetate-free treatment formulations comprising Metal derivatives and Hydrogen peroxide

An aqueous treatment formulation was prepared by mixing in water using a magnetically driven stirrer, the treatment formulation consisting essentially of an aqueous treatment formulation of 4% zinc chloride, 5% hydrogen peroxide, 0.33% sodium stearate, and 1.8% sodium hydroxide (approximately equal to 75% of the amount required to raise the pH of the solution to 7.5). The formulation was homogenized in a common kitchen blender so that it passed through a mesh of approximately 200 microns in pore size. A second aqueous treatment formulation was prepared by mixing the following ingredients in water using a magnetically driven stirrer, wherein the treatment formulation consists essentially of another aqueous treatment formulation of 4% zinc nitrate, 5% hydrogen peroxide, 0.33% sodium stearate, and 1.8% sodium hydroxide. Homogenization of the formulation using a common kitchen mixer produced a thick gel-like emulsion that was not possible through a mesh of about 200 micron pore size. It thus demonstrates that some chloride ion is preferred in the practice of the invention when zinc nitrate is used. In other words, the combination of chloride and nitrate is preferred to either alone.

Example 10: effect of addition of Long chain fatty acids on Long-lasting antibacterial Activity

Antimicrobial textiles were prepared using the acetate-free treatment formulations of the present invention comprising a metal derivative and hydrogen peroxide according to the methods and formulations described herein. The retention of antimicrobial efficacy of the antimicrobial textiles was tested after various number of wash cycles using the methods described herein. As a result, it was found that the addition of about 0.25 to 0.50% of a fatty acid or fatty acid salt to an acetate-free treatment formulation improved the retention of antimicrobial properties after washing of the treated textiles; and longer chain fatty acids work best. For example, sodium stearate (C18) is more effective than sodium laurate (C12) or sodium caprylate (C8).

Example 11: use of an acetate-free treatment preparation comprising a metal derivative and hydrogen peroxide for producing an antimicrobial wound dressing

Homogenizing a treatment formulation in a blender, and filtering through a 200 micron screen, wherein the treatment formulation comprises about 2% zinc chloride, 3% hydrogen peroxide, and about 1% sodium hydroxide. The preparation is used for impregnating absorbent matrix such as knitted cotton gauze or non-knitted viscose feeling material. The wetted absorbent substrate is pressed to remove excess liquid. The moist substrate is then dried. The dried matrix can be used directly as an antimicrobial wound dressing or optionally rinsed with distilled water until the conductivity of the distilled water drops to a predetermined level indicating that no leachable material is present, and then re-dried. The re-dried material can be used directly as a wound dressing or optionally subjected to tests for antimicrobial activity and biocompatibility. The results of these tests can be used to select concentrations of modifying components in subsequent treatment formulations to optimize antimicrobial efficacy and biocompatibility of subsequent samples until a beneficial and desirable balance of properties is achieved. The treatment formulation may also optionally contain zinc nitrate, EDTA, or a binder.

Example 12: use of an acetate-free treatment preparation comprising a metal derivative and hydrogen peroxide for producing an antimicrobial animal bedding or bedding material

A treatment formulation substantially similar to the treatment formulation used in example 3, run 6 was prepared. Add 50 grams of conventional clay cat litter to about 250 grams of the treatment formulation. The mixture was briefly shaken, allowed to stand for about two minutes, and then the liquid was decanted. Air dries the wet mat. The process was repeated using a treatment formulation diluted with two volumes of water (to 33% of the original concentration). By placing 1 gram of pad into a culture tube and then adding 1.5mL of bacterial suspension (10)⁵cfu/mL) to each litter sample the samples and the dried litter were tested for antimicrobial activity. The catheters were stored overnight at 37 ℃ and counted using standard microbiological techniques before extraction with 20mL Letheen broth. Log reduction of E.coli (EC) and S.aureus (SA) was calculated based on untreated litterIn (1). The results are shown in table 12.1, which shows very good antibacterial efficacy against materials. It is expected that an antimicrobial animal litter or substrate will reduce odor and reduce the spread of pathogens. Such materials may also be used to absorb spills, particularly spills containing biological material such as blood, urine, food, and the like.

Table 12.1: efficacy of antimicrobial cat litter

^*Show the killing of all

Example 13: proof of fastness to staining of antibacterial textile

A treatment formulation substantially similar to the treatment formulation used in example 3, run 6 was prepared. The formulations were padded into two different white textile substrate materials: about 5oz/yd²Knitted 100% polyester fabric and about 4oz/yd²Knitting 100% cotton fabric. The discoloration was tested by the adaptive AATCC method 151, which is intended to measure the sensitivity of textiles to soil redeposition during the wash (superficially intended to simulate 100 "normal" cycles). It was found that the samples tested in this way were virtually indistinguishable from the control (untreated) used as reference. This test is important because one of the major drawbacks of many antibacterial textiles based on cationic bactericides (the most commonly used type) is their extreme susceptibility to discoloration in this process-especially because the process uses soils containing large amounts of clay to simulate washed soils and the negatively charged clay colloids readily bind to cationic surface sites. To confirm this effect, the Aegis biocide treated, locally purchased antimicrobial T-shirts (JC Penney Stafford Ease (60% cotton, 40% polyester) and Stafford Heavyweight (100% cotton)) were evaluated in the same manner and exhibited higher discoloration than the material of the present invention.

Example 14: demonstration of biocompatibility of antibacterial textiles

A green cotton knitted substrate (as described in example 3) is a substrate treated according to the compositions and methods of the present invention using conditions and components substantially similar to those described in example 3, run 8. Samples of the treated substrate were rinsed or washed with water and then tested according to ISO10993-5 and ASTM F895-84 guidelines, "culture screening Standard test method for agar spreading cytotoxicity", according to the procedures described herein. The test requires that the test article be placed on an agar overlay to protect the cell monolayer from mechanical damage and to assess changes in the cellular environment after 24 hours and 48 hours. The test is intended to qualitatively assess the potential cytotoxicity of the matrix by detecting and describing areas of cellular change beyond the edges of the material sample. These areas are visualized by a key neutral red dye. As a result, the measured sample was found to be a score of 2 or less, indicating that the sample was biocompatible and not cytotoxic.

Example 15: acetate-and peroxide-free aqueous binder compositions suitable for hydrogen peroxide comprising a metal derivative and a source of hydroxide ions useful for treating substrates and imparting durable antimicrobial activity to said substrates

An aqueous treatment solution is prepared in accordance with the teachings of the present invention. For example, the solution is essentially composed as follows: 3.0% zinc chloride, 4.2% zinc nitrate, 0.5% sodium stearate, 2.7% sodium hydroxide, 0.05% EDTA and 89.55% water. The treatment formulation is prepared by dispersing the required amounts of each ingredient in a known volume of water and then agitating and homogenizing the treatment solution in an agitator, for example, until it readily and completely passes through a mesh filter having a pore size of 200 microns to produce an acetate-free and substantially peroxide-free binder composition comprising a metal derivative and a source of hydroxide ions which can be used to treat a substrate and impart a persistent antimicrobial activity to the substrate upon addition of hydrogen peroxide. The adhesive composition can be stored until mixed with sufficient hydrogen peroxide to provide a treatment solution containing a hydrogen peroxide concentration of about 2% to 7% (or as otherwise specified in the preferred embodiment). The mixture of the adhesive composition and hydrogen peroxide can be used to treat a substrate to impart antimicrobial properties to the substrate. The binder composition or mixture of binder solution and hydrogen peroxide may be diluted with water or other aqueous solution prior to use. A concentrated form of the binder composition may be prepared by repeating the steps while increasing the concentration of all ingredients by a desired concentration factor (e.g., 2x, 3x, 4, or higher) with an appropriate reduction in the "known volume of water" described above. Prior to use, the adhesive composition in concentrated form is mixed with the required (or desired) amount of hydrogen peroxide and then diluted with water or other aqueous solution for use as a treatment formulation to impart antimicrobial properties to the substrate. For the application of peroxide-containing compositions, the adhesive composition may also be applied directly to a substrate using the methods described herein without the need for further addition of hydrogen peroxide. The treated substrate (dried or not) may then be exposed to a sufficient amount of hydrogen peroxide to impart durable antimicrobial properties to the treated substrate.

Example 16: demonstration of regenerative antimicrobial efficacy of treated substrates

Substrates, such as cotton textiles, were treated with the acetate-free treatment formulation described in example 3 and antimicrobial efficacy was measured according to the methods described herein. The treated substrate is then used in its intended normal application and/or washed, rinsed, aged, or stored until subsequent antimicrobial efficacy measurements indicate that efficacy has been lost in whole or in part. The treated substrate is then "regenerated" by exposure to an aqueous hydrogen peroxide source, which may be the actual hydrogen peroxide solution, or a compound that forms a salt or addition compound with hydrogen peroxide; including sodium perborate, sodium percarbonate, sodium peroxyphosphate, carbamide peroxide, potassium persulfate, and others; when water is added, it hydrolyzes to hydrogen peroxide. The treated substrate was then dried and tested for antimicrobial efficacy. If the antimicrobial effect has been restored, the treated substrate may then be used as an antimicrobial article with a lasting antimicrobial efficacy until further regeneration is found to no longer enhance the antimicrobial efficacy.

Example 17: production of laboratory-scale antimicrobial textiles with a mixture of zinc chloride, zinc nitrate, hydrogen peroxide, sodium hydroxide, EDTA and sodium stearate: effect of Total solution concentration on the persistence of the antibacterial Effect

An antimicrobial cotton textile material was prepared according to the method described in example 3. The treatment formulation was substantially similar to that in run 6 (table 3.1). This sample is designated as "100%". Other samples were prepared by diluting the treatment formulation used to prepare the 100% sample with water and concentrations were diluted to 75%, 50%, 30%, 20% and 10% of the treatment formulation used to prepare the 100% sample. All samples were sent to a commercial laboratory and washed repeatedly in hot water (120 ° f) according to AATCC standard methods. The washed samples were tested for antimicrobial efficacy using the methods described herein. It was found that all samples (except 10% of samples) retained full efficacy after 25 washes in hot water (> 6log reduction, "full kill" klebsiella pneumoniae). 10% of the samples lost efficacy after 25 washes, only a 0.7log reduction.

Example 18: demonstration of treatment of elastic bandages with diluted acetate-free treatment formulations and antimicrobial efficacy

The elastic bandages (compression type bandages, commonly referred to as "cloth-knit" bandages) were treated by dipping the elastic bandages into a treatment formulation having the components substantially as set forth in table 18.1. The elastic bandage had the following approximate composition (10% polyester, 20% spandex, and 70% cotton).

In all cases, sufficient sodium hydroxide was added to neutralize the solution to 80% of the neutralization required to bring the pH of the solution to 7.5. The samples were passed through nip rolls to remove excess treatment formulation and the moist bandages were dried in an oven at 80 ℃. Dried samples were tested for antimicrobial efficacy using the methods described herein. In all cases, the antimicrobial bandage was found to reduce klebsiella pneumoniae by > 8-log (total kill).

Table 18.1: composition of treatment preparation (remainder water)

Example 19: preparation of pressure-treated wood

A treatment solution having a composition substantially similar to that of the treatment solution in example 3 (operation #6) was prepared. The solution was diluted (i.e. 33% strength) with two portions of water mixing and one portion of solution. 20 wooden (pine) stakes, approximately 0.5 "x 1.25" x 18 "(2,283 grams total dry weight) were placed in a metal box, then sealed and evacuated using a vacuum pump. Thirteen liters (13L) of the 33% solution were introduced into a vacuum chamber and then pressurized to 50psi with argon and allowed to stand for one hour. The box was opened, the stakes removed, excess liquid wiped off the surface of the wood, the wet stakes (4,140g) weighed and then air dried for several days. The process was repeated on a second set of pine stakes with a more dilute treatment solution (16.5%). After drying, ten samples from each set of stakes, along with ten untreated (control) stakes, were buried into the ground in shady woodland located in srville, florida, so that about half the length of the stakes were buried and in direct contact with the soil. After about 7.5 months, the stakes were inspected for damage by fungi and insects. Stakes exposed to the above-described treatment solutions exhibit significantly less damage than untreated stakes. The stakes are placed back to the ground for further evaluation at some future date. It was thus demonstrated that the pressure-treated wood of the present invention can be used for the purpose of preservation against the attack of fungi and insects.

Example 20: demonstration of antiviral efficacy of treated textiles

The antibacterial material produced in example 3 (operation #6) was tested for antiviral effects as follows:

influenza a (H1N 1; ATCC VR-1469) virus was propagated using the madin canine kidney epithelial cell type I (MDCK) single membrane (ATCC CCL-34) as the host and the most approximate number (MPN) was calculated. Cells were grown in 6-well cell culture dishes.

For counting, aliquots of virus-containing samples were inoculated into monolayers of freshly prepared MDCK monolayers. The cells were then cultured in DMEM (MediaTech, USA) medium containing trypsin for 5-7 days at 35 deg.C under 5% CO 2. The signs of cell deterioration were monitored by conventional microscopy. Cells that showed signs of infection in the wells (cytopathic effect; CPE) were recorded as positive (+) and those that did not show any CPE were recorded as negative (-). The most likely number of infectious viruses in the sample was then calculated using the MPNCALC software (version 0.0.0.23). For challenge experiments, the cryopreserved virus stock (typically 2X 106iu/ml) was rapidly reconstituted by a 35 ℃ water bath on the day of the experiment. The stock was then diluted 1/100 with Phosphate Buffered Saline (PBS) supplemented with 2% Bovine Serum Albumin (BSA).

The protocol used is comparable to ASTM E1053-97 (Standard test method for the efficacy of virucidal agents on inanimate surfaces). The material was cut into 1 "square pieces. Each plate was placed in a sterile petri dish. Triplicate samples of each material were taken and analyzed. One hundred microliters of the above-described virus dilution was uniformly applied to the surface of each test sample. The inoculum was then incubated at 25 ℃ for 120 minutes, and then each material was transferred to a 50ml sterile conical bottom centrifuge tube (fisher science, pa). 25ml of sterile Difco Letheen broth (Becton Dickinson #263010, Md.) was added to each tube. The centrifuge tubes described above containing 25ml of Letheen broth and 0.1ml of diluted virus inoculum served as positive controls (initial). The centrifuge tubes were then placed on an orbital shaker and shaken at low speed for 15 minutes. After shaking, 5ml of liquid was removed from each tube and added to a 15ml sterile conical bottom centrifuge tube (fisher science, pa). The virus suspension was diluted 10-fold with PBS. The number of surviving (infectious) influenza a in each tube was counted by the MPN procedure described above using a martindaca canine kidney epithelial cell type I (MDCK) cell monolayer (ATCC CCL-34). All analyses were performed in triplicate. Initial challenge concentrations were obtained using the positive control tube viral MPN and the percent reduction produced was calculated. The overall percent reduction was calculated to be 78%.

Example 21: demonstration of resistance of antimicrobial fabrics to mold growth

Several antimicrobial textiles were prepared according to the materials and methods of the present invention, including those prepared by treating white cotton knit materials in a laboratory using a treatment solution and prepared by substantially similar methods to those described in example 3 (operation # 6). Evaluation of textile materials according to AATCC method 30 "antifungal activity: anti-mildew and anti-rot test of textile materials "antimicrobial textiles. The method consists of the following steps: fabric samples were placed on growth plates that had been inoculated with mold or fungus. The test bacteria were Aspergillus niger (Aspergillus niger) and Cladosporium sp. Seven (7) days later, the textile surface was visually evaluated for mold growth. The treated textile prepared according to the method of the present invention exhibited much lower growth than the untreated (control) textile.

Standard test and analysis methods for evaluating the properties of the treated articles described herein:

a: laboratory washing method:

the washing method is based on AATCC standard method. In standard-sized domestic washing machines (e.g. Siels)KenrorHeavy duty washing machine), the samples were washed using the following settings: the water level is low; temperature of waterCold (about 20 ℃); cycle set-up normal (wash 6 minutes). Forty (40) mL tide was required for each wash cycleLiquid detergent is used for the front end feed opening. Ten pieces of washing cloth (100% white cotton jiabao) were added for each washDiapers, each weighing about 35 grams). The washing machine is started and allowed to fill, then detergent is added, followed by textile and cosecant cloths. The sample was removed after each 5 wash cycles and placed in a standard home dryer (Huifpu) along with two rinse clothsHeavy duty dryer), dried at a high heat setting for twenty minutes. After a specified number of wash cycles, the samples are cut from the textile sample for antimicrobial efficacy testing, and the remainder of the textile sample is further washed in cycles, if necessary.

The standard laboratory washing methods described above may vary in certain circumstances, including: optionally rinsing the sample prior to starting the wash cycle; replacing tide with AATCC standard detergent; using a hot temperature setting (120 ° f); and drying after each wash cycle, rather than drying after every five wash cycles.

B: microbiological assay for verifying antimicrobial properties of treated textile materials

Materials prepared by the various methods and examples of the present invention were analyzed for antimicrobial activity using a modified version of the American Association of textile dyeing chemists (AATCC) test method 100 ("Antibacterial fabrics on Textiles: Association of"). An overnight culture (ONC) of the test microorganism was generated in appropriate medium using standard methods. Preparing an inoculum solution using ONC, the solution comprising Phosphate Buffered Saline (PBS) of the test microorganism, the test microorganismThe microorganisms are diluted to about 10⁶CFU/ml. The treated matrix material (specimen) and untreated matrix control material (control) were cut into 2.5cm squares, respectively, and autoclaved at 121 ℃ for 30 minutes to eliminate the microbial contamination that existed before. After autoclaving, the samples and controls (textile substrates of the same substrate without antimicrobial treatment) were allowed to cool at room temperature for 15 minutes. The samples and controls were divided into a number of one square inch three layers of textile material for analysis. Samples and controls were inoculated with 500 μ L of inoculum, respectively. The inoculated samples were incubated in sterile petri dishes at 37 ℃. After 18 to 24 hours of inoculation, samples were taken with sterile forceps and placed in 15mL separate tubes containing 15mL PBS, and shaken for 30 seconds to suspend all remaining viable microorganisms that entered the solution. These suspensions were suitably diluted ten-fold with PBS solution and spread onto bacterial culture dishes containing media suitable for growth of the desired organism, followed by overnight incubation at 37 ℃. After overnight incubation, colonies grown on each dish were counted to determine antimicrobial efficacy. Data reported are% kill or log reduction compared to untreated controls cultured with the same bacterial inoculum. It is convenient to use "log kill", "log reduction", or simply "LR" to indicate the antimicrobial efficacy of a particular formulation against a particular bacterial species. In the discussion that follows, the LR numbers will be followed by the use of an asterisk (e.g., 6.0)^*) Total kill (i.e. 100% reduction in viable bacteria) is noted or indicated. Independent LR values were calculated for each replicate for a given sample relative to the average colony number for the untreated (negative) control sample. The individual LR values for the samples were then averaged and the averaged LR recorded as the result. If the bacterial count of the control sample is measured immediately after inoculation, the result is recorded as "t-0". If the number of controls is determined after the same incubation time as the test sample, the result is recorded as "t ═ x", where x equals the incubation time used for the test sample (typically overnight, i.e. 18-24 hours). All LR values reported herein refer to t-overnight measurements unless otherwise specified. Note that LR values for t-0 are generally less than those for t-overnight, since the number of bacteria on untreated controls increases over timePlus trend. A value of t ═ 0 can be considered to reflect a bactericidal value; and the value of T-overnight may be considered to reflect a combination of bactericidal and bacteriostatic effects. Dilution, diffusion, plate culture and enumeration were performed using standard microbiological techniques. The following bacterial species and species were used in this test:

staphylococcus Aureus (SA)	ATCC 6538
		Escherichia Coli (EC)	ATCC 15597
Klebsiella Pneumoniae (KP)	ATCC 13883

Claims (25)

1.A method of making an antimicrobial article, the method comprising the steps of:

(a) providing an aqueous mixture consisting essentially of (1) hydrogen peroxide and (2) a metal salt consisting of one or more chlorides, bromides, nitrates, or sulfates of magnesium, zinc, or zirconium,

(b) adding a source of hydroxide ions to the aqueous mixture to produce an antimicrobial treatment formulation comprising a metal derivative, hydrogen peroxide and hydroxide ions, without vinegarAn acid radical complex, wherein the neutralization degree of the antibacterial treatment preparation is 50 to 100%,

(c) applying the antimicrobial treatment formulation to an article, and thereafter

(d) (ii) drying the treated article of manufacture,

wherein the molar ratio of hydrogen peroxide to metal salt in the aqueous mixture is equal to or greater than 1:1, wherein the acetate-free complex of the metal derivative, hydrogen peroxide and hydroxide ion imparts a persistent antimicrobial activity to the treated article.

2.The method of claim 1, further comprising the step of homogenizing the antimicrobial treatment formulation prior to applying the antimicrobial treatment formulation to the article in step (c).

3.The method of claim 1, wherein the metal salt of step (a) is one or more chloride, bromide, nitrate, or sulfate salts of zinc.

4.The method of claim 1, wherein the treatment formulation of step (b) further comprises an additive selected from the group consisting of: ultraviolet protective agent, processing aid, softening agent, antistatic agent, colorant, indicator, medicine, oil, microsphere, nutrient, growth factor, emollient, humectant, and perfume.

5.The method of claim 1, wherein the treatment formulation of step (b) further comprises an additive selected from the group consisting of: dyes, temporary visual indicators, lubricating oils, vitamins, and perfumes.

6.The method of claim 1, wherein the treatment formulation further comprises at least 0.1 wt% of an endurance enhancing agent selected from the group consisting of: polymers, long chain fatty acids, and long chain fatty acid salts.

7.A method of making an antimicrobial article, the method comprising the steps of:

(a) providing a homogenized mixture of an aqueous solution of an aqueous hydroxide and a metal salt consisting of one or more chlorides, bromides, nitrates, or sulfates of zinc, thereby producing an aqueous binder composition,

(b) adding sufficient aqueous hydrogen peroxide to the aqueous binder composition to produce a treatment formulation comprising an acetate-free complex of a metal derivative, hydrogen peroxide and hydroxide ions, wherein the molar ratio of hydrogen peroxide to the metal salt is equal to or greater than 1:1, and thereafter

(c) Applying the treatment formulation to the article, and

(d) drying the treated article, which has been treated with the treatment formulation, wherein the acetate-free complex of the metal derivative, hydrogen peroxide and hydroxide ion imparts a persistent antimicrobial activity to the treated article.

8.The method of claim 7, further comprising, after step (c) and before step (d), the step of removing excess of said treatment formulation from said article by roller, nip, press, centrifuge, wring, or suction.

9.The method of claim 7, further comprising the step of homogenizing the treatment formulation prior to applying the treatment formulation to the article in step (c).

10.The method of claim 7, wherein the aqueous binder composition of step (a) further comprises an additive selected from the group consisting of: ultraviolet protective agent, processing aid, softening agent, antistatic agent, colorant, indicator, medicine, oil, microsphere, nutrient, growth factor, emollient, humectant, and perfumeAnd (5) feeding.

11.The method of claim 7, wherein the aqueous binder composition of step (a) further comprises an additive selected from the group consisting of: dyes, temporary visual indicators, lubricating oils, vitamins, and perfumes.

12.The method of claim 7, wherein the aqueous adhesive composition further comprises at least 0.1 wt% of a durability enhancing agent selected from the group consisting of: polymers, long chain fatty acids, and long chain fatty acid salts.

13.A method of making an antimicrobial textile material, the method comprising the steps of:

(a) providing a homogenized mixture of an aqueous hydroxide and an aqueous solution of one or more chlorides, bromides, nitrates, or sulfates of magnesium, zinc, or zirconium, thereby producing an aqueous binder composition,

(b) applying the aqueous adhesive composition to a textile material, followed by

(c) Exposing the textile material to aqueous hydrogen peroxide, and

(d) drying the treated textile material, which has been treated with the binder composition and aqueous hydrogen peroxide,

wherein an acetate-free complex of a metal derivative, hydrogen peroxide and a source of hydroxide ions is produced and imparts a durable antimicrobial activity to the treated textile material, said activity being effective for at least 10 wash cycles.

14.The method of claim 13, further comprising, after step (c) and before step (d), the step of removing excess aqueous binder composition and aqueous hydrogen peroxide from the textile material.

15.The method of claim 13, further comprising a drying step after step (b) and before step (c).

16.The method of claim 13, wherein step (a) is providing a homogenized mixture of an aqueous hydroxide and one or more aqueous chloride, bromide, nitrate, or sulfate solutions of zinc, thereby producing an aqueous binder composition.

17.The method of claim 13, wherein the aqueous binder composition of step (a) further comprises an additive selected from the group consisting of: ultraviolet protective agent, processing aid, softening agent, antistatic agent, colorant, indicator, medicine, oil, microsphere, nutrient, growth factor, emollient, humectant, and perfume.

18.The method of claim 13, wherein the aqueous binder composition of step (a) further comprises an additive selected from the group consisting of: dyes, temporary visual indicators, lubricating oils, vitamins, and perfumes.

19.The method of claim 13, wherein the aqueous adhesive composition further comprises at least 0.1 wt% of a durability enhancing agent selected from the group consisting of: polymers, long chain fatty acids, and long chain fatty acid salts.

20.The method of any one of claims 1 to 12, wherein the metal concentration of the metal salt by weight in the treatment formulation is between 0.05% and 3.0%.

21.A method as claimed in any one of claims 13 to 19The method of clause, wherein the molar ratio of hydrogen peroxide to metal salt in the aqueous mixture is equal to or greater than 1: 1.

22.An antimicrobial article made according to the method of any one of claims 1 to 21.

23.The antimicrobial article of claim 22 wherein the article is a textile material and wherein an antimicrobial textile material is produced.

24.The antimicrobial article of claim 22 wherein the antimicrobial article is a component of a wound dressing, a sanitary napkin, an incontinence pad, a tampon, an inherently antimicrobial absorbent dressing, a diaper, toilet tissue, a sanitary wipe, a cotton swab, a surgical gown, a barrier garment, a lab coat, a glove, a surgical scrubs, a head cover, a hair cover, a mask, a suture, a floor mat, a light cover, an examination table top, a plaster liner, a splint liner, padding, gauze, packaging material, bedding, a towel, underwear, a sock, a shoe cover, an automotive air filter, an aircraft air filter, an air conditioning system air filter, a military protective garment, a food processing garment, a carpet, or a window covering.

25.The antimicrobial article of claim 23 wherein the treated antimicrobial textile material is not significantly or undesirably discolored, stained, or otherwise aesthetically adversely affected by the antimicrobial treatment even if the textile material is a colored or dyed textile.