JP2010506945A - Antibacterial article and manufacturing method - Google Patents

Abstract

  Antibacterial articles and methods of manufacturing such articles are provided.

Description

  The present invention relates to an antibacterial article containing silver and a method for producing such an article.

  Although skin wounds heal more efficiently in a moist environment, the risk of bacterial infection is increased in the presence of moisture. In addition, bacteria can build resistance to antibiotics, eventually making them ineffective. Silver compounds are known to impart antibacterial effects to surfaces (eg, wound tissue) with minimal risk of developing bacterial resistance. In the moist environment of the wound bed, for example, silver is delivered by sustained release of silver ions to the wound.

  In the literature, silver salts coated on cotton or other substrates are not color stable when exposed to ultraviolet ("UV") or visible light without a stabilizer. However, the stabilizer also reduces the solubility of the silver salt, which also inhibits the release of silver ions. If the release of silver ions is too low (less than 0.01 mg / g dressing in water in 30 minutes), its antibacterial action will also be reduced and may no longer be effective for wound treatment.

  It would be desirable to provide a color stable antimicrobial article that provides antimicrobial activity when used as a wound dressing or the like and a method of making such an article.

  The present invention provides an article and a method of manufacturing such an article.

  In one aspect of the present invention, a method for producing an antibacterial article is provided, the method comprising applying a silver composition to a substrate to provide a liquid coated substrate, wherein the silver composition Includes a silver salt other than silver sulfate in a solvent, the silver composition includes a stabilizer in an amount of less than about 100 parts per million (about 100 ppm), and the substrate comprises polyamide, polyester, polyacetate, Polyacrylic acid, polyolefin, polyurethane, polyvinyl chloride, polyvinyl alcohol, polycarbonate, polyvinyl pyrrolidone, polylactic acid, ethylene-vinyl acetate, polystyrene, cellulose acetate, polyacrylate, polyacrylamide, polyacrylonitrile, polyvinylidene difluoride, polytetrafluoro Ethylene, polyoxymethylene, polyvinyl ether, styrene A process comprising a material selected from the group consisting of ethylene butylene-styrene elastomer, styrene-butylene-styrene elastomer, styrene-isoprene-styrene elastomer, glass fiber, ceramic, and combinations of two or more thereof, and the liquid Drying the coated substrate to provide a color stable antibacterial article comprising a silver salt applied to the substrate.

  In another aspect, the present invention is a silver salt other than silver sulfate, the silver salt applied to the substrate, polyamide, polyester, polyacetate, polyacrylic acid, polyolefin, polyurethane, polyvinyl chloride, polyvinyl chloride Alcohol, polycarbonate, polyvinyl pyrrolidone, polylactic acid, ethylene-vinyl acetate, polystyrene, cellulose acetate, polyacrylate, polyacrylamide, polyacrylonitrile, polyvinylidene difluoride, polytetrafluoroethylene, polyoxymethylene, polyvinyl ether, styrene-ethylene butylene -Styrene elastomers, styrene-butylene-styrene elastomers, styrene-isoprene-styrene elastomers, glass fibers, ceramics and combinations of two or more thereof. Providing an article comprising a substrate comprising a material selected from the group, the article is antimicrobial, a color stability.

  In another aspect of the present invention, a step of applying a silver composition to a substrate to provide a liquid coated substrate, the silver composition comprising silver acetate, silver benzoate, silver carbonate, silver chloride, Silver oxide, silver iodate, silver lactate, silver nitrate, silver nitrite, silver oxalate, silver phosphate, silver sulfadiazine, silver saccharinate, silver anthranilate, silver chlorite, silver fluorosilicate, trihydrogen paraperiodate Selected from the group consisting of silver, silver hyponitrite, silver rebnilate, silver myristate, silver palmitate, silver propionate, silver stearate, silver tartrate, mild silver protein, silver protein and combinations of two or more thereof A color-stable antibacterial article comprising silver metal nanoparticles and a silver salt by heating the liquid-coated substrate at a temperature sufficient to produce silver metal from the silver salt. Providing a process; No method is provided.

  In another aspect, the present invention provides a liquid-coated substrate by applying a silver composition to a substrate, wherein the silver composition contains a silver salt other than silver sulfate, and the liquid Heating the coated substrate at a temperature sufficient to produce silver metal from the silver salt to provide a color-stable antibacterial article comprising silver metal nanoparticles and a silver salt; A method for manufacturing an article is provided.

  In yet another aspect, the present invention provides an article comprising silver metal and a silver salt disposed on a substrate, wherein the silver salt is silver acetate, silver benzoate, silver carbonate, silver chloride, silver citrate. , Silver iodate, silver lactate, silver nitrate, silver nitrite, silver oxalate, silver phosphate, silver sulfadiazine, silver saccharinate, silver anthranilate, silver chlorite, silver fluorosilicate, silver triperiodate, It is selected from the group consisting of silver hyponitrite, silver revenylate, silver myristate, silver palmitate, silver propionate, silver stearate, silver tartrate, mild silver protein, silver protein and combinations of two or more thereof.

  In yet another aspect, the present invention provides an article comprising silver metal and a silver salt applied to a substrate, the silver salt comprising a silver salt other than silver sulfate.

  Terms used herein are understood to have the same meaning as understood by those skilled in the art. Regardless of the foregoing, it should be understood that certain terms have the meanings set forth herein.

  As used herein, “ambient temperature” means the room temperature present, typically within the range of about 15 ° C. to about 30 ° C.

  “Relative humidity” means the ratio of the amount of water vapor actually present in the air to the maximum amount that can be taken at the same temperature.

  As used herein, “a”, “an”, “the”, “at least one”, and “one or more” are used interchangeably. The

  Those skilled in the art will more fully understand the scope of the present invention in view of the remainder of the disclosure, including the detailed description, various examples, and the appended claims. Let's go.

  The present invention provides an antibacterial article containing silver. The article is color stable (when exposed to ultraviolet or visible light), releases antibacterial levels of silver ions, is surprisingly easy to manufacture, and is directly applied to the wound dressing, wound packing material, or wound Other materials suitable for application can be made.

  In the description of embodiments of the present invention, the term “color stable” means that an article has significant significance in color and / or color uniformity over time (eg, at least 4 hours after exposure to light). It means that it does not show the visible change. The color change can be evaluated in any of a variety of ways, and the invention is not limited to a particular method or technique for determining the color change.

  In some embodiments of the invention, the color change is assessed by observation.

  In some embodiments, the color change is evaluated using a scaled scale. For example, the color change may be assessed by observing the sample under fluorescence and comparing it to a chromaticity standard and scoring the sample color from 0 to 10. A score of 0, 1 or 2 is considered “white”, including white to cream. A score of 3 to 5 is “yellow” including light yellow to golden yellow, and a score of 6 to 10 is classified as reddish brown to dark brown. The numerical value of the color change is obtained by subtracting the initial score from the score after processing. A positive score for color change represents blackening of the appearance, and a negative score represents whitening of the appearance. A color change of 1 or less on this scale is considered acceptable (eg, no significant change) as long as the color is initially homogeneous and remains homogeneous. If the color is initially heterogeneous, a color change of 0.5 is considered significant.

  In some embodiments, the color change is made from Minolta Chroma Meter (Konica Minolta Photo Imaging USA, Inc., Mahwah, NJ). It is also possible to measure using tristimulus values using a colorimeter such as CR-300). A color change of 15% or less in this “Y” value on this scale is considered acceptable as long as the color of the sample remains homogeneous. If the colors are inhomogeneous, a 5% color change in the “Y” value is considered significant.

In still other embodiments, the color change can be measured using a colorimeter according to test method ASTM D2244. The resulting CIELAB color difference (DE ^* ) between the sample after exposure for the indicated period and the unexposed sample can be determined. For control purposes only, a DE ^* or color change of about 2 units is considered a limit for visual detection, while a DE ^* of 20 or more represents a substantial or significant color change.

  Typically, the art has relied on the use of chemical compounds known as stabilizers to provide color stability to articles including silver salts. However, such stabilizers also reduce the solubility of the silver salt so that the release of silver ions may be too low to be effective on the wound (less than 0.01 mg / g dressing in water in 30 minutes). .

  In one embodiment of the invention, color stability is achieved by applying a silver composition to the substrate and drying the article. When a suitable substrate is used to produce the article of the present invention, the dried article is color stable without having to include a stabilizer or the like.

  In another embodiment of the invention, color stability is achieved by drying a portion of the silver salt applied to the substrate (preferably less than 30%) by nanoscale silver metal particles (“nanoparticles”) by drying at an elevated temperature. ) And as a result of the formation of silver metal nanoparticles, it is achieved by making a product that is color stable with the color often observed as pale yellow to golden brown.

  In one aspect of the present invention, a method for producing an antimicrobial article comprises applying a silver compound (s) (eg, coated) on a substrate to provide a color stable antimicrobial comprising a silver salt. It is provided by providing a sex article.

  In another aspect of the present invention, a method for manufacturing an antimicrobial article includes applying a silver compound (s) (eg, coated) on a substrate to provide a color stabilization comprising silver metal and a silver salt. Provided by providing an antibacterial article.

  In some embodiments, the silver composition is first prepared by dissolving the silver salt in a suitable solvent (eg, water) to provide a coatable liquid silver composition in the form of a silver salt solution. The In some embodiments, the solvent used in the silver composition consists of water. In some embodiments, the solvent in the silver composition is primarily water, with other components that increase the solubility of the silver salt. Silver salts suitable for use in the present invention include silver acetate, silver benzoate, silver carbonate, silver chloride, silver citrate, silver iodate, silver lactate, silver nitrate, silver nitrite, silver oxalate, silver phosphate, silver sulfadiazine , Silver saccharinate, silver anthranilate, silver chlorite, silver fluorosilicate, silver triperiodate, silver hyponitrite, silver levulinate, silver myristate, silver palmitate, silver propionate, silver stearate, It can be selected from the group consisting of silver tartrate, mild silver protein, silver protein and combinations of two or more thereof.

  In certain embodiments, any one of the aforementioned salts is suitable by itself or in combination with any other silver salt. Silver sulfate is not included with the aforementioned salts.

  In some embodiments, the silver salt is silver acetate, silver benzoate, silver carbonate, silver chloride, silver citrate, silver lactate, silver nitrate, silver nitrite, silver chlorite, silver fluorosilicate, paraperiodic acid. It is selected from the aforementioned subsets of salts consisting of silver trihydrogen, silver levylate, silver propionate, silver tartrate, mild silver protein, silver protein and combinations of two or more thereof.

  In some embodiments, the silver salt comprises silver iodate, silver oxalate, silver phosphate, silver sulfadiazine, silver saccharinate, silver anthranilate, silver hyponitrite, silver myristate, silver palmitate, silver stearate and Selected from another subset of salts consisting of combinations of two of these.

  In some embodiments, the silver salt is selected to exclude silver sulfate. In some embodiments, the silver salt is silver nitrate. In some embodiments, the salt is silver benzoate.

  The silver composition may be formulated such that the total silver content is up to about 1.0% by weight in the composition, typically from about 0.01% to about 0.5% by weight. . In some embodiments, the pH of the silver composition is maintained at a desired target value to avoid adverse reactions to the substrate when the composition is applied to the substrate. In some embodiments, the pH of the silver composition is maintained at 9 or less. In some embodiments, the pH of the silver composition is maintained greater than 4 but less than 7, for example, to minimize adverse reactions to cellulosic substrates.

  Color stability in the final article of the present invention is achieved without the need to include the addition of stabilizer (s) to the silver composition, but in some embodiments of the present invention, in the silver composition It will be appreciated that small amounts of stabilizer (s) may be included in Stabilizers include ammonia, ammonium salts (eg, ammonium acetate, ammonium sulfate, ammonium carbonate, etc.), thiosulfates, metal water-insoluble salts (eg, halides such as chloride), peroxides, magnesium trisilicate, And / or polymers. If present in the silver composition, the stabilizer may be present in an amount of less than 100 ppm. In some embodiments, the stabilizer may be present in an amount less than 50 ppm based on the total weight of the silver salt composition, and in some embodiments, less than 20 ppm. Alternatively, the stabilizer is present in an amount less than 1000 ppm based on the total weight of the dry color stable antimicrobial article. In still other embodiments, the stabilizer is present in an amount less than 500 ppm based on the total weight of the dry color-stable antibacterial article, and in still other embodiments, the stabilizer is a dry color-stable antibacterial. Present in an amount of less than 100 ppm based on the total weight of the active article.

  In some embodiments, the silver composition may optionally include a compound for promoting dissolution of the silver salt in a solvent (eg, water). Depending on the solubility of the salt (s) selected for use in the present invention, embodiments of the present invention may include ammonium pentaborate, ammonium acetate, ammonium carbonate, ammonium peroxyborate, ammonium tetraborate (ammonium tertraborate), triammonium citrate, ammonium carbamate, ammonium bicarbonate, ammonium malate, ammonium nitrate, ammonium nitrite, ammonium succinate, ammonium sulfate, ammonium tartrate, and combinations of two or more thereof Solubilizers may be included. In selecting a solubilizer for inclusion in the silver composition of the present invention, materials that evaporate or decompose after application of the composition to a substrate and heating as described herein are preferred.

  The silver composition thus formulated is applied to the substrate to provide a liquid coated substrate. In some embodiments, the silver composition penetrates and is impregnated inside the substrate. For example, in the case of an absorbent material (eg, gauze), the silver composition is impregnated between the fibers of the substrate. Application of the silver composition to the substrate can be accomplished as a continuous process or can be done in a separate manner and even in a single step.

  Any of various materials may be used as a base material or a base material to which the silver composition is applied.

  In certain embodiments, suitable materials can include polymeric materials or are composed of large long chain molecules. In certain embodiments, the material for the substrate is typically not easily oxidized in the presence of silver salts (eg, silver nitrate) when heated to temperatures below about 120 ° C. Selected to be “non-oxidizing”. Suitable substrates include polyamide, polyester, polyacetate, polyacrylic acid, polyolefin (eg, polypropylene polyethylene, ethylene propylene copolymer, and ethylene-butylene copolymer), polyurethane (including polyurethane foam), polyvinyl chloride, polyvinyl Alcohol, polycarbonate, polyvinyl pyrrolidone, polylactic acid, ethylene-vinyl acetate, polystyrene, cellulose acetate, polyacrylate, polyacrylamide, polyacrylonitrile, polyvinylidene difluoride, polytetrafluoroethylene, polyoxymethylene, polyvinyl ether, styrene-ethylene butylene -Styrene elastomer, styrene-butylene-styrene elastomer, styrene-isoprene-styrene elastomer Tomah, glass fibers, the material can be mentioned which is selected from ceramic and the group consisting of combinations of two or more thereof.

  In some embodiments of the invention, the substrate comprises or consists of cellulose acetate. In some embodiments, the substrate comprises or consists of a polyamide (eg, nylon 6,6).

  In certain embodiments, suitable materials include, for example, cotton, rayon, hemp, jute, bamboo fiber, cellulose acetate, carboxymethylated solvent spun cellulose fiber, polyamide, polyacetate, alginate, collagen, gelatin, natural rubber, Mention may be made of cellulosic and non-cellulosic materials, such as paper, natural or synthetic fibers, yarns and yarns, made from materials such as polyacrylamide and combinations of two or more of these.

  In addition, the above materials or combinations thereof include polyester, polyacrylic acid, polyolefin (eg, polypropylene polyethylene, ethylene propylene copolymer, and ethylene-butylene copolymer), polyurethane (including polyurethane foam), polyvinyl chloride. Vinyl, polystyrene, fiber glass, ceramic fiber, polyacrylate, polyacrylonitrile, polyvinylidene difluoride, polytetrafluoroethylene, polyoxymethylene, polyvinyl alcohol, polylactic acid, polyvinyl ether, polyvinyl pyrrolidone, polycarbonate, styrene-ethylene butylene Styrene elastomer, styrene-butylene-styrene elastomer, styrene-isoprene-styrene elastomer, and the same Such as a combination of two or more of the may be combined with other materials. A combination of materials may be included in the substrate. In some embodiments, the substrate comprises a material selected from the group consisting of cellulosic materials, nylon, polyester fibers, and combinations of two or more thereof.

  The substrate can be porous or non-porous, and the silver composition can be coated, for example, on the surface of the substrate or impregnated in the substrate. In embodiments of the present invention, the substrate can be flexible and can include woven or non-woven materials made from natural or synthetic compounds. In embodiments of the present invention, the substrate may be selected from a polymeric web (nonwoven or woven), polymeric film, hydrocolloid, foam, paper, and / or combinations thereof.

  In some embodiments, the substrate can be an absorbent cotton gauze.

Porous substrates made from the aforementioned materials include knits, woven fabrics (eg, cheesecloth and gauze), nonwoven fabrics (spunbond nonwoven fabrics, and BMF (including blown microfibers), extruded porous sheets, The openings in the porous substrate (ie, the openings) are of sufficient size and sufficient number to promote high breathability. The porous substrate has at least one aperture per square centimeter, hi certain embodiments, the porous substrate has no more than 225 apertures per square centimeter. Having an average opening size (ie, the maximum dimension of the opening) of at least 0.1 millimeters (mm). , Apertures, in. Some embodiments having 0.5 cm (cm) or less of the average opening size (i.e., the largest dimension of the opening), the porous substrate is at least 5 g / m ² In some embodiments, the porous substrate has a basis weight of 1000 g / m ² or less, and in some embodiments, 200 g / m ² or less. In some embodiments, the thickness of the porous substrate is at least about 0.0125 millimeters (mm), while being flexible, it may be resistant to tearing. , The thickness of the porous substrate is about 15 mm or less, and for certain embodiments, about 3 mm or less.

  In some embodiments, the substrate includes a permeable material (s) that allows the permeation of water vapor. For some embodiments, the substrate is a hydrocolloid such as a hydrophilic polymer or hydrophobic polymer matrix containing hydrophilic particles as described in US Published Patent Application Nos. 2004/0180093 and 2005/0124724. Good.

  Cellulosic materials, including polysaccharides or modified polysaccharides, regenerated cellulose (eg, rayon), paper, cotton, carboxymethylcellulose, and the like may be suitable for use in certain embodiments of the invention. In embodiments of the invention where the final article is intended to be used as a wound dressing or used in a wet or wet environment, it is advantageous to provide a substrate comprising an absorbent material. There is a case. Suitable harvesting materials include those made from or incorporating cellulose fibers, such as carboxymethylated materials-carboxymethylated cotton, carboxymethylated cellulose, carboxymethylated rayon. Suitable commercially available cellulosic fibers include solvent-spun cellulosic fibers known by the trade name “TENCEL” available from Lenzing Fibers, Inc. The carboxymethylated variants of the aforementioned TENCEL fibers as disclosed in PCT International Publication No. WO1993012275 A1 are also suitable for use in certain embodiments of the present invention.

  In some embodiments, the substrate is substantially impermeable to liquids, particularly wound exudates.

  The silver composition can be applied at room temperature, typically below about 70 ° C. The silver composition can be coated on the substrate using any of a variety of known coating techniques, such as gravure coating, curtain coating, die coating, knife coating, roll coating, spray coating, and the like. In some embodiments, it is possible to immerse or pass the substrate in a bath of silver composition.

  Following application of the silver salt, gentle heating may be applied to the liquid coated substrate at a temperature sufficient for a sufficient duration to dry the article to provide a color stable antimicrobial article. Good. A sufficiently high temperature may be obtained in an oven, and in certain embodiments of the invention, the temperature is less than 100 ° C and typically in the range of about 50 ° C to about 90 ° C. Alternatively, the liquid coated substrate may be air dried at ambient or room temperature. The actual drying temperature may vary depending on the length of time devoted to drying, the silver load on the liquid coated substrate, the type and weight of the substrate, and the like. Those skilled in the art will appreciate that the temperature should be high enough to dry the article without reducing the silver salt or oxidizing the substrate. In this aspect, the dried article is color stable. While not wishing to be bound by theory, the articles of the invention made in this manner are partly color-stable due to the non-oxidizing substrate (s) being used. Conceivable. In some embodiments of the present invention, the drying temperature is greater than 100 ° C. unless the substrate is oxidized by silver nitrate to form silver metal or the substrate does not melt or burn. It can be increased. Polyester is an example of this type of substrate.

  In certain embodiments, the article is dried (by removing the solvent from the silver composition) and at a temperature sufficient for a sufficient duration to reduce at least a portion of the silver salt to silver metal. Heat is applied to the liquid coated substrate to provide a color stable antimicrobial article. At least a portion of the silver metal is in the form of silver nanoparticles. As used herein, “nanoparticles” refers to fine particles whose size is measured in nanometers (nm) and at least one dimension is less than about 200 nm. In order to achieve the formation of silver metal, the drying temperature for the liquid coated substrate is higher than room temperature. A sufficiently high temperature is achieved in the oven, and in certain embodiments of the invention the temperature is greater than about 95 ° C. and in the range of about 95 ° C. to about 225 ° C. In some embodiments, the liquid coated substrate is dried at a temperature of about 100 ° C to about 200 ° C. In still other embodiments, the liquid coated substrate is dried at a temperature of about 110 ° C to about 180 ° C. In still other embodiments, the liquid coated substrate is dried at a temperature of about 130 ° C to about 175 ° C. The actual drying temperature may vary depending on the length of time devoted to drying, the silver load on the liquid coated substrate, the type and weight of the substrate, and the like. Those skilled in the art will appreciate that in the desired embodiment, the temperature should be high enough to achieve the reduction of silver (I). However, consideration must also be given to the melting point of the substrate and the possibility of oxidation. Substrate materials suitable for use as a wound dressing may include, for example, materials that are readily oxidizable at high temperatures (eg, cellulosic materials), resulting in prolonged heating or very high temperatures. One skilled in the art will understand that exposure can be detrimental to the quality and / or integrity of the final article. Excessively high drying temperatures can burn or melt some substrate materials, making them incompatible with their intended purpose (eg, as a wound dressing).

  In certain embodiments, the final article includes silver metal and silver salt affixed to the substrate. Without wishing to be bound by theory, it is believed that heating the liquid-coated substrate, in certain embodiments, oxidizes the substrate and reduces the silver salt to silver metal. It is believed that the oxidation of the substrate and the formation of metallic silver nanoparticles are responsible for the color (s) and color stability observed in certain of the final antimicrobial articles of the present invention. On white substrates (eg, cellulosic materials), the heat treating liquid coated substrate causes the final article to be non-white (eg, yellow to brown) that is stable for long periods after exposure to light and / or heat. ).

  Preferably, the articles of the present invention remain color stable because they remain stable to light (eg, visible light, ultraviolet light). Preferably they release an antibacterial effective level of silver ions and in certain embodiments of the invention are readily applicable as a wound dressing to skin wounds. The article is simple to manufacture and generally no stabilizer is added.

  In certain embodiments, the present invention provides a wound dressing comprising an easily soluble silver salt (s) applied to a substrate. In another embodiment, the present invention provides a wound dressing comprising silver metal nanoparticles and readily dissolvable silver salt (s) applied to and disposed on a substrate. As used herein, “applied to” and “placed on” means placing silver on a substrate such that the silver and / or silver salt is on the substrate surface. In the case of an absorbent material, it may be distributed within the substrate (eg, across the entire absorbent structure between the outermost surfaces).

  In embodiments where the final article is to be used as a wound dressing, an antimicrobial effective amount of silver is available for delivery from the article to the wound bed or the like. The article typically maintains an effective level of silver release (eg, greater than 0.01 mg / g dressing in 100 g water for 30 minutes). The color of the final article is stable (eg against heat and light). In certain embodiments of the invention, the article is longer than 4 hours, in some embodiments longer than 8 hours, and in some embodiments 24 hours after exposing the article to visible or ultraviolet light. Longer and more color stable. The light stability of the article of the present invention can be extended by wrapping the article in a light-blocking package or storing the article in a light-free environment until when it should be used. it can.

  The concentration of silver on the dried substrate (as a silver salt in certain embodiments and as a silver salt plus silver metal in certain embodiments) is preferably about 1 per kilogram (kg) of substrate. Less than 40,000 milligrams (mg) Ag, and in some embodiments less than about 20,000 mg Ag / kg substrate. In still other embodiments, the silver concentration is less than about 10,000 mg Ag / kg substrate.

  In embodiments of the invention in which silver is present as a silver salt and silver metal, less than 30% of the total amount of silver on the substrate is typically present as silver metal.

  In some embodiments, the articles of the present invention are medical articles such as wound dressings and wound packing materials or other materials that are applied directly to or in contact with a wound. However, the articles of the invention may be used in other applications where medical antibacterial properties of silver are needed or desired (medical and non-medical applications). Other potential products include clothing, bedding, masks, dust cloths, insoles, diapers, and hospital materials such as blankets, surgical drapes, and gowns.

  The stability of the articles of the present invention may persist and / or improve when the relative humidity at room temperature is maintained at 50% or less, more preferably 30% or less, and most preferably 20% or less. For example, 1) place the article in an environment with a relative humidity of 30% or less, preferably 20% or less, and then package the article in the same environment. 2) Liquid coated substrate 30%, preferably 20%, by a number of methods including drying the oven in an oven and immediately packaging the resulting article, and / or 3) adding a desiccant into the package of the article. Or it can be lowered below. Suitable environments for maintaining low humidity include packages made of materials with low moisture vapor transmission (MVTR), eg, Techni-Pouch package with PET / aluminum foil / LLDPE material structure (For example, Technipaq, Inc. (commercially available from Crystal Lake, Illinois)).

  In certain embodiments, the articles of the present invention are non-adhesive, but it will be understood that an adhesive (eg, a pressure sensitive adhesive) can be applied to the article in a known manner. Any pressure sensitive adhesive suitable for use in medical articles can be used in the articles of the present invention. That is, a pressure sensitive adhesive can be applied to the surface of the article of the present invention to facilitate adhesion of the article to the skin. An adhesive may be applied, for example, around the surface of the article such that the silver-containing surface of the article is adhered and held to the skin in contact with the wound or the like. In this embodiment, under the moisture conditions of the wound bed, the article releases silver ions into the wound to prevent microbial growth.

  In certain embodiments, one or both sides of a substrate coated with a silver composition can be coated with a permeable non-adhesive outer layer to reduce adhesion and adhesion to the wound. The non-adhesive layer can be attached to the substrate, for example, by coating or lamination. Alternatively, the coated substrate can be encapsulated in a non-adhesive layer such as a sleeve. The non-adhesive layer can be made of a non-adhesive woven or non-woven fabric such as a nylon or perfluoro material coating on cotton gauze. The non-adhesive layer prevents attachment of the wound dressing to the wound. At the same time, the non-adhesive layer does not adversely affect the sustained release of silver from the coated substrate.

  In another embodiment, the substrate or support substrate can be composed of a non-adhesive material. For example, using a non-adhesive hydrophilic polymer as a substrate or support material, as described in U.S. Published Patent Application Nos. 2004/01800093, 2005/0123590, and 2005/0124724, or permeable porous It can be coated on a substrate.

  If desired, the coated substrate can be coated with two protective films (eg, a thin polyester film). These films may optionally include an anti-stick process and can function to facilitate extraction from the package and handling of the article. If desired, the coated substrate can be cut into individual compresses of a size suitable for use, packaged in a sealed sachet, and sterilized.

Representative Examples
Applying a silver composition to a substrate to provide a liquid-coated substrate, the silver composition comprising a silver salt other than silver sulfate in a solvent, wherein the silver composition comprises about 100 ppm of stabilizer. Containing less than
The base material is polyamide, polyester, polyacetate, polyacrylic acid, polyolefin, polyurethane, polyvinyl chloride, polyvinyl alcohol, polycarbonate, polyvinyl pyrrolidone, polylactic acid, ethylene-vinyl acetate, polystyrene, cellulose acetate, polyacrylate, polyacrylamide , Polyacrylonitrile, polyvinylidene difluoride, polytetrafluoroethylene, polyoxymethylene, polyvinyl ether, styrene-ethylene butylene-styrene elastomer, styrene-butylene-styrene elastomer, styrene-isoprene-styrene elastomer, glass fiber, ceramic and the like Including a material selected from the group consisting of two or more of the combinations;
Drying the liquid-coated substrate to provide a color-stable antibacterial article containing a silver salt applied to the substrate.

  2. The silver salt is silver acetate, silver benzoate, silver carbonate, silver chloride, silver citrate, silver lactate, silver nitrate, silver nitrite, silver chlorate, silver fluorosilicate, silver trihydrogen periodate, silver levulinate, The method of embodiment 1, wherein the method is selected from the group consisting of silver propionate, silver tartrate, mild silver protein, silver protein, and combinations of two or more thereof.

  3. The method of embodiment 2, wherein the silver salt is silver nitrate.

  4). The method of embodiment 2, wherein the silver salt is silver benzoate.

  5. The silver salt is silver iodate, silver oxalate, silver phosphate, silver sulfadiazine, silver saccharinate, silver anthranilate, silver hyponitrite, silver myristate, silver palmitate, silver stearate and two of these Embodiment 2. The method of embodiment 1 selected from the group consisting of the above combinations.

  6). Embodiment 6. Any one of embodiments 1-5, wherein the substrate comprises a polyolefin selected from the group consisting of polypropylene, polyethylene, ethylene propylene copolymer, ethylene butylene copolymer, and combinations of two or more thereof. the method of.

  7). Embodiment 6. The method according to any one of embodiments 1-5, wherein the substrate comprises polyamide.

  8). Embodiment 6. The method of any one of Embodiments 1-5, wherein the substrate comprises cellulose acetate.

  9. Embodiment 9. The method of any one of embodiments 1-8, wherein the substrate comprises a material selected from the group consisting of knits, woven fabrics, nonwoven fabrics, extruded porous sheets, and perforated sheets.

  10. The method of any one of embodiments 1-9, wherein the silver composition comprises a stabilizer in an amount of less than 50 ppm based on the total weight of the silver salt composition.

  11. The method of embodiment 10, wherein the silver composition does not comprise a stabilizer.

  12 The method of any one of embodiments 1-11, wherein the drying of the liquid-coated substrate is accomplished at room temperature.

  13. The method of any one of embodiments 1-11, wherein the drying of the liquid-coated substrate is accomplished at a temperature of less than about 100 <0> C.

  14 The color-stable antibacterial article comprises the silver salt applied to the substrate such that the concentration of silver on the substrate is less than about 40,000 mg Ag / kg substrate. The method according to any one of the above.

  15. Embodiment 15. The color-stable antimicrobial article comprises a silver salt applied to the substrate such that the concentration of silver on the substrate is less than about 20,000 mg Ag / kg substrate. Method.

  16. The embodiment of embodiment 15, wherein the color-stable antimicrobial article comprises a silver salt applied to the substrate such that the concentration of silver on the substrate is less than about 10,000 mg Ag / kg substrate. Method.

17. A silver salt other than silver sulfate, and a silver salt applied to the substrate;
Polyamide, polyester, polyacetate, polyacrylic acid, polyolefin, polyurethane, polyvinyl chloride, polyvinyl alcohol, polycarbonate, polyvinylpyrrolidone, polylactic acid, ethylene-vinyl acetate, polystyrene, cellulose acetate, polyacrylate, polyacrylamide, polyacrylonitrile, poly Vinylidene difluoride, polytetrafluoroethylene, polyoxymethylene, polyvinyl ether, styrene-ethylene butylene-styrene elastomer, styrene-butylene-styrene elastomer, styrene-isoprene-styrene elastomer, glass fiber, ceramic and two or more thereof A substrate comprising a material selected from the group consisting of:
The article is antibacterial and color stable.

  18. The silver salt is silver acetate, silver benzoate, silver carbonate, silver chloride, silver citrate, silver iodate, silver lactate, silver nitrate, silver nitrite, silver oxalate, silver phosphate, silver sulfadiazine, silver saccharinate, anthranyl Silver oxide, silver chlorite, silver fluorosilicate, silver triperiodate, silver hyponitrite, silver levulinate, silver myristate, silver palmitate, silver propionate, silver stearate, silver tartrate, mild silver protein Embodiment 18. The article of embodiment 17, selected from the group consisting of: silver protein and combinations of two or more thereof.

  19. The silver salt is silver acetate, silver benzoate, silver carbonate, silver chloride, silver citrate, silver lactate, silver nitrate, silver nitrite, silver chlorate, silver fluorosilicate, silver trihydrogen periodate, silver levulinate, The article of embodiment 18, selected from the group consisting of silver propionate, silver tartrate, mild silver protein, silver protein and combinations of two or more thereof.

  20. The article of embodiment 19, wherein the silver salt is silver nitrate.

  21. Embodiment 20. The article of embodiment 19, wherein the silver salt is silver benzoate.

  22. The silver salt is silver iodate, silver oxalate, silver phosphate, silver sulfadiazine, silver saccharinate, silver anthranilate, silver hyponitrite, silver myristate, silver palmitate, silver stearate and two of these The article of embodiment 18 selected from the group consisting of the above combinations.

  23. The article of any one of embodiments 17-22, wherein the substrate comprises a polyamide.

  24. The article of any one of embodiments 17-22, wherein the substrate comprises cellulose acetate.

  25. The article of any one of embodiments 17-24, wherein the concentration of silver on the substrate is less than about 40,000 mg Ag / kg substrate.

  26. The article of embodiment 25, wherein the concentration of silver on the substrate is less than about 20,000 mg Ag / kg substrate.

  27. The article of embodiment 26, wherein the concentration of silver on the substrate is less than about 10,000 mg Ag / kg substrate.

  28. Embodiment 28. The article of any one of embodiments 17 through 27, wherein the stabilizer concentration is less than about 1000 ppm based on the total weight of the article.

  29. The article of embodiment 28, wherein the stabilizer concentration is less than about 500 ppm based on the total weight of the article.

  30. The article of embodiment 29, wherein the concentration of stabilizer is less than about 100 ppm based on the total weight of the article.

31. Applying a silver composition to a substrate to provide a liquid-coated substrate, the silver composition comprising silver acetate, silver benzoate, silver carbonate, silver chloride, silver citrate, silver iodate, lactic acid Silver, silver nitrate, silver nitrite, silver oxalate, silver phosphate, silver sulfadiazine, silver saccharinate, silver anthranilate, silver chlorite, silver fluorosilicate, silver trihydrogen periodate, silver hyponitrite, silver levulinate A silver salt selected from the group consisting of silver myristate, silver palmitate, silver propionate, silver stearate, silver tartrate, mild silver protein, silver protein and combinations of two or more thereof;
Heating the liquid coated substrate at a temperature sufficient to produce silver metal from a silver salt to provide a color stable antimicrobial article comprising silver metal nanoparticles and a silver salt. A method for producing an antibacterial article.

  32. The silver salt is silver acetate, silver benzoate, silver carbonate, silver chloride, silver citrate, silver lactate, silver nitrate, silver nitrite, silver chlorate, silver fluorosilicate, silver trihydrogen periodate, silver levulinate, 32. The method of embodiment 31, wherein the method is selected from the group consisting of silver propionate, silver tartrate, mild silver protein, silver protein, and combinations of two or more thereof.

  33. The method of embodiment 32, wherein the silver salt is silver nitrate.

  34. The method of embodiment 32, wherein the silver salt is silver benzoate.

  35. The silver salt is silver iodate, silver oxalate, silver phosphate, silver sulfadiazine, silver saccharinate, silver anthranilate, silver hyponitrite, silver myristate, silver palmitate, silver stearate and two of these 32. The method of embodiment 31 selected from the group consisting of the above combinations.

  36. The substrate comprises a material selected from the group consisting of cellulosic materials, nylon, polyamide, polyacetate, collagen, gelatin, polyacrylamide, natural rubber, alginate, and combinations of two or more thereof. The method according to any one of Forms 31-35.

  37. The substrate also includes polyester, polyacrylic acid, polyolefin, polyurethane, polyvinyl chloride, including polyvinyl chloride, polystyrene, fiber glass, ceramic fiber, polyacrylate, polyacrylonitrile, polyvinylidene difluoride, polytetrafluoroethylene, polyoxy Group consisting of methylene, polyvinyl alcohol, polylactic acid, polyvinyl ether, polyvinyl pyrrolidone, polycarbonate, styrene-ethylene butylene-styrene elastomer, styrene-butylene-styrene elastomer, styrene-isoprene-styrene elastomer, and combinations of two or more thereof The method of embodiment 36, comprising a material selected from:

  38. 38. The method of embodiment 36 or 37, wherein the substrate comprises a cellulosic material.

  39. Absorbent carboxymethyl wherein the cellulosic material is selected from the group consisting of carboxymethylated cotton, carboxymethylated cellulose, carboxymethylated solvent spun cellulose fibers, carboxymethylated rayon and combinations of two or more thereof 39. The method of embodiment 38, wherein the method is a chemical material.

  40. 39. The embodiment of embodiment 38, wherein the cellulosic material is selected from the group consisting of cotton, rayon, hemp, jute, bamboo fiber, cellulose acetate, carboxymethylated solvent spun cellulose fiber, and combinations of two or more thereof. the method of.

  41. 41. The method of any one of embodiments 31-40, wherein the substrate comprises a material selected from the group consisting of knits, woven fabrics, non-woven fabrics, extruded porous sheets, and perforated sheets.

  42. 42. The method of any one of embodiments 31-41, wherein the heating of the liquid-coated substrate is accomplished at a temperature in the range of about 95 ° C. to about 225 ° C.

  43. 43. The method of embodiment 42, wherein the heating of the liquid coated substrate is accomplished at a temperature in the range of about 100 ° C to about 200 ° C.

  44. 44. The method of embodiment 43, wherein the heating of the liquid coated substrate is accomplished at a temperature in the range of about 110 ° C to about 180 ° C.

  45. 45. The method of embodiment 44, wherein the heating of the liquid coated substrate is accomplished at a temperature in the range of about 130 ° C to about 175 ° C.

  46. The method according to any one of embodiments 31-45, wherein the silver salt solution comprises a stabilizer in an amount of less than 100 ppm based on the total weight of the silver composition.

  47. 47. The method of embodiment 46, wherein the silver salt solution does not contain a stabilizer.

  48. 48. The method according to any one of embodiments 31-47, wherein the antimicrobial article has a non-white color and is color stable.

49. Applying a silver composition to a substrate to provide a liquid-coated substrate, wherein the silver composition comprises a silver salt other than silver sulfate;
Heating the liquid coated substrate at a temperature sufficient to produce silver metal from a silver salt to provide a color stable antimicrobial article comprising silver metal nanoparticles and a silver salt. The manufacturing method of an antimicrobial article.

  50. The silver salt is silver acetate, silver benzoate, silver carbonate, silver chloride, silver citrate, silver lactate, silver nitrate, silver nitrite, silver chlorate, silver fluorosilicate, silver trihydrogen periodate, silver levulinate, 50. The method of embodiment 49, selected from the group consisting of silver propionate, silver tartrate, mild silver protein, silver protein, and combinations of two or more thereof.

  51. The method of embodiment 50, wherein the silver salt is silver nitrate.

  52. The method of embodiment 50, wherein the silver salt is silver benzoate.

  53. The silver salt is silver iodate, silver oxalate, silver phosphate, silver sulfadiazine, silver saccharinate, silver anthranilate, silver hyponitrite, silver myristate, silver palmitate, silver stearate and two of these 50. The method of embodiment 49, selected from the group consisting of the above combinations.

  54. An embodiment wherein the substrate comprises a material selected from the group consisting of cellulosic materials, nylon, polyamide, polyacetate, collagen, gelatin, polyacrylamide, natural rubber, alginate, and combinations of two or more thereof. The method according to any one of 49 to 53.

  55. The substrate is also polyester, polyacrylic acid, polyolefin, polyurethane, polyvinyl chloride, polystyrene, fiberglass, ceramic fiber, polyacrylate, polyacrylonitrile, polyvinylidene difluoride, polytetrafluoroethylene, polyoxymethylene, polyvinyl alcohol Selected from the group consisting of polylactic acid, polyvinyl ether, polyvinyl pyrrolidone, polycarbonate, styrene-ethylene butylene-styrene elastomer, styrene-butylene-styrene elastomer, styrene-isoprene-styrene elastomer, and combinations of two or more thereof. 56. The method of embodiment 54, which also includes a material.

  56. 56. The method of embodiment 54 or 55, wherein the substrate comprises a cellulosic material.

  57. Absorbent carboxymethyl wherein the cellulosic material is selected from the group consisting of carboxymethylated cotton, carboxymethylated cellulose, carboxymethylated solvent spun cellulose fibers, carboxymethylated rayon and combinations of two or more thereof 57. The method of embodiment 56, comprising a chelating material.

  58. Embodiment 56. The embodiment 56 wherein the cellulosic material is selected from the group consisting of cotton, rayon, hemp, jute, bamboo fiber, cellulose acetate, carboxymethylated solvent spun cellulose fiber and combinations of two or more thereof. the method of.

  59. 59. The method of any one of embodiments 49-58, wherein the substrate comprises a material selected from the group consisting of knits, woven fabrics, nonwoven fabrics, extruded porous sheets, and perforated sheets.

  60. 60. The method of any one of embodiments 49 through 59, wherein the heating of the liquid coated substrate is accomplished at a temperature in the range of about 95 ° C to about 225 ° C.

  61. 61. The method of embodiment 60, wherein the heating of the liquid coated substrate is accomplished at a temperature in the range of about 100 ° C to about 200 ° C.

  62. 62. The method of embodiment 61, wherein the heating of the liquid coated substrate is accomplished at a temperature in the range of about 110 ° C. to about 180 ° C.

  63. 64. The method of embodiment 62, wherein the heating of the liquid coated substrate is accomplished at a temperature in the range of about 130 ° C to about 175 ° C.

  64. Embodiment 64. The method of any one of embodiments 49 through 63, wherein the silver salt solution comprises a stabilizer in an amount of less than 100 ppm based on the total weight of the silver composition.

  65. The method of embodiment 64, wherein the silver salt solution does not comprise a stabilizer.

  66. Embodiment 66. The method of any one of embodiments 49 through 65, wherein the antimicrobial article has a non-white color and is color stable.

  67. An article comprising silver metal and a silver salt disposed on a substrate, wherein the silver salt is silver acetate, silver benzoate, silver carbonate, silver chloride, silver citrate, silver iodate, silver lactate, silver nitrate, Silver nitrite, silver oxalate, silver phosphate, silver sulfadiazine, silver saccharinate, silver anthranilate, silver chlorite, silver fluorosilicate, silver triperiodate, silver hyponitrite, silver levulinate, silver myristate An article selected from the group consisting of: silver palmitate, silver propionate, silver stearate, silver tartrate, mild silver protein, silver protein, and combinations of two or more thereof.

  68. The silver salt is silver acetate, silver benzoate, silver carbonate, silver chloride, silver citrate, silver lactate, silver nitrate, silver nitrite, silver chlorate, silver fluorosilicate, silver trihydrogen periodate, silver levulinate, 68. The article of embodiment 67, selected from the group consisting of silver propionate, silver tartrate, mild silver protein, silver protein, and combinations of two or more thereof.

  69. 69. The article of embodiment 68, wherein the silver salt is silver nitrate.

  70. The article of embodiment 68, wherein the silver salt is silver benzoate.

  71. The silver salt is silver iodate, silver oxalate, silver phosphate, silver sulfadiazine, silver saccharinate, silver anthranilate, silver hyponitrite, silver myristate, silver palmitate, silver stearate and two of these 68. The article of embodiment 67, selected from the group consisting of the above combinations.

  72. An embodiment wherein the substrate comprises a material selected from the group consisting of cellulosic materials, nylon, polyamide, polyacetate, collagen, gelatin, polyacrylamide, natural rubber, alginate, and combinations of two or more thereof. The article according to any one of 67 to 71.

  73. The substrate is also polyester, polyacrylic acid, polyolefin, polyurethane, polyvinyl chloride, polystyrene, fiberglass, ceramic fiber, polyacrylate, polyacrylonitrile, polyvinylidene difluoride, polytetrafluoroethylene, polyoxymethylene, polyvinyl alcohol , Polylactic acid, polyvinyl ether, polyvinyl pyrrolidone, polycarbonate, styrene-ethylenebutylene-styrene elastomer, styrene-butylene-styrene elastomer, styrene-isoprene-styrene elastomer, and combinations of two or more thereof The article of embodiment 72, also comprising a material.

  74. The article of embodiment 72 or embodiment 73, wherein the substrate comprises a cellulosic material.

  75. Absorbent carboxymethyl wherein the cellulosic material is selected from the group consisting of carboxymethylated cotton, carboxymethylated cellulose, carboxymethylated solvent spun cellulose fibers, carboxymethylated rayon and combinations of two or more thereof 75. The article of embodiment 74, comprising a chelating material.

  76. Embodiment 75. The embodiment 74 wherein the cellulosic material is selected from the group consisting of cotton, rayon, hemp, jute, bamboo fiber, cellulose acetate, carboxymethylated solvent spun cellulose fiber, and combinations of two or more thereof. Goods.

  77. The article according to any one of embodiments 67 to 76, wherein the substrate is a material selected from the group consisting of knits, woven fabrics, nonwoven fabrics, extruded porous sheets, and perforated sheets.

  78. 80. The article of any one of embodiments 67 through 77, wherein the antimicrobial article has a non-white color and is color stable.

  79. The article of any one of embodiments 67 through 78, wherein the concentration of silver on the substrate is less than about 40,000 mg Ag / kg substrate.

  80. 80. The article of embodiment 79, wherein the concentration of silver on the substrate is less than about 20,000 mg Ag / kg substrate.

  81. The article of embodiment 80, wherein the concentration of silver on the substrate is less than about 10,000 mg Ag / kg substrate.

  82. An article comprising silver metal and a silver salt applied to a substrate, wherein the silver salt comprises a silver salt other than silver sulfate.

  83. The silver salt is silver acetate, silver benzoate, silver carbonate, silver chloride, silver citrate, silver lactate, silver nitrate, silver nitrite, silver chlorate, silver fluorosilicate, silver trihydrogen periodate, silver levulinate, 83. The article of embodiment 82, selected from the group consisting of silver propionate, silver tartrate, mild silver protein, silver protein, and combinations of two or more thereof.

  84. 84. The article of embodiment 83, wherein the silver salt is silver nitrate.

  85. 84. The article of embodiment 83, wherein the silver salt is silver benzoate.

  86. The silver salt is silver iodate, silver oxalate, silver phosphate, silver sulfadiazine, silver saccharinate, silver anthranilate, silver hyponitrite, silver myristate, silver palmitate, silver stearate and two of these The article of embodiment 82, selected from the group consisting of the above combinations.

  87. An embodiment wherein the substrate comprises a material selected from the group consisting of cellulosic materials, nylon, polyamide, polyacetate, collagen, gelatin, polyacrylamide, natural rubber, alginate, and combinations of two or more thereof. The article according to any one of 82 to 86.

  88. The substrate is also polyester, polyacrylic acid, polyolefin, polyurethane, polyvinyl chloride, polystyrene, fiberglass, ceramic fiber, polyacrylate, polyacrylonitrile, polyvinylidene difluoride, polytetrafluoroethylene, polyoxymethylene, polyvinyl alcohol , Polylactic acid, polyvinyl ether, polyvinyl pyrrolidone, polycarbonate, styrene-ethylenebutylene-styrene elastomer, styrene-butylene-styrene elastomer, styrene-isoprene-styrene elastomer, and combinations of two or more thereof 90. The article of embodiment 87, also comprising a material.

  89. The article of embodiment 87 or embodiment 88, wherein the substrate comprises a cellulosic material.

  90. Absorbent carboxymethyl wherein the cellulosic material is selected from the group consisting of carboxymethylated cotton, carboxymethylated cellulose, carboxymethylated solvent spun cellulose fibers, carboxymethylated rayon and combinations of two or more thereof 90. The article of embodiment 89, comprising a chelating material.

  91. Embodiment 90. The embodiment wherein the cellulosic material is selected from the group consisting of cotton, rayon, hemp, jute, bamboo fiber, cellulose acetate, carboxymethylated solvent spun cellulose fiber and combinations of two or more thereof. Goods.

  92. Embodiment 92. The article according to any one of embodiments 82-91, wherein the substrate is a material selected from the group consisting of knits, woven fabrics, extruded porous sheets, and perforated sheets.

  93. 95. The article of any one of embodiments 82 through 92, wherein the antimicrobial article has a non-white color and is color stable.

  94. 94. The article of any one of embodiments 82 through 93, wherein the concentration of silver on the substrate is less than about 40,000 mg Ag / kg substrate.

  95. 95. The article of embodiment 94, wherein the concentration of silver on the substrate is less than about 20,000 mg Ag / kg substrate.

  96. 96. The article of embodiment 95, wherein the concentration of silver on the substrate is less than about 10,000 mg Ag / kg substrate.

  The objects and advantages of this invention are further illustrated by the following examples, which, however, are not limited to the specific materials and amounts listed in these examples, as well as other conditions and details. It should not be construed as limiting. Unless otherwise indicated, all parts and percentages are by weight, all water is distilled water, and all molecular weights are weight average molecular weights.

I.
Example I-1
0.316 grams (g) of silver nitrate (Aldrich Chemical Co. (Milwaukee, Wis.)) And 200 g of distilled water are placed in a glass bottle, the bottle is capped, and at room temperature. A silver nitrate coating solution was prepared by mixing overnight in a shaker. Approximately 6 grams of this silver nitrate solution (approximately 1000 microgram (μg) Ag / gram (g)) solution was pipetted to saturate the mesh contained in the polystyrene dish to saturate the mesh contained in the American Fiber and On a piece of approximately 10 cm (4 inches) × 10 cm (4 inches) of 100% nylon woven fabric (SR-823-32 × 28, 60 gsm) from American Fiber and Finishing (Albemarle, NC) Coated. Approximately 1 gram of coating solution dropped from the mesh before it was suspended in the oven for drying. Some additional solution dropped from the mesh in the oven (estimated 1 g). The coated mesh is placed in a forced air oven (Memmert Universal Oven, available from Wisconsin Oven Company, East Troy, Wis.) At 80 ° C. Dried by heating for 12 minutes. The material obtained after drying had a white appearance. These coated samples can be rolled into aluminum foil (protected from light) or fluorescent (Philips, F32T8 / TL735, Universal / Hi-Vision) in an environment of approximately 20-30% relative humidity. (Hi-Vision), E4) or exposed to fluorescence (Phillips, F32T8 / TL735, Universal / Hivision, K4) in an environment with a relative humidity of 45-50%. The color scores of these samples are determined by Minolta Chroma Meter (Konica Minolta Photo Imaging USA, Inc.) (Mahwah, NJ). ) And CR-300), and the results are shown in Table I-1.

Example I-2
The silver solution was silver benzoate (Alfa Aesar (Ward Hill, Mass.)) And this solution was added 0.459 g silver benzoate and 200 g distilled water in a glass bottle. A sample was prepared in the same manner as in Example I-1, except that it was prepared by putting it in. The resulting silver benzoate solution was approximately 1000 μg Ag / g. The sample color was white. The results of the color monitoring experiment are shown in Table I-2.

Example I-3 (comparative example)
During exposure to light, the number of color points over time of a commercial wound dressing was also measured. This commercial wound dressing, trade name AQUALCEL Ag from ConvaTec, Lot 5F05519, contains silver chloride / silver alginate with a high concentration of chloride acting as a stabilizer, initially an off-white color Have During exposure to light, the color of the sample becomes visibly gray. The results of these experiments are shown in Table I-3.

Example I-4
Example 1-1, except that the substrate was a membrane filter (0.22 μM filter, GSWP 0470) consisting of cellulose nitrate and cellulose acetate from Millipore (Billerica, Mass.). A sample was prepared in the same manner as above. The initial color of the sample was white. The results of the color monitoring experiment are shown in Table I-4.

Example I-5
Example I-2 except that the substrate was a membrane filter (0.22 μM filter, GSWP 04700) consisting of cellulose nitrate and cellulose acetate from Millipore (Billerica, Mass.). A sample was prepared in the same manner as above. The initial color of the sample was white. The results of color monitoring experiments are shown in Table I-5.

Example I-6
Examples, except that the substrate was 100% polyester spunlace nonwoven (SONTARA 8010, 45 gsm) from EI du Pont de Nemours and Company (Wilmington, Del.) A sample was prepared in the same manner as in 1-1. The polyester nonwoven fabric was moistened by mechanically guiding the silver nitrate solution into the pores of the polyester substrate with the fingertips covered with gloves. (The gloves were SAFESKIN powder free purple nitrile exam gloves (Ref 55083 large) by Kimberly Clark (Roswell, GA)). The initial color of the sample was white. The results of the color monitoring experiment are shown in Table I-6.

Example I-7
A sample was prepared in the same manner as Example I-6 except that the silver nitrate solution was prepared by placing 1.261 g of silver nitrate and 200 g of distilled water into a glass bottle. The resulting silver nitrate solution was approximately 4000 μg Ag / g. The initial color of the sample was white. The results of the color monitoring experiment are shown in Table I-7.

Example I-8 (Comparative Example)
Example I-1 with the exception that the substrate was a 100% cotton non-woven from Suntec Union, Japan (Nisshinbo, AN20601050 60 gsm, containing less than 50 ppm chloride). Samples were prepared in a similar manner. The initial color of the sample was off-white. The results of the color monitoring experiment are shown in Table I-8.

Example I-9 (comparative example)
Example I-2 with the exception that the substrate was a 100% cotton non-woven from Suntec Union, Japan (Nisshinbo, AN20601050 60 gsm, containing less than 50 ppm chloride). Samples were prepared in a similar manner. The initial color of the sample was off-white. The results of the color monitoring experiment are shown in Table I-9.

Example I-10 (Comparative Example)
Example I, except that the substrate was a 70% viscose / 30% PET fiber nonwoven fabric (507030RPET P1, white, 50 gsm) from FA-MA JERSEY spa (Italy). Samples were prepared in the same manner as in -1. The initial color of the sample was off-white. The results of color monitoring experiments are shown in Table I-10.

Example I-11 (comparative example)
Example I, except that the substrate was a 70% viscose / 30% PET fiber nonwoven fabric (507030RPET P1, white, 50 gsm) from FA-MA JERSEY spa (Italy). Samples were prepared in the same manner as -2. The initial color of the sample was off-white. The results of color monitoring experiments are shown in Table I-11.

Example I-12 (Comparative Example)
The substrate is 70% LYOCELL fiber / 30% from Ahlstrom Green Bay, Inc. (Green Bay, Wis.) Containing less than 40 ppm chloride. A sample was prepared in the same manner as in Example I-1, except that a PET nonwoven fabric (SX-156, white, 50 gsm, perforated FT-10) was used. The initial color of the sample was off-white. The results of color monitoring experiments are shown in Table I-12.

II.
Example II-1
0.0792 g of silver nitrate (Aldrich Chemical Co. (Milwaukee, Wis.)) And 200 g of distilled water are placed in a glass bottle, the bottle is capped and placed in a shaker at room temperature. A silver nitrate coating solution was prepared by mixing overnight. Approximately 6 grams of this silver nitrate solution (approximately 250 μg Ag / g) solution was transferred from the Suntec Union, Japan by pipetting the solution to saturate the mesh contained in the polystyrene dish. % Cotton non-woven fabric (Nissinbo, AN20601050 60 gsm, containing less than 50 ppm chloride) was coated on approximately 10 cm (4 inch) × 10 cm (4 inch) pieces. Approximately 1 gram of coating solution dropped from the mesh before it was suspended in the oven for drying. Some additional solution dropped from the mesh in the oven (estimated 1 g). The coated mesh is placed in a forced air oven (Memmert Universal Oven, available from Wisconsin Oven Company, East Troy, Wis.) For 12 minutes at 105 ° C. Dried by heating. The material obtained after drying had a white appearance. These coated samples can be wrapped in aluminum foil (protected from light) or fluorescent (Philips, F32T8 / TL735, Universal / Hi-Vision) in an environment of approximately 10-20% relative humidity. (Hi-Vision), E4) or exposed to fluorescence (Phillips, F32T8 / TL735, Universal / Hivision, K4) in an environment with a relative humidity of 45-50%. The color scores of these samples are given by Minolta Chroma Meter (Konica Minolta Photo Imaging USA, Inc.) (Mahwah, NJ) The results were measured with time using CR-300), and the results are shown in Table II-1.

  After the color stability test was completed, samples protected in foil and samples exposed to fluorescence at 10-20% relative humidity were analyzed for silver ion release. Silver release from the above samples is available from a silver ion-selective electrode (Orion, VWR International (Batavia, Ill.)) In a solution of distilled water and sodium nitrate. It measured using. A 0.1341 g sample that was exposed to light at approximately 20% relative humidity for 168 hours received 0 per gram of sample within 30 minutes of placing the sample in 98 g of distilled water and 2.96 g of 5M sodium nitrate. Released 45 mg of silver ions. In contrast, a 0.1140 g sample held in foil for 168 hours released 1.23 mg of silver ions per gram of sample into 98 g of distilled water and 2.96 g of sodium nitrate.

  Total silver content measurements were also made on replicates of the coating samples held in the foil. For silver content, the sample was first digested with nitric acid and hydrogen peroxide (see EPA method 6010), then inductively coupled plasma-atomic emission spectroscopy (ICP-AES; Varian, Total silver was measured using VistaPro, AX (Varian, Vista-Pro, AX). The average silver content was 1700 mg Ag / kg sample. Silver metal analysis was performed by first extracting the sample with a 2.8 wt% (w / w) ammonium carbonate solution overnight at room temperature. The leachate was then discarded and the sample was digested to determine the silver content as described above. For the sample retained in the foil, the silver metal content of the sample was 120 mg / kg sample.

Example II-2 (control)
The number of color points over time of the uncoated cotton substrate used in Example II-1 was also measured. These results are included in Table II-2.

Example II-3 (comparative example)
During exposure to light, the number of color points over time of a commercial wound dressing was also measured. This commercial wound dressing, available from ConvaTec under the trade name AQUACEL Ag, Lot 5F05519, contains silver chloride / silver alginate with a high concentration of chloride acting as a stabilizer, initially off-white. Have the color of During exposure to light, the color of the sample became visibly gray. The results of these experiments are shown in Table II-3.

Example II-4
A sample was prepared in the same manner as in Example II-1, except that the silver nitrate solution was prepared by placing 0.316 g of silver nitrate and 200 g of distilled water in a glass bottle. The resulting silver nitrate solution was approximately 1000 μg Ag / g. The sample color was off-white. The results of color monitoring experiments are shown in Table II-4.

  Silver ion release and total silver content measurements were performed as described in Example II-1. An amount of 0.1320 g of sample exposed to light at approximately 20% relative humidity for 168 hours was less than 30 minutes after placing the sample in 98 g of distilled water and 2.96 g of 5M sodium nitrate. 4.46 mg of silver ions were released per unit. In contrast, a 0.1626 g sample held in foil for 168 hours released 5.21 mg of silver ions per gram of sample into 98 g of distilled water and 2.96 g of sodium nitrate. The average total silver content was 6950 mg Ag / kg sample. The silver metal content was 350 mg / kg sample.

Example II-5
A sample was prepared in the same manner as in Example II-1, except that the drying temperature was 130 ° C. The sample color was cream (light yellow). The results of color monitoring experiments are shown in Table II-5.

  Silver ion release and total silver content measurements were performed as described in Example II-1. An amount of 0.1341 g sample exposed to light at approximately 20% relative humidity for 168 hours was measured within 30 minutes after placing the sample in 98 g distilled water and 2.96 g 5M sodium nitrate. 0.49 mg of silver ions were released per unit. In contrast, a 0.1280 g sample held in foil for 168 hours released 1.06 mg of silver ion per gram of sample into 98 g of distilled water and 2.96 g of sodium nitrate. The average total silver content was 2000 mg Ag / kg sample. The silver metal content was 160 mg / kg sample.

Example II-6
A sample was prepared in the same manner as in Example II-4 except that the drying temperature was 130 ° C. The color of the sample was light yellow. The results of color monitoring experiments are shown in Table II-6.

  Silver ion release and total silver content measurements were performed as described in Example II-1. An amount of 0.1376 g of sample exposed to light at approximately 20% relative humidity for 168 hours was less than 30 minutes after placing the sample in 98 g of distilled water and 2.96 g of 5M sodium nitrate. 4.28 mg of silver ions were released per unit. In contrast, a 0.1462 g sample held in foil for 168 hours released 5.18 mg of silver ions per gram of sample into 98 g of distilled water and 2.96 g of sodium nitrate. The average total silver content was 7650 mg Ag / kg sample. The silver metal content was 530 mg / kg sample.

Example II-7
A sample was prepared in the same manner as in Example II-1, except that the drying temperature was 155 ° C. The sample color was yellow. The results of color monitoring experiments are shown in Table II-7.

  Silver ion release and total silver content measurements were performed as described in Example II-1. An amount of 0.1426 g of sample exposed to light at approximately 20% relative humidity for 168 hours was less than 30 minutes after placing this sample in 98 g of distilled water and 2.96 g of 5M sodium nitrate. 0.31 mg of silver ions were released per unit. In contrast, a 0.1307 g sample held in foil for 168 hours released 0.95 mg silver ion per gram sample into 98 g distilled water and 2.96 g sodium nitrate. The average total silver content was 1850 mg Ag / kg sample. The silver metal content was 250 mg / kg sample.

Example II-8
A sample was prepared in the same manner as in Example II-4 except that the drying temperature was 155 ° C. The sample color was yellow. The results of color monitoring experiments are shown in Table II-8.

  Silver ion release and total silver content measurements were performed as described in Example II-1. An amount of 0.1366 g of sample exposed to light at approximately 20% relative humidity for 168 hours was less than 30 minutes after placing this sample in 98 g of distilled water and 2.96 g of 5M sodium nitrate. 2.49 mg of silver ions were released per unit. In contrast, a 0.1351 g sample held in foil for 168 hours released 4.97 mg of silver ions per gram of sample in 98 g of distilled water and 2.96 g of sodium nitrate. The average total silver content was 6900 mg Ag / kg sample. The silver metal content was 900 mg / kg sample.

Example II-9
A sample was prepared in the same manner as Example II-8, except that the silver nitrate solution was prepared by placing 0.632 g of silver nitrate and 200 g of distilled water in a glass bottle. The resulting silver nitrate solution was approximately 2000 μg Ag / g. The sample color was golden yellow. The results of color monitoring experiments are shown in Table II-9.

  Silver ion release and total silver content measurements were performed as described in Example II-1. The amount of 0.1308 g of sample exposed to light at approximately 20% relative humidity for 168 hours was less than 30 minutes after placing this sample in 98 g of distilled water and 2.96 g of 5M sodium nitrate. 9.2 mg of silver ions were released per unit. In contrast, a 0.1431 g sample held in foil for 168 hours released 10.8 mg of silver ions per gram of sample into 98 g of distilled water and 2.96 g of sodium nitrate. The average total silver content was 16,000 mg Ag / kg sample. The silver metal content was 1400 mg / kg sample.

Example II-10
The silver solution was silver benzoate (Alfa Aesar; Ward Hill, Mass.), Except that it was prepared by placing 0.230 g of silver benzoate and 200 g of distilled water in a glass bottle. A sample was prepared in the same manner as in Example II-8. The resulting silver benzoate solution was approximately 500 μg Ag / g. The sample color was yellow. The results of color monitoring experiments are shown in Table II-10.

  Silver ion release and total silver content measurements were performed as described in Example II-1. An amount of 0.1341 g sample exposed to light at approximately 20% relative humidity for 168 hours was measured within 30 minutes after placing the sample in 98 g distilled water and 2.96 g 5M sodium nitrate. 0.22 mg of silver ions were released per unit. In contrast, a 0.1323 g sample held in foil for 168 hours released 0.71 mg of silver ions per gram of sample into 98 g of distilled water and 2.96 g of sodium nitrate. The average total silver content was 3350 mg Ag / kg sample.

Example II-11
Samples were prepared in the same manner as Example II-10 except that the silver solution was silver benzoate and this solution was prepared by placing 0.459 g of silver benzoate and 200 g of distilled water in a glass bottle. Prepared. The resulting silver benzoate solution was approximately 1000 μg Ag / g. The sample color was yellow. The results of color monitoring experiments are shown in Table II-11.

  Silver ion release and total silver content measurements were performed as described in Example II-1. An amount of 0.1352 g of sample exposed to light for 168 hours at approximately 20% relative humidity was measured within 30 minutes after placing the sample in 98 g of distilled water and 2.96 g of 5M sodium nitrate. 0.80 mg of silver ions were released per unit. In contrast, a 0.1502 g sample held in foil for 168 hours released 1.50 mg of silver ions per gram of sample in 98 g of distilled water and 2.96 g of sodium nitrate. The average total silver content was 6750 mg Ag / kg sample.

Example II-12
The substrate is a SX from 100% TENCEL fiber nonwoven (Green Bay Nonwovens, Inc., Green Bay, Wis.) Containing less than 40 ppm chloride. -152, white, 65 gsm, 24 mesh), a sample was prepared in the same manner as in Example II-11. The color of the sample was golden brown. The results of color monitoring experiments are shown in Table II-12.

  Silver ion release and total silver content measurements were performed as described in Example II-1. An amount of 0.1662 g of sample exposed to light at approximately 20% relative humidity for 168 hours was less than 30 minutes after placing the sample in 98 g of distilled water and 2.96 g of 5M sodium nitrate. 1.61 mg of silver ions were released per unit. In contrast, a 0.1524 g sample held in foil for 168 hours released 2.34 mg of silver ions per gram of sample into 98 g of distilled water and 2.96 g of sodium nitrate. The average total silver content was 7650 mg Ag / kg sample.

Example II-13
A sample was prepared in the same manner as in Example II-4 except that the drying temperature was 180 ° C. The sample color was golden yellow. The results of color monitoring experiments are shown in Table II-13.

  Silver ion release and total silver content measurements were performed as described in Example II-1. An amount of 0.1476 g of sample exposed to light at approximately 20% relative humidity for 168 hours was less than 30 minutes after placing this sample in 98 g of distilled water and 2.96 g of 5M sodium nitrate. 0.44 mg of silver ions were released per unit. In contrast, a 0.1550 g sample held in foil for 168 hours released 0.88 mg of silver ions per gram of sample into 98 g of distilled water and 2.96 g of sodium nitrate. The average total silver content was 6900 mg Ag / kg sample. The silver metal content was 1200 mg / kg sample.

Example II-14
The silver solution was charged with 0.127 g silver carbonate (Alfa Aesar (Ward Hill, Mass.)), 0.48 g ammonium carbonate (Mallinckroft Baker, Inc.) A sample was prepared in the same manner as Example II-10 except that it consisted of Phillipsburg, New Jersey)) and 100 g of distilled water. The color of the coated cotton sample was golden yellow. The results of color monitoring experiments are shown in Table II-14.

  Silver ion release and total silver content measurements were performed as described in Example II-1. An amount of 0.1386 g of sample exposed to light at approximately 20% relative humidity for 168 hours was less than 30 minutes after placing the sample in 98 g of distilled water and 2.96 g of 5M sodium nitrate. 0.44 mg of silver ions were released per unit. In contrast, a 0.1498 g sample held in foil for 168 hours released 0.48 mg of silver ions per gram of sample into 98 g of distilled water and 2.96 g of sodium nitrate. The average total silver content was 8150 mg Ag / kg sample.

Example II-15
The silver solution was silver acetate, and this solution was added to 0.309 g of silver acetate (Matheson, Coleman, and Bell (Norwood, Ohio)) and 200 g of distilled water in a glass bottle. A sample was prepared in the same manner as in Example II-10 except that the drying temperature was 170 ° C. The resulting silver acetate solution was approximately 1000 μg Ag / g. The sample color was yellow. The results of color monitoring experiments are shown in Table II-15.

  Silver ion release measurements were performed as described in Example II-1. An amount of 0.1525 g sample exposed to light at approximately 20% relative humidity for at least 14 days was measured within 30 minutes after placing the sample in 98 g distilled water and 2.96 g 5M sodium nitrate. 0.71 mg of silver ions were released per gram. In contrast, a 0.1528 g sample held in foil during this experiment released 0.69 mg of silver ion per gram of sample into 98 g of distilled water and 2.96 g of sodium nitrate.

Example II-16
A sample was prepared in the same manner as Example II-1, except that the silver nitrate solution was prepared by placing 0.632 g of silver nitrate and 200 g of distilled water in a glass bottle. The resulting silver nitrate solution was approximately 2000 μg Ag / g. The sample color was off-white. The results of color monitoring experiments are shown in Table II-16.

  Silver ion release and total silver content measurements were performed as described in Example II-1. An amount of 0.1516 g of sample exposed to light at approximately 20% relative humidity for 168 hours was less than 30 minutes after placing the sample in 98 g of distilled water and 2.96 g of 5M sodium nitrate. 10.6 mg of silver ions were released per unit. In contrast, a 0.1368 g sample held in foil for 168 hours released 12.4 mg of silver ions per gram of sample into 98 g of distilled water and 2.96 g of sodium nitrate. The average total silver content was 14000 mg Ag / kg sample. The silver metal content was 800 mg / kg sample.

Example II-17
A sample was prepared in the same manner as Example II-1, except that the silver nitrate solution was prepared by placing 1.261 g of silver nitrate and 200 g of distilled water in a glass bottle. The resulting silver nitrate solution was approximately 4000 micrograms (μg) Ag / gram (g). The color of the sample was initially off-white and a gray area (mottled) developed upon exposure to light. The results of color monitoring experiments are shown in Table II-17.

  Silver ion release and total silver content measurements were performed as described in Example II-1. An amount of 0.1360 g of sample exposed to light at approximately 20% relative humidity for 168 hours was less than 30 minutes after placing the sample in 98 g of distilled water and 2.96 g of 5M sodium nitrate. 35.35 mg of silver ions were released per unit. In contrast, a 0.1211 g sample held in foil for 168 hours released 27.37 mg of silver ions per gram of sample into 98 g of distilled water and 2.96 g of sodium nitrate. The average total silver content was 28,500 mg Ag / kg sample. The silver metal content was 1400 mg / kg sample.

Example II-18
A sample was prepared in the same manner as in Example II-16 except that the drying temperature was 130 ° C. The color of the sample was light yellow. The results of color monitoring experiments are shown in Table II-18.

  Silver ion release and total silver content measurements were performed as described in Example II-1. An amount of 0.1423 g of sample exposed to light at approximately 20% relative humidity for 168 hours was less than 30 minutes after placing the sample in 98 g of distilled water and 2.96 g of 5M sodium nitrate. 14.81 mg of silver ions were released per unit. In contrast, a 0.1411 g sample held in foil for 168 hours released 10.36 mg of silver ions per gram of sample into 98 g of distilled water and 2.96 g of sodium nitrate. The average total silver content was 13,000 mg Ag / kg sample. The silver metal content was 970 mg / kg sample.

Example II-19
A sample was prepared in the same manner as in Example II-17 except that the drying temperature was 130 ° C. The color of the sample was non-uniform and a pale yellow containing a gray / black irregular region giving a slightly mottled appearance. The results of color monitoring experiments are shown in Table II-19.

  Silver ion release and total silver content measurements were performed as described in Example II-1. An amount of 0.1176 g of sample exposed to light at approximately 20% relative humidity for 168 hours was less than 30 minutes after placing the sample in 98 g of distilled water and 2.96 g of 5M sodium nitrate. 35.25 mg of silver ions were released per unit. In contrast, a 0.1313 g sample held in foil for 168 hours released 24.93 mg of silver ion per gram of sample into 98 g of distilled water and 2.96 g of sodium nitrate. The average total silver content was 28,000 mg Ag / kg sample. The silver metal content was 1500 mg / kg sample.

Example II-20
A sample was prepared in the same manner as in Example II-19 except that the drying temperature was 155 ° C. The color of the sample was non-uniform, with one side being a darker goldish yellow compared to the other side. The lighter side was tested for color. These results are shown in Table II-20.

  Silver ion release and total silver content measurements were performed as described in Example II-1. An amount of 0.1358 g of sample exposed to light at approximately 20% relative humidity for 168 hours was less than 30 minutes after placing this sample in 98 g of distilled water and 2.96 g of 5M sodium nitrate. 26.32 mg of silver ions were released per unit. In contrast, a 0.1395 g sample that was held in foil for 168 hours released 18.21 mg of silver ions per gram of sample into 98 g of distilled water and 2.96 g of sodium nitrate. The average total silver content was 27,500 mg Ag / kg sample. The silver metal content was 3100 mg / kg sample.

Example II-21
A sample was prepared in the same manner as in Example II-1, except that the drying temperature was 180 ° C. The sample color was golden yellow. The results of color monitoring experiments are shown in Table II-21.

  Silver ion release and total silver content measurements were performed as described in Example II-1. An amount of 0.1405 g sample exposed to light at approximately 20% relative humidity for 168 hours was measured within 30 minutes after placing the sample in 98 g distilled water and 2.96 g 5M sodium nitrate. 0.10 mg of silver ions were released per unit. In contrast, a 0.1371 g sample held in foil for 168 hours released 0.52 mg of silver ions per gram of sample into 98 g of distilled water and 2.96 g of sodium nitrate. The average total silver content was 1850 mg Ag / kg sample. The silver metal content was 450 mg / kg sample.

Example II-22
A sample was prepared in the same manner as in Example II-16 except that the drying temperature was 180 ° C. The color of the sample was dark golden yellow. The results of color monitoring experiments are shown in Table II-22.

  Silver ion release and total silver content measurements were performed as described in Example II-1. An amount of 0.1364 g of sample exposed to light at approximately 20% relative humidity for 168 hours was less than 30 minutes after placing the sample in 98 g of distilled water and 2.96 g of 5M sodium nitrate. 0.80 mg of silver ions were released per unit. In contrast, a 0.1340 g sample held in foil for 168 hours released 1.88 mg of silver ions per gram of sample in 98 g of distilled water and 2.96 g of sodium nitrate. The average total silver content was 16000 mg Ag / kg sample. The silver metal content was 2700 mg / kg sample.

Example II-23
A sample was prepared in the same manner as in Example II-17 except that the drying temperature was 180 ° C. The color of the sample was dark brown with a black portion giving a dark brown appearance. The results of color monitoring experiments are shown in Table II-23.

  Silver ion release and total silver content measurements were performed as described in Example II-1. An amount of 0.1443 g of sample exposed to light at approximately 20% relative humidity for 168 hours was less than 30 minutes after placing this sample in 98 g of distilled water and 2.96 g of 5M sodium nitrate. 1.50 mg of silver ions were released per unit. In contrast, a 0.1496 g sample held in foil for 168 hours released 3.30 mg silver ion per gram sample in 98 g distilled water and 2.96 g sodium nitrate. The average total silver content was 27500 mg Ag / kg sample. The silver metal content was 7500 mg / kg sample.

Example II-24
A sample was prepared in the same manner as in Example II-10, except that the drying temperature was 130 ° C. The color of the sample was light yellow. The results of color monitoring experiments are shown in Table II-24.

  Silver ion release and total silver content measurements were performed as described in Example II-1. An amount of 0.1385 g sample exposed to light at approximately 20% relative humidity for 168 hours was measured within 30 minutes after placing the sample in 98 g distilled water and 2.96 g 5M sodium nitrate. 0.84 mg of silver ions were released per unit. In contrast, a 0.1286 g sample held in foil for 168 hours released 1.93 mg of silver ions per gram of sample in 98 g of distilled water and 2.96 g of sodium nitrate. The average total silver content was 3750 mg Ag / kg sample.

Example II-25
A sample was prepared in the same manner as in Example II-11 except that the drying temperature was 130 ° C. The sample color was tan. The results of color monitoring experiments are shown in Table II-25.

  Silver ion release and total silver content measurements were performed as described in Example II-1. An amount of 0.1377 g of sample exposed to light at approximately 20% relative humidity for 168 hours was less than 30 minutes after placing the sample in 98 g of distilled water and 2.96 g of 5M sodium nitrate. 3.14 mg of silver ions were released per unit. In contrast, a 0.1540 g sample held in foil for 168 hours released 4.01 mg of silver ions per gram of sample into 98 g of distilled water and 2.96 g of sodium nitrate. The average total silver content was 6850 mg Ag / kg sample.

Example II-26
The substrate is a SX from 100% TENCEL fiber nonwoven (Green Bay Nonwovens, Inc., Green Bay, Wis.) Containing less than 40 ppm chloride. -152, white, 65 gsm, 24 mesh), and a sample was prepared in the same manner as in Example II-8. The sample color was golden yellow. The results of color monitoring experiments are shown in Table II-26.

  Silver ion release and total silver content measurements were performed as described in Example II-1. An amount of 0.1902 g of sample exposed to light at approximately 20% relative humidity for 168 hours was less than 30 minutes after placing the sample in 98 g of distilled water and 2.96 g of 5M sodium nitrate. 2.19 mg of silver ions were released per unit. In contrast, a 0.1931 g sample held in foil for 168 hours released 2.87 mg of silver ions per gram of sample into 98 g of distilled water and 2.96 g of sodium nitrate. The average total silver content was 7350 mg Ag / kg sample.

Example II-27
The substrate is a 70% LYOCELL fiber / 30% PET nonwoven (Ahlstrom Green Bay, Inc.) (Green Bay, Wis.) Containing less than 40 ppm chloride. Samples were prepared in the same manner as Example II-8, except that SX), SX-156, white, 50 gsm, porous FT-10). The sample color was golden yellow. The results of color monitoring experiments are shown in Table II-27.

  Silver ion release and total silver content measurements were performed as described in Example II-1. An amount of 0.1608 g of sample exposed to light at 168 hours (hr) at approximately 20% relative humidity is within 30 minutes after placing the sample in 98 g of distilled water and 2.96 g of 5M sodium nitrate. Released 2.99 mg of silver ions per gram of sample. In contrast, a 0.1515 g sample held in foil for 168 hours released 6.53 mg of silver ion per gram of sample in 98 g of distilled water and 2.96 g of sodium nitrate. The average total silver content was 8450 mg Ag / kg sample.

Example II-28 (comparative example)
A sample was prepared in the same manner as in Example II-4 except that the drying temperature was 80 ° C. The initial color of the sample was off-white. The results of color monitoring experiments are shown in Table II-28.

Example II-29 (comparative example)
A sample was prepared in the same manner as in Example II-11 except that the drying temperature was 80 ° C. The initial color of the sample was off-white. The results of color monitoring experiments are shown in Table II-29.

Example II-30 (comparative example)
Example, except that the substrate was a 70% viscose / 30% PET fiber nonwoven (507030RPET P1, white, 50 gsm from FA-MA JERSEY SpA, Italy) A sample was prepared in the same manner as II-28. The initial color of the sample was off-white. The results of color monitoring experiments are shown in Table II-30.

Example II-31 (comparative example)
Example, except that the substrate was a non-woven fabric of 70% viscose / 30% PET fiber (507030RPET P1, white, 50 gsm from FA-MA JERSEY SpA (Italy)) A sample was prepared in the same manner as II-29. The initial color of the sample was off-white. The results of color monitoring experiments are shown in Table II-31.

Example II-32 (Comparative Example)
A sample was prepared in the same manner as in Example II-27 except that the drying temperature was 80 ° C. The initial color of the sample was off-white. The results of color monitoring experiments are shown in Table II-32.

Example II-33
A sample was prepared in the same manner as in Example II-30 except that the drying temperature was 155 ° C. The initial color of the sample was golden brown. The results of color monitoring experiments are shown in Table II-33.

Example II-34
A sample was prepared in the same manner as in Example II-31 except that the drying temperature was 155 ° C. The initial color of the sample was golden brown. The results of color monitoring experiments are shown in Table II-34.

Example II-35
Except that the substrate was woven nylon fiber (SR-823-32 × 28, 60 gsm from American Fiber and Finishing, Albemarle, NC) A sample was prepared in the same manner as in Example II-8. The initial color of the sample was brown. The results of color monitoring experiments are shown in Table II-35.

Example II-36
Except that the substrate was woven nylon fiber (SR-823-32 × 28, 60 gsm from American Fiber and Finishing, Albemarle, NC) A sample was prepared in the same manner as in Example II-11. The initial color of the sample was brown. The results of color monitoring experiments are shown in Table II-36.

Example II-37
Examples, except that the substrate was a membrane filter consisting of cellulose nitrate and cellulose acetate (0.22 μM filter, GSWP 0470, available from Millipore, Billerica, Mass.). A sample was prepared in the same manner as II-8. The initial color of the sample was light brown. The results of color monitoring experiments are shown in Table II-37.

Example II-38
Examples, except that the substrate was a membrane filter consisting of cellulose nitrate and cellulose acetate (0.22 μM filter, GSWP 0470, available from Millipore, Billerica, Mass.). A sample was prepared in the same manner as II-11. The initial color of the sample was light brown. The results of color monitoring experiments are shown in Table II-38.

  The complete disclosures of the patents, patent documents, and publications cited herein are incorporated by reference in their entirety as if each were individually incorporated. Various changes and modifications to the present invention will become apparent to those skilled in the art without departing from the scope and spirit of the invention. The present invention is not intended to be unduly limited by the exemplary embodiments and examples presented herein, and such examples and embodiments are described below, as shown below. It should be understood that they are presented only as examples along the scope of the present invention, which are intended to be limited only by the claims set forth herein.

Claims (96)

Applying a silver composition to a substrate to provide a liquid coated substrate, wherein the silver composition comprises a silver salt other than silver sulfate in a solvent, the silver composition comprising about 100 ppm of stabilizer. Containing less than
The base material is polyamide, polyester, polyacetate, polyacrylic acid, polyolefin, polyurethane, polyvinyl chloride, polyvinyl alcohol, polycarbonate, polyvinyl pyrrolidone, polylactic acid, ethylene-vinyl acetate, polystyrene, cellulose acetate, polyacrylate, polyacrylamide , Polyacrylonitrile, polyvinylidene difluoride, polytetrafluoroethylene, polyoxymethylene, polyvinyl ether, styrene-ethylene butylene-styrene elastomer, styrene-butylene-styrene elastomer, styrene-isoprene-styrene elastomer, glass fiber, ceramic and the like Including a material selected from the group consisting of two or more of the combinations;
Drying the liquid-coated substrate to provide a color-stable antibacterial article containing a silver salt applied to the substrate.   The silver salt is silver acetate, silver benzoate, silver carbonate, silver chloride, silver citrate, silver lactate, silver nitrate, silver nitrite, silver chlorate, silver fluorosilicate, silver trihydrogen periodate, silver levulinate, 2. The method of claim 1 selected from the group consisting of silver propionate, silver tartrate, mild silver protein, silver protein and combinations of two or more thereof.   The method of claim 2, wherein the silver salt is silver nitrate.   The method of claim 2, wherein the silver salt is silver benzoate.   The silver salt is silver iodate, silver oxalate, silver phosphate, silver sulfadiazine, silver saccharinate, silver anthranilate, silver hyponitrite, silver myristate, silver palmitate, silver stearate and two of these 2. The method of claim 1 selected from the group consisting of the above combinations.   6. The substrate of any one of claims 1 to 5, wherein the substrate comprises a polyolefin selected from the group consisting of polypropylene, polyethylene, ethylene propylene copolymers, ethylene butylene copolymers, and combinations of two or more thereof. The method described in 1.   The method according to any one of claims 1 to 5, wherein the substrate comprises polyamide.   The method according to any one of claims 1 to 5, wherein the substrate comprises cellulose acetate.   The method according to any one of claims 1 to 8, wherein the substrate comprises a material selected from the group consisting of a porous substrate, a knit, a woven fabric, a nonwoven fabric, an extruded porous sheet and a perforated sheet. .   The method according to any one of claims 1 to 9, wherein the silver composition comprises a stabilizer in an amount of less than 50 ppm, based on the total weight of the silver salt composition.   The method of claim 10, wherein the silver composition does not comprise a stabilizer.   12. A method according to any one of claims 1 to 11, wherein the drying of the liquid coated substrate is accomplished at room temperature.   12. A method according to any one of the preceding claims, wherein drying of the liquid coated substrate is achieved at a temperature below about 100 <0> C.   14. The color stable antimicrobial article comprises a silver salt applied to the substrate such that the concentration of silver on the substrate is less than about 40,000 mg Ag / kg substrate. The method according to any one of the above.   15. The color-stable antibacterial article comprises a silver salt applied to the substrate such that the concentration of silver on the substrate is less than about 20,000 mg Ag / kg substrate. Method.   16. The color stable antimicrobial article of claim 15, comprising a silver salt applied to the substrate such that the concentration of silver on the substrate is less than about 10,000 mg Ag / kg substrate. Method. A silver salt other than silver sulfate, and a silver salt applied to the substrate;
Polyamide, polyester, polyacetate, polyacrylic acid, polyolefin, polyurethane, polyvinyl chloride, polyvinyl alcohol, polycarbonate, polyvinylpyrrolidone, polylactic acid, ethylene-vinyl acetate, polystyrene, cellulose acetate, polyacrylate, polyacrylamide, polyacrylonitrile, poly Vinylidene difluoride, polytetrafluoroethylene, polyoxymethylene, polyvinyl ether, styrene-ethylene butylene-styrene elastomer, styrene-butylene-styrene elastomer, styrene-isoprene-styrene elastomer, glass fiber, ceramic and two or more thereof A substrate comprising a material selected from the group consisting of:
The article is antibacterial and color stable.   The silver salt is silver acetate, silver benzoate, silver carbonate, silver chloride, silver citrate, silver iodate, silver lactate, silver nitrate, silver nitrite, silver oxalate, silver phosphate, silver sulfadiazine, silver saccharinate, anthranyl Silver oxide, silver chlorite, silver fluorosilicate, silver triperiodate, silver hyponitrite, silver levulinate, silver myristate, silver palmitate, silver propionate, silver stearate, silver tartrate, mild silver protein 18. The article of claim 17, wherein the article is selected from the group consisting of: silver protein and combinations of two or more thereof.   The silver salt is silver acetate, silver benzoate, silver carbonate, silver chloride, silver citrate, silver lactate, silver nitrate, silver nitrite, silver chlorate, silver fluorosilicate, silver trihydrogen periodate, silver levulinate, 19. The article of claim 18, selected from the group consisting of silver propionate, silver tartrate, mild silver protein, silver protein, and combinations of two or more thereof.   The article of claim 19, wherein the silver salt is silver nitrate.   The article of claim 19, wherein the silver salt is silver benzoate.   The silver salt is silver iodate, silver oxalate, silver phosphate, silver sulfadiazine, silver saccharinate, silver anthranilate, silver hyponitrite, silver myristate, silver palmitate, silver stearate and two of these The article of claim 18 selected from the group consisting of the above combinations.   The article according to any one of claims 17 to 22, wherein the substrate comprises a polyamide.   The article according to any one of claims 17 to 22, wherein the substrate comprises cellulose acetate.   25. The article according to any one of claims 17 to 24, wherein the concentration of silver on the substrate is less than about 40,000 mg Ag / kg substrate.   26. The article of claim 25, wherein the concentration of silver on the substrate is less than about 20,000 mg Ag / kg substrate.   27. The article of claim 26, wherein the concentration of silver on the substrate is less than about 10,000 mg Ag / kg substrate.   28. The article of any one of claims 17-27, wherein the stabilizer concentration is less than about 1000 ppm based on the total weight of the article.   30. The article of claim 28, wherein the concentration of stabilizer is less than about 500 ppm based on the total weight of the article.   30. The article of claim 29, wherein the concentration of stabilizer is less than about 100 ppm based on the total weight of the article. Applying a silver composition to a substrate to provide a liquid-coated substrate, the silver composition comprising silver acetate, silver benzoate, silver carbonate, silver chloride, silver citrate, silver iodate, lactic acid Silver, silver nitrate, silver nitrite, silver oxalate, silver phosphate, silver sulfadiazine, silver saccharinate, silver anthranilate, silver chlorite, silver fluorosilicate, silver trihydrogen periodate, silver hyponitrite, silver levulinate A silver salt selected from the group consisting of silver myristate, silver palmitate, silver propionate, silver stearate, silver tartrate, mild silver protein, silver protein and combinations of two or more thereof;
Heating the liquid coated substrate at a temperature sufficient to produce silver metal from the silver salt to provide a color stable antibacterial article comprising silver metal nanoparticles and a silver salt. A method for producing an antibacterial article.   The silver salt is silver acetate, silver benzoate, silver carbonate, silver chloride, silver citrate, silver lactate, silver nitrate, silver nitrite, silver chlorate, silver fluorosilicate, silver trihydrogen periodate, silver levulinate, 32. The method of claim 31, wherein the method is selected from the group consisting of silver propionate, silver tartrate, mild silver protein, silver protein, and combinations of two or more thereof.   33. The method of claim 32, wherein the silver salt is silver nitrate.   33. The method of claim 32, wherein the silver salt is silver benzoate.   The silver salt is silver iodate, silver oxalate, silver phosphate, silver sulfadiazine, silver saccharinate, silver anthranilate, silver hyponitrite, silver myristate, silver palmitate, silver stearate and two of these 32. A method according to claim 31 selected from the group consisting of the above combinations.   The substrate comprises a material selected from the group consisting of cellulosic materials, nylon, polyamide, polyacetate, collagen, gelatin, polyacrylamide, natural rubber, alginate, and combinations of two or more thereof. Item 34. The method according to any one of Items 31 to 35.   The substrate also includes polyester, polyacrylic acid, polyolefin, polyurethane, polyvinyl chloride, including polyvinyl chloride, polystyrene, fiber glass, ceramic fiber, polyacrylate, polyacrylonitrile, polyvinylidene difluoride, polytetrafluoroethylene, polyoxy Group consisting of methylene, polyvinyl alcohol, polylactic acid, polyvinyl ether, polyvinyl pyrrolidone, polycarbonate, styrene-ethylene butylene-styrene elastomer, styrene-butylene-styrene elastomer, styrene-isoprene-styrene elastomer, and combinations of two or more thereof 37. The method of claim 36, comprising a material selected from:   38. A method according to claim 36 or 37, wherein the substrate comprises a cellulosic material.   Absorbent carboxymethyl wherein the cellulosic material is selected from the group consisting of carboxymethylated cotton, carboxymethylated cellulose, carboxymethylated solvent spun cellulose fibers, carboxymethylated rayon and combinations of two or more thereof 40. The method of claim 38, wherein the method is a chemical material.   39. The cellulosic material of claim 38, wherein the cellulosic material is selected from the group consisting of cotton, rayon, hemp, jute, bamboo fiber, cellulose acetate, carboxymethylated solvent spun cellulose fiber, and combinations of two or more thereof. the method of.   41. The method of any one of claims 31 to 40, wherein the substrate comprises a material selected from the group consisting of a knit, a woven fabric, a nonwoven fabric, an extruded porous sheet, and a perforated sheet. The method described.   42. The method of any one of claims 31 to 41, wherein heating of the liquid coated substrate is accomplished at a temperature in the range of about 95 [deg.] C to about 225 [deg.] C.   43. The method of claim 42, wherein the heating of the liquid coated substrate is accomplished at a temperature in the range of about 100 <0> C to about 200 <0> C.   44. The method of claim 43, wherein the heating of the liquid coated substrate is accomplished at a temperature in the range of about 110 <0> C to about 180 <0> C.   45. The method of claim 44, wherein the heating of the liquid coated substrate is accomplished at a temperature in the range of about 130 <0> C to about 175 <0> C.   46. A method according to any one of claims 31 to 45, wherein the silver salt solution comprises a stabilizer in an amount of less than 100 ppm based on the total weight of the silver composition.   47. The method of claim 46, wherein the silver salt solution does not contain a stabilizer.   48. The method of any one of claims 31 to 47, wherein the antimicrobial article has a non-white color and is color stable. Applying a silver composition to a substrate to provide a liquid-coated substrate, wherein the silver composition comprises a silver salt other than silver sulfate;
Heating the liquid coated substrate at a temperature sufficient to produce silver metal from the silver salt to provide a color stable antibacterial article comprising silver metal nanoparticles and a silver salt. The manufacturing method of an antimicrobial article.   The silver salt is silver acetate, silver benzoate, silver carbonate, silver chloride, silver citrate, silver lactate, silver nitrate, silver nitrite, silver chlorate, silver fluorosilicate, silver trihydrogen periodate, silver levulinate, 50. The method of claim 49, selected from the group consisting of silver propionate, silver tartrate, mild silver protein, silver protein, and combinations of two or more thereof.   51. The method of claim 50, wherein the silver salt is silver nitrate.   51. The method of claim 50, wherein the silver salt is silver benzoate.   The silver salt is silver iodate, silver oxalate, silver phosphate, silver sulfadiazine, silver saccharinate, silver anthranilate, silver hyponitrite, silver myristate, silver palmitate, silver stearate and two of these 50. The method of claim 49, selected from the group consisting of the above combinations.   The substrate comprises a material selected from the group consisting of cellulosic materials, nylon, polyamide, polyacetate, collagen, gelatin, polyacrylamide, natural rubber, alginate, and combinations of two or more thereof. The method according to any one of 49 to 53.   The substrate is also polyester, polyacrylic acid, polyolefin, polyurethane, polyvinyl chloride, polystyrene, fiberglass, ceramic fiber, polyacrylate, polyacrylonitrile, polyvinylidene difluoride, polytetrafluoroethylene, polyoxymethylene, polyvinyl alcohol Selected from the group consisting of polylactic acid, polyvinyl ether, polyvinyl pyrrolidone, polycarbonate, styrene-ethylene butylene-styrene elastomer, styrene-butylene-styrene elastomer, styrene-isoprene-styrene elastomer, and combinations of two or more thereof. 55. The method of claim 54, wherein the method comprises:   56. A method according to claim 54 or 55, wherein the substrate comprises a cellulosic material.   Absorbent carboxymethyl wherein the cellulosic material is selected from the group consisting of carboxymethylated cotton, carboxymethylated cellulose, carboxymethylated solvent spun cellulose fibers, carboxymethylated rayon and combinations of two or more thereof 57. The method of claim 56, comprising an activating material.   57. The cellulosic material is selected from the group consisting of cotton, rayon, hemp, jute, bamboo fiber, cellulose acetate, carboxymethylated solvent spun cellulose fiber, and combinations of two or more thereof. the method of.   59. The method of any one of claims 49 to 58, wherein the substrate comprises a material selected from the group consisting of a porous substrate including a knit, woven fabric, nonwoven fabric, extruded porous sheet, and perforated sheet. The method described.   60. The method of any one of claims 49 to 59, wherein the heating of the liquid coated substrate is accomplished at a temperature in the range of about 95C to about 225C.   61. The method of claim 60, wherein the heating of the liquid coated substrate is accomplished at a temperature in the range of about 100 <0> C to about 200 <0> C.   64. The method of claim 61, wherein the heating of the liquid coated substrate is accomplished at a temperature in the range of about 110 <0> C to about 180 <0> C.   64. The method of claim 62, wherein the heating of the liquid coated substrate is accomplished at a temperature in the range of about 130 <0> C to about 175 <0> C.   64. A method according to any one of claims 49 to 63, wherein the silver salt solution comprises a stabilizer in an amount of less than 100 ppm based on the total weight of the silver composition.   65. The method of claim 64, wherein the silver salt solution does not contain a stabilizer.   66. The method of any one of claims 49 to 65, wherein the antimicrobial article has a non-white color and is color stable.   An article comprising silver metal and a silver salt disposed on a substrate, wherein the silver salt is silver acetate, silver benzoate, silver carbonate, silver chloride, silver citrate, silver iodate, silver lactate, silver nitrate, Silver nitrite, silver oxalate, silver phosphate, silver sulfadiazine, silver saccharinate, silver anthranilate, silver chlorite, silver fluorosilicate, silver triperiodate, silver hyponitrite, silver levulinate, silver myristate An article selected from the group consisting of: silver palmitate, silver propionate, silver stearate, silver tartrate, mild silver protein, silver protein, and combinations of two or more thereof.   The silver salt is silver acetate, silver benzoate, silver carbonate, silver chloride, silver citrate, silver lactate, silver nitrate, silver nitrite, silver chlorate, silver fluorosilicate, silver trihydrogen periodate, silver levulinate, 68. The article of claim 67, selected from the group consisting of silver propionate, silver tartrate, mild silver protein, silver protein, and combinations of two or more thereof.   69. The article of claim 68, wherein the silver salt is silver nitrate.   69. The article of claim 68, wherein the silver salt is silver benzoate.   The silver salt is silver iodate, silver oxalate, silver phosphate, silver sulfadiazine, silver saccharinate, silver anthranilate, silver hyponitrite, silver myristate, silver palmitate, silver stearate and two of these 68. The article of claim 67, selected from the group consisting of the above combinations.   The substrate comprises a material selected from the group consisting of cellulosic materials, nylon, polyamide, polyacetate, collagen, gelatin, polyacrylamide, natural rubber, alginate, and combinations of two or more thereof. The article according to any one of 67 to 71.   The substrate is also polyester, polyacrylic acid, polyolefin, polyurethane, polyvinyl chloride, polystyrene, fiberglass, ceramic fiber, polyacrylate, polyacrylonitrile, polyvinylidene difluoride, polytetrafluoroethylene, polyoxymethylene, polyvinyl alcohol Selected from the group consisting of polylactic acid, polyvinyl ether, polyvinyl pyrrolidone, polycarbonate, styrene-ethylene butylene-styrene elastomer, styrene-butylene-styrene elastomer, styrene-isoprene-styrene elastomer, and combinations of two or more thereof. 75. The article of claim 72, comprising a material.   74. The article of claim 72 or claim 73, wherein the substrate comprises a cellulosic material.   Absorbent carboxymethyl wherein the cellulosic material is selected from the group consisting of carboxymethylated cotton, carboxymethylated cellulose, carboxymethylated solvent spun cellulose fibers, carboxymethylated rayon and combinations of two or more thereof 75. The article of claim 74, comprising a chelating material.   75. The cellulosic material of claim 74, wherein the cellulosic material is selected from the group consisting of cotton, rayon, hemp, jute, bamboo fiber, cellulose acetate, carboxymethylated solvent spun cellulose fiber, and combinations of two or more thereof. Goods.   77. The substrate according to any one of claims 67 to 76, wherein the substrate is a material selected from the group consisting of a porous substrate, a knit, a woven fabric, a nonwoven fabric, an extruded porous sheet, and a perforated sheet. Goods.   78. The article of any one of claims 67 to 77, wherein the antimicrobial article has a non-white color and is color stable.   79. The article of any one of claims 67 to 78, wherein the concentration of silver on the substrate is less than about 40,000 mg Ag / kg substrate.   80. The article of claim 79, wherein the concentration of silver on the substrate is less than about 20,000 mg Ag / kg substrate.   81. The article of claim 80, wherein the concentration of silver on the substrate is less than about 10,000 mg Ag / kg substrate.   An article comprising silver metal and a silver salt applied to a substrate, wherein the silver salt comprises a silver salt other than silver sulfate.   The silver salt is silver acetate, silver benzoate, silver carbonate, silver chloride, silver citrate, silver lactate, silver nitrate, silver nitrite, silver chlorate, silver fluorosilicate, silver trihydrogen periodate, silver levulinate, 83. The article of claim 82, selected from the group consisting of silver propionate, silver tartrate, mild silver protein, silver protein, and combinations of two or more thereof.   84. The article of claim 83, wherein the silver salt is silver nitrate.   84. The article of claim 83, wherein the silver salt is silver benzoate.   The silver salt is silver iodate, silver oxalate, silver phosphate, silver sulfadiazine, silver saccharinate, silver anthranilate, silver hyponitrite, silver myristate, silver palmitate, silver stearate and two of these 83. The article of claim 82, selected from the group consisting of the above combinations.   The substrate comprises a material selected from the group consisting of cellulosic materials, nylon, polyamide, polyacetate, collagen, gelatin, polyacrylamide, natural rubber, alginate, and combinations of two or more thereof. The article according to any one of 82 to 86.   The substrate is also polyester, polyacrylic acid, polyolefin, polyurethane, polyvinyl chloride, polystyrene, fiberglass, ceramic fiber, polyacrylate, polyacrylonitrile, polyvinylidene difluoride, polytetrafluoroethylene, polyoxymethylene, polyvinyl alcohol Selected from the group consisting of polylactic acid, polyvinyl ether, polyvinyl pyrrolidone, polycarbonate, styrene-ethylene butylene-styrene elastomer, styrene-butylene-styrene elastomer, styrene-isoprene-styrene elastomer, and combinations of two or more thereof. 90. The article of claim 87, comprising a material.   89. The article of claim 87 or claim 88, wherein the substrate comprises a cellulosic material.   Absorbent carboxymethyl wherein the cellulosic material is selected from the group consisting of carboxymethylated cotton, carboxymethylated cellulose, carboxymethylated solvent spun cellulose fibers, carboxymethylated rayon and combinations of two or more thereof 90. The article of claim 89, comprising a chelating material.   90. The cellulosic material is selected from the group consisting of cotton, rayon, hemp, jute, bamboo fiber, cellulose acetate, carboxymethylated solvent spun cellulose fiber, and combinations of two or more thereof. Goods.   92. The article according to any one of claims 82 to 91, wherein the substrate is a material selected from the group consisting of a porous substrate, a knit, a woven fabric, an extruded porous sheet, and a perforated sheet.   93. The article of any one of claims 82 to 92, wherein the antimicrobial article has a non-white color and is color stable.   94. The article of any one of claims 82 to 93, wherein the concentration of silver on the substrate is less than about 40,000 mg Ag / kg substrate.   95. The article of claim 94, wherein the concentration of silver on the substrate is less than about 20,000 mg Ag / kg substrate.   96. The article of claim 95, wherein the concentration of silver on the substrate is less than about 10,000 mg Ag / kg substrate.