Patent Application
20200102673
The present disclosure relates to antimicrobial materials and methods for making the same. In one non-limiting application of the disclosure, there is provided antimicrobial fibers, methods of manufacturing the same, and articles including the antimicrobial fibers. More particularly, the antimicrobial fibers include antimicrobial nanoparticles substantially uniformly dispersed in a polymer matrix and, even more particularly, the antimicrobial fibers include metal antimicrobial nanoparticles substantially uniformly dispersed in a polymer matrix. In another non-limiting application of the disclosure, there is provided a device that is at least partially formed of a polymer material that includes antimicrobial nanoparticles substantially uniformly dispersed in a polymer matrix.
With rising living standards, people are paying more attention to their health. Many commonly used items such as clothing, towels, mops, sheets, pillow cases, shoes, caps, hats, gloves, and the like carry a large number of microorganisms. For microorganisms in nature, the skin provides a barrier to undesirable microorganisms. In general, some resident bacteria on the skin plays a role in protecting the skin from undesirable microorganisms. However, a small number of those undesirable microorganisms can multiply on and through the skin, respiratory tract, digestive tract, and/or genital tract mucosa and potentially cause harm to an individual. Textiles, in the nature of human wear, come into contact with sweat, sebum and other human secretions, and are also contaminated by environmental exposures (e.g., dirt, food, smoke, etc.) which can also spread pathogens. Antibacterial products are a control means to inhibit bacterial growth and repress bacterial reproduction, which protect the human body from the invasion of foreign microbial activities. At present, it is common to use physical antimicrobial products to contact and destroy common microbial components.
The existing antibacterial textiles are divided into two main categories. The first kind of antimicrobial textile is processed (i.e., the antimicrobial agent is added) after the textile has been formed or finished. This process is widely used because of its simplicity, suitability with a large number of antimicrobial agents, and wide applicability. Surface coating, resin finishing, or microencapsulation of the textile are commonly used in such a process. The antimicrobial material is typically distributed on the surface of fibers and fabrics.
Although this type of antibacterial textile is commonly used, these treated textiles do not adequately maintain antibacterial effectiveness after continuous washing and reuse because the antimicrobial material tends to fall off or be removed after one or more washing or uses of the textiles. In some cases, almost all of the antibacterial effectiveness is lost (e.g., antibacterial fibers no longer have antibacterial properties) after only a few uses or washes.
The second kind of antibacterial textile is made from antibacterial fibers. Permanent antibacterial fibers show greater advantages than the finished antibacterial textiles. Inorganic antibacterial agents have attracted much attention due to their long effectiveness. Inorganic antibacterial agents have different antibacterial effectiveness. For antibacterial metals, the order of antibacterial activity is: Hg>Ag>Cd>Cu>Zn>Fe>Ni. However, antibacterial activity alone is not the only criteria for use in a fiber since some metals can be harmful to the human body. For example, mercury, cadmium, and lead have antibacterial properties, but they are harmful to the human body. The order of safety for metal ions is: Ag>Co>Ni>Al>Zn>Cu═Fe>Mn>Sn>Ba>Mg>Ca. Therefore, when considering the safety and antimicrobial properties, silver is the best and calcium is the least desirable of the non-toxic metals. Currently silver, zinc and copper have found preference in textiles. However, the color of copper can affect the performance of the product. Silver is limited in use due to its easy oxidation and discoloration, high price, and tendency to high agglomeration.
In addition to textiles, other items that are commonly in contact with human skin (such as children's toys, toothbrush handles, razorblade handles, brush handles, etc.) have been treated to reduce bacterial growth Typically, these devices are coated with an antibacterial coating which, like textile coatings, typically wears off after a period of time. Some devices have included metal salts incorporated into a polymer material; however, such salts generally do not disperse properly in the plastic, thereby limiting the effectiveness of the antibacterial properties of the device.
Zinc is internationally recognized as a “safety” material. The changes of surface electron and crystal structure of fine zinc nanoparticle grains will produce surface and volume effects, quantum size, and macro-tunneling effects which macro-objects do not have. Zinc also exhibits excellent photo-catalytic, UV-shielding, antibacterial and photoluminescence properties. Zinc has shown important application value in the fields of ceramics, chemical industry, environmental protection, optoelectronics, biology, and medicine.
Because zinc can inhibit the growth of bacteria, viruses, and fungi, and promote the metabolism of human skin, zinc-based antibacterial fibers have good antibacterial properties and are healthy for the skin. Zinc is also an essential trace element for the human body. Zinc particles have many positive characteristics, such as high stability (non-oxidation, non-color, non-toxic, tasteless), low dosage, high antibacterial efficiency, safety, non-toxic, and long antibacterial effectiveness. Zinc has passed the toxicity test of SGS, European Compulsory Standard (ROHS), acute toxicity oral test, skin irritation test, skin allergy test and Japanese Industrial Standard (JIS) antibacterial test. Zinc is highly safe, non-toxic, harmless, non-irritating, and has no allergic reaction to the human body.
Nanometer inorganic antibacterial agents have excellent antibacterial properties and small particle size. However, nano-powders are very fine, easy to agglomerate, have poor compatibility with fiber resins and other types of polymers, and are very difficult to uniformly disperse in a formed fiber or polymer device.
In view of the current state of the art, there is a need for a polymer fiber or polymer device that can be formed with a nanoparticle antibacterial agent, when such nanoparticle antibacterial agent is evenly disbursed throughout the polymer fiber or polymer device.
The present disclosure relates to antimicrobial materials such as fibers or devices, methods of manufacturing the same, and articles including the antimicrobial fibers or devices.
In one non-limiting aspect of the disclosure, there is provided antimicrobial fibers that include antimicrobial nanoparticles substantially uniformly dispersed in a polymer matrix and, even more particularly, the antimicrobial fibers include metal antimicrobial nanoparticles substantially uniformly dispersed in a polymer matrix. As defined herein, “antimicrobial fibers having substantially uniformly dispersed antimicrobial nanoparticles in a polymer matrix” means that 1) a certain volume (e.g., 150-1000 cubic microns and all values and ranges therebetween) of the fiber is located in different locations of the fiber, such certain volumes will have 60-100% (and all values and ranges therebetween) of the same weight percent of antimicrobial nanoparticles, and 2) 50-100% (and all values and ranges therebetween) of the antimicrobial nanoparticles in such certain volume are spaced apart from one another. As such, if two different sections of a fiber having the same volume were cut off and analyzed, the first analyzed section would have 60-167 wt. % of the particles in the second analyzed section, and for both the first and second analyzed sections, 50-100% of the antimicrobial nanoparticles in such sections will be spaced apart from one another. In one non-limiting embodiment, the antimicrobial fibers, for a certain volume of the fiber in different locations, has within 70-100% of the same weight percent of antimicrobial nanoparticles and at least 60% of the antimicrobial nanoparticles in such certain volumes are spaced apart from one another; typically, for a certain volume of the fiber in different locations, has within 80-100% of the same weight percent of antimicrobial nanoparticles and at least 70% of the antimicrobial nanoparticles in such certain volumes are spaced apart from one another; more typically, for a certain volume of the fiber in different locations, has within 80-100% of the same weight percent of antimicrobial nanoparticles and at least 75% of the antimicrobial nanoparticles in such certain volumes are spaced apart from one another; and still more typically, for a certain volume of the fiber in different locations, has within 90-100% of the same weight percent of antimicrobial nanoparticles and at least 90% of the antimicrobial nanoparticles in such certain volumes are spaced apart from one another.
The size of the antimicrobial nanoparticles are generally no more than 200 nanometers, and typically about 10-200 nanometers (and all values and ranges therebetween), more typically about 10-150 nanometers, still more typically 25-120 nanometers, and even more typically 50-100 nanometers.
The fibers can be used as a partial or full substitute for thread and/or fabric that is used to form articles such as, but not limited to, clothing, bedding, towels, cloths, rags, mops, shoes and other types of footwear, caps, hats, luggage, purses, backpacks, carrying cases, furniture fabric, curtains, awnings, tents, umbrellas, furniture covers, grill covers, laundry containers, storage containers, rugs, carpeting, pillow covers, blankets, throws, seat covers, bandages, straps, rope, twine, yarn, string, gowns, scrubs, masks, bandages, dressings, pillows, life jackets, bathmats, pads, diapers, wipes, sleeping bags, pet beds, pet toys, canvas products, and any other device or material that is fully or partially formed from threads and/or fabric.
In another non-limiting aspect of the disclosure, there are provide antimicrobial devices in which antimicrobial nanoparticles are substantially uniformly dispersed in a polymer matrix and, even more particularly, the antimicrobial devices include metal antimicrobial nanoparticles substantially uniformly dispersed in a polymer matrix. Such devices are generally molded, extruded, 3D printed, etc. As defined herein, “antimicrobial device having substantially uniformly dispersed antimicrobial nanoparticles in a polymer matrix” means that for a certain volume of the polymer device (e.g., 150-1000 cubic microns and all values and ranges therebetween) that includes the antimicrobial nanoparticles in different locations, such certain volumes will have within 60-100% (and all values and ranges therebetween) of the same weight percent of antimicrobial nanoparticles and 50-100% (and all values and ranges therebetween) of the antimicrobial nanoparticles in such certain volume will be spaced apart from one another. The device can be any type of device that is at least partially formed of a polymer material wherein it is desirable to inhibit or prevent bacteria growth on the outer surface of all or a portion of the device. Non-limiting devices include, but are not limited to, healthcare-related products (e.g., furniture, flooring, medical devices, light fixtures, brushes, combs, beds, eating utensils, wheelchairs or other patient transport devices, crutches, walking aids, toilet seats, wash basins, wash basin hardware, door handles, wall panels, doors or door panels, trash bags, trash cans or receptacles, shower curtains, containers, counter tops, TVs and other appliances, clocks and other electronic devices, etc.); transportation-related products (e.g., seats, floorings, cabin walls, masks, eating utensils, toilet seats, shower curtains, wash basins, wash basin hardware, door handles, wall panels, doors or door panels, trash bags, trash cans or receptacles, security containers or other types of containers, security scanning equipment, counter tops, TVs and other appliances, clocks and other electronic devices, picture frames, etc.); hotel/motel-related products (e.g., furniture, carpet, sheets, bathmats, shower curtains, light fixtures, brushes, combs, bathrobes, toilet seats, wash basins, wash basin hardware, door handles, wall panels, doors or door panels, trash bags, trash cans or receptacles, containers, counter tops, TVs and other appliances, clocks and other electronic devices, picture frames and other types of frames, pens and other writing implements, etc.); military-related products (clothing, masks, furniture, flooring, light fixtures, curtains, footwear, brushes, combs, beds, eating utensils, toilet seats, wash basins, wash basin hardware, door handles, wall panels, doors or door panels, trash bags, trash cans or receptacles, containers, counter tops, TVs and other appliances, clocks and other electronic devices, walls and other structures, life jackets, weapons, communication equipment, etc.); building-related products (e.g., flooring, roofing, wall panels, windows, grout, tile, counter tops, carpeting, furniture, toilet seats, wash basins, wash basin hardware, door handles, wall panels, doors or door panels, trash bags, trash cans or receptacles, containers, counter tops, TVs and other appliances, clocks and other electronic devices, walls and other structures, paints, sealants, surface protectants, etc.); cosmetic-related products; personal healthcare-related products; athletic products (e.g., pads, helmets, grips, shoes, sports equipment, etc.); personal electronic devices (e.g., cell phones, TVs, stereos, clocks, keyboards, computers, headphones, 3D eyewear, game consoles, game controllers, projectors, printers, scanners, displays, 3D printers, etc.); infant and children and adult products (e.g., diapers, furniture, toys, strollers, cribs, pacifiers, baby bottles, sippy cups, teething rings, diaper pails, crib rockers, bikes, transportation devices, baby carriers, car seats, furniture, sheets, footwear, brushes, combs, beds, etc.); other products (e.g., food storage products, pet beds, pet toys, hunting gear, towels, sponges, cleaning brushes and plungers, bath mats, shower curtains, shelf liners, bread boxes, trash cans, trash bags, shoes, shoe inserts, luggage, backpacks, purses, wallets, belts, etc.). In essence, any polymer material can container the antimicrobial technology of the present disclosure.
Non-limiting antimicrobial nanoparticles include one or more metal materials selected from the group of zinc metal, copper metal, silver metal, iron metal, zinc oxide, copper oxide, silver oxide, iron oxide, and/or salts of zinc, copper, silver, and/or iron. In one particular non-limiting embodiment, the antimicrobial nanoparticles include or are fully formed of zinc metal, salts of zinc, and/or zinc oxide. In another particular non-limiting embodiment, the antimicrobial nanoparticles include or are fully formed of zinc metal and/or zinc oxide. In another particular non-limiting embodiment, the antimicrobial nanoparticles include or are fully formed of zinc metal. When the antimicrobial nanoparticles include or are fully formed of metal, the purity of the metal is at least about 90%, typically have a purity of at least about 98%, more typically have a purity of at least about 99%, and even more have a purity of at least about 99.95%. Generally, the metal used as the antimicrobial nanoparticle is a single metal; however, it can be a metal alloy that includes two or more of zinc metal, copper metal, silver metal, iron metal (e.g., Zn—Cu alloy, Zn—Ag alloy, Ag—Cu alloy, Fe—Ag alloy, Fe—Zn alloy, etc.).
In accordance with one non-limiting embodiment of the present disclosure, thread, yarn, fabric and/or textile is partially or fully formed of antimicrobial fibers. One or more of the antimicrobial fibers includes a polymer matrix and antimicrobial nanoparticles dispersed substantially uniformly throughout the polymer matrix.
In accordance with one non-limiting embodiment of the present disclosure, a device can be formed that is partially or fully formed of an antimicrobial polymer material. The antimicrobial polymer material includes a polymer matrix and antimicrobial nanoparticles dispersed substantially uniformly throughout the polymer matrix.
In accordance with another non-limiting embodiment of the present disclosure, there is provided an antimicrobial fiber with a non-circular-shaped cross section that includes antimicrobial nanoparticles dispersed substantially uniformly throughout the polymer matrix. As can be appreciated, the cross-sectional shape of the antibacterial fibers can be circular. In one non-limiting embodiment, the antimicrobial fibers of the present disclosure have a non-circular cross-sectional shape (e.g., clover-shaped, cross-shaped, fibers having one or more grooves along the outer surface and length of the fiber, etc.). Such a non-circular cross-sectional shape can be used to improve moisture absorption properties, quick drying properties, breathability properties, flexibility properties, and/or resilience properties of the antimicrobial fiber as compared to circular-shaped cross section fibers.
In accordance with another non-limiting embodiment of the present disclosure, there is provided a method for forming antimicrobial fibers which includes forming spun antimicrobial fibers from a spinning heated mixture, wherein the heated mixture includes one or more antimicrobial nanoparticles, one or more polymeric components, and at least one additive selected from the group of one or more surfactants and/or one or more coupling agents. The mixture can optionally include other materials (e.g., colorant, aromatic material for smell, mica to make fiber feel cool, tourmaline to make fiber feel warm, thinning agent, etc.). The surfactant and/or coupling agent facilitate in the uniform dispersion of the nanoparticles in the heated mixture so that the formed fibers have a uniform dispersion of the antimicrobial nanoparticles in the formed fibers. The thinning agent (when used) is generally used to obtain a desired viscosity of the heated mixture for purposes of proper mixing and/or proper formation of the fibers. The thinning agent can be or include water and/or some other neutral liquid. In one non-limiting application, the surfactant and/or coupling agent also facilitate in inhibiting the agglomeration of the antimicrobial nanoparticles in the heated mixture and to also inhibit the agglomeration of the antimicrobial nanoparticles to the formed fibers. Generally, a formed fiber that includes antimicrobial nanoparticles will contain less than 10 vol. % agglomerated antimicrobial nanoparticles having an average size that is greater than 2 micrometers. In non-limiting configuration, a formed fiber that includes antimicrobial nanoparticles will contain less than 5 vol. % agglomerated antimicrobial nanoparticles having an average size that is greater than 2 micrometers. In non-limiting configuration, a formed fiber that includes antimicrobial nanoparticles will contain less than 5 vol. % agglomerated antimicrobial nanoparticles having an average size that is greater than 1.75 micrometer. In non-limiting configuration, a formed fiber that includes antimicrobial nanoparticles will contain less than 5 vol. % agglomerated antimicrobial nanoparticles having an average size that is greater than 1.5 micrometers. In non-limiting configuration, a formed fiber that includes antimicrobial nanoparticles will contain less than 2 vol. % agglomerated antimicrobial nanoparticles that have an average size of greater than 1.5 micrometers. In non-limiting configuration, a formed fiber that includes antimicrobial nanoparticles will contain less than 1 vol. % agglomerated antimicrobial nanoparticles that have an average size of greater 1.5 micrometers. In non-limiting configuration, a formed fiber that includes antimicrobial nanoparticles will contain less than 0.5 vol. % agglomerated antimicrobial nanoparticles that have an average size of greater than 1.5 micrometers.
In accordance with another non-limiting embodiment of the present disclosure, the surfactants can be anionic surfactants, cationic surfactants and/or non-ionic surfactants. Non-limiting surfactants that can be used in the present disclosure include, but are not limited to, stearic acid, sodium dodecyl sulfonate surfactants, quaternary ammonium surfactants, amino acid surfactants, betaine surfactants, fatty acid glyceride ester surfactants, fatty acid sorbitan surfactants, lecithin surfactants, and/or Tween™ series surfactants (e.g., polyethoxylated sorbitan ester surfactants, nonionic polyoxyethylene surfactants, etc.).
In accordance with another non-limiting embodiment of the present disclosure, there is provided a method for forming a masterbatch from a melted mixture that comprises one or more antimicrobial nanoparticles, one or more polymeric components, and at least one additive selected from the group of one or more surfactants and/or one or more coupling agents, by cooling the mixture and optionally granulating the mixture to form the masterbatch. Other materials can optionally be used to form the final masterbatch (e.g., colorant, aromatic material for smell, mica to make fiber feel cool, tourmaline to make fiber feel warm, etc.). These other materials, other than possibly the thinning agent (when used), are selected to at least partially remain in the final fiber. When a thinning agent is optionally used to form the final solid or granulated masterbatch, the thinning agent is generally removed from the final masterbatch by evaporation, degradation, etc. Generally, less than 2% of the thinning agent remains in the final solid or granulated masterbatch, typically less than 1% of the thinning agent remains in the final solid or granulated masterbatch, more typically less than 0.5% of the thinning agent remains in the final solid or granulated masterbatch, still more typically less than 0.1% of the thinning agent remains in the final solid or granulated masterbatch, and yet more typically less than 0.01% of the thinning agent remains in the final solid or granulated masterbatch.
In accordance with another non-limiting embodiment of the present disclosure, there is provided a method for forming antimicrobial fibers which includes the step of extruding and/or spinning a heated mixture of a masterbatch and additional polymeric component, wherein the masterbatch includes a mixture of one or more types of antimicrobial nanoparticles, one or more polymeric components, and at least one additive selected from the group of one or more surfactants and/or one or more coupling agents. During the final formation of the antimicrobial fiber, generally at least about 80%, and typically about 90-100% of the additives are burned off, degraded, or are otherwise removed from the final formed antimicrobial fiber. Other materials can optionally be used to form the final masterbatch (e.g., thinning agent, colorant, aromatic material for smell, mica to make fiber feel cool, tourmaline to make fiber feel warm, etc.). These other materials, other than possibly the thinning agent (when used), are selected to at least partially remain in the final fiber. When a thinning agent is optionally used to form the final solid or granulated masterbatch, the thinning agent is generally removed from the final masterbatch by evaporation, degradation, etc. Generally, less than 2% of the thinning agent remains in the final solid or granulated masterbatch, typically less than 1% of the thinning agent remains in the final solid or granulated masterbatch, more typically less than 0.5% of the thinning agent remains in the final solid or granulated masterbatch, still more typically less than 0.1% of the thinning agent remains in the final solid or granulated masterbatch, and yet more typically less than 0.01% of the thinning agent remains in the final solid or granulated masterbatch.
In accordance with another non-limiting embodiment of the present disclosure, there is provided an antimicrobial fiber that has a substantially uniform dispersion of antimicrobial nanoparticles in the fiber, and wherein such fiber retains its antibacterial effectiveness after many standard wash cycles (i.e., a standard wash cycle in a commercially available household washing machine for about 20-60 minutes at water temperatures of 20-70° C. and wherein commercially available household washing detergent that is approved for the commercially available household washing machine may or may not be used). After testing by independent testing institutions, the antibacterial effectiveness of the antimicrobial fiber of the present disclosure against Escherichia coli (E. coli), Staphylococcus aureus (S. aureus), and Candida albicans (C. albicans) after one wash was at least 90% the antibacterial effectiveness of the unwashed antimicrobial fiber. In one non-limiting embodiment, the antibacterial effectiveness of the antimicrobial fiber of the present disclosure against E. coli, S. aureus, and C. albicans after one standard wash cycle was at least 95% the antibacterial effectiveness of the unwashed antimicrobial fiber, and more typically the antibacterial effectiveness of the antimicrobial fiber of the present disclosure against E. coli, S. aureus, and C. albicans after one standard wash cycle was at least 99% the antibacterial effectiveness of the unwashed antimicrobial fiber. In one non-limiting embodiment, the antibacterial effectiveness of the antimicrobial fiber of the present disclosure against E. coli, S. aureus, and C. albicans after 100 standard wash cycles was at least 85% the antibacterial effectiveness of the unwashed antimicrobial fiber, typically the antibacterial effectiveness of the antimicrobial fiber of the present disclosure against E. coli, S. aureus, and C. albicans after 100 standard wash cycles was at least 90% the antibacterial effectiveness of the unwashed antimicrobial fiber, more typically the antibacterial effectiveness of the antimicrobial fiber of the present disclosure against E. coli, S. aureus, and C. albicans after 100 standard wash cycles was at least 95% the antibacterial effectiveness of the unwashed antimicrobial fiber, and yet more typically the antibacterial effectiveness of the antimicrobial fiber of the present disclosure against E. coli, S. aureus, and C. albicans after 100 standard wash cycles was at least 98% the antibacterial effectiveness of the unwashed antimicrobial fiber. During the testing of the fibers, the fibers were washed in pure water, and in water that included a standard consumer washing machine detergent and the temperature of the water was set at all common temperature settings for consumer washing machines. The antimicrobial fiber was also tested for irritation to skin; no evidence of irritation occurred for prewashed and post-washed fibers. The antibacterial fibers of the present disclosure have good antibacterial effect and durable antibacterial property, as well as good hygroscopicity, fast drying resistance, ultraviolet resistance, softness, resilience, and smoothness. At the same time, chemical modification of the nanoparticles (e.g., forming metal salts or metal oxides) is not required.
In accordance with another non-limiting embodiment of the present disclosure, there is provided an antimicrobial fiber that has a substantially uniform dispersion of antimicrobial nanoparticles in the fiber, and wherein such fiber retains its antibacterial effectiveness after many washes, and wherein less than 1% of the antimicrobial nanoparticles in the fiber leaches from the fiber after the fiber is subjected to one standard wash cycle (i.e., a standard wash cycle in a commercially available household washing machine for at least 20 minutes at water temperatures of 20-70°, and wherein commercially available household washing detergent that is approved for the commercially available household washing machine may or may not be used). In one non-limiting embodiment, less than 1% of the antimicrobial nanoparticles in the fiber leaches from the fiber after the fiber is subjected to 100 standard wash cycles. In another non-limiting embodiment, less than 0.1% of the antimicrobial nanoparticles in the fiber leaches from the fiber after the fiber is subjected to one standard wash cycle. In another non-limiting embodiment, less than 0.1% of the antimicrobial nanoparticles in the fiber leaches from the fiber after the fiber is subjected to 100 standard wash cycles.
In accordance with another non-limiting embodiment of the present disclosure, there is provided a method for forming an antimicrobial device which includes molding, extruding, etc., a heated mixture to form an antimicrobial device, wherein the heated mixture includes one or more types of antimicrobial nanoparticles, one or more polymeric components, and at least one additive selected from the group of one or more surfactants and/or one or more coupling agents. Additional materials can be optionally used in the mixture (e.g., thinning agent, colorant, aromatic material for smell, etc.). The surfactant and/or coupling agent are used to facilitate in the uniform dispersion of the nanoparticles in the heated mixture so that the formed device has a substantially uniform dispersion of the antimicrobial nanoparticles. In one non-limiting application, the surfactant and/or coupling agent are also used to facilitate in inhibiting the agglomeration of the antimicrobial nanoparticles in the heated mixture and also inhibit the agglomeration of the antimicrobial nanoparticles in the formed device.
In accordance with another non-limiting embodiment of the present disclosure, there is provided a method for forming a masterbatch from a melted mixture that comprises one or more antimicrobial nanoparticles, one or more polymeric components, and at least one additive selected from the group of one or more surfactants and/or one or more coupling agents, by cooling the mixture and optionally granulating the mixture to form the masterbatch. Additional materials can be optionally used in the mixture (e.g., thinning agent, colorant, aromatic material for smell, etc.).
In accordance with another non-limiting embodiment of the present disclosure, there is provided a method for forming an antimicrobial device which includes the step of 1) molding, extruding, etc., a heated mixture of a masterbatch and additional polymeric component, wherein the masterbatch includes a mixture of one or more types of antimicrobial nanoparticles, one or more polymeric components, and at least one additive selected from the group of one or more surfactants, and/or one or more coupling agents. During the final formation of the antimicrobial device, generally at least about 80%, and typically about 90-100% of the additives are burned off, degraded, or otherwise removed from the final formed antimicrobial device. Additional materials can be optionally used in the mixture (e.g., thinning agent, colorant, aromatic material for smell, etc.). These other or additional materials, other than possibly the thinning agent, are designed to remain in the final formed antimicrobial device.
One non-limiting object of the disclosure is the provision of a textile comprising antimicrobial fibers, wherein at least one of the antimicrobial fibers includes a polymer matrix and antimicrobial nanoparticles dispersed substantially uniformly throughout the polymer matrix.
Another and/or alternative non-limiting object of the disclosure is the provision of a textile wherein the substantially uniform dispersion of the antimicrobial nanoparticles in the antimicrobial fibers at least partially a result of a mixture of a) polymer used to form the polymer matrix, b) the antimicrobial nanoparticles, and c) a surfactant and/or coupling agent included in the mixture prior to the formation of said antimicrobial fibers.
Another and/or alternative non-limiting object of the disclosure is the provision of a textile wherein the mixture includes both surfactant and coupling agent.
Another and/or alternative non-limiting object of the disclosure is the provision of a textile wherein the antimicrobial nanoparticles include one or more metal materials selected from the group of zinc metal, copper metal, silver metal, iron metal, zinc oxide, copper oxide, silver oxide, iron oxide, zinc salt, copper salt, silver salt, and iron salt.
Another and/or alternative non-limiting object of the disclosure is the provision of a textile wherein the polymer used to form the polymer matrix includes one or more polymer materials selected from the group consisting of a polyester, a polyamide, a polyolefin, a polycarbonate, and an acrylonitrile butadiene styrene polymer.
Another and/or alternative non-limiting object of the disclosure is the provision of a textile wherein the polymer used to form said polymer matrix includes polyester, and the polyester includes polyethylene terephthalate.
Another and/or alternative non-limiting object of the disclosure is the provision of a textile wherein the antimicrobial nanoparticles have a median particle size of less than or equal to 0.1 μm.
Another and/or alternative non-limiting object of the disclosure is the provision of a textile wherein the antimicrobial nanoparticles have a median particle size of about 50-200 nm.
Another and/or alternative non-limiting object of the disclosure is the provision of a textile wherein the antimicrobial fibers comprise about 0.5-12 wt. % of the antimicrobial nanoparticles.
Another and/or alternative non-limiting object of the disclosure is the provision of a textile wherein the antimicrobial fibers have a cross section shape selected from the group consisting of a clover, cross, hollow cylinder, triangle, and dumbbell.
Another and/or alternative non-limiting object of the disclosure is the provision of a textile wherein the mixture includes surfactant.
Another and/or alternative non-limiting object of the disclosure is the provision of a textile wherein the surfactant includes one or more compounds selected from the group consisting of stearic acid, sodium dodecyl sulfonate surfactants, quaternary ammonium surfactants, amino acid surfactants, betaine surfactants, fatty acid glyceride ester surfactants, fatty acid sorbitan surfactants, lecithin surfactants, and Tween™ series surfactants.
Another and/or alternative non-limiting object of the disclosure is the provision of a textile wherein the mixture includes coupling agent.
Another and/or alternative non-limiting object of the disclosure is the provision of a textile wherein the coupling agent includes a silane and/or titanate coupling agent.
Another and/or alternative non-limiting object of the disclosure is the provision of a textile wherein the coupling agent includes one or more compounds selected from the group consisting of silane coupling agent A-150, silane coupling agent A-151, silane coupling agent A-171, silane coupling agent A-172, silane coupling agent A-1100, and silane coupling agent. Agent A-187, silane coupling agent A-174, silane coupling agent A-1891, silane coupling agent A-189, silane coupling agent A-1120, silane coupling agent KH-550, silane coupling agent KH-560, silane coupling agent KH-570, silane coupling agent KH-580, silane coupling agent KH-590, silane coupling agent KH-902, silane coupling agent KH-903, silane coupling agent KH-792, phenyltrimethoxysilane, phenyltriethoxysilane, methyltriethoxysilane, titanate coupling agent 101, titanate coupling agent 102, and titanate coupling agent 105.
Another and/or alternative non-limiting object of the disclosure is the provision of a textile wherein the antimicrobial fibers include mica, colorant, tourmaline, and/or aromatic material.
Another and/or alternative non-limiting object of the disclosure is the provision of a textile wherein the textile is in the form of, but not limited to, the group consisting of a clothing, bedding, towels, cloths, rags, mops, shoes and other types of footwear, caps, hats, luggage, purses, backpacks, carrying cases, furniture fabric, curtains, awnings, tents, umbrellas, furniture covers, grill covers, laundry containers, storage containers, rugs, carpeting, pillow covers, blankets, throws, seat covers, bandages, straps, rope, twine, yarn, string, gowns, scrubs, masks, bandages, dressings, pillows, life jackets, bathmats, pads, diapers, wipes, sleeping bags, pet beds, pet toys, canvas products, and any other device or material that is fully or partially formed from threads and/or fabric.
Another and/or alternative non-limiting object of the disclosure is the provision of a textile wherein the textile is at least partially formed from threads of material, and wherein at least a plurality of the threads used to at least partially form the textile includes said antimicrobial fibers, and wherein threads that include the antimicrobial fibers formed of at least 10 wt. % of said textile.
Another and/or alternative non-limiting object of the disclosure is the provision of a textile wherein the threads are formed of at least 30 wt. % of the antimicrobial fibers.
Another and/or alternative non-limiting object of the disclosure is the provision of a method for forming antimicrobial fibers, wherein the method includes spinning a heated mixture to form spun antimicrobial fibers, and wherein the heated mixture includes antimicrobial nanoparticles, polymeric component, and at least one additive selected from the group consisting of surfactant and coupling agent.
Another and/or alternative non-limiting object of the disclosure is the provision of a method for forming antimicrobial fibers further comprising the step of winding, stretching, and/or cooling the spun fibers.
Another and/or alternative non-limiting object of the disclosure is the provision of a method for forming a masterbatch for use in mixing with another polymer to form an antimicrobial fiber, wherein the method includes a) blending a mixture comprising antimicrobial nanoparticles, a polymeric component, and at least one additive selected from the group consisting of surfactants and coupling agents, and b) granulating said blended mixture to form granulated pieces of the masterbatch.
Another and/or alternative non-limiting object of the disclosure is the provision of a method for forming a masterbatch for use in mixing with another polymer to form an antimicrobial fiber wherein the step of blending is at a temperature of about 100-350° C.
Another and/or alternative non-limiting object of the disclosure is the provision of a method for forming a masterbatch for use in mixing with another polymer to form an antimicrobial fiber wherein the antimicrobial nanoparticles constitute about 4-49 wt. % of the masterbatch, and the polymeric component constitutes about 40-95 wt. % of the masterbatch.
Another and/or alternative non-limiting object of the disclosure is the provision of a method for forming a masterbatch for use in mixing with another polymer to form an antimicrobial fiber wherein at least one additive constitutes about 0.001-30 wt. % of the masterbatch.
Another and/or alternative non-limiting object of the disclosure is the provision of a method for forming antimicrobial fibers, wherein the method includes a) extruding a mixture comprising masterbatch particles and polymer particles, and b) spinning the extruded mixture into spun fibers; and wherein the masterbatch particles comprise antimicrobial nanoparticles, a masterbatch polymer, and at least one additive selected from the group consisting of surfactants and coupling agents.
Another and/or alternative non-limiting object of the disclosure is the provision of a method for forming antimicrobial fibers wherein the step of extruding is at a temperature about 200-350° C.
Another and/or alternative non-limiting object of the disclosure is the provision of a method for forming antimicrobial fibers wherein the mixture comprises about 2-20 wt. % of the masterbatch particles and about 80-98 wt. % of the polymer particles.
Another and/or alternative non-limiting object of the disclosure is the provision of a method for forming antimicrobial fibers further comprising the step of winding, stretching, and/or cooling said spun fibers.
Another and/or alternative non-limiting object of the disclosure is the provision of an antimicrobial thread comprising antimicrobial fibers and non-antimicrobial fibers, and wherein the antimicrobial fibers constitute about 15-90 wt. % of the antimicrobial thread, and the non-antimicrobial fibers constitute about 10-85 wt. % of the antimicrobial thread, and wherein the antimicrobial fibers formed of a polymer matrix having antimicrobial nanoparticles are dispersed substantially uniformly throughout said polymer matrix, and wherein the substantially uniform dispersion of the antimicrobial nanoparticles in the antimicrobial fibers is at least partially a result of a mixture of a) polymer used to form the polymer matrix, b) antimicrobial nanoparticles, and c) surfactant and/or coupling agent prior to the formation of the antimicrobial fibers, and wherein the non-antimicrobial fibers include one or more materials selected from the group consisting of cotton fibers, wool fibers, silk fibers, linen fibers, hemp fibers, flax fibers, rayon fibers, polyester fibers, nylon fibers, mylar fibers, glitter fibers and metallic fibers, and wherein the non-antimicrobial fibers are absent antimicrobial nanoparticles.
Another and/or alternative non-limiting object of the disclosure is the provision of an antimicrobial thread wherein less than 1% of the antimicrobial nanoparticles in the antimicrobial fibers leach from the antimicrobial fibers after the antimicrobial thread has been subjected to one standard wash cycle.
Another and/or alternative non-limiting object of the disclosure is the provision of an antimicrobial thread wherein less than 1% of the antimicrobial nanoparticles in the antimicrobial fibers leach from the antimicrobial fibers after the antimicrobial thread has been subjected to 100 standard wash cycles.
Another and/or alternative non-limiting object of the disclosure is the provision of an antimicrobial thread wherein the antimicrobial fibers after the antimicrobial thread has been subjected to one standard wash cycle retains at least 90% of an antibacterial effectiveness as compared to the antimicrobial fibers prior to being subjected to a standard wash cycle.
Another and/or alternative non-limiting object of the disclosure is the provision of an antimicrobial thread wherein the antimicrobial fibers after the antimicrobial thread has been subjected to 100 standard wash cycles retains at least 90% of an antibacterial effectiveness as compared to the antimicrobial fibers prior to being subjected to a standard wash cycle.
These and other objects and advantages will become apparent from the discussion of the distinction between the disclosure and the prior art and when considering the preferred embodiment shown in the accompanying drawings.
Reference may now be made to the drawings, which illustrate various embodiments that the disclosure may take in physical form and in certain parts and arrangements of parts wherein:
A more complete understanding of the articles/devices, processes, and components disclosed herein can be obtained by reference to the accompanying drawings. These figures are merely schematic representations based on convenience and the ease of demonstrating the present disclosure, and are, therefore, not intended to indicate relative size and dimensions of the devices or components thereof and/or to define or limit the scope of the exemplary embodiments.
Although specific terms are used in the following description for the sake of clarity, these terms are intended to refer only to the particular structure of the embodiments selected for illustration in the drawings and are not intended to define or limit the scope of the disclosure. In the drawings and the following description below, it is to be understood that like numeric designations refer to components of like function.
The singular forms “a,” “an,” and “the” include plural referents unless the context clearly dictates otherwise.
As used in the specification and in the claims, the term “comprising” may include the embodiments “consisting of” and “consisting essentially of.” The terms “comprise(s),” “include(s),” “having,” “has,” “can,” “contain(s),” and variants thereof, as used herein, are intended to be open-ended transitional phrases, terms, or words that require the presence of the named ingredients/steps and permit the presence of other ingredients/steps. However, such description should be construed as also describing compositions or processes as “consisting of” and “consisting essentially of” the enumerated ingredients/steps, which allows the presence of only the named ingredients/steps, along with any unavoidable impurities that might result therefrom, and excludes other ingredients/steps.
Numerical values in the specification and claims of this application should be understood to include numerical values which are the same when reduced to the same number of significant figures and numerical values which differ from the stated value by less than the experimental error of conventional measurement technique of the type described in the present application to determine the value.
All ranges disclosed herein are inclusive of the recited endpoint and independently combinable (for example, the range of “from 2 grams to 10 grams” is inclusive of the endpoints, 2 grams and 10 grams, and all the intermediate values).
The terms “about” and “approximately” can be used to include any numerical value that can vary without changing the basic function of that value. When used with a range, “about” and “approximately” also disclose the range defined by the absolute values of the two endpoints, e.g. “about 2 to about 4” also discloses the range “from 2 to 4.” Generally, the terms “about” and “approximately” may refer to plus or minus 10% of the indicated number.
Percentages of elements should be assumed to be percent by weight of the stated element, unless expressly stated otherwise.
Referring now to the drawings,
As noted in
Referring now to
The masterbatch can be formed of a single type of polymeric component or be formed of two or more different polymeric components. The antimicrobial nanoparticles in the masterbatch can be a single type of antimicrobial nanoparticle or be formed of two or more different types of antimicrobial nanoparticles. In one non-limiting embodiment, the antimicrobial nanoparticles are formed partially or fully of zinc metal nanoparticles. The size and shape of the antimicrobial nanoparticles in the masterbatch can be the same or different.
The one or more additives include surfactant and/or coupling agent (e.g., a silane coupling agent). The one or more additives in the masterbatch generally constitute about 0.002-30 wt. % of the masterbatch (and all values and ranges therebetween), typically 0.002-18 wt. % additive, and more typically about 0.002-12 wt. % additive. When surfactant is included as an additive in the masterbatch, the surfactant generally constitutes about 0.001-20 wt. % of the masterbatch (and all values and ranges therebetween), typically about 0.001-12 wt. %, and more typically about 0.001-8 wt. %. When a coupling agent is included as an additive in the masterbatch, the coupling agent generally constitutes about 0.001-20 wt. % of the masterbatch (and all values and ranges therebetween), typically about 0.001-12 wt. %, and more typically about 0.001-8 wt. %. The amount of surfactant and coupling agent in the masterbatch can the same or different. When the additive includes both surfactant and coupling agent, the weight ratio of the surfactant to the coupling agent is about 1:1.5 to 1.5:1 (and all values and ranges therebetween). In one non-limiting embodiment, equal amounts of coupling agent and surfactant are added to the masterbatch.
The masterbatch can potentially include other materials (e.g., thinning agent, colorant, mica, tourmaline, etc.). Mica can be added to improve the softness and texture of the fiber and to make the fiber feel cool to the touch. When mica is added, it generally constitutes 0.1-15 wt. % of the masterbatch (and all values and ranges therebetween), typically 2-12 wt. %, and more typically 6-10 wt. %. When colorant is used, the colorant generally includes 0.01-3 wt. % of the masterbatch (and all values and ranges therebetween). Tourmaline can be added to make the fiber feel warmer to the touch. When tourmaline is added, it generally constitutes 0.1-15 wt. % of the masterbatch (and all values and ranges therebetween), and typically 2-12 wt. %. Thinning agent can be used to reduce the viscosity of the melted masterbatch. When thinning agent is added, it generally constitutes 0.1-25 wt. % of the masterbatch (and all values and ranges therebetween), and typically 1-15 wt. %.
Non-limiting examples of formulations that are used to form the masterbatch in accordance with the present disclosure are set forth below in weight percent:
The masterbatch may be formed by mixing the components at a temperature that will not degrade or adversely affect the components of the masterbatch. Typically, the temperature is maintained below a temperature that will damage or burn off the one or more additives and/or damage the polymeric material. In one non-limiting embodiment, the mixing temperature of the masterbatch is at least 10° C. above the crystallization temperature of the polymetric component. In another non-limiting embodiment, the mixing temperature of the masterbatch is less than the boiling point of the polymetric component. In one non-limiting example, the polymeric material in the masterbatch is or includes PET, and the mixing temperature of the components of the masterbatch is 120-220° C., typically 130-200° C., more typically 130-180° C., and still more typically 130-165° C.
After the components of the masterbatch are sufficiently mixed together, the masterbatch may be cooled and be formed into any suitable form (e.g., flakes, pellets, etc.). The one or more additives can be optionally mixed with a portion or all of the antimicrobial nanoparticles prior to or after adding the antimicrobial nanoparticles to the polymeric component. As can be appreciated, the polymeric component can be melted prior to the addition of the antimicrobial nanoparticles and/or the one or more additives when forming the masterbatch. The final masterbatch in solid form generally has little or no thinning agent (when used) in the solid masterbatch. During the formation of the solid masterbatch, most, if not all, of the thinning agent (when used) evaporates and/or degrades.
Non-limiting examples of formulations of the final masterbatch composition in accordance with the present disclosure are set forth below in weight percent:
The masterbatch can be blended 120 with a second polymeric component to form the final fiber or device, or the masterbatch can be used to form the fiber or device.
When the fiber or device is formed from a mixture of masterbatch and a second polymeric component, the masterbatch and second polymeric component can be heated to melt together, or the masterbatch can be added to the second polymeric component when the second polymeric component is already melted or vice versa. Typically, the masterbatch constitutes about 2-50 wt. % (and all values and ranges therebetween) of the mixture and the second polymeric component constitutes about 50-98 wt. % (and all values and ranges therebetween) of the mixture, more typically the masterbatch constitutes about 2-25 wt. % of the mixture and the second polymeric component constitutes about 75-98 wt. % of the mixture, still more typically the masterbatch constitutes about 3-15 wt. % of the mixture and the second polymeric component constitutes about 85-97 wt. % of the mixture, yet still more typically the masterbatch constitutes about 4-12 wt. % of the mixture and the second polymeric component constitutes about 88-96 wt. % of the mixture, and even still more typically the masterbatch constitutes about 4-10 wt. % of the mixture and the second polymeric component constitutes about 90-96 wt. % of the mixture.
Typically, the temperature of the mixture of the masterbatch and second polymeric component is maintained below a temperature that will damage the polymeric material in the masterbatch or the second polymeric component. The second polymeric component can be formed of a single type of polymer (e.g., polyester, PET, PA, PP, PBT, Aramid, PE, PC, ABS, etc.) or two or more different types of polymer. The type of polymer used to form the second polymeric component can be the same or different from the polymeric component used in the masterbatch. In one non-limiting embodiment, at least a portion or all of the second polymeric component is the same as a portion or all of the polymeric component in the masterbatch. In some embodiments, both the polymeric component in the masterbatch and the second polymeric component are or contain a polyester.
The masterbatch and the second polymeric component are mixed at a temperature that will not adversely affect the components of the masterbatch and the second polymeric component (e.g., 120-350° C., 165-290° C., etc.). The second polymetric component can be formed of one or more polymer materials. Typically, the temperature is maintained below the temperature that will damage the polymeric component. The mixing process used to mix the masterbatch and the second polymeric component can be by a standard mechanical stirring process (e.g., mechanical mixing, etc.). During the mixing process of the masterbatch and the second polymeric component, most, if not all, of the components of the masterbatch remain in the blended mixture. During the mixing process of the masterbatch and the second polymeric component, additional thinning agent can be added to the mixture; however, this is not required. Also, during the mixing process of the masterbatch and the second polymeric component, additional surfactant and/or coupling agent can be added to the mixture; however, this is not required.
The blended mixture is then extruded 130, spun into fibers 140, optionally stretched, and wound and/or cooled 150. During the final formation of the fibers, the mixture is subjected to heat and other conditions so that at least about 80% of the additive (e.g., coupling agent, surfactant, thinning agent) is removed (e.g., evaporated) or otherwise burned from the formed fiber, typically at least about 90% of the additive is removed or otherwise burned from the formed fiber, more typically at least about 95% of the additive is removed or otherwise burned from the formed fiber, still more typically at least about 99% of the additive is removed or otherwise burned from the formed fiber, and still even more typically at least about 99.9% of the additive is removed or otherwise burned from the formed fiber. Additives such as colorant, mica, tourmaline, etc., typically at least partially remain in the final formed fiber. For example, when colorant, tourmaline, and/or mica are included in the mixture used to form the final fiber, generally at least 40% of the colorant, tourmaline, and/or mica remain in the final formed fiber, and typically at least 50% of the colorant, tourmaline, and/or mica remain in the final formed fiber. Generally, the mixture is at a temperature above the softening point of the polymeric components in the mixture, and typically at or above the melting point of the polymeric components in the mixture when the mixture is extruded and/or spun into fiber during the fiber forming process.
The formed fibers generally include about 0.2-5 wt. % (and all values and ranges therebetween) antimicrobial nanoparticles, typically 0.5-3 wt. % antimicrobial nanoparticles, and more typically 1-2 wt. % (e.g., 1.5 wt. %, etc.) antimicrobial nanoparticles. The formed fibers can optionally include 0.1-2.5 wt. % (and all values and ranges therebetween) other materials (e.g., colorant, mica, tourmaline, etc.). Due to the surfactant and coupling agent in the mixture during the fiber forming process, the antimicrobial nanoparticles are uniformly distributed throughout the formed fiber and the amount of agglomeration in the formed fiber is significantly reduced as compared to a fiber that includes antimicrobial nanoparticles without the use of surfactant and coupling agent. The use of the surfactant and coupling agent in the mixture during the fiber forming process results in less than 50% of the antimicrobial nanoparticles agglomerating in the formed fiber, and typically results in less than 30% of the antimicrobial nanoparticles agglomerating in the formed fiber. As such, the average density of the formed fiber along the length of the formed fiber does not vary by more than 20%, typically no more than 10%, and more typically no more than 5%.
The formed fibers can be interwoven, spun, or otherwise combined with one or more other fibers (e.g., natural fiber [cotton, wool, silk, linen, hemp, flax, etc.] synthetic fibers [rayon, polyester, nylon, mylar, glitter], and/or metallic fibers) to form a final fiber mixture that can be used to form a thread that can be later used to form various types of textiles (e.g., sheets, pillow cases, table clothes, towels, napkins, clothing, shoes, etc.) or other articles that are partially or fully formed from threads. As can be appreciated, the final thread can be formed of 100% of the formed fiber. When the thread is formed of a combination of the formed fiber and one or more other fibers, the formed fiber generally constitutes about 2-90 wt. % (and all values and ranges therebetween) of the thread, typically 5-80 wt. % of the thread, more typically 10-75 wt. % of the thread, and still more typically 30-70 wt. % of the thread. In one particular example, the thread contains at least 30 wt. % of the formed fiber.
Referring now to
Typically, the temperature is maintained below the temperature that will damage or burn off the one or more additives. The blended composition is then extruded 220, spun 230, and wound and/or cooled 240. During the final formation of the fibers, the mixture is subjected to heat and other conditions so that at least about 80% and typically about 90-100% of the additive is removed or otherwise burned from the formed fiber. The formed fiber generally includes about 0.2-5 wt. % (and all values and ranges therebetween) antimicrobial nanoparticles, typically 0.5-3 wt. % antimicrobial nanoparticles, and more typically 1-2 wt. % (e.g., 1.5 wt. %, etc.) antimicrobial nanoparticles. The formed fiber generally includes little or no additive such as surfactant, coupling agent, and thinning agent (e.g., less than 0.5 wt. %, and typically less than 0.1 wt. %). The formed fiber can optionally include colorant, mica, tourmaline, etc.
Other methods included within the scope of the present disclosure include the use of multiple masterbatches and/or multiple polymer addition steps.
In some embodiments, a special-shaped antibacterial fiber includes nanometer-scale antibacterial powder (e.g., zinc antibacterial powder, etc.) and polyester. The cross section of the antibacterial fiber may be any non-circular cross-sectional shape such as, but not limited to, clover-shaped, cross-shaped, oval-shaped, or some other non-circular cross-sectional shape.
The median diameter (D50) of the antibacterial nanoparticles may be less than or equal to 0.1 μm, including within the range of from about 50 nm to about 200 nm (and all values and ranges therebetween). In a particular non-limiting embodiment, the D50 of the antibacterial nanoparticles is about 60-80 nm. It has been found that antibacterial nanoparticles above 200 nm and below 50 nm do not distribute evenly in the formed fiber.
In particular non-limiting embodiments, a cross-shaped antibacterial fiber according to the disclosure is prepared using the following steps:
Step 1: A functional masterbatch is prepared by mixing zinc nanoparticles, additives, and polyester according to the specific mass ratio of different purposes. The mass ratio of the zinc nanoparticles to the polyester is 15:80 to 40:55 (and all values and ranges therebetween). The percentage of additive to the total mass of the functional masterbatch is 0.001-10 wt. % (e.g., 0.002-5 wt. %). The zinc nanoparticles, additives, and polyester may be stirred and mixed at 130-290° C., and then granulated to obtain the functional masterbatch. In particular non-limiting embodiments, the masterbatch contains 15-40 wt. % zinc nanoparticles, and typically 20-38 wt. %, and more typically 25-30 wt. %.
Step 2: The special-shaped antibacterial fiber is prepared by mixing together and melting the functional masterbatch of Step 1 and additional polyester. The mixture is formed by blending and melting together the functional masterbatch with the polyester chips such that the chips of the masterbatch constitute 4-12 wt. % of the total mixture. The mixture can then be spun into fibers using standard technology used to form polymer fibers.
Zinc nanoparticles in the formed fibers have good dispersibility in the fibers. The additives are used to facilitate in the zinc nanoparticles being uniformly mixed and dispersed in the melted polyester. The additives can also be used to improve the spinnability of the material to form the final fiber.
The masterbatch and/or the mixture of masterbatch and polymer can have coloring added to the mixture to color the fiber without adversely affecting the antibacterial properties of the fiber, nor the uniform dispersal of the nanoparticles in the fiber. Other materials such as mica, tourmaline, etc., can be added to improve the texture of the fiber.
In one non-limiting embodiment, the additive that is included in the mixture used to form the fiber includes one or more surfactants and/or one or more coupling agents. In some embodiments, both the surfactant and the coupling agent are included in the mixture used to form the fiber.
A surfactant can be optionally coated on the surface of the antibacterial nanoparticle (e.g., zinc nanoparticle powder) prior to mixing the antibacterial nanoparticle with the polymer; however, this is not required. The surfactant is used to increase the surface activity and fluidity of the nanoparticle powder, prevent the oxidation of the nanoparticle powder, and/or inhibit or prevent weakening of the antibacterial effect of the nanoparticle powder. The one or more surfactants can be selected from anionic surfactants, cationic surfactants, non-ionic surfactants, and any combination of two or more thereof.
Non-limiting examples of surfactants include stearic acid, sodium dodecyl sulfonate surfactants, quaternary ammonium surfactants, amino acid surfactants, betaine surfactants, fatty acid glyceride ester surfactants, fatty acid sorbitan surfactants, lecithin surfactants, Tween™ series surfactants, and polysorbate surfactants. Combinations of two or more surfactants may also be utilized.
The coupling agent (e.g., silane coupling agent) is used to facilitate in the dispersion of the nanoparticle powder in the melted polymer mixture prior to and/or during fiber formation and/or inhibit or prevent agglomeration of the nanoparticle powder in the melted polymer mixture prior and/or during fiber formation.
The coupling agent can be selected as silicon silane coupling agents, such as silane and/or titanate. Non-limiting examples of coupling agents include silane coupling agent A-150, silane coupling agent A-151, silane coupling agent A-171, silane coupling agent A-172, silane coupling agent A-1100, silane coupling agent A-187, silane coupling agent A-174, silane coupling agent A-1891, silane coupling agent A-189, silane coupling agent A-1120, silane coupling agent KH-550, silane coupling agent KH-560, silane coupling agent KH-570, silane coupling agent KH-580, silane coupling agent KH-590, silane coupling agent KH-902, silane coupling agent KH-903, silane coupling agent KH-792, and at least one of phenyltrimethoxysilane, phenyltriethoxysilane, methyltriethoxysilane, titanate coupling agent 101, titanate coupling agent 102, and titanate coupling agent 105. Combination of two or more coupling agents may also be utilized.
Nanoparticles have a tendency to agglomerate during the mixing processes. Agglomeration prevents nanoparticles from being uniformly dispersed in the melted polymer and the formed fiber. However, the use of a surfactant and/or a coupling agent increases the surface activity and fluidity of the nanoparticles, inhibits or prevents oxidation, and/or inhibits or prevents weakening the antibacterial effect of the nanoparticles. The dispersity of nanoparticles in the melted polymer is enhanced and the agglomeration of the nanoparticles during mixing is reduced or prevented, so that the nanoparticles are evenly distributed in the melted polymer and formed fiber.
The mixing techniques used to mix the masterbatch with the additional polymer material are not particularly limited. In some embodiments, the nanoparticles, additive, and polymeric component are sequentially mixed in a high-mixer according to a process flow.
Stirring speeds of 100±10 r/min. and a stirring time of 1-10 min. may be used.
The masterbatch may be stirred and mixed with a second polymeric component (which may be the same as or different from the first polymeric component). The mixed raw material may be added into a screw extruder and spun by a special spinneret such as a clover and a cross, so as to obtain a special-shaped zinc antibacterial fiber with a cross section shape such as a clover and/or a cross.
In some non-limiting embodiments, the spinning speed is 1000-1500 m/min. The spinning may use a spinneret having a diameter of 0.2-0.8 mm.
The spun fibers may be wound and cooled (e.g., blow cooled).
The winding speed may be 950-1450 m/min.
Blow cooling may be horizontal blow cooling, and the blowing temperature may be 20-30° C.
In some non-limiting embodiments, the nanoparticles have a lighter color which simplifies dyeing and processing. Zinc, for example, has a light color.
The substantially uniform distribution of the nanoparticles in the fibers beneficially reduces the likelihood of the nanoparticles falling out in subsequent printing, dyeing and washing treatment, ensuring the stability and antibacterial durability of the fibers.
Compared to fibers with circular-shaped cross sections, fibers with higher surface areas exhibit good moisture absorption, quick drying, softness, resilience, and smoothness.
In some non-limiting embodiments, the metal nanoparticles are added to the polymer without the need for chemical modifiers. The preparation method of the fiber with reduced or eliminated chemical modifiers shortens the process flow, reduces the equipment and process investment, reduces the cost, and is suitable for large-scale industrial production.
The metal nanoparticles are fine particles, thus agglomeration has been found to occur in the absence of additive(s). Therefore, a surfactant and/or a coupling agent can be used to increase the surface activity and fluidity of nanoparticles, thereby ensuring dispersion, preventing agglomeration, and evenly distributing the nanoparticles in the polymeric component.
Composite clover-shaped cross section fibers and other special-shaped fibers have excellent properties that circular fibers do not have and increase the surface area of the fiber. Textiles formed from the fibers have good antibacterial properties and moisture absorption, are fast drying, UV resistant, soft, resilient, and smooth. The composite compositions of the present disclosure are suitable for, but not limited to, various shapes of fiber cross sections: clover, cross, hollow, flat, triangular, dumbbell, and the like. Hollow fibers (fiber having one or more cavities along the length of the fiber) have been found to better mimic the feel and softness of cotton fibers and other natural fibers.
(1) Nano-zinc powders, polyester chips, silane coupling agent, and surfactant were melted and mixed in a high shear mixer in sequence according to the technological process at 150° C. Thinning agent was optionally added to the mixture to obtain a target mixing viscosity. The composition was fully mixed and evenly stirred, and then granulated into a granulator to make the functional masterbatch. Based on the total mass of the functional masterbatch, the mass percentage of zinc powder was 20-30 wt. % and the silane coupling agents and surfactants constituted 0.001-10 wt. %.
(2) The functional masterbatch and polyester chips were added into a spinning box, melted and mixed at 220° C., while stirred to ensure melting and even mixing and to produce mixed raw materials. The weight ratio of the polyester chips to the functional masterbatch was about 10:1 to 15:1.
(3) When the mixed material was added to the screw extruder, the temperature in the heating box of the screw extruder was 260° C., and the mixed material was heated slowly. Zinc antibacterial fiber with cross-shaped cross section was prepared by spinning with a cross-shaped spinneret having an aperture size of 0.35 mm.
(4) The obtained zinc antibacterial fibers with clover- and cross-shaped cross sections were wound and cooled by blowing.
The antibacterial activity of the zinc antibacterial fibers and the zinc antibacterial fibers after washing 100 times were tested.
The results showed that the antibacterial rate of the zinc antibacterial fibers to S. aureus (>95%), E. coli (>95%) and C. albicans (>90%) were high.
After 100 industrial washings, the bacteriostatic rates of S. aureus (>95%), E. coli (>95%), and C. albicans (>80%) remained high.
(1) This aspect was similar to Example 1, the difference being, according to the total mass of functional masterbatch, the mass percent of nanometer zinc powder was 25%, the mass percent of silane coupling agent and surfactant was 10%.
(2) This aspect was similar to Example 1, the difference being that the temperature was 230° C.
(3) This aspect was similar to Example 1, the difference being that the temperature of the heating box assembly of the screw extruder was 270° C.
(4) The above-mentioned special-shaped zinc antibacterial fibers, with clover- and cross-shaped cross sections, were wound and cooled by cross-blowing at 25° C.
The antibacterial activity of the zinc antibacterial fiber and the zinc antibacterial fiber after 100 washings were tested.
The results showed that the antibacterial rate of zinc antibacterial fiber to S. aureus (>95%), E. coli (>95%) and C. albicans (>90%) was high.
After 100 industrial washings, the bacteriostatic rate of S. aureus (>95%), E. coli (>95%), and C. albicans (>80%) remained high.
(1) 200-350 kg. of nano-zinc powders and 590-795 kg. PET chips where dry mixed together for about 2-20 minutes until the chips and powder are generally evenly mixed together.
(2) Silane coupling agent and surfactant and optionally other materials (e.g., colorant, mica, thinning agent, tourmaline) are added to the mixture of nano-zinc powder and PET chips. The silane coupling agent and surfactant and optionally other materials can be added to the mixture of nano-zinc powder and PET chips prior to, during, or after the PET has been melted. About 2-10 kg. of silane coupling agent and surfactant and optionally about 1-120 kg. of thinning agent are used. About a 0.8:1 to 1.2:1 weight ratio of silane coupling agent to surfactant is used.
(3) The mixture of nano-zinc powder and PET chips is heated to 165° C. to begin the melting of the PET chips. The silane coupling agent and surfactant and optionally other materials can be added to the mixture of nano-zinc powder and PET chips prior to, during, or after the PET has been melted.
(4) After all of the components of the masterbatch are mixed together (e.g., high shear mixer, etc.), the mixture is heated from 165° C. to about 250-350° C. over a time period of about 10-60 minutes.
(5) After the mixture has been heated to the desired temperature, the mixture can then be extruded, cooled, and then chopped onto pieces of masterbatch.
After the masterbatch is formed, it can be mixed with additional polymer to form fibers or various types of polymer devices.
When antimicrobial fibers are to be formed, the chips of masterbatch are mixed with additional PET chips. The masterbatch chips constitute about 3-10 wt. % of the mixture. The mixture is melted together at a temperature of about 200-350° C. The heated mixture is then formed into fibers. The method for forming the fibers can be by standard fiber-forming methods (e.g., extrusion, spinneret, blowing technology, etc.). The formed fibers generally include about 1.6-2.5 wt. % nano-zinc powder.
The formed fibers can then be formed into thread for use in fully or partially forming various types of textile, etc. The formed thread can be combined with 1-15 wt. % (and all values and ranges therebetween) modal to form a softer fiber.
In one nonlimiting embodiment, antimicrobial sheets can be formed from 20-100% (and all values and ranges therebetween) antimicrobial fibers and 0-80% (and all values and ranges therebetween) other fibers (e.g., cotton fibers, silk fibers, polymer fibers, etc.). In one particular non-limiting embodiment, sheets are formed of 20-30% antimicrobial fibers and the balance cotton fibers. The total content of nano-zinc powder in the sheets are about 0.2-0.6 wt. %.
The cross-shaped zinc antibacterial fiber in accordance with the present disclosure exhibits good antibacterial performance, high antibacterial rate against S. aureus, E. coli and C. albicans, and no reduction in antibacterial rate against S. aureus and E. coli after 100 washings. Meanwhile, due to the cross-shaped cross section of the zinc antibacterial fiber, the zinc antibacterial fiber has good hygroscopicity, fast drying resistance, ultraviolet resistance, flexibility, resilience, smoothness, and makes sweat evaporate rapidly, which is not conducive to the survival of bacteria. Compounded with zinc antibacterial function, the moisture absorption and antimicrobial properties of the fiber do not interfere with each other and promote each other, and the hydrophilic, moisture absorption, and quick drying characteristics are not affected by the washing times of the fabric. Additionally, the preparation method of the cross-shaped zinc antibacterial fiber not only reduces the use of chemical modifiers, but is also simple, feasible, and suitable for large-scale industrial production.
It will thus be seen that the objects set forth above, among those made apparent from the preceding description, are efficiently attained, and since certain changes may be made in the constructions set forth without departing from the spirit and scope of the disclosure, it is intended that all matter contained in the above description and shown in the accompanying drawings shall be interpreted as illustrative and not in a limiting sense. The disclosure has been described with reference to preferred and alternate embodiments. Modifications and alterations will become apparent to those skilled in the art upon reading and understanding the detailed discussion of the disclosure provided herein. This disclosure is intended to include all such modifications and alterations insofar as they come within the scope of the present disclosure. It is also to be understood that the following claims are intended to cover all of the generic and specific features of the disclosure herein described and all statements of the scope of the disclosure, which, as a matter of language, might be said to fall there between. The disclosure has been described with reference to the preferred embodiments. These and other modifications of the preferred embodiments as well as other embodiments of the disclosure will be obvious from the disclosure herein, whereby the foregoing descriptive matter is to be interpreted merely as illustrative of the disclosure and not as a limitation. It is intended to include all such modifications and alterations insofar as they come within the scope of the appended claims.
The present disclosure claims priority on U.S. Provisional Patent Application Ser. No. 62/740,121 filed Oct. 2, 2018; 62/749,280 filed Oct. 23, 2018; and 62/837,956 filed Apr. 24, 2019, all of which are incorporated herein by reference.
| Number | Date | Country | |
|---|---|---|---|
| 62740121 | Oct 2018 | US | |
| 62749280 | Oct 2018 | US | |
| 62837956 | Apr 2019 | US |
