EA040966B1 - SILVER-CONTAINING ANTIMICROBIAL MATERIALS - Google Patents

Description

The invention relates to antimicrobial materials and articles such as fibers, textile threads, and their incorporation into textile materials, food or beverage packaging, or garments such as gloves. The antimicrobial fibers and textile threads may be derived from the polymer and may have silver particles dispersed therein. The present invention provides a fiber precursor polymer blend of the invention and other products derived from the fiber of the invention, and also articles derived from the polymer blend, such as textiles. The present invention also relates to a method for the production of antimicrobial materials.

State of the art

Silver has been used as an antimicrobial agent for many years. The antimicrobial activity of silver is used in a variety of applications, such as wound dressings, creams, and as a coating on medical devices.

The use of silver as a coating on fibers is disclosed in US 2010/0166832. US 2010/0166832 discloses silver coated nylon fibers. The paper shows the possibility of producing fabrics with one surface coated with silver, thereby allowing dye to be applied to the opposite side of the nylon fabric. Silver is applied to nylon fabrics using a chemical reduction method. There is also a product sold as XSTATIC® which is a silver-plated nylon textile thread. The silver completely covers the nylon textile thread. Coating a fiber or textile thread with silver has the disadvantage that silver can be removed from the fiber or textile thread when washing fabrics containing the coated fiber or textile thread. Consequently, the antimicrobial effectiveness of the fiber is reduced. This effect may be exacerbated by the use of detergents or elevated temperatures. For this reason, X-STATIC® is recommended to be washed without harsh detergents, without fabric conditioners, without bleaches and at low temperatures.

Thus, a fiber that is resistant to silver loss due to laundering is desirable. Also desirable is a fiber that can be washed at high temperatures and that can be washed in any detergent with or without fabric conditioner or bleach. Finally, the antimicrobial X-STATIC® is only available in dark colors. This is believed to be a feature of the technology used to provide antimicrobial activity. It is desirable to create fabrics in various colors, including light colors.

US 2014/0141073 uses copper salts for the production of antiviral polymeric materials. Antiviral materials are prepared by dispersing a powder of copper salts, copper semioxide and copper oxide in a suspension of a hydrophilic polymeric material. However, the introduction of copper salts is not applicable to a wide range of polymers. Poly(ester) fibers containing copper salts are noted to have copper oxide protruding from the surface of the polymer. This technology results in textiles that are distinguished by a bronze or light brown color.

Textile yarns formed from a polymer containing copper are commercially available. Cupron produces textile yarn based on copper, where copper is directly incorporated into fibers and textile yarns. However, textile yarns containing copper must be used in an amount of approximately 45 to 50% of any textile product to be most effective. Such a high amount of copper-containing textile yarns required in the textile material increases the cost of the textile.

Related applications US 2012/0094120 and US 2014/0374941 disclose the use of metal alloy powders as an antimicrobial agent in extruded polymer fiber.

Silver nanoparticles and colloidal silver are also used to impart antimicrobial properties to polymer fibers. However, the use of silver in the form of nanoparticles is undesirable due to the regulatory controls that accompany the use of nanoparticles. In addition, silver nanoparticles and colloidal silver are not approved due to the possibility of silver nanoparticles migrating into a subject using a product containing silver nanoparticles. It is also likely that the silver nanoparticles may leach out of the material in which the silver nanoparticles have been placed.

Thus, there is a need for an antimicrobial fiber, textile thread and/or textile material that does not contain silver in the form of nanoparticles or colloidal silver. However, it is generally accepted in the art that the silver particles must be in the nanoscale range to allow the polymer to be extruded to form a polymer fiber. Particles larger than those in the nanoscale range are known to block extruders due to the larger particle size and also due to agglomeration of the silver particles. It is also necessary to provide an antimicrobial fiber that can produce economical textile materials, and in general, the antimicrobial fiber is present in a relatively small amount within the textile material. In some embodiments, the implementation of the present invention solves these and other problems.

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Brief description of the drawings

Further embodiments of the invention are also described with reference to the accompanying drawings.

Fig. 1A and 1B are SEM (Scanning Electron Microscope) images of particles obtained by grinding silver foil.

Fig. 2A, 2B, 3A and 3B are enlarged image areas in the SEM of FIG. 1A and 1B, respectively.

Fig. 4 is an enlarged version of FIG. 1B showing particle thickness measurement.

Fig. 5 is a representation of an article of the present invention in the form of a pack containing milk. The bag marked O does not contain any silver particles and is not a bag according to the invention. The bag labeled 2 contains silver particles as defined in the invention and is therefore an article of the present invention.

The present invention aims to provide a solution to the above problems by using silver particles obtained by grinding silver foil. In accordance with the present invention, there is provided a polymer mixture comprising a polymer material and silver particles, in which the silver particles have a size characteristic of particles obtained by grinding silver foil. The polymer mixture may be in solid form, such as chips, or the polymer mixture may be in molten form.

Accordingly, in one aspect of the invention, there is provided a polymer blend comprising a polymer material and silver particles, wherein the silver particles are obtained by grinding silver foil. The polymeric material may be melted.

The polymer mixture may contain silver particles in an amount of from about 0.1 to 10 wt% of the polymer mixture. Optionally, the polymer blend contains silver particles in an amount of from about 0.1 to 5% by weight of the polymer blend. Preferably, the polymer blend contains silver particles in an amount of about 0.5 to 4%, about 0.5 to 3%, about 0.1 to 3% by weight. In a particularly preferred embodiment, the polymer mixture contains silver particles in an amount of approximately 1.5 to 2.5 wt.%, polymer mixture, for example, 2%. The polymer mixture containing such amounts of silver particles may be a masterbatch. The masterbatch may be a solid mixture, such as chips, or may be molten.

The masterbatch may be combined with other polymeric material. The masterbatch may be mixed with another polymeric material in an amount of 1 to 10% by weight of another polymeric material. Optionally, the masterbatch is mixed in an amount of 2 to 8% (preferably 3 to 5% by weight) of another polymeric material.

Accordingly, in one embodiment, the invention provides a polymer blend containing 1 to 10% masterbatch, where the masterbatch is a blend as defined herein, and a polymeric material. Optionally, the masterbatch is present in an amount of 2 to 8% (preferably 3 to 5%).

Thus, the invention provides a polymer mixture containing polymeric material and silver particles in an amount of from about 0.003 to 0.5 wt.%, optionally from about 0.03 to 0.5%, from about 0.03 to 0.25%, about 0.05 to 0.15%, about 0.06 to 0.15%, about 0.03 to 0.1%, or about 0.06 to 0.1%. Preferably the silver particles are present in an amount of 0.05 to 0.15% or 0.06 to 0.1%.

The combined masterbatch and other polymeric material can be extruded into fibers. Accordingly, the present invention provides a fiber containing a polymeric material and silver particles, in which the silver particles have a size characteristic of particles obtained by grinding silver foil. On the other hand, the present invention provides a fiber containing a polymeric material and silver particles, where the silver particles are obtained by grinding silver foil.

The fiber may contain silver particles in an amount of from about 0.003 to 0.5 wt.%, optionally from about 0.03 to 0.5%, from about 0.03 to 0.25%, from about 0.05 to 0.15 %, from about 0.06 to 0.15%, from about 0.03 to 0.1%, or from about 0.06 to 0.1%. Preferably the silver particles are present in an amount of 0.05 to 0.15% or 0.06 to 0.1%.

The fiber may be 1 to 3 denier. The fiber may have a diameter of 0.5 to 5 mm, optionally 1 to 4 mm, 1 to 3 mm, 2 to 4 mm, 2 to 2.5 mm. Preferably the fiber will have a dimension of 2 to 2.5 mm.

The fibers of the invention can be processed into textile threads or textile materials. Textile threads can also be processed into textile materials. Thus, the present invention provides textile yarns containing a plurality of fibers of the invention. In addition, the present invention provides textile materials containing a plurality of fibers

- 2 040966 and/or textile threads according to the invention.

The textile yarns of the invention optionally comprise a plurality of fibers of the invention and a plurality of other non-inventive fibers. The fibers of the invention and other fibers may be the same or a different polymeric material. Similarly, the textile materials of the invention may comprise a plurality of fibers and/or textile yarns of the invention and a plurality of other fibers and/or textile yarns not of the invention. The fibers or textile yarns of the invention and the other fibers or textile yarns may be the same or a different polymeric material.

Textile yarns according to the invention can be obtained by blending fibers according to the invention with other textile fibers, for example poly(ester) fibers, cotton fibers, wool fibers, polypropylene fibers, nylon fibers or polyamide fibers. Thus, the textile yarns of the invention may comprise fibers of the invention and fibers selected from polyester fibers, cotton fibers, wool fibers, polypropylene fibers, nylon fibers or polyamide fibers, preferably cotton fibers.

The textile yarns of the invention are multifilament yarns and may be 40 to 200 denier, for example 50 to 150 denier. Optionally, the textile yarns are 50 denier, 75 denier, or 150 denier.

Textile materials according to the invention may contain fibers or textile threads according to the invention in an amount of from about 1 to 10 wt.% textile material. Optionally, the textile material makes up about 1 to 6% (preferably about 2 to 5% or about 4 to 8% by weight) of the textile product.

The thickness of the silver foil used to form the silver particles is believed to play an important role in the invention. The silver foil may have a thickness of less than 1 µm, optionally less than 0.5 µm, or less than 0.1 µm. Preferably the silver foil has a thickness of 0.01 to 0.1 microns, for example about 0.03 microns. On the other hand, the silver foil may have a thickness of less than 1 µm, optionally less than 0.5 µm, or less than 0.3 µm. The thickness of the silver foil may be from 0.01 to 0.5 µm or from 0.1 to 0.3 µm, for example about 0.2 µm.

The silver particles of the invention are preferably non-spherical. As will be appreciated by those skilled in the art, non-spherical particles will typically have three dimensions: length, width, and height. Throughout this application, the height of the silver particles will be considered to originate from the thickness of the silver foil. Thus, any expansion of the thickness of the silver foil will correspond to the height of the silver particles.

The thickness or height of the silver particles can be measured by any suitable method. However, the scanning electron microscope provides a particularly useful tool for measuring the size of the silver particles present in the invention.

Thus, in another aspect of the invention, there is provided a polymer blend comprising a polymer material and silver particles, wherein the silver particles have a height of less than 1 µm, optionally less than 0.5 µm, or less than 0.1 µm. The silver particles may have a size of approximately 0.1 to 10 microns. Preferably, the silver particles have a height of 0.01 to 0.1 µm, for example about 0.03 µm. On the other hand, the silver particles may have a height of less than 1 µm, optionally less than 0.5 µm, or less than 0.3 µm. The height of the silver particles can be from 0.01 to 0.5 µm or from 0.1 to 0.3 µm, for example about 0.2 µm.

Any reference to the size of the silver particles refers to the length and width of the silver particles. The silver particles may have a size characteristic of particles obtained by grinding silver foil, a size, i.e., length and/or width, of from about 0.1 to 10 microns, optionally from about 0.5 to 10 microns, or from about 0, 5 to 8 µm, or about 1 to 6 µm, or about 1 to 4 µm, or about 2 to 3 µm. Preferably, the silver particles will be about 2 to 3 microns in size.

The silver particles may have a size of about 0.5 to 10 microns and a height of less than 0.5 microns or less than 0.1 microns; or a size of about 0.5 to 8 µm and a height of less than 0.5 µm or less than 0.1 µm; or a size of about 1 to 6 µm and a height of less than 0.5 µm or less than 0.1 µm; or a size of about 1 to 4 µm and a height of less than 0.5 µm or less than 0.1 µm; or a size of about 2 to 3 µm and a height of less than 0.5 µm or less than 0.1 µm.

The silver particles may have a size of about 0.5 to 10 microns and a height of less than 0.5 microns or less than 0.3 microns; or a size of about 0.5 to 8 µm and a height of less than 0.5 µm or less than 0.3 µm; or a size of about 1 to 6 µm and a height of less than 0.5 µm or less than 0.3 µm; or a size of about 1 to 4 µm and a height of less than 0.5 µm or less than 0.3 µm; or a size of about 2 to 3 µm and a height of less than 0.5 µm or less than 0.3 µm.

Preferably, the silver particles are about 1 to 10 µm in size and less than

- 3 040966 than 0.5 µm, less than 0.3 µm or less than 0.1 µm. Preferably, the silver particles are about 2 to 3 µm in size and less than 0.5 µm, less than 0.3 µm, or less than 0.1 µm in height.

Preferably, the silver particles in any aspect or embodiment of the invention may have a length of about 0.1 to 10 µm, a width of about 0.1 to 10 µm, and a height of less than 1 µm, optionally less than 0.5 µm, less than 0. 3 µm or less than 0.1 µm.

The textile materials of the present invention may be in the form of a product selected from home textiles (e.g. towels, sheets, socks or denim), pet products (e.g. pet bedding, pet wraps or pet collars), medical products (e.g. gloves) or any other type of textiles. Thus, the present invention provides any of such articles containing the fibers, textile yarns or textile materials of the present invention.

In one aspect, the present invention provides an article containing a polymer blend as defined herein. The product can be obtained from a polymer mixture. Accordingly, the article may contain or may be formed from a polymeric material containing silver particles as defined herein. The article may contain fibers or textile threads according to the invention, or the article may be obtained from a single piece of polymeric material. In one embodiment of the invention, the product may be a package (for example, a food bag or a drink bag). The article may be vacuum formed, cast, extruded, knitted, woven, or otherwise processed in a manner known to those skilled in the art.

The product may be a garment, a household product, or a plastic product. The product can be made from the fibers of the present invention or made in one piece. The garment can be selected from: underwear, panties, bras, vests, undershirts, men's briefs, outerwear, trousers, shorts, socks, shirts, polo shirts, T-shirts, blouses, sweatshirts, hoodies, gloves, skirts, trouser suits, dresses, coats, towel fabrics, training trousers, training tops, raincoats, coat linings, anoraks, jackets, hats, baseball caps, irham, niqabs, saris, burqas, loose home clothes, capes, scarves, pajamas, nightgowns, peignoirs, sportswear, shoes, shoe linings, padded tops, padded leggings, uniforms, nurse uniforms, tunics, personal protective clothing, surgical suits, all-in-one sets, coveralls, military clothing and police clothing.

Household products can be selected from: blankets, bedspreads, furniture covers, upholstery, kitchen towels, flannels, carpets, rugs, rugs, stoles, curtains, drapes, wraps, pillowcases, mattress fabrics, mattress toppers, quilts, tablecloths , lampshades, woven bags, interlining fabrics for handbags, pet mats, pet clothes, pet blankets, car seat covers, car mats, horse covers, horse protection material, seat covers, awnings, canopies, raincoats, flyers, sails and duffel bags.

Plastic products can be selected from: food storage containers, utensils, cutting boards, mixing bowls, toothbrushes, cosmetic brushes, cosmetic applicators, cosmetic containers, food bags, extruded products, tubes, drainage products, gutters, tubing, shells, phone cases, screen covers, keyboards, keyboard overlays, medical packs, rubber gloves, latex-free rubber gloves, food packaging, thread, rope, cable ties, nozzle covers, remote controls, molded and extruded plastic covers, and coils, gaskets, gaskets, trays, refrigerator components, toothpicks, makeup cases, toilet seats, water filters, plastic cups, baby milk bottles, milk bottles, milk bags, bathroom curtains, electrical cables, automotive plastic components and plastics headphone elements.

In one aspect, the present invention provides a glove comprising a polymeric material and silver particles as defined herein. In an embodiment, the glove is not made of fibers, but is a single piece of polymeric material.

In one aspect of the invention, there is provided a method for producing fiber, comprising preparing silver particles by shredding silver foil;

mixing silver particles with a polymeric material (the polymeric material can be powdered or melted); and extruding the mixture of silver particles and polymeric material into fibers.

The method may also include intermediate steps for preparing the masterbatch after mixing the silver particles with the molten polymeric material. That is, the fiber production method may include preparing silver particles by grinding silver foil;

- 4 040966 mixing silver particles with a polymeric material (the polymeric material can be powdered or melted);

optionally melting a mixture of polymeric material and silver particles when the polymeric material is a powder;

extruding a mixture of silver particles and a polymeric material;

granulating the extruded mixture to form masterbatch granules;

mixing the masterbatch granules with another polymeric material; and extruding the molten mixture of masterbatch granules and polymeric material into fibers.

In one aspect of the invention, pellets are provided comprising a polymeric material and wherein the silver particles have a size characteristic of particles obtained by grinding silver foil. The silver particles may have a size that is defined in the document.

In embodiments of the method, the silver particles may have the same size as discussed above. The silver particles may be present in the fiber or in the masterbatch in the same amounts as discussed above.

The masterbatch granules may be mixed with another polymeric material in an amount of 1 to 10% by weight of the other polymeric material. Optionally, the masterbatch is mixed in an amount of 2 to 8% (preferably 3 to 5% by weight) of another polymeric material.

The other polymeric material may be the same polymeric material or may be different from the polymeric material in the masterbatch. Preferably, the polymeric material and the other polymeric material are the same material.

The polymeric material may be any suitable polymer which is solid and can be melted. For example, the polymeric material may be solid at room temperature. The polymeric material may be a plastic material or a rubber material. The polymeric material may be a poly(ester) polyamide (eg nylon), polypropylene, natural rubber, latex-free rubber, elastane rubber or synthetic rubber.

The polymeric material may be suitable for transformation into an article of the invention. The polymeric material containing the silver particles as defined herein may be suitable for vacuum forming, molding, extrusion, or other processing known to those skilled in the art to form articles such as garments (e.g., gloves and other uniforms discussed in this document), food packaging (e.g. fruit bags, thin films, packaging film, plastic boxes or plastic crates and other household items or plastic items discussed in this document), or beverage packaging ( e.g. bottles, bags, boxes, milk bottles, milk bags, milk cartons, fruit juice bottles, fruit juice bags or fruit juice cartons).

In one aspect of the invention, there is provided a fiber obtainable by the method of the present invention.

Textile materials according to the present invention can be obtained using known methods for the production of textile materials. In embodiments, the textile materials of the present invention comprise the fibers or textile yarns of the present invention in at least the weft. Optionally, the textile materials of the invention comprise the fibers or yarns of the invention in the weft but not in the warp or (where present) in the pile. The weft may be a fiber according to the invention. On the other hand, the weft may be a combination of fibers according to the invention and a fiber not according to the invention, a standard fiber, for example, fibers from cotton, polyester, polyamide (for example, nylon), polypropylene, natural rubber, latex-free rubber, elastane rubber or synthetic rubber. The weft can be formed from a fiber according to the invention and a fiber not according to the invention (standard fiber), where the fiber according to the invention is present in a ratio of 1:1 to 1:5 relative to the standard fiber. Optionally, the weft can be formed in a ratio of 1:1 ((fiber according to the invention): (standard fiber)) or the weft is obtained from the fiber according to the invention.

Preferably the weft is formed from a fiber or textile thread according to the invention.

The silver particles contained in all aspects and embodiments of the present invention can be obtained by grinding silver foil. Any suitable grinder can be used that results in the largest silver particles in the size range from 0.1 to 20 microns. For example, silver particles can be produced with a 1000W grinder having two stainless steel blades such as the Panasonic Mixer Grinder. Fig. 1-4 show SEM images of silver particles that can be produced using either a jet mill or a ball mill.

The amount of silver particles in the polymer mixture, in the masterbatch, in the fiber or textile thread can be determined using X-ray fluorescence analysis (XRF). XRF can

- 5 040966 be used to measure the amount of silver per unit area. XRF spectrometers are commercially available and any method for determining the silver content per unit area can be used.

The particle size of silver can be measured using a scanning electron microscope (SEM). Methods for measuring particle size using SEM are known to those skilled in the art.

In an embodiment, the fibers, textile yarns and textile materials of the invention have essentially the same antimicrobial activity after 25 washes, 50 washes, 75 washes or 100 washes at 60°C. The fibers, textile yarns and textile materials of the present invention are also suitable for washing in the presence of detergents (for example, harsh detergents, enzymatic detergents and non-enzymatic detergents), and/or in the presence of bleaches, and/or in the presence of fabric softeners. underwear. In addition, the fibers, textile yarns and textile materials of the present invention are suitable for tumble drying at any temperature. In contrast, prior art silver textiles can only be tumble dried at low heat.

In embodiments of the present invention, the fiber or textile thread is suitable for incorporation into a textile material of any color.

In a preferred embodiment, the polymer mixture does not contain an agglomeration inhibitor. Accordingly, in preferred embodiments, the masterbatch, fibrous textile or product of the invention does not contain an agglomeration inhibitor. For example, a contemplated agglomeration inhibitor is colloidal (pyrogenic) silica.

Example 1 Polypropylene fibers.

The fiber of the present invention is prepared as follows:

1) grind silver foil having a thickness of 0.03 µm into a powder with a size between 1 and 10 µm;

2) mix about 20 g of silver powder into 980 g of polypropylene resin powder in a high speed mixer;

3) put the powder into the extruder and melt the polymer;

4) after melting the polypropylene, extrude the polypropylene to obtain an extrudate from 2 to 2.5 mm in diameter;

5) pass the extrudate through a water bath to cool and solidify the polypropylene;

6) Put the extrudate into a granulating machine, which gives granules with a length of 2 to 3 mm.

The granules are then mixed with a polypropylene polymer and extruded into fibers in accordance with methods known in the prior art.

Example 2 Polyester fibers.

Polyester fibers can be made by following the procedure of Example 1 and replacing polypropylene with polyester throughout the process.

Example 3 Antimicrobial activity of polypropylene fibers.

A terry towel is made using 7% fibers of example 1 and 93% cotton.

The terry towel is evaluated for antimicrobial activity following ISO 20743:2011(E), quantitative method. This method is designed to evaluate the ability of tissues that have been treated with antimicrobial agents to prevent the growth of microorganisms and kill microorganisms. Antimicrobial testing is performed on a towel that has been washed at 60°C for 0 washes, 50 washes and 100 washes.

Antimicrobial activity is tested over a 20 hour period.

Test conditions.

Sample sterilization: autoclaving.

Neutralizing agent used: buffered saline with Triton X 100 (0.01%).

Contact time: 20 hours

Contact temperature: 37°C.

Medium and reagent: casein digested soy agar.

Antimicrobial activity after 0 washes is shown below in table. 1 and 2.

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Table 1. Test bacterium: Escherichia coli ATCC 11229

Quantification ISO 20743: 2007(E) (Plate counting method) Lab. control: Inoculum concentration at 0 hour (C _o ) =1.05x10 ⁵ CFU/ml Log: 5.02 Lab. control: The concentration of bacteria after 20 hours (C _t ) = 3.50x10 ⁶ CFU/ml Log: 6.80 Growth value F (F=Log C _t - Log C ₀ )=l.7 8 Sample Description Inoculum concentration at 0 h Test tissue (T _o ) Bacteria concentration after 20 hours Test tissue (T _t ) Growth value G ⁼ Log T _t -T ₀ Antimicrobial Value A=F - G cfu/m l Log/m l cfu/m l Log/m l Terry towel sample - 0 washes 10000 0 5.00 55000 4.74 -0.26 2.04

Table 2. Test bacterium: methicillin-resistant Staphylococcus aureus (MRSA) - S 129

Quantification ISO 20743: 2007(E) (Plate counting method) Lab. control: Inoculum concentration at 0 hour (C _o ) = 7.50x10 ⁴ CFU/ml Log: 4.87 Lab. control: The concentration of bacteria after 20 hours (C _t ) = 5.90x10 ⁶ CFU / ml Log: 6.77 Growth value F (F=Log C _t - Log C _o )=1.9O Sample Description Inoculum concentration at 0 h Test tissue (T _o ) Bacteria concentration after 20 hours Test tissue (T _t ) Growth value G=Log T _t -T ₀ Antimicrobial value A=F - G cfu/m L Log/m l cfu/m L log/m Terry towel sample - 0 washes 80000 4.90 54000 4.73 -0.17 2.07

Antimicrobial activity after 100 washes is shown in Tables 3 and 4 below. ______Table 3. Test bacteria: Escherichia coli ATCC 11229.

Quantification ISO 20743: 2007(E) (Plate counting method) Lab. control: Inoculum concentration at 0 hour (C _o ) =9, 60x10 ⁴ cfu/ml Log: 4.98 Lab. control: The concentration of bacteria after 20 hours (C _t ) = 4.90x10 ^b CFU / ml Log: 6.69 Growth value F (F=Log C _t - Log C ₀ )=l.71 Sample Description Inoculum concentration at 0 h Test tissue (T _o ) Bacteria concentration after 20 hours Test tissue (T _t ) Growth value G=Log T _t -T ₀ Antimicrobial value A=F - G cfu/m l Log/m l cfu/m l Log/m l Terry towel - 100 washes 97000 4.98 47000 4, 67 -0.31 2.02

Table 4. Test bacterium: methicillin-resistant Staphylococcus aureus (MRSA) - S 129 Quantification ISO 20743: 2007(E) (Plate scoring method)

Lab. control: Inoculum concentration at 0 hour Log: 5.00 (C _o ) =1, 000 ⁵ cfu/ml

Lab. control: Bacteria concentration after 20 hours Log: 6.70

(C _t ) \u003d 5.10x10 ^b CFU / ml Growth value F (F=Log C _t - Log C _o )=l.7O Sample Description Inoculum concentration at 0 h Test tissue (T _o ) Bacteria concentration after 20 hours Test tissue (T _t ) Growth value G=Log T _t -T ₀ Antimicrobial value A=F - G cfu/m l log/m cfu/m l Log/m l Terry towel - 100 washes 10400 0 5, 01 51000 4.70 -0.31 2.01

The growth value and antimicrobial value of a towel after 50 washes is comparable to the values of a towel after 100 washes.

These data show that the towel according to the invention, containing the fiber according to the invention, has a strong antimicrobial activity even after a significant number of washes at high temperature.

Example 4 Antimicrobial activity of polyester fibers.

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A terry towel is made using 7% fibers of example 2 and 93% cotton.

The terry towel is tested for antimicrobial activity following JIS L 1902. This method is designed to evaluate the ability of fabrics that have been treated with antimicrobial agents to prevent the growth of microorganisms and kill microorganisms. Antimicrobial testing is carried out on a towel that has been subjected to 0 washes, 75 washes and 100 washes.

The JIS L 1902 standard has a pass or fail scoring system where the pass score is achieved with an R value greater than 2. The towel of the invention is tested against two microorganisms: staphylococcus aureus (CECT 240, ATCC 6538P) and Escherichia coli (CECT 516, ATCC 8739) .

The tested terry towel gives an R value greater than 2 for all tested washes and with respect to both tested microorganisms. This shows that polyester fibers and textiles containing such fibers exhibit antimicrobial activity. Example 5 Antibacterial activity

In another example, the textile material of the present invention is subjected to an antimicrobial evaluation. The textile material is a sock fabric containing the textile yarns of the present invention. The test procedure is shown below in table. 5.

Table 5

Test method ASTM WK#45351 test organism Escherichia coli (ATCC # 25922) Nutrient load test solution substances Trypsin soy broth (TSB) in deionized H ₂ O (1:500) Dimension of the test sample 0.40 ± 0.05 g, cut into squares Inoculum applied to test sample 0.2 ml contact time 24 hours ±10 min Neutralizing agent 10 ml Day-Engley Neutralizing Broth (D/E) (x1) Method for measuring the number of live bacteria Dilution method on trypsin soy agar (TSA) Sterilization method No Washing method No

The test results (Table 6, 900BS-2) show almost complete removal of E. coli present on a square of textile or invention after 24 hours of incubation. The control sample, N110, does not show a reduction in bacteria as expected.

Table 6

ASTM WK#45351 Quantification of the bactericidal activity of treated products (relative to E. coli) Inoculum concentration (cfu/ml) 2.25x10 ⁵ \u003d 5.36 log Standard control after 24 hours (CFU/g) 3.43x10 ⁵ =5.53 log Significance of Growth Control + 0.17log Sample name Bacteria isolated (CFU/g) Log selection log reduction % reduction N110 7.02EZ 3.85 - - 900BS- 2 <2.48E+00 <0.39 >3, 45 >99.96%

Example 6 Antiwashout.

A sheet of the present invention containing 9% polyester fiber containing silver particles and 94% cotton is subjected to a test to determine the degree of leaching of silver particles from the textile material. In table. 7 details the test method used.

Table 7

Test method ASTM E 2149 Test organism(s) E. coli (ATCC # 25922) Wednesday Trypsin soy broth/agar Test sample dimensions Samples 1 + 0.1 g contact time 1 hour + 5 minutes Method for measuring the number of live bacteria Breeding Method and Colony Counting Sterilization Method No Washing method No

Below in table. 8 shows the test results. Antibacterial efficacy is observed in the case of the sheet sample according to the invention in comparison with the control test 5. In addition, washing out of silver particles is not observed.

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Table 8

Number of repeated experiments 2 Mean Inoculum Concentration (CFU/mL) 1.27E+0.5 Average control growth -0.29 Sample name Average % reduction relative to 5 Observations 5 (28/1RS-5248) 0 6 (28/1RS-6535 BS) -4.17% Washout not detected 7 (30/2RS-6535 BS) -19.42% Washout not detected

Example 7 Antibacterial activity against E. coli.

Woven textiles with weft consisting entirely of weft yarns containing 20% fibers of the invention blended with 80% cotton show complete eradication of E. coli after 24 hours of incubation. Textiles that do not contain the fibers of the invention are unable to reduce bacterial growth and actually show an increase in E. coli concentrations after 24 hours of incubation. This result is illustrated by the data given in table. 9.

Table data. 9 obtained using the following technique. Broth cultures of E. coli (ATCC #35984) are prepared by transferring one colony to 20 ml of sterilized trypsin soy broth (TSB). The culture is then maintained at 37°C on an orbital shaker at 200 rpm for 18 hours. On the day of the test, a liquid inoculum of 6.25x105 colony forming units (CFU)/ml in nutrient medium (TSB diluted 1:500 in sterilized deionized H ₂ O). Cut out three square samples of 0.40+0.05 g of each type of fabric per time point (2) and record the dry weights. Each sample is placed in labeled 50 ml tubes so that the tissue squares form a cup shape. An aliquot of 0.2 ml of the inoculum solution is placed on the samples at several points, taking care that the inoculum does not touch the surface of the vessel. The tubes are loosely capped. Samples are incubated for 0 and 24 hours. Bacteria from 0 hour samples are isolated immediately in D/E neutralizing buffer (1x). Samples 24 hours incubated at 37°C for 24 hours in a humidified chamber. After incubation, the bacteria are isolated for 24 hours in D/E neutralizing buffer (1x). After isolation, all tubes are vortexed for 1 min. The bacterial samples are then seeded by dilution and incubated overnight at 37°C. For each plate, the number of colonies is counted and recorded. The percentage or log reduction is based on the geometric mean of the data. Experiments are carried out three times. The results are expressed as CFU/g textile.

Table 9

Weft type of fabric The fiber according to the invention is missing 2 cotton weft threads and 1 fiber weft thread according to the invention All weft threads of fiber according to the invention Immediately after inoculation and 1.74x10 ⁵ cfu/g (5.23 log) 2.41x10 ⁵ cfu/g (5.29 log) 2.21x10 ⁵ cfu/g (5.27 log) 24 hour after inoculation and 2.68x10 ⁷ cfu/g (7.26 log) 1.24x10 ⁷ cfu/g (7.06 log) 0 CFU/g (0.00 log) Change from 0 to 24 hours + 2.03 + 1.77 -5.27 (at least -7 regarding the option without (log) fiber invention

Example 8 Antimicrobial efficacy against MRSA.

Product samples.

Two sleeve fabrics, one containing silver embedded in polyester polymer threads in accordance with the invention, and one control fabric with only polyester threads. Tissues are cut into 0.4 g samples. Three replicate samples are used per time point.

Description of experiments for this task.

The study of the bactericidal effect of polyester fabric materials with the introduction of silver wet incubation.

This test is based on the Hong Kong test for silver products. Methicillin-resistant Staphylococcus aureus (MRSA) is grown overnight in 5 ml Luria-Bertani Broth (LB) at 37° C. with shaking at 150 rpm. This culture is used to inoculate pieces of material with 200 µl of MRSA culture diluted 1/10 (for sample sizes of 0.4 g), placed in stoppered tubes and incubated at 37°C for 0, 1, or 24 hours. used as a negative control and all of the samples mentioned are present in those copies

- 9 040966 for each time point. Upon reaching the time point, the samples are transferred to 5 ml of phosphate buffered saline (PBS) containing glass beads. Samples are then vortexed for 25 seconds before being diluted in PBS and plated on Luria Bertani agar plates. The plates are incubated at 37° C., viable cells are counted and the plates are returned to the incubator at 37° C. for an additional 24 hours before counting. Viable MRSA numbers are recorded as colony forming units (CFU) per ml.

Study of the bactericidal effect of polyester fabric materials with introduced silver - dry incubation.

This test is based on the Hong Kong test for silver products with the following modifications to obtain a more realistic evaluation of samples. Methicillin-resistant Staphylococcus aureus (MRSA) is grown overnight in 5 ml of Luria-Bertani (LB) broth at 37° C. with shaking at 150 rpm. This culture is used to inoculate pieces of material with 200 µl of MRSA culture diluted 1/10 (for a sample size of 0.4 g), placed in closed, but not sealed, Petri dishes and set in an incubator at 37°C at 0.1 or 24 hours. A standard sock is used as a negative control and all samples mentioned above are in triplicate for each time point. Upon reaching the time point, the samples are transferred to 5 ml of phosphate buffered saline (PBS) containing glass beads. Samples are then vortexed for 25 seconds before being diluted in PBS and plated on LB agar. The plates are incubated overnight at 37°C, viable cells are counted and the plates are returned to incubate at 37°C for an additional 24 hours before recounting. The number of viable MRSAs is recorded as colony forming units (CFU) per ml.

The test results for both dry and wet incubation are presented in table. 10. The results show that socks containing the fibers of the invention provide a significant reduction in the number of MRSA cells in both wet and dry incubation.

Table 10

Sample average Time (hour) Log decline after 1 hour Log decline after 24 hours 0 1 24 Sock with wet silver 1.71E+0 7 6.03E+ 05 2.44E + 03 1.5 3.8 control wet sock, 1.89E+0 7 1.69E+ 07 2.44E + 07 0.0 -o, 1 Toe with dry silver 3.56E+0 7 2.61E+ 06 5.78E+ 03 1.1 3.8 Control dry SOCK, 6.61E+0 7 2,3E+ 07 1.75E+ 05 0.5 2.6

Example 9 Antibacterial activity of a towel.

In another example, the towel of the present invention is subjected to an antimicrobial evaluation. The towel is a 700GSM terry towel consisting of 97% cotton and 3% polyester fiber containing silver particles according to the invention. The test procedure is described below in table. eleven.

Table 11

Test method ASTM WK#45351 test organism Escherichia coli (ATCC #25922) Nutrient load test solution substances Trypsin soy broth (TSB) in deionized H ₂ O (1:500) Test sample dimensions 0.40 ± 0.05 g, cut into squares Inoculum applied to test sample 0.2 ml contact time 24 hours ± 10 min Neutralizing agent 10 ml Day-Engley Neutralizing Broth (D/E) (xl) Method for measuring the number of live bacteria Dilution method on trypsin soy agar (TSA) Sterilization method No Washing method No

The test results (Table 12) show almost complete removal of E. coli present on a square of the terry towel according to the invention (designated Bioshield) after 24 hours of incubation. The non-Bioshield control sample did not show a reduction in bacteria as expected.

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Claims (22)

Table 12 ASTM WK#45351 Quantification of the bactericidal activity of treated products (relative to E. coli) Number of repeated experiments 2 Mean inoculum concentration (cfu/ml) 4.46x10 ⁵ =5.65 log ± 0.24 log Average control after 24 hours of incubation (CFU/g) 5.78x10 ⁴ =4.76 log Average control growth + 0.41log Sample name Average number of isolated bacteria (CFU/g) Average log selection Average log reduction Medium abbreviated IA 1&2 (not Bioshield) 7.35x10 ⁶ 6.87 - - 4 (Bioshield) 1.52+10 ² 2.18 4.69 99.998% Example 10 In FIG. 5 shows plastic bags labeled 2 made from a polymer blend containing silver particles in accordance with the present invention. The bag is obtained by extruding a thin film from the polymer mixture according to the invention and sealing the edges to form a bag. The package in this example contains milk, as can be seen in the example in FIG. 5. A comparative example of a standard plastic bag is labeled O. This bag does not contain silver particles and also contains milk. Both packages and their contents are stored at room temperature for 5 days. From FIG. 5, it is clear that the milk in the bag of Comparative Example (0) gives solid deposits, indicating that the milk is no longer suitable for consumption. However, on the contrary, the milk in the bag of the present invention (2) does not show the appearance of hard deposits. The bag of the present invention thus demonstrates food keeping fresher than the comparative plastic bag. Throughout the description and in the claims of this specification, the words contains and includes and their various variations mean including, but not limiting, and they also do not imply (and do not) exclude other fragments, additives, components, integers or steps. Throughout the description and in the claims of this description, the singular form covers the plural form, unless the context requires otherwise. In particular, when the indefinite article is used, the description should be understood to mean the plurality as well as the singular case, unless the context otherwise requires. Features, integers, characteristics, compounds, chemical moieties, or groups described in conjunction with a particular aspect, embodiment, or example of the invention are to be understood to apply to any other aspect, embodiment, or example described herein, unless they are incompatible with them. All features disclosed in this specification (including any accompanying claims, abstract and drawings) and/or all of the steps of any method or process thus disclosed may be combined in any combination, except for combinations where at least , some of these features and/or steps are mutually exclusive. The invention is not limited to the details of any of the embodiments described above. The invention extends to any new feature, or any new combination, of the features disclosed in this specification (including any accompanying claims, abstract, and drawings), or to any new step, or any new combination, of the steps of any method or process disclosed. Thus. Attention is directed to all publications and documents that are filed at the same time or earlier than this description in conjunction with this application and which are open for public inspection with this description, and the contents of all such publications and documents are incorporated in this description by reference. CLAIM 1. A polymer mixture containing a polymer material and silver particles, where the silver particles have a size characteristic of particles, which are particles of crushed silver foil, where the silver particles have a height of less than 1 μm and a length and/or width of 0.1 to 10 μm where the polymeric material is a plastic material or a rubber material. 2. The polymer mixture according to claim 1, which is in solid or molten form. 3. A polymer blend according to any one of the preceding claims, wherein the silver particles are present in an amount of 0.1 to 10% by weight of the polymer charge. 4. A polymer blend according to any one of the preceding claims, wherein the silver particles are present in an amount of 0.1 to 5% by weight, 0.5 to 4% by weight, 0.5 to 3% by weight, 0. 1 to 3 wt% or 1.5 to 2.5 wt%. 5. Polymer mixture according to claim 1 or 2, in which silver particles are present in an amount of from 0.003 - 11 040966 up to 0.5 wt.%, from 0.03 to 0.5 wt.%, from 0.03 to 0.25 wt.%, from 0.05 to 0.15 wt.%, from about 0 06 to 0.15 wt.%, from 0.03 to 0.1 wt.% or from 0.06 to 0.1 wt.%. 6. A polymer blend according to any one of the preceding claims, wherein the silver foil has a height of less than 1 µm, optionally less than 0.5 µm, less than 0.3 µm, or less than 0.1 µm. 7. A polymer blend according to any one of the preceding claims, wherein the silver particles have a height of less than 0.5 µm, less than 0.3 µm, or less than 0.1 µm. 8. Polymer blend according to any one of the preceding claims, wherein the silver particles have a length and/or width of 0.5 to 10 µm, or 0.5 to 8 µm, or 1 to 6 µm, or 1 to 4 µm , or from 2 to 3 µm. 9. A polymer blend according to any one of the preceding claims, wherein the polymeric material comprises at least a material of polyester, polyamide (eg nylon), polypropylene, natural rubber, latex-free rubber, elastane rubber or synthetic rubber. 10. An article containing a polymer blend according to any one of the preceding claims. 11. The product according to claim 10, in which the product is obtained from a single piece. 12. Fiber obtained from a polymer mixture according to any one of claims 1 to 9. 13. A fiber containing a polymeric material and silver particles, where the silver particles have a size characteristic of particles, which are particles of crushed silver foil obtained by grinding silver foil, where the silver particles have a height of less than 1 μm and a length and/or width of 0 ,1 to 10 µm, where the polymeric material is a plastic material or a rubber material. 14. The fiber according to claim 13, in which silver particles are present in an amount of from 0.003 to 0.5 wt.%, from 0.03 to 0.5 wt.%, from 0.03 to 0.25 wt.%, from 0.05 to 0.15% by weight, 0.06 to 0.15% by weight, 0.03 to 0.1% by weight, or 0.06 to 0.1% by weight. 15. A fiber according to claim 13 or 14, wherein the silver foil has a height of less than 1 µm, optionally less than 0.5 µm, less than 0.3 µm, or less than 0.1 µm. 16. A fiber according to any one of claims 13-15, wherein the silver particles have a height of less than 1 µm, optionally less than 0.5 µm, less than 0.3 µm, or less than 0.1 µm. 17. A fiber according to any one of claims 13 to 16, wherein the silver particles have a length and/or width of 0.1 to 10 µm, optionally 0.5 to 10 µm, or 0.5 to 8 µm, or 1 to 6 µm, or 1 to 4 µm, or 2 to 3 µm. 18. Textile thread containing fiber according to any one of claims 12-17. 19. Textile material containing fiber according to any one of claims 12-17. 20. Textile material containing a textile thread according to claim 18. 21. The method of obtaining fibers, including the preparation of particles of silver by grinding silver foil; mixing silver particles with a polymer material, which is a plastic material or a rubber material, to obtain a polymer mixture according to claim 1; and extruding the mixture of silver particles and polymer material to form a fiber. 22. The method according to item 21, in which the method includes the preparation of particles of silver by grinding silver foil; mixing silver particles with a polymeric material (the polymeric material can be ground to a powder or melted); optionally melting a mixture of polymeric material and silver particles if the polymeric material is a powder; extruding a mixture of silver particles and a polymeric material; granulating the extruded mixture to form masterbatch granules; mixing the masterbatch granules with the additional polymeric material; and extruding the molten mixture of the masterbatch granules and the polymeric material to form fibers. -