Water repellent article

Abstract

An article is contacted with a micellar solution, antibacterial compound and binder, dried and then treated with water repellent. Preferably the solution comprises saponin and the binder comprises pol

Description

The present invention relates to articles which are water repellent and to methods for their manufacture. A type of glove which is presently available comprises a fabric layer which has been contacted with a liquid polymer coating. Such gloves are sold by Traffi Safe Ltd, of Traffi Safe Ltd, Innovation House Unit 18, Caker Stream Road, Mill Lane Industrial Estate, Alton, Hampshire, GU34 2QA, United Kingdom. They are sold under the Traffiglove® mark. An example of this type of glove (reference number TG5360) is shown in figures 1 and 2. The glove has a fabric layer (101) with an elasticated wrist portion (103). To manufacture the glove the fabric layer (101) is typically dipped in a bath of a liquid polymer. The glove is then removed from the bath and the polymer coating solidifies / dries. The polymer coating (102) provides a protective outer coating over portions of the external surface of the fabric layer. In some gloves the coating may completely cover the fabric layer. The polymer coating may cover the palm and the fingers of a glove. It is desirable for articles such as gloves to be water repellent so that they can remain water free. Water repellent compositions are speciality chemicals which, if used in large amounts, will lead to high costs and an expensive end product. It is therefore desirable to reduce the amount of water repellent composition required to manufacture articles. This will lower the CO2 footprint of the articles themselves, and also the CO2 footprint of the factory which manufactures the articles. To improve sustainability of article (e.g. glove) manufacture it is desirable to eliminate the use of fluorocarbon additives. Fluorocarbon chemicals, whilst being very water repellent, persist in nature without breaking down and can have a negative environmental impact. It is also desirable to provide water repellent articles which have an improved water repellence when compared to existing articles. Gloves and other articles are often exposed to sweat on their inner surfaces. Articles may also come into contact with external contaminants and these contaminants can lead to the formation of malodours. It is therefore desirable that articles such as gloves are provided with anti-bacterial properties. It also desirable for articles to maintain water repellent and / or antibacterial properties and / or anti-odour properties after repeated washing cycles. Wash durability of water repellence generally depends on the strength of bonding between fabric or polymer portions of the article (e.g. the glove) and the associated water repellent composition. Increased wash durability of the water repellence increases the lifetime of an article and therefore contributes to an improved sustainability of the article because fewer articles need to be manufactured to fulfil demand. Additionally, the presence of odour elimination technology may mean that gloves need to be washed less often, thereby saving water and energy during their useable life cycle. It is amongst the objects of the invention to solve one or more of these problems. In a first aspect the invention provides a method of forming an article comprising the steps of; i) contacting the article with an antibacterial composition which comprises a micellar solution, antibacterial compounds and a binder, ii) drying the article, and iii) contacting the article with a water repellent composition. The action of water repellent compositions is hindered by residual molecules which are present. These residuals are hydrophilic molecules, which weakens the effect of water repellent compositions. They can be left-overs from the manufacturing process of the material itself, such as dyes. In the present invention it is thought that the micellular solution (which may be a micellar emulsifier solution) which is used to deliver the antibacterial molecules reduces the effect of residual molecules present on the effect of the added water repellent composition. The micelles may act to mop up residuals and impurities by virtue of their structure which is well adapted to swallow up hydrophilic molecules and prevent them from interacting with other molecules. The micellular solution may also provide an enhanced effect by keeping (generally hydrophilic) antibactierial molecules well contained within the micelles so that those hydrophilic molecules do not detrimentally interact with the water repellent properties. Once the residuals have been effectively removed or reduced, the water repellent composition can perform its action unhindered. This provides a water repellent article with a high water repellent effect and a high wash durability. It also provides a more cost-effective article because extra processing steps (either before or after the application of the antibacterial composition) are not required to remove residuals. This avoids expensive extra process steps. It also enables the use of plant-based sustainable water repellent materials. It has been found that plant-based water repellents are particularly susceptible to the effects of residual molecules. The invention can address this in embodiments where plant-based water repellents are used, for example plant extracts. The articles may be articles of clothing or personal protective equipment for example, jackets / coats, headwear, outerwear, trousers, footwear, gloves or protective sleeves. The article may also be an item of sports equipment. The article may also be an upholstery item. The micellar solution may comprise amphiphilic glycoside molecules. These types of molecules provide good micelle forming ability, and are also readily extracted from plants, making their use much more sustainable than fluorocarbon based water repellents. Amphiphilic glycosides suitable for use in the invention may comprise 1,2 or 3 monosaccharide groups (hydrophilic groups) bonded to a second functional group selected from; i) a triterpene ii) a steroid, iii) a steroidal alkaloid, or iv) an acyclic carbon chain which is preferably a C1-11 carbon chain or a 2-5 (branched or unbranched) carbon chain. The monosaccharide groups provide a polar end of the molecule which forms the outer surface of the micelle when the molecules coagulate. Any of the groups i)-iv) provide a more hydrophobic tail to the molecules which is orientated towards the centre of the micelles when the molecules coagulate. The monosaccharide group(s) may comprise glucose or galactose or groups derived therefrom. In some embodiments the second functional group may be a terpenoid. In some embodiments the amphiphilic glycoside may be triterpene glycoside. In some embodiments the amphiphilic glycoside may be a saponin. Preferably, the amphiphilic glycoside non-toxic to humans. In some embodiments the amphiphilic glycoside is an extract from a plant. This provides a sustainable article. The plant may be selected from; i) the Saponaria family, for example Caryophyllaceae (e.g. soapwort, Saponaria officinalis), ii) the Sapindus family, for example Sapindaceae, Aceraceae, Hippocastanaceae, such as Sapindus mukarossi, iii) the Cucurbita family, for example Cucurbitaceae (e.g. Gynostemma pentaphyllum- in the form of Gypenosides), iv) the Panax family, for example Araliaceae (e.g. ginseng or red ginseng) v) Manilkara zapota fruit, or vi) the Apocynaceae family such as Nerium oleander. The antibacterial composition may be Resefin OE®. The micellar solution may comprise a saponin or saponin-derived compound. The antibacterial additive may comprise hydrophilic molecules. The antibacterial composition may comprise a plant extract. The antibacterial composition may comprise one or more active ingredients which may be selected from one or more of geraniol, peppermint extract (e.g. peppermint oil), or lemongrass extract (e.g. lemongrass oil). The CAS numbers for these components are: Lemongrass oil: 8007-02-1, Peppermint oil: 8006-90-4, Geraniol: 106-24-1. The active anti-bacterial agents may constitute around 7-10% of the anti-bacterial composition. The micellar solution may constitute 90-93% by weight of the antibacterial composition. The water repellent composition may comprise a wax, an unsaturated monomer, a solvent, and an emulsifier, which are polymerized. Preferably the wax is a petrochemical wax, a natural wax, a paraffin wax, an artificial wax, or a combination thereof. The unsaturated monomer is preferably a Ce-Cso carbon chain having an unsaturated functional group and / or a Ce-Cso aromatic having an unsaturated functional group. Said unsaturated functional group may comprise an acrylic group, methacrylic group, vinyl group, or a combination thereof. Alternatively, said unsaturated monomer of Ce-Cso can be substituted or unsubstituted. Preferably, the substituted or unsubstituted Ce-Cso unsaturated monomer is: phenylethylene, stearyl acrylate, propyl acrylate, propyl methacrylate, glycidyl methacrylate, glycidyl acrylate, hydroxyethyl methacrylate, hydroxyethyl acrylate, 3-chloro-2-hydroxypropyl methacrylate, N-methylolacrylamide, N-(hydroxy)acrylamide, or a combination thereof. The solvent is preferably propylene glycol, dipropylene glycol methyl ether, 4-oxa-2,6-heptandiol, acetone, or a combination thereof. Preferably, said emulsifier is a cationic emulsifier, an anionic emulsifier, a non-ionic emulsifier, or a combination thereof. Preferably, said emulsifier is octadearyl dimethyl ammonium chloride, stearyl alcohol polyoxyethylene, lauryl alcohol polyoxyethylene, oleyl alcohol polyoxyethylene, or a combination thereof. Preferably the water repellent composition comprises Jintexguard BIO DWR 2.0, or one of the compositions shown in table 1 below. The binder may comprise polyurethane. The binder in the anti-bacterial composition may be a polyurethane binder which comprises around 10-20% of a polyurethane (or polyurethane-derived) entity and around 80-90% water (by weight of the binder composition). The article may comprise a polymer layer selected from one or more of nitrile butadiene rubber, latex (for example natural rubber latex), polyurea, polyurethane, neoprene and silicon. The method further may comprise a step of contacting the article with a coagulant before step i). The method may comprise a step of contacting the article with a postcoagulant after step i). The polymer layer may comprise nitrile or latex or a combination thereof and the method further may further comprise a step of contacting the article with a coagulant before step i). The polymer layer may comprise nitrile or latex or a combination thereof and the method may further comprise a step of contacting the article with a post-coagulant after step i). The coagulant reduces penetration through the knitted liner and improves adhesion. Suitable coagulants are disclosed in AU2015281780B2, the contents of which are incorporated herein by reference. The coagulant and its neutralization by the postcoagulant enable the leaching of the glove and removal of remaining surfactants in subsequent steps. The water repellent composition may be polymerized using an initiator. The antibacterial compounds, the compounds forming micelles in the micellar solution, or the water repellent composition may comprise molecules which have been extracted from a plant or plants. The amount of the antibacterial additive may be between 1 -3 wt%, or greater than 1 wt%, relative to the weight of the article in step i). Preferably the antibacterial additive is between 1-1.5 wt% (relative to the weight of the article in step i). The minimum amount of the binder may be 0.5 wt% relative to the weight of the article in step i). The solution strength of the water repellent composition may be 10% or greater. The antibacterial composition may be provided as a mixture with a liquid polymer in step i). The liquid polymer may be any one of the polymers which form a polymer part of the article as described herein. For example, when the article is a glove, the liquid polymer may be the polymer which eventually forms a polymer dipped portion of the glove. The article may be dipped into a liquid polymer after step ii). The liquid polymer may be any one of the polymers which form a polymer part of the final article as described herein. For example, when the article is a glove, the liquid polymer may be the polymer which eventually forms the polymer dipped portion of the glove. The article may be a glove. The article may comprise a fabric which has been subjected to a dyeing process. The article may comprise a combination of a fabric layer and a polymer layer. The fabric layer may have been subjected to a dyeing process. The polymer layer, when present, may be foamed, microfoamed or textured-especially if nitrile butadiene rubber. Preferred embodiments of articles (e.g. gloves) according to the invention may have foamed or microfoamed polymer components. Preferred embodiments of the methods according to the invention may also utilize articles (e.g. gloves) having foamed or microfoamed polymer layers. This provides a surface to which the water repellent may easily adhere. This provides gloves with a high water repellence and a high wash durability. The foamed or microfoamed polymer layer may comprise nitrile butadiene or styrene butadiene rubber. The polymer layer may have been dip, spray, dot or transfer coated onto the fabric portion of the article (e.g. the glove). The polymer may comprise one or more polymers selected from the group of polyurethane, polyurea, styrene butadiene rubber, nitrile butadiene rubber, latex (such as natural latex rubber), polydimethylsiloxane rubber, silicon, neoprene and thermoplastic elastomers. The fabric portion may comprise one or more of; nylon, polyester, cotton, a polyester and cotton blend, a polyester and nylon blend, ultra high molecular weight polyethylene (LIHMWPE) combined with elastane and nylon, LIHMWPE combined with elastane and polyester, UHMWPE combined with elastane and nylon and glass fibre, UHMWPE combined with elastane and polyester and glass fibre, UHMWPE combined with elastane and nylon and stainless steel, UHMWPE combined with elastane and polyester and stainless steel, aromatic polyamides (para-aramids) combined with elastane and polyester, aromatic polyamides (para-aramids) combined with elastane and nylon, aromatic polyamides (para-aramids) combined with elastane and polyester and glass fibre, aromatic polyamides (para-aramids) combined with elastane and nylon and glass fibre, aromatic polyamides (paraaramids) combined with elastane and polyester and stainless steel, aromatic polyamides (para-aramids) combined with elastane and nylon and stainless steel, UHMWPE fibre and nylon, and UHMWPE fibre and polyester. These fabrics provide good absorbance of fluorocarbon polymer. Preferably the fabric portion is knitted or woven. Specific combinations of fabric and polymer components may be: Embodiment number Fabric component Polymer component 1 Ultra high molecular weight polyethylene, elastane, nylon and glass fibre Nitrile butadiene rubber 2 Ultra high molecular weight polyethylene, elastane and nylon Polyurethane 3 Ultra high molecular weight polyethylene, elastane, nylon and glass fibre Polyurethane 4 Nylon and elastane Polyurethane 5 Nylon and elastane Microfoam nitrile butadiene rubber 6 Polyester, nylon and elastane Foamed nitrile butadiene 7 Nylon Polyurethane 8 Nylon Nitrile butadiene rubber 9 Nylon and elastane Polyurethane 10 Polyester, nylon and elastane Foamed nitrile butadiene rubber 11 Ultra high molecular weight polyethylene, elastane and nylon Polyurethane 12 Ultra high molecular weight polyethylene, elastane and nylon Polyurethane 13 Ultra high molecular weight polyethylene, elastane, nylon and glass fibre Foamed nitrile butadiene rubber 14 Ultra high molecular weight polyethylene, elastane, nylon and glass fibre Polyurethane 15 Ultra high molecular weight polyethylene, elastane, nylon and glass fibre Microfoam nitrile butadiene rubber 16 Aromatic polyamides (para-aramids), elastane, polyester and glass fibre Textured nitrile butadiene rubber 17 Nylon and polyester Textured nitrile butadiene rubber 18 Aromatic polyamides (para-aramids), elastane and polyester Textured nitrile butadiene rubber The glove may be a polymer dipped glove in which the polymer is disposed on at least part of the outside surface of a fabric layer. In a further aspect the invention provides an article, preferably a glove, obtainable by a method as described herein. The glove may incorporate any of the features which result from the method steps defined herein. In a further aspect the invention provides a glove comprising a fabric portion and an outer layer, which outer layer comprises a first polymer on the outside of the fabric portion, wherein the outer layer comprises a surface portion and a sub-surface portion, and wherein the fabric portion and the surface portion of the outer layer both comprise a dried micellar solution, antibacterial compounds, binder and a water repellent composition. Gloves according to this statement of invention may be obtained in a process in which the antibacterial compounds and the micellar solution are applied as part of a mixture with a liquid polymer which liquid polymer dries / sets to form the outer layer of the glove. In some embodiments the sub-surface portion of the outer layer contains substantially none of the dried micellar solution, antibacterial compounds, binder nor water repellent composition. This type of glove results from a process in which the antibacterial compounds and the micellar solution are applied after the outer layer has been applied to the fabric portion of the glove. Any features described in connection with the other aspects of the invention may be incorporated into this aspect of the invention, including ‘product’ features which result from the method steps described herein. The dried micellar solution contains the moieties which provide the micelles in the solution used to manufacture the glove. A substantial proportion of the solvent (e.g. usually water) having been removed during the drying process. The skilled person could simply test the glove for the presence of the components which form micelles (as described herein) in solution to determine whether a given glove comprises these features. In a further aspect the invention provides a method of method of forming an article comprising the steps of contacting the article with a micellar solution, drying the article, and contacting the article with a water repellent composition. This aspect of the invention is similar to the other aspects of the invention, except that no step comprising the addition of anti-bacterial compounds is present. This provides a more effective application method for applying a water repellent to an article. The article may be any article as described herein. Further method steps and features according to any other aspect of the invention may be incorporated into the method according to this aspect of the invention. Specific embodiments of the invention will now be described with reference to the figures of the drawings in which Figures 1 and 2 show a polymer dipped work glove according to the prior art. Four different types of glove according to the invention were manufactured according to methods of the invention. Manufacturing method The antibacterial composition used in these examples was Resefin OE®. This composition is referred to as ‘Reseda additive(s)’ in the following. This composition is manufactured and available from Reseda Lifesciences Limited of C / O D&M Financial Services, Anumerate Office 2.05, Clockwise, Old Town Hall, 30 Tweedy Road, Bromley, United Kingdom, BR1 3FE. This Reseda® additive comprises the Reseda additives mentioned below and a Reseda polyurethane binding agent. The Resefin OE® is a plant-based product. It contains raw material which comprises naturally occurring saponins, for example those from the plant Sapindus Mukarossi. These saponins are amphiphilic glycosides (as described in the statements of invention above), which are extracted from the plant to form an oil. The Resefin OE® solution is aqueous and the saponins form micelles in the aqueous solution. The composition further comprises geraniol, lemon grass oil and peppermint oil. The CAS RN numbers for these compounds is as follows: Lemongrass oil: 8007-02-1, Peppermint oil: 8006-90-4, Geraniol: 106-24-1. These compounds / oils produce the antibacterial effect of the composition. It is thought that any of these compounds / oils, alone or in combination, would provide the antibacterial effect. Equally these compounds / oils could be substituted with other plant-based compound or group of compounds which are known to have antibacterial properties. These antibacterial oils / compounds are, in the aqueous solution product, generally encapsulated within the micelles formed by the saponin products. This encapsulation enables them to be delivered in hydrophilic environments because the hydrophilic outer surface of the micelle is readily bound with solvent (e.g. water) molecules. The encapsulation by the micelles is also thought to stop the encapsulated compounds from interfering with other surface bonding effects between other components in a product to which they are applied. The water repellent composition used was Jintexguard BIO DWR 2.0. This product is manufactured and available from Jintex Corporation Limited, of 12F., No.126, Sector 4, Nanjing East Road, Songshan District, Taipei City 105, Taiwan. Further details of this composition are disclosed in the patent publication US 2015 / 0204010 A1, which is incorporated herein in its entirety. This water repellent comprises a wax (paraffin wax 12-17 parts), an unsaturated monomer, a solvent, and an emulsifier, which are polymerized. Options for these compositions are thought to be disclosed in example 1 (specifically table 1) of US 2015 / 0204010 A1, which is included as table 1 herein. Both the water repellent and the antibacterial composition are wholly or substantially plant-based. They do not contain fluorocarbons. The 4 exemplary gloves all have a fabric inner (liner) which is coated (on the palm and fingers of the glove) with either a nitrile, a polyurethane, a polyurea or a latex coating. The gloves were manufactured according to the following processes: Nitrile (NBR) coating 1. Glove liners placed onto alloy formers. 2. Liners immersed in coagulant. 3. Gloves dipped in Nitrile compound which contains Resefin OE®. 4. Dipped gloves immersed in post-coagulant. 5. Gloves dipped into leaching tank (water tank). 6. Gloves air dried on track. 7. Gloves dipped into Jintexguard BIO DWR 2.0 application tank. 8. Drying on track conveyor. 9. Gloves proceed through track conveyor tunnel dryer. 10. Back of hand printing / examination / packing. Polyurethane (PU) coating 1. Glove liners placed onto alloy formers. 2. Gloves dipped in Polyurethane compound which contains Resefin OE®. 3. Gloves dipped into leaching tank (water tank). 4. Gloves air dried on track. 5. Gloves dipped into Jintexguard BIO DWR 2.0 application tank. 6. Drying on track conveyor. 7. Gloves proceed through track conveyor tunnel dryer. 8. Back of hand printing / examination / packing. Polyurea coating 1. Glove liners placed onto alloy formers. 2. Gloves dipped in Polyurea compound which contains Resefin OE®. 3. Gloves air dried on track. 4. Gloves dipped into Jintexguard BIO DWR 2.0 application tank. 5. Drying on track conveyor. 6. Gloves proceed through track conveyor tunnel dryer. 7. Back of hand printing / examination / packing. Latex natural rubber coating 1. Glove liners placed onto alloy formers. 2. Liners immersed in coagulant. 3. Gloves dipped in Latex natural rubber compound which contains Resefin OE® 4. Dipped gloves immersed in post-coagulant. 5. Gloves air dried on track. 6. Gloves dipped into Jintexguard BIO DWR 2.0 application tank. 7. Drying on track conveyor. 8. Gloves proceed through track conveyor tunnel dryer. 9. Back of hand printing / examination / packing. In the above methods, suitable coagulants (where present) will be known to those skilled in the art. The coagulant reduces penetration through the knitted liner and improves adhesion. Suitable coagulants are disclosed in AU2015281780B2, the contents of which are incorporated herein by reference. The coagulant and its neutralization by the post-coagulant enable the leaching of the glove and removal of remaining surfactants in subsequent steps. All of these processes produced gloves which were suitable for use. Test Methods The gloves having the PU and NBR coatings were tested to demonstrate their properties. In the results below, the TG5360 PU reference number denotes a glove having a fabric liner and a polyurethane polymer dipped palm and fingers. The TG5360 NBR denotes a glove having a fabric liner and a nitrile butadiene rubber polymer dipped palm and fingers. The TG5360 gloves have a fabric liner which comprises an engineered yarn comprising 20% Nylon, 30% HPPE, 15% Polyester, 10% Glass, 20% Steel and 5% Elastane. Both of these types of glove are produced and sold by Traffi Safe Ltd, Innovation House, Unit 18, Caker Stream Road, Mill Lane Industrial Estate, Alton, Hampshire, GU34 2QA, United Kingdom. They are sold under the Traffiglove® mark. Anit-odour test This test was conducted after the gloves had been subjected to 10 washes. This test method measured the amount of elemental odour markers (sulphur and nitrogen) compared to a control untreated glove. After the wash cycles, the examples returned a reading of 0 ppm for both sulphur and nitrogen markers whereas the untreated control glove provided a reading of 6 ppm sulphur and 8 ppm nitrogen. Generally, greater than 2 ppm of either of the nitrogen or sulphur markers would be identified as a malodourous by someone with normal olfactory capabilities. Levels of nitrogen were determined using the standard Kjeldal method consisting of three steps: digestion, distillation and titration. Concentrated sulphuric acid was used for digestion followed by addition of 35 % (w / v) sodium hydroxide in the distillation step. The distillate was back-titrated with 0.1 M hydrochloric acid. The percentage of nitrogen was determined using the formula: Percentage of nitrogen in the sample =1.4 V x N / W Where V = acid used in titration (ml), N = normality of standard acid and W = weight of sample (g). Sulphur levels were measured by determining the level of sulphur dioxide using the following method (but can alternatively be measured using other methods). A series of labelled 10 mL volumetric flasks were arranged. To each flask, 2 mL of 0.025 % hydrogen peroxide, aliquots of the test solution containing 3.57-64.26 pg / mL (0.1,0.2, 0.3,0.5, 0.7, 1.0, 1.2, 1.5, 1.8, or 2.0 mL) of sodium sulphite, 3 mL of 0.01 M ammonium metavanadate, and 3 mL of 2 M sulfuric acid were added. The solution in each flask was then diluted to the mark with water. The absorbance of each solution as well as the blank (the same test solution containing no sodium metabisulfite) was measured against water at 470 nm. This procedure provides a calibration curve which can be used to interpolate the amount of sulphur dioxide in a sample. The calibration graph was constructed by plotting the absorbance values of the (blank test) solutions against the concentration, pg / mL sulphur dioxide. To measure the sulphur dioxide in the samples, 40 g of the fabric sample was transferred into a 250 mL beaker. It was mixed well in water. The resulting solution was transferred into a 100 mL volumetric flask. About 4 mL of 0.1 M sodium hydroxide solution was added and diluted to the mark with water. From that, a 1 mL aliquot of this solution and a 0.2 mL 357 pg / mL sulphur dioxide solution per trial were examined for sulphur dioxide content by measuring the absorbance of the solution and interpolation with the calibration graph. The results are shown in table 1 (columns 4-5). This test shows that the antibacterial additive provides good anti-odour properties even over a high number of wash cycles for this type of product. Anti-bacterial test This test was to measure the antimicrobial efficacy of the antimicrobial additive. Results are shown for control samples and existing products in the market. The base test protocol was according to: ISO 20743 (Absorption method) and JIS L 1902. This method is usually used to determine the efficacy of antimicrobial-treated specimens. It is a rapid method for evaluating the efficacy of the product. Test protocol: A square fabric sample swatch of 1 cm x 1 cm is placed on an agar plate. A known concentration of the bacterial inoculum (~102) is spread using a pipette. The value of the bacterial inoculum placed is determined by the serial dilution method. The agar plates with the fabric sample are then incubated for 24 hrs at 37°C. The number of bacteria on the fabric sample is counted. The fabric sample is removed from the agar plate and checked for any bacterial growth under the fabric sample touching the agar plate and on the agar plate where the fabric sample was sitting earlier. The total count is the bacterial count of the culture, inoculated onto the fabric sample and determined by the dilution method, taken as the Ohr reading. The reading obtained after 24 hr is taken as the 24 hr reading. The reduction (%) in cfu (colony forming unit) / ml is calculated using the formula: Reduction (%) = [cfu / ml (at 0 hour) - cfu / ml (at 24 hour)] / (cfu / ml (at 0 hour)) (cfu / ml represents colony-forming units / millilitre) Test results were obtained after 10 washes for both gram positive and gram negative bacterial strains - staphylococcus aureus and Escherichia coli (E.Coli). This test method measures the reduction in bacterial growth in the presence of “ideal” growth conditions (temperature, moisture, nutrient and time) compared to an untreated control glove. The results are provided in table 2 (columns 2-3): After the ten wash cycles all of the exemplary gloves provide >99.9% reduction of both bacterial strains. The embodiments having the higher proportion of Reseda additive and binder seem to have less degradation of antibacterial effect over 10 washes. The degradation of antibacterial effect when comparing the PU and the NBR coated gloves is similar. This suggests that the wash durability of the antibacterial coating is not particularly dependent upon the type of glove coating used. Durable water repellence test Water repellence was measured after both 3 and 10 washes (in water) by using the “spray rating” test method AATCC 22. The wash method was according to ISO 6330:2021 - Textiles - Domestic washing and drying procedures for textile testing. Washing was done at 40°C with 2 Kg load and a commercially available washing detergent. This test method is a globally recognised method of assessing the water repellence performance of a water repellent fabric or article. It is a dynamic test method in which 250 ml of cold distilled water are poured onto the test specimen through a splitting nozzle (hence “spray”) and from a height of approximately 15 cm (the sample is at a 45° angle to the water flow). The results are a visual subjective grade where 100 = no wetting or sticking of any water droplets, 90 = slight sticking of small droplets of water (no wetting), 80 = slight wetting or sticking at the spray points and so on until 0 = total wetting of the face and reverse of the test specimen. The results are shown in table 3 below. The glove sample numbers correspond to those mentioned in table 2. The exemplary gloves achieved mostly grades 100 and 90+ in the 3 wash results and at the 10 wash stage the lowest result is grade 80. This test also included C6 fluorocarbon coating (Texfin FC6®) technology as a comparative example. This control example, at the 10 wash stage gave spray a rating grade 70, which is surprisingly lower than the plant-based water repellents according to the invention. This demonstrates that the invention provides a surprisingly enhanced water repellence over the prior art. It also shows that a better wash durability of the water repellence is obtained when compared to the fluorocarbon prior art. Antibacterial mixture number Wax paraffin / parts Unsaturated monomer phenylethylene; stearyl acrylate; propyl methacrylate / parts Solvent propylene glycol / parts Water deionised water Emulsifier octadearyl dimethyl ammonium chloride, and stearyl alcohol polyoxyethylene Vinyl-terminated polydialkylsiloxane vinyl-terminated polydimethylsiloxane Polymerization initiator 2,2’-Azodiisobutyramidine Dihydrochloride 1 17.0 1.5; 6.5; 0.0 4.5 68.0 2.2 none 0.3 2 12.0 1.5; 5.0; 0.0 4.5 68.0 2.2 6.5 0.3 3 12.0 1.5; 5.0; 3.0 4.5 65.0 2.2 6.5 0.3 4 12.0 1.5; 5.0; 3.0 4.5 60.0 2.2 6.5 0.3 Table 1 Table 2 (anti-Bacterial and anti-odour properties) Sample number (% values are wt% based on the weight of the fabric treated) Antimicrobial efficacy against Staphylococcus aureus / % after 0 washes Antimicrobial efficacy against Staphylococcus aureus / % after 10 washes Antimicrobial efficacy against Escherichia coli / % after 0 washes Antimicrobial efficacy against Escherichia coli / % after 10 washes Nitrogen / ppm Sulphur / ppm Control (untreated glove) Not applicable Not applicable Not applicable Not applicable 8 6 1. TG5360 PU glove + 1% Resefin OE + 10% Jintexguard BIO DWR 2.0 99.996 99.923 99.994 99.919 0 0 2. TG5360 PU glove + 1.5% Resefin OE + 15% Jintexguard BIO DWR 2.0 99.998 99.939 99.996 99.932 0 0 3. TG5360 NBR glove + 1% Resefin OE + 10% Jintexguard BIO DWR 2.0 99.996 99.915 99.995 99.916 0 0 4. TG5360 NBR glove +1.5% Resefin OE + 15% Jintexguard BIO DWR 2.0 99.997 99.937 99.997 99.936 0 0 Table 3 (Wash durability of water repellence) Glove sample number Polymer Reseda additive wt% Jintex 2.0 DWR wt% Initial spray rating Spray rating after 3 washes Spray rating after 10 washes Comparative example (Texfin FC6 fluorocarbon treated glove) 0.0 0.0 100- 80 - 70 (control) PU 0.0 0.0 111^0111 1111110111111 1 PU 1.0 10 100- 100 - 90 + 2 PU 1.5 15 100- 100 - 90 + (control) NBR 0.0 0.0 0 0 0 3 NBR 1.0 10 90 + 90 80 4 NBR 1.5 15 100- 90 90

Claims

31 10 251. A method of forming an article comprising the steps of;i) contacting the article with an antibacterial composition which comprises a micellar solution, antibacterial compounds and a binder, wherein the micellar solution comprises a saponin compound,ii) drying the article, andiii) contacting the article with a water repellent composition.

2. A method according to claim 1 wherein the water repellent composition comprises a wax, an unsaturated monomer, a solvent, and an emulsifier, which are polymerized.

3. A method according to any preceding claim wherein the binder comprises polyurethane.

4. A method according any preceding claim wherein the article comprises a polymer layer and wherein the polymer is selected from one or more of nitrile butadiene rubber, latex, polyurea, polyurethane, neoprene and silicon.

5. A method according to claim 4 wherein the polymer layer comprises nitrile or latex or a combination thereof and the method further comprises a step of contacting the article with a coagulant before step i).

6. A method according to claim 4 wherein the polymer layer comprises nitrile or latex or a combination thereof and the method further comprises a step of contacting the article with a post-coagulant after step i).

7. A method according to any preceding claim wherein the water repellent composition is polymerized using an initiator.31 10 258. A method according to any preceding claim wherein the antibacterial compounds, the compounds forming micelles in the micellar solution, or the water repellent composition comprise molecules which have been extracted from a plant or plants.

9. A method according to any preceding claim wherein the amount of the antibacterial additive is greater than 1 wt%, relative to the weight of the article in step i).

10. A method according to any of claims 1 -8 wherein the amount of the antibacterial additive is between 1-3 wt%, relative to the weight of the article in step i).

11. A method according to any preceding claim wherein the minimum amount of the binder is 0.5 wt% relative to the weight of the article in step i).

12. A method according to any preceding claim wherein the solution strength of water repellent composition is 10% or greater.

13. A method according to any preceding claim wherein the antibacterial composition is provided as a mixture with a liquid polymer in step i).

14. A method according to any of claims 1-12 wherein the article is dipped into a liquid polymer after step ii).

15. A method according to any preceding claim wherein the article is a glove.

16. A method according to claim 15 wherein the glove is a polymer dipped glove in which the polymer is disposed on at least part of the outside surface of a fabric layer.

17. A glove obtainable by the method of any preceding claim.

18. A glove comprising a fabric portion and an outer layer, which outer layer comprises a first polymer on the outside of the fabric portion,wherein the outer layer comprises a surface portion and a sub-surface portion, andwherein the fabric portion and the surface portion of the outer layer both comprise a dried micellar solution, antibacterial compounds, binder and a water repellent composition.

19. A glove according to claim 18 wherein the sub-surface portion of the outer layer contains substantially none of the dried micellar solution, antibacterial compounds, binder nor water repellent composition.31 10 25

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