WO2025248121A1 - Antimicrobial textiles - Google Patents

Abstract

The present disclosure provides a method of treating a fibrous textile surface and the fibrous textile obtained thereby.

Description

ANTIMICROBIAL TEXTILES

Cross-Reference to Related Applications: this application claims the benefit of GB Application No. 2407695.2, filed May 30, 2024, and U.S. Provisional Application No. 63/718,263, filed November 8, 2024, the content of each of which is incorporated by reference in its entirety.

The present invention relates to textiles that have antibacterial, antifungal and/or antiviral properties. In particular, these properties are intrinsic to the material by virtue of the manufacturing process which includes treatment with a formulation that imparts antibacterial, antifungal and/or antiviral properties. The invention has particular application to semi-synthetic (i.e. viscose) and natural cellulosic textiles which contain hydroxyl (-OH) groups such as cotton.

Treatment of textiles or fabrics with natural antimicrobial agents dates back to ancient times, but antimicrobial textiles have gained considerable attention recently because of their potential to mitigate infection transmission. Antimicrobial textiles can be termed based on their specificity against microbes, i.e. antibacterial, antifungal and/or antiviral, but may also be active against bacteria, fungi and viruses simultaneously. Antimicrobial textiles are functionally active textiles, which may kill the microorganisms or inhibit their growth. Such antimicrobial textiles are used in a variety of applications ranging from households to commercial including air filters, food packaging, health care, hygiene, medical, sportswear, storage, ventilation and water purification systems. There are also noticeable unfulfilled requirements for odor control, which is another expanding research area in this field.

The most conventional way to reduce microbial load from a textile is by continuous laundering. However, this is not always effective or possible. In addition, laundering does not always kill microbes, and it has been evidenced that bacteria can persist in washing machines and recolonise textiles (Dirk P. Bockrmihl et cd.. Microbial cell, 2019 Jul 1; 6(7): 299-306). Another way to reduce the transmission of microbial infection from one person to others is by developing antimicrobial textiles. Similarly, antimicrobial textiles may also be useful in place of non-plastic bags and food packaging where readily degradable material is safer for the environment. Despite advances in recent years, the share of antimicrobial textiles in the overall global textile market remains modest at 1.35%. This can be largely attributed to the prevalent use of antimicrobial textiles that rely on heavy metal ions. These products, while being less effective, also incur significant costs and pose environmental concerns.

Nanoparticle-based coatings are quite common in both natural, as well as synthetic, textiles. In recent years, a growing amount of evidence has indicated that silver nanoparticles (AgNPs) exhibit toxicity to the environment and present significant risks to human and animal health. Besides silver, other metals and metal oxide nanoparticles including titanium, tin, zinc, gold and copper have also been applied on different natural, as well as synthetic, textiles. Agglomeration prevention, desired morphology and uniform size of nanoparticles have always been challenging in nanoparticle-related studies and capping with ligands is generally used to overcome such issues. Cellulose-based fabric requires pre-activation or pre-treatment to attain efficient stability of the nanoparticles on the surface.

Other antimicrobial fabric treatments include plasma treatment, halogens, graphene, and chitosan, as well as natural extracts such as curcumin, Manuka honey, and essential oils, including thyme, oregano, eugenol, carvacrol, allyl isothiocyanate, geraniol, limonene, linalool, and thymol. The integration of natural ingredients especially essential oils into various materials, including textiles, poses a challenge due to the inherently low thermal stability of these compounds which restricts their utilization within the current manufacturing process conditions. Plasma treatment provides a chemical-free method but is not easily incorporated into existing textile production lines.

Natural fibers, such as cotton, mainly consist of cellulose fibers and are known for being breathable and soft, making them widely used for textile production. The breathability of cotton fabrics allows for air circulation, moisture evaporation, and heat dissipation, creating an environment that is less conducive to the growth and proliferation of microorganisms. However, such properties may not affect a wide range of microbes and so has a narrow spectrum of effectiveness. Synthetic fibers including acrylic, nylon, polyester, polypropylene and tetrafluoroethylene may also have some biostatic properties, which can further be enhanced through the treatment of antimicrobial compounds.

Antimicrobial compounds can be integrated into fabric using different methods and techniques and their effectiveness and incorporation also depends on the chemical and physical properties of the yarns, including the diameter of the yams, weaving/knitting construction, thickness of the fabric, polymeric content of the fabric, and processing conditions including the pre-treatment, dyeing/printing, and finishing of the fabric. Antimicrobial treatment may also be applied to the fibers once twisted into yarns. However, it is speculated that because of the forces that yarns are exposed to during fabric production, especially weaving, as well as the pretreatment for all types of fabrics both knitted and woven, yams will most likely lose most of the antimicrobial activity during processing. Antimicrobial treatment of a knitted, woven, nonwoven or bonded fabric is preferred to allow a broad range of antimicrobial attributes and be applied to different fabrics of choice. Most of the antimicrobial agents used in the textile industry use a controlled release or leaching mechanism in the presence of moisture. The leaching action leads to the gradual decrease in the active substance. However, in some circumstances, a non-leaching mechanism may be required.

Additives can be introduced directly into the synthetic fibers during synthesis by embedding into the fiber during extrusion spinning, or by treating the natural yams once they are manufactured, through dip coating, spray coating, exhaust, or by introducing into the spin finish for synthetic fibers. In the case of nonwoven products, antimicrobials can be incorporated either during the bonding or during finishing processes. On the other hand, they can be applied to textile fabrics by a conventional coating or impregnation process, such as padding and exhaustion. For example, knitted or woven textiles are typically treated through a pad-dry-cure and exhaust method.

While synthetic chemicals and metal nanoparticle-based antimicrobial textiles are effective, they also seem to be a threat toward damaging the environment as there is very limited information available about the exact impact of chemicals that can leach into the environment. Accordingly, it is against this background that the present invention has been devised.

In one aspect, the present invention encompasses a novel finishing formulation with which cellulosic materials, including cotton fabrics, can be treated with environmentally friendly, safe, efficacious and cost-effective materials using a widely used technique in textile manufacturing known as pad-dry-cure process.

Specifically, the present invention resides in an antimicrobial composition for treating a fibrous textile, the composition comprising: one or more organic acids selected from a carboxylic acid, a polycarboxylic acid, or an anhydride; a wetting agent; a solvent; and optionally a catalyzer, wherein the fibrous textile includes cellulose, and wherein the optional catalyzer when present catalyzes a reaction between the cellulose in the textile and the one or more organic acid. In embodiments, the organic acid is a polycarboxylic acid or an anhydride (e.g., cyclic anhydride)

For the avoidance of doubt, the term “antimicrobial” encompasses bacteria, fungi and viruses. In the composition of the present invention, it is the organic acid that is the active and imparts antimicrobial properties to the composition.

The definition of “textile” is any material such as yarns or surfaces made of interlacing fibers/yarns, including knitted or woven fabric, nonwoven materials, and papers. A textile is a yam or surface made from yams such as staple yarn or filament yam or thread. Textiles are created by processing yarns by weaving, knitting, or nonwoven methods typically used to manufacture goods such as clothing and bedding, or any type of technical textiles including but not limited to plastic, industrial, agricultural or medical fabric.

Fabrics are woven and knitted, as well as non-woven materials. Fabrics made of yams connect to each other with an intersecting and winding relationship. Common examples of non-woven fabric include teabag paper, fiber paper and wet wipes. A fabric is typically an “ingredient” mixed with other materials, creating a finished product. Fibrous fabrics are wovens, knits, or nonwovens, while non-fibrous fabrics include plastic films, rubber sheets, or metal foil. Unique structures such as paper, cardboard and leather can also be classified as fibrous fabrics.

In the context of the present invention the term “textile” encompasses material, cloth, fabric, a woven material or fabric, a non-woven material or fabric, a bonded material or fabric, material or fabric resembling woven cloth, a knitted material or fabric.

The fibrous textile of the present invention is a fabric, material, textile or papers and cardboard that contains, includes, is, or is derived from cellulose. It will be appreciated that the cellulose may be natural, such as cotton, flax (linen), hemp, jute and ramie, or may be a semi-synthetic that either is or includes natural cellulosic yarns. Examples of human-made cellulosic textiles include viscose (rayon), cellulose acetate, cellulose triacetate, lyocell and modal. Yams or fabrics of natural cellulose, semi-synthetic cellulose, or blends of both natural or semi-synthetic cellulose, blends of natural cellulose and synthetic materials including but are not limited to polyesters including polyethylene terephthalate, nylons such as nylon 6, nylon 6.6, acrylics such as polyacrylonitrile, polyurethane, blends of semi-synthetic cellulose and above-mentioned synthetic materials, as well as the blends of natural cellulose, semi-synthetic cellulose, and synthetic materials are also encompassed by the term.

Cellulose is a straight chain polymer derived from D-glucose units, which condense through P(1 — >4)-glycosidic bonds. No coiling or branching occurs, and the molecule adopts an extended and rather stiff rod-like conformation, aided by the equatorial conformation of the glucose residues. The multiple hydroxyl groups on the glucose from one chain form hydrogen bonds with oxygen atoms on the same or on a neighbor chain, holding the chains firmly together side-by- side and forming microfibrils that have a high tensile strength. As discussed herein, the hydroxyl groups (“OH) of cellulose can be partially or fully reacted with various reagents to provide derivatives with useful antimicrobial properties.

In the present invention, and without being limited by theory, the -OH groups on cellulose react with the one or more organic acid in the composition to produce a modified fibrous textile. In embodiments when a polycarboxylic acid or cyclic anhydride is present in the composition, the reaction results in the presence of free carboxylic acids on the textile surface and produces a chemical fixation of the textile fibers with the treatment. The resulting fibrous textile material has a lower pH and antimicrobial properties. When polycarboxylic acids or cyclic anhydride are used, some poly carboxylic acids may cross-link adjacent glucose residues (by reacting with -OH groups on adjacent glucose residues), while other poly carboxylic acids will present one or more free carboxylic acids on the textile surface In embodiments, about 5% to about 95% of the hydroxyl groups on the surface of the fibrous textile treated by the method or composition disclosed herein are modified by the one or more polycarboxylic acid or cyclic anhydride. In embodiments, at least about 5%, at least about 10%, at least about 15%, at least about 20%, at least about 25%, at least about 30%, at least about 35%, at least about 40%, at least about 45%, at least about 50%, at least about 55%, at least about 60%, at least about 65%, at least about 70%, at least about 75%, at least about 80%, at least about 85%, at least about 90%, or at least about 95% of the hydroxyl groups are modified, including all values and ranges therein.

The modifications to the fibrous textile may be measured using FTIR. In embodiments, the fibrous textile comprises an increase in absorbance at about 1725-1735 cm’¹, as measured using FTIR. Carboxylic acid peaks in FTIR are detected between 1725-1735 cm’¹, such as at 1728 cm’¹ or 1729 cm’¹. In embodiments, the fibrous textile comprises an increase in absorbance of about 5% to about 100% at about 1725-1735 cm’¹, as measured using FTIR. For example, the absorbance may increase by about 5%, about 10%, about 15%, about 20%, about 25%, about 30%, about 35%, about 40%, about 45%, about 50%, about 55%, about 60%, about 65%, about 70%, about 75%, about 80%, about 85%, about 90%, about 95%, or about 100%, including all values and ranges therein. In embodiments, the fibrous textile comprises an increase in absorbance of at least about 5%, at least about 10%, at least about 15%, at least about 20%, at least about 25%, at least about 30%, at least about 35%, at least about 40%, at least about 45%, at least about 50%, at least about 55%, at least about 60%, at least about 65%, at least about 70%, at least about 75%, at least about 80%, at least about 85%, at least about 90%, or at least about 95% at about 1725-1735 cm’¹, as measured using FTIR, including all values and ranges therein. In embodiments, absorbance is measured at 1727-1730 cm’¹. In embodiments, absorbance is measured at 1728 or 1729 cm’¹. The increase is compared to the same fibrous textile before treatment with the composition disclosed herein that provides antimicrobial activity.

An organic acid is an organic compound with acidic properties (e.g., a hydrogen bond donor). The most common organic acids are carboxylic acids, whose acidity is associated with their carboxyl group -COOH. In the context of the present invention, the organic acid should have at least two of the acid functionalities, namely i) to produce chemical fixation with hydroxyl groups of cellulose and ii) rendering a free carboxylic acid on the surface of the cellulose.

The organic acid(s) impart(s) antimicrobial properties to the composition. Without being bound by theory, the mechanism of action is based on acidifying the intracellular environment. This disrupts normal physiology and negatively impacts purine bases and denatures essential enzymes decreasing bacteria viability. While some bacteria can survive extreme pH conditions, many bacteria are neutrophiles with minimal tolerance to wide external pH changes. Examples of those bacteria are Escherichia coli, Staphylococcus aureus, Salmonella spp., Clostridium, perfringens, Listeria monocytogenes, and Campylobacter species.

As a result, the organic acid has two functions in the composition, namely, to provide an antimicrobial property and to bind the composition to cellulose fibers in a textile treated with the composition. The latter enables the composition to endure washing so the textile retains its antimicrobial property.

While carboxylic acids and polycarboxylic acids are well known entities, for the avoidance of doubt, examples include: tartaric acid, citric acid, formic acid, acetic acid, propionic acid, stearic acid, malic acid, amino acids, fatty acids, 1,2,3,4-Butanetetracarboxylic acid, pyromellitic acid, Benzene tricarboxylic acid, EDTA, maleic acid, itaconic acid, succinic acid, malonic acid, glutaric acid, 1,4 cyclohexane dicarboxylic acid, adipic acid, aconitic acid, trimesic acid, terephthalic acid. Suitable polycarboxylic acids include poly acrylic acid, hyaluronic acid. Mono metal salts of carboxylic acids, such as sodium citrate, are also encompassed where appropriate. In embodiments, the organic acid is a polycarboxylic acid. In embodiments, the polycarboxylic acid is polycarboxylic acid or cyclic anhydride is selected from tartaric acid, citric acid, propionic enanthic acid, malic acid, one or more amino acids, 1,2,3,4-butanetetracarboxylic acid, pyromellitic acid, benzene tricarboxylic acid, EDTA, maleic acid, itaconic acid, succinic acid, malonic acid, glutaric acid, 1,4 cyclohexane dicarboxylic acid, adipic acid, aconitic acid, trimesic acid, terephthalic acid, poly acrylic acid, and hyaluronic acid.

In one example, the organic acid is tartaric acid. In another example, the organic acid is citric acid. A total amount of between about 0.1% w/v and about 30% w/v of organic acid has been found to be suitable.

It will be appreciated that cyclic anhydrides may also be used as an organic acid because such compounds are converted to carboxylic acids in water. Suitable cyclic anhydrides include citric anhydride, maleic anhydride, pyromellitic anhydride, Malonic anhydride, 1,2,4- benzenetricarboxylic anhydride.

In one embodiment, the composition comprises two or more organic acids. The use of more than one organic acid enhances the antimicrobial effect of the composition, either cumulatively or synergistically. For example, one organic acid may act as a chelator while a second organic acid in the formulation may act in a different way, either chemically or in effect on one or more particular microbes. In one example, the organic acids tartaric acid and citric acid have been found to be suitable.

In a specific example, amounts of 3.8% (w/v) tartaric acid and 4.8% (w/v) citric acid have been found to be particularly effective.

Due to the residual carboxylic acid after treating the textile surface, the fibrous textile surface possesses an acidic pH.

In one embodiment, the fibrous textile has a surface pH of about 2.5 to about 6.5. In one embodiment, the fibrous textile has a surface pH of about 2.5 to about 6.0. In one embodiment, the fibrous textile has a surface pH of about 2.5 to about 5.5. In one embodiment, the fibrous textile has a surface pH of about 2.5 to about 5.0. In one embodiment, the fibrous textile has a surface pH of about 2.5 to about 4.5. In one embodiment, the fibrous textile has a surface pH of about 2.5 to about 4.0. In one embodiment, the fibrous textile has a surface pH of about 2.5 to about 3.5. In one embodiment, the fibrous textile has a surface pH of about 2.5 to about 3.0. In one embodiment, the fibrous textile has a surface pH of about 3.0 to about 5.5. In one embodiment, the fibrous textile has a surface pH of about 3.0 to about 5.0. In one embodiment, the fibrous textile has a surface pH of about 3.0 to about 4.5. In one embodiment, the fibrous textile has a surface pH of about 3.0 to about 4.0. In one embodiment, the fibrous textile has a surface pH of about 3.0 to about 3.5. In one embodiment, the fibrous textile has a surface pH of about 3.5 to about 5.5. In one embodiment, the fibrous textile has a surface pH of about 3.5 to about 5.0. In one embodiment, the fibrous textile has a surface pH of about 3.5 to about 4.5. In one embodiment, the fibrous textile has a surface pH of about 3.5 to about 4.0. In one embodiment, the fibrous textile has a surface pH of about 4.0 to about 5.5. In one embodiment, the fibrous textile has a surface pH of about 4.0 to about 5.0. In one embodiment, the fibrous textile has a surface pH of about 4.0 to about 4.5. In one embodiment, the fibrous textile has a surface pH of about 4.5 to about 5.5. In one embodiment, the fibrous textile has a surface pH of about 4.5 to about 5.0. In embodiments the fibrous textile has a pH of about 2.5, 2.6, 2.7, 2.8, 2.9, 3.0, 3.1, 3.2, 3.3, 3.4, 3.5, 3.6, 3.7, 3.8, 3.9, 4.0, 4.1, 4.2, 4.3, 4.4, 4.5, 4.6, 4.7, 4.8, 4.9, 5.0, 5.1, 5.2, 5.3, 5.4, 5.5, 5.6, 5.7, 5.8, 5.9. 6.0. 6.1, 6.2, 6.3, 6.4, or 6.5, including all values and ranges therein. In embodiments, pH is measured according to IS03071 :2020.

In embodiments, a catalyzer is used to modify the fibrous textile material disclosed herein. Catalyzers are used to increase the rate of crosslinking reaction on cellulose molecules. However, in the present invention, the catalyzer catalyzes the functionalization of hydroxyl groups on cellulose with the organic acid. For the avoidance of doubt, a catalyzer causes a reaction to happen, and is also consumed or changed in the process. Suitable catalyzers in the context of the present invention are phosphates and phosphites, particular examples of which include sodium hypophosphite, di sodium hydrogen phosphite, mono sodium phosphate, disodium phosphate, and tetrasodium pyrophosphate.

In one example, an amount of between about 0.05% (w/v) and up to about 10% (w/v), between 0.1% (w/v) and 7% (w/v), between about 0.5 %(w/v) and about 4 % (w/v), or between about 2% (w/v) and about 4% (w/v) of catalyzer has been found to be suitable. In a specific example, sodium hypophosphite at a concentration of 2.9% (w/v) has been found to be effective.

The wetting agent in the composition of the invention is a surfactant which ensures that the composition spreads across the surface and penetrates the textile fibers evenly and deeply. For water-based compositions, the wetting agent reduces the surface tension of water and thus helps water-based solutions to spread, thereby enhancing coverage of the textile with the composition.

Any wetting agent (anionic, cationic, amphoteric, or non-ionic) may be used providing the agent is and remains soluble in the presence of the other components of the composition. Examples include Pluronics such as Pluronic F127, Tweens such as Tween 80, sodium dodecyl benzene sulphonate, acacia, pectin, sodium lauryl sulphate, polysorbate 80, Dimethyl sulphoxide, purified water, ethyl alcohol, poloxamers, ammonium lauryl sulphate, sodium laureth sulphate, sodium lauryl sarcosinate, sodium myreth sulphate, sodium pareth sulphate, sodium stearate, sodium lauryl sulphate, a olefin sulphonate, and ammonium laureth sulphate.

In one example, the wetting agent may be present in the composition in an amount of between about 0.1% (w/v) and about 5% (w/v). In a specific example, 0.5% (w/v) Pluronic F127 has been found to be suitably effective.

The solvent in the composition acts to dissolve the constituent parts and may be aqueous, such as water, an organic solvent selected from an alcohol or a glycol, or a mixture thereof. In one embodiment, the solvent also acts as a diluent for the constituents.

It will be appreciated that the composition is acidic in its nature and that a solution that is too acidic risks dissolving cellulose and compromising the textile. As a result, an amount of a base or alkali, such as sodium hydroxide, may be added to the composition to reduce the acidity. It will be appreciated that the degree of likely damage to the textile and consequently the amount of neutralization will depend on both the acidity of the composition and the textile components. In some instances, no neutralization may be required, and/or the textile is able to withstand a composition having a pH of about 1.8. However, other textiles may benefit from having a composition that has a pH of nearer about 5. Accordingly, in embodiments, the composition has a pH of between about 1.5 and about 7, between about 2 and 5 or between about 2.2 and about 4. In embodiments the composition has a pH of about 1.5, 1.6, 1.7, 1.8, 1.9. 2.0, 2.1, 2.2, 2.3, 2.4, 2.5, 2.6, 2.7, 2.8, 2.9, 3.0, 3.1, 3.2, 3.3, 3.4, 3.5, 3.6, 3.7, 3.8, 3.9, 4.0, 4.1, 4.2, 4.3, 4.4, 4.5, 4.6, 4.7, 4.8, 4.9, 5.0, 5.1, 5.2, 5.3, 5.4, 5.5, 5.6, 5.7, 5.8, 5.9. 6.0. 6.1, 6.2, 6.3, 6.4, 6.5, 6.6, 6.7, 6.8, 6.9, or 7.0 including all values and ranges therein.

In an embodiment, to treat cotton, the pH of the composition can be adjusted to range from about 3.0 to about 6.5. In a particular example, where tartaric and citric acids are the organic acids, an amount of between about 1% (w/v) to about 6% (w/v) sodium hydroxide to produce a composition with a pH of about 3.5 has been found suitable to treat cotton. It has been noted that increasing neutralization maintains the mechanical properties of a textile but reduces the antimicrobial effect of the composition.

In one embodiment, the composition comprises of: Tartaric acid, Citric acid, Pluronic F127 or Sodium Dodecyl Benzene Sulphonate (SDBS), Sodium hypophosphite, Water, and Sodium hydroxide. In one embodiment, the composition consists of: Tartaric acid, Citric acid, Pluronic F127 or Sodium Dodecyl Benzene Sulphonate (SDBS), Sodium hypophosphite, Water, and Sodium hydroxide.

In one embodiment, the antimicrobial composition of the present invention comprises: Tartaric acid about 0.1% (w/v) to about 30% (w/v); Citric acid about 0.1% (w/v) to about 30% (w/v);

Pluronic F127 or Sodium Dodecyl Benzene Sulphonate (SDBS) about 0.1% (w/v) to about 5% (w/v);

Sodium hypophosphite about 0.05% (w/v) to about 10% (w/v); and Sodium hydroxide about 1% (w/v) to about 6% (w/v) and optionally water.

In one embodiment, a batch is provided comprising antimicrobial composition comprising:

Tartaric acid about 0.1% (w/v) to about 30% (w/v); Citric acid about 0.1% (w/v) to about 30% (w/v);

Pluronic F127 or Sodium Dodecyl Benzene Sulphonate (SDBS) about 0.1% (w/v) to about 5% (w/v);

Sodium hypophosphite about 0.05% (w/v) to about 10% (w/v); and

Sodium hydroxide about 1% (w/v) to about 6% (w/v) and optionally water; and

Fibrous textile material comprising cellulose (e.g., cotton).

In one embodiment, the antimicrobial composition of the present invention consists of:

Tartaric acid about 0.1% (w/v) to about 30% (w/v);

Citric acid about 0.1% (w/v) to about 30% (w/v);

Pluronic F127 or Sodium Dodecyl Benzene Sulphonate (SDBS) about 0.1% (w/v) to about 5% (w/v);

Sodium hypophosphite about 0.05% (w/v) to about 10% (w/v); and

Sodium hydroxide about 1% (w/v) to about 6% (w/v) and optionally water.

In a specific embodiment, the composition consists of: Tartaric acid, Citric acid, Pluronic F 127 or Sodium Dodecyl Benzene Sulphonate (SDBS), Sodium hypophosphite, Water, and Sodium hydroxide, and has a pH of 3.5.

In a particularly specific embodiment, the composition consists of Tartaric acid 3.8% (w/v), Citric acid 4.8% (w/v), Pluronic F127 or Sodium Dodecyl Benzene Sulphonate (SDBS) 0.50% (w/v), Sodium hypophosphite 2.9% (w/v), and Sodium hydroxide 2-6% (w/v).

In a particularly specific embodiment, the composition consists of Tartaric acid 3.8% (w/v), Citric acid 4.8% (w/v), Pluronic F127 or Sodium Dodecyl Benzene Sulphonate (SDBS) 0.50% (w/v), Sodium hypophosphite 2.9% (w/v), Sodium hydroxide 2-6% (w/v), and water.

It will also be appreciated that the textile may be any fabric or material that is suitable for use in the likes of clothing, apparel and uniforms, for commercial use including carpets, coverings for seats, dusting cloths, and tents, in healthcare and laboratories for bandages, theater and working scrubs, masks and lab coats, and for household use for articles including bedding, curtains, covers, towels and mops.

The composition of the invention is to be used to treat textiles after pre-treatment of woven, knitted, or non-woven textile fabrics and after any dyeing or printing. This ensures that the textile is in a condition to absorb chemicals, including the treatment of the present invention. The antimicrobial finishing treatment may be applied before, with or after additional treatments, where applicable, such as softening or stiffening, crease or wrinkle resistance, flame retardance, water retardance, water repellence, stain and/or oil repellence, antistatic, and/or antipilling treatments. Ideally the treatment should be in the later stages of textile finishing so the treatment and its coverage is not hindered by other chemicals and treatments.

In embodiments, the fibrous textile is treated using an exhaustion process. Textile exhaustion refers to a batch dyeing and finishing treatment method that involves the transfer of the chemicals from the bath to a textile material. In this process, the fibrous textile material is placed in a machine and brought into equilibrium with a solution containing finishing agents and the composition described herein (e.g., comprising the one or more polycarboxylic acid or cyclic anhydride, a wetting agent, and a catalyzer) over a period of time.

In one aspect, the disclosure provides antimicrobial compositions for treating a fibrous textile, the composition comprising: one or more organic acid selected from a carboxylic acid, a polycarboxylic acid, and a cyclic anhydride; a wetting agent; and a solvent, wherein the fibrous textile includes cellulose. In embodiments, the composition comprises two or more organic acids. In embodiments, the one or more organic acid is present in the composition in a range of between about 0.1% (w/v) and about 30% (w/v).

In embodiments, the one or more organic acid is selected from one or more of: tartaric acid, citric acid, formic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, enanthic acid, caprylic acid, pelargonic acid, capric acid, undecylic acid, lauric acid, tridecyclic, myristic acid, pentadecyclic acid, palmitic acid, margaric acid, stearic acid, nonadecyclic acid, arachidic acid, malic acid, amino acids, fatty acids, 1,2,3,4-Butanetetracarboxylic acid, Pyromellitic acid, Benzene tricarboxylic acid, EDTA, Maleic acid, Itaconic acid, Succinic acid, malonic acid, glutaric acid, 1,4 cyclohexane dicarboxylic acid, adipic acid, aconitic acid, trimesic acid, terephthalic acid, poly acrylic acid, and hyaluronic acid.

In embodiments, the composition comprises a catalyzer. In embodiments, the catalyzer catalyzes a reaction between the cellulose in the textile and the one or more organic acid.

In embodiments, the catalyzer comprises a phosphate and/or a phosphite. In embodiments, the catalyzer is selected from: sodium hypophosphite, Disodium hydrogen phosphite, mono sodium phosphate, disodium phosphate, and tetrasodium pyrophosphate.

In embodiments, the amount of catalyzer is between about 0.05% (w/v) and about 10% (w/v). In embodiments, the amount of catalyzer is between about 2% (w/v) and about 4% (w/v).

In embodiments, the wetting agent is selected from Pluronics such as Pluronic F127, Tweens such as Tween 80, Tween 20, sodium dodecyl benzene sulphonate, acacia, pectin, sodium lauryl sulphate, polysorbate 80, Dimethyl sulphoxide, purified water, ethyl alcohol, poloxamers, ammonium lauryl sulphate, sodium laureth sulphate, sodium lauryl sarcosinate, sodium myreth sulphate, sodium pareth sulphate, sodium stearate, sodium lauryl sulphate, a olefin sulphonate, and ammonium laureth sulphate.

In embodiments, the wetting agent is present in the composition in an amount of between about 0.1% (w/v) and about 5% (w/v).

In embodiments, the solvent is aqueous, organic or a mixture thereof, wherein the organic solvent is selected from an alcohol or a glycol.

In embodiments, the composition further comprises an alkali.

In embodiments, the composition has a pH of between about 1.5 and about 7.

In embodiments, the composition comprises or consists of: Tartaric acid; Citric acid; Pluronic F127 or Sodium Dodecyl Benzene Sulphonate (SDBS); Sodium hypophosphite; Water; and Sodium hydroxide. In embodiments, the composition comprises or consists of: Tartaric acid about 0.1% (w/v) to about 30% (w/v); Citric acid about 0.1% (w/v) to about 30% (w/v); Pluronic F127 or Sodium Dodecyl Benzene Sulphonate (SDBS) about 0.1% (w/v) to about 5% (w/v); Sodium hypophosphite about 0.05% (w/v) to about 10% (w/v)); and Sodium hydroxide about 1% (w/v) to about 6% (w/v).

In one aspect, the disclosure provides methods of treating a fibrous textile comprising cellulose, the method comprises treating the fibrous textile with a composition comprising one or more polycarboxylic acid or cyclic anhydride; a wetting agent; and a catalyzer for catalyzing esterification reaction between one or more hydroxyl groups on the cellulose with the polycarboxylic acid or cyclic anhydride, thereby conferring antimicrobial activity on the fibrous textile.

In embodiments, after the treating, the fibrous textile has a pH of about 2.5 to about 6.5, as measured by a ISO3071 :2020.

In embodiments, the fiber is a natural fiber or a semi-synthetic fiber. In embodiments, the fiber is a natural fiber, wherein the natural fiber is cotton fiber, linen fiber, flax fiber, or hemp fiber; or the fiber is a semi-synthetic fiber, wherein the semi -synthetic fiber is viscose fiber, lyocell fiber, or modal fiber; or the fiber is a blend of a natural fiber and a semi-synthetic fiber. In embodiments, the fiber is a natural fiber. In embodiments, the natural fiber is cotton fiber.

In embodiments, the one or more polycarboxylic acid or cyclic anhydride is selected from tartaric acid, citric acid, propionic enanthic acid, malic acid, one or more amino acids, 1, 2,3,4- butanetetracarboxylic acid, pyromellitic acid, benzene tricarboxylic acid, EDTA, maleic acid, itaconic acid, succinic acid, malonic acid, glutaric acid, 1,4 cyclohexane dicarboxylic acid, adipic acid, aconitic acid, trimesic acid, terephthalic acid, poly acrylic acid, and hyaluronic acid. In embodiments, the one or more polycarboxylic acid or cyclic anhydride is selected from tartaric acid or citric acid.

In embodiments, the one or more polycarboxylic acid or cyclic anhydride is present in the composition in a range of between about 0.1% (w/v) and about 30% (w/v). In embodiments, the catalyzer comprises a phosphate and/or a phosphite. In embodiments, the catalyzer is selected from sodium hypophosphite, disodium hydrogen phosphite, mono sodium phosphate, disodium phosphate, and tetrasodium pyrophosphate.

In embodiments, the catalyzer is present in an amount of about 0.05% (w/v) to about 10% (w/v). In embodiments, the catalyzer is present in an amount of about 2% (w/v) to about 4% (w/v).

In embodiments, wetting agent is selected from Pluronics such as Pluronic F127, Tweens such as tween 80, tween 20, sodium dodecyl benzene sulphonate, acacia, pectin, sodium lauryl sulphate, polysorbate 80, dimethyl sulphoxide, purified water, ethyl alcohol, poloxamers, ammonium lauryl sulphate, sodium laureth sulphate, sodium lauryl sarcosinate, sodium myreth sulphate, sodium pareth sulphate, sodium stearate, sodium lauryl sulphate, a olefin sulphonate, and ammonium laureth sulphate.

In embodiments, the wetting agent is present in an amount of about 0.1% (w/v) to about 5% (w/v).

In embodiments, the composition further comprises a solvent. In embodiments, the solvent is an aqueous solvent or an organic solvent, or a mixture thereof. In embodiments, the organic solvent is an alcohol.

In embodiments, the composition further comprises a base. In embodiments, the base is an alkali base.

In embodiments, the composition has a pH of about 1.5 to about 7.

In embodiments, the composition comprises: tartaric acid; citric acid; Pluronic F127 or sodium dodecyl benzene sulphonate (SDBS); sodium hypophosphite; water; and sodium hydroxide.

In embodiments, the composition comprises: tartaric acid, present in an amount of about 0.1% (w/v) to about 30% (w/v); citric acid, present in an amount of about 0.1% (w/v) to about 30% (w/v); Pluronic Fl 27 or sodium dodecyl benzene sulphonate (SDBS), present in an amount of about 0.1% (w/v) to about 5% (w/v); sodium hypophosphite, present in an amount of about 0.05% (w/v) to about 10% (w/v); and sodium hydroxide, present at an amount of about 1% (w/v) to about 6% (w/v).

In one aspect, the disclosure provides fibrous textiles comprising cellulose treated by the method of the disclosure. In embodiments, the fibrous textile has antimicrobial properties. In embodiments, the fibrous textile kills at least 90% of bacteria, fungi and/or viruses within about 5 minutes of contacting the bacteria, fungi and/or viruses.

In one aspect, the disclosure provides fibrous textiles comprising cellulose treated by the method of the disclosure. In embodiments, at least one hydroxyl group on the cellulose is modified.

In one aspect, the disclosure provides fibrous textiles comprising cellulose treated by the method of the disclosure. In embodiments, about 5% to about 95% of the hydroxyl groups on the surface of the fibrous textile are modified by the one or more polycarboxylic acid or cyclic anhydride.

In embodiments, the fibrous textile comprises an increase in absorbance at about 1725-1735 cm’ ¹, as measured using FTIR.

In embodiments, the fibrous textile comprises an increase in absorbance of about 5% to about 100% at about 1725-1735 cm’¹, as measured using FTIR.

In embodiments, the fibrous textile has antimicrobial properties. In embodiments, the fibrous textile kills at least 90% of bacteria, fungi and/or viruses within about 5 minutes of contacting the bacteria, fungi and/or viruses.

In embodiments, the fibrous textile is clothing, a bag, carpet, a seat covering, cloth, bandage, mask, bedding, curtain, towel or mop. In embodiments, the clothing is a sock, a shirt, an undergarment, a pair of shorts, a pair of pants, a coat (e.g., lab coat), or an apron.

In embodiments, the fibrous textile is a non-woven fabric. In embodiments, the non-woven fabric is a paper product. In embodiments, the paper product is a teabag paper, a fiber paper, or a wet wipe. The invention will now be described further with reference to the following, non-limiting experiments and figures, in which:

Figure 1: A flow diagram illustrating a method of producing antimicrobial woven bed linen.

Figure 2: A bar chart showing the antibacterial activity of cotton fabrics treated with a composition of the invention before and after antimicrobial and softener treatments against S. aureus as an example of gram-positive bacteria.

Figure 3: A bar chart showing the antibacterial activity of cotton fabrics treated with a composition of the invention before and after antimicrobial and softener treatments against E. coli as an example of gram-negative bacteria.

Figure 4: A bar chart showing the antibacterial activity of cotton fabrics treated with a composition of the invention before and after washing against S. aureus as an example of grampositive bacteria.

Figure 5: A bar chart showing the antibacterial activity of cotton fabrics treated with a composition of the invention before and after washing against E. coli as an example of gramnegative bacteria.

Figure 6: A bar chart showing the effect of contact time on antibacterial activity against S. aureus for a cotton fabric treated with a composition of the invention. For each time point, the left-side bar represents the uncoated control, and the right-side bar represents base formulation. Figure 7: A bar chart showing the effect of contact time on antibacterial activity against E. coli for a cotton fabric treated with a composition of the invention. For each time point, the left-side bar represents the uncoated control, and the right-side bar represents base formulation.

Figure 8: A bar chart showing the antifungal activity of a cotton fabric treated with a composition of the invention against Aspergillus brasiliensis and Candida albicans.

Figure 9: FTIR of Ranforce woven 100% cotton fabric untreated and treated with a composition of the disclosure having a pH of 3.5.

Figure 10: FTIR of Satin woven 100% cotton fabric untreated and treated with a composition disclosure herein having a pH of 3.5.

Figure 11: FTIR of Ranforce woven 100% cotton fabric untreated and treated with a composition of the disclosure having a pH of 2, and subjected to multiple washes. Figure 12: FTIR of Ranforce woven 100% cotton fabric treated with a composition of the disclosure having a pH of 2 before and after up to 50x wash according to ASTM 3162-18.

METHODS

The antimicrobial formulation tested had the following components:

Antimicrobial agent 1, Antimicrobial agent 2, catalyst, and wetting agent dissolved in 1 L of water. pH was then adjusted to desired value by adding a base, e.g. NaOH.

Citric acid (47.9 g; antimicrobial agent), L-Tartaric acid (37.5 g; antimicrobial agent), Sodium hypophosphite monohydrate (29.1 g; catalyst) and Pluronic F127 (5 g; wetting agent) were mixed at ambient temperature in distilled water (1 L). Once dissolved, sodium hydroxide (NaOH ) was added to obtain a solution pH of 3.5.

The formulation solution was poured into the bath of a pad-dry-cure machine and a piece of fabric was passed through the solution at 3 m/min. Two types of fabrics (satin-woven optic white cotton fabric-pre-softener finish-134 gsm and Ranforce woven pigment printed cotton fabric-pre- softener finish- 120 gsm) were treated (Figure 1 Step 2).

The soaked fabric was passed through a mangle until the weight of the solution absorbed into the fabric was between 80 to 120% of the original fabric weight (termed “wet pickup”). The fabric was then dried in an oven at between 100 and 140°C for between 1 and 5 minutes, before being cured at between 170°C and 190°C for between 1 and 5 minutes (Figure 1 Step 3).

The cured fabric was then passed through water using a pad-dry-cure machine for rinsing (Figure 1 Step 4). This (optional) step ensures unreacted materials are removed and washed off.

Finally, the fabric was dried at 120°C, yielding an antimicrobial treated fabric (Figure 1 Step 5).

A commercially available softener solution was also applied (a standard process in cotton finishing factories). The softener solution was applied in a pad-dry-cure machine and the fabrics were then dried at between 120°C and 180°C for between 1 and 5 minutes in the oven, as recommended by manufacturer (Figure 1 Steps 6-7). Washing

Fabrics were washed up to fifty times using the ASTM 3162-18 method (“Standard Practice Measuring the Durability of Antibacterial Agents Applied to Textiles under Simulated Home Laundering Conditions”).

Microbiology

Antibacterial efficacy testing was conducted according to ISO 20743 (“Determination of antibacterial activity of textile products”) which evaluates antibacterial activity after 24-hours of contact. Test and control samples were tested with three replicates. This method was also modified for further in-house testing with shorter contact times, to show speed of efficacy. Here the bacteria inoculum concentration was higher, between 10⁷ CFU/ml and 10⁸ CFU/ml, to allow for higher log reduction in samples that show high antibacterial activity. Bacteria strains used for testing were Staphylococcus aureus NCTC10788 and Escherichia coli NCTC1224.

Antifungal testing was performed according to ISO 13629-2:2014 (Textiles - Determination of antifungal activity of textile products by plate count method) which evaluates antifungal activity after 48-hours of contact. Fungal strains used for testing were Aspergillus brasiliensis ATCC 16404 and Candida albicans ATCC 10231. Test and control samples were tested with six replicates.

EXPERIMENT 1

The aim of this experiment was to test the antibacterial properties of two different woven cotton fabrics treated with the antimicrobial formulation, before and after the addition of the softening treatment.

Samples:

The antimicrobial activity results of fabrics before treatment, after antimicrobial treatment, and after softener treatment are shown in Figure 2 and 3. Samples #3-4 exhibited around 5-6 logs of antibacterial activity against S. aureus and E. coli after antimicrobial treatment. In addition, these samples did not lose their activity after softener treatment (Samples #5-6).

EXPERIMENT 2

This following experiment aimed to investigate the durability of the antimicrobial treatment of the cotton fabric after laundering. Samples were washed 50 times, and the antibacterial activity was compared.

Samples:

The antibacterial activity results of the fabrics before and after washing are shown in Figures 4 and 5. The control sample did not show any antimicrobial activity. Sample #2 exhibited around 6 and 4 logs of antibacterial activity after antimicrobial treatment for S. aureus and E. coli, respectively. The antibacterial activity of the samples reduced to around 4 logs after 50 times washing, according to ASTM 3162-18 treatment (Sample #3), showing that the antimicrobial treatment is durable and resistant to washing.

EXPERIMENT 3

This experiment investigated the effect of contact time on antibacterial activity against S. aureus and E. coli. The test sample was post-printed ranforce woven cotton fabric which was treated with a composition with Citric acid 47.9g, L-Tartaric acid 37.5g, SDBS 5 g, and SHP 29.1 g.

As shown in Figures 6 and 7, the samples exhibited 4 logs of antibacterial activity in 5 minutes contact time and activity increased up to 6 logs in 2 hours for S. aureus. For E. coh. the samples showed 1 log of antibacterial activity starting from 30 minutes of contact time which increased to around 4 logs after 2 hours of contact time.

EXPERIMENT 4

This experiment tested the antifungal activity of a composition of the invention in accordance with ISO 13629-2:2014 (Textiles - Determination of antifungal activity of textile products by plate count method) using Aspergillus brasiliensis ATCC 16404 and Candida albicans ATCC 10231. The fabric tested was a post-printed ranforce woven cotton fabric which was treated with a composition including Citric acid 47.9g, L-Tartaric acid 37.5g, Sodium Dodecyl Benzene Sulphonate (SDBS) 5 g, sodium hypophosphite SHP 38.8 g.

Samples were inoculated with replicates (n=6, 0.4g per sample) and incubated for 48 hours at 30°C with >95% relative humidity. Log reduction (log CFU/ml) values of test samples were calculated and compared to the un-treated textile control.

As can be seen in Figure 8, the test samples showed fungistatic activity with full effect against the mold Aspergillus brasiliensis (4.1 log reduction) and yeast Candida albicans (5.47 log reduction).

Ensuring the optimal antimicrobial efficacy of textiles is contingent upon the efficient transport of active constituents to targeted microorganisms, achieved through either leaching or the nonleaching extermination of microorganisms upon surface contact. This invention belongs to the non-leaching category and focuses on a composition for the fixation of organic antimicrobial acids to hydroxyl groups in cellulose, emphasizing the sustained and affixed antimicrobial effects after up to fifty washing cycles. In addition, the composition is suitable for use with existing and widely used industrial production lines and so may be readily integrated into the commercial finishing of textiles. EXPERIMENT 5

This example measured the absorbance spectra of the fibrous textile comprising cellulose treated according to the disclosure. Fibrous textiles known as Satin and Ranforce woven 100% cotton fabric were treated with two types of compositions disclosed herein (e.g., comprising one or more poly carboxylic acid, wetting agent, and a catalyzer): (1) composition at pH 2 and (2) a composition at pH 3.5 (partial neutralization performed before treatment). The modified fibrous textile was analyzed using FTIR. Regarding the composition at pH 2, FTIR indicated detected ester and carboxylic acid functional groups. Regarding the composition at pH 3.5, FTIR detected sodium carboxylate peaks in addition to ester and acid. Table 1 below provides pH of surface of fibrous textiles in Figures 9-12.

Table 1: pH Test According to IS03071:2020 (KC1 Method) Prophetic Example: Quantitative analysis of the surface pH and surface charge of the fibrous textile material

Reacting the hydroxyl groups of cellulose on the surface of the fibrous textile with carboxylic acids changes the pH of the surface of the fibrous textile. It may also change the charge. The surface pH and surface charge of the antimicrobial fibrous textile manufactured according to the disclosure can be measured using Surface pH Meter PCE-228SF at room temperature, according to the specification and standard protocol as described in the link: world wide web (www).pce- instruments.com/english/measuring-instruments/test-meters/ph-meter-ph-tester-pce-instruments- surface-ph-meter-pce-228sf-det_5860016.htm. The surface pH is expected to decrease, for example, to a range of 2.5 to 5.5.

Claims

1. An antimicrobial composition for treating a fibrous textile, the composition comprising: one or more organic acid selected from a carboxylic acid, a polycarboxylic acid, and a cyclic anhydride; a wetting agent; a solvent, and optionally, a catalyzer wherein the fibrous textile includes cellulose, and wherein the optional catalyzer when present catalyzes a reaction between the cellulose in the textile and the one or more organic acid.

2. The antimicrobial composition according to claim 1, wherein the one or more organic acid is selected from one or more of: tartaric acid, citric acid, formic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, enanthic acid, caprylic acid, pelargonic acid, capric acid, undecylic acid, lauric acid, tridecyclic, myristic acid, pentadecyclic acid, palmitic acid, margaric acid, stearic acid, nonadecyclic acid, arachidic acid, malic acid, amino acids, fatty acids, 1, 2,3,4- Butanetetracarboxylic acid, Pyromellitic acid, Benzene tricarboxylic acid, EDTA, Maleic acid, Itaconic acid, Succinic acid, malonic acid, glutaric acid, 1,4 cyclohexane dicarboxylic acid, adipic acid, aconitic acid, trimesic acid, terephthalic acid, poly acrylic acid, and hyaluronic acid.

3. The antimicrobial composition according to any one of claim 1 or claim 2, wherein the composition comprises two or more organic acids.

4. The antimicrobial composition according to any one of claims 1 to 3, wherein the one or more organic acid is present in the composition in a range of between about 0.1% (w/v) and about 30% (w/v).

5. The antimicrobial composition according to any one of claims 1 to 4, wherein the catalyzer comprises a phosphate and/or a phosphite.

6. The antimicrobial composition according to any one of claims 1 to 5, wherein the catalyzer is selected from: sodium hypophosphite, Di sodium hydrogen phosphite, mono sodium phosphate, disodium phosphate, and tetrasodium pyrophosphate.

7. The antimicrobial composition according to any one of claims 1 to 6, wherein the amount of catalyzer is between about 0.05% (w/v) and about 10% (w/v).

8. The antimicrobial composition according to any one of claims 1 to 7, wherein the amount of catalyzer is between about 2% (w/v) and about 4% (w/v).

9. The antimicrobial composition according to any one of claims 1 to 8, wherein the wetting agent is selected from Pluronics such as Pluronic F127, Tweens such as Tween 80, Tween 20, sodium dodecyl benzene sulphonate, acacia, pectin, sodium lauryl sulphate, polysorbate 80, Dimethyl sulphoxide, purified water, ethyl alcohol, poloxamers, ammonium lauryl sulphate, sodium laureth sulphate, sodium lauryl sarcosinate, sodium myreth sulphate, sodium pareth sulphate, sodium stearate, sodium lauryl sulphate, a olefin sulphonate, and ammonium laureth sulphate.

10. The antimicrobial composition according to any one of claims 1 to 9, wherein the wetting agent is present in the composition in an amount of between about 0.1% (w/v) and about 5% (w/v).

11. The antimicrobial composition according to any one of claims 1 to 10, wherein the solvent is aqueous, organic or a mixture thereof, wherein the organic solvent is selected from an alcohol or a glycol.

12. The antimicrobial composition according to any one of claims 1 to 11, wherein the composition further comprises an alkali.

13. The antimicrobial composition according to any one of claims 1 to 12, wherein the composition has a pH of between about 1.5 and about 7.

14. The antimicrobial composition of any one of claims 1 to 13, wherein the composition consists of:

Tartaric acid;

Citric acid;

Pluronic Fl 27 or Sodium Dodecyl Benzene Sulphonate (SDBS);

Sodium hypophosphite;

Water; and

Sodium hydroxide.

15. The antimicrobial composition of any one of claims 1 to 13, wherein the composition consists of:

Tartaric acid about 0.1% (w/v) to about 30% (w/v);

Citric acid about 0.1% (w/v) to about 30% (w/v); Pluronic F127 or Sodium Dodecyl Benzene Sulphonate (SDBS) about 0.1% (w/v) to about 5% (w/v);

Sodium hypophosphite about 0.05% (w/v) to about 10% (w/v)); and

Sodium hydroxide about 1% (w/v) to about 6% (w/v).

16. A method of treating a fibrous textile comprising cellulose, the method comprises treating the fibrous textile with a composition comprising one or more polycarboxylic acid or cyclic anhydride; a wetting agent; and a catalyzer for catalyzing esterification reaction between one or more hydroxyl groups on the cellulose with the polycarboxylic acid or cyclic anhydride, thereby conferring antimicrobial activity on the fibrous textile.

17. The method of claim 16, wherein, after the treating, the fibrous textile has a pH of about 2.5 to about 6.5, as measured by a IS03071 :2020.

18. The method of claim 16 or 17, wherein the fiber is a natural fiber or a semi -synthetic fiber.

19. The method of claims 18, wherein the fiber is a natural fiber, wherein the natural fiber is cotton fiber, linen fiber, flax fiber, or hemp fiber; or the fiber is a semi-synthetic fiber, wherein the semi -synthetic fiber is viscose fiber, lyocell fiber, or modal fiber; or the fiber is a blend of a natural fiber and a semi-synthetic fiber.

20. The method of claim 19, wherein the fiber is a natural fiber, wherein the natural fiber is cotton fiber.

21. The method of any one of claims 16-20, wherein the one or more poly carboxylic acid or cyclic anhydride is selected from tartaric acid, citric acid, propionic enanthic acid, malic acid, one or more amino acids, 1,2,3,4-butanetetracarboxylic acid, pyromellitic acid, benzene tricarboxylic acid, EDTA, maleic acid, itaconic acid, succinic acid, malonic acid, glutaric acid, 1,4 cyclohexane dicarboxylic acid, adipic acid, aconitic acid, trimesic acid, terephthalic acid, poly acrylic acid, and hyaluronic acid.

22. The method of claim 21, wherein the one or more poly carboxylic acid or cyclic anhydride is selected from tartaric acid or citric acid.

23. The method of any one of claims 16-22, wherein the one or more poly carboxylic acid or cyclic anhydride is present in the composition in a range of between about 0.1% (w/v) and about 30% (w/v).

24. The method of any one of claims 16-23, wherein the catalyzer comprises a phosphate and/or a phosphite.

25. The method of claim 24, wherein the catalyzer is selected from sodium hypophosphite, di sodium hydrogen phosphite, mono sodium phosphate, di sodium phosphate, and tetrasodium pyrophosphate.

26. The method of any one of claims 16-25, wherein the catalyzer is present in an amount of about 0.05% (w/v) to about 10% (w/v).

27. The method of any one of claims 16-26, wherein the catalyzer is present in an amount of about 2% (w/v) to about 4% (w/v).

28. The method of any one of claims 16-27, wherein the wetting agent is selected from Pluronics such as Pluronic F127, Tweens such as tween 80, tween 20, sodium dodecyl benzene sulphonate, acacia, pectin, sodium lauryl sulphate, polysorbate 80, dimethyl sulphoxide, purified water, ethyl alcohol, poloxamers, ammonium lauryl sulphate, sodium laureth sulphate, sodium lauryl sarcosinate, sodium myreth sulphate, sodium pareth sulphate, sodium stearate, sodium lauryl sulphate, a olefin sulphonate, and ammonium laureth sulphate.

29. The method of any one of claims 16-28, wherein the wetting agent is present in an amount of about 0.1% (w/v) to about 5% (w/v).

30. The method of any one of claims 16-29, wherein the composition further comprises a solvent.

31. The method of claim 30, wherein the solvent is an aqueous solvent or an organic solvent, or a mixture thereof.

32. The method of claim 31, wherein the organic solvent is an alcohol.

33. The method of any one of claims 16-32, wherein the composition further comprises a base.

34. The method of claim 33, wherein the base is an alkali base.

35. The method of any one of claims 16-34, wherein the composition has a pH of about 1.5 to about 7.

36. The method of any one of claim 16-35, wherein the composition comprises: tartaric acid; citric acid;

Pluronic Fl 27 or sodium dodecyl benzene sulphonate (SDBS); sodium hypophosphite; water; and sodium hydroxide.

37. The method of any one of claims 16-36, wherein the composition comprises: tartaric acid, present in an amount of about 0.1% (w/v) to about 30% (w/v); citric acid, present in an amount of about 0.1% (w/v) to about 30% (w/v);

Pluronic Fl 27 or sodium dodecyl benzene sulphonate (SDBS), present in an amount of about 0.1% (w/v) to about 5% (w/v); sodium hypophosphite, present in an amount of about 0.05% (w/v) to about 10% (w/v); and sodium hydroxide, present at an amount of about 1% (w/v) to about 6% (w/v).

38. A fibrous textile comprising cellulose treated by the method of any one of claims 16-37, wherein the fibrous textile has antimicrobial properties.

39. The fibrous textile of claim 38, wherein the fibrous textile kills at least 90% of bacteria, fungi and/or viruses within about 5 minutes of contacting the bacteria, fungi and/or viruses.

40. A fibrous textile comprising cellulose treated by the method of any one of claims 16-38, wherein at least one hydroxyl group on the cellulose is modified.

41. A fibrous textile comprising cellulose treated by the method of any one of claims 16-38, wherein about 5% to about 95% of the hydroxyl groups on the surface of the fibrous textile are modified by the one or more polycarboxylic acid or cyclic anhydride.

42. The fibrous textile of claim 41, wherein the fibrous textile comprises an increase in absorbance at about 1725-1735 cm’¹, as measured using FTIR.

43. The fibrous textile of claim 41, wherein the fibrous textile comprises an increase in absorbance of about 5% to about 100% at about 1725-1735 cm’¹, as measured using FTIR.

44. The fibrous textile of any one of claims 40-43, wherein the fibrous textile has antimicrobial properties.

45. The fibrous textile of claim 44, wherein the fibrous textile kills at least 90% of bacteria, fungi and/or viruses within about 5 minutes of contacting the bacteria, fungi and/or viruses.

46. The fibrous textile of any one of the preceding claims, where the fibrous textile is clothing, a bag, carpet, a seat covering, cloth, bandage, mask, bedding, curtain, towel or mop.

47. The fibrous textile of claim 46, wherein the clothing is a sock, a shirt, an undergarment, a pair of shorts, a pair of pants, a coat (e.g., lab coat), or an apron.

48. The fibrous textile of any one of the preceding claims, wherein the fibrous textile is a non-woven fabric.

49. The fibrous textile of claim 48, wherein the non-woven fabric is a paper product.

50. The fibrous textile of claim 49, wherein the paper product is a teabag paper, a fiber paper, or a wet wipe.