Method for producing reinforced textile fiber compositions

Abstract

The presentation disclosure relates to a method for producing a reinforced textile fiber composition comprising a) providing a textile fiber composition b) optionally forming a textile from the textile fiber composition, and c) subjecting the textile fiber composition or textile in a buffered reaction medium to a first mediator molecule activated by an oxidoreductase catalyst at a pH between 5 to 6, thereby promoting the covalent crosslinking of fibers by the oxidoreductase catalyst / mediator thereby reinforcing the textile fiber composition or textile.

Description

Method for producing reinforced textile fiber compositions.Technical Field

[0001] The present disclosure relates to methods for improving reinforcement and / or functionality of covalently crosslinked textile fiber compositions made using oxidoreductase catalysts and mediators. The present disclosure further relates to the improved textile compositions.Background

[0002] Patent application PCT / EP2023 / 082823 describes methods for increasing strength textiles or for adding other benefits to textiles by catalytic crosslinking textile fibers. However there remains a need for improving and optimizing the methods described in PCT / EP2023 / 082823. Further US2006 / 272102 Al describes chemically treating textiles with sodium hypophosphite and butane tetracarboxylic acid (BTCA) or sodium hypophosphite and dimethyloldihydroxy-ethylene urea (DMDHEU)). Further US2003 / 154555 Al describes treating wool or animal hair with transglutaminase. Further US 2003 / 145390 Al describes treating cellulosic textiles by nitroxide oxidation, where the the primary ("C6") alcohols on the cellulose portion of cellulosic textiles, are selectively oxidized with a suitable oxidant in the presence of a nitroxide radical mediator.

[0003] The present invention allows for the making of even higher quality textiles from recycled fibers and / or from fibers that do not initially have the properties for making of high-quality textiles using know production methods.Summary

[0004] The methods and improved textile fiber compositions described herein provides further benefits and advantages over the technology described in PCT / EP2023 / 082823, included herein by reference. The improved textile fiber compositions treated by the methods described herein have an even higher quality compared to the textile fiber compositions of PCT / EP2023 / 082823 and compared to untreated textile fiber compositions for example those made from premium virgin natural fibers or premium man-made fibers or combinations of these types of fibers. Using the methods provided for herein, there is even less need for blending in fiber materials with more preferred material properties such as length distribution (natural or synthetic) to improve processability and / or properties of the manufactured textile. Still further the methods provided for herein enable even more flexibility and tolerance to recycling, reprocessing and remanufacturing of fiber materials (such as pre- and post-consumer textile wastes) which are hard to separate into pure fiber categories by mechanical means, e.g., assisted by manual or analytical sorting technologies such as NIR and UV spectroscopy.Still further the methods provided for herein offers even further benefits to the textile production and use by even further improving the material properties of the fiber structures that constitutes textile end-products at process stages such as spinning, weaving, knitting, manufacturing (including nonwoven) of textiles, fabrics and garment or technical equipment, and wash & wear and general use at the end application. Alternatively, or additionally the methods provided for herein further improves critical material properties of the fiber materials (including materials such as yarn, thread, fabric, garment and technical items like filters and masks) by providing remedy to the shortcomings associated with variables that affects the quality the textile materials including fiber sources, processing and manufacturing conditions and use / maintenance. The improvement in critical material properties is particularly relevant in technical applications including but not limited to membranes, filters, technical textiles where there is significant tear and wear, such as work clothing, such as clothing for crafts, hospitals, kitchen, military, hotels and the like, or upholstery in cars, trains, busses, airplanes and the like. The method described herein is also useful for rejuvenating critical material properties of such textile materials if lowered due to wear and tear. Alternatively, or additionally, the methods provided for herein offers even further solutions to the selection of fiber sources for textile production by providing even further remedying shortcomings due to undesired distribution of fiber lengths in particular the short -fiber content (typically defined as the g / g fraction of fibers shorter than half the mean length of the premium references), and enabling the use of lower quality (organic / ecological) natural or manmade fibers, recycled fibers and renewable fibers. Alternatively, or additionally the methods provided for herein provides further benefits at the stage of processing of the raw fibers before spinning by improving the quality parameters of the rowing's and slivers, e.g., by further enabling production of lower linear density materials due to lower fiber fineness and smaller Tex values (g / km) of the rowing's and slivers. Alternatively, or additionally the methods provided for herein provides further benefits at the stage of spinning by improving processability of fiber materials and tolerance towards variability in fiber properties such as length distribution and evenness of the rowing's and slivers. The invention improves further both quality parameters (e.g., tenacity, breaking force, elongation, cohesion, flexibility, elasticity, evenness, linear density, pilling, linting, felting) and feasibility for processing (e.g., via rotor, ring or dry-jet wet spinning) which are defining for the spinning end-products (yarn and thread). Alternatively, or additionally the methods provided for herein provides further benefits at the stage of manufacturing of textile or fabric materials (e.g., by weaving, knitting, or nonwoven procedures) before they are made into garments or technical items by improving mechanical, physical, chemical and thermal properties of the materials. Alternatively, or additionally the methods provided for herein improves further both quality parameters of the yarn and thread materials as well as the textile and fabric materials (e.g.,fabric hand characteristics, resistance / tolerance to stress / strain of mechanical, chemical and / or thermal nature, color / dye binding and fastness) and in turn feasible for manufacturing into e.g., garments or technical items. Alternatively or additionally the methods provided for herein provides further benefits at the stage of manufacturing of, e.g., garment or technical items by improving the quality parameters of the textile and fabric items going into the manufacturing process as well as to the final items (including cross-sectional shape, surface characteristics, crimp, shrinkage, luster / color, strength, stiffness / flexibility, elastic recovery, tenacity / elongation, abrasion / chemical resistance, printing / color / dye binding and fastness). Alternatively, or additionally the methods provided for herein provides benefits at the stage of use, maintenance and reuse by improving quality parameters of textile, fabric, garment items such as longevity of initial quality attributes (including visual and touch / feel sensorial), durability and robustness towards wash & wear, abrasion, and lifetime of use and reuse.

[0005] Accordingly, in a first aspect described herein is a method for producing a reinforced textile fiber composition comprising: a) providing a textile fiber composition b) optionally forming a textile from the textile fiber composition, and c) subjecting the textile fiber composition or textile in a buffered reaction medium to a first mediator molecule activated by an oxidoreductase catalyst at a pH between 5 to 6, thereby promoting the covalent crosslinking of fibers by the oxidoreductase catalyst / mediator thereby reinforcing the textile fiber composition or textile.

[0006] In a further aspect described herein is a reinforced textile obtainable from the said method, comprising a textile fiber and a mediator molecule selected from a modified at least partially water- soluble cellulose, a polyimin, a polyamine or a combination thereof covalently bound to the textile fiber.

[0007] In a still further aspect described herein is a method for making a garment or an apparel comprising subjecting the said reinforced textile to one or more cutting and / or sewing / seaming steps, whereby the reinforced textile is shaped into the garment or apparel.

[0008] In a still further aspect described herein is the use of the said garment or apparel for dressing a subject.

[0009] In a still further aspect described herein is a method for making a filter comprising subjecting the reinforced textile of this disclosure to one or more cutting and / or sewing / seaming steps, whereby the reinforced textile fiber composition is shaped into the filter.Brief description of the figures

[0010] Figure 1 shows the principle of reinforcing textile fiber compositions using the methods described herein, illustrating:Build-up of fiber bundle in textile materials (such as yarn, woven fabric, and clothes) made from premium virgin cotton typically containing long and dense fiber bundles of predominantly longer cotton fibers (black filaments in the fiber bundle in the figure) providing for high strength and longevity.Build-up of fiber bundle in textile materials made from lower-quality fibers (such as recycled fibers) and / or higher-quality fibers upon aging and wash / wear of fibers described in (A). Here, the textile materials are weaker and less robust, and the fiber bundles characterized in (B) being shorter and coarser and containing a larger fraction of free shorter fibers (individual dotted filaments in the figure).Build-up of fiber bundle in textile materials made from fibers of (B) treated and reinforced by the methods described herein, thereby reducing the fraction of free shorter fibers in the fiber bundles and effectively regaining longer and denser fiber bundles as in (A) and higher strength and longevity.Blow-up image of the build-up of fiber bundle in (C) showing the covalent cross-linking (stars) of the fibers in the fiber bundles.

[0011] Figures 2-4 show samples from relative break force assessments of yarn subjected to treatment with different compositions of catalytic compositions including buffer systems of the reaction medium:Figure 2 shows the results of the relative break force assessment from pulling 5 pairs of yarn samples of 50 / 50 conventional and pre-consumer-waste recycled cotton where the conditions without (control) versus with enzyme catalyst (laccase) are compared, all in the plain tap water medium. In 4 out of 5 tests, the yarn treated with enzyme / mediator (A) is the strongest and the control yarn not treated with enzyme / mediator (B) breaks.Figure 3 shows the results of the relative break force assessment from pulling 5 pairs of yarn samples of 50 / 50 conventional and pre-consumer-waste recycled cotton where the medium conditions Mcllvaine buffer (pH 6.2) versus plain tap water are compared, all with laccase / Guaiacol. In 4 out of 5 tests, the yarn treated with enzyme / mediator in the Mcllvaine buffer (A) is the strongest and the yarn in medium not containing buffer (tap water) treated with enzyme / mediator (B) breaks.Figure 4 shows the results of the relative break force assessment from pulling 5 pairs of yarn samples of 50 / 50 conventional and pre-consumer-waste recycled cotton where the medium conditions potassium phosphate buffer (pH 6.2) versus acetate buffer (pH 5.0) are compared,all with laccase / Guaiacol. In this experiment results are comparable. In 3 out of 5 tests, the yarn treated with enzyme / mediator in the acetate buffer (A) is the strongest and the yarn in potassium phosphate buffer treated with enzyme / mediator (B) breaks.

[0012] Figures 5-6 show the effects of cross-linking technology on 100% organic cotton fabric properties by visual inspection of onset of multiple surface defects woven samples as function of number of rubbing abrasions. The samples treated with cross-binding agents that include a catalyst (Figure 6) show a significantly higher number for abrasions (rubs) until fabric damages occur relative to control samples without a catalyst (Figure 5), respectively.

[0013] Figures 7-8 show the effects of cross-linking technology on 100% manmade cellulose jersey knitted Tencel fabric properties assessed from the average of Martindale pilling scores as function of number of abrasions / rubs for each condition. The samples treated with cross-binding agents that include a catalyst show a significantly higher Martindale pilling score as function of abrasions / rubs (Figure 8) than control samples without a catalyst (Figure 7), respectively.

[0014] Figure 9 is an illustration of Martindale test of treated and untreated textile showing photos after 6000 rubs for the untreated sample and 8000 rubs for the treated sample.Incorporation by reference

[0015] All publications, patents, and patent applications referred to herein are incorporated by reference to the same extent as if each individual publication, patent, or patent application was specifically and individually indicated to be incorporated by reference. In the event of a conflict between a term herein and a term in an incorporated reference, the term herein prevails and controls.Detailed Description

[0016] The features and advantages of the present invention is readily apparent to a person skilled in the art by the below detailed description of embodiments and examples of the invention with reference to the figures and drawings included herein.Definitions

[0017] The term "textile" as used herein refers to a flexible material made by creating an interlocking bundle of yarns or threads of the textile fibers, which are produced by procedures such as spinning or extrusion of the raw fibers (from either natural or synthetic sources) into long and twisted lengths (Kadolph, Sara J. (1998)). Textiles are then formed by weaving, knitting, crocheting, knotting, tatting, felting, bonding, or braiding these yarns together.

[0018] In addition, fibers / filaments / yarns may be transformed into textile materials by so-callednonwoven methods where interlocking is obtained by means such as physical (incl. needle punching, hydroentanglement) and / or chemical (incl. latex binders).

[0019] The related terms "fabric", "clothes", and "material" which may be used herein interchangeably, are also often used in textile assembly trades (such as tailoring and dressmaking) as synonyms for textile. However, there are subtle differences in these terms in specialized usage. A textile is any material made of interlacing fibers, including carpeting and geotextiles, which may not necessarily be used in the production of further goods, such as clothing and upholstery. A fabric is a material made through weaving, knitting, spreading, felting, stitching, crocheting, or bonding that may be used in the production of further products, such as clothing and upholstery, thus requiring a further step of the production. Cloth may also be used synonymously with fabric, but often specifically refers to a piece of fabric that has been processed or cut.]

[0020] The term "garment" as used herein refers to clothing (also known as clothes, apparel, and attire) are items worn on the body. Typically, clothing is made of fabrics or textiles, but over time it has included garments made from animal skin and other thin sheets of materials and natural products found in the environment, put together. The wearing of clothing is mostly restricted to human beings and is a feature of all human societies. The amount and type of clothing worn depends on gender, body type, social factors, and geographic considerations. Garments cover the body, footwear covers the feet, gloves cover the hands, while hats and headgear cover the head.]The term "physical entanglement" as used herein refers to [textile fibers being subjected to devises such as needle-punching and / or one or more air or water jets that result in intercalating or intertwining the fibers. Hydroentanglement is a bonding process for wet or dry fibrous webs made by either carding, air-laying or wet-laying, the resulting bonded fabric being a nonwoven. It uses fine, high-pressure jets of water which penetrate the web, hit the conveyor belt (or "wire" as in papermaking conveyor) and bounce back causing the fibers to entangle. Hydroentanglement is sometimes known as spun-lacing, because early nonwovens were entangled on conveyors with a patterned weave which gave the nonwovens a lacy appearance. It can also be regarded as a two- dimensional equivalent of spinning fibers into yarns prior to weaving. The water pressure has a direct bearing on the gsm, and strength of the web, and very high pressures not only entangle but can also split fibers into micro- and nano-fibers which give the resulting hydroentangled nonwoven a leatherlike or even silky texture. This type of nonwoven can be as strong and tough as woven fabrics made from the same fibers (US 7530150 and Xiang et al. (2008))

[0021] The term "virgin fiber" as used herein refers to [the new or first production of fibers from their original source (natural or synthetic).]

[0022] The term "natural fiber" as used herein refers to natural fibers developed or occur in the fibershape, and include those produced by plants, animals, and geological processes. They can be classified according to their origin: a) Plant fibers are generally based on arrangements of cellulose, often with lignin: examples include cotton, hemp, jute, flax, abaca, pina, ramie, sisal, bagasse, and banana. Plant fibers are employed in the manufacture of paper and textile (cloth), and dietary fiber is an important component of human nutrition; b) Wood fiber, distinct from vegetable fiber, is from tree sources. Forms include groundwood, lacebark, bamboo, thermomechanical pulp (TMP), and bleached or unbleached kraft or sulfite pulps. Kraft and sulfite refer to the type of pulping process used to remove the lignin bonding the original wood structure, thus freeing the fibers for use in paper and engineered wood products such as fiber board; c) Animal fibers are largely composed of particular proteins. Instances are silkworm silk, spider silk, sinew, catgut, wool, sea silk and hair such as cashmere wool, mohair and angora, fur such as sheepskin, rabbit, mink, fox, beaver, etc.; d) Mineral fibers include the asbestos group. Asbestos is the only naturally occurring long mineral fiber. Six minerals have been classified as "asbestos" including chrysotile of the serpentine class and those belonging to the amphibole class: amosite, crocidolite, tremolite, anthophyllite and actinolite. Short, fiber-like minerals include wollastonite and palygorskite; and e) Biological fibers, also known as fibrous proteins or protein filaments, consist largely of biologically relevant and biologically very important proteins, including for example the collagen family of proteins, tendons, muscle proteins like actin, cell proteins like microtubules and many others, such as spider silk, sinew, and hair.

[0023] The term "manmade fiber" as used herein refers to fibers which chemical composition, structure, and properties are significantly modified during the manufacturing process (typically involving polymerization of monomeric building blocks and / or condensation of smaller units of fiber components). Man-made fibers (or filaments) include regenerated (natural) fibers and synthetic fibers (see Encyclopedia Britannica).

[0024] The term "recycled fiber" as used herein refers to fibers resulting from a process of recovering fiber, yarn or fabric and reprocessing the textile material into useful products. Textile waste products are gathered from different sources and are then sorted and processed depending on their condition, composition, and resale value. Refurbishing recycled fibers by strengthening them using the methods described herein is a key objective, as a huge impact on the resource consumption and world climate can be achieved by enabling use of recycled fibers for making quality textilematerials with better longevity . Improving the quality of fibers or mixtures of fiber materials with inferior properties (for clothing making), to make them useful for production, manufacturing of quality textiles is another key objective. Such fiber materials include MMCF (man-made cellulose fibers), hemp, flax, kapok, hemp, jute, ramie, kenaf, roselle, sunn, urena, nettle, manila, abaca, cantala, henequen, maguey, phormium, sisal, akund floss, bagasse, bamboo, bombax cotton, coir and / or wood, and more environmentally friendly produced fibers of traditionally higher quality, such as cotton, produced with e.g. less fertilizers, pesticides and other yield and quality-enhancers.

[0025] The term "renewable fiber" as used herein refers to fibers produced from renewable resources such as wood, grasses and / or agricultural waste.

[0026] The term "textile components" as used herein to refer to materials included in the final textile product in addition to the fibers such as but not limited to dye molecules, coating agents, and inherent or added compounds that may take part in crosslinking textile fibers. Also included are so-called mediators, such as laccase mediators which are typically water soluble molecules which a oxidoreductase catalyst can catalyze to form reactive radicals which reacts with textile fibers or other textile components. Accordingly the term "mediator" are used herein to refer to molecules which a oxidoreductase catalyst can catalyze to form reactive radicals which reacts with textile fibers or other mediators.

[0027] The term "Martindale" as used herein refers to standardized methods for mimicking accelerated wear & tear or abrasion scenarios to assess textile properties such as strength, durability and robustness, cf. DS / EN ISO 12945-2:2020, DIN EN ISO 12945-2 (2021-04) and DIN EN ISO 12945-4 (2021-04).

[0028] The term "Elasticity" as used herein refers to the elastic behavior of textile materials. Here assessment is made of differences in yarn elasticity by measuring the reversible % elongation from force-elongation experiments according to a modified DS / EN ISO 14704-1. Elasticity can be determined as the average reversible % elongation at 90% of breaking force from repeated testing of 5 samples of a given condition.

[0029] The term "Breaking Force" as used herein refers to the force at breaking of the yarn samples in a force-elongation experiment at constant elongation rate according to ISO 2062.

[0030] The term "elongation" as used herein refers to the elongation at breaking of the yarn samples in a force-elongation experiment at constant elongation rate according to ISO 2062.

[0031] The term "Pilling" as used herein refers to the formation of pilling surface defects as generated by, e.g. the Martindale abrasion test according to DIN EN ISO 12945-2 (2021-04) and DIN EN ISO 12945- 4 (2021-04) which further describe the changes in wear / tear in terms of pilling, linting and felting as a function of a fixed number of abrasions / rubs. The visual changes are noted according to a score tablefrom 5 to 1 where 5 is no changes and 1 is severe changes.

[0032] The term "Linting" as used herein refers to the formation of linting surface defects as generated by, e.g. the Martindale abrasion test according to DIN EN ISO 12945-2 (2021-04) and DIN EN ISO 12945- 4 (2021-04) which further describe the changes in wear / tear in terms of pilling, linting and felting as a function of a fixed number of abrasions / rubs. The visual changes are noted according to a score table from 5 to 1 where 5 is no changes and 1 is severe changes.

[0033] The term "Felting" as used herein refers to the formation of felting surface defects as generated by, e.g. the Martindale abrasion test according to DIN EN ISO 12945-2 (2021-04) and DIN EN ISO 12945-4 (2021-04) which further describe the changes in wear / tear in terms of pilling, linting and felting as a function of a fixed number of abrasions / rubs. The visual changes are noted according to a score table from 5 to 1 where 5 is no changes and 1 is severe changes.Detailed description of aspects and embodiments.

[0034] The methods provided for herein comprises: a) Providing a textile fiber composition b) Optionally forming a textile from the textile fiber composition, optionally with additional textile components, and c) subjecting the textile fiber composition or textile in a buffered reaction medium to a first mediator molecule activated by an oxidoreductase catalyst at a pH between 5 to 6, thereby promoting the covalent crosslinking of fibers by the oxidoreductase catalyst / mediator thereby reinforcing the textile fiber composition or textile.

[0035] In some embodiments the activated mediator covalently binds to and crosslinks the textile fibers.

[0036] The said crosslinking can occur before, during or after preparing a textile from the textile fiber composition.

[0037] The textile fibers can be natural fibers or manmade fibers of natural or synthetic origin or a combination thereof. In some embodiments the textile fibers the textile fibers comprise virgin fibers or recycled or renewable fibers or a combination thereof. In particular textiles comprising manmade cellulose (MMCF) can greatly benefit from the method of strengthening textiles.

[0038] In particular embodiments the MMCF, in particular Lyocell or Tencel, made from wood pulp by processing wood (chips) into cellulose pulp, which is dried and dissolved in a solvent (typically N- methylmorpholine N-oxide (NMMO), which is pressurized through a nozzle or spinneret into a spinning bath in where cellulose fibers solidify and from which yarns can be processed. Alternatively, pulp may be obtained from recycling other sources of cellulose, including textile. The virgin textilefibers (natural or man-made) can suitably be trimmed for processing to a suitable average length (upper-half mean or staple length) between 0.1-1000 mm depending on type of manufacturing, such as between 2-100 mm, such as between 2-50 mm, for example between 15-50 mm. Preferably, textiles comprise longer fibers and fewer shorter length fibers, and textiles made from recycled fibers have more shorter fibers than textile made from virgin fibers, and therefore textiles made from recycled (or inferior quality) fibers alone are typically weaker. Nowadays, such weakness is remedied by addition of filamentous fibers such as polyester and / or MMCF. However, including synthetic fibers are counterproductive for further recycling because the fibers cannot be easily separated again. In some embodiments where the fibers are recycled, the fibers have an average length of less than 5 mm, such as less than 3 mm, less than 2 mm such as less than 1 mm, while still having a minimum length of at least 0,01 mm.

[0039] In some embodiments the textile fibers comprise natural or biological plant derived fibers optionally derived from cotton, kapok, hemp (Cannabis sativa or Apocynum cannabinum or Furcraea foetida), flax (Linum usitatissimum), jute (Corchorus species including C. olitorius and C. capsularis), ramie (Boehmeria nivea), kenaf (Hibiscus cannabinus), roselle (Hibiscus sabdariffa), sunn (Crotalaria juncea), urena (Urena lobata), nettle, manila, abaca (Musa textilis), cantala (Agave cantala), henequen (Agave fourcroydes), maguey (Agave americana and other species), phormium (Phormium tenax), sisal (Agave sisalana), akund floss (Calotropis procera and C. gigantea), bagasse (Saccharum officinarum), bamboo (various species), bombax cotton (Bombax species), coir (Cocos nucifera) and / or wood. Fibers suitable for applications such as artificial leather are also comprised, e.g., from pineapple. The natural or biological plant derived fibers suitably comprise a cellulosic material and / or galactoglucomannan. In one preferred embodiment the textile fibers are Man-Made Cellulose Fibers (MMCF). In another preferred embodiment the textile fibers comprise natural or biological fibers derived from animal such as those derived from birds, sheep, rabbits, lama, alpaca, camel, goats, and / or silkworm. In particular textile fibers comprising wool or silk benefits from the methods described herein.

[0040] In other embodiments the textile fibers are of a synthetic material, optionally polyester, polyamide, acrylic, polyolefin, polypropylene and / or elastane. Such synthetic fibers (filaments) may be trimmed to have an average length (upper-half mean) between 1-500 mm depending on type of manufacturing, such as between 2-100 mm, such as between 4-50 mm, for example between 15-50 mm.

[0041] The fibers described herein can be spun fibers (yarns) or they can be non-spun fibers, and further in the methods described herein the textile to be reinforced can be a woven, knitted, braided, crocheted, felted or non-woven fabric, in particular those fabrics where textile fibers are spun fibers. In particular the textile to be reinforced is a woven eco cotton.

[0042] In one embodiment the textile material is sliver or roving fibers or a spun yarn or a woven textile such as cotton by the meter or a fashioned garment. In some embodiments the textile is a knitted textiles is a knitwear. In some embodiments the textile is a braided textile such as carpets made from wool or silk. It follows that where the strengthening treatment according to the reinforcement methods described herein is made on fibers and / or yarns the increased strength will extend also to any textile material such as fabric or garment made from such reinforced fibers / yarns.

[0043] The textile to be reinforced may however also be non-woven or felted and the textile fibers, and in particular where the textile fibers are non-spun fibers. Since the present method of reinforcement acts on the molecular level of the textile materials, these results also demonstrate that textiles and cloths made from such yarns will also be strengthened by treatment according to the methods described herein, either by treating the fibers making up the yarn, treating the yarns or treating the textile after weaving / knitting.

[0044] The fibers described herein, manmade or natural or a combination thereof may also be pretreated for example with synthetic polymers to deliver wash & wear benefits such as stain repelling or anti-wrinkle properties, or optionally the reverse synthetic polymers coated with cellulose-like compounds to improve, e.g., touch / feel, moist management and dye binding.

[0045] In some embodiments the reinforced textile fiber composition resulting from the methods described herein is a textile, a fabric or a cloth.

[0046] In some embodiments the fibers are spun fibers comprised in a yarn. The yarn is in some embodiments made up of a blend of recycled and virgin fibers, such as a 60% / 40% mixture. In some embodiments yarns of such blends are selected that have an averaged tenacity of 5 to 8 cN / tex (500 g to 800 g weight at breakpoint), such as about 6,7 cN / tex, and average elongation at breakpoint of 2,5% to 6,5%, such as about 4,5%. One example of such yarn is the commercially available ET_ITY020_80160 greggio type yarn from https: / / www.ecologicaltextiles.com / contents / en- uk / p!4498 Yarn Nm 202 recycled cotton greggio.html. The yarn is in other embodiments made up of natural virgin fibers. In some embodiments the yarns of such natural virgin fibers are selected that have an averaged tenacity of 100 to 200 cN / tex (10000 g to 20000 g weight at breakpoint), such as about 155 cN / tex, and an average elongation at breakpoint of 6% to 10%, such as about 8,05%. One example of such yarn is the commercially available ET_TKY020 natural type yarn from https: / / www.ecologicaltextiles.com / contents / en-uk / p70131 Qrganic-cotton-yarn-Nm-20-2natural- colour.html. The yarn is in other embodiments made up of a blend of recycled and virgin fibers, such as a 50% / 50% mixture. In some embodiments yarns of such blends are selected that have an averaged tenacity of 5 to 8 cN / tex (500 g to 800 g weight at breakpoint), such as about 7,4 cN / tex, and an average elongation at breakpoint of 5% to 6,5%, such as about 4,9%. One example of such yarn is thecommercially ET_ITY034_grigio melange type yarn available from (https: / / www.ecologicaltextiles.com / contents / en- uk / p!4508 Yarn Nm 342 recycled cotton grigiomelange.html .The yarn is in other embodiments made up of natural virgin fibers. In some embodiments the yarns of such natural virgin fibers are selected that have an averaged tenacity of 150 to 250 cN / tex (15000 g to 25000 g weight at breakpoint), such as about 205 cN / tex, and an average elongation at breakpoint of 6% to 10%, such as about 8,50%. One example of such yarn is the commercially available ET_TKY040 natural type yarn from https: / / www.ecologicaltextiles.com / contents / en-uk / pll283_Organic-cotton-yarn- naturalcolour-Nm85-2.html.

[0047] In some embodiments fibers are spun fibers comprised in a woven fabric. In some embodiments the woven fabric is made up of 100% organic GOTS cotton and has a material density of between 50 and 100 g / m2, such as from 60 to 70 g / m2or from 80 to 100 g / m2, such as about 65 g / m2or about 90 g / m2. Examples of such fabrics are ET_TKW004_l from https: / / www.ecologicaltextiles.com / contents / en-uk / pl4374 Voile-light-organiccotton-offwhite- 155cm.html, or ET_TKW005_0 from https: / / www.ecologicaltextiles.com / contents / en- uk / p259 Batist-organic-cottonoffwhite-PFP.html.

[0048] In some embodiments the oxidoreductase catalyst activates the mediator by catalyzing oxidation or reduction of the mediator to form a reactive radical whereby the activated mediator react with and form cross-links between moieties in the textile fibers or to other mediators.

[0049] The cross-linking between fibers in the textile fiber composition be either directly between moieties in the fibers and / or can be between moieties of the fibers and an added textile component acting as linker between the fibers. It is to be understood that the activation of the mediator to make it reactive can take place while the mediator is present in the textile fiber composition or the activation can take place outside the textile fiber composition and then the activated mediator is brought in contact with the textile fiber composition to accomplish cross-linking.

[0050] The catalyst is an oxidoreductase. Such oxidoreductases can suitably be selected from lipoxygenases, (lysyl) oxidases, peroxidases, tyrosinases, and laccases capable of activating the mediators in a selected reaction medium. Suitable laccases can be derived from fungi or bacteria, such as those of the genus Myceliophtora, optionally of the species Myceliophtora thermophila (Thermothelomyces thermophilus), or from the genus Trametes, optionally from the species Trametes versicolor, or from the genus Bacillus, optionally from the species Bacillus subtilis, optionally derived from organisms described in: https: / / microbialcellfactories.biomedcentral.eom / articles / 10.1186 / sl2934-019-1248-0#citeas and Brugnari et al. (2021) and Energies (2022). Particularly useful laccases are laccases from the genusThermothelomyces, such as Thermothelomyces thermophilus (formerly known as Mycelioptera thermophilus) including laccases having laccase activity and comprising an amino acid sequence which is at least 70%, such as at least 80%, such as at least 90%, such as at least 95%, such as at least 99%, such as at least 100% identical to the laccase comprised in SEQ ID NO: 2. Other useful laccases are those from the genus of Trametes, such as Trametes versicolor, including laccases having laccase activity and comprising an amino acid sequence which is at least 70%, such as at least 80%, such as at least 90%, such as at least 95%, such as at least 99%, such as at least 100% identical to the laccase comprised in SEQ ID NO: 1. Still further useful laccases are those from the genus Bacillus, such as Bacillus subtilis, including laccases having laccase activity and comprising an amino acid sequence which is at least 70%, such as at least 80%, such as at least 90%, such as at least 95%, such as at least 99%, such as at least 100% identical to the laccase comprised in SEQ ID NO: 3. Useful laccases include the commercially available laccases such as product numbers SAE0050 and 38429 from Sigma-Aldrich (product catalog 2023). Laccases and / or other enzyme oxidoreductase catalysts can advantageously be added to the cross-linking reaction medium in concentrations of 0,01 U / mL to 100 U / mL, such as from 0,1 U / mL to 10 U / mL, such as from 0,5 U / mL to 2 U / mL, such as from 0,75 U / mL to 1,5 U / mL, such as about 1 U / mL.

[0051] For laccase catalysts, such as SEQ ID NO: 1, 2, or 3, in combination with a phenolic mediator it has been found that employing a laccase concentration of 0,05 to 0,2 U / mL reaction medium is particularly effective for increasing breaking force and / or elongation and / or elasticity of cotton yarns. For laccase catalysts, such as SEQ ID NO: 1, 2, or 3, in combination with a phenolic mediator it has been found that employing a concentration of 0,05 to 0,2 U / mL reaction medium is particularly effective for improving / lowering pilling, linting and / or felting of woven cotton (containing) textile fabrics.

[0052] Application of an enzyme oxidoreductase catalyst, in particular oxidoreductases such as laccases, can suitably be carried out at a pH between 3 to 10, optionally between 4 to 7, optionally around 5.5. More specifically where the catalyst is a laccase the pH in the reaction medium is preferably between 5 and 6. For laccase catalysts, such as SEQ ID NO: 1, 2, or 3, in combination with a phenolic mediator it has been found that employing a pH of 5,8 to 6,2 in the reaction medium is particularly effective for increasing breaking force and / or elongation and / or elasticity of cotton yarns. For laccase catalysts, such as SEQ ID NO: 1, 2, or 3, in combination with a phenolic mediator it has been found that employing a pH of 5,8 to 6,2 in the reaction medium is particularly effective for improving / lowering pilling, linting and / or felting of woven cotton (containing) textile fabrics.

[0053] It has been observed that using buffered reaction medium with pH between 5 and 6, preferably pH around 5 or around 6, preferably without calcium is advantageous over unbuffed tap water (0-20dH, such as 0-2 mM CaCL). It is however surprising that performing the crosslinking process in regular tap water also produced good results which is a huge benefit when integrating the methods described herein in industrial applications. For laccase catalysts, such as SEQ ID NO: 1, 1, or 3, in combination with a phenolic mediator it has been found that employing a water hardness of 0 to 20 dH, is particularly effective for increasing breaking force and / or elongation and / or elasticity of cotton yarns. For the laccase catalysts, such as SEQ ID NO: 1, 2, or 3, in combination with a phenolic mediator it has been found that employing a water hardness of 0 to 20 dH is particularly effective for improving / lowering pilling, linting and / or felting of woven cotton (containing) textile fabrics.

[0054] In some embodiments the treatment time suitably between lOmin to 120 min, such as 20 min to 60 min, such as 20 min to 40 min, typically around 30 min. The appropriate treatment time will depend on the pH and temperature stability and efficiency of the oxidoreductase catalyst as well as for the mediator and / or functional / reactive groups in the of the textile fibers.

[0055] In some embodiments the temperature of reaction medium is preferably kept between 20°C to 60°C, in particular when using protein catalysts such as enzymes. In more specific embodiments the temperature of reaction medium is held (at least throughout most of the reaction process) between 30°C to 50°C, such as 40°C to 50°C. Enzyme catalyst function usually deteriorates when temperature raises beyond the denaturation temperature for the protein, but they can usually sustain function if temperature is only raised over short periods of time. For laccase catalysts, such as SEQ ID NO: 1, 2, or 3, in combination with a phenolic mediator it has been found that employing a temperature in the reaction medium between 42°C to 48°C is particularly effective for increasing breaking force and / or elongation and / or elasticity of cotton yarns. For laccase catalysts, such as SEQ ID NO: 1, 2, or 3, in combination with a phenolic mediator, it has been found that employing a temperature between 42°C to 48°C in the reaction medium is particularly effective for improving / lowering pilling, linting and / or felting of woven cotton (containing) textile fabrics.

[0056] For laccase catalysts, such as SEQ ID NO: 1, 2, or 3, in combination with a phenolic mediator it has been found that employing a treatment time between 45 min. to 75 min. is particularly effective for increasing breaking force, elongation and / or elasticity of cotton yarns. For laccase catalysts, such as SEQ ID NO: 1, 2, or 3, in combination with a phenolic mediator it has been found that employing a treatment time between 45 min. to 75 min. is particularly effective for improving / lowering pilling, linting and / or felting of woven cotton (containing) textile fabrics.

[0057] Useful peroxidases can be derived from Horseradish.

[0058] A particular advantage for this method and the use of oxidoreductases is to immobilize the oxidoreductase. Benefits of immobilization include better stability and reuse of the oxidoreductase. Accordingly, in one embodiment the oxidoreductase is applied in an immobilized form. Methods forimmobilizing enzymes are known in the art, e.g. from Front. Bioeng. Biotechnol. (2021) and Brugnari et al. Bioresources and Bioprocessing (2021). A preferred method for immobilization of oxidoreductases is to compartmentalize the enzymes within polyelectrolyte (PE) layers using the layer- by-layer (LbL) approach as described in the art to increase enzymatic activities by creating optimal conditions between specific layers of enzymes, limitation of contact with external environment and very limited blocking effect on biomolecules' active sites caused by enzymes sticking together (elevated temperature stability and tolerance is a further benefit of enzyme immobilization). This type of immobilization can be effectively used for a wide variety of both enzymes and immobilization supports such as membranes, making it possible to carry out the enzymatic bioconversion processes in e.g., fed-batch or continuous reactors. One specific preferred approach is making multifunctional biocatalytic polyelectrolyte multilayer (PEM) membranes via PE LbL assembly, using poly-L-lysine (PLL) and polyethylenimine (PEI) as cationic PEs and poly(sodium 4- styrenesulfonate) (PSS) as anionic PE. Preferred methods of enzyme immobilization, in particular for oxidoreductases such as laccases, on PEM membranes to make biocatalytic PEM membranes is 1) to immobilize the enzyme between PE layers and 2) to entrap enzymes within the cationic PE layers. Additional methodology for immobilizing enzymes is described e.g. in Chemosphere (2022). Immobilized oxidoreductase catalysts can be used to optimize performance, cost, environmental and safety aspects of the production and use of the textile materials. A preferred solution for providing crosslinking to textile materials, where the immobilized oxidoreductase needs to be maintained separated from the bulk medium and from directly being in contact with the textile (e.g. due to mechanical instability and / or for cost optimization) is the perfusion basket reactor. This is a variation on the tea bag concept which involves confining the oxidoreductase in a filtration membrane-like module that is suspended in the stirred tank reactor (STR) in order to avoid contact with the stirrer, this is useful where the oxidoreductase activates a mediator which in turn crosslink the textile fiber. Further refinement includes using a rotating bed reactor, such the reactor developed by SpinChem (www.spinchem.com), comprising a oxidoreductase-containing compartment attached to the propeller stirrer. This technology combines the benefits of an STR and a packed bed and can be scaled up. Another preferred solution in the context of biocatalyst separation is to use enzyme membrane reactors (EMRs), e.g., available from Degussa. An additional preferred solution is the use of immobilized oxidoreductases in membrane slurry reactors (MSRs) whereby immobilized oxidoreductases are retained inside the reactor because they are too large to pass through the pores of a membrane patch in the reactor wall. This enables the use of a broad range of oxidoreductase (particle or molecule) sizes including the relatively small particles / molecules of cross-linked enzyme aggregates (CLEAs) including so-called metal-organic frameworks (MOF). In some embodiment MOF is a preferred vehicle for immobilizing theoxidoreductase. The reaction and oxidoreductase separation can be combined into a single operation. High enzyme loadings, longer enzyme life-times owing to reduced mechanical attrition, and higher volumetric and enzyme productivities are some of the many advantages. Additional methodology for using immobilized enzymes is described in e.g. Chem. Soc. Rev., (2021). The extended viability or reuse of the oxidoreductase catalyst for multiple treatments has tremendous impact on process economy and is an important leverage in the attractiveness of implementing this new technology in the textile industry.

[0059] The mediator is in some embodiments a lignin derivative, such as lignosulphonate, such as particularly alkali or earth alkali salts of lignosulphonate. Sodium or calcium lignosulphonates are found to be particularly useful as reactive textile component. The lignin derivative suitably has a size of 1000 Da to 20000 Da, such as 1000 Da to 10000 Da, such as 1000 Da to 5000 Da. Smaller molecule sizes are found to provide for better penetration of the textile material, while larger molecule sizes can cross-link over greater distances.

[0060] Additionally or alternatively, the mediator is a phenolic compound, such as an aromatic phenol aryl ether or a radical thereof preferably comprising at least one free OH group and optionally comprising one or more alkoxy groups. Said alkoxy groups can suitably comprise one or more methoxy groups, one example being a methoxyphenol, such as guaiacol.

[0061] The textile fiber composition is suitably subjected to the mediator in an aqueous solution having a concentration of the mediator from 0,0001 M to 1 M, such as from 0,005 M to 0,5M, such as from 0,0025 M to 0,25M, such as from 0,002 M to 0,2M, such as from 0,002 M to 0,05M, such as about 0,01M.

[0062] For laccase catalysts, such as SEQ ID NO: 1, 2, or 3, in combination with a phenolic mediator it has been found that employing a mediator concentration of 8 mM to 12 mM is particularly effective for increasing breaking force and / or elongation and / or elasticity of cotton yarns. For laccase catalysts, such as SEQ ID NO: 1, 2, or 3, in combination with a phenolic mediator it has been found that employing a mediator concentration of 8 mM to 12 mM is particularly effective for improving / lowering pilling, linting and / or felting of woven cotton (containing) textile fabrics.

[0063] A particular advantage of addition of these mediators is the ability of these compounds to penetrate and diffuse effectively into the textile and fiber structures in order to establish cross-linking into the structures. Of importance for optimizing the combination of catalytic ingredients, and in particular the additional textile components such as lignins or derivatives thereof (suitable sources and types of lignins may for instance be found in Materials (2022), is to select the best combination of molecular weight and functionality to optimize reactivity (including lifetime of free radicals), diffusion / perfusion into textile structure, and color compatibility with the application or embodiment(where higher molecular weight compounds may be utilized for nonwoven applications). An additional advantage is for optimizing performance, cost, environmental and safety aspects of the production and use of the textile materials.

[0064] Accordingly, in some preferred embodiments, the cross-linking of textile fibers is accomplished through the use of more than one size or type of mediator, such as multiple single mediators of different molecular sizes and / or multiple mediators of different types and / or a combination of both.

[0065] One advantage of using combinations of different type of activated textile components / mediators is that such mediators can covalently bind to different moieties or molecules in the textile fiber. One advantage of using combinations of mediator sizes is that such mediators differ in their penetration into the textile fiber composition and textile fiber and thus covalently bind to and cross-link different parts of the textile fibers. A further advantage of using combinations of different types / sizes of mediators is that it allows for cross-binding processes to be optimized for different oxidoreductase catalysts. As described herein, in some processes it can be desired to keep the oxidoreductase catalyst separate or even confined from the textile fiber composition and in such a setup a barrier, such as a membrane of filter may be placed between the textile fiber composition and the oxidoreductase catalyst. In such a setup it advantageously be exploited to use a barrier that allows mediators smaller than the oxidoreductase to pass the barrier, so that the oxidoreductase can activate the mediator in one compartment and then the activated mediator can pass the barrier and then attach to a textile fiber or activate another different mediator which then attach to a textile fiber or both reactions may occur at the same time. In the choice of mediators for cross-linking fibers in the textile fiber composition and process conditions for achieving optimal properties of the textile endproducts, the critical properties of the mediator(s) to be considered include molecular size, water solubility, number and characteristics of reactive groups as well as soft parameters such as low toxicity and market acceptance in use. In an example we show that a combination of low- and medium- molecular weight mediators renders superior textile properties compared with treatment with no or either low- or medium-molecular weight mediators alone. In some embodiments the mediator includes a water-soluble low-molecular weight lignin derivative, such as mono- and oligo-lignins, including DMP (2,6-dimethoxyphenol or syringol) and guaiacol (2-methoxyphenol). In other embodiments the mediator includes a water-soluble medium-molecular weight lignin such as alkali lignin and / or earth alkali lignin including earth alkali lignosulfonates, such as calcium lignosulfonates. Lignosulphonates are often prepared from natural wood sources and as such may be available as compositions of lignosulphonate molecules having some range of different molecule sizes. One example of such calcium lignosulfonate is the commercially available Borrement Ca 120, another example is Alkali Lignin (370959) from Sigma-Aldrich. In a further embodiment the mediators includea combination of water-soluble low-molecular weight lignins (such as mono- and oligo-lignins, including DMP and guaiacol) with medium-molecular weight lignins such as alkali lignin and / or earth alkali lignosulfonates, such as calcium lignosulfonates, for example the commercially available Borrement Ca 120. In some embodiments the mediator is selected from a modified at least partially water-soluble cellulose, such as CarboxyMethylCellulose (CMC), in particular CMC which has a water solubility of at least 10 mg / mL, such as at least 20 mg / mL, such as at least 30 mg / mL, such as at least 40 mg / mL, such as at least 50 mg / mL. Further in some embodiments to the CMC is a low viscosity CMC generating a viscosity of 10 CP to 500 CP, such as 20 CP to 400 CP, such as 30 CP to 300 CP, such as 40 CP to 200 CP in a 4 %wt aqueous solution. Oln further embodiments the CMC has a degree of substitution of carboxymethyl groups per anhydroglucose unit of 0.25 to 0,90, such as 0.35 to 0,90, such as 0.50 to 0,90, such as 0.65 to 0,90.

[0066] In some embodiments the mediator is a polyimine. Polyimines are a class of polymers characterized by the presence of imine groups (-C=N-) (subclass of polyamines). The polyimine can be selected from polyethyleneimine (PEI) ([-CH2CH2NH-]n)), Polypropylenimine (PPI) ([- CH2CH2CH(NH2)-]n), Polyazomethines (PAM) ([-RCH=NR-]n) (where R can be various organic groups), Poly(m-phenylene isophthalamide) (Nomex) ([-C6H4-CONH-C6H4-NH-]n), Poly(p-phenylene terephthalamide) (Kevlar) ([-C6H4-CONH-C6H4-NH-]n), Polyvinylamine (PVAm) ([-CH2CH(NH2)-]n), Polyallylamine (PAA) ([-CH2CH(CH2NH2)-]n), Polyaniline (PANI) (Complex structure with repeating units containing imine (-C=N-) and amine (-NH-) groups, Poly(oxime-ester) (Contains repeating oxime (-C=N-O-) and ester groups, Poly(2-ethyl-2-oxazoline) (PEtOx) ([-CH2CH2N(C2H5)CO-]n).

[0067] In some embodiments the mediator is a polyamine. Polyamines are organic compounds having two or more primary amino groups (-NH2). The polyamine can be selected from Ethylenediamine (EDA) (H2N-CH2-CH2-NH2), Tetramethylenediamine (Putrescine) (H2N-(CH2)4-NH2), Pentamethylenediamine (Cadaverine (H2N-(CH2)5-NH2), 1,3-Diaminopropane (H2N-(CH2)3-NH2), Hexamethylenediamine (HMDA) (H2N-(CH2)6-NH2), Spermidine (H2N-(CH2)3-NH-(CH2)4-NH2), Spermine (H2N-(CH2)3-NH-(CH2)4-NH-(CH2)3-NH2), Diethylenetriamine (DETA)(H2N-CH2-CH2-NH- CH2-CH2-NH2), Triethylenetetramine (TETA) (H2N-CH2-CH2-NH-CH2-CH2-NH-CH2-CH2-NH2), N,N'- Dimethylethylenediamine (DMEDA) (H3C-NH-CH2-CH2-NH-CH3).

[0068] Further the polyimine or polyamine preferably has a Weight Average molecular weight (Mw) between 500 to 1000 Da, such as between 600 to 900 Da, such as between 750 to 850 Da. In addition or additionally the polyethylene imine has a Number Average molecular weight (Mn) between 200 to 900 Da, such as between 200 to 1000 Da, such as between 300 to 900 Da, such as between 400 to 800 Da, such as between 500 to 700 Da, such as between 550 to 650 Da.

[0069] In further embodiments the textile fiber composition or textile is also exposed to a secondactivated mediator molecule selected from Guiacol and / or 2,6-dimethoxyphenol (DMP). Preferably the the ratio between the first and the second activated mediator molecule is....

[0070] Surprisingly it was found that Guaiacol and lignosulfonate were superior to DMP, and that combinations of Guaiacol with PEI and / or CMC synergistically boost the strength of textile compositions or textiles treated with the combination, so that the strength improvements obtained with the combination of activated mediators are higher that improvements obtained by the individual mediators.

[0071] The textile fiber composition is suitably subjected to the activated mediator in an aqueous solution having a concentration of the mediator from 0,0001 M to 1 M, such as from 0,005 M to 0,5M, such as from 0,0025 M to 0,25M, such as from 0,002 M to 0,2M, such as from 0,002 M to 0,05M, such as about 0,01M. In some embodiments where the mediator concentration is 0,0001M to 0,lM, such as 0,001M to 0,01M in the reaction medium. In further embodiments, where the mediator is lignosulphonate, the mediator is present in the reaction medium in a concentration of 0,01 wt% to 10 wt% of the textile fiber composition or textile, such as from 0,1 wt% to 5 wt%, such as 0,5 wt% to 2 wt%, such as 0,75 wt% to 2 wt%, optionally 1 wt%. In further embodiments the mediator can act as electron donors for the oxidoreductase. The mediator compounds can improve the electron transfer between the oxidoreductase and the textile fibers. In further embodiments the mediators can have the chemical structure:wherein Ul, U2 and U3 can be identical or different groups of O, S and / or NOH; and R1 and R2 are identical or different, hydrogen, hydroxyl, formyl, carbamoyl or sulfono radical, ester or salt of the sulfono radical, sulfamoyl, nitro, nitroso, amino, cyano, phenyl, benzyl, Cl-C4-alkyl, Cl-C4-alkoxy, Cl- C4-carbonyl, carbonyl-Cl-C4-alkyl. In further embodiments Ul, U2 and U3 are identical or different O or S; and R1 and R2 are identical or different, hydrogen, hydroxyl, formyl, carbamoyl or sulfono radical, ester or salt of the sulfono radical, sulfamoyl, nitro, nitroso, amino, cyano, phenyl, benzyl, C1-C4- alkyl, Cl-C4-alkoxy, Cl-C4-carbonyl, carbonyl-Cl-C4-alkyl. In further embodiments Ul, U2 and U3 are O; and R1 and R2 are identical or different, and are hydrogen, hydroxyl, formyl, carbamoyl or sulfono radical, ester or salt of the sulfono radical, sulfamoyl, nitro, nitroso, amino, cyano, phenyl, benzyl, C1-C4- alkyl,Cl-C4-alkoxy, Cl-C4-carbonyl, carbonyl-Cl-C4-alkyl. In further embodiments, Ul, U2 and U3 are identical or different, O, S or NOH; and R1 and R2 are identical or different, hydrogen, hydroxyl, methyl, ethyl, phenyl, benzyl, formyl, amino, cyano, nitroso, methoxy and / or ethoxy. In further embodiments, Ul, U2 and U3 are identical or different, and are O or S; and R1 and R2 are identical or different, and are hydrogen, hydroxyl, methyl, ethyl, phenyl, benzyl, formyl, amino, cyano, nitroso, methoxy and / or ethoxy. In further embodiments, Ul, U2 and U3 are O; and R1 and R2 are identical or different, and are hydrogen, hydroxyl, methyl, ethyl, phenyl, benzyl, formyl, amino, cyano, nitroso, methoxy and / or ethoxy. In some embodiments the mediator is selected from 1-methylvioluric acid, 1,3-dimethylvioluric acid, thiovioluric acid and violuric acid (alloxan-4,5-dioxime). In further embodiments the mediator is alloxan-5-oxime (violuric acid) and / or its esters, ethers or salts. In further embodiments the mediator is hydroxyl benzoate or hydroxyl benzotriazole. In further embodiments the mediator is selected from aliphatic, cyclo-aliphatic, heterocyclic or aromatic compounds containing the moiety >N-OH. In further embodiments the mediator has a general formula I:wherein Rl, R2, R3, R4 are individually selected from the group consisting of hydrogen, halogen, hydroxy, formyl, carboxy and salts and esters thereof, amino, nitro, Cl-12-alkyl, Cl-6-alkoxy, carbonyl(Cl-12-alkyl), aryl, in particular phenyl, sulfo, aminosulfonyl, carbamoyl, phosphono, phosphonooxy, and salts and esters thereof, wherein the Rl, R2, R3, R4 may be substituted with R5 wherein R5 represents hydrogen, halogen, hydroxy, formyl, carboxy and salts and esters thereof, amino, nitro, Cl-12-alkyl, Cl-6-alkoxy, carbonyl(Cl-12-alkyl), aryl, in particular phenyl, sulfo, aminosulfonyl, carbamoyl, phosphono, phosphonooxy, and salts and esters thereof; [X] represents agroup selected from (-N=N-), (-N=CR6)m, (-CR6=N-)m, (-CR7=CR8-)m, (-CR6=N-NR7-), (-N=N-CHR6-), (- N=CR6-NR7-), (-N=CR6-CHR7-), (-CR6=N-CHR7-), (-CR6=CR7-NR8-), and (-CR6=CR7-CHR8-), wherein R6, R7, and R8 independently of each other are selected from H, OH, NH,, COOH, SO3H, Cl-6-alkyl, NO2, CN, Cl, Br, F, CH2OCH3 OCH3, and COOCH3, and m is 1 or 2. The term "Cl-n-alkyl" wherein n can be from 2 through 12, as used herein, represent a branched or straight alkyl group having from one to the specified number of carbon atoms. Typical Cl-6 -alkyl groups include, but are not limited to, methyl, ethyl, n-propyl, iso-propyl, butyl, iso-butyl, sec-butyl, tert-butyl, pentyl, iso-pentyl, hexyl, isohexyl and the like. In further embodiments the mediator is a compound of the general formula II: wherein Rl, R2, R3, R4 are individually selected from the group consisting of hydrogen, halogen, hydroxy, formyl, carboxy and salts and esters thereof, amino, nitro, Cl-12-alkyl, Cl-6-alkoxy, carbonyl(Cl-12-alkyl), aryl, in particular phenyl, sulfo, aminosulfonyl, carbamoyl, phosphono, phosphonooxy, and salts and esters thereof, wherein the Rl, R2, R3, R4 may be substituted with R5 , wherein R5 represents hydrogen, halogen, hydroxy, formyl, carboxy and salts and esters thereof, amino, nitro, Cl-12-alkyl, Cl-6-alkoxy, carbonyl(Cl-12-alkyl), aryl, in particular phenyl, sulfo, aminosulfonyl, carbamoyl, phosphono, phosphonooxy, and salts and esters thereof. In further embodiments the mediator is a salt or an ester of formula I or II. In further embodiments the mediator is an oxo derivative or an N-hydroxy derivative of heterocyclic compounds or an oxime of oxo- and formyl-derivatives of heterocyclic compounds, said heterocyclic compounds including five-membered nitrogen-containing heterocycles, in particular pyrrol, pyrazole and imidazole and their hydrogenated counterparts (e.g. pyrrolidine) as well as triazoles, such as 1,2,4-triazole; six-membered nitrogencontaining heterocycles, in particular mono-, di- and triazinanes (such as piperidine and piperazine), morpholine and their unsaturated counterparts (e.g. pyridine and pyrimidine); and condensed heterocycles containing the above heterocycles as substructures, e.g. indole, benzothiazole, quinoline and benzoazepine. In further embodiments the mediator is a pyridine aldoxime; N- hydroxypyrrolidinedione such as N-hydroxysuccinimide and N-hydroxyphthalimide; 3,4-dihydro-3- hydroxybenzo[l,2,3]triazine-4-one; formaldoxime trimer (N,N',N"-trihydroxy-l,3,5-triazinane); and violuric acid (l,3-diazinane-2,4,5,6-tetrone-5-oxime). In further embodiments the mediator is an oxime of oxo- and formyl-derivatives of aromatic compounds, such as benzoquinone dioxime and salicylaldoxime (2-hydroxybenzaldehyde oxime), and N-hydroxyamides and N-hydroxyanilides, such as N-hydroxyacetanilide. In further embodiments the mediator is selected from the group of 1- hydroxybenzotriazole; 1-hydroxybenzotriazole hydrate; 1-hydroxybenzotriazole sodium salt; 1-hydroxybenzotriazole potassium salt; 1-hydroxybenzotriazole lithium salt; 1-hydroxybenzotriazole ammonium salt; 1-hydroxybenzotriazole calcium salt; 1-hydroxybenzotriazole magnesium salt; and / or l-hydroxybenzotriazole-6-sulphonic acid. In further embodiments the mediator is 1- hydroxybenzotriazole. All the specifications of N-hydroxy compounds above are to be understood as including tautomeric forms such as N-oxides whenever relevant. In further embodiments the mediator comprises a -CO-NOH- group and has the general formula III:in which A is:and B is the same as A; or B is H or Cl-12-alkyl, said alkyl may contain hydroxy, ester or ether groups (e.g. wherein the ether oxygen is directly attached to A-N(OH)C=O-, thus including N-hydroxy carbamic acid ester derivatives), and R2, R3, R4, R5 and R6 independently of each other are H, OH, NH„ COOH, SOH, Cl-8-alkyl, acyl, NO,, CN, Cl, Br, F, CF3, NOH-CO-phenyl, CO-NOH-phenyl, C1-6-CO-NOH-A, CO- NOH-A, COR12, phenyl-CO-NOH-A, OR7, NR8R9, COORIO, or NOH-CO-R11, wherein R7, R8, R9, RIO, Rll and R12 are Cl-12-alkyl or acyl. R2, R3, R4, R5 and R6 of A are preferably H, OH, NH2, COOH, SO3H, Cl-3-alkyl, acyl, NO2, CN, Cl, Br, F, CF3, NOH-CO-phenyl, CO-NOH-phenyl, COR12, OR7, NR8R9, COORIO, or NOH-CO-R11, wherein R7, R8 and R9 are Cl-3-alkyl or acyl, and RIO, Rll and R12 are Cl- 3-alkyl; more preferably R2, R3, R4, R5 and R6 of A are H, OH, NH2, COOH, SO3H, CH3, acyl, NO2, CN, Cl, Br, F, CF3, CO-NOH-phenyl, COCH3, OR7, NR8R9, or COOCH3, wherein R7, R8 and R9 are CH3 or COCH3; even more preferably R2, R3, R4, R5 and R6 of A are H, OH, COOH, SO3H, CH3, acyl, NO, CN, Cl, Br, F, CO-NOH-phenyl, OCH3, COCH3, or COOCH3; and in particular R2, R3, R4, R5 and R6 of A areH, OH, COOH, SO3H, CH3, NO2, CN, Cl, Br, CO-NOH-phenyl, or OCH3.R2, R3, R4, R5 and R6 of B are preferably H, OH, NH2, COOH, SO3H, Cl-3 -alkyl, acyl, NO2, CN, Cl, Br, F, CF3, NOH-CO-phenyl, CO-NOH-phenyl, COR12, OR7, NR8R9, COORIO, or NOH-CO-R11, wherein R7, R8 and R9 are Cl-3-alkyl or acyl, and RIO, Rll and R12 are Cl-3-alkyl; more preferably R2, R3, R4, R5 and R6 of B are H, OH, NH„ COOH, SOH, CH3, acyl, NO2, CN, Cl, Br, F, CF3, CO-NOH-phenyl, COCH3, OR7, NR8R9, or COOCH3, wherein R7, R8 and R9 are CH3 or COCH3; even more preferably R2, R3, R4, R5 and R6 of B are H, OH, COOH, SO%H, CH„ acyl, NO,, CN, Cl, Br, F, CO-NOH-phenyl, OCH3„ COCH3, or COOCH3; and in particular R2, R3, R4, R5 and R6 of B are H, OH, COOH, SO3H, CH3, NO2, CN, Cl, Br, CO-NOH-phenyl, or OCH3. In further embodiments the mediator is H or Cl-3-alkyl, said alkyl may contain hydroxy, ester or ether groups; preferably said alkyl may contain ester or ether groups; more preferably said alkyl may contain ether groups. In further embodiments A and B independently of each other are:or B is H or Cl-3-alkyl, said alkyl may contain hydroxy, ester or ether groups (e.g. wherein the ether oxygen is directly attached to A-N(OH)C=O-, thus including N-hydroxy carbamic acid ester derivatives), and R2, R3, R4, R5 and R6 independently of each other are H, OH, NH2, COOH, SOH, Cl-3-alkyl, acyl, NO2, CN, Cl, Br, F, CF3, NOH-CO-phenyl, CO-NOH-phenyl, COR12, OR7, NR8R9, COORIO, or NOH-CO- Rll, wherein R7, R8 and R9 are Cl-3-alkyl or acyl, and RIO, Rll and R12 are Cl-3-alkyl. In further embodiments A and B independently of each other are:or B is H or Cl-3-alkyl, said alkyl may contain hydroxy or ether groups (e.g. wherein the ether oxygen is directly attached to A-N(OH)C=O-, thus including N-hydroxy carbamic acid ester derivatives), and R2, R3, R4, R5 and R6 independently of each other are H, OH, NH2, COOH, SO3H, CH3, acyl, NO2, CN, Cl, Br, F, CF3, CO-NOH-phenyl, COCH3, OR7, NR8R9, or COOCH3, wherein R7, R8 and R9 are CH3 or COCH3. In further embodiments A and B independently of each other are:or B is H or Cl-3-alkyl, said alkyl may contain hydroxy or ether groups (e.g. wherein the ether oxygen is directly attached to A-N(OH)C=O-, thus including N-hydroxy carbamic acid ester derivatives), and R2, R3, R4, R5 and R6 independently of each other are H, OH, COOH, SO3H, CH„ acyl, NO, CN, Cl, Br, F, CO-NOH-phenyl, OCH3, COCH3, or COOCH3. In further embodiments A and B independently of each other are:or B is Cl-3-alkyl, said alkyl may contain ether groups (e.g. wherein the ether oxygen is directly attached to A-N(OH)C=O-, thus including N-hydroxy carbamic acid ester derivatives), and R2, R3, R4, R5 and R6 independently of each other are H, OH, COOH, SO3H, CH3, NO2, CN, Cl, Br, CO-NOH-phenyl, or OCH3. The term "Cl-n-alkyl" wherein n can be from 2 through 12, as used herein, represent a branched or straight alkyl group having from one to the specified number of carbon atoms. Typical Cl-6-alkyl groups include, but are not limited to, methyl, ethyl, n-propyl, iso-propyl, butyl, iso-butyl, sec-butyl, tert-butyl, pentyl, iso-pentyl, hexyl, iso-hexyl and the like. The term "acyl" as used herein refers to a monovalent substituent comprising a Cl-6-alkyl group linked through a carbonyl group; such as e.g. acetyl, propionyl, butyryl, isobutyryl, pivaloyl, valeryl, and the like, n further embodiments at least one of the substituents R2, R3, R4, R5 and R6 of A are H, preferably at least two of the substituents R2, R3, R4, R5 and R6 of A are H, more preferably at least three of the substituents R2,R3, R4, R5 and R6 of A are H, most preferably at least four of the substituents R2, R3, R4, R5 and R6 of A are H, in particular all of R2, R3, R4, R5 and R6 of A are H. In further embodiments at least one of the substituents R2, R3, R4, R5 and R6 of Bare H, preferably at least two of the substituents R2, R3, R4, R5 and R6 of B are H, more preferably at least three of the substituents R2, R3, R4, R5 and R6 of Bare H, most preferably at least four of the substituents R2, R3, R4, R5 and R6 of Bare H, in particular all of R2, R3, R4, R5 and R6 of B are H. In further embodiments the mediator is selected from the group consisting of 4-nitrobenzoic acid-N-hydroxyanilide; 4-methoxybenzoic acid-N-hydroxyanilide; N,N'- dihydroxy-N,N'-diphenylterephthalamide; decanoic acid-N-hydroxyanilide; N-hydroxy-4- cyanoacetanilide; N-hydroxy-4-acetylacetanilide; N-hydroxy-4-hydroxyacetanilide; 20 N-hydroxy-3- (N'-hydroxyacetamide )acetanilide; 4-cyanobenzoic acid-N-hydroxyanilide; N-hydroxy-4- nitroacetanilide; N-hydroxyacetanilide; N-hydroxy-N-phenyl-carbamic acid isopropyl ester; N- hydroxy-N-phenyl-carbamic acid methyl ester; N-hydroxy-N-phenyl-carbamic acid phenyl ester; N- hydroxy-N-phenyl-carbamic acid ethyl ester; and N-hydroxy-N-(4-cyanophenyl)-carbamic acid methyl ester. In further embodiments the mediator is a phenolic compound (alkylsyringates) of the general formula IV: wherein the letter A in said formula denotes be a group such as -D, -CH=CH-D, -CH=CH-, CH=CH-D, - CH=N-D, -N=N-D, or -N=CH-D, in which D is selected from the group consisting of -CO-E, -SO-E, -N-XY, and -N'-XYZ, in which E may be -H, -OH, -R, or -OR, and X and Y and Z may be identical or different and selected from -H and -R; R being a Cr-Cs alkyl, preferably a Cl-16-alkyl, which alkyl may be saturated or unsaturated, branched or unbranched and optionally substituted with a carboxy, sulpho or amino group; and B and C may be the same or different and selected from CmH2m+l, where m = 1, 2, 3, 4 or 5. In the above mentioned general formula IV, A may be placed meta to the hydroxy group insteadof being placed in the para-position as shown. In further embodiments the mediator is selected from the group having the general formula V: in which A is a group such as -H, -OH, -CH3, -OCH3, -O(CH2)nCH3 where n = 1, 2, 3, 4, 5, 6, 7 or 8. In further embodiments the mediator is a compound having a general formula VI:in which general formula A represents a single bond, or one of the following groups: (-CH-), (-CH=CH- ), (-NR11-), (-CH=N-), (-N=N-), (-CH=N-N=CH-), or (>C=O); and in which general formula the substituent groups Rl-Rll, which may be identical or different, independently represents any of the following radicals: hydrogen, halogen, hydroxy, formyl, acetyl, carboxy and esters and salts hereof, carbamoyl, sulfo and esters and salts hereof, sulfamoyl, methoxy, nitro, amino, phenyl, Cl-8-alkyl; which carbamoyl, sulfamoyl, phenyl, and amino groups may furthermore be unsubstituted or substituted once or twice with a substituent group R12; and which Cl-8-alkyl group may be saturated or unsaturated, branched or unbranched, and may furthermore be unsubstituted or substituted with one or more substituent groups R12; which substituent group R12 represents any of the following radicals: hydrogen, halogen, hydroxy, formyl, acetyl, carboxy and esters and salts hereof, carbamoyl, sulfo and esters and salts thereof, sulfamoyl, methoxy, nitro, amino, phenyl, or Cl-8-alkyl; which carbamoyl, sulfamoyl, and amino groups may furthermore be unsubstituted or substituted once or twice with hydroxy or methyl; and in which general formula R5 and R6 may together form a group -B-, in which B represents a single bond, one of the following groups (-CH,-), (-CH=CH-), (-CH=N-); or B represents sulfur, or oxygen. In further embodiments the mediator has the general formula VII:in which general formula X represents a single bond, oxygen, or sulphur; and in which general formulathe substituent groups R1-R9, which may be identical or different, independently represents any of the following side groups: hydrogen, halogen, hydroxy, formyl, acetyl, carboxy and esters and salts hereof, carbamoyl, sulfo and esters and salts hereof, sulfamoyl, methoxy, nitro, amino, phenyl, Cl-8 - alkyl; which carbamoyl, sulfamoyl, phenyl, and amino groups may furthermore be unsubstituted or substituted once or twice with a substituent group RIO; and which Cl-8-alkyl group may be saturated or unsaturated, branched or unbranched, and may furthermore be unsubstituted or substituted with one or more substituent groups RIO; which substituent group RIO represents any of the following radicals: hydrogen, halogen, hydroxy, formyl, acetyl, carboxy and esters and salts hereof, carbamoyl, sulfo and esters and salts hereof, sulfamoyl, methoxy, nitro, amino, phenyl, or Cl-8-alkyl; which carbamoyl, sulfamoyl, and amino groups may furthermore be unsubstituted or substituted once or twice with hydroxy or methyl. In further embodiments the mediator is 2,2',6,6'-tetramethyl- piperidine-N-oxyl (TEMPO):

[0072] The mediator can alternatively also be present in the reaction medium in a concentration from 0.01 mM to 1000 mM, preferably in the range of from 0.05 mM to 500 mM, more preferably in the range of from 0.1 mM to 100 mM, and most preferably in the range of from 0.1 mM to 50 mM. Further examples of mediators are disclosed in EP 705327; WO 98 / 56899; EP677102; EP 781328; and EP 707637.

[0073] Additionally in a preferred embodiment the textile fibers are supplemented with additional textile components such as one or more reactive or non-reactive, preferably water soluble, additives or textile components selected from but not limited to dye molecules, coating agents, and inherent or added compounds that may take part in crosslinking textile fibers, said components including but not limited to lignin derivatives, such as lignosulphonates, phenolic compounds hydroxyl, aldehyde, ketone, acid, and / or ester moieties, aromatic molecules (ortho- and para-diphenols, amino phenols, methoxy-phenols, poly-phenols), aliphatic amines, and inorganic cations), phenoxy radicals, semiquinones, quinones, 1,2, 3, 4- butanetetracarboxylic acid, polycarboxylates, glutaraldehydes, formaldehydes, carbodiimides, imidoesters, and / or proteins such as chitosan or reactive radicals of the aforementioned. Textile components or additives, particularly where such additives are activated- T1 -through enzymatic catalysis, are also interchangeably referred to as mediators as defined, supra. Other examples of binders and crosslinking agents utilized for crosslinking Include keratin, collagen (a renewable source is from traditional food waste such as fish scales), gelatin, casein, chitosan, cellulose and lignin derivatives (including oligomers, nanoparticles, and functionalized molecules, see e.g. https: / / www.borregaard.com / product-areas / and Materials (2022) and combinations thereof. The polycarboxylate can suitably be 1,2, 3,4- butanetetracarboxylic acid (BTCA).

[0074] Useful concentrations of the additional supplemental textile components in the medium where the cross-linking of textile fibers take place can be from 0,0001 M to 1 M depending on the type and / or size of the mediator, such as from 0,005 M to 0,5M, such as from 0,0025 M to 0,25M, such as from 0,002 M to 0,2M, such as from 0,002 M to 0,05M, such as about 0,01M.

[0075] The selection of oxidoreductase and mediator(s) can be purposely further optimized with regard to the specific fiber, textiles, or garment to the reinforced, further properties may also be included in such optimization, such as anchoring of colors components or other desired benefit agents, such as fire retardants, UV protectors, insect repellants, water and chemical repellants, anti-wrinkle- or softening- or dirt-repellant agents and the like. Further optimization can be made regarding desired process parameters such as the optimal temperature and pH for both oxidoreductase catalyst and mediator in the process, and for the textile process in which this new technology is to be implemented. In some embodiment the method described herein is implemented in an existing textile manufacturing process, in particular a wet process step such as washing or dyeing. °

[0076] In the methods described herein the reinforced textile fiber composition preferably comprises less than 5 %wt of binders, activators, mordants (such as metal salts acting as bridging agents - alum), and / or adhesive / glue added to the textile. For instance, undertaking reinforcement with transglutaminase reactivity (e.g. from Streptomyces hygroscopicus WSH03-13 or S. mobraensias or other sources suitable for biotechnological production) that may involve a transferase-mediated, acyltransfer reaction between glutamine and lysine with the formation of carboxylamide groups of peptide-bound glutamine. Inherent (peptide) activators as wool keratin chitosan or non-native activators may be added to the textile composition. Of particular advantage for this invention are the calcium-independent microbial or procaryotic transglutaminases.

[0077] The effect of the cross-linking oxidoreductase catalyst may be further augmented by treatment of the textile fibers with a hydrolytic enzyme, catalyzing hydrolysis of cellulosic bonds (cellulytic enzymes) thereby creating targets for a crosslinking reactions. Such cellulytic enzymes include cellulases, optionally an endoglucanase derived from a bacterium or a fungus. In particular the method comprises treatment of the textile fibers with a combination of a) a hydrolase (EC 3) and b) an oxidoreductase (EC 1).

[0078] In addition the method may can further comprise a step of adding a cofactor for the crosslinking oxidoreductase catalyst to the textile fibers either before or during the cross-binding reaction.

[0079] In addition, the covalent cross-linking can further include the binding of a textile benefit agent (to the textile fibers or components) such as a dye or anti-wrinkle- or softening- or dirt-repellant agent to the textile fibers.

[0080] In a special embodiment the oxidoreductase catalyst is kept separate from the textile fiber to be cross-linked. This is useful where the oxidoreductase catalyst is expensive and reuse of the oxidoreductase catalyst in subsequent batches of textile fibers is desirable or where the oxidoreductase catalyst should be kept in a confined environment for cost, efficiency, stability and / or safety reasons. This is possible where the oxidoreductase catalyst is not (only) acting directly on the textile fiber but can provide for the cross-linking through one or more mediators which the oxidoreductase catalyst activates. In such embodiments, the oxidoreductase catalyst can advantageously be kept separate from the textile fiber by a barrier such as a membrane or filter. This separation is particularly attractive where the oxidoreductase catalyst has a macromolecular size, such as an enzyme protein, which can be entrapped and / or encapsulated into a space confined by one or more barriers allowing passage of mediators and medium in and out of the confined space, but blocks passage of the enzyme. This approach allows for improved production economy, and the ability to separate the oxidoreductase catalyst from the textile, production equipment and waste streams. The present inventor has found that catalytic activity is retained and reused up and beyond 75% of initial activity by entrapment and / or encapsulation of the oxidoreductase catalyst. Preferred technologies include simple entrapment into containers separated by a barrier such as a dialysis membrane, immobilization into metal-organic frameworks or polymeric matrices. The reinforcement methods described herein also suitable includes treatment of the textile with a mechanical treatment, promoting the penetration of oxidoreductase catalyst and mediator into the fibers and thereby promoting the covalent crosslinking of fibers by the oxidoreductase catalyst / mediator. This mechanical treatment includes agitating or tumbling or stirring the textile with the oxidoreductase catalyst and / or mediator (optionally together with other desired benefit agents) so that the textile is mechanically impacted. However mechanical treatment can also be accomplished by apply the oxidoreductase catalyst and / or mediator the fiber / textile by liquid jets, described below as hydroentanglement.

[0081] In some embodiments it has been found that very attractive increase in breaking force and / or, elongation and / or elasticity of cotton (containing) yarns can be reached when employing treatment of the cotton (containing) yarns with an aqueous reaction medium characterized by:a) comprising a laccase, such as SEQ ID NO: 1, 2, or 3, in a concentration of 0,05 to 0,2 U / mL reaction medium; b) comprising a phenolic mediator in a concentration of 8 mM to 12 mM; c) having a pH between 5,8 to 6,2 in the reaction medium d) having a water hardness between 0 to 20 dH e) having a temperature between 42°C to 48°C; wherein the cotton (containing) yarn is treated in the reaction medium for 45 min. to 75 min.

[0082] In other embodiments it has been found that very attractive improvement / lowering of pilling, linting and / or felting of woven cotton (containing) textile fabrics can be reached when employing treatment of the woven cotton (containing) textile fabric with an aqueous reaction medium characterized by: a) comprising a laccase, such as SEQ ID NO: 1, 2, or 3, in a concentration of 0,05 to 0,2 U / mL reaction medium; b) comprising a phenolic mediator in a concentration of 8 mM to 12 mM; c) having a pH between 5,8 to 6,2 in the reaction medium d) having a water hardness between 0 to 20 dH e) having a temperature between 42°C to 48°C; wherein the woven cotton (containing) textile fabric is treated in the reaction medium for 45 min. to 75 min.

[0083] Additionally, the method described herein can include physical and / or mechanical entanglement of textile fibers in some embodiments by subjecting the textile fibers to devices such as needle-punching and / or one or more air or water jets (known as hydroentanglement) that result in intercalating or intertwining the fibers. A particular advantage of these types of process engineering devices, and in particular of hydroentanglement, is to boost penetration and perfusion of the catalytic ingredients and reactants, including the additional textile components and / or reaction ingredients into the textile and fiber structures in order to establish cross-linking into the structures. An additional advantage is for optimizing performance, cost, environmental and safety aspects of the production and use of the textile materials.

[0084] Also, when using physical entanglement of textile fibers, the method may include adding one or more benefit agents for coloring, printing, or coating of the textile fibers or reinforced textile fiber composition.

[0085] Further, the method can comprise one or more steps of preparing the textile fibers selected froma) Shredding (including other physical or chemical means for separating or opening or making fibers available) a waste material (including but not limited to pre- and post-consumer textile items) containing the textile fibers, optionally (renewable) fibers; b) Washing the shredded material of step a); and / or c) Refining the shredded and / washed material for removing one or more residues selected from but not limited to compounds such as lignin, dye, wax, protein, or print- or glue- or finishing agents from recycled materials.

[0086] Still further, the method may include one or more steps selected from a) Colleting materials containing the textile fibers, optionally recycled / renewable waste materials; and b) Transporting the collected material to a processing facility for processing the materials according to the methods described herein as well as in the background and detailed description herein.

[0087] It has further been found that the crosslinking of textile fibers using catalysts and mediators described herein improve critical quality parameters of both cotton (containing) yarns and cotton (containing) textile fabrics.

[0088] Accordingly, in a further aspect, the methods described herein includes a method of reducing pilling, linting and / or felting, optionally as determined by Martindale evaluation of a cotton (containing) textile fabric comprising: a) providing a cotton (containing) textile fabric; and b) subjecting the cotton (containing) textile fabric in a reaction medium to a mediator molecule activated by a catalyst, whereby the activated mediator promotes the covalent crosslinking of fibers in the cotton (containing) textile fabric thereby reducing the pilling, linting and / or felting of the cotton (containing) textile fabric.

[0089] In a further aspect the methods described herein includes a method of increasing breaking force and / or elongation and / or elasticity of a cotton (containing) yarn comprising: a) providing a cotton (containing) yarn; and b) subjecting the cotton (containing) yarn in a reaction medium to a mediator molecule activated by a catalyst, whereby the activated mediator promotes the covalent crosslinking of fibers in the cotton (containing) yarn thereby increasing breaking force and / or elongation and / or elasticity of the cotton (containing) yarn.

[0090] A further aspect described herein is a reinforced textile fiber composition obtainable from themethods of this disclosure. Such reinforced textile fiber composition distinguishes from known textile fiber compositions by comprising fibers reinforced by crosslinking optionally in combination with physical entanglement. Accordingly, the reinforced textile obtainable from the method described herein comprises textile fibers and mediator molecules selected from a modified at least partially water-soluble cellulose, a polyimin, a polyamine or a combination thereof covalently bound to and crosslinking moieties of the textile fiber.

[0091] A further aspect described herein is a method for making a garment or an apparel comprising subjecting the reinforced textile fiber composition obtained by the methods described herein to one or more cutting and / or sewing / seaming steps, whereby the reinforced textile fiber composition is shaped into the garment or apparel, which can be used for dressing a subject. The textile fiber composition obtained by the methods described herein can alternatively also be processed into filters for use in for example but not limited to face masks or air supply systems.

[0092] A further aspect described herein is a method for reinforcing new, used, or recycled textile or textile made from inferior quality textile fibers (including alternative fibers) or from textile production processes where quality of end-products is desired be elevated. The textile items obtained by the methods described herein can be processed to obtain superior material and use properties to boost quality and extend lifetime of textile items.Manufacturing of textile fabrics, such as by weaving from yarns are processes that set strict requirements for the yarn quality, because if the yarn breaks during the weaving process the entire process stops, and the fabric quality is compromised or even ruined. However, in a further aspect, it has been found that using the methods described herein to reinforce and strengthen yarns, yarns which before a treatment as described herein do not have the required quality for weaving fabric, can after the reinforcing treatment be used in a weaving process. As a result, yarns made of inferior quality materials can now be used for weaving fabric offering huge economical and environmental benefits. Accordingly, in a separate aspect also provided for herein is a method of manufacturing of a textile fabric comprising reinforcing a yarn using the method described herein and using the yarn in a weaving process.Working examplesExample 1 - Improving mechanical properties of yarn of natural fibers with enzyme / mediator crossbinding agents at different pH and buffer conditions.

[0093] New yarns of 50 / 50% of recycled consumer-waste cotton and conventional cotton, of 100% organic cotton, and of pure new wool are used in this example (commercially available from e.g. Ecological Textiles as, product no. ET_ITY034_82192, grigio melange, yarn count Nm 34 / 2, and productno. ET_TKY040, natural, Nm 85 / 2, respectively, and the latter from Isager, Spinni, color code 0, singlethread 100 g / 600 m). The yarn is cut into 600 cm samples which are manually and carefully rinsed in tap water at 30 °C. Four Media are prepared containing 1) plain tap water (starting pH near 5 and approximately 15 dH water hardness or 2 mM CaCL (previously indicated as 70 mM CaCL, 2) 1500 mM citrate-phosphate Mcllvaine buffer solution (adjusted to pH 6.2), 3) 100 mM potassium phosphate buffer (KPO, adjusted to pH 6.2), and 4) 100 mM acetate buffer (adjusted to pH 5.0) . In 3 repetitions, one sample of each type of yarn is submerged in 100 mL (1 condition, 30 replica of each type of yarn) of the Medium either without a catalyst (control) or with a catalyst: a laccase from Myceliophthora thermophila, expressed in Aspergillus sp. (commercially available as Novozym 51003 from Novozymes or as Laccase from Aspergillus sp. (SAE0050) from Sigma-Aldrich ), dosed at 1 U / mL, cf. supplier declaration), with or without a phenolic mediator (commercially available from Sigma-Aldrich as Guaiacol, 2-methoxyphenol (W253200), dosed at 2 mM, and incubated for 60 min with agitation to secure non-limiting and effective oxygenation and perfusion of reactants into the textile structure, at 40 °C. After treatment samples are soaked for 5 min at 40 °C in a 100 mM carbonate buffer solution, adjusted to pH 10.5, and finally rinsed in cold tap water and dried (24 h, 21 °C, 65% relative humidity). The tensile strength is assessed using a manual procedure, similar to the ISO2062 and the 1-5ST Electromechanical Universal Testing Machines from Tinius Olsen Test Equipment or similar. For the manual procedure the yarn samples are cut into 20 cm pieces where samples are connected by a knot such that the relative strength versus control is tested from 5 repeated pulling-experiments for each condition. This procedure is able to discriminate a relative difference in break force greater than 233 g based on pulling yarn reference samples of 50 / 50 and 60 / 40% recycled / conventional cotton (from Ecological Textiles as, product no. ET_ITY034_82192, yarn count Nm 34 / 2, tenacity in grams 437, and product no. ET_TKY040_12363, Nm 20 / 2, tenacity in grams 670, respectively) with the outcome 0:5 in favor of the latter reference sample.Results:Effect of cross-linking technology on yarn properties - ranking relative to control based on break force.

[0094] Irrespectively, the type of yarn, the samples treated with cross-binding agents that include an enzyme / mediator show a significantly higher relative break force than control samples without an enzyme, respectively. Further, enzyme / mediator samples subjected to a buffer medium adjusted to a pH in the range of 5-6.2 show a significantly higher relative break force than enzyme / mediator samples subjected to a plain tap water medium in this example.

[0095] Figure 2 shows the results of the relative break force assessment from pulling 5 pairs of yarn samples of 50 / 50 conventional and pre-consumer-waste recycled cotton where the conditions without (control) versus with enzyme catalyst (laccase) are compared, all in the plain tap water medium. In 4 out of 5 tests, the yarn treated with enzyme / mediator (A) is the strongest and the control yarn not treated with enzyme / mediator (B) breaks. Figure 3 shows the results of the relative break force assessment from pulling 5 pairs of yarn samples of 50 / 50 conventional and pre-consumer-waste recycled cotton where the medium conditions Mcllvaine buffer (pH 6.2) versus plain tap water are compared, all with laccase / Guaiacol. In 4 out of 5 tests, the yarn treated with enzyme / mediator in the Mcllvaine buffer (A) is the strongest and the yarn in medium not containing buffer (tap water) treated with enzyme / mediator (B) breaks. Figure 4 shows the results of the relative break force assessment from pulling 5 pairs of yarn samples of 50 / 50 conventional and pre-consumer-waste recycled cotton where the medium conditions potassium phosphate buffer (pH 6.2) versus acetate buffer (pH 5.0) are compared, all with laccase / Guaiacol. In this experiment results are comparable. In 3 out of 5 tests, the yarn treated with enzyme / mediator in the acetate buffer (A) is the strongest and the yarn in potassium phosphate buffer treated with enzyme / mediator (B) breaks.

[0096] Since the present method of reinforcement acts on the molecular level of the textile materials, these results also demonstrate that textiles and cloths made from such yarns will also be strengthened by treatment according to the methods described herein, either by treating the fibers making up the yarn, treating the yarns or treating the textile after weaving / knitting.Example 2 - Improving mechanical properties (breaking force) of yarn of natural fibers with enzyme / mediator cross-binding agents in a reactor.

[0097] New yarns of 50 / 50% of recycled consumer-waste cotton and conventional cotton, and of 100% organic cotton, were used in this example (commercially available from e.g. Ecological Textiles as, product no. ET_ITY034_82192, grigio melange, yarn count Nm 34 / 2, and product no. ET_TKY040,natural, Nm 85 / 2, respectively). The yarn was cut into 30 m samples. Also included in this example were two types of woven organic cotton fabric: 1.6 m2 of voile (veil) and 1.4 m2 batist (commercially available from e.g. Ecological Textiles as, product no. ET_TKW004_l offwhitePFP155cm, 100% organic GOTS cotton, 50 / 1 yarn, 65 g / m2, 155 cm width, and ET_TKW005_0 offwhitePFP, 100% organic GOTS cotton. 50 / 1 yarn, 90 g / m2, 140 cm width, respectively). Yarn and fabric were manually prewashed in warm tap water with a standard detergent for white wash and carefully rinsed in cold tap water. Additionally, 15 prewashed cotton pillowcases were used as ballast (to ensure even distribution and agitation in the reactor) and defined in total as the load of the experiment. The load was placed into a horizontally rotating reactor, operated with an intake of tap water. First was run a blank experiment for generating reference samples. The reactor was operated with a textile temperature of approximately 45 °C. The reactor experiment for reference samples was ended after 1 hr, and the reference yarn and the voile (veil) and batiste samples were pulled out, and an identical new load was placed into the reactor for treating with enzyme / mediator cross-binding agents. The experiment was conducted as before; however, a catalytic composite was added to the reactor to a final concentration of 1 mM of a phenolic mediator, in this example Guaiacol as use in Example 1, and 0.1 U / mL of a catalyst: a laccase from Myceliophthora thermophila as used in Example 1. The reactor experiment for treatment with enzyme / mediator cross-binding agents was ended after 1 hr. The yarn and fabric samples were pulled out of the reactor and together with the reference yarn and fabric samples they were manually washed in warm tap water with a standard detergent for white wash and carefully rinsed in cold tap water. All samples were hereafter line dried for a minimum of 24 h, 21 °C, 65% relative humidity. For the yarn samples, changes in single-end breaking force and elongation at break were assessed according to ISO 2062 using 250 mm samples and 50mm / min constant pulling speed.Results:Effect of cross-linking technology on yarn properties. Average of testing 10 samples for each condition.

[0098] Irrespectively, the type of yarn, the samples treated with cross-binding agents that included a catalyst showed a significantly higher break force than control samples without a catalyst, respectively. Since the present method acted on the molecular level of the textile materials, these results also demonstrated that textiles and cloths made from such yarns will also be strengthened by treatment according to the methods described herein, either by treating the fibers making up the yarn, treating the yarns or treating the textile after weaving / knittingExample 3 - Improving mechanical properties (elasticity) of yarn of natural fibers with enzyme / mediator cross-binding agents in a reactor.

[0099] New yarns of 50 / 50% recycled consumer-waste cotton and conventional cotton, and of 100% organic cotton, were used in this example (commercially available from e.g. Ecological Textiles as, product no. ET_ITY034_82192, grigio melange, yarn count Nm 34 / 2, and product no. ET_TKY040, natural, Nm 85 / 2, respectively). The yarn was cut into 30 m samples. Also included in this example were two types of woven organic cotton fabric: 1.6 m2 of voile (veil) and 1.4 m2 batist (commercially available from e.g. Ecological Textiles as, product no. ET_TKW004_l offwhitePFP155cm, 100% organic GOTS cotton, 50 / 1 yarn, 65 g / m2, 155 cm width, and ET_TKW005_0 offwhitePFP, 100% organic GOTS cotton. 50 / 1 yarn, 90 g / m2, 140 cm width, respectively). Yarn and fabric were manually prewashed in warm tap water with a standard detergent for white wash and carefully rinsed in cold tap water. Additionally, 15 prewashed cotton pillowcases were used as ballast (to ensure even distribution and agitation in the reactor) and defined in total as the load of the experiment. The load was placed into a horizontally rotating reactor, operated with an intake of tap water. First was run a blank experiment for generating reference samples. The reactor was operated with a textile temperature of approximately 45 °C. The reactor experiment for reference samples was ended after 1 hr, and the reference yarn and the voile (veil) and batist samples were pulled out, and an identical new load was placed into the reactor for treating with enzyme / mediator cross-binding agents. The experiment was conducted as before; however, a catalytic composite was added to the reactor to a final concentration of 1 mM of a phenolic mediator, in this example Guaiacol as use in Example 1, and 0.1 U / mL of a catalyst: a laccase from Myceliophthora thermophila as used in Example 1. The reactor experiment for treatment with enzyme / mediator cross-binding agents was ended after 1 hr. The yarn and fabric samples were pulled out of the reactor and together with the reference yarn and fabric samples they were manually washed in warm tap water with a standard detergent for white wash and carefully rinsed in cold tap water. All samples were hereafter line dried for a minimum of 24 h, 21 °C, 65%relative humidity.

[0100] For the yarn samples, changes in elasticity (reversible % elongation) were assessed according to a modified DS / EN ISO 14704-1 using 250 mm samples and lOmm / min constant pulling speed to 90% (repeated 5 time for each sample) of the average breaking force as determined in Example 2.Results:Effect of cross-linking technology on yarn properties. Elasticity determined as average reversible % elongation at 90% of breaking force from testing 5 samples pulled repeatedly 5 times for each condition.

[0101] In this example with 100% organic cotton yarn, the samples treated with cross-binding agents that included a catalyst show a significantly higher elasticity than control samples without a catalyst, respectively. Since the present method acts on the molecular level of the textile materials, these results also demonstrate that textiles and cloths made from such yarns will also be strengthened by treatment according to the methods described herein, either by treating the fibers making up the yarn, treating the yarns or treating the textile after weaving / knitting.Example 4 - Improving mechanical properties (abrasion rubs until significant damages) of fabric of natural fibers with enzyme / mediator cross-binding agents in a reactor.

[0102] This example was a continuation of the experiments in Examples 2 where the effects were evaluated of improving mechanical properties of fabric of natural fibers with enzyme / mediator crossbinding agents in a reactor. For the fabric samples, changes in durability were assessed using the Martindale abrasion test according to DS / EN ISO 12945-2:2020, using a load of 595 g and nominal pressure 9 kPa.Results:Effect of cross-linking technology on fabric properties. Visual inspection of onset of multiple surface defects of woven samples as function of number of rubbing abrasions.

[0103] In this example with 100% organic cotton fabric, the samples treated with cross-binding agents that included a catalyst (Figure 6) show a significantly higher number for abrasions (rubs) until fabric damages occur relative to control samples without a catalyst (Figure 5), respectively. This result is also illustrated in Figure 9 where photos were taken after 6000 rubs for the untreated sample and 8000 rubs for the treated sample. Since the present method acts on the molecular level of the textile materials, these results also demonstrate that textiles and cloths made from such yarns will also be strengthened by treatment according to the methods described herein, either by treating the fibers making up the yarn, treating the yarns or treating the textile after weaving / knitting.Example 5 - Improving mechanical properties (relative abrasion scores) of fabric of natural fibers with enzyme / mediator cross-binding agents in a reactor.

[0104] New yarns of 50 / 50% of recycled consumer-waste cotton and conventional cotton, and of 100% organic cotton, were used in this example (commercially available from e.g. Ecological Textiles as, product no. ET_ITY034_82192, grigio melange, yarn count Nm 34 / 2, and product no. ET_TKY040, natural, Nm 85 / 2, respectively). The yarn was cut into 30 m samples. Also included in this example were two types of woven organic cotton fabric: 1.6 m2 of voile (veil) and 1.4 m2 batist (commercially available from e.g. Ecological Textiles as, product no. ET_TKW004_l offwhitePFP155cm, 100% organic GOTS cotton, 50 / 1 yarn, 65 g / m2, 155 cm width, and ET_TKW005_0 offwhitePFP, 100% organic GOTS cotton. 50 / 1 yarn, 90 g / m2, 140 cm width, respectively) as well as 1.7 m2 of a knitted jersey fabric of manmade cellulose fibers (commercially available from e.g. Ecological Textiles as, product no. ET_TKS001_5 offwhite, 100% Tencel, 165 g / m2, 170 cm width). Yarn and fabric were manually prewashed in warm tap water with a standard detergent for white wash and carefully rinsed in cold tap water. Additionally, 10 prewashed cotton pillowcases were used as ballast (to ensure even distribution and agitation in the reactor) and defined in total as the load of the experiment. The load was placed into a horizontally rotating reactor, operated with an intake of tap water. First was run ablank experiment for generating reference samples. The reactor was operated with a textile temperature of approximately 35 °C. The reactor experiment for reference samples was ended after 1 hr, and the reference yarn and fabric samples were pulled out, and an identical new load was placed into the reactor for treating with enzyme / mediator cross-binding agents. The experiment was conducted as before, however, added to the reactor was a catalytic composite to a final concentration of 10 mM of a phenolic mediator, in this example Guaiacol as use in Example 1, and 0.2 U / mL of a catalyst: a laccase from Myceliophthora thermophila as used in Example 1. The reactor experiment for treatment with enzyme / mediator cross-binding agents was ended after 1 hr. The yarn and fabric samples were pulled out of the reactor and together with the reference yarn and fabric samples they were manually washed in warm tap water with a standard detergent for white wash and carefully rinsed in cold tap water. All samples were hereafter line dried for a minimum of 24 h, 21 °C, 65% relative humidity.

[0105] For the fabric samples, changes in durability were assessed using the Martindale abrasion test according to DIN EN ISO 12945-2 (2021-04) and DIN EN ISO 12945-4 (2021-04) which further describe the changes in wear / tear in terms of pilling, linting and felting as a function of a fixed number of abrasions / rubs. The visual changes were noted according to a score table from 5 to 1 where 5 is no changes and 1 is severe changes.Results:Effect of cross-linking technology on fabric properties. Average of Martindale pilling score as function of number of abrasions / rubs for each condition.

[0106] In this example with 100% manmade cellulose jersey knitted Tencel fabric, the samples treated with cross-binding agents that included a catalyst show a significantly higher Martindale pilling score as function of abrasions / rubs (Figure 8) than control samples without a catalyst (Figure 7), respectively. Since the present method acts on the molecular level of the textile materials, these results also demonstrate that textiles and cloths made from such yarns will also be strengthened by treatment according to the methods described herein, either by treating the fibers making up the yarn, treating the yarns or treating the textile after weaving / knitting.ReferencesXiang, P. et al. (2008). "A Porous Medium Model of the Hydro entanglement Process". Journal of Porous Media. 11 (1): 35-49. doi:10.1615 / JPorMedia.vll.il.30. ISSN 1091-028X.Roy Choudhury, A.K. (2014). Sustainable Textile Wet Processing: Applications of Enzymes. In: Muthu, S. (eds) Roadmap to Sustainable Textiles and Clothing. Textile Science and Clothing Technology. Springer, Singapore. https: / / doi.org / 10.1007 / 978-981-287-Q65-0 7.Enzyme-catalyzed protein crosslinking, Applied Microbiology and Biotechnology (2012), DOI: 10.1007 / s00253-012-4569-z.Maddock RMA et al; Enzyme-catalyzed polymer cross-linking: Biocatalytic tools for chemical biology, materials science and beyond; Biopolymers; 2020;lll:e23390. https: / / doi.org / 10.1002 / bip.23390.Applications of Transglutaminase in Textile, Wool, and Leather Processing, International Journal of Textile Science (2014), 3(4): 64-69. DOI: 10.5923 / j.textile.20140304.02.Kadolph, Sara J. (1998). Textiles. Internet Archive. Upper Saddle River, N.J. : Merrill, pp. 4, 5. ISBN 978-0-13-494592-7.Brugnari et al. Bioresources and Bioprocessing (2021) 8:131https: / / doi.org / 10.1186 / s40643- 021-00484-1Energies 2022, 15(5), 1835; https: / / doi.org / 10.3390 / enl5051835Front. Bioeng. Biotechnol. 9:778239. doi: 10.3389 / fbioe.2021.778239Applied Microbiology and Biotechnology (2012), 97(2), DOI:10.1007 / s00253-012-4569-z.- Materials 2022, 15, 953. https: / / doi.org / 10.3390 / mal5030953 and DOI: 10.1002 / app.51951) Childs and Bardsley (1975), Biochem. J. 145(1), 93- 103.Kondo et al. (1994), J. Ferment. Bioeng. 77(6), 700-703- Chemosphere 304 (2022) 135374 (DOI: 10.1016 / j.chemosphere.2022.135374)- Chem. Soc. Rev., 2021, 50, 5850-5862 (DOI: 10.1039 / dlcs00015b)* * *

Claims

Claims1. A method for producing a reinforced textile fiber composition comprising a) providing a textile fiber composition b) optionally forming a textile from the textile fiber composition, and c) subjecting the textile fiber composition or textile in a buffered reaction medium to a first mediator molecule activated by an oxidoreductase catalyst at a pH between 5 to 6, thereby promoting the covalent crosslinking of fibers by the oxidoreductase catalyst / mediator thereby reinforcing the textile fiber composition or textile.

2. The method of claim 1, wherein the textile fibers comprise natural or biological textile fibres or a combination thereof.

3. The method of claim 2 wherein the textile fibres are Man-Made Cellulose Fibers (MMCF).

4. The method of claim 2 to 3, wherein the textile fibers comprise virgin fibers or recycled or renewable fibers or a combination thereof.

5. The method of any preceding claim, wherein the textile fibers comprise natural or biological plant derived fibers optionally derived from cotton, kapok, hemp (Cannabis sativa or Apocynum cannabinum or Furcraea foetida), flax (Linum usitatissimum), jute (Corchorus species including C. olitorius and C. capsularis), ramie (Boehmeria nivea), kenaf (Hibiscus cannabinus), roselle (Hibiscus sabdariffa), sunn (Crotalaria juncea), urena (Urena lobata), nettle, manila, abaca (Musa textilis), cantala (Agave cantala), henequen (Agave fourcroydes), maguey (Agave americana and other species), phormium (Phormium tenax), sisal (Agave sisalana), akund floss (Calotropis procera and C. gigantea), bagasse (Saccharum officinarum), bamboo (various species), bombax cotton (Bombax species), coir (Cocos nucifera) and or wood.

6. The method of claim 2 to 5, wherein the textile fibers comprise a cellulosic material.

7. The method of claim 2 to 6, wherein the textile fibers comprise galactoglucomannan.

8. The method of claim 2 to 7 wherein the textile fibers comprise natural or biological animal derived fibers optionally derived from sheep, rabbits, lama, alpaca, camel, goats, and / or silkworm.

9. The method of claim 8 wherein the textile fibers comprise wool or silk.

10. The method of claim 2 to 9, wherein the textile fibers further comprise a synthetic material, optionally polyester, polyamide, acrylic, polyolefin, polypropylene and / or elastane.

11. The method of any preceding claim, wherein the textile fibers have an average length of between 0,01 mm to 1000 mm, optionally less than 1 mm.

12. The method of any preceding claim, wherein the textile fibers are spun fibers13. The method of claim 1 to 12, wherein the textile fibers are non-spun fibers14. The method of any preceding claim, wherein the reinforced textile is a woven, knitted, braided, crocheted, felted or non-woven fabric.

15. The method of claim 14, wherein the reinforced textile is woven, knitted, braided or crocheted and the textile fibers are spun fibers.

16. The method of claim 1 to 13, wherein the reinforced textile is non-woven or felted and the textile fibers are non-spun fibers.

17. The method of any preceding claim, wherein the reinforced textile comprises less than 5% wt of binders, activators, adhesives / glues added to the textile.

18. The method of any preceding claim, wherein the reinforced textile is a fabric or cloth.

19. The method of any preceding claim wherein the catalyst activates the mediator by catalyzing oxidation or reduction of the mediator to form a reactive radical whereby the activated mediator react with and form cross-links between moieties in the textile fibers or to other mediators.

20. The method of any preceding claim wherein the oxidoreductase is selected from lipoxygenases, (lysyl) oxidases, peroxidases, tyrosinases, laccases, .

21. The method of claim 20, wherein the laccase is derived from:a) a fungus of the genus Thermothelomyces, optionally of the species Thermothelomyces thermophila; b) a fungus of the genus Trametes, optionally of the species Trametes versicolor; or c) a bacterium of the genus Bacillus, optionally of the species Bacillus subtilis.

22. The method of claim 20 to 21, wherein the laccase comprises an amino acid sequence which is at least 70%, such as at least 80%, such as at least 90%, such as at least 95%, such as at least 99%, such as at least 100% identical to the laccase comprised in anyone of SEQ. ID NO: 1, 2 or 3.

23. The method of claim 20, wherein the catalyst is peroxidase.

24. The method of claim 23, wherein the peroxidase is derived from Horseradish.

25. The method of any preceding claim wherein the first mediator molecule selected from a modified at least partially water-soluble cellulose, a polyimin, a polyamine or a combination thereof.

26. The method of any preceding claim wherein the modified at least partially water-soluble cellulose is Carboxy Methyl Cellulose (CMC).

27. The method of any preceding claim wherein the CMC has a water solubility of at least 10 mg / mL, such as at least 20 mg / mL, such as at least 30 mg / mL, such as at least 40 mg / mL, such as at least 50 mg / mL.

28. The method of claim 27 wherein the CMC is a low viscosity CMC generating a viscosity of 10 CP to 500 CP, such as 20 CP to 400 CP, such as 30 CP to 300 CP, such as 40 CP to 200 CP in a 4 %wt aqueous solution.

29. The method of claim 27 to 28 wherein the CMC has a degree of substitution of carboxymethyl groups per anhydro glucose unit of 0.25 to 0,90, such as 0.35 to 0,90, such as 0.50 to 0,90, such as 0.65 to 0,90.

30. The method of any preceding claim wherein the polyimine is a polyethyleneimine (PEI).

31. The method of claim 30 wherein the polyethylene imine has a Weight Average molecular weight(Mw) between 500 to 1000 Da, such as between 600 to 900 Da, such as between 750 to 850 Da.

32. The method of claim 30 to 31 wherein the polyethylene imine has a Number Average molecular weight (Mn) between 200 to 900 Da, such as between 200 to 1000 Da, such as between 300 to 900 Da, such as between 400 to 800 Da, such as between 500 to 700 Da, such as between 550 to 650 Da.

33. The method of any preceding claim comprising subjecting the textile fiber composition or textile to a second activated mediator molecule selected from Guaiacol and / or 2,6-dimethoxyphenol (DMP).

34. The method of claim 33 wherein the ratio between the first and the second activated mediator molecule is ....

35. The method of any preceding claim wherein the textile fiber composition is subjected to the activated mediator in an aqueous reaction medium having a concentration of the mediator from 0,0001 M to 1 M, such as from 0,005 M to 0,5M, such as from 0,0025 M to 0,25M, such as from 0,002 M to 0,2M, such as from 0,002 M to 0,05M, such as about 0,01M.

36. The method of any preceding claim wherein the mediator concentration is 0,0001M to 0,lM, such as 0,001M to 0,01M.

37. The method of any preceding claim wherein the mediator is lignosulfonate present in the reaction medium in a concentration of 0,01 wt% to 10 wt% of the textile fiber composition or textile, such as from 0,1 wt% to 5 wt%, such as 0,5 wt% to 2 wt%, such as 0,75 wt% to 2 wt%, optionally 1 wt%.

38. The method of any preceding claim, further comprising a step of adding a cofactor or activating agent for the catalyst.

39. The method of any preceding claim, further comprising a mechanical treatment of the textile fiber composition providing increased penetration of a liquid comprising a catalyst and / or mediator into the textile fiber composition, thereby promoting the covalent crosslinking of fibers by the catalyst / mediator compared to a method without the mechanical treatment of the textile fiber composition.

40. The method of claim 39, wherein the mechanical treatment comprises one or step selected fromagitation, tumbling, stirring and liquid jets.

41. The method of any preceding claim, further comprising physical entanglement of the textile fibers in the textile composition, wherein the physical entanglement comprises subjecting the textile fibers to one or more air and / or waterjets (Hydro-entanglement) and / or needle-punch devices intercalating the fibers.

42. The method of any preceding claim further comprising a step of adding one or more benefit agents for coloring, printing, or coating of the textile fibers or reinforced textile.

43. The method of any preceding claim further comprising one or more steps prior to the covalent crosslinking selected from a) Colleting materials containing the textile fibers, optionally waste materials; b) Transporting the collected material to a processing facility for processing the materials; c) Shredding the material containing the textile fibers; d) Washing the shredded material of step a); and / or e) Refining the shredded and / washed material by removing one or more residues selected from lignin, colors, wax or protein.

44. The method of any preceding claim wherein the textile fiber composition is a cotton containing yarn or a cotton containing textile fabric.

45. The method of any preceding claim wherein the first mediator molecule is a phenolic mediator, the oxidoreductase catalyst is a laccase, wherein- textile fiber composition is a cotton containing yarn or a cotton containing textile fabric;- the concentration of the laccase in the reaction medium is between 0,05 to 0,2 U / mL;- the concentration of the mediator in the reaction medium is between 8 mM to 12 mM;- the pH of the reaction medium is between 5,8 to 6,0- the water hardness of the reaction medium is between 0 to 20 dH;- the temperature of the reaction medium is between 42°C to 48°C; and- wherein the cotton (containing) yarn or fabric is subjected to the first mediator molecule for 45 min. to 75 min. whereby the breaking force, elongation and / or elasticity of the cotton (containing) yarn is increased or whereby the pilling, linting and / or felting of the cotton (containing) fabrics is improved / lowered.

46. A reinforced textile composition obtainable from the method of any preceding claim, comprising a textile fiber and a mediator molecule selected from a modified at least partially water-soluble cellulose, a polyimin, a polyamine or a combination thereof covalently bound to the textile fiber.

47. The textile composition of claim 46 being a reinforced yarn.

48. The textile composition of claim 46 being a reinforced textile fabric.

49. A method for making a garment or an apparel comprising subjecting the reinforced textile fabric of claim 48 to one or more cutting and / or sewing / seaming steps, whereby the reinforced textile is shaped into the garment or apparel.

50. A method for making a textile fabric comprising subjecting the reinforced yarn of claim 47 to a weaving process producing the textile fabric from the reinforced yarn.

51. A garment or apparel obtainable from the method of claim 49.

52. Use of the garment or apparel of claim 51, for dressing a subject53. A method for making a filter comprising subjecting the reinforced textile of claim 48 to one or more cutting and / or sewing / seaming steps, whereby the reinforced textile is shaped into the filter.* * *

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