WO2024110574A1 - Method for producing reinforced textile fiber compositions - Google Patents

Method for producing reinforced textile fiber compositions Download PDF

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Publication number
WO2024110574A1
WO2024110574A1 PCT/EP2023/082823 EP2023082823W WO2024110574A1 WO 2024110574 A1 WO2024110574 A1 WO 2024110574A1 EP 2023082823 W EP2023082823 W EP 2023082823W WO 2024110574 A1 WO2024110574 A1 WO 2024110574A1
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Prior art keywords
textile
fibers
optionally
cross
catalyst
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PCT/EP2023/082823
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French (fr)
Inventor
Thomas Erik Hønger CALLISEN
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Ligamore Aps
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Publication of WO2024110574A1 publication Critical patent/WO2024110574A1/en

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    • DTEXTILES; PAPER
    • D04BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04HMAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H1/00Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/40Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
    • D04H1/42Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
    • D04H1/425Cellulose series
    • DTEXTILES; PAPER
    • D04BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04HMAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H1/00Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/40Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
    • D04H1/42Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
    • D04H1/4266Natural fibres not provided for in group D04H1/425
    • DTEXTILES; PAPER
    • D04BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04HMAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H1/00Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/40Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
    • D04H1/58Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties by applying, incorporating or activating chemical or thermoplastic bonding agents, e.g. adhesives
    • D04H1/587Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties by applying, incorporating or activating chemical or thermoplastic bonding agents, e.g. adhesives characterised by the bonding agents used
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06MTREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/10Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing oxygen
    • D06M13/152Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing oxygen having a hydroxy group bound to a carbon atom of a six-membered aromatic ring
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06MTREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/10Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing oxygen
    • D06M13/184Carboxylic acids; Anhydrides, halides or salts thereof
    • D06M13/192Polycarboxylic acids; Anhydrides, halides or salts thereof
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06MTREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/01Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with natural macromolecular compounds or derivatives thereof
    • D06M15/03Polysaccharides or derivatives thereof
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06MTREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/70Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment combined with mechanical treatment
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06MTREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M16/00Biochemical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. enzymatic
    • D06M16/003Biochemical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. enzymatic with enzymes or microorganisms
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06MTREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2101/00Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
    • D06M2101/02Natural fibres, other than mineral fibres
    • D06M2101/04Vegetal fibres
    • D06M2101/06Vegetal fibres cellulosic
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06MTREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2400/00Specific information on the treatment or the process itself not provided in D06M23/00-D06M23/18
    • D06M2400/01Creating covalent bondings between the treating agent and the fibre

Definitions

  • the present disclosure relates to methods for producing a reinforced textile fiber composition comprising textile fibers which are covalently crosslinked, and optionally supplied with additional textile components, and optionally combined with methods for physical entanglement of the fibers. Further the disclosure relates reinforced textile compositions obtained from the said methods and methods for making garments or other textile containing objects from the reinforced textile composition.
  • Known methods of making textiles includes methods for making woven and nonwoven fabrics (see for example https://en.wikipedia.org/wiki/Textile_manufacturing). Textile manufacturing is a major industry largely based on the conversion of fibers into yarns and then yarns into fabric. The fabrics are then dyed or printed and fabricated into cloth which is then converted into useful consumer goods such as clothing, household items, upholstery and various useful industrial products. [0003] In the art different types of fibers are used to produce yarns. Cotton remains the most widely used and common natural fiber making up 90% of all-natural fibers used in the textile industry. People often use cotton clothing's and accessories due to the comfort offered by cotton fabrics.
  • 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 into each other.
  • Hydroentanglement is also known as spun-lacing, and this term arose because the 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 grams per square meter (gsm), and the 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 (see Xiang, P. et al. (2008); and US 7530150).
  • the methods and reinforced textile fiber compositions described herein provides benefits and advantages over known ways of producing textiles and/or to textile end products by chemically or biochemically cross-linking/binding/connecting fibers of the textile, whereby the textile is reinforced.
  • the reinforced textile fiber compositions described herein have a high quality normally only achieved by employing premium virgin natural fibers or premium man-made fibers or combinations with these types of fibers despite being made from more sustainable and/or cost-effective fiber materials, processing, and manufacturing.
  • Using the methods provided for herein there is 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.
  • the methods provided for herein enable 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 benefits to the textile production and use by 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.
  • the methods provided for herein 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 methods provided for herein offers solutions to the selection of fiber sources for textile production by providing remedy to the shortcomings due the 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).
  • the short -fiber content typically defined as the g/g fraction of fibers shorter than half the mean length of the premium references.
  • the methods provided for herein provides 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 enabling production of lower linear density materials due to lower fiber fineness and smaller Tex values (g/km) of the rowing's and slivers.
  • the methods provided for herein provides 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 further improves both quality parameters (e.g., tenacity, elongation, cohesion, flexibility, evenness, linear density) and feasible for processing (e.g., via rotor, ring or dry-jet wet spinning) which are defining for the spinning end-products (yarn and thread).
  • quality parameters e.g., tenacity, elongation, cohesion, flexibility, evenness, linear density
  • feasible for processing e.g., via rotor, ring or dry-jet wet spinning
  • the methods provided for herein provides 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.
  • the methods provided for herein improves 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.
  • 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
  • the methods provided for herein provides 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).
  • 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), robustness towards wash-&-wear, lifetime of use and reuse.
  • 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 to covalent crosslinking thereby reinforcing the textile.
  • a reinforced textile obtainable from the said method.
  • 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.
  • Figure 1 shows the results of 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 enzyme catalyst (control) versus with enzyme catalyst (laccase) are compared, all containing Guaiacol mediator in the medium. In all 5 tests the yarn treated with enzyme/mediator (A) is the strongest and the control yarn not treated with enzyme/mediator (B) breaks.
  • Figure 2 shows the principle of reinforcing textile fiber compositions using the methods described herein, illustrating: a) 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. b) 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).
  • 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).
  • 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.
  • fibers/filaments/yarns may be transformed into textile materials by so-called nonwoven methods where interlocking is obtained by means such as physical (incl. needle punching, hydroentanglement) and/or chemical (incl. latex binders).
  • 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.
  • 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.]
  • Physical entanglement 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))
  • Natural fiber refers to natural fibers developed or occur in the fiber shape, 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;
  • 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.;
  • Mineral fibers include the asbestos group. Asbestos is the only naturally occurring long mineral fiber.
  • chrysotile of the serpentine class include 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.
  • Man-made fiber 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 include regenerated (natural) fibers and synthetic fibers (see Encyclopedia Britannica).
  • recycled fiber 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 textile materials 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.
  • the term "renewable fiber” as used herein refers to fibers produced from renewable resources such as wood, grasses and/or agricultural waste.
  • compositions are 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.
  • mediators such as laccase mediators which are typically water soluble molecules which a catalyst can catalyze to form reactive radicals which reacts with textile fibers or other textile components.
  • Mediators include but is not limited to phenolic and aromatic molecules (ortho- and para-diphenols, amino phenols, methoxy-phenols, polyphenols, aliphatic amines, and inorganic cations).
  • 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 to covalent crosslinking thereby reinforcing the textile.
  • the said crosslinking and/or physical entanglement can occur before, during or after preparing a textile from the textile fiber composition.
  • the textile fibers can be natural fibers or manmade fibers of natural or synthetic origin or a combination thereof.
  • the textile fibers comprise virgin fibers or recycled or renewable fibers or a combination thereof.
  • the virgin textile fibers 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • the textile fibers are Man-Made Cellulose Fibers (MMCF).
  • 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.
  • 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.
  • 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.
  • 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.
  • the textile is a knitted textiles is a knitwear.
  • the textile is a braided textile such as carpets made from wool or silk.
  • 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.
  • 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.
  • 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.
  • the reinforced textile fiber composition resulting from the methods described herein is a textile, a fabric or a cloth.
  • 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.
  • 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.
  • 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.
  • 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 the commercially 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.
  • 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.
  • fibers are spun fibers comprised in a woven fabric.
  • the woven fabric is made up of 100% organic GOTS cotton and has a material density of between 50 and 100 g/m 2 , such as from 60 to 70 g/m 2 or from 80 to 100 g/m 2 , such as about 65 g/m 2 or about 90 g/m 2 .
  • Covalently crosslinking the textile fibers is in some embodiments achieved by subjecting the textile fibers to one or more cross-linking catalysts, to one or more reactive additives (also referred to textile components and in some embodiments mediators).
  • the textile fibers may be cross-linked by subjecting them to both such one or more cross-linking catalysts, and to such one or more reactive textile components.
  • the catalysts suitably catalyzes: a) Oxidation or reduction of a substrate comprised in the textile fibers, optionally the textile components, optionally lignin, lipids, polysaccharides and/or proteins, whereby the oxidized or reduced substrate react with and form cross-links to other moieties in the textile fibers; optionally oxidation of lysine in the substrate and formation of dilysine cross-linking bonds; and/or optionally oxidation of phenolic hydroxyl (Ph-OH) moieties in the substrate and formation of cross-linking aromatic ring coupling (C-C and C-0) between Ph-OH groups or Ph-OOH (phenolic carboxyl's); and/or optionally oxidation of aromatic moieties in the substrate e.g.
  • the catalysts can catalyze: a) Oxidation or reduction of a textile fiber and/or a textile component in the textile fiber composition, optionally being lignin or derivatives thereof, lipids, polysaccharides, proteins, phenolic or aromatic molecules, ortho- or para-diphenols, amino phenols, methoxy-phenols, polyphenols, aliphatic amines, and inorganic cations, whereby the oxidized or reduced textile fiber and/or component react with and form cross-links to other textile fibers or components; optionally oxidation of lysine in the textile fiber and/or component and formation of dilysine cross-linking bonds; and/or optionally oxidation of phenolic hydroxyl, aldehyde, ketone, acid, and/or ester moieties in the textile fiber and/or component and formation of cross-linking aromatic ring coupling (C-C and C-O) between phenolic reactive groups; and/or optionally
  • the catalyst catalyzes oxidation or reduction of a water soluble textile component (mediator) in the textile fiber composition selected from lignosulphonates, phenolic or aromatic molecules, ortho- or para-diphenols, amino phenols, methoxy-phenols, polyphenols, and/or aliphatic amines, whereby the oxidized or reduced textile component react with and form cross-links between the fibers in the textile fiber composition.
  • a water soluble textile component selected from lignosulphonates, phenolic or aromatic molecules, ortho- or para-diphenols, amino phenols, methoxy-phenols, polyphenols, and/or aliphatic amines
  • 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.
  • the oxidation or reduction (also referred to as "activation") of the textile component to make it reactive can take place while the textile component is present in the textile fiber composition or the activation can take please outside the textile fiber composition and then the activated textile component is brought in contact with the textile fiber composition to accomplish cross-lining.
  • the catalyst is preferably an organic catalyst, more specifically a polypeptide, more specifically an enzyme.
  • useful enzymes include ligases further including redox-active enzymes, optionally oxidoreductases.
  • redox-active enzymes can suitably be selected from lipoxygenases, (lysyl) oxidases, peroxidases, tyrosinases, and laccases, including those acting on textile fibers or components, lignin, lipids, and proteins, as well as disulfide reductases, sulfhydryl oxidases, dehydrogenases, disulfide isomerases, lytic polysaccharide monooxygenases (LPMO's), and peroxidases.
  • 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.com/articles/10.1186/ sl2934-019-1248-0#citeas and Brugnari et al. (2021) and Energys (2022).
  • 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
  • laccases from the genus Thermothelomyces, 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.
  • Thermothelomyces thermophilus (formerly known as Mycelioptera thermophilus)
  • 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 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.
  • an enzyme 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, and with a 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.
  • a 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 pH and treatment time will depend on the pH and temperature stability and efficiency of the enzyme/catalyst as well as for the mediator and/or functional/reactive groups in the of the textile fibers.
  • Useful peroxidases catalyze the formation of dityrosine cross-links between peptide chains comprised in the textile fibers.
  • Such peroxidases can be derived from Horseradish.
  • a particular advantage for this method and the use of redox-active catalysts, and in particular enzymes, is to immobilize the catalyst. Benefits of immobilization include better stability and reuse of the catalyst/enzyme. Accordingly, in one embodiment the catalyst/enzyme is applied in an immobilized form. Methods for immobilizing 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 enzymes 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.
  • PEM biocatalytic polyelectrolyte multilayer
  • PLM poly-L-lysine
  • PEI polyethylenimine
  • PSS poly(sodium 4- styrenesulfonate)
  • 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 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 enzyme 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 catalyst 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 enzyme activates a crosslinking agent which in turn crosslink the textile fiber.
  • STR stirred tank reactor
  • FIG. 1 Further refinement includes using a rotating bed reactor, such the reactor developed by SpinChem (www.spinchem.com), comprising a catalyst-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.
  • EMRs enzyme membrane reactors
  • An additional preferred solution is the use of immobilized enzymes in membrane slurry reactors (MSRs) whereby immobilized enzymes are retained inside the reactor because they are too large to pass through the pores of a membrane patch in the reactor wall.
  • MMRs membrane slurry reactors
  • MOF metal-organic frameworks
  • CLSAs cross-linked enzyme aggregates
  • MOF metal-organic frameworks
  • the reaction and biocatalyst separation can be combined into a single operation.
  • High catalyst loadings, longer catalyst life-times owing to reduced mechanical attrition, and higher volumetric and catalyst 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 catalyst for multiple treatments has tremendous impact on process economy and is an important leverage the attractiveness of implementing this new technology in the textile industry.
  • the enzyme catalyst can also be a polymerase, optionally a transferase (EC 2) such as transglutaminase, catalyzing intermolecular e-(y-glutamyl)lysine bonds, and wherein the crosslinking by transglutaminase is a transamidation reaction via reactive thioester intermediates.
  • EC 2 transferase
  • the crosslinking can comprise 1,4 additions to -XH groups optionally -NH2 and -SH on the textile fibers and/or the crosslinking comprises lysyl oxidase and/or amine oxidase catalyzed Aldol-condensation Schiff-base formation. Further details and examples of useful enzyme-catalyzed crosslinking can be found in the art e.g. Applied Microbiology and Biotechnology (2012).
  • the covalent cross-linking of textile fibers can be accomplished by supplementing the textile fibers with additional textile components such as to 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, methoxyphenols, poly-phenols), aliphatic amines, and inorganic cations), phenoxy radicals, semi-quinones, quinones, 1,2, 3,4- butanetetracarboxylic acid, polycarboxylates, glutaraldehydes, formaldehydes, carbodiimides, imidoesters,
  • additional textile components such as to one or more reactive or
  • Textile components or additives are also interchangeably referred to as mediators as defined, supra.
  • 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 whereof.
  • the polycarboxylate can suitably be 1, 2,3,4- butanetetracarboxylic acid (BTCA).
  • the lignin derivative is a 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.
  • phenolic compound or radical thereof is a substituted phenolic compound 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.
  • the textile fiber composition is suitably subjected to the water soluble reactive textile component in an aqueous solution having a concentration of the reactive textile component 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.
  • a particular advantage of addition of these additional textile components or reaction ingredients 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.
  • An additional advantage is for optimizing performance, cost, environmental and safety aspects of the production and use of the textile materials.
  • 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.
  • 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 catalysts. As described herein, in some processes it can be desired to keep the 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 catalyst.
  • 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.
  • 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).
  • 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.
  • the mediators include a 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.
  • water-soluble low-molecular weight lignins such as mono- and oligo-lignins, including DMP and guaiacol
  • 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.
  • Useful concentrations of the mediator 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.
  • catalyst and mediator(s) can be purposely 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 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.
  • 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.
  • undertaking reinforcement with transglutaminase reactivity e.g. from Streptomyces hygroscopicus WSH03-13 or S. mobraensias or other sources suitable for biotechnological production
  • Inherent (peptide) activators as wool keratin chitosan or non-native activators may be added to the textile composition.
  • the calcium-independent microbial or procaryotic transglutaminases are the calcium-independent microbial or procaryotic transglutaminases.
  • the covalent cross-linking of textile fibers can be accomplished by subjecting the textile fibers to photo oxidation.
  • the effect of the cross-linking catalyst may further be augmented by treatment of the textile fibers with a hydrolytic enzyme, catalyzing hydrolysis of cellulosic bonds (cell ulytic enzymes) thereby creating targets for a crosslinking reactions.
  • cellulytic enzymes include cellulases, optionally an endoglucanase derived from a bacterium or a fungus.
  • the method comprises treatment of the textile fibers with a combination of a) a hydrolase (EC 3) and b) an oxido-reductase (EC 1).
  • the method may further comprise a step of adding a cofactor for the crosslinking catalyst to the textile fibers either before or during the cross-binding reaction.
  • the covalent cross-linking further includes 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.
  • a textile benefit agent such as a dye or anti-wrinkle- or softening- or dirt-repellant agent to the textile fibers.
  • the cross-linking catalyst is kept separate from the textile fiber to be cross-linked. This is useful where the catalyst is expensive and reuse of the catalyst in subsequent batches of textile fibers is desirable or where the catalyst should be kept in a confined environment for cost, efficiency, stability and/or safety reasons. This is possible where the catalyst is not (only) acting directly on the textile fiber but can provide for the cross-linking through one or more mediators which the catalyst activates. In such embodiments, the catalyst can advantageously be kept separate from the textile fiber by a barrier such as a membrane or filter.
  • the 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 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 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 catalyst and mediator into the fibers and thereby promoting the covalent crosslinking of fibers by the catalyst/mediator.
  • This mechanical treatment includes agitating or tumbling or stirring the textile with the catalyst and/or mediator (optionally together with other desired benefit agents) so that the textile is mechanically impacted.
  • mechanical treatment can also be accomplished by apply the catalyst and/or mediator the fiber/textile by liquid jets, described below as hydroentanglement.
  • the method described herein comprise 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.
  • 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.
  • hydroentanglement air or water jets
  • the method may include adding one or more benefit agents for coloring, printing, or coating of the textile fibers or reinforced textile fiber composition.
  • the method can comprise one or more steps of preparing the textile fibers selected from a) 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.
  • 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.
  • a further aspect described herein is a reinforced textile fiber composition obtainable from the methods 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.
  • 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.
  • 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.
  • 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 to covalent crosslinking of the textile fibers, optionally in combinations with physical entanglement thereby reinforcing the textile.
  • 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.
  • the textile fibers comprise a synthetic material, optionally polyester, polyamide, acrylic, polyolefin, polypropylene and/or elastane.
  • the reinforced textile is a woven, knitted, braided, crocheted, felted or non-woven fabric.
  • the reinforced textile comprises less than 5% wt of binders, activators, adhesives/glues added to the textile.
  • the catalyst catalyzes: a) Oxidation or reduction of a substrate comprised in the textile fiber composition, optionally lignin, lipids, polysaccharides and/or proteins, whereby the oxidized or reduced substrate react with and form cross-links to other moieties in the textile fibers; optionally oxidation of lysine in the substrate and formation of dilysine cross-linking bonds; and/or optionally oxidation of phenolic hydroxyl (Ph-OH) moieties in the substrate and formation of cross-linking aromatic ring coupling (C-C and C-O) between Ph-OH groups; and/or optionally oxidation of aromatic moieties in the substrate e.g.
  • the catalyst catalyzes: a) Oxidation or reduction of a textile component in the textile fiber composition selected from lignin, lipids, polysaccharides, proteins phenolic or aromatic molecules, ortho- or para-diphenols, amino phenols, methoxy-phenols, polyphenols, aliphatic amines, and inorganic cations, whereby the oxidized or reduced textile component react with and form cross-links to other moieties in the textile fibers; optionally oxidation of lysine in the substrate and formation of dilysine crosslinking bonds; and/or optionally oxidation of phenolic hydroxyl (Ph-OH) moieties in the substrate and formation of cross-linking aromatic ring coupling (C-C and C-O) between Ph-OH groups or Ph-OOH (phenolic carboxyl's); and/or optionally oxidation of aromatic moieties in the substrate e.g.
  • a textile component in the textile fiber composition selected from lignin,
  • redox-active enzyme is selected from lipoxygenases, (lysyl) oxidases, peroxidases, tyrosinases, laccases acting on lignin, lipids, and proteins, disulfide reductases, sulfhydryl oxidases, dehydrogenases, disulfide isomerases, lytic polysaccharide monooxygenases (LPMO's), and peroxidases.
  • 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.
  • cross-binding reaction comprises treatment of the textile fibers with a combination of a) a hydrolase (EC 3) and b) an oxido-reductase (EC 1) and/or a transferase (EC 2).
  • cellulytic enzyme is a cellulase, optionally an endoglucanase derived from a bacterium or a fungus.
  • covalent cross-linking of textile fibers further comprises subjecting the textile fibers to one or more reactive additives selected from phenoxy radicals, semi-quinones, quinones, 1,2, 3,4- butanetetracarboxylic acid, polycarboxylates, glutaraldehydes, formaldehydes, imidoesters and/or proteins such as chitosan.
  • one or more reactive additives selected from phenoxy radicals, semi-quinones, quinones, 1,2, 3,4- butanetetracarboxylic acid, polycarboxylates, glutaraldehydes, formaldehydes, imidoesters and/or proteins such as chitosan.
  • any preceding item further comprising one or more steps of 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.
  • a reinforced textile obtainable from the method of any preceding item.
  • a method for making a garment or an apparel comprising subjecting the reinforced textile of item 47 to one or more cutting and/or sewing/seaming steps, whereby the reinforced textile is shaped into the garment or apparel.
  • a garment or apparel obtainable from the method of item 48.
  • a method for making a filter comprising subjecting the reinforced textile of item 47 to one or more cutting and/or sewing/seaming steps, whereby the reinforced textile is shaped into the filter.
  • Example 1 Improving mechanical properties of used woven textile of synthetic and/or natural fibers with enzyme/mediator cross-binding agents at 40 degrees Celsius.
  • the swatches treated with the cross-binding agents that include an enzyme/mediator show a significantly higher tensile strength than control- and enzyme swatches, respectively.
  • Further swatches subjected to the Alkali Lignin mediator show a significantly higher tensile strength than swatches subjected to the Guaiacol mediator in this example.
  • Example 2 Improving mechanical properties of new woven textile of synthetic and/or natural fibers with enzyme/mediator cross-binding agents at room temperature.
  • New standard woven men's shirts, size XL, of conventional cotton, organic cotton, and recycled cotton are purchased at a local department store.
  • the shirts are washed 3 times in a laundry washer at 30 °C a standard care program using a commercial detergent (free of perfume, softeners, and enzymes) and line-dried at room temperature.
  • a Medium containing a 150 mM citrate-phosphate buffer solution, adjusted to pH 6, is prepared.
  • 15 Swatches of 8x20 cm2 are cut out of the back the same shirt and submerged in 1000 mL (1 condition, 3 types of textile incl.
  • the static contact angle of the swatches of different treatment conditions is determined using a Kruss DSA100 Drop Shape Analyzer or similar. For each condition, 3 spots on the edge of each swatch are measured and the results are averaged.
  • the swatches treated with cross-binding agents that include an enzyme/mediator show a significantly higher tensile strength (and static contact angle) than control- and enzyme swatches, respectively.
  • swatches subjected to the Alkali Lignin mediator show a significantly higher tensile strength than swatches subjected to the Guaiacol mediator in this example (opposite ranking for static contact angle).
  • Example 3 Improving mechanical properties of woven fabrics of natural fibers with two-enzyme cross-binding agent.
  • a two-step enzymatic treatment is done by following the conditions of Example 2.
  • First step is to treat the swatches with a cellulase from Trichoderma sp. (commercially available as C1794 from Sigma-Aldrich), dosed at 0.50 U/mL (cf. Kondo et al. (1994)) at 40 °C for 30 min with agitation to secure non-limiting and effective oxygenation and perfusion of reactants into the textile structure, in a Medium containing 150 mM citrate-phosphate buffer solution, adjusted to pH 5.
  • Second step is to treat and assess the textile swatches with the laccase/mediator system as done in Example 2.
  • New non-woven textile 100% GOTS organic cotton, is purchased (commercially available from Ecological Textiles, product no. ET_NL020, 500 g/m2, 2 cm thickness).
  • the non-woven textile is cut into 10x10 cm2 swatches and are manually and carefully rinsed in tap water at 30 °C.
  • 5 swatches are submerged in 1000 mL (1 condition, 5 replica) of the Medium either without (control) or with a cross binding agent: a laccase from Myceliophthora thermophila, expressed in Aspergillus sp.
  • the swatches are carefully washed in cold tap water and dried (24 h in a constant temperature/humidity environment, 21 °C, 65% relative humidity) and the tensile strength is assessed using ISO9073-3 and a 1-5ST Electromechanical Universal Testing Machines from Tinius Olsen Test Equipment or similar. Prior to tensile strength assessment, the static contact angle of the swatches of different treatment conditions is determined using a Kruss DSA100 Drop Shape Analyzer or similar. For each condition, 3 spots on the edge of each swatch are measured and the results are averaged.
  • the swatches treated with cross-binding agents that include an enzyme/mediator show a significantly higher tensile strength than control- and enzyme swatches, respectively. Further, swatches subjected to the Alkali Lignin mediator show a significantly higher tensile strength than swatches subjected to the Guaiacol mediator in this example (where the latter show an increase in static contact angle).
  • Example 5 Improving mechanical properties of new non-woven textile of synthetic and/or natural fibers with enzyme/mediator cross-binding agents at room temperature.
  • New non-woven compress textile size 10x10 cm2, of 30/70 % polyester/viscose are purchased at a local pharmacy (commercially available as Mesoft Kompres, product no. 209813, from Mblnlycke Health Care).
  • the non-woven textile items denoted as swatches, are manually and carefully rinsed in tap water at 30 °C.
  • 15 swatches are submerged in 1000 mL (1 condition, 15 replica) of the Medium either without (control) or with a cross binding agent: a laccase from Myceliophthora thermophila, expressed in Aspergillus sp.
  • the swatches are carefully washed in cold tap water and dried (24 h in a constant temperature/humidity environment, 21 °C, 65% relative humidity) and the tensile strength is assessed using ISO9073-3 and a 1-5ST Electromechanical Universal Testing Machines from Tinius Olsen Test Equipment or similar. Prior to tensile strength assessment, the static contact angle of the swatches of different treatment conditions is determined using a Kruss DSA100 Drop Shape Analyzer or similar. For each condition, 3 spots on the edge of each swatch are measured and the results are averaged.
  • the swatches treated with cross-binding agents that include an enzyme/mediator show a significantly higher tensile strength than control- and enzyme swatches, respectively. Further, swatches subjected to the Alkali Lignin mediator show a significantly higher tensile strength than swatches subjected to the Guaiacol mediator in this example (where the latter show an increase in static contact angle).
  • Example 6 Improving mechanical properties of yarn of natural fibers with enzyme/mediator crossbinding agents at room temperature.
  • New yarn of 60/40% recycled pre-consumer-waste cotton/conventional cotton and of 50/50% recycled post-consumer-waste cotton/Tencel are purchased (commercially available from Ecological Textiles as, product no. ET_ITY020_80160 greggio, yarn count Nm 20/2, and product no. ET NLY016, Nm 20/1, respectively).
  • the yarn is cut into 60 cm samples which are manually and carefully rinsed in tap water at 30 °C.
  • a Medium containing a 150 mM citrate-phosphate buffer solution, adjusted to pH 6, is prepared.
  • 50 samples are submerged in 1000 mL (1 condition, 50 replica) of the Medium either without (control) or with a cross binding agent: a laccase from Myceliophthora thermophila, expressed in Aspergillus sp. (commercially available as Novozym51003 from Novozymes or as Laccase from Aspergillus sp. (SAE0050) from Sigma-Aldrich), dosed at 5 U/mL (cf.
  • samples treated with cross-binding agents that include an enzyme/mediator show a significantly higher tensile strength than control- and enzyme samples, respectively.
  • samples subjected to the Alkali Lignin mediator show a significantly higher tensile strength than samples subjected to the Guaiacol mediator in this example.
  • Example 7 Improving mechanical properties of yarn of natural fibers with enzyme/mediator crossbinding agents.
  • New yarns of 50/50% of recycled pee-consumer-waste cotton and conventional cotton, of 100% organic cotton, and of pure new wool are used in this example provided purchased (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, and the latter from Isager, Spinni, color code 0, single-thread 100 g/600 m).
  • the yarn is cut into 600 cm samples which are manually and carefully rinsed in tap water at 30 °C.
  • a Medium containing a 150 mM citrate-phosphate buffer solution, adjusted to pH 6, is prepared.
  • 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.
  • phenolic mediators commercially available as Guaiacol and Alkali Lignin (370959) from Sigma-Aldrich
  • dosed at 5 mM and incubated for 30 min with agitation to secure non-limiting and effective oxygenation and perfusion of reactants into the textile structure, at 40 °C.
  • 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.
  • 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 brake 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.
  • the type of yarn, the samples treated with cross-binding agents that include an enzyme/mediator shows a significantly higher relative break force than control samples without an enzyme, respectively.
  • enzyme/mediator samples subjected to the Guaiacol mediator shows a significantly higher relative break force than enzyme/mediator samples subjected to the Alkali Lignin mediator in this example.
  • Figure 1 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 containing Guaiacol in the medium. In all 5 tests the yarn treated with enzyme/mediator (A) is the strongest and the control yarn not treated with enzyme/mediator (B) breaks.
  • Example 8 Reinforcement with Trametes versicolor laccase.
  • Example 7 is repeated with a laccase from Trametes versicolor (commercially available from Sigma-Aldrich as product no. 38429). The laccase is dosed at 10 laccase units/g, cf. supplier declarations; other conditions as in Example 7. Similar results are achieved for this alternative catalyst system as in Example 7.
  • Example 1 is repeated with a laccase from Trametes versicolor (commercially available from Sigma-Aldrich as product no. 38429).
  • Example 2 is repeated with a laccase from Trametes versicolor (commercially available from Sigma-Aldrich as product no. 38429).
  • the swatches treated with cross-binding agents that include an enzyme/mediator shows a significantly higher tensile strength (and static contact angle) than control- and enzyme swatches, respectively.
  • swatches subjected to the Guaiacol mediator shows a higher tensile strength than swatches subjected to the Alkali Lignin mediator in this example (opposite ranking for static contact angle). The results are consistent with the results of example 2.
  • Example 3 is repeated with a laccase from Trametes versicolor (commercially available from Sigma-Aldrich as product no. 38429).
  • the swatches treated with cross- binding agents that include an enzyme/mediator shows a significantly higher tensile strength (and static contact angle) than control- and enzyme swatches, respectively.
  • swatches subjected to the Guaiacol mediator shows a higher tensile strength than swatches subjected to the Alkali Lignin mediator in this example (opposite ranking for static contact angle). The results are consistent with the results of example 3.
  • Example 4 is repeated with a laccase from Trametes versicolor (commercially available from Sigma-Aldrich as product no. 38429).
  • the swatches treated with cross-binding agents that include an enzyme/mediator shows a significantly higher tensile strength than control- and enzyme swatches, respectively. Further, swatches subjected to the Guaiacol mediator shows a higher tensile strength than swatches subjected to the Alkali Lignin mediator in this example (opposite ranking for static contact angle). The results are consistent with the results of example 4.
  • Example 5 is repeated with a laccase from Trametes versicolor (commercially available from Sigma-Aldrich as product no. 38429).
  • the swatches treated with cross-binding agents that include an enzyme/mediator shows a significantly higher tensile strength than control- and enzyme swatches, respectively. Further, swatches subjected to the Guaiacol mediator shows a higher tensile strength than swatches subjected to the Alkali Lignin mediator in this example (opposite ranking for static contact angle). The results are consistent with the results of example 5.
  • Example 6 is repeated with a laccase from Trametes versicolor (commercially available from Sigma-Aldrich as product no. 38429).
  • the samples treated with cross-binding agents that include an enzyme/mediator shows a significantly higher tensile strength than control- and enzyme samples, respectively.
  • swatches subjected to the Guaiacol mediator shows a higher tensile strength than swatches subjected to the Alkali Lignin mediator in this example. The results are consistent with the results of example 6.
  • Example 15 Improving mechanical properties of yarn of natural fibers with enzyme/mediator cross-binding agents with and without agitation.
  • Example 7 is repeated, but with and without agitation (0 or 250 rpm of magnetic stir bar). Similar results are achieved for tests with agitation as in Example 7. However, although the pullingexperiments on samples without enzyme/mediator shows no effect of agitation on the strength of the yarn, surprisingly yarns treated with enzyme/mediator with agitation show higher strength compared to yarns treated with enzyme/mediator without agitation. This effect is even more pronounced when using guaiacol as mediator.

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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 to covalent crosslinking of the textile fibers, optionally in combinations with physical entanglement thereby reinforcing the textile.

Description

Method for producing reinforced textile fiber compositions.
Technical Field
[0001] The present disclosure relates to methods for producing a reinforced textile fiber composition comprising textile fibers which are covalently crosslinked, and optionally supplied with additional textile components, and optionally combined with methods for physical entanglement of the fibers. Further the disclosure relates reinforced textile compositions obtained from the said methods and methods for making garments or other textile containing objects from the reinforced textile composition.
Background
[0002] Known methods of making textiles includes methods for making woven and nonwoven fabrics (see for example https://en.wikipedia.org/wiki/Textile_manufacturing). Textile manufacturing is a major industry largely based on the conversion of fibers into yarns and then yarns into fabric. The fabrics are then dyed or printed and fabricated into cloth which is then converted into useful consumer goods such as clothing, household items, upholstery and various useful industrial products. [0003] In the art different types of fibers are used to produce yarns. Cotton remains the most widely used and common natural fiber making up 90% of all-natural fibers used in the textile industry. People often use cotton clothing's and accessories due to the comfort offered by cotton fabrics. There are many variable processes available for spinning textile fibers such as cotton into yarns and fabrication into cloth or fabric-forming stages coupled with the complexities of the finishing and coloration processes to the production of a wide range of products, see e.g. https://en.wikipedia.org/wiki/Wet_process_engineering],
[0004] Also the art includes hydroentanglement.
(https://en.wikipedia.org/wiki/Hydroentanglement). 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 into each other.
[0005] Hydroentanglement is also known as spun-lacing, and this term arose because the 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 grams per square meter (gsm), and the 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 (see Xiang, P. et al. (2008); and US 7530150).
[0006] It is further known to apply enzymes in textile production, see e.g., Roy Choudhury, A.K. (2014). [0007] Also known is crosslinking in technical applications by means of chemistry or (bio)chemical catalysis, see e.g. Enzyme-catalyzed protein crosslinking (2012); Maddock RMA et al.; (2020), and Applications of Transglutaminase in Textile, Wool, and Leather Processing (2014).
[0008] The textile industry, including manufacturing and consumption, represents a global environmental challenge due to massive resource consumption and pollution. Recycling of textile into new high-quality textile is very limited. The use of alternative sources of fibers, with better environmental profiles, have limited use since they do not meet the standards for cost-performance of textile from classical fibers such as cotton. In general, scalable, cost-effective and flexible solutions to these problems are lacking, see review article and references therein: https://www.bbc.com/future/article/20200710-why-clothes-are-so-hard-to-recycle and https://www.sciencedirect.com/science/article/pii/S0959652618305985 .
[0009] Accordingly, there is a need for methods allowing the making of high-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
[0010] The methods and reinforced textile fiber compositions described herein provides benefits and advantages over known ways of producing textiles and/or to textile end products by chemically or biochemically cross-linking/binding/connecting fibers of the textile, whereby the textile is reinforced. The reinforced textile fiber compositions described herein have a high quality normally only achieved by employing premium virgin natural fibers or premium man-made fibers or combinations with these types of fibers despite being made from more sustainable and/or cost-effective fiber materials, processing, and manufacturing. Using the methods provided for herein, there is 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 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 benefits to the textile production and use by 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 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. Alternatively, or additionally, the methods provided for herein offers solutions to the selection of fiber sources for textile production by providing remedy to the shortcomings due the 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). Hereby 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 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 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 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 further improves both quality parameters (e.g., tenacity, elongation, cohesion, flexibility, evenness, linear density) and feasible 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 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 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 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), robustness towards wash-&-wear, lifetime of use and reuse.
[0011] 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 to covalent crosslinking thereby reinforcing the textile. [0012] In a further aspect described herein is a reinforced textile obtainable from the said method.
[0013] 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.
[0014] In a still further aspect described herein is the use of the said garment or apparel for dressing a subject.
[0015] 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
[0016] Figure 1 shows the results of 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 enzyme catalyst (control) versus with enzyme catalyst (laccase) are compared, all containing Guaiacol mediator in the medium. In all 5 tests the yarn treated with enzyme/mediator (A) is the strongest and the control yarn not treated with enzyme/mediator (B) breaks.
[0017] Figure 2 shows the principle of reinforcing textile fiber compositions using the methods described herein, illustrating: a) 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. b) 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). c) 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. d) 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.
Incorporation by reference
[0018] 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
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
[0019] 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.
[0020] In addition, fibers/filaments/yarns may be transformed into textile materials by so-called nonwoven methods where interlocking is obtained by means such as physical (incl. needle punching, hydroentanglement) and/or chemical (incl. latex binders).
[0021] 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.]
[0022] 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))
[0023] The term "virgin fiber" as used herein refers to [the new or first production of fibers from their original source (natural or synthetic).]
[0024] The term "natural fiber" as used herein refers to natural fibers developed or occur in the fiber shape, 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.
[0025] 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).
[0026] 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 textile materials 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. [0027] The term "renewable fiber" as used herein refers to fibers produced from renewable resources such as wood, grasses and/or agricultural waste.
[0028] The term "textile components" are 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 catalyst can catalyze to form reactive radicals which reacts with textile fibers or other textile components. Mediators include but is not limited to phenolic and aromatic molecules (ortho- and para-diphenols, amino phenols, methoxy-phenols, polyphenols, aliphatic amines, and inorganic cations).
Methods for preparing the reinforced textile fiber composition.
[0029] 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 to covalent crosslinking thereby reinforcing the textile.
[0030] The said crosslinking and/or physical entanglement can occur before, during or after preparing a textile from the textile fiber composition.
[0031] 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. The virgin textile fibers (natural or manmade) 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 of 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.
[0032] 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.
[0033] 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.
[0034] 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. [0035] 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. [0036] 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.
[0037] 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.
[0038] In some embodiments the reinforced textile fiber composition resulting from the methods described herein is a textile, a fabric or a cloth.
[0039] 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 the commercially 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.
[0040] 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/m2 or from 80 to 100 g/m2, such as about 65 g/m2 or 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.
Crosslinking textile fibers
[0041] Covalently crosslinking the textile fibers is in some embodiments achieved by subjecting the textile fibers to one or more cross-linking catalysts, to one or more reactive additives (also referred to textile components and in some embodiments mediators). In particular, the textile fibers may be cross-linked by subjecting them to both such one or more cross-linking catalysts, and to such one or more reactive textile components.
[0042] Where cross-linking catalysts are applied the catalysts suitably catalyzes: a) Oxidation or reduction of a substrate comprised in the textile fibers, optionally the textile components, optionally lignin, lipids, polysaccharides and/or proteins, whereby the oxidized or reduced substrate react with and form cross-links to other moieties in the textile fibers; optionally oxidation of lysine in the substrate and formation of dilysine cross-linking bonds; and/or optionally oxidation of phenolic hydroxyl (Ph-OH) moieties in the substrate and formation of cross-linking aromatic ring coupling (C-C and C-0) between Ph-OH groups or Ph-OOH (phenolic carboxyl's); and/or optionally oxidation of aromatic moieties in the substrate e.g. bound to hemicellulose, and formation of cross-linking bonds between the aromatic moieties; and/or optionally oxidation of aromatic and aliphatic amines, hydroxyl- or carboxyl groups; b) Hydrolyzation of substrates comprised in the textile fibers, optionally cellulose, whereby the hydrolyzed substrates allow for increased access to cross-linking moieties comprised in the textile fibers; and/or c) Polymerization of substrates comprised in the textile fibers, optionally proteins, whereby the polymerized substrates are cross-linked optionally by intermolecular e-(y-glutamyl)lysine bonds.
[0043] In further embodiments the catalysts can catalyze: a) Oxidation or reduction of a textile fiber and/or a textile component in the textile fiber composition, optionally being lignin or derivatives thereof, lipids, polysaccharides, proteins, phenolic or aromatic molecules, ortho- or para-diphenols, amino phenols, methoxy-phenols, polyphenols, aliphatic amines, and inorganic cations, whereby the oxidized or reduced textile fiber and/or component react with and form cross-links to other textile fibers or components; optionally oxidation of lysine in the textile fiber and/or component and formation of dilysine cross-linking bonds; and/or optionally oxidation of phenolic hydroxyl, aldehyde, ketone, acid, and/or ester moieties in the textile fiber and/or component and formation of cross-linking aromatic ring coupling (C-C and C-O) between phenolic reactive groups; and/or optionally oxidation of aromatic moieties in the textile fiber and/or component and formation of crosslinking bonds between the aromatic moieties; and/or optionally oxidation of aromatic and aliphatic amines in the textile fiber and/or component; b) Hydrolyzation of substrates comprised in the textile fibers, optionally cellulose, whereby the hydrolyzed substrates allow for increased access to cross-linking moieties comprised in the textile fibers; and/or c) polymerization of substrates comprised in the textile fibers, optionally proteins, whereby the polymerized substrates are cross-linked optionally by intermolecular e-(y-glutamyl)lysine bonds.
[0044] In still further embodiments the the catalyst catalyzes oxidation or reduction of a water soluble textile component (mediator) in the textile fiber composition selected from lignosulphonates, phenolic or aromatic molecules, ortho- or para-diphenols, amino phenols, methoxy-phenols, polyphenols, and/or aliphatic amines, whereby the oxidized or reduced textile component react with and form cross-links between the fibers in the textile fiber composition.
[0045] 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 oxidation or reduction (also referred to as "activation") of the textile component to make it reactive can take place while the textile component is present in the textile fiber composition or the activation can take please outside the textile fiber composition and then the activated textile component is brought in contact with the textile fiber composition to accomplish cross-lining.
[0046] The catalyst is preferably an organic catalyst, more specifically a polypeptide, more specifically an enzyme. Useful enzymes include ligases further including redox-active enzymes, optionally oxidoreductases. Such redox-active enzymes can suitably be selected from lipoxygenases, (lysyl) oxidases, peroxidases, tyrosinases, and laccases, including those acting on textile fibers or components, lignin, lipids, and proteins, as well as disulfide reductases, sulfhydryl oxidases, dehydrogenases, disulfide isomerases, lytic polysaccharide monooxygenases (LPMO's), and peroxidases. 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.com/articles/10.1186/ sl2934-019-1248-0#citeas and Brugnari et al. (2021) and Energies (2022). Particularly useful laccases are laccases from the genus Thermothelomyces, 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 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. Application of an enzyme 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, and with a 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 pH and treatment time will depend on the pH and temperature stability and efficiency of the enzyme/catalyst as well as for the mediator and/or functional/reactive groups in the of the textile fibers.
[0047] Useful peroxidases catalyze the formation of dityrosine cross-links between peptide chains comprised in the textile fibers. Such peroxidases can be derived from Horseradish.
[0048] A particular advantage for this method and the use of redox-active catalysts, and in particular enzymes, is to immobilize the catalyst. Benefits of immobilization include better stability and reuse of the catalyst/enzyme. Accordingly, in one embodiment the catalyst/enzyme is applied in an immobilized form. Methods for immobilizing 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 enzymes 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 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 enzyme 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 catalyst 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 enzyme activates a crosslinking agent 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 catalyst-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 enzymes in membrane slurry reactors (MSRs) whereby immobilized enzymes 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 catalyst (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 the catalyst. The reaction and biocatalyst separation can be combined into a single operation. High catalyst loadings, longer catalyst life-times owing to reduced mechanical attrition, and higher volumetric and catalyst 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 catalyst for multiple treatments has tremendous impact on process economy and is an important leverage the attractiveness of implementing this new technology in the textile industry.
[0049] The enzyme catalyst can also be a polymerase, optionally a transferase (EC 2) such as transglutaminase, catalyzing intermolecular e-(y-glutamyl)lysine bonds, and wherein the crosslinking by transglutaminase is a transamidation reaction via reactive thioester intermediates.
[0050] Alternatively or additionally the crosslinking can comprise 1,4 additions to -XH groups optionally -NH2 and -SH on the textile fibers and/or the crosslinking comprises lysyl oxidase and/or amine oxidase catalyzed Aldol-condensation Schiff-base formation. Further details and examples of useful enzyme-catalyzed crosslinking can be found in the art e.g. Applied Microbiology and Biotechnology (2012).
[0051] Alternatively, or additionally in a preferred embodiment the covalent cross-linking of textile fibers can be accomplished by supplementing the textile fibers with additional textile components such as to 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, methoxyphenols, poly-phenols), aliphatic amines, and inorganic cations), phenoxy radicals, semi-quinones, 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 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 whereof. The polycarboxylate can suitably be 1, 2,3,4- butanetetracarboxylic acid (BTCA). Preferably the lignin derivative is a 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. Additionally or alternatively, phenolic compound or radical thereof is a substituted phenolic compound 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.
[0052] The textile fiber composition is suitably subjected to the water soluble reactive textile component in an aqueous solution having a concentration of the reactive textile component 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.
[0053] A particular advantage of addition of these additional textile components or reaction ingredients 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.
[0054] 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.
[0055] 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 catalysts. As described herein, in some processes it can be desired to keep the 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 catalyst. In such a setup it advantageously be exploited to use a barrier that allows mediators smaller than the catalyst to pass the barrier, so that the catalyst 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 end-products, 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 include a 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.
[0056] Useful concentrations of the mediator 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.
[0057] The selection of catalyst and mediator(s) can be purposely 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 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.
[0058] 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.
[0059] Alternatively, or additionally the covalent cross-linking of textile fibers can be accomplished by subjecting the textile fibers to photo oxidation.
[0060] The effect of the cross-linking catalyst may further be augmented by treatment of the textile fibers with a hydrolytic enzyme, catalyzing hydrolysis of cellulosic bonds (cell ulytic 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 oxido-reductase (EC 1).
[0061] In addition the method may further comprise a step of adding a cofactor for the crosslinking catalyst to the textile fibers either before or during the cross-binding reaction.
[0062] In addition, the covalent cross-linking further includes 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.
[0063] In a special embodiment the cross-linking catalyst is kept separate from the textile fiber to be cross-linked. This is useful where the catalyst is expensive and reuse of the catalyst in subsequent batches of textile fibers is desirable or where the catalyst should be kept in a confined environment for cost, efficiency, stability and/or safety reasons. This is possible where the catalyst is not (only) acting directly on the textile fiber but can provide for the cross-linking through one or more mediators which the catalyst activates. In such embodiments, the 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 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 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 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 catalyst and mediator into the fibers and thereby promoting the covalent crosslinking of fibers by the catalyst/mediator. This mechanical treatment includes agitating or tumbling or stirring the textile with the 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 catalyst and/or mediator the fiber/textile by liquid jets, described below as hydroentanglement.
Entangling fibers
[0064] Alternatively, or additionally, the method described herein comprise 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.
[0065] 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.
[0066] Further, the method can comprise one or more steps of preparing the textile fibers selected from a) 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.
[0067] 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.
Reinforced textile fiber compositions garments and uses thereof.
[0068] A further aspect described herein is a reinforced textile fiber composition obtainable from the methods 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.
[0069] 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.
[0070] 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.
Items of the disclosure
The present disclosure further provides the following embodiments and items:
1. 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 to covalent crosslinking of the textile fibers, optionally in combinations with physical entanglement thereby reinforcing the textile.
2. The method of item 1, wherein the textile fibers comprise natural or biological or synthetic textile fibres or a combination thereof.
3. The method of item 1 or 2, wherein the textile fibers comprise virgin fibers or recycled or renewable fibers or a combination thereof.
4. The method of any preceding item, 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.
5. The method of any preceding item, wherein the textile fibers comprise a cellulosic material.
6. The method of any preceding item, wherein the textile fibers comprise galactoglucomannan.
7. The method of any preceding item, wherein the textile fibers comprise a synthetic material, optionally polyester, polyamide, acrylic, polyolefin, polypropylene and/or elastane.
8. The method of any preceding item, wherein the textile fibers have an average length of between 0,01 mm to 1000 mm, optionally less than 1 mm.
9. The method of any preceding item, wherein the textile fibers are spun fibers
10. The method of item 1 to 9, wherein the textile fibers are non-spun fibers
11. The method of any preceding item, wherein the reinforced textile is a woven, knitted, braided, crocheted, felted or non-woven fabric.
12. The method of item 11, wherein the reinforced textile is woven, knitted, braided or crocheted and the textile fibers are spun fibers.
13. The method of item 1 to 10, wherein the reinforced textile is non-woven or felted and the textile fibers are non-spun fibers.
14. The method of any preceding item, wherein the reinforced textile comprises less than 5% wt of binders, activators, adhesives/glues added to the textile.
15. The method of any preceding item, wherein the reinforced textile is a fabric or cloth.
16. The method of any preceding item, wherein the covalent cross-linking of textile fibers comprises subjecting the textile fibers to one or more cross-linking catalysts, to one or more reactive additives or to one or more physical entanglements, or any combination thereof.
17. The method of item 16, wherein the covalent cross-linking of textile fibres comprises subjecting the textile fibers to one or more cross-linking catalysts.
18. The method of item 17, wherein the catalyst catalyzes: a) Oxidation or reduction of a substrate comprised in the textile fiber composition, optionally lignin, lipids, polysaccharides and/or proteins, whereby the oxidized or reduced substrate react with and form cross-links to other moieties in the textile fibers; optionally oxidation of lysine in the substrate and formation of dilysine cross-linking bonds; and/or optionally oxidation of phenolic hydroxyl (Ph-OH) moieties in the substrate and formation of cross-linking aromatic ring coupling (C-C and C-O) between Ph-OH groups; and/or optionally oxidation of aromatic moieties in the substrate e.g. bound to hemicellulose, and formation of cross-linking bonds between the aromatic moieties; and/or optionally oxidation of aromatic and aliphatic amines; b) Hydrolyzation of substrates comprised in the textile fibers, optionally cellulose, whereby the hydrolyzed substrates allow for increased access to cross-linking moieties comprised in the textile fibers; and/or c) polymerization of substrates comprised in the textile fibers, optionally proteins, whereby the polymerized substrates are cross-linked optionally by intermolecular e-(y-glutamyl)lysine bonds.
19. The method of item 17, wherein the catalyst catalyzes: a) Oxidation or reduction of a textile component in the textile fiber composition selected from lignin, lipids, polysaccharides, proteins phenolic or aromatic molecules, ortho- or para-diphenols, amino phenols, methoxy-phenols, polyphenols, aliphatic amines, and inorganic cations, whereby the oxidized or reduced textile component react with and form cross-links to other moieties in the textile fibers; optionally oxidation of lysine in the substrate and formation of dilysine crosslinking bonds; and/or optionally oxidation of phenolic hydroxyl (Ph-OH) moieties in the substrate and formation of cross-linking aromatic ring coupling (C-C and C-O) between Ph-OH groups or Ph-OOH (phenolic carboxyl's); and/or optionally oxidation of aromatic moieties in the substrate e.g. bound to hemicellulose, and formation of cross-linking bonds between the aromatic moieties; and/or optionally oxidation of aromatic and aliphatic amines, hydroxyl- or carboxyl groups; b) Hydrolyzation of substrates comprised in the textile fibers, optionally cellulose, whereby the hydrolyzed substrates allow for increased access to cross-linking moieties comprised in the textile fibers; and/or c) Polymerization of substrates comprised in the textile fibers, optionally proteins, whereby the polymerized substrates are cross-linked optionally by intermolecular e-(y-glutamyl)lysine bonds.
20. The method of item 17 to 18, wherein the catalyst is an organic catalyst.
21. The method of item 19, wherein the catalyst is an organic catalyst is a polypeptide
22. The method of item 21, wherein the catalyst is an organic catalyst is an enzyme
23. The method of item 22, wherein the enzyme is a ligase (EC 6.1 to EC 6.6).
24. The method of item 22, wherein the enzyme is a redox-active enzyme, optionally an oxidoreductase.
25. The method of item 24, wherein the redox-active enzyme is selected from lipoxygenases, (lysyl) oxidases, peroxidases, tyrosinases, laccases acting on lignin, lipids, and proteins, disulfide reductases, sulfhydryl oxidases, dehydrogenases, disulfide isomerases, lytic polysaccharide monooxygenases (LPMO's), and peroxidases.
26. The method of item 25, 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.
27. The method of item 25 to 26, 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 SEQ. ID NO: 1, 2 or 3.
28. The method of item 25, wherein the catalyst is peroxidase catalyzing formation of dityrosine crosslinks between peptide chains.
29. The method of item 28, wherein the peroxidase is derived from Horseradish. 30. The method of item 22, wherein the enzyme is a polymerase, optionally a transglutaminase, catalyzing intermolecular e-(y-glutamyl)lysine bonds.
31. The method of item 30, wherein the transglutaminase catalyzes a transamidation reaction via reactive thioester intermediates.
32. The method of item 30 to 31, wherein crosslinking comprise 1,4 additions to -XH groups optionally -NH2 and/or -SH on the textile fibres.
33. The method of item 22, wherein the enzyme is a lysyl oxidase and/or amine oxidase catalyzing an aldol-condensation Schiff-base formation.
34. The method of item 22, wherein the cross-binding reaction comprises treatment of the textile fibers with a combination of a) a hydrolase (EC 3) and b) an oxido-reductase (EC 1) and/or a transferase (EC 2).
35. The method of item 34, wherein the hydrolase is a cellulytic enzyme, catalyzing hydrolysis of cellulosic bonds.
36. The method of item 35, wherein the cellulytic enzyme is a cellulase, optionally an endoglucanase derived from a bacterium or a fungus.
37. The method of any preceding item, wherein the covalent cross-linking of textile fibers further comprises subjecting the textile fibers to one or more reactive additives selected from phenoxy radicals, semi-quinones, quinones, 1,2, 3,4- butanetetracarboxylic acid, polycarboxylates, glutaraldehydes, formaldehydes, imidoesters and/or proteins such as chitosan.
38. The method of item 37, wherein the polycarboxylate is 1,2, 3,4- butanetetracarboxylic acid, (BTCA),
39. The method of any preceding item, wherein the covalent cross-linking of textile fibers further comprises subjecting the textile fibers to photo oxidation.
40. The method of any preceding item, further comprising a step of adding a cofactor or activating agent for the catalyst.
41. The method of any preceding item, wherein the covalent cross-linking further comprises binding of a dye or a dirt-repellent agent to the textile fibers.
42. The method of any preceding item, 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.
43. The method of item 42, wherein the mechanical treatment comprises one or step selected from agitation, tumbling, stirring and liquid jets.
44. The method of any preceding item, 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 waterjets intercalating the fibers (Hydro-entanglement).
45. The method of any preceding item further comprising a step of adding one or more benefit agents for coloring, printing, or coating of the textile fibers or reinforced textile.
46. The method of any preceding item further comprising one or more steps of 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.
47. A reinforced textile obtainable from the method of any preceding item.
48. A method for making a garment or an apparel comprising subjecting the reinforced textile of item 47 to one or more cutting and/or sewing/seaming steps, whereby the reinforced textile is shaped into the garment or apparel.
49. A garment or apparel obtainable from the method of item 48.
50. Use of the garment or apparel of item 49, for dressing a subject
51. A method for making a filter comprising subjecting the reinforced textile of item 47 to one or more cutting and/or sewing/seaming steps, whereby the reinforced textile is shaped into the filter.
Working examples
Example 1 - Improving mechanical properties of used woven textile of synthetic and/or natural fibers with enzyme/mediator cross-binding agents at 40 degrees Celsius.
[0071] Used standard woven men's shirts, size XL, of cotton, polyester, and 65/35 % polyester/cotton blend are collected at a local second-hand clothing pickup place. The shirts are washed 3 times in a laundry washer at 40 °C a standard care program using a commercial detergent (free of perfume, softeners, and enzymes) and line-dried at room temperature. A medium containing a 150 mM citratephosphate buffer solution, adjusted to pH 5, is prepared. 15 swatches of 8x20 cm2 are cut out of the back of the same shirt, randomized, and selected for one of three conditions, and submerged in 1000 mL of the medium (1 condition, 3 types of textile incl. internal control, 5 replica) either without (control) or with a cross binding agent. A laccase from Myceliophthora thermophila, expressed in Aspergillus sp. (commercially available as Novozym51003 from Novozymes or a Laccase from Aspergillus sp. (SAE0050) from Sigma-Aldrich), dosed at 1 U/mL (cf. Childs and Bardsley (1975)), and a phenolic mediator (commercially available as Guaiacol or Alkali Lignin (370959) from Sigma-Aldrich), dosed at 5 mM, are incubated with the swatches for 30 min with agitation to secure non-limiting and effective oxygenation and perfusion of reactants into the textile structure, at 40 °C. After the treatment the swatches are carefully washed in cold tap water and dried (24 h in a constant temperature/humidity environment, 21 °C, 65% relative humidity) and the tensile strength is assessed using ISO13934 and a 1-5ST Electromechanical Universal Testing Machines from Tinius Olsen Test Equipment or similar.
Results:
Effect of cross-linking technology on textile properties - ranking relative to control based on tensile strength.
Figure imgf000027_0001
Figure imgf000028_0001
[0072] The swatches treated with the cross-binding agents that include an enzyme/mediator show a significantly higher tensile strength than control- and enzyme swatches, respectively. Further swatches subjected to the Alkali Lignin mediator show a significantly higher tensile strength than swatches subjected to the Guaiacol mediator in this example.
Example 2 - Improving mechanical properties of new woven textile of synthetic and/or natural fibers with enzyme/mediator cross-binding agents at room temperature.
[0073] New standard woven men's shirts, size XL, of conventional cotton, organic cotton, and recycled cotton are purchased at a local department store. The shirts are washed 3 times in a laundry washer at 30 °C a standard care program using a commercial detergent (free of perfume, softeners, and enzymes) and line-dried at room temperature. A Medium containing a 150 mM citrate-phosphate buffer solution, adjusted to pH 6, is prepared. 15 Swatches of 8x20 cm2 are cut out of the back the same shirt and submerged in 1000 mL (1 condition, 3 types of textile incl. internal control, 5 replica) of the Medium either without (control) or with a cross binding agent: a laccase from Myceliophthora thermophila, expressed in Aspergillus sp. (commercially available as Novozym51003 from Novozymes or as Laccase from Aspergillus sp. (SAE0050) from Sigma-Aldrich), dosed at 5 U/mL (cf. Childs and Bardsley (1975)), with or without a phenolic mediator (commercially available as Guaiacol or Alkali Lignin (370959) from Sigma-Aldrich), dosed at 5 mM, and incubated for 30 min with agitation to secure non-limiting and effective oxygenation and perfusion of reactants into the textile structure, at 25 °C. After the treatment the swatches are carefully washed in cold tap water and dried (24 h in a constant temperature/humidity environment, 21 °C, 65% relative humidity) and the tensile strength is assessed using ISO13934 and a 1-5ST Electromechanical Universal Testing Machines from Tinius Olsen Test Equipment or similar. Prior to tensile strength assessment, the static contact angle of the swatches of different treatment conditions is determined using a Kruss DSA100 Drop Shape Analyzer or similar. For each condition, 3 spots on the edge of each swatch are measured and the results are averaged.
Results:
Effect of cross-linking technology on textile properties - ranking relative to control based on tensile strength and static contact angle in parentheses.
Figure imgf000028_0002
Figure imgf000029_0001
[0074] Irrespectively the type of textile, the swatches treated with cross-binding agents that include an enzyme/mediator show a significantly higher tensile strength (and static contact angle) than control- and enzyme swatches, respectively. Further, swatches subjected to the Alkali Lignin mediator show a significantly higher tensile strength than swatches subjected to the Guaiacol mediator in this example (opposite ranking for static contact angle).
Example 3 - Improving mechanical properties of woven fabrics of natural fibers with two-enzyme cross-binding agent.
[0075] A two-step enzymatic treatment is done by following the conditions of Example 2. First step is to treat the swatches with a cellulase from Trichoderma sp. (commercially available as C1794 from Sigma-Aldrich), dosed at 0.50 U/mL (cf. Kondo et al. (1994)) at 40 °C for 30 min with agitation to secure non-limiting and effective oxygenation and perfusion of reactants into the textile structure, in a Medium containing 150 mM citrate-phosphate buffer solution, adjusted to pH 5. After the treatment the swatches are carefully washed in cold tap water, second step is to treat and assess the textile swatches with the laccase/mediator system as done in Example 2.
Results:
Effect of cross-linking technology on textile properties - ranking relative to control based on tensile strength and static contact angle in parentheses.
Figure imgf000029_0002
[0076] Irrespectively the type of textile (all pretreated with cellulase), the swatches treated with crossbinding agents that include an enzyme/mediator show a significantly higher tensile strength (and static contact angle) than control- and enzyme swatches, respectively. Further, swatches subjected to the Alkali Lignin mediator show a significantly higher tensile strength than swatches subjected to the Guaiacol mediator in this example (opposite ranking for static contact angle). Example 4 - Improving mechanical properties of new non-woven textile of natural fibres with enzyme/mediator cross-binding agents at room temperature.
[0077] New non-woven textile, 100% GOTS organic cotton, is purchased (commercially available from Ecological Textiles, product no. ET_NL020, 500 g/m2, 2 cm thickness). The non-woven textile is cut into 10x10 cm2 swatches and are manually and carefully rinsed in tap water at 30 °C. A Medium containing a 150 mM citrate-phosphate buffer solution, adjusted to pH 6, is prepared. In 3 repetitions, 5 swatches are submerged in 1000 mL (1 condition, 5 replica) of the Medium either without (control) or with a cross binding agent: a laccase from Myceliophthora thermophila, expressed in Aspergillus sp. (commercially available as Novozym51003 from Novozymes or as Laccase from Aspergillus sp. (SAE0050) from Sigma-Aldrich), dosed at 5 U/mL (cf. Childs and Bardsley (1975)), with or without a phenolic mediator (commercially available as Guaiacol or Alkali Lignin (370959) from Sigma-Aldrich), dosed at 5 mM, and incubated for 30 min with agitation to secure non-limiting and effective oxygenation and perfusion of reactants into the textile structure, at 25 °C. After the treatment the swatches are carefully washed in cold tap water and dried (24 h in a constant temperature/humidity environment, 21 °C, 65% relative humidity) and the tensile strength is assessed using ISO9073-3 and a 1-5ST Electromechanical Universal Testing Machines from Tinius Olsen Test Equipment or similar. Prior to tensile strength assessment, the static contact angle of the swatches of different treatment conditions is determined using a Kruss DSA100 Drop Shape Analyzer or similar. For each condition, 3 spots on the edge of each swatch are measured and the results are averaged.
Results:
Effect of cross-linking technology on textile properties - ranking relative to control based on tensile strength and static contact angle in parentheses.
Figure imgf000030_0001
[0078] The swatches treated with cross-binding agents that include an enzyme/mediator show a significantly higher tensile strength than control- and enzyme swatches, respectively. Further, swatches subjected to the Alkali Lignin mediator show a significantly higher tensile strength than swatches subjected to the Guaiacol mediator in this example (where the latter show an increase in static contact angle).
Example 5 - Improving mechanical properties of new non-woven textile of synthetic and/or natural fibers with enzyme/mediator cross-binding agents at room temperature.
[0079] New non-woven compress textile, size 10x10 cm2, of 30/70 % polyester/viscose are purchased at a local pharmacy (commercially available as Mesoft Kompres, product no. 209813, from Mblnlycke Health Care). The non-woven textile items, denoted as swatches, are manually and carefully rinsed in tap water at 30 °C. A Medium containing a 150 mM citrate-phosphate buffer solution, adjusted to pH 6, is prepared. In 3 repetitions, 15 swatches are submerged in 1000 mL (1 condition, 15 replica) of the Medium either without (control) or with a cross binding agent: a laccase from Myceliophthora thermophila, expressed in Aspergillus sp. (commercially available as Novozym51003 from Novozymes or as Laccase from Aspergillus sp. (SAE0050) from Sigma-Aldrich), dosed at 5 U/mL (cf. Childs and Bardsley (1975)), with or without a phenolic mediator (commercially available as Guaiacol or Alkali Lignin (370959) from Sigma-Aldrich), dosed at 5 mM, and incubated for 30 min with agitation to secure non-limiting and effective oxygenation and perfusion of reactants into the textile structure, at 25 °C. After the treatment the swatches are carefully washed in cold tap water and dried (24 h in a constant temperature/humidity environment, 21 °C, 65% relative humidity) and the tensile strength is assessed using ISO9073-3 and a 1-5ST Electromechanical Universal Testing Machines from Tinius Olsen Test Equipment or similar. Prior to tensile strength assessment, the static contact angle of the swatches of different treatment conditions is determined using a Kruss DSA100 Drop Shape Analyzer or similar. For each condition, 3 spots on the edge of each swatch are measured and the results are averaged.
Results:
Effect of cross-linking technology on textile properties - ranking relative to control based on tensile strength and static contact angle in parentheses.
Figure imgf000031_0001
[0080] The swatches treated with cross-binding agents that include an enzyme/mediator show a significantly higher tensile strength than control- and enzyme swatches, respectively. Further, swatches subjected to the Alkali Lignin mediator show a significantly higher tensile strength than swatches subjected to the Guaiacol mediator in this example (where the latter show an increase in static contact angle).
Example 6 - Improving mechanical properties of yarn of natural fibers with enzyme/mediator crossbinding agents at room temperature.
[0081] New yarn of 60/40% recycled pre-consumer-waste cotton/conventional cotton and of 50/50% recycled post-consumer-waste cotton/Tencel are purchased (commercially available from Ecological Textiles as, product no. ET_ITY020_80160 greggio, yarn count Nm 20/2, and product no. ET NLY016, Nm 20/1, respectively). The yarn is cut into 60 cm samples which are manually and carefully rinsed in tap water at 30 °C. A Medium containing a 150 mM citrate-phosphate buffer solution, adjusted to pH 6, is prepared. In 3 repetitions, 50 samples are submerged in 1000 mL (1 condition, 50 replica) of the Medium either without (control) or with a cross binding agent: a laccase from Myceliophthora thermophila, expressed in Aspergillus sp. (commercially available as Novozym51003 from Novozymes or as Laccase from Aspergillus sp. (SAE0050) from Sigma-Aldrich), dosed at 5 U/mL (cf. Childs and Bardsley (1975)), with or without a phenolic mediator (commercially available as Guaiacol or Alkali Lignin (370959) from Sigma-Aldrich), dosed at 5 mM, and incubated for 30 min with agitation to secure non-limiting and effective oxygenation and perfusion of reactants into the textile structure, at 25 °C. After the treatment the samples are carefully washed in cold tap water and dried (24 h in a constant temperature/humidity environment, 21 °C, 65% relative humidity) and the tensile strength is assessed using ISO2062 and a 1-5ST Electromechanical Universal Testing Machines from Tinius Olsen Test Equipment or similar.
Results:
Effect of cross-linking technology on yarn properties - ranking relative to control based on tensile strength.
Figure imgf000032_0001
[0082] Irrespectively the type of yarn, the samples treated with cross-binding agents that include an enzyme/mediator show a significantly higher tensile strength than control- and enzyme samples, respectively. Further, samples subjected to the Alkali Lignin mediator show a significantly higher tensile strength than samples subjected to the Guaiacol mediator in this example.
Example 7 - Improving mechanical properties of yarn of natural fibers with enzyme/mediator crossbinding agents.
[0083] New yarns of 50/50% of recycled pee-consumer-waste cotton and conventional cotton, of 100% organic cotton, and of pure new wool are used in this example provided purchased (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, and the latter from Isager, Spinni, color code 0, single-thread 100 g/600 m). The yarn is cut into 600 cm samples which are manually and carefully rinsed in tap water at 30 °C. A Medium containing a 150 mM citrate-phosphate buffer solution, adjusted to pH 6, is prepared. 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 phenolic mediators (commercially available as Guaiacol and Alkali Lignin (370959) from Sigma-Aldrich), dosed at 5 mM, and incubated for 30 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 brake 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.
Figure imgf000033_0001
Figure imgf000034_0001
[0084] Irrespectively, the type of yarn, the samples treated with cross-binding agents that include an enzyme/mediator shows a significantly higher relative break force than control samples without an enzyme, respectively. Further, enzyme/mediator samples subjected to the Guaiacol mediator shows a significantly higher relative break force than enzyme/mediator samples subjected to the Alkali Lignin mediator in this example.
[0085] Figure 1 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 containing Guaiacol in the medium. In all 5 tests the yarn treated with enzyme/mediator (A) is the strongest and the control yarn not treated with enzyme/mediator (B) breaks.
[0086] 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 8 - Reinforcement with Trametes versicolor laccase.
[0087] Example 7 is repeated with a laccase from Trametes versicolor (commercially available from Sigma-Aldrich as product no. 38429). The laccase is dosed at 10 laccase units/g, cf. supplier declarations; other conditions as in Example 7. Similar results are achieved for this alternative catalyst system as in Example 7.
Example 9 - Reinforcement with Trametes versicolor laccase
[0088] Example 1 is repeated with a laccase from Trametes versicolor (commercially available from Sigma-Aldrich as product no. 38429).
Effect of cross-linking technology on textile properties - ranking relative to control based on tensile strength.
Figure imgf000034_0002
[0089] The swatches treated with the cross-binding agents that included an enzyme/mediator shows a significantly higher tensile strength than control- and enzyme swatches, respectively. Further swatches subjected to the guaiacol mediator shows a higher tensile strength than swatches subjected to the alkali lignin mediator in this example. The results are consistent with the results of example 1.
Example 10 - Reinforcement with Trametes versicolor laccase
[0090] Example 2 is repeated with a laccase from Trametes versicolor (commercially available from Sigma-Aldrich as product no. 38429).
Effect of cross-linking technology on textile properties - ranking relative to control based on tensile strength and static contact angle in parentheses.
Figure imgf000035_0001
[0091] Irrespectively the type of textile, the swatches treated with cross-binding agents that include an enzyme/mediator shows a significantly higher tensile strength (and static contact angle) than control- and enzyme swatches, respectively. Further, swatches subjected to the Guaiacol mediator shows a higher tensile strength than swatches subjected to the Alkali Lignin mediator in this example (opposite ranking for static contact angle). The results are consistent with the results of example 2.
Example 11 - Reinforcement with Trametes versicolor laccase
[0092] Example 3 is repeated with a laccase from Trametes versicolor (commercially available from Sigma-Aldrich as product no. 38429).
Effect of cross-linking technology on textile properties - ranking relative to control based on tensile strength and static contact angle in parentheses.
Figure imgf000035_0002
[0093] Irrespectively the type of textile (all pretreated with cellulase), the swatches treated with cross- binding agents that include an enzyme/mediator shows a significantly higher tensile strength (and static contact angle) than control- and enzyme swatches, respectively. Further, swatches subjected to the Guaiacol mediator shows a higher tensile strength than swatches subjected to the Alkali Lignin mediator in this example (opposite ranking for static contact angle). The results are consistent with the results of example 3.
Example 12 - Reinforcement with Trametes versicolor laccase
[0094] Example 4 is repeated with a laccase from Trametes versicolor (commercially available from Sigma-Aldrich as product no. 38429).
Effect of cross-linking technology on textile properties - ranking relative to control based on tensile strength and static contact angle in parentheses.
Figure imgf000036_0001
[0095] The swatches treated with cross-binding agents that include an enzyme/mediator shows a significantly higher tensile strength than control- and enzyme swatches, respectively. Further, swatches subjected to the Guaiacol mediator shows a higher tensile strength than swatches subjected to the Alkali Lignin mediator in this example (opposite ranking for static contact angle). The results are consistent with the results of example 4.
Example 13 - Reinforcement with Trametes versicolor laccase
[0096] Example 5 is repeated with a laccase from Trametes versicolor (commercially available from Sigma-Aldrich as product no. 38429).
Effect of cross-linking technology on textile properties - ranking relative to control based on tensile strength and static contact angle in parentheses.
Figure imgf000036_0002
[0097] The swatches treated with cross-binding agents that include an enzyme/mediator shows a significantly higher tensile strength than control- and enzyme swatches, respectively. Further, swatches subjected to the Guaiacol mediator shows a higher tensile strength than swatches subjected to the Alkali Lignin mediator in this example (opposite ranking for static contact angle). The results are consistent with the results of example 5.
Example 14 - Reinforcement with Trametes versicolor laccase
[0098] Example 6 is repeated with a laccase from Trametes versicolor (commercially available from Sigma-Aldrich as product no. 38429).
Effect of cross-linking technology on yarn properties - ranking relative to control based on tensile strength.
Figure imgf000037_0001
[0099] Irrespectively the type of yarn, the samples treated with cross-binding agents that include an enzyme/mediator shows a significantly higher tensile strength than control- and enzyme samples, respectively. Further, swatches subjected to the Guaiacol mediator shows a higher tensile strength than swatches subjected to the Alkali Lignin mediator in this example. The results are consistent with the results of example 6.
Example 15 - Improving mechanical properties of yarn of natural fibers with enzyme/mediator cross-binding agents with and without agitation.
[0100] Example 7 is repeated, but with and without agitation (0 or 250 rpm of magnetic stir bar). Similar results are achieved for tests with agitation as in Example 7. However, although the pullingexperiments on samples without enzyme/mediator shows no effect of agitation on the strength of the yarn, surprisingly yarns treated with enzyme/mediator with agitation show higher strength compared to yarns treated with enzyme/mediator without agitation. This effect is even more pronounced when using guaiacol as mediator.
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- 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

Claims
1. 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 to covalent crosslinking of the textile fibers thereby reinforcing the 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 fibers
13. The method of claim 1 to 12, wherein the textile fibers are non-spun fibers
14. 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 covalent cross-linking of textile fibers in the textile fiber composition comprises subjecting the textile fibers to one or more cross-linking catalysts and/or to one or more reactive additives (mediators) or any combination thereof.
20. The method of claim 19, wherein the covalent cross-linking of textile fibres comprises subjecting the textile fibers to one or more cross-linking catalysts and to one or more reactive additives.
21. The method of claim 20, wherein a catalyst catalyzes: a) Oxidation or reduction of a textile fiber and/or a textile component in the textile fiber composition, optionally being lignin or derivatives thereof, lipids, polysaccharides, proteins, phenolic or aromatic molecules, ortho- or para-diphenols, amino phenols, methoxy-phenols, polyphenols, aliphatic amines, and inorganic cations, whereby the oxidized or reduced textile fiber and/or component react with and form cross-links to other textile fibers or components; optionally oxidation of lysine in the textile fiber and/or component and formation of dilysine cross-linking bonds; and/or optionally oxidation of phenolic hydroxyl, aldehyde, ketone, acid, and/or ester moieties in the textile fiber and/or component and formation of cross-linking aromatic ring coupling (C-C and C-O) between phenolic reactive groups; and/or optionally oxidation of aromatic moieties in the textile fiber and/or component and formation of crosslinking bonds between the aromatic moieties; and/or optionally oxidation of aromatic and aliphatic amines in the textile fiber and/or component; b) Hydrolyzation of substrates comprised in the textile fibers, optionally cellulose, whereby the hydrolyzed substrates allow for increased access to cross-linking moieties comprised in the textile fibers; and/or c) polymerization of substrates comprised in the textile fibers, optionally proteins, whereby the polymerized substrates are cross-linked optionally by intermolecular e-(y-glutamyl)lysine bonds.
22. The method of claim 21, wherein the catalyst catalyzes oxidation or reduction of a water soluble textile component (mediator) in the textile fiber composition selected from lignosulphonates, phenolic or aromatic molecules, ortho- or para-diphenols, amino phenols, methoxy-phenols, polyphenols, and/or aliphatic amines, whereby the oxidized or reduced textile component react with and form cross-links to other moieties in the textile fibers.
23. The method of claim 20 to 21, wherein the catalyst is an organic catalyst.
24. The method of claim 22, wherein the catalyst is an organic catalyst is a polypeptide.
25. The method of claim 24, wherein the catalyst is an organic catalyst is an enzyme.
26. The method of claim 25, wherein the enzyme is a ligase (EC 6.1 to EC 6.6).
27. The method of claim 25, wherein the enzyme is a redox-active enzyme, optionally an oxidoreductase.
28. The method of claim 27, wherein the redox-active enzyme is selected from lipoxygenases, (lysyl) oxidases, peroxidases, tyrosinases, laccases including those acting on lignin, lipids, and proteins, disulfide reductases, sulfhydryl oxidases, dehydrogenases, disulfide isomerases, lytic polysaccharide monooxygenases (LPMO's), and peroxidases.
29. The method of claim 28, 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.
30. The method of claim 28 to 29, 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.
31. The method of claim 28, wherein the catalyst is peroxidase catalyzing formation of dityrosine cross-links between peptide chains.
32. The method of claim 31, wherein the peroxidase is derived from Horseradish.
33. The method of claim 25, wherein the enzyme is a polymerase, optionally a transglutaminase, catalyzing intermolecular e-(y-glutamyl)lysine bonds.
34. The method of claim 33, wherein the transglutaminase catalyzes a transamidation reaction via reactive thioester intermediates.
35. The method of claim 33 to 34, wherein crosslinking comprise 1,4 additions to -XH groups optionally -NH2 and/or -SH on the textile fibres.
36. The method of claim 25, wherein the enzyme is a lysyl oxidase and/or amine oxidase catalyzing an aldol-condensation Schiff-base formation.
37. The method of claim 25, wherein the cross-binding reaction comprises treatment of the textile fibers with a combination of a) a hydrolase (EC 3) and b) an oxido-reductase (EC 1) and/or a transferase (EC 2).
38. The method of claim 37, wherein the hydrolase is a cellulytic enzyme, catalyzing hydrolysis of cellulosic bonds.
39. The method of claim 38, wherein the cellulytic enzyme is a cellulase, optionally an endoglucanase derived from a bacterium or a fungus.
40. The method of any preceding claim, wherein the covalent cross-linking of textile fibers further comprises subjecting the textile fibers to one or more water soluble reactive textile components (mediators).
41. The method of claim 40 wherein the water soluble reactive textile component is selected from the group consisting of lignin derivatives, such as lignosulphonates, phenolic compounds hydroxyl, aldehyde, ketone, acid, and/or ester moieties, phenolic and aromatic molecules (ortho- and paradiphenols, amino phenols, methoxy-phenols, poly-phenols), aliphatic amines, and inorganic cations), phenoxy radicals, semi-quinones, quinones, 1,2, 3, 4- butanetetracarboxylic acid, polycarboxylates, glutaraldehydes, formaldehydes, carbodiimides, imidoesters, and/or proteins such as chitosan or reactive radicals of the aforementioned.
42. The method of claim 41 wherein the lignin derivative is a lignosulphonate.
43. The method of claim 42 wherein the lignosulphonate is an alkali or earth alkali salt of lignosulphonate.
44. The method of claim 43 wherein the lignosulphonate is a sodium or calcium lignosulphonate.
45. The method of claim 41 to 44 wherein the lignin has a size of 1000 Da to 20000 Da, optionally 1000 Da to 10000 Da, optionally 1000 Da to 5000 Da.
46. The method of claim 41 wherein the phenolic compound or radical thereof is a substituted phenolic compound comprising at least one free OH group and optionally comprising one or more alkoxy groups.
47. The method of claim 46 wherein the one or more alkoxy groups comprise one or more methoxy groups.
48. The method of claim 47 wherein substituted phenolic compound comprise a methoxyphenol, optionally guaiacol.
49. The method of claim 40, wherein the polycarboxylate is 1,2, 3, 4- butanetetracarboxylic acid, (BTC A),
50. The method of claim 40 to 49 wherein the textile fiber composition is subjected to the water soluble reactive textile component in an aqueous solution having a concentration of the reactive textile component 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.
51. The method of any preceding claim, wherein the covalent cross-linking of textile fibers further comprises subjecting the textile fibers to photo oxidation.
52. The method of any preceding claim, further comprising a step of adding a cofactor or activating agent for the catalyst.
53. 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.
54. The method of claim 53, wherein the mechanical treatment comprises one or step selected from agitation, tumbling, stirring and liquid jets.
55. 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.
56. 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.
57. The method of any preceding claim further comprising one or more steps of 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.
58. A reinforced textile obtainable from the method of any preceding claim.
59. A method for making a garment or an apparel comprising subjecting the reinforced textile of claim 58 to one or more cutting and/or sewing/seaming steps, whereby the reinforced textile is shaped into the garment or apparel.
60. A garment or apparel obtainable from the method of claim 59.
61. Use of the garment or apparel of claim 60, for dressing a subject
62. A method for making a filter comprising subjecting the reinforced textile of claim 58 to one or more cutting and/or sewing/seaming steps, whereby the reinforced textile is shaped into the filter.
* * *
PCT/EP2023/082823 2022-11-23 2023-11-23 Method for producing reinforced textile fiber compositions WO2024110574A1 (en)

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