EP4355943A1 - Flame retardant fabric comprising cotton alternative - Google Patents

Flame retardant fabric comprising cotton alternative

Info

Publication number
EP4355943A1
EP4355943A1 EP22729249.7A EP22729249A EP4355943A1 EP 4355943 A1 EP4355943 A1 EP 4355943A1 EP 22729249 A EP22729249 A EP 22729249A EP 4355943 A1 EP4355943 A1 EP 4355943A1
Authority
EP
European Patent Office
Prior art keywords
fabric
fibres
lyocell
treatment
yarns
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
EP22729249.7A
Other languages
German (de)
French (fr)
Inventor
Simone Christina Frederique KARKDIJK
André Aelredus Laurentius VAN RIJN
Gerrit Beert VAN DIJK
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Ten Cate Protect BV
Original Assignee
Ten Cate Protect BV
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Ten Cate Protect BV filed Critical Ten Cate Protect BV
Publication of EP4355943A1 publication Critical patent/EP4355943A1/en
Pending legal-status Critical Current

Links

Classifications

    • 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
    • D06M13/244Treating 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 sulfur or phosphorus
    • D06M13/282Treating 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 sulfur or phosphorus with compounds containing phosphorus
    • D06M13/285Phosphines; Phosphine oxides; Phosphine sulfides; Phosphinic or phosphinous acids or derivatives thereof
    • DTEXTILES; PAPER
    • D02YARNS; MECHANICAL FINISHING OF YARNS OR ROPES; WARPING OR BEAMING
    • D02GCRIMPING OR CURLING FIBRES, FILAMENTS, THREADS, OR YARNS; YARNS OR THREADS
    • D02G3/00Yarns or threads, e.g. fancy yarns; Processes or apparatus for the production thereof, not otherwise provided for
    • D02G3/02Yarns or threads characterised by the material or by the materials from which they are made
    • D02G3/04Blended or other yarns or threads containing components made from different materials
    • DTEXTILES; PAPER
    • D02YARNS; MECHANICAL FINISHING OF YARNS OR ROPES; WARPING OR BEAMING
    • D02GCRIMPING OR CURLING FIBRES, FILAMENTS, THREADS, OR YARNS; YARNS OR THREADS
    • D02G3/00Yarns or threads, e.g. fancy yarns; Processes or apparatus for the production thereof, not otherwise provided for
    • D02G3/44Yarns or threads characterised by the purpose for which they are designed
    • D02G3/443Heat-resistant, fireproof or flame-retardant yarns or threads
    • DTEXTILES; PAPER
    • D03WEAVING
    • D03DWOVEN FABRICS; METHODS OF WEAVING; LOOMS
    • D03D1/00Woven fabrics designed to make specified articles
    • D03D1/0035Protective fabrics
    • DTEXTILES; PAPER
    • D03WEAVING
    • D03DWOVEN FABRICS; METHODS OF WEAVING; LOOMS
    • D03D15/00Woven fabrics characterised by the material, structure or properties of the fibres, filaments, yarns, threads or other warp or weft elements used
    • D03D15/20Woven fabrics characterised by the material, structure or properties of the fibres, filaments, yarns, threads or other warp or weft elements used characterised by the material of the fibres or filaments constituting the yarns or threads
    • D03D15/208Woven fabrics characterised by the material, structure or properties of the fibres, filaments, yarns, threads or other warp or weft elements used characterised by the material of the fibres or filaments constituting the yarns or threads cellulose-based
    • D03D15/217Woven fabrics characterised by the material, structure or properties of the fibres, filaments, yarns, threads or other warp or weft elements used characterised by the material of the fibres or filaments constituting the yarns or threads cellulose-based natural from plants, e.g. cotton
    • DTEXTILES; PAPER
    • D03WEAVING
    • D03DWOVEN FABRICS; METHODS OF WEAVING; LOOMS
    • D03D15/00Woven fabrics characterised by the material, structure or properties of the fibres, filaments, yarns, threads or other warp or weft elements used
    • D03D15/20Woven fabrics characterised by the material, structure or properties of the fibres, filaments, yarns, threads or other warp or weft elements used characterised by the material of the fibres or filaments constituting the yarns or threads
    • D03D15/208Woven fabrics characterised by the material, structure or properties of the fibres, filaments, yarns, threads or other warp or weft elements used characterised by the material of the fibres or filaments constituting the yarns or threads cellulose-based
    • D03D15/225Woven fabrics characterised by the material, structure or properties of the fibres, filaments, yarns, threads or other warp or weft elements used characterised by the material of the fibres or filaments constituting the yarns or threads cellulose-based artificial, e.g. viscose
    • DTEXTILES; PAPER
    • D03WEAVING
    • D03DWOVEN FABRICS; METHODS OF WEAVING; LOOMS
    • D03D15/00Woven fabrics characterised by the material, structure or properties of the fibres, filaments, yarns, threads or other warp or weft elements used
    • D03D15/20Woven fabrics characterised by the material, structure or properties of the fibres, filaments, yarns, threads or other warp or weft elements used characterised by the material of the fibres or filaments constituting the yarns or threads
    • D03D15/283Woven fabrics characterised by the material, structure or properties of the fibres, filaments, yarns, threads or other warp or weft elements used characterised by the material of the fibres or filaments constituting the yarns or threads synthetic polymer-based, e.g. polyamide or polyester fibres
    • DTEXTILES; PAPER
    • D03WEAVING
    • D03DWOVEN FABRICS; METHODS OF WEAVING; LOOMS
    • D03D15/00Woven fabrics characterised by the material, structure or properties of the fibres, filaments, yarns, threads or other warp or weft elements used
    • D03D15/40Woven fabrics characterised by the material, structure or properties of the fibres, filaments, yarns, threads or other warp or weft elements used characterised by the structure of the yarns or threads
    • D03D15/47Woven fabrics characterised by the material, structure or properties of the fibres, filaments, yarns, threads or other warp or weft elements used characterised by the structure of the yarns or threads multicomponent, e.g. blended yarns or threads
    • 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
    • D06M13/322Treating 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 nitrogen
    • D06M13/402Amides imides, sulfamic acids
    • D06M13/432Urea, thiourea or derivatives thereof, e.g. biurets; Urea-inclusion compounds; Dicyanamides; Carbodiimides; Guanidines, e.g. dicyandiamides
    • 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
    • D06M13/322Treating 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 nitrogen
    • D06M13/44Treating 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 nitrogen containing nitrogen and phosphorus
    • 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
    • D06M15/19Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/37Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/39Aldehyde resins; Ketone resins; Polyacetals
    • D06M15/423Amino-aldehyde resins
    • 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
    • D06M15/19Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/37Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/39Aldehyde resins; Ketone resins; Polyacetals
    • D06M15/423Amino-aldehyde resins
    • D06M15/43Amino-aldehyde resins modified by phosphorus compounds
    • D06M15/431Amino-aldehyde resins modified by phosphorus compounds by phosphines or phosphine oxides; by oxides or salts of the phosphonium radical
    • 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
    • D06M2101/00Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
    • D06M2101/16Synthetic fibres, other than mineral fibres
    • 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
    • D06M2200/00Functionality of the treatment composition and/or properties imparted to the textile material
    • D06M2200/30Flame or heat resistance, fire retardancy properties
    • 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
    • D06M2200/00Functionality of the treatment composition and/or properties imparted to the textile material
    • D06M2200/35Abrasion, pilling or fibrillation resistance
    • DTEXTILES; PAPER
    • D10INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10BINDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B2201/00Cellulose-based fibres, e.g. vegetable fibres
    • D10B2201/01Natural vegetable fibres
    • D10B2201/02Cotton
    • DTEXTILES; PAPER
    • D10INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10BINDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B2201/00Cellulose-based fibres, e.g. vegetable fibres
    • D10B2201/20Cellulose-derived artificial fibres
    • DTEXTILES; PAPER
    • D10INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10BINDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B2331/00Fibres made from polymers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. polycondensation products
    • D10B2331/04Fibres made from polymers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. polycondensation products polyesters, e.g. polyethylene terephthalate [PET]
    • DTEXTILES; PAPER
    • D10INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10BINDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B2501/00Wearing apparel
    • D10B2501/04Outerwear; Protective garments

Definitions

  • the present invention relates to a heat and flame retardant fabric as well as a method of making the same.
  • the fabric comprises a cellulose-based cotton alternative having heat and flame retardant properties.
  • Said garments must pass minimum thermal performance requirements such as flame- and/or heat-retardance, resistance to molten metal, electric arc resistance, low percentage of (estimated) body burns in thermal manikin testing, limited after flame time and high resilience against combustion, as well as protection against radiant heat.
  • the garment provides adequate comfort, for instance by allowing vapour to be transported away from the body and ensuring that the garment is not too stiff. Also the garment must be durable in the sense that the above disclosed parameters last at least for the intended or certified lifetime of the product. This may be defined by a number of wash cycles.
  • the garment must be printable or dyeable with a durable result such that, for instance, the garment can be dyed to increase visibility.
  • An often used standard for performance requirements for heat and flame retardant clothing made from flexible materials is ISO 11612.
  • a known treatment for rendering cellulosic fibres or textile articles comprising cellulosic fibres flame retardant is the Proban® treatment.
  • This treatment comprises padding a textile article with an aqueous solution comprising tetrakishydroxyalkylphosphonium (THP) salt which is pre-reacted with urea and pH adjusted to 5-8.
  • THP does not react substantially with the cellulosic fibre, nor does it substantially react with the textile article comprising said fibre, but instead forms an enveloping network around and/or throughout the molecular structure of the cellulosic fibre.
  • the Proban® treatment is a non-cellulose-reactive treatment which means that there is substantially no chemical reaction between the THP and the cellulosic fibre.
  • Alternative non-cellulose-reactive treatments to Proban and THP may achieve the same effects.
  • An alternative flame-retardant treatment is a treatment with a N-methylol phosphonate compound, such as N-methylol dialkyl phosphonopropionamide.
  • a N-methylol phosphonate compound such as N-methylol dialkyl phosphonopropionamide.
  • Commercially such treatments are offered under the brands Pyrovatex® CP and Aflammit® KWB.
  • the flame-retardant compound is grafted onto the cellulose by a reaction on the C(6) hydroxyl group of the cellulose resulting in grafted protective phosphonopropionamide molecules on the outside of the cellulose fibre.
  • This is therefore an example of a cellulose-reactive, phosphorous-comprising compound as there is a reaction between the cellulose and the phosphorous comprising compound.
  • the Pyrovatex treatment thus has a fundamentally different chemistry and mechanism to the Proban process.
  • fibres that are inherently flame retardant by their nature and do not require treatment in order to achieve this retardancy are inherently flame retardant by their nature and do not require treatment in order to achieve this retardancy.
  • Such fibres including para- aramid and meta-aramid fibres, PPS, PBO and PBI may be referred to as flame resistant fibres.
  • Other flame resistant fibres that are inherently flame retardant include fibres that are extruded from a fibre spin dope to which flame retardant additives have been added before spinning e.g as a masterbatch.
  • the resulting fibres include FR Lyocell, Modacrylic, FR polyester and FR polyamide FR.
  • flame retardant (FR) is used to refer to fibres that are treated to render them flame retardant as opposed to those with inherent flame retardant properties.
  • lyocell One cotton alternative made from responsibly-sourced wood-chip cellulose is lyocell. This is a material similar to rayon but without the disadvantages of the viscose process. It also has a considerably lower , water footprint than cotton, using up to 95% less water. As yet however, it has not been possible to adequately substitute lyocell for cotton where flame retardancy is required in combination with durability and other workwear requirements. In particular, the tendency of lyocell to fibrillate has been seen as a major drawback.
  • a flame retardant (FR) treated fabric comprising yarns formed from a mixture of natural and/or synthetic fibres, the fabric further comprising FR treated lyocell fibres, wherein the FR treatment is a non- cellulose-reactive FR treatment and the FR treated lyocell fibres are rendered low- fibrillating.
  • FR treatment is a non- cellulose-reactive FR treatment and the FR treated lyocell fibres are rendered low- fibrillating.
  • lyocell is used to denote artificial, cellulose- based cotton alternatives. In particular, these may denote cellulosic fibre obtained by an organic solvent spinning process although the present invention may also be applicable to some cellulosic fibres obtained by the viscose process.
  • lyocell such as the Tencell ® product available from Lenzing AG is well known, other similar cellulose-based cotton alternatives are available and may be equally applicable.
  • the lyocell may be present in the form of short staple fibres, long staple fibre or as filaments or ribbons.
  • reference to natural and synthetic fibres is intended to exclude the lyocell fibres i.e. these are in addition to the lyocell.
  • any amount of lyocell may be present. In particular, from 1 - 99 wt% lyocell may be present, preferably from 10- 70 wt %, more preferably from 15 - 50 wt % lyocell or from 20 to 35 wt% lyocell.
  • lyocell is prone to fibrillation. It is also understood that lyocell has reduced tensile strength when it has absorbed water i.e. in the wet fabric state. As a result of investigation in the context of the present invention, it has also been revealed that the fibrillation is further exacerbated by carrying out THP type FR treatments. In the wet state, water can penetrate into the lyocell fibrillar bundles, causing exposure of fibrils at the fibre surface. The rate of fibrillation increases with increased pH and increased temperature as experienced during conventional FR treatments. Unlike cotton, lyocell does not naturally cross-link and it is therefore desirable to provide a finish that at least partially compensates for the increased fibrillation.
  • fibrils are at least partially held together by hydrogen bonding between neighbouring fibrils.
  • a reduction in the degree of hydrogen bonding e.g. in the presence of water or as a result of certain treatments can lead to increased fibrillation.
  • An anti-fibrillation finish can be performed on the fabric by application of suitable additives.
  • the additive is a substance that reacts with the hydroxyl groups of the cellulose to stabilise the fibrils. This may be either by increasing the presence of hydrogen bonding or by the formation of covalent bonds, whereby improved cross- linking of the fibrils is achieved.
  • Additives that cross-link by formation of covalent bonds to the hydroxyl groups of the cellulose material may be referred to as reactant resins, thermosetting resins or easy-care finishes.
  • Reactant resins include ethylene urea formaldehyde, propylene urea formaldehyde, methylated uron formaldehyde and Dimethylol dihydroxyethyleneurea (DMDHEU) modified resin.
  • DMDHEU Dimethylol dihydroxyethyleneurea
  • low-fibrillating may be determined qualitatively, by the presence of cross-linking to the hydroxyl groups of the lyocell. Alternatively, it may be determined experimentally e.g. by the pilling, abrasion, colour retention or other tests defined below
  • the natural fibres comprise FR cotton.
  • the fabric may have the general feel of a cotton fabric whereby a portion of the cotton has been replaced by the lyocell alternative. Up to around 50% of the cotton may be replaced without significantly affecting the overall performance of the fabric. Nevertheless, the softness of the fabric increases significantly and is generally experienced as very comfortable in use.
  • an amount of a stronger fibre such as a synthetic fibre may be required to offset the loss in certain properties or otherwise complement the lyocell.
  • lyocell generally has slightly lower wet strength than cotton but is significantly reduced in strength after THP processing. Therefore polyester may be added to the fibre blend to compensate.
  • the synthetic fibres comprise polyester.
  • Other synthetic fibres such as polyamides oraramids may also be contemplated and it is not excluded that additional small volumes of high-performance synthetic fibres may be included.
  • the synthetic fibres comprise recycled polyester.
  • One preferred source of recycled polyester is Repreve ® from Unifi Inc, which is a mechanically recycled polyester. Chemically recycled polyester may also be used. Recycled polyester has many appealing advantages such as having energy consumption reduction by 45% in comparison to virgin polyester; water consumption reduction nearly 20% in comparison to virgin polyester; and greenhouse gas emission reduction of over 30% in comparison to virgin polyester.
  • Recycled polyester has excellent strength properties and adds durability, although it does not respond to many FR treatments.
  • the synthetic fibres may be present in various forms including short staple fibres, long staple fibres and filaments.
  • a woven fabric is preferred.
  • the woven fabric may have any appropriate construction, being formed from warp and weft yarns in a chosen weave or pattern. The yarns in both the warp and the weft may all be the same or may be different in terms of their composition, weight etc.
  • Each yarn may be a spun yarn.
  • a spun yarn is understood to comprise an intimate blend of the constituent fibres.
  • a number of ends of yarns may be twisted together to form a ply.
  • a ply may also be formed by twisting a spun fibre with one or more filaments.
  • the lyocell fibres may be present in the warp yarns only.
  • the lyocell may be reinforced by the presence of synthetic fibres also blended into the warp yarn.
  • the warp yarns comprise lyocell fibres, synthetic fibres and natural fibres.
  • the blend may thus be of lyocell, cotton and polyester staple fibres, which together make up at least 95% of the warp.
  • as much as 50% of the warp yarn may comprise lyocell with equal amounts of cotton and polyester accounting for the remainder.
  • they may preferably be present in the warp in a wt % ratio of around 50/25/25 respectively.
  • an increase in usage of lyocell requires a commensurate increase in the amount of stronger synthetic fibre required for compensating for loss in strength of the lyocell (especially after being subjected to FR treatment).
  • the synthetic fibre is then present in the yarn direction corresponding to the increased lyocell.
  • the total amount of the synthetic fibre that can be introduced will depend on the degree of FR treatment of the natural fibre and the lyocell. For reasons that are explained further below, a limited degree of FR treatment may be preferred in order to avoid excess fibrillation. As such, the overall amount of non-FR synthetic fibre that can be present in the mix may be limited. For this reason, the above 50/25/25 mix in the warp has been found rather suitable and obvious variants thereof will achieve the same advantageous effect.
  • polyester up to 50 wt% polyester may be present in the overall fabric.
  • other fibres such as polyamide, up to 20 wt% may be present.
  • Alternative fibre proportions that remain below the upper limits for compatibility with THP FR treatment, may be chosen depending on the end-use and also fall within the scope of the current application. For example, to provide desired strength to softness to colour retention ratios, or to contain greater amounts of green fibres.
  • the weft yarn may comprise a preponderance of natural fibres, preferably between 70 wt % and 95 wt % of natural fibres, in particular cotton.
  • the fabric may be woven as a twill weave, preferably a 2/1 twill. Satin weaves may also be used, where it is desired to provide a particular drape or ensure that certain yarns are exclusively provided to one face or the other.
  • the fabric may also be a double-cloth having distinct properties of the respective front and back cloths, a two faced fabric, or a fabric with two identical faces.
  • the fabric comprises an anti fibrillation finish to prevent the lyocell from fibrillating.
  • lyocell does not naturally cross-link and it is therefore desirable to provide a finish that at least partially compensated for the increased fibrillation.
  • the non-fibrillating finish is detrimental to the application of the flame retardant treatment to the lyocell fibres.
  • the anti-fibrillating resin finish may be applied subsequently to the FR treatment. It has however also been found that the FR treatment may itself have a subsequent negative effect on the anti-fibrillating finishing process. This is believed to be due to steric hindrance of the hydroxyl groups as a result of the THP treatment. According to an aspect of the invention the degree of FR treatment is kept to a minimum. In this context, the amount of phosphor in the final fabric may be kept to below 2.5 wt%, preferably below 2.4 wt % or even below 2.2 wt %.
  • the fabric further comprises a water and/or oil repellent finish.
  • Suitable finishes include conventional PFAS (perfluorinated alkylated substances) finishes such as PTFE, Teflon® and the like.
  • PFAS perfluorinated alkylated substances
  • the fabric of the current disclosure may also be made with a PFAS-free finish, thereby being further eco- friendly.
  • the fabric may also include other fibres or yarns for specific technical purposes.
  • antistatic fibres may be included either as fibres in the blend or as separate antistatic yarns or filaments.
  • the fabric may comprise antistatic fibres or filaments in an amount of between 0.2 wt % and 3 wt %. In the case that antistatic staple filaments are used, an amount of as much as 5 wt% may be required, depending on whether the antistatic fibres are distributed or localised.
  • An exemplary fabric according to the invention may comprise in the warp: 40 - 60 wt %, preferably around 50 wt % lyocell,
  • the fabric is desirably durable to laundering at least 50x according to ISO
  • the fabric should preferably also exhibit fabric abrasion resistance to more than 15 000 cycles, preferably more than 20 000 cycles according to the Martindale Method and fulfilling ISO 12947-2 for an applied force of 12KPa.
  • the non-cellulose-reactive treatment may be any suitable such treatment, preferably based on a THP salt such as the Proban ® treatment.
  • the invention also relates to a method of producing a heat and flame retardant fabric comprising a mixture of natural and/or synthetic fibres and lyocell fibres having accessible hydroxyl groups, the method comprising first subjecting the fabric to a non-cellulose-reactive FR treatment and subsequently finishing the fabric by application of a resin to stabilise fibrillation of the lyocell.
  • the term ‘accessible hydroxyl groups’ is intended to refer to the fact that the lyocell fibres are not treated with an anti-fibrillation additive such as a cross-linking resin. According to the present invention, it has been shown that the presence of such additives prior to the FR treatment can reduce the efficacy of the treatment. For this reason, it is desirable that the FR treatment is carried out on fabric where the lyocell fibres provided in the yarns are not yet stabilised against fibrillation by a treatment that can occupy the hydroxyl groups.
  • the fabric Prior to the FR treatment, the fabric may be pre-treated by one or more of processes selected from the group: desizing, scouring, bleaching, mercerising, dying, including reactive and non-reactive dyes.
  • the fabric may be any suitable fabric, including a woven or a knitted fabric and the method may include first constructing the fabric from the individual yarns, prior to carrying out the FR treatment.
  • Constructing the fabric may comprise weaving the yarns with a warp and a weft, preferably in a twill weave.
  • the lyocell is present in the yarns in the warp direction only.
  • Finishing the fabric by application of a resin may comprise the use of any appropriate chemistry for preventing fibrillation.
  • the resin is a substance that reacts with the hydroxyl groups of the cellulose to stabilise the fibrils.
  • Such resins may be referred to as reactant resins, thermosetting resins or easy-care finishes.
  • Reactant resins include ethylene urea formaldehyde, propylene urea formaldehyde, methylated uron formaldehyde and Dimethylol dihydroxyethyleneurea (DMDHEU) modified resin.
  • DMDHEU Dimethylol dihydroxyethyleneurea
  • the finishing step may be completed by cross-linking of the resin, e.g. by the application of heat.
  • Finishing may further comprise a water and/or oil repellent treatment, preferably provided in a separate step after the application of the resin to prevent fibrillation.
  • Both treatments may be applied together although for existing treatments, it has been found that better effectivity is achieved by first performing the anti-fibrillation finish and subsequently applying the water/oil repellent finish.
  • Heat treatment may take place for both treatments together but preferably, the anti-fibrillation resin is cross-linked by heat treatment prior to commencing the water/oil repellent finish.
  • Suitable oil and/or water repellent finishes include conventional PFAS (perfluorinated alkylated substances) finishes such as PTFE, Teflon® and the like.
  • the fabric of the current disclosure may also be made with a PFAS- free finish, thereby being further eco-friendly
  • the invention also relates to a garment manufactured by a method as described above or hereinafter.
  • Flame retardant is hereby defined in this application to mean flame- and/or heat-retardance conferred by a treatment to the filament, fibre, yarn or fabric. This may provide a fabric with low percentage of (estimated) body burns in thermal manikin testing, limited after-flame time and highly resilient against combustion, as well as protective against radiant heat, resistances to electric arcs and molten metal. For example as meet the performance requirements for flame retardant clothing made from flexible materials of ISO 11612. DETAILED DESCRIPTION OF EXEMPLARY EMBODIMENTS
  • One or two FR treatment steps can be performed involving impregnation of the fabric and ammonia curing.
  • the staple fibres which are formed into the yarns include cotton, Lyocell and recycled polyester.
  • Cotton is a natural fibre that provides comfort and better moisture management than synthetic fibres. Cotton is the traditionally used fibre for FR-treated fabrics.
  • Lyocell is a synthetic cellulosic fibre.
  • Other alternative cellulose based cotton alternatives exist such as LivaecoTM, Birla ModalTM, Birla ExcelTM, Birla ViscoseTM and Birla SpunshadesTM provided by Birla Cellulose.
  • Lyocell is an industrial and launderable fibre which loses strength in the wet state. Lyocell in fact has a strength similar to cotton in the wet state and is more sustainable than cotton. Compared to cotton, the water usage of Lyocell is 95% less than of cotton. Lyocell is more comfortable than cotton with better moisture management and is generally smoother to the skin.
  • polyester can be mechanically or chemically recycled. Polyester is used in the FR-treated fabric to increase durability as it a relatively stronger material, however it is also heavier than cellulose based fabrics. Polyester cannot be made flame retardant with Proban chemistry. Mechanical recycled polyester can be used to improve sustainability. Use of recycled polyester provides an energy consumption reduction by 45% in comparison to use of virgin polyester, and has a water consumption reduction of nearly 20% in comparison to virgin polyester. The greenhouse gas emissions are reduced over 30% in comparison to virgin Polyester.
  • Negastat filament 17% Negastat filament
  • the EC9600 fabric is woven in a 2/1 twill weave with the above warp and weft yarns.
  • An anti-static yarn is included at a spacing of every 1 :20 in the weft direction.
  • the overall weight percentages of the respective fibres in the final fabric are:
  • Amount of THP is measured by P, N analysis with the following results:
  • Fabric is after FR-treatment still vulnerable to fibrillation. Finishing the fabric after FR-treatment with a suitable resin prevents fibrillation of lyocell in the product.
  • the resin is applied in a foulard process and the application process includes water removal by pressing and heating, followed by thermal treatment for cross linking the resin.
  • non-fibrillating as used herein will be understood to mean substantially non-fibrillating, and to be exchangeable with low-fibrillating.
  • the application of a non-fibrillation resin provides a fabric having a reduced fibrillation compared to that in its virgin state.
  • a second finish is required to make the fabric water-and/or oil repellent finish through fluorocarbon resin (FC) to meet ISO 13034.
  • FC fluorocarbon resin
  • the resin and the FC may be combined in one bath or, to improve the fibrillation and prevent loss of colour, the resin and FC finish may be applied after each other in a 2-step process.
  • This 2- step process reduces the fibrillation after laundering. Further improvement is to cross-link the resin first before applying the FC finish.
  • the final product has the following advantages:
  • the technical specifications of the fabric of the invention are comparable and commensurate with the standard FR fabric and an alternative inherently flame retardant fabric known as Modal/TencelTM in terms of properties.
  • the improved FR fabric of the invention further has improved comfort and reduced carbon footprint. Comparison of the technical specifications is as follows:

Abstract

The present disclosure relates to a flame retardant (FR) treated fabric, comprising yarns formed from a mixture of natural and/or synthetic fibres, the fabric further comprising FR treated lyocell fibres, wherein the FR treatment is a non-cellulose-reactive FR treatment and the FR treated lyocell fibres are rendered low-fibrillating e.g. whereby at least some of the hydroxyl groups are cross-linked with a reactant resin.

Description

Flame Retardant Fabric Comprising Cotton Alternative
FIELD OF THE INVENTION
[001] The present invention relates to a heat and flame retardant fabric as well as a method of making the same. The fabric comprises a cellulose-based cotton alternative having heat and flame retardant properties.
BACKGROUND OF THE INVENTION
[002] Numerous professions require individuals to risk exposure to extreme heat and/or flames. Typical examples are industrial workers, fire fighters, police and military personnel. Such personnel are, wherever possible, provided with appropriate flame-protective garments. These garments are distinctly different from normal, every-day-use garments as they are at least partly constructed from flame retardant textiles.
[003] Said garments must pass minimum thermal performance requirements such as flame- and/or heat-retardance, resistance to molten metal, electric arc resistance, low percentage of (estimated) body burns in thermal manikin testing, limited after flame time and high resilience against combustion, as well as protection against radiant heat.
[004] In addition to specialist flame-protective garments, more general workwear is often required to have elevated flame resistance, which may be certified according to one or more standards. Other important performance requirements are tensile and tear strength, elongation at break, abrasion resistance, snagging resistance and resistance to penetration by water and liquid chemicals.
[005] In addition it is considered important that the garment provides adequate comfort, for instance by allowing vapour to be transported away from the body and ensuring that the garment is not too stiff. Also the garment must be durable in the sense that the above disclosed parameters last at least for the intended or certified lifetime of the product. This may be defined by a number of wash cycles.
[006] Furthermore the garment must be printable or dyeable with a durable result such that, for instance, the garment can be dyed to increase visibility. An often used standard for performance requirements for heat and flame retardant clothing made from flexible materials is ISO 11612.
[007] A known treatment for rendering cellulosic fibres or textile articles comprising cellulosic fibres flame retardant is the Proban® treatment. This treatment comprises padding a textile article with an aqueous solution comprising tetrakishydroxyalkylphosphonium (THP) salt which is pre-reacted with urea and pH adjusted to 5-8. [008] THP does not react substantially with the cellulosic fibre, nor does it substantially react with the textile article comprising said fibre, but instead forms an enveloping network around and/or throughout the molecular structure of the cellulosic fibre. Hence the Proban® treatment is a non-cellulose-reactive treatment which means that there is substantially no chemical reaction between the THP and the cellulosic fibre. Alternative non-cellulose-reactive treatments to Proban and THP may achieve the same effects.
[009] An alternative flame-retardant treatment is a treatment with a N-methylol phosphonate compound, such as N-methylol dialkyl phosphonopropionamide. Commercially such treatments are offered under the brands Pyrovatex® CP and Aflammit® KWB. In this case the flame-retardant compound is grafted onto the cellulose by a reaction on the C(6) hydroxyl group of the cellulose resulting in grafted protective phosphonopropionamide molecules on the outside of the cellulose fibre. This is therefore an example of a cellulose-reactive, phosphorous-comprising compound as there is a reaction between the cellulose and the phosphorous comprising compound. The Pyrovatex treatment thus has a fundamentally different chemistry and mechanism to the Proban process.
[0010] Pyrovatex and Proban were developed to make cotton flame retardant and have many associated problems for the resulting fabric. US 3816068 A1 discloses a flame retardant for cellulose fabrics and describes disadvantages of the Pyrovatex process The disadvantages of Pyrovatex treated fabric include incompatibility with many other treatments and its tendency to hydrolyse over time. Pyrovatex treated products require washing at least once a year after production (regardless of use) to prevent hydrolysis and the unpleasant smells associated therewith. Typically, the degree of fire retardancy achieved is more limited than THP treatments and the process is only compatible with a maximum of 20% synthetic fibres. EP 0709518 A1 discloses a Proban treated cotton fabric. This document is directed to solving the problems of rigidity of Proban treated cotton. [0011] Also existing are fibres that are inherently flame retardant by their nature and do not require treatment in order to achieve this retardancy. Such fibres, including para- aramid and meta-aramid fibres, PPS, PBO and PBI may be referred to as flame resistant fibres. Other flame resistant fibres that are inherently flame retardant include fibres that are extruded from a fibre spin dope to which flame retardant additives have been added before spinning e.g as a masterbatch. The resulting fibres include FR Lyocell, Modacrylic, FR polyester and FR polyamide FR. In the following, the term flame retardant (FR) is used to refer to fibres that are treated to render them flame retardant as opposed to those with inherent flame retardant properties.
[0012] An increasing concern in the field of clothing manufacture is the choice of environmentally friendly options. Although natural fibres such as cotton may be advantageous over synthetic fibres in some respects, cotton is known to be relatively high impact in terms of the requirements for its production, in particular, water usage. It would be desirable to provide cotton alternatives to at least partially replace cotton or other natural fibres in flame retardant clothing.
[0013] One cotton alternative made from responsibly-sourced wood-chip cellulose is lyocell. This is a material similar to rayon but without the disadvantages of the viscose process. It also has a considerably lower , water footprint than cotton, using up to 95% less water. As yet however, it has not been possible to adequately substitute lyocell for cotton where flame retardancy is required in combination with durability and other workwear requirements. In particular, the tendency of lyocell to fibrillate has been seen as a major drawback.
[0014] It would be desirable to provide an alternative to conventional FR cotton having a smaller environmental footprint that nevertheless satisfies at least certain quality requirements expected of protective clothing. SUMMARY OF THE INVENTION
[0015] According to the invention, there is provided a flame retardant (FR) treated fabric, comprising yarns formed from a mixture of natural and/or synthetic fibres, the fabric further comprising FR treated lyocell fibres, wherein the FR treatment is a non- cellulose-reactive FR treatment and the FR treated lyocell fibres are rendered low- fibrillating. In the following, the term lyocell’ is used to denote artificial, cellulose- based cotton alternatives. In particular, these may denote cellulosic fibre obtained by an organic solvent spinning process although the present invention may also be applicable to some cellulosic fibres obtained by the viscose process. Although lyocell such as the Tencell ® product available from Lenzing AG is well known, other similar cellulose-based cotton alternatives are available and may be equally applicable. The lyocell may be present in the form of short staple fibres, long staple fibre or as filaments or ribbons. Furthermore, in this context, reference to natural and synthetic fibres is intended to exclude the lyocell fibres i.e. these are in addition to the lyocell. Depending on the properties required, any amount of lyocell may be present. In particular, from 1 - 99 wt% lyocell may be present, preferably from 10- 70 wt %, more preferably from 15 - 50 wt % lyocell or from 20 to 35 wt% lyocell. [0016] It is well known that lyocell is prone to fibrillation. It is also understood that lyocell has reduced tensile strength when it has absorbed water i.e. in the wet fabric state. As a result of investigation in the context of the present invention, it has also been revealed that the fibrillation is further exacerbated by carrying out THP type FR treatments. In the wet state, water can penetrate into the lyocell fibrillar bundles, causing exposure of fibrils at the fibre surface. The rate of fibrillation increases with increased pH and increased temperature as experienced during conventional FR treatments. Unlike cotton, lyocell does not naturally cross-link and it is therefore desirable to provide a finish that at least partially compensates for the increased fibrillation. For lyocell-like materials, is believed that fibrils are at least partially held together by hydrogen bonding between neighbouring fibrils. A reduction in the degree of hydrogen bonding e.g. in the presence of water or as a result of certain treatments can lead to increased fibrillation.
[0017] An anti-fibrillation finish can be performed on the fabric by application of suitable additives. Preferably the additive is a substance that reacts with the hydroxyl groups of the cellulose to stabilise the fibrils. This may be either by increasing the presence of hydrogen bonding or by the formation of covalent bonds, whereby improved cross- linking of the fibrils is achieved. Additives that cross-link by formation of covalent bonds to the hydroxyl groups of the cellulose material may be referred to as reactant resins, thermosetting resins or easy-care finishes. Reactant resins include ethylene urea formaldehyde, propylene urea formaldehyde, methylated uron formaldehyde and Dimethylol dihydroxyethyleneurea (DMDHEU) modified resin. The latter is a preferred choice. The skilled person will be well aware that alternatives and equivalents to the above may also be applied. In this context, low-fibrillating may be determined qualitatively, by the presence of cross-linking to the hydroxyl groups of the lyocell. Alternatively, it may be determined experimentally e.g. by the pilling, abrasion, colour retention or other tests defined below
[0018] In one embodiment, the natural fibres comprise FR cotton. The fabric may have the general feel of a cotton fabric whereby a portion of the cotton has been replaced by the lyocell alternative. Up to around 50% of the cotton may be replaced without significantly affecting the overall performance of the fabric. Nevertheless, the softness of the fabric increases significantly and is generally experienced as very comfortable in use. In general however, where cotton is replaced by lyocell, an amount of a stronger fibre such as a synthetic fibre may be required to offset the loss in certain properties or otherwise complement the lyocell. In particular, lyocell generally has slightly lower wet strength than cotton but is significantly reduced in strength after THP processing. Therefore polyester may be added to the fibre blend to compensate. It is however not excluded that other natural fibres may be present, such as linen, or wool in greater or lesser quantities. [0019] In an embodiment, the synthetic fibres comprise polyester. Other synthetic fibres such as polyamides oraramids may also be contemplated and it is not excluded that additional small volumes of high-performance synthetic fibres may be included. In one embodiment, the synthetic fibres comprise recycled polyester. One preferred source of recycled polyester is Repreve ® from Unifi Inc, which is a mechanically recycled polyester. Chemically recycled polyester may also be used. Recycled polyester has many appealing advantages such as having energy consumption reduction by 45% in comparison to virgin polyester; water consumption reduction nearly 20% in comparison to virgin polyester; and greenhouse gas emission reduction of over 30% in comparison to virgin polyester. Recycled polyester has excellent strength properties and adds durability, although it does not respond to many FR treatments. The synthetic fibres may be present in various forms including short staple fibres, long staple fibres and filaments. [0020] It will be understood that various possible fabrics may be envisaged, including woven and knitted fabrics. A woven fabric is preferred. The woven fabric may have any appropriate construction, being formed from warp and weft yarns in a chosen weave or pattern. The yarns in both the warp and the weft may all be the same or may be different in terms of their composition, weight etc. Each yarn may be a spun yarn. A spun yarn is understood to comprise an intimate blend of the constituent fibres. A number of ends of yarns may be twisted together to form a ply. A ply may also be formed by twisting a spun fibre with one or more filaments. [0021] In one embodiment, the lyocell fibres may be present in the warp yarns only.
This has been found most suitable for the case that the lyocell has been adequately stabilised against fibrillation by the finishing process. In that case, the lyocell may be reinforced by the presence of synthetic fibres also blended into the warp yarn. In cases where the lyocell is still subject to fibrillation, it may be preferred to include it instead only in the weft yarns in order to decrease its exposure to the exterior of the fabric, e.g. in a twill weave.
[0022] In a particular embodiment, the warp yarns comprise lyocell fibres, synthetic fibres and natural fibres. The blend may thus be of lyocell, cotton and polyester staple fibres, which together make up at least 95% of the warp. In an embodiment, as much as 50% of the warp yarn may comprise lyocell with equal amounts of cotton and polyester accounting for the remainder. In one embodiment, they may preferably be present in the warp in a wt % ratio of around 50/25/25 respectively. [0023] It has been observed that there are certain relations between the different characteristics of the fabric that lead to an optimised result. In particular, it may be noted that an increase in usage of lyocell requires a commensurate increase in the amount of stronger synthetic fibre required for compensating for loss in strength of the lyocell (especially after being subjected to FR treatment). The synthetic fibre is then present in the yarn direction corresponding to the increased lyocell. In the case of a synthetic fibre that is neither inherently FR nor FR treatable, the total amount of the synthetic fibre that can be introduced, will depend on the degree of FR treatment of the natural fibre and the lyocell. For reasons that are explained further below, a limited degree of FR treatment may be preferred in order to avoid excess fibrillation. As such, the overall amount of non-FR synthetic fibre that can be present in the mix may be limited. For this reason, the above 50/25/25 mix in the warp has been found rather suitable and obvious variants thereof will achieve the same advantageous effect.
[0024] However, when synthetic fibres are introduced in one direction, the fabric may become destabilised with respect to e.g. shrinkage. For this reason, a limited amount of synthetic fibres may also be required in the other weave direction e.g. a 90/10 cotton/polyester blend may be appropriate. An overall blend of around 50/30/20 cotton/lyocell/polyester may ensue. It will be noted that in general, a low amount of synthetic fibre may be preferred as its primary purpose is strength compensation and it negatively influences the degree of FR of the overall fabric. Nevertheless, amounts of synthetic fibre may be achieved which exceed the amount of synthetic fibre that is achievable for Pyrovatex type treatments.
[0025] In the case of polyester, up to 50 wt% polyester may be present in the overall fabric. For other fibres such as polyamide, up to 20 wt% may be present. Alternative fibre proportions that remain below the upper limits for compatibility with THP FR treatment, may be chosen depending on the end-use and also fall within the scope of the current application. For example, to provide desired strength to softness to colour retention ratios, or to contain greater amounts of green fibres.
[0026] In an embodiment, the weft yarn may comprise a preponderance of natural fibres, preferably between 70 wt % and 95 wt % of natural fibres, in particular cotton.
[0027] Any suitable weave construction may be contemplated and the skilled person will be well aware of the respective advantages of such weaves. In an embodiment, the fabric may be woven as a twill weave, preferably a 2/1 twill. Satin weaves may also be used, where it is desired to provide a particular drape or ensure that certain yarns are exclusively provided to one face or the other. The fabric may also be a double-cloth having distinct properties of the respective front and back cloths, a two faced fabric, or a fabric with two identical faces.
[0028] According to an important aspect of the invention, the fabric comprises an anti fibrillation finish to prevent the lyocell from fibrillating. As noted above, lyocell does not naturally cross-link and it is therefore desirable to provide a finish that at least partially compensated for the increased fibrillation. Importantly, while the use of finished lyocell fibres is well known in preventing fibrillation, it has now been found that the non-fibrillating finish is detrimental to the application of the flame retardant treatment to the lyocell fibres. By using untreated lyocell fibres i.e. lyocell fibres that have not been provided with an anti-fibrillation treatment, an improved application of the FR treatment may be achieved. This has been found especially to be the case for the Proban type (THP) treatment. Without wishing to be bound by theory, it is believed that the presence of cross-linked resins such as formaldehyde prevents operation of the THP mechanism, which requires formation of an enveloping network around and/or throughout the molecular structure of the lyocell fibre.
[0029] According to the present invention, the anti-fibrillating resin finish may be applied subsequently to the FR treatment. It has however also been found that the FR treatment may itself have a subsequent negative effect on the anti-fibrillating finishing process. This is believed to be due to steric hindrance of the hydroxyl groups as a result of the THP treatment. According to an aspect of the invention the degree of FR treatment is kept to a minimum. In this context, the amount of phosphor in the final fabric may be kept to below 2.5 wt%, preferably below 2.4 wt % or even below 2.2 wt %. Values for Nitrogen also reflect the extent of the FR treatment and these may be kept below 1.7 wt % or below 1.6 wt % or even below 1.5 wt %. These values have still been found to ensure adequate FR compliance. Nevertheless, as mentioned above, the reduced degree of FR treatment limits the overall volume of the synthetic fibres that can be present in the blend - for the case that those synthetic fibres are non-FR. [0030] In an embodiment, the fabric further comprises a water and/or oil repellent finish.
Suitable finishes include conventional PFAS (perfluorinated alkylated substances) finishes such as PTFE, Teflon® and the like. Alternatively, the fabric of the current disclosure may also be made with a PFAS-free finish, thereby being further eco- friendly.
[0031] As mentioned above, the fabric may also include other fibres or yarns for specific technical purposes. For protective workwear, antistatic fibres may be included either as fibres in the blend or as separate antistatic yarns or filaments. In an embodiment, the fabric may comprise antistatic fibres or filaments in an amount of between 0.2 wt % and 3 wt %. In the case that antistatic staple filaments are used, an amount of as much as 5 wt% may be required, depending on whether the antistatic fibres are distributed or localised.
[0032] An exemplary fabric according to the invention may comprise in the warp: 40 - 60 wt %, preferably around 50 wt % lyocell,
15 - 35 wt %, preferably around 25 wt % cotton; and
15 - 35 wt %, preferably around 25 wt % recycled polyester; and in the weft:
70 - 99 wt %, preferably around 90 wt % cotton, 1 - 20 wt %, preferably around 10 wt % recycled polyester.
[0033] The fabric is desirably durable to laundering at least 50x according to ISO
15797 without losing its required properties. These may include one or more of:
• a color retention score of greater than 2 or greater than 3 according to the greyscale comparison of ISO 105-A02;
• exceed the ignition to surface requirement of IS011612 according to the test procedure of ISO15025 (2000);
• exceed the bottom edge ignition requirement of IS011612 according to the test procedure of ISO15025 (2000); · tear strength greater than 10N according to IS013937-2 (2000);
• tensile strength greater than 300N according to IS013934-1 (2013).
• The fabric should preferably also exhibit fabric abrasion resistance to more than 15 000 cycles, preferably more than 20 000 cycles according to the Martindale Method and fulfilling ISO 12947-2 for an applied force of 12KPa.
[0034] The non-cellulose-reactive treatment may be any suitable such treatment, preferably based on a THP salt such as the Proban ® treatment.
[0035] The invention also relates to a method of producing a heat and flame retardant fabric comprising a mixture of natural and/or synthetic fibres and lyocell fibres having accessible hydroxyl groups, the method comprising first subjecting the fabric to a non-cellulose-reactive FR treatment and subsequently finishing the fabric by application of a resin to stabilise fibrillation of the lyocell. [0036] In this context, the term ‘accessible hydroxyl groups’ is intended to refer to the fact that the lyocell fibres are not treated with an anti-fibrillation additive such as a cross-linking resin. According to the present invention, it has been shown that the presence of such additives prior to the FR treatment can reduce the efficacy of the treatment. For this reason, it is desirable that the FR treatment is carried out on fabric where the lyocell fibres provided in the yarns are not yet stabilised against fibrillation by a treatment that can occupy the hydroxyl groups.
[0037] Prior to the FR treatment, the fabric may be pre-treated by one or more of processes selected from the group: desizing, scouring, bleaching, mercerising, dying, including reactive and non-reactive dyes.
[0038] The fabric may be any suitable fabric, including a woven or a knitted fabric and the method may include first constructing the fabric from the individual yarns, prior to carrying out the FR treatment. In other words, the FR treatment is carried out on the fabric rather than being applied to the yarns themselves. Constructing the fabric may comprise weaving the yarns with a warp and a weft, preferably in a twill weave. In an embodiment the lyocell is present in the yarns in the warp direction only. [0039] Finishing the fabric by application of a resin, may comprise the use of any appropriate chemistry for preventing fibrillation. Preferably the resin is a substance that reacts with the hydroxyl groups of the cellulose to stabilise the fibrils. Such resins may be referred to as reactant resins, thermosetting resins or easy-care finishes. Reactant resins include ethylene urea formaldehyde, propylene urea formaldehyde, methylated uron formaldehyde and Dimethylol dihydroxyethyleneurea (DMDHEU) modified resin. The latter is a preferred choice although equivalents and alternatives may equally be applied. The finishing step may be completed by cross-linking of the resin, e.g. by the application of heat. [0040] Finishing may further comprise a water and/or oil repellent treatment, preferably provided in a separate step after the application of the resin to prevent fibrillation. Both treatments may be applied together although for existing treatments, it has been found that better effectivity is achieved by first performing the anti-fibrillation finish and subsequently applying the water/oil repellent finish. Heat treatment may take place for both treatments together but preferably, the anti-fibrillation resin is cross-linked by heat treatment prior to commencing the water/oil repellent finish. Suitable oil and/or water repellent finishes include conventional PFAS (perfluorinated alkylated substances) finishes such as PTFE, Teflon® and the like. Alternatively, the fabric of the current disclosure may also be made with a PFAS- free finish, thereby being further eco-friendly
[0041] The invention also relates to a garment manufactured by a method as described above or hereinafter.
[0042] This combination of materials results in an eco-friendly fabric that is breathable, comfortable, durable (avoids fast fibrillation) and FR. The advantageous ranges of cotton provide both sustainability and breathability to the fabric.
[0043] Several materials are particularly appealing for consideration in an eco-friendly product. Recycled materials, sustainable materials and materials have a low water scarcity have less environmental impact..
[0044] Flame retardant (FR) is hereby defined in this application to mean flame- and/or heat-retardance conferred by a treatment to the filament, fibre, yarn or fabric. This may provide a fabric with low percentage of (estimated) body burns in thermal manikin testing, limited after-flame time and highly resilient against combustion, as well as protective against radiant heat, resistances to electric arcs and molten metal. For example as meet the performance requirements for flame retardant clothing made from flexible materials of ISO 11612. DETAILED DESCRIPTION OF EXEMPLARY EMBODIMENTS
[0045] By way of a non-limiting example, the below process steps from source to product are described.
[0046] The steps of an exemplary manufacturing process are described as follows.
• Initially the staple fibres are formed into yarns by spinning.
• These yarns are then woven to greige cloth according to the desired and optimal specification.
• The greige cloth is inspected.
• There is a pre-treatment comprising desizing, scouring and bleaching.
• In a further pre-treatment step the cotton and lyocell are mercerised. • The fabric is then dyed in a continuous dye process including dyeing and fixing.
• The cloth is then checked for colour deficiencies before entering the finishing process line.
• One or two FR treatment steps can be performed involving impregnation of the fabric and ammonia curing.
• The fabric is mechanically softened in an aero-tumbler to become more flexible.
• The product is stretched onto a tenter frame and treated with resin to prevent fibrillation.
• The fabric is subsequently heat treated to cross link the applied resin.
• A further finish is applied to obtain oil and water repellence.
• The product is treated with heat/annealed
• The fabric is Sanforized to reduce shrinkage.
• Quality control then occurs.
• This is followed by packaging and shipping to a clothing manufacturer where it is shaped for a specific use such as a specific workplace uniform.
[0047] The staple fibres which are formed into the yarns include cotton, Lyocell and recycled polyester. Cotton is a natural fibre that provides comfort and better moisture management than synthetic fibres. Cotton is the traditionally used fibre for FR-treated fabrics.
[0048] Lyocell is a synthetic cellulosic fibre. Other alternative cellulose based cotton alternatives exist such as Livaeco™, Birla Modal™, Birla Excel™, Birla Viscose™ and Birla Spunshades™ provided by Birla Cellulose. Lyocell is an industrial and launderable fibre which loses strength in the wet state. Lyocell in fact has a strength similar to cotton in the wet state and is more sustainable than cotton. Compared to cotton, the water usage of Lyocell is 95% less than of cotton. Lyocell is more comfortable than cotton with better moisture management and is generally smoother to the skin. It is however a fibrillating fibre; for example as in the wet state water penetrates inside the fibrillar bundles causing exposure of fibrils at the fibre surface. The rate of fibrillation increases with increased pH and increased temperature. [0049] (Recycled) polyester can be mechanically or chemically recycled. Polyester is used in the FR-treated fabric to increase durability as it a relatively stronger material, however it is also heavier than cellulose based fabrics. Polyester cannot be made flame retardant with Proban chemistry. Mechanical recycled polyester can be used to improve sustainability. Use of recycled polyester provides an energy consumption reduction by 45% in comparison to use of virgin polyester, and has a water consumption reduction of nearly 20% in comparison to virgin polyester. The greenhouse gas emissions are reduced over 30% in comparison to virgin Polyester.
[0050] For the exemplary EG 9600 fabric, yarns were spun using the following staple fibres:
Cotton (middling)
• Count 3,8 - 4,4 Micronair
• Length 27 mm
• T enacity 26 - 30 cN/tex
Tencel Lyocell Standard
• Count 1,25 dtex
• Length 38 mm
• Tenacity 38 cN/tex
• Tenacity wet 31 cN/tex
Repreve recycled Polyester
• Count 1,3 dtex
• Length 38 mm
• Tenacity 59 cN/tex
Nega-Stat® P190
• Count 39/6 dtex
• Length= filament
[0051] An exemplary formulation of the fabric yarns is: Warp Yarn:
50% Lyocell;
25% Cotton; and 25% Recycled polyester. Weft Yarn:
90% Cotton; and 10% Recycled polyester. AS twisted Yarn:
75 % Cotton;
8 % Recycled polyester.
17% Negastat filament [0052] The EC9600 fabric is woven in a 2/1 twill weave with the above warp and weft yarns. An anti-static yarn is included at a spacing of every 1 :20 in the weft direction. The overall weight percentages of the respective fibres in the final fabric are:
50 % Cotton; 30 % Lyocell;
19 % Recycled polyester.
1% Negastat filament
[0053] After a single pass THP treatment, the fabric was measured to have the following flame retardant characteristic values:
[0054] Amount of THP is measured by P, N analysis with the following results:
EG 9600: P 2.1% N 1.7%
Traditional cotton product: P 2.9% N 1.9%.
[0055] Fabric is after FR-treatment still vulnerable to fibrillation. Finishing the fabric after FR-treatment with a suitable resin prevents fibrillation of lyocell in the product. The resin is applied in a foulard process and the application process includes water removal by pressing and heating, followed by thermal treatment for cross linking the resin. The term non-fibrillating as used herein will be understood to mean substantially non-fibrillating, and to be exchangeable with low-fibrillating. The application of a non-fibrillation resin provides a fabric having a reduced fibrillation compared to that in its virgin state. [0056] A second finish is required to make the fabric water-and/or oil repellent finish through fluorocarbon resin (FC) to meet ISO 13034. The resin and the FC may be combined in one bath or, to improve the fibrillation and prevent loss of colour, the resin and FC finish may be applied after each other in a 2-step process. This 2- step process reduces the fibrillation after laundering. Further improvement is to cross-link the resin first before applying the FC finish.
[0057] Laundering according to the standard ISO 15797, 75oC, j requirements is possible and results in reduced and homogeneous fibrillation. The fabric remains durable even up to 50 of the rigorous launders according ISO 15797, 75oC, j.
[0058] The final product has the following advantages:
• 50% green materials,
• durable and sustainable,
• 28% lower water footprint than traditional FR-treated fabric, · 10% lower C02 footprint than traditional FR-treated fabric,
• Ultra-soft with breathability thanks to lyocell,
• Low water vapour resistance (breathability) and good short-time vapour absorbency,
• Better performance than traditional FR-treated fabric, · Traditional FR-treated cotton fabrics feel stiff and sturdy, the EG9600 feels supple and soft to the skin,
• FR performance equal to traditional FR-treated cotton fabrics,
• Low pilling. [0059] Three batches of the improved FR fabric were tested and the measured properties after the final finish are shown to be repeatable and in accordance with the technical specifications with details as follows:
[0060] The technical specifications of the fabric of the invention are comparable and commensurate with the standard FR fabric and an alternative inherently flame retardant fabric known as Modal/Tencel™ in terms of properties. The improved FR fabric of the invention further has improved comfort and reduced carbon footprint. Comparison of the technical specifications is as follows:

Claims

1. A flame retardant (FR) treated fabric, comprising yarns formed from a mixture of natural and/or synthetic fibres, the fabric further comprising FR treated lyocell fibres, wherein the FR treatment is a non-cellulose-reactive FR treatment and the FR treated lyocell fibres are rendered low-fibrillating.
2. The fabric of claim 1 , wherein the fabric is a woven fabric comprising warp yarns and weft yarns.
3. The fabric of claim 1 or claim 2, wherein the natural fibres comprise cotton.
4. The fabric of any one of the preceding claims, wherein the synthetic fibres comprise polyester, polyamide and/or aramid, preferably recycled.
5. The fabric of any one of the claims 2 to 4, wherein the lyocell fibres are present in the warp yarns only.
6. The fabric according to claim 5, wherein the warp yarns comprise lyocell fibres, synthetic fibres and natural fibres, preferably in a wt % ratio of around 50/25/25.
7. The fabric according to claim 5 or claim 6, wherein the weft yarns comprise a preponderance of natural fibres, preferably between 70 wt % and 95 wt %.
8. The fabric according to any one of the preceding claims, woven as a twill weave, preferably a 2/1 twill.
9. The fabric of any one of the preceding claims, further comprising an anti fibrillation finish, preferably comprising an anti-fibrillation additive, optionally a resin cross-linkable to the hydroxyl groups of the, FR lyocell, preferably DMDHEU resin.
10. The fabric of any one of the preceding claims, further comprising a water and/or oil repellent finish, preferably comprising a fluorocarbon
11. The fabric of any one of the preceding claims further comprising antistatic fibres, preferably in an amount of between 0.2 wt % and 5 wt %.
12. The fabric according to claim 2, comprising in the warp:
40 - 60 wt %, preferably around 50 wt % lyocell,
15 - 35 wt %, preferably around 25 wt % cotton; and 15 - 35 wt %, preferably around 25 wt % recycled polyester; and in the weft:
70 - 99 wt %, preferably around 90 wt % cotton,
1 - 20 wt %, preferably around 10 wt % recycled polyester.
13. The fabric of any one of the preceding claims, wherein the fabric is durable to laundering at least 50x according to ISO 15797 and retains at least one or more of the following properties:
- a color retention score of greater than 2 or greater than 3 according to the greyscale comparison of ISO 105-A02;
- exceed the ignition to surface requirement of IS011612 according to the test procedure of ISO15025 (2000)
- exceed the bottom edge ignition requirement of IS011612 according to the test procedure of ISO15025 (2000);
- tear strength greater than 10N according to IS013937-2 (2000);
- tensile strength greater than 300N according to IS013934-1 (2013)
14. The fabric of any one of the preceding claims wherein the fabric has abrasion resistance to more than 15000 cycles, preferably more than 20000 cycles according to the Martindale Method and fulfilling ISO 12947-2 for an applied force of 12 KPa.
15. The fabric according to any one of the preceding claims, wherein the non- cellulose-reactive treatment comprises a THP salt and preferably an amount of phosphor in the final fabric is below 2.5 wt%, and/or an amount of nitrogen in the final fabric is below 2.0 wt %.
16. A method of producing a flame retardant fabric comprising yarns including a mixture of natural and/or synthetic fibres and lyocell fibres having accessible hydroxyl groups, the method comprising first subjecting the fabric to a non- cellulose-reactive FR treatment and subsequently finishing the fabric by application of a resin to stabilise fibrillation of the lyocell.
17. The method of claim 16, comprising constructing the fabric by weaving the yarns with a warp yarn and a weft yarn, preferably in a twill.
18. The method of claim 17, wherein the lyocell is present in the warp yarns only.
19. The method according to any one of claims 16 to 18, wherein the FR treatment is a THP based process.
20. The method according to any one of claims 16 to 19, wherein finishing the fabric by application of a resin, comprises cross-linking the resin, preferably a formaldehyde resin.
21. The method of any one of claims 16 to 20, wherein finishing further comprises a water and/or oil repellent treatment, preferably provided in a separate step after the application of the resin to prevent fibrillation.
22. The method according to any one of claims 16 to 21 wherein, prior to subjecting the fabric to the FR treatment, the fabric is pre-treated by one or more process selected from the group consisting of: desizing, scouring, bleaching, mercerising, dying, including reactive and non-reactive dyes.
23. The method according to any one of claims 16 to 22, wherein the yarns are spun yarns comprising an intimate mix of staple fibres.
24. A garment manufactured of a fabric according to any one of claims 1 to 15 or by a method according to any one of claims 16 to 23.
EP22729249.7A 2021-06-18 2022-06-16 Flame retardant fabric comprising cotton alternative Pending EP4355943A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
NL2028484A NL2028484B1 (en) 2021-06-18 2021-06-18 Flame Retardant Fabric Comprising Cotton Alternative
PCT/EP2022/066529 WO2022263615A1 (en) 2021-06-18 2022-06-16 Flame retardant fabric comprising cotton alternative

Publications (1)

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EP4355943A1 true EP4355943A1 (en) 2024-04-24

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EP (1) EP4355943A1 (en)
KR (1) KR20240046483A (en)
CN (1) CN117730179A (en)
AU (1) AU2022292113A1 (en)
BR (1) BR112023026230A2 (en)
CA (1) CA3223279A1 (en)
NL (1) NL2028484B1 (en)
WO (1) WO2022263615A1 (en)

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3816068A (en) 1971-07-12 1974-06-11 Burlington Industries Inc Flame retardant for cellulosic fabrics
GB9421424D0 (en) 1994-10-25 1994-12-07 Albright & Wilson Flame-retardent and fabric-softening treatment of textile materials
AT513761A1 (en) * 2012-12-27 2014-07-15 Chemiefaser Lenzing Ag Non-fibrillating, flame retardant cellulosic sheet, its use and method of making the same
WO2019101852A1 (en) * 2017-11-22 2019-05-31 Ten Cate Protect Bv Method for producing a flame-resistant textile article

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CA3223279A1 (en) 2022-12-22
AU2022292113A1 (en) 2024-01-04
WO2022263615A1 (en) 2022-12-22
KR20240046483A (en) 2024-04-09
CN117730179A (en) 2024-03-19
BR112023026230A2 (en) 2024-03-05

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