WO2019101852A1 - Procédé de fabrication d'un article textile ignifugé - Google Patents

Procédé de fabrication d'un article textile ignifugé Download PDF

Info

Publication number
WO2019101852A1
WO2019101852A1 PCT/EP2018/082209 EP2018082209W WO2019101852A1 WO 2019101852 A1 WO2019101852 A1 WO 2019101852A1 EP 2018082209 W EP2018082209 W EP 2018082209W WO 2019101852 A1 WO2019101852 A1 WO 2019101852A1
Authority
WO
WIPO (PCT)
Prior art keywords
flame
phosphorous
cellulose
textile article
resistant
Prior art date
Application number
PCT/EP2018/082209
Other languages
English (en)
Inventor
Tatjana TOPALOVIC JOCIC
Michael T. Stanhope
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
Priority claimed from US15/821,106 external-priority patent/US20190153663A1/en
Priority claimed from NL2020326A external-priority patent/NL2020326B1/en
Application filed by Ten Cate Protect Bv filed Critical Ten Cate Protect Bv
Publication of WO2019101852A1 publication Critical patent/WO2019101852A1/fr

Links

Classifications

    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/244—Treating 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
    • D06M13/282—Treating 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
    • D06M13/285—Phosphines; Phosphine oxides; Phosphine sulfides; Phosphinic or phosphinous acids or derivatives thereof
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F1/00—General methods for the manufacture of artificial filaments or the like
    • D01F1/02—Addition of substances to the spinning solution or to the melt
    • D01F1/07—Addition of substances to the spinning solution or to the melt for making fire- or flame-proof filaments
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F2/00—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/244—Treating 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
    • D06M13/282—Treating 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
    • D06M13/288—Phosphonic or phosphonous acids or derivatives thereof
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/322—Treating 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
    • D06M13/44—Treating 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
    • D06M13/447—Phosphonates or phosphinates containing nitrogen atoms
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/39—Aldehyde resins; Ketone resins; Polyacetals
    • D06M15/423—Amino-aldehyde resins
    • D06M15/43—Amino-aldehyde resins modified by phosphorus compounds
    • D06M15/431—Amino-aldehyde resins modified by phosphorus compounds by phosphines or phosphine oxides; by oxides or salts of the phosphonium radical

Definitions

  • the present invention relates to a method for making a textile article flame-resistant as well as to textile articles obtained by said method.
  • the method comprises providing at least part of the textile article with a non-cellulose-reactive, phosphorous-containing, flame-retardant compound and also providing at least part of the article with a cellulose-reactive, phosphorous-containing, flame-retardant compound.
  • Said garments must pass minimum thermal performance requirements such as flame- and/or heat- 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.
  • 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.
  • 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.
  • the garment must be durable in the sense that the above disclosed parameters last at least for the lifetime of the product.
  • 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 flame-resistant clothing made from flexible materials is ISO 1 1612.
  • Flame- and/or heat-resistance relates to a generic property of an article and indicates how resilient the article is against flames or high heat without suffering damage.
  • the term flame-retardant is generally used to describe a treatment, which may be used to render an article flame-resistant.
  • the article may be a flame-resistant garment that protects the wearer of the garment against flames or heat.
  • a suitable manner to measure and quantify the flame- and/or heat-resistance is the thermal manikin test (ISO test 13506). In this test a manikin equipped with temperature sensors is submitted to a high heat-fluxfor a short time. Based on the read-out of the temperature sensors, an accurate prediction of the bum injury can be made.
  • the after-flame time is that amount of time that a visible flame is present after the heat source has been removed. A limited or zero after-flame time is especially important when working in confined spaces, which is the case for helicopter and tank crews. In these cases a decrease in after-flame of only a few seconds can make an important difference. This includes the direct protection against burning garments, as well as the reduction of the chance that the prolonged flame sets off an external fire. As described above, the afterflame can be assessed using the thermal manikin test. Alternatively, and perhaps more accurately, the afterflame time can be determined using ISO 15025.
  • procedure A refers to surface ignition - i.e. the case where the burner is orthogonal to the fabric and the flame is directed to the middle of the fabric - and procedure B refers to bottom ignition - i.e. the case where the burner is positioned 30° from the vertical axis and the flame is directed to the bottom of the fabric.
  • procedure B refers to bottom ignition - i.e. the case where the burner is positioned 30° from the vertical axis and the flame is directed to the bottom of the fabric.
  • the time that the material continues to burn after the flame has been removed is measured and recorded as the after-flame time.
  • resilience against combustion upon exposure to a substantial level of thermal energy is a key property. Typically this is referred to as resilience against exotherm.
  • This property relates to the level of thermal energy to which a system may be exposed before the system starts to produce a significant release of heat/combustion energy or, put in other words, before the system starts to“exotherm”.
  • the exotherm can be assessed using the above mentioned manikin test (ISO test 13506) and varying for instance the heat flux density and/or the exposure time. The higher the exotherm, the lower the level of thermal energy that can be withstood prior to combustion.
  • the intensity and initiation timing of the exotherm is dependent on intensity of thermal exposure, fabric mass, level of flame-retarding phosphorous contained in the fabric, and finally the way flame-retarding phosphorous is bonded with fibres in the fabric. It is theorized that upon exposure to an ignition source of sufficient magnitude, for example ⁇ 8.0 cal/cm 2 with a 2.0 cal/cm 2 /sec exposure flux on a 300 g/m 2 fabric, the“free” cellulose in a treated system begins to rapidly oxidize, or burn.
  • LOI limiting oxygen index
  • a known treatment for rendering cellulosic fibres or textile articles comprising cellulosic fibres flame-resistant 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 can be manufactured according to the process disclosed in US 4,31 1 ,855 of which examples 1 and 2 are hereby incorporated herein by reference. Subsequently the textile article is brought into contact with gaseous ammonia. More details can be found in examples 3 and 4 of US 4,31 1 ,855 or in the example covering columns 3 and 4 of US 4,078,101 , all of which are incorporated herein by reference.
  • 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.
  • Proban® treatment is a non-cellulose-reactive treatment which means that there is substantially no chemical reaction between the THP and the cellulosic fibre.
  • Proban® treated fabrics or garments can exotherm which means that these fabrics or garments may not sufficiently protect against very intensive heat or longer-duration flash fires, e.g. flash fires that last for 3 seconds or longer at 2.0 cal/cm 2 /sec heat flux.
  • a flame-retardant chemical is usually provided as a solid particulate or masterbatch which has been ground into fine particles that are added to the spinning solution prior to extrusion or spinning of the fibre.
  • a flame-retardant compound is usually provided as a solid particulate or masterbatch which has been ground into fine particles that are added to the spinning solution prior to extrusion or spinning of the fibre.
  • the particulates are dispersed throughout the fibre yielding a very durable flame protection.
  • Lenzing FR® which comprises an organic, non-halogenated, phosphorous containing flame-retardant such as Exolit® 5060 PK.
  • Exolit® 5060 PK flame-retardant
  • 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) hydroxylgroup 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.
  • a benefit of using cellulose-reactive treatments with N-methylol phosphate is that they do not exhibit an exotherm. Hence fabrics or garments treated with said treatment offer better protection against very intensive heat or longer-term flash fires compared to, for instance, non-cellulose reactive treatments. Also articles treated with cellulose-reactive treatments with N-methylol phosphate hardly suffer from an afterflame.
  • a disadvantage of above described cellulose-reactive treatment is that the phosphorous comprising molecules may detach from the cellulose-containing textile article which leads to a reduction of the flame- resistant properties. This detachment may be the result of washing the treated article, especially when washed using a bleach containing detergent. Also the bonds between the phosphorous molecules and the treated article may hydrolyse due to the presence of free acids in the treated article. As a result of this, treated textile articles have a limited shelf life. Free acids can be removed by washing the article every six months using an alkaline detergent. However, the need to wash articles that are not used is very inconvenient. Also each wash to remove the free acids will to some extent result in lower phosphorous content of the article.
  • US 2016/0201236 aims to produce an inexpensive flame-resistant fabric that performs at par with the currently available flame- resistant fabrics in order to facilitate the spread of safer products.
  • phosphorous containing regenerated cellulose fibre FR Rayon
  • antimony containing modacrylic fibre FR Rayon
  • a fabric comprising a natural cellulose fibre and an antimony containing modacrylic fibre is subjected to a phosphorous treatment.
  • this treatment uses phosphorous-comprising compounds as these are compatible with cellulose fibres. More specifically there is a need for a textile article that protects against body burns, has a limited after-flame time under substantial thermal exposure and a high activation-energy before it starts to exotherm. In addition this fabric may need to meet some or all other relevant parameters on tensile and tear strength, abrasion resistance, snagging resistance and resistance to penetration by water and liquid chemicals. Furthermore and desirably, the fabric needs to be comfortable, have adequate moisture management and be durable in that it has a long shelf life and can withstand at least 50 washes, and more preferably even more than 100 washes.
  • This method for making a textile article flame-resistant, wherein the textile article comprises cellulose-containing fibres comprises: a. providing at least part of the textile article with a non-cellulose-reactive, phosphorous-containing, flame-retardant compound, and b. providing at least part of the textile article with a cellulose-reactive, phosphorous- containing, flame-retardant compound, wherein the parts treated in a. and b. coincide at least partially.
  • a cellulose-reactive compound may be defined as a compound that reacts with cellulose in such a manner that the compound will be chemically bound to the cellulose.
  • a non-cellulose-reactive compound may be defined as one that does not chemically react with the cellulose.
  • a non-cellulose-reactive, flame-retardant compound does not react with the cellulose and thus needs to have another mechanism for fixing the compound to the fibre in order to provide the required flame-retardant properties.
  • This mechanism may be the formation of a cross-linked network around and throughout the molecular structure of the cellulose-comprising fibre or it may be that the flame- retardant compound is present throughout the fibre and hence physically enclosed by the cellulose polymers.
  • treatments a. and b. are provided on cellulose containing fibres before they are combined to form the textile article. In this context, reference is given to a. and b. as being‘treatments’ but it will be understood that these need not be separate treatments.
  • a. and/or b. there are several suitable processes to provide a textile article with the flame retardant compounds referred to in a. and/or b.. These processes, which typically rely on bringing the textile article in contact with a flame- retardant compound such that the textile article becomes flame resistant, may be referred to as flame- retardant treatments.
  • a treatment with a cellulose-reactive compound is denoted as a cellulose-reactive treatment.
  • the associated treatment with said non-cellulose-reactive compound is denoted as a non- cellulose-reactive treatment.
  • Both the non-cellulose-reactive compound and the cellulose-reactive compound may be provided by bringing the textile article in contact with the compound.
  • bringing in contact can encompass dipping, padding, soaking, rolling, spraying, coating and the like.
  • bringing in contact can refer to printing techniques such as digital printing.
  • a textile article with a compound - usually a non-cellulose-reactive compound - implies that the textile article is provided with fibres or yarns comprising said compound.
  • a regenerated cellulosic spun fibre may be produced by adding non-cellulose-reactive, phosphorous-containing, flame-retardant particulates during production of the fibre prior to spinning.
  • the flame-retardant compound is provided during fibre production. It may be beneficial to also include the cellulose-reactive compound to the spinning solution in such a manner that the spun fibre comprises a non-cellulose-reactive and a cellulose-reactive flame-retardant compound.
  • a textile article may be provided with a non-cellulose-reactive, phosphorous- containing, flame-retardant compound by providing it with regenerated cellulosic spun fibres comprising said compound.
  • the part of the textile article that has been provided with a non- cellulose-reactive compound is a regenerated cellulose fibre comprising flame-retardant particulates.
  • said flame-resistant particulates are organic, non-halogenated, phosphorous- containing, flame-retardant particulates.
  • the regenerated cellulose fibre comprising flame-retardant particulates may be Lenzing FR® or a similar equivalent.
  • the method according to the invention wherein different flame retardant compounds are provided and wherein the flame retardant compounds bind to the textile article using different chemical and/or physical bonds may lead to synergistic effects. For instance, it may lead to the articles having improved durability of their flame-resistant properties.
  • the network formed by the non-reactive-cellulose compound may increase the fixation of the cellulose-reactive compound. Hence the cellulose-reactive compound is less likely to be removed rendering the flame- resistant textile article more durable.
  • step b. the opposite might be true, meaning that it is beneficial to first provide the cellulose-reactive compound (step b.) and then the non-cellulose-reactive compound (step a). In yet another alternative, it might be beneficial to provide the non-cellulose reactive compound (step a.) together with the cellulose-reactive compound (step b.).
  • steps a. and b. are performed on the textile article.
  • the textile article may be first provided with a non-cellulose-reactive, phosphorous-containing, flame-retardant compound (step a.) and subsequently provided with a cellulose-reactive, phosphorous-containing, flame-retardant compound (step b.).
  • the non-cellulose-reactive, phosphorous-containing, flame-retardant compound is a tetrakishydroxyalkylphosphonium salt.
  • the non-cellulose-reactive, phosphorous-containing, flame-retardant compound is Proban® or a similar equivalent.
  • a typical process for performing a Proban® 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 tetrakishydroxyalkylphosphonium
  • the textile article can be soaked, impregnated, dipped, soaked, rolled, sprayed, coated, printed or the like. After the Proban® has been applied to the textile article, it may be cured using ammonia.
  • the cellulose-reactive, phosphorous-containing, flame-retardant compound is a N-methylol phosphonate compound such as N-methylol dialkyl phosphonopropionamide.
  • the cellulose-reactive, phosphorous- containing, flame-retardant compound may be Pyrovatex® CP LF, Aflammit® KWB or the like.
  • a process for performing a flame-retardant treatment using Pyrovatex® CP LF is impregnating the textile article with a solution containing the Pyrovatex® until the liquid has sufficiently penetrated the fabric.
  • the textile article can be soaked, impregnated, dipped, soaked, rolled, sprayed, coated, printed or similar.
  • the fabric may be squeezed at a carefully controlled rate.
  • the fabric may be pre-dried and heat-treated to help bind the phosphorous compound to the cellulose molecules.
  • This process is also applicable when Aflammit® KWB or the like is used.
  • the concentration of the Pyrovatex® or Aflammit® KWB in the flame-retardant treatment liquid (also referred to as treatment agent) is not particularly limited. In the art concentrations up to 500 g/L of Pyrovatex® or Aflammit® may be found. The method of the current invention will also work with such a high concentration but preferably a lower concentration is used.
  • This may be 50 to 400 g/L, more preferably 50 to 300 g/L, or even more preferably 50 to 100 g/L. It is common to include additional chemicals in the liquid. Phosphoric acid or similar acid is used as additive that promotes the esterification reaction of hydroxyl groups of the cellulosic fibres.
  • Melamine based resins, urea based resins or similar may be used as a cross- linking agent to increase crease resistance of the fabric. As example of such a resin is Knittex® MLF NEW.
  • Penetrants such as Invadine® PBN may be used to increase the ability of the phosphorous to penetrate the fabric.
  • the textile article that has been made flame-resistant using the method of the invention may have a phosphorous content of at least 1 .5 wt%, more preferable at least 2.0 wt%, even more preferably at least 2.2 wt%, even more preferably at least 2.5 wt% and most preferably at least 3.0 wt%.
  • wt% is short for weight percent and - unless indicated differently for specific cases - is used to quantify the relative weight of a chemical in comparison to the weight of the textile article including said relative amount of the chemical.
  • the phosphorous content may be less than 3.0 wt%, or may be less than 5.0 wt%, or may be less than 7.0 wt% or may be less than 10.0 wt%.
  • the phosphorous may be present both as chemically- bound phosphorous and as non-chemically-bound phosphorous.
  • chemically-bound is intended to refer to the fact that the phosphorous is chemically reacted either directly or indirectly to the cellulose i.e. phosphorous that has been provided by the cellulose reactive compound.
  • Non-chemically- bound phosphorous is phosphorous that is not chemically reacted to the cellulose although of course, it may be chemically bonded to another molecule as in the case for THP. This phosphorous may be provided by the non-cellulose reactive compound.
  • the amount of phosphorous that has been provided by the noncellulose reactive compound is preferably at least 1 .5 wt%, more preferably at least 1 .7 wt%, even more preferably at least 1 .9 wt% and most preferably at least 2.0 wt%.
  • the amount of phosphorous provided by the non-cellulose-reactive compound is between 1 .5 and 2.0 wt%, more preferably between 1 .6 and 1 .9 wt%, and most preferably between 1 .7 and 1 .9 wt%.
  • the amount of phosphorous provided by the cellulose reactive compound is preferably at least 0.1 wt%, more preferred at least 0.2 wt% and most preferred at least 0.3 wt%.
  • the amount of phosphorous provided by the cellulose-reactive compound is between 0.1 and 1 .0 wt%, more preferably between 0.2 and 0.7 wt% and even more preferably between 0.3 and 0.5 wt%.
  • 70-90 wt% of the phosphorous may have been provided by the non-cellulose reactive compound and 30-10 wt% by the cellulose-reactive treatment.
  • reducing the absolute amount of both the non-cellulose-reactive compound and the chemically-bound phosphorous may be beneficial to the resultant article.
  • chemically-bound phosphorous is believed to weaken cellulose fibres and also suffers from detachment of phosphorous containing molecules by hydrolysis. Operating with a lower initial percentage of chemically-bound phosphorous is believed to ensure better long term performance and article strength.
  • a fluorocarbon finish may be applied to increase the water and oil repellence of the article.
  • This can be performed with a (perfluoralkyl) acrylate such as Nuva® 21 10.
  • a penetrant such as Invadine® PBN may be used.
  • a smoothing agent such as Perapret® PEP may be used.
  • a weak acid such as acetic acid may be used to control the pH. It will be understood that any number of additional compounds or treatments may be applied to the article according to the required end use.
  • the method of the invention gives considerable improvements in flame-resistant properties compared to the individual treatments.
  • a textile article which has been rendered flame-resistant using the method of the invention will normally meet the requirements of ISO 11612.
  • the estimated body burns, after-flame time, exotherm behaviour and/or phosphorous-content are improved.
  • the phosphorous content - as determined by the colour shift following a reduction of the phosphorous with molybdic acid in isobutyl alcohol - of the fabric treated with the method according to the invention is at least 2.0 wt%, preferably at least 2.1 wt%, more preferably at least 2.3 wt% and most preferably at least 2.5 wt% or even at least 3.0 wt%.
  • the abrasion resistance, as measured using ISO 12947 Part 2 is at least 50,000 rubs, more preferably at least 60,000 rubs, even more preferably at least 75,000 rubs and most preferably at least 100,000 rubs.
  • the flame-resisting textile article obtained by the method according to the invention suitably has tear strength (as measured using ISO 13937-2) and a tensile strength (as measured using ISO 13934-1 ) of at least 80% of that of the corresponding untreated material. More preferably the tear strength and tensile strength are at least 85%, even more preferably 90%, even more preferably 95% and most preferably at least 100% of that of the corresponding untreated material.
  • washes relate to a process for cleaning a fabric or garment in either a domestic or an industrial setting. Normally a detergent is used that comprises several chemicals which are beneficial for the cleaning process and/or help to obtain the desired end result.
  • Said chemicals typically include an anionic surfactant such as sodium alkyl benzene sulfonate, a non-ionic surfactant, a carbonate buffer, antiredeposition polymers, phosphonates, optical whiteners, enzymes and a bleach system.
  • an anionic surfactant such as sodium alkyl benzene sulfonate, a non-ionic surfactant, a carbonate buffer, antiredeposition polymers, phosphonates, optical whiteners, enzymes and a bleach system.
  • the detergent is formulated such that the wash liquor comprising the dissolved detergent will be alkaline.
  • the alkalinity of the wash liquor and/or the presence of bleach in said wash liquor are considered to be detrimental for any flame retardant treatment.
  • reference detergent 6 (see Annex N of ISO 6330) is considered the preferred detergent for laboratorial testing as detergent 6 comprises 20% of perborate bleach and 3% TAED bleach activator making it a stress test for any flame resistant fabric or garment.
  • stable to X washes is intended to denote that the article and property remain at a level exceeding 90% of the original value after X washes of the given type, which in the present context will be a wash according to ISO 6330 6N unless otherwise stated. .
  • the method according to the invention allows to obtain flame-retardant textile articles that are stable in the sense that the phosphorous content is at a level exceeding 90% of the original value after 5 washes, more preferably 25 washes, more preferably 50 washes or most preferably 100 washes. Also said method allows to obtain flame-retardant textile articles that are stable in the sense that the phosphorous content is at a level exceeding 90% of the original value after 6 months of storage and subsequently after been washed for 5 washes, more preferably 25 washes, more preferably 50 washes or most preferably 100 washes.
  • the flame-resisting properties, and especially the after-flame properties are maintained at a level exceeding 90% after 5 washes, more preferably 25 washes, more preferably 50 washes or most preferably 100 washes.
  • the flame-resistant properties, and especially the after-flame properties are maintained at 90% of their original value after 6 months of storage and subsequently after been washed for 5 washes, more preferably 25 washes, more preferably 50 washes or most preferably 100 washes.
  • the method allows to obtain flame-retardant textile articles that are stable in the sense that the phosphorous content is at a level exceeding 90% of the original value after 12 months of storage and subsequently after been washed for 5 washes, more preferably 25 washes, more preferably 50 washes or most preferably 100 washes.
  • the flame-resistant properties, and especially the afterflame properties are maintained at 90% of their original value after 12 months of storage and subsequently after been washed for 5 washes, more preferably 25 washes, more preferably 50 washes or most preferably 100 washes.
  • a textile article can be any useful object such as a garment or other end product, a fabric - which can be woven, non-woven or otherwise - , a yarn or a fibre.
  • a textile article can be any useful object such as a garment or other end product, a fabric - which can be woven, non-woven or otherwise - , a yarn or a fibre.
  • Non-limiting examples include personal protective clothing - such as flame-resistant coats, trousers, uniforms, vests and coveralls, as well as helmets, seats, and trims - in particular for military vehicles and welding gloves.
  • the invention also relates to the use of a non-cellulose-reactive, phosphorous-containing, flame-retardant compound and a cellulose-reactive, phosphorous-containing, flame-retardant compound in any of the above-described methods. Furthermore the invention covers the use of the flame-resistant textile article produced according to any one of the methods described above for protecting individuals from heat and/or flames.
  • the flame-resistant method according to the invention allows production of textile articles that have a high and durable phosphorous content without having substantial negative effects of the phosphorous system on the physical properties of the textile articles. More specifically, the tensile strength, tear strength, abrasion resistance and/or snagging resistance are no worse than fibres treated by either of the two systems individually.
  • the phosphorous is durably bound to the fibre, yarn and/or fabric and can withstand at least 25, more preferably 50, even more preferably 100, or most preferably 150 washes without significant degradation. Also it is not very susceptible to spontaneous hydrolyzation which results in a long shelf life of the product.
  • the textile article produced according to the invention with a cellulose content of at least 10 wt%, or at least 25 wt%, or at least 40 wt%, or at least 50 wt%, or at least 60 wt%, or at least 70 wt%, or even at least 75 wt% may have beneficial properties relating to comfort.
  • the textile article according to the invention comprising between 30-80 wt% cellulose, more specifically between 50-75 wt% or still more specifically, 60-65 wt% cellulose may have beneficial properties relating to comfort.
  • the textile article of the invention may comprise other fibres besides the cellulose fibres.
  • These fibres can include, but are not limited to, meta-Aramid, para-Aramid, polyamide imide, polyamide, modacrylic, melamine, poly(p-phenylene benzobisoxazole) (PBO), polybenzimidazole (PBI), polysulphonamide (PSA), Panox (oxidized acrylic), semicarbon, partially oxidized acrylic (including partially oxidized polyacrylonitrile), rayon , lyocell, phenolic (novoloid), polyphenylene sulphide (PPS), PTFE, polyimide, polyester, acrylic, wool, viscose, flax, hemp, silk, nylon, anti-static fibers, and combinations thereof.
  • the fabric of the invention also comprises para-Aramid, meta-Aramid, modacrylic, acrylic, wool, silk and/or anti-static fibers.
  • meta-Aramid and/or antistatic fibers may be highly desirable.
  • the textile article can be a fibre, yarn, fabric or garment.
  • Said fabric may be a woven fabric, a knitted fabric or a non-woven fabric.
  • Woven fabrics consist of two sets of interlocked yarns and are typically produced on a loom. Both sets consist of straight yarns which run in parallel. The set of yarns that runs in the direction of weaving is referred to as the warp. The set of yarns that runs orthogonal to the direction of weaving is referred to as the weft. Depending on how the weft and warp are interlocked, different types of woven fabrics may be produced according to the invention, such as twill or ripstop. Knitted fabrics also consist of interlocked yarns, however in this case the yams are interlocked using loops.
  • a non-woven fabric consists of sheets of entangled fibres that are mechanically, thermally or chemically bonded.
  • the article is particularly useful in the form of a light weight fabric having a weight of between 100 and 300 g/m2, alternatively from 150 to 250 g/m2 or alternatively in the range of 180 to 210 g/m2.
  • a fabric may be ideal for manufacture of protective clothing.
  • the article may be a fabric having good air permeability, in particular, values of air permeability of more than 100 L/m2/s, or more than 200 L/m2/s or even greater than 300 L/m2/s may be provided, measured according to ISO 9237.
  • the invention may also be applied to heavier weight fabrics such as fabrics having weights of between 300 and 600 g/m2. In such situations, better comfort may be achieved since the fabric has relatively more cellulose-containing fibre such as cotton for example, and relatively less chemicals than is the case when a single treatment of non-reactive phosphorous is applied.
  • a flame-resistant fabric was woven from a fibre blend comprising 64% Lenzing FR® - which is a Rayon fibre that has been made flame retardant by a non-cellulose-reactive treatment -, 24% aramid, 10% polyamide, 2% antistatic fibre to a twill construction at approximately 180 g/m 2 .
  • the same type of yarns was used in both directions (warp and weft).
  • the fabric was printed with a 100% coverage standard camouflage pattern composed of 7 colours. After the fabric was printed, a cellulose-reactive, phosphorous- containing, flame-retardant compound was applied to the fabric.
  • This compound was applied by impregnating the fabric with an aqueous solution comprising Pyrovatex® CP LF, Knittex® MLF NEW , Phosphoric acid 85% and Invadin® PBN according to the concentrations as indicated in the top half of Table 1 .
  • the fabric was squeezed at a predetermined squeezing rate, pre-dried, and heat-treated by curing on a tenter frame for 1 minute at 170°C to help bind the phosphorus compound to cellulose molecules. Subsequently it was neutralized by soaking it in a 12 g/L sodium hydroxide solution at 60°C for 2 minutes and thoroughly rinsed using hot water.
  • the samples received a standard fluorocarbon finish according to the bottom half of Table 1 .
  • This finish improves the water and oil repellent properties of the fabrics.
  • the process of applying the finish consisted of soaking the samples in an aqueous solution comprising the ingredients according to Table 1 and rapid curing of the treated samples on a tenter frame for 1 minute at 170°C.
  • Table 1 Flame-retardant treatment.
  • Comparative example 1 was produced by the same procedure as the other samples except that no cellulose-reactive flame-retardant treatments was applied.
  • Table 2 Flame protection and physical properties.
  • the flame-retardant treatment resulted in a considerable improvement in flame-resistant properties, particularly in after-flame time and phosphorous content. Both improvements were retained after 5 washings. Surprisingly the tensile strength and elongation at break were not compromised by the treatment but even marginally increased. Also after 5 washings the tensile strength and elongation at break were not compromised. The tensile strength even maintained its increment after 5 washings.
  • Example 1 The experiment of Example 1 was repeated on a fabric woven to a plain ripstop construction at approximately 210 g/m 2 .
  • the yarns used to produce the fabric and the treatment received by the samples are identical to Example 1 .
  • Said fabric was tested for relevant properties. Results of these tests are presented in Table 3. All washes referred to in Table 3 are performed using ISO 6330 using detergent 6 from Annex N and tumble drying. If not specifically indicated, the fabric was not washed.
  • Table 3 Flame protection and physical properties.
  • Flame-resistant fabric was woven to a twill construction at approximately 180 g/m 2 .
  • the same type of yarns were used in both directions (warp and weft), for which the fibre blend comprised 64% Lenzing FR ® which is a Rayon fibre that has been made frame retardant by a non-cellulose-reactive treatment, 24% aramid, 10% polyamide, 2% antistatic fibre.
  • the fabric was printed with a 100% coverage standard camouflage pattern composed of 7 colours.
  • a cellulose-reactive, phosphorous-containing, flame-retardant compound was applied to the fabric according to the conditions given in Table 4: (1 ) in combination with a standard finish with the fluorocarbon (in one step) or (2) before a standard finish with the fluorocarbon had been carried out.
  • Table 4 Application of a flame-retardant treatment in combination with a fluorocarbon finish (recipe 1) or as a separate process step (recipe 2).
  • Aflammit ® KWB was used as the cellulose-reactive, phosphorous-containing, flame-retardant compound.
  • the fabric was impregnated with an aqueous solution comprising Aflammit ® KWB, Knittex® MLF NEW , Phosphoric acid 85% and Invadin® PBN in the concentrations as indicated in Table 4.
  • the fabric was squeezed at a predetermined squeezing rate, pre-dried, and heat-treated to bind the phosphorus compound to cellulose molecules.
  • Phosphoric acid was used as the catalysts that promotes esterification reaction of hydroxyl groups of cellulosic fibres.
  • Knittex® MLF NEW was used as cross-linking agent and to increase crease resistance of the fabric.
  • Invadine® PBN manufactured by Huntsman was used as penetrant in order to increase the ability of the phosphorous compound to penetrate the fabric.
  • Process step 1 (related to a flame-retardant treatment with or without fluorocarbon finish) consisted of the following steps:
  • Process step 2 consisted of (related to a fluorocarbon finish alone)
  • comparative example 3 was produced by the same procedure as the other samples except that no flame-retardant treatments and related process steps were used for this fabric.
  • Table 5 Flame protection and physical properties.
  • Flame-resistant fabric was woven to a twill construction at approximately 180 g/m 2 .
  • the same type of yarns were used in both directions (warp and weft), for which the fibre blend comprised 64% Lenzing FR ® which is a Rayon fibre that has been made frame retardant by a non-cellulose-reactive treatment, 24% aramid, 10% polyamide, 2% antistatic fibre and was for use in garments offering protection to brief exposure to substantial thermal fluxes.
  • the fabric was printed with a 100% coverage standard camouflage pattern composed of 7 colours. After the fabric was printed a cellulose-reactive phosphorous-containing, flame- retardant compound was applied to the fabric according to the conditions given in Table 6. Also a standard finish with a fluorocarbon was carried out according to the conditions in Table 6.
  • the comparative example 4 was produced by the same procedure as the other samples except that no flame-retardant treatments and related process steps were used for this fabric.
  • the fabrics were subjected to storage and washing before being tested for after-flame properties.
  • the washing conditions were according to ISO 6330 using detergent 6 from Annex N, a 40°C program and tumble drying. Results of these tests are showed in Table 7.
  • Table 8 LOI and Phosphorous/Nitrogen content after applying flame-retardant treatment as given in Table 6.
  • Table 9 Physical properties after applying flame-retardant treatment as given in Table 6.
  • Flame-resistant fabric was woven to a plain ripstop construction at approximately 190 g/m 2 .
  • the same type of yams were used in both directions (warp and weft), for which the fibre blend comprised 64% Lenzing FR® which is a Rayon fibre that has been made frame retardant by a non-cellulose-reactive treatment, 24% aramid, 10% polyamide, 2% antistatic fibre and was for use in garments offering protection to brief exposure to substantial thermal fluxes.
  • the fabric was printed with a 100% coverage standard camouflage pattern composed of 7 colours. After the fabric was printed a cellulose-reactive phosphorous-containing, flame-retardant compound was applied to the fabric according to the conditions given in Table 6 of Example 4. Further process steps are also as in Example 4.
  • Example 4 Thereafter, a standard finish with a fluorocarbon was carried out as in Example 4. The resulting fabric was tested and the results of said tests are presented in Tables 10-13.
  • the washing conditions referred to in any of these tables were according to ISO 6330 using detergent 6 from Annex N, a 40°C program and tumble drying
  • the comparative example 5 was produced by the same procedure as the other samples except that no flame-retardant treatments and related process steps were used for this fabric.
  • Table 10 Flame protection after applying flame-retardant treatment as given in Table 6.
  • Table 12 Physical properties after applying flame-retardant treatment as given in Table 6.

Landscapes

  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
  • Woven Fabrics (AREA)

Abstract

L'invention concerne un procédé de fabrication d'un article textile ignifugé comportant de la cellulose, comprenant de multiples traitements ignifugeants. Le procédé comprend les étapes consistant à : fournir à au moins une partie de l'article textile un composé ignifugeant contenant du phosphore et non réactif à la cellulose, et b. fournir à au moins une partie de l'article textile un composé ignifugeant contenant du phosphore et réactif à la cellulose. Le procédé est approprié pour produire des articles textiles ignifugés, tels que des vêtements ignifugés. Ces vêtements peuvent être utilisés pour protéger des personnes contre le feu et/ou la chaleur.
PCT/EP2018/082209 2017-11-22 2018-11-22 Procédé de fabrication d'un article textile ignifugé WO2019101852A1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
US15/821,106 US20190153663A1 (en) 2017-11-22 2017-11-22 Method for Producing a Flame-Resistant Textile Article
US15/821,106 2017-11-22
NL2020326 2018-01-26
NL2020326A NL2020326B1 (en) 2018-01-26 2018-01-26 Method for Producing a Flame-Resistant Textile Article

Publications (1)

Publication Number Publication Date
WO2019101852A1 true WO2019101852A1 (fr) 2019-05-31

Family

ID=64901471

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2018/082209 WO2019101852A1 (fr) 2017-11-22 2018-11-22 Procédé de fabrication d'un article textile ignifugé

Country Status (1)

Country Link
WO (1) WO2019101852A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2022263615A1 (fr) * 2021-06-18 2022-12-22 Ten Cate Protect Bv Tissu ignifuge comprenant une alternative au coton

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4026808A (en) * 1972-03-30 1977-05-31 Hooker Chemicals & Plastics Corporation Flame retardant textile finishes
US4063883A (en) * 1974-08-20 1977-12-20 Hoechst Aktiengesellschaft Manufacture of flame-retardant regenerated cellulose fibres
US4078101A (en) 1972-08-11 1978-03-07 Albright & Wilson Ltd. Flameproofing of textiles
US4311855A (en) 1979-01-26 1982-01-19 Albright & Wilson Ltd. Flameproofing agents
GB2352447A (en) * 1999-07-28 2001-01-31 Bolton Inst Higher Education Flame-retardant polymeric materials
WO2014107750A1 (fr) * 2013-01-11 2014-07-17 Lenzing Ag Tissu ignifuge pour vêtement de protection et applications de garnissage et son utilisation
US20160201236A1 (en) 2013-08-23 2016-07-14 Kaneka Corporation Flame-retardant fabric, method for producing same and fireprotective clothes comprising same

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4026808A (en) * 1972-03-30 1977-05-31 Hooker Chemicals & Plastics Corporation Flame retardant textile finishes
US4078101A (en) 1972-08-11 1978-03-07 Albright & Wilson Ltd. Flameproofing of textiles
US4063883A (en) * 1974-08-20 1977-12-20 Hoechst Aktiengesellschaft Manufacture of flame-retardant regenerated cellulose fibres
US4311855A (en) 1979-01-26 1982-01-19 Albright & Wilson Ltd. Flameproofing agents
GB2352447A (en) * 1999-07-28 2001-01-31 Bolton Inst Higher Education Flame-retardant polymeric materials
WO2014107750A1 (fr) * 2013-01-11 2014-07-17 Lenzing Ag Tissu ignifuge pour vêtement de protection et applications de garnissage et son utilisation
US20160201236A1 (en) 2013-08-23 2016-07-14 Kaneka Corporation Flame-retardant fabric, method for producing same and fireprotective clothes comprising same

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2022263615A1 (fr) * 2021-06-18 2022-12-22 Ten Cate Protect Bv Tissu ignifuge comprenant une alternative au coton
NL2028484B1 (en) * 2021-06-18 2022-12-27 Ten Cate Protect B V Flame Retardant Fabric Comprising Cotton Alternative

Similar Documents

Publication Publication Date Title
RU2634242C2 (ru) Огнестойкие пряжи и ткани, включающие частично ароматическое полиамидное волокно и другие огнестойкие волокна
CN105283593B (zh) 布帛和纤维制品
JP6282272B2 (ja) 耐洗熱特性および快適性のための繊維混合物
RU2552248C2 (ru) Пряжа и ткани из смеси волокон, содержащей окисленные полимерные волокна
US10072365B2 (en) Knit fabrics and base layer garments made therefrom with improved thermal protective properties
US6287686B1 (en) Fire retardant and heat resistant yarns and fabrics made therefrom
US9920474B2 (en) Flame-resistant fiber blend, yarn, and fabric, and method for making same
US11078608B2 (en) Fabric, method for manufacturing same, and fiber product
RU2526551C2 (ru) Огнестойкий текстиль
Gaan et al. Flame retardant functional textiles
WO2016035638A1 (fr) Tissu et produit en fibres
CN103857837A (zh) 具有优异的防电弧性的高回潮率纱线、织物、和服装
US11873587B2 (en) Flame resistant fabrics
JP6487228B2 (ja) 難燃制電性布帛及び衣服
JP7434366B2 (ja) 撥水性を示す仕上げされた難燃性布地およびその製造方法
EP0155834A2 (fr) Produit fibreux ignifuge
US20200190710A1 (en) Flame retardant fabric composed of thermoplastic core-spun yarns
KR101302974B1 (ko) 난연 직물의 제조 방법 및 그 난연 직물을 이용하여 제조되는 방화포
US20180245251A1 (en) Wearable protective denim fabrics
WO2019101852A1 (fr) Procédé de fabrication d'un article textile ignifugé
US20190153663A1 (en) Method for Producing a Flame-Resistant Textile Article
WO2013109416A1 (fr) Mélange de fibres, filé de fibres, matière textile, et procédé d'utilisation de la matière textile
JP2020026596A (ja) 布帛および防護製品
JP2018168477A (ja) 難燃性織編物
NL2028484B1 (en) Flame Retardant Fabric Comprising Cotton Alternative

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 18826955

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 18826955

Country of ref document: EP

Kind code of ref document: A1