EP2643508A1 - Flame resistant fabric for protective clothing - Google Patents

Flame resistant fabric for protective clothing

Info

Publication number
EP2643508A1
EP2643508A1 EP11793645.0A EP11793645A EP2643508A1 EP 2643508 A1 EP2643508 A1 EP 2643508A1 EP 11793645 A EP11793645 A EP 11793645A EP 2643508 A1 EP2643508 A1 EP 2643508A1
Authority
EP
European Patent Office
Prior art keywords
fibres
fabric
yarn
fabric according
fibre
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.)
Granted
Application number
EP11793645.0A
Other languages
German (de)
French (fr)
Other versions
EP2643508B1 (en
Inventor
Alexander Gstettner
Tom Burrow
Ulf Mathes
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.)
Lenzing AG
Original Assignee
Lenzing AG
Chemiefaser Lenzing AG
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 Lenzing AG, Chemiefaser Lenzing AG filed Critical Lenzing AG
Publication of EP2643508A1 publication Critical patent/EP2643508A1/en
Application granted granted Critical
Publication of EP2643508B1 publication Critical patent/EP2643508B1/en
Not-in-force legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • D—TEXTILES; PAPER
    • D02—YARNS; MECHANICAL FINISHING OF YARNS OR ROPES; WARPING OR BEAMING
    • D02G—CRIMPING OR CURLING FIBRES, FILAMENTS, THREADS, OR YARNS; YARNS OR THREADS
    • D02G3/00—Yarns or threads, e.g. fancy yarns; Processes or apparatus for the production thereof, not otherwise provided for
    • D02G3/44—Yarns or threads characterised by the purpose for which they are designed
    • D02G3/443—Heat-resistant, fireproof or flame-retardant yarns or threads
    • D—TEXTILES; PAPER
    • D03—WEAVING
    • D03D—WOVEN FABRICS; METHODS OF WEAVING; LOOMS
    • D03D15/00—Woven fabrics characterised by the material, structure or properties of the fibres, filaments, yarns, threads or other warp or weft elements used
    • D03D15/20—Woven 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
    • D03D15/208—Woven 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
    • D—TEXTILES; PAPER
    • D02—YARNS; MECHANICAL FINISHING OF YARNS OR ROPES; WARPING OR BEAMING
    • D02G—CRIMPING OR CURLING FIBRES, FILAMENTS, THREADS, OR YARNS; YARNS OR THREADS
    • D02G3/00—Yarns or threads, e.g. fancy yarns; Processes or apparatus for the production thereof, not otherwise provided for
    • D02G3/02—Yarns or threads characterised by the material or by the materials from which they are made
    • D02G3/04—Blended or other yarns or threads containing components made from different materials
    • D—TEXTILES; PAPER
    • D02—YARNS; MECHANICAL FINISHING OF YARNS OR ROPES; WARPING OR BEAMING
    • D02G—CRIMPING OR CURLING FIBRES, FILAMENTS, THREADS, OR YARNS; YARNS OR THREADS
    • D02G3/00—Yarns or threads, e.g. fancy yarns; Processes or apparatus for the production thereof, not otherwise provided for
    • D02G3/02—Yarns or threads characterised by the material or by the materials from which they are made
    • D02G3/04—Blended or other yarns or threads containing components made from different materials
    • D02G3/047—Blended or other yarns or threads containing components made from different materials including aramid fibres
    • D—TEXTILES; PAPER
    • D03—WEAVING
    • D03D—WOVEN FABRICS; METHODS OF WEAVING; LOOMS
    • D03D15/00—Woven fabrics characterised by the material, structure or properties of the fibres, filaments, yarns, threads or other warp or weft elements used
    • D03D15/20—Woven 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
    • D03D15/208—Woven 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
    • D03D15/225—Woven 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
    • D—TEXTILES; PAPER
    • D03—WEAVING
    • D03D—WOVEN FABRICS; METHODS OF WEAVING; LOOMS
    • D03D15/00—Woven fabrics characterised by the material, structure or properties of the fibres, filaments, yarns, threads or other warp or weft elements used
    • D03D15/20—Woven 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
    • D03D15/283—Woven 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
    • D—TEXTILES; PAPER
    • D03—WEAVING
    • D03D—WOVEN FABRICS; METHODS OF WEAVING; LOOMS
    • D03D15/00—Woven fabrics characterised by the material, structure or properties of the fibres, filaments, yarns, threads or other warp or weft elements used
    • D03D15/50—Woven fabrics characterised by the material, structure or properties of the fibres, filaments, yarns, threads or other warp or weft elements used characterised by the properties of the yarns or threads
    • D03D15/513—Woven fabrics characterised by the material, structure or properties of the fibres, filaments, yarns, threads or other warp or weft elements used characterised by the properties of the yarns or threads heat-resistant or fireproof
    • D—TEXTILES; PAPER
    • D03—WEAVING
    • D03D—WOVEN FABRICS; METHODS OF WEAVING; LOOMS
    • D03D15/00—Woven fabrics characterised by the material, structure or properties of the fibres, filaments, yarns, threads or other warp or weft elements used
    • D03D15/50—Woven fabrics characterised by the material, structure or properties of the fibres, filaments, yarns, threads or other warp or weft elements used characterised by the properties of the yarns or threads
    • D03D15/533—Woven fabrics characterised by the material, structure or properties of the fibres, filaments, yarns, threads or other warp or weft elements used characterised by the properties of the yarns or threads antistatic; electrically conductive
    • D—TEXTILES; PAPER
    • D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B2201/00—Cellulose-based fibres, e.g. vegetable fibres
    • D—TEXTILES; PAPER
    • D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B2201/00—Cellulose-based fibres, e.g. vegetable fibres
    • D10B2201/20—Cellulose-derived artificial fibres
    • D—TEXTILES; PAPER
    • D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B2201/00—Cellulose-based fibres, e.g. vegetable fibres
    • D10B2201/20—Cellulose-derived artificial fibres
    • D10B2201/22—Cellulose-derived artificial fibres made from cellulose solutions
    • D—TEXTILES; PAPER
    • D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B2201/00—Cellulose-based fibres, e.g. vegetable fibres
    • D10B2201/20—Cellulose-derived artificial fibres
    • D10B2201/22—Cellulose-derived artificial fibres made from cellulose solutions
    • D10B2201/24—Viscose
    • D—TEXTILES; PAPER
    • D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B2401/00—Physical properties
    • D10B2401/04—Heat-responsive characteristics
    • D—TEXTILES; PAPER
    • D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B2401/00—Physical properties
    • D10B2401/16—Physical properties antistatic; conductive
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/249921—Web or sheet containing structurally defined element or component
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T442/00—Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
    • Y10T442/30—Woven fabric [i.e., woven strand or strip material]
    • Y10T442/3976—Including strand which is stated to have specific attributes [e.g., heat or fire resistance, chemical or solvent resistance, high absorption for aqueous composition, water solubility, heat shrinkability, etc.]
    • Y10T442/3984—Strand is other than glass and is heat or fire resistant
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T442/00—Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
    • Y10T442/40—Knit fabric [i.e., knit strand or strip material]
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T442/00—Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
    • Y10T442/60—Nonwoven fabric [i.e., nonwoven strand or fiber material]
    • Y10T442/696—Including strand or fiber material which is stated to have specific attributes [e.g., heat or fire resistance, chemical or solvent resistance, high absorption for aqueous compositions, water solubility, heat shrinkability, etc.]

Definitions

  • a new flame resistant fabric has been invented that uses the properties of known flame resistant fibres combined with non-flame resistant fibres to produce a fabric with exceptional resistance to flame, surprising physical properties and enhanced comfort to the user compared to other flame resistant fabrics.
  • “Flame resistance” is a characteristic of a material such as a fibre or fabric that does not burn in a normal air atmosphere. When exposed to a flame, it will not support combustion when the flame is removed. "Flame resistance” should not be confused with “flame retardant” which is a term used to describe a chemical substance that imparts flame resistance to fabric. Flame retardant is also used to describe fabrics which exhibit a reduced rate of burning but may not offer any protection to the user from flames.
  • flame resistant fabrics especially those made from flame resistant fibres, can be used to give protection against exposure to flame. It is normal practice that firefighters wear garments that will protect the user from flame in a hazardous situation. The garment is expected to prevent direct exposure to flames of the clothed user's skin, thereby reducing the risk of suffering bum injuries.
  • Protective clothing for molten metal splash protection is used by welders and metal industry workers. In the metal industry high levels of energy are used to melt metal and to create electric arcs. Therefore protective clothing is needed to protect against liquid metal splashes and against electric arcs. Utility personnel working on high voltage installations may be exposed to small metal splashes, when electric arc is produced accidentally. It is highly desirable that fabrics used in these applications should be comfortable to wear, should perform well physically and be aesthetically suited to the task - colour appearance, style and feel.
  • cellulosic fibres can give enhanced comfort compared to synthetic fibres. This is, because cellulosic fibres are hydrophilic and absorb moisture vapour and liquid water. Controlling the movement and distribution of water in the fabric is an inherent property of a cellulosic fibre.
  • fabrics are expected to be unaffected by all activities that they are subjected to. This means they need to have high tear strength, high abrasion resistance and good resistance to snagging. Fabrics also need to retain their appearance over a prolonged period of use and care. Therefore fabrics need to be washable and have good washing stability, low shrinkage, good pilling performance, and good colour fastness to washing and light. It is common for organizations that equip workers with personal protective clothing to require that the clothing conforms tb the organisation's corporate colours. There are also many cases where the colour of a garment is important for its function such as black for riot police or high visibility yellow, orange or green for firefighters and industrial workers. Therefore it is highly desirable that fabrics used for these applications can be dyed easily to a wide range of colours and give good fastness performance.
  • This invention is a flame resistant fabric suitable for use in garments intended to protect workers in the metal industry and the utility industry from accidental exposure to flame, molten metal - except alumina - and electric arcs.
  • the fabric produces garments which are comfortable to wear, have a minimal effect on the physiological performance of the wearer and have excellent physical properties,
  • Textile materials vary considerably in their ability to resist flame and hence protect underlying materials. Most fabrics made from natural fibres and from synthetic fibres will burn when exposed to flame. The rate of burn and ease of ignition are determined primarily by the chemical nature of the polymer from which the fibre is made and the construction of the fabric. Many polymers, such as cellulose, polyester and nylon will burn readily. The rate of burn is lower the heavier a fabric is. Wool is the most common natural fibre which has flame resistant properties to some degree - heavy weight wool fabrics will not burn readily and are used in firefighter's clothing historically.
  • Fabrics for protection against molten metal splash as used in the metal industry including welding application are often extremely heavy and stiff. Fabric weights are ranging from 330 to 600g/m 2 . They are made from materials such as flame resistant treated cotton.
  • Fabrics can be treated to make them flame resistant by applying an
  • the first FR treated fabrics used inorganic salts such as aluminium hydroxide, antimony trioxide and borates ' to make cotton fabrics flame resistant. These were effective but were non-durable to washing. Organic phosphorous containing compounds that are reacted onto the cotton either by grafting or network formation are more durable and are widely used. Two of the leading brand names are Proban® and Pyrovatex®. While these finishes are durable, they can be removed by harsh chemical treatments and the level of finish reduces with the number of washing cycles. The finish application has an adverse stiffening effect on the fabric. Fabrics of this type are in use for protection from flame, molten metal splash and electric arc.
  • E1 characterizes the lowest resistance while E3 stands for the highest molten iron resistance.
  • E3 stands for the highest molten iron resistance.
  • FR treated Cotton is needed for an E3-fabric.
  • Common FR treated cotton fabrics of a fabric weight of 290g/m 2 only shows E1 properties.
  • the first flame resistant man made fibres produced were made by the viscose process.
  • a high viscosity liquid flame resistant additive was dispersed in the spinning solution prior to extrusion of the fibre.
  • the liquid was trapped in the cellulose by physical means as very small bubbles.
  • the result was effective as a flame resistant fibre, but the additive could be removed by repeated washing.
  • the strength of the fibre is reduced in proportion to the amount of additive included.
  • the additive was withdrawn from the market due to safety concerns and production of the fibre was discontinued.
  • An improved flame resistant, viscose fibre can be produced by using a solid pigment flame retardartt. Fibre of this type will be referred to as FR viscose. , The pigment is finely ground and mixed with the spinning solution prior to extrusion of the fibre. The result is a dispersion of the insoluble particulate additive in the fibre. The strength of the fibre is reduced in proportion to the amount of additive included. All of the cellulose in the fibre contains some of the additive and the additive cannot be removed by washing or normal fabric dyeing or finishing processes. Hence the result of the process is an inherently flame resistant fibre. A well-known fibre of this kind is Visil®, which contains silica pigment flame retardant.
  • a further improvement can be achieved by incorporating the solid pigment flame retardant in the spinning solution used to produce modal fibre.
  • the modal process is a modified viscose process designed to produce a fibre with a higher strength and higher wet modulus than normal viscose.
  • the resultant fibre containing the flame retardant pigment is inherently flame resistant. It is stronger than fibre produced by the viscose process and gives fabrics with : higher strength and better stability.
  • Fibre of this type will be referred to for the purposes of this invention as "FR Modal” but note that the properties of the fibre do not conform to the BISFA (INTERNATIONAL BUREAU FOR THE STANDARDISATION OF MAN-MADE FIBRES) definition of modal fibre.
  • Proven flame retardant pigments for this kind of fibres are organic
  • Exolith® (2'-oxybis[5,5- dimethyl-I .S ⁇ -dioxaphosphorinan ⁇ 'disulfid).
  • FR Modal is used in 100% form in only a few applications in the field of apparel such as metallised fabrics or fabrics which are mixtures of two or more yarns. On its own its performance is inadequate in a number of respects compared to other products.
  • Lyocell fibres can be made flame resistant. Due to the different manufacturing conditions usually different pigments are suitable. Fibre of this type will be referred to as Lyocell FR.
  • An alternative approach to producing an FR fibre is to modify the polymer from which the fibre is made so that it is inherently flame resistant but can still be formed into a fibre.
  • Such fibres There are many examples of such fibres but the leading ones being used in personal protective clothing are meta-aramid, para-aramid, Polybenzimidazole (PBI), FR polyester and modacrylic.
  • Flame resistant fibres can often be used on their own to make fabrics which function well. They can also be used in blends with each other and with non flame resistant fibres to produce fabrics: Such blend fabrics can have properties which are a combination of the properties of the component fibres.
  • Meta-aramid / FR Modal blend (typ 50/50; Meta-aramid / FR Modal blend (typ 35/65)).
  • Table 2 The fabric selection process used by garment makers and specifiers is based on a judgement of the overall performance and the required level based on risk analysis. None of the fabrics provides all of the criteria of an ideal fabric listed in Table 2.
  • FR treated cotton and cotton blend fabrics give poor to medium performance, fair comfort, relatively easy processing and are the most affordable.
  • Modacrylic blends give fair performance but poor comfort and cost more.
  • Aramid fabrics give good performance and washing performance but are not comfortable and are expensive. None of the fabrics currently available are rated as good for metal splash or for electric arc. Only the meta-aramid/FR Modal fabric is rated as good for break open behaviour.
  • Adding FR Modal to an aramid fabric improves its overall performance and reduces the cost.
  • the objective of this invention is to produce a fabric for use in personal protective clothing which resolves the deficiencies of the prior art described above. It should show excellent performance in terms of safety of the user, . especially in respect of metal splash protection, electric arc protection and break open behaviour. It should also be at lower cost and with better comfort and aesthetic properties than current products to ensure that garments made from it have all of the required performance for the intended applications.
  • o Fabric can be piece dyed
  • the product of the invention is a flame resistant fabric for use in personal protective clothing which provides a high level of protection from flames and other sources of heat such as molten metal splash and electric arc, which is made from a yarn which is an intimate blend of FR cellulosic fibres with high temperature resistant polymer fibres and standard flammable synthetic fibres
  • the blend ratio of the yarn is preferably: from 65 to 90% FR cellulosic fibres, from 10 to 20 % high temperature resistant polymer fibres and from 10 to 20% standard synthetic fibres, more preferably from 65 to 75 % FR Modal , from 12,5 to 17,5 % high temperature resistant polymer fibres and from 12,5 to 17,5 % standard flammable synthetic fibres.
  • the fabric of the invention contains a high percentage of FR cellulosic fibre and yet performs better than currently available fabrics made using a high percentage of aramid fibre.
  • Anti static properties of the fabric can be achieved by adding 1 to 5% antistatic staple fibre to the blend, or by creating an antistatic grid by including in the fabric yarns consisting of the ground yarn twisted with antistatic continuous filament yarns. All fibres used in the blend can be dope dyed (spun dyed) ' fibres.
  • the FR cellulosic fibre of the yarn is a cellulosic fibre that has been made flame resistant by addition of an FR agent during or after fibre production.
  • the FR cellulosic fibres of the yarn are chosen from the group consisting of FR Modal, FR viscose and FR Lyocell. More specifically the FR cellulosic fibres of the yarn are FR Modal fibres. Fibres can be dope dyed (spun dyed) or dyed in flock, tops, yarn or fabric.
  • the high temperature resistant polymer fibres are chosen from the group consisting of para-aramid, meta-aramid , aromatic polyester (PES), PBI and blends of these fibres.
  • the high temperature resistant polymer fibres are para-aramid fibres.
  • Fibres can be dope dyed (spun dyed) or stock dyed as staple fibre or top dyed.
  • the standard flammable synthetic fibres are chosen from the group consisting of polyamid 6 (PA6), polyamid 6 (PA6.6) and polyester (PES).
  • PA6 polyamid 6
  • PA6.6 polyamid 6
  • polyester polyester
  • the fibres are PA6 and especially preferred is a high-tenacity PA6 fibre. Fibres can be dope dyed (spun dyed) or stock dyed as staple fibre or dyed as tops, yarn or fabric.
  • the product of the invention is a fabric consisting of a yarn ⁇ which is a blend of FR Modal, and a para-aramid or meta-aramid or a blend of the two aramids and flammable high tenacity PA6.
  • the fabric may be Woven, knitted or produced with non-woven technologies.
  • the woven fabric has a warp and weft composed of the yarn according to the invention.
  • the fabric includes a percentage of flammable standard synthetic fibres, the fabric has exceptional flammability and protective performance, !t will not burn, it does not break open when exposed to a flame and continues to provide a barrier to flame. Furthermore, the fabric provides a high level of molten iron ("metal splash”) protection even at a low fabric weight, as well as superior electric arc protection. For good orders sake it should be mentioned that the fabric of the invention does not protect against molten alumina.
  • Each of the fibres in the blend may be dope dyed (i. e. spun dyed). This will produce a fabric with very high colour fastness. Only very expensive Aramids have been available as dope dyed fibres so far.
  • the yarn is produced from staple fibre by spinning the yarn using conventional techniques such as ring spinning, open end spinning, vortex spinning, worsted spinning, semi-worsted spinning or any of the variations on these used in the yarn spinning industry.
  • the staple length of the fibres for the primary yarn may be between 35 mm up to 160 mm. Especially preferred are fibres with a staple length of between 75 and 90 mm. The staple length will need to be
  • At least the FR cellulosic fibres in the yarn according to the invention should be of this staple length, but in a preferred embodiment of the invention all fibres in the yarn according to the invention should be of this staple length.
  • the use of fibres with a staple length of between 75 and 90 mm provides for a high durability of even lightweight fabrics with a low pilling and high tenacity, tear strength and abrasion resistance.
  • the yarns according to the invention and also the fabrics made of these yarns have a more plain;, less hairy appearance.
  • the high temperature resistant polymer fibre and the standard flammable synthetic fibres are blended together in the required proportions.
  • the yarn according to the invention is an intimate blend of the three fibres with each of the fibres well dispersed throughout the final yarn. This blending can be done during opening of the fibres, during carding or during drawing of the sliver.
  • the blend ratio of the yarn according to the invention in an especially preferred embodiment is T2011/000448
  • Anti static properties of the fabric can be added by blending 1 to 5% antistatic fibre in or by creating an anti static grid in the fabric using yarns that are made by twisting the ground yarn (according to the invention) with antistatic
  • the proportion of para-aramid fibre in the yarn may be up to 30%, but the cost of the fabric increases with increasing para-aramid content with no
  • One or more of the individual fibre components in the fabric are dope dyed, stock dyed or dyed tops or can be dyed in the yam or fabric.
  • temperature resistant polymer fibres can be either dope dyed or dyed in flock or tops state. By using 100% dope dyed fibres the fabric colour fastness will be improved while at the same time a cost saving on fabric dyeing can be achieved.
  • the fabric weight, construction and weave of the woven fabric are selected to deliver a fabric of the style and properties required for the application.
  • the fabric construction may be a plain weave, twill, hopsack, satin, sateen or any other weave which is appropriate to a protective clothing application.
  • the fabric may be a lightweight (i. e. a weight per unit area of 100 to 150 g/m 2 ) plain weave for shirting applications.
  • the fabric of the invention may aiso be produced using a nonwoven fabric production method.
  • a yarn is not required but all what was said above about the nature, properties and treatment of the yarn fibres as well as for the blend ratios applies for the composition of such nonwovens as well.
  • the fibre components are blended together and made into a nonwoven fabric without first spinning a yarn.
  • An example of such a fabric is a needlefelt fabric where the individual fibre components are mixed together in a blending device and then carded, crosslaid and needled to give a fabric.
  • Such a fabric is of use e. g. as an insulating liner in a garment or could be used to make simple garments such as aprons. '
  • the product of this invention is intended to be used as one of the primary components of clothing for personal protection in situations where there is a risk of exposure to flame, electric arc and liquid metal splash.
  • the fabric is used to make garments that cover the body of the user to protect the skin from exposure to flames or to other sources of heat such as metal splash - except alumina - and electric arc that would cause injury.
  • Garments are usually made by assembling cut shaped pieces of fabric by ; sewing them together.
  • the product of this invention may be the sole fabric . used in making a garment or may be one component of a garment; the other components consisting of fabrics of different design and purpose. It may also be combined with other fabrics by laminating prior to cutting the shaped pieces for garment assembly.
  • the product of this invention may be used as a layer of fabric on the inside of a garment. It may be used as a layer on the outside of a garment or it may be used as an internal component between two or more other fabrics. It may also be used to provide more than one layer in the garment. For example it could be used as the inner layer of the garment and as the outer layer of the garment with a third layer of a flame resistant wadding between the inner and outer layers.
  • the fabric of the invention may be used for the production of all types of garments where protection from flames is a primary purpose.
  • the fabric can be used for jackets, coats, trousers, shirts, polos, sweaters and jumpers, sweatshirts, T-shirts, socks, aprons, gloves and gauntlets, hoods for head protection other headwear and any other garment that may be worn for the purpose of protecting the wearer from flame and similar hazards.
  • the fabric may also be used in other articles which are intended to provide protection of people or ; property from exposure to flame such as shoe and boot components, welding screens, fire curtains, tents, sleeping bags, tarpaulins and any other similar articles made in whole or in part from fabric.
  • Coloured fabrics for the intended applications are preferably achieved by using spun dyed fibres, by piece dyeing or by printing, but in general all dyeing techniques are applicable.
  • a twill weave fabric was woven from the following components:
  • Lenzing FR® is an FR modal fibre available from Lenzing AG, Austria, which is produced according to a modal process (see AT-A 1371/2009) and which contains Exolith® as an incorporated FR pigment. The three fibre components were blended together in drafting of the slivers during preparatory
  • the fabric warp count was 30 threads per cm.
  • the weft count was 26 threads per cm.
  • the resulting fabric had a mass per unit area of 260 g/m 2 Flame protection:
  • the resulting fabric could not be ignited in normal atmospheric conditions. On exposure to flame directed at the surface of the fabric, the fabric charred but maintained its structure and continued to act as a barrier to flame. No holes were formed in the fabric. The fabric remained soft and flexible without any break open after flame exposure according to EN ISO 15025 procedure A (surface ignition). Furthermore no heat shrinkage of the fabric was observed when the flame was directed at the fabric surface and during the whole flaming time of 10 seconds.
  • the garment made from the fabric of the invention showed far less burns in comparison with 00% Aramid garments. After the flame exposure the garments were removed from the manikin to measure the size and shrinkage of the garment. Parts of the 00% Aramid garments were too brittle to measure - the jacket upper arm and the trouser thigh. The fabric of the invention remained intact in one piece. No severe damage was observed. The fabric remained flexible and did not break open.
  • the fabric of the invention does not shrink during the flame exposure. In fact the opposite occurs - some parts of the garment increased in dimensions.
  • the 100% Aramid garment show significant flame shrinkage.
  • the fabric of the invention was tested according to ISO 9185 and
  • the fabric of the invention was tested according to EN ISO IEC 61482 1-2, 4kA and 7kA.
  • the fabric passed with excellent values the required Stoll criteria for 4kA, and exhibited no break open of the fabric in a single layer, when tested to 7kA.
  • the Stoll curve is a curve of thermal energy and time produced from data on human tissue tolerance to heat and used to predict the onset of second-degree burn injury (cited from EN ISO IEC 61482 1-2).. !VSec anica! Performance testing:
  • the fabric of the invention has a higher tear strength compared with most of the other materials on the market.
  • Comfort testing Results ' according to Table 3 .
  • Alam beta - Heat penetration coefficient Alam beta - Heat penetration coefficient:
  • the fabric was tested for its comfort properties.
  • the Alambeta test measures the rate of transmission of body heat through the fabric. Fabrics with a high heat penetration coefficient feel cooler and this makes them more comfortable to wear. Referring to the results of Table 3 the fabric of the invention shows the highest heat penetration coefficient, resulting in the coolest fabric touch.
  • the fabric was tested for short term water vapour absorption (Fi) according to

Abstract

The fabric of the invention is a flame resistant fabric for use in personal protective clothing which provides a high level of comfort, protection from flames and other heat sources such as electric arc and liquid metal splash characterized in that it is made from a yarn, which is an intimate blend of FR cellulosic fibres With high temperature resistant polymer fibres and standard flammable synthetic fibres.

Description

Flame Resistant Fabric for Protective Clothing
Field of application
A new flame resistant fabric has been invented that uses the properties of known flame resistant fibres combined with non-flame resistant fibres to produce a fabric with exceptional resistance to flame, surprising physical properties and enhanced comfort to the user compared to other flame resistant fabrics.
"Flame resistance" is a characteristic of a material such as a fibre or fabric that does not burn in a normal air atmosphere. When exposed to a flame, it will not support combustion when the flame is removed. "Flame resistance" should not be confused with "flame retardant" which is a term used to describe a chemical substance that imparts flame resistance to fabric. Flame retardant is also used to describe fabrics which exhibit a reduced rate of burning but may not offer any protection to the user from flames.
It is well known that flame resistant fabrics, especially those made from flame resistant fibres, can be used to give protection against exposure to flame. It is normal practice that firefighters wear garments that will protect the user from flame in a hazardous situation. The garment is expected to prevent direct exposure to flames of the clothed user's skin, thereby reducing the risk of suffering bum injuries.
Other professions where protection from flame is required include police and security personnel, military personnel, and workers in the gas and petroleum industries.
Protective clothing for molten metal splash protection is used by welders and metal industry workers. In the metal industry high levels of energy are used to melt metal and to create electric arcs. Therefore protective clothing is needed to protect against liquid metal splashes and against electric arcs. Utility personnel working on high voltage installations may be exposed to small metal splashes, when electric arc is produced accidentally. It is highly desirable that fabrics used in these applications should be comfortable to wear, should perform well physically and be aesthetically suited to the task - colour appearance, style and feel.
■ ■ '■ · .
It is common for workers who use personal protective clothing to be working in a high stress environment with a high work load leading to high physiological energy consumption. This physiological strain leads to generation of body heat and moisture inside the garment. It is highly desirable that fabrics used for the construction of the garments should be capable of dissipating body heat and moisture to prevent over heating (heat stress) of the user's body. Fabrics that allow body heat and moisture to escape produce garments that feel more comfortable to wear and also prolong the working time that can be achieved without exceeding maximum physiological stress levels.
It is well known, that cellulosic fibres can give enhanced comfort compared to synthetic fibres. This is, because cellulosic fibres are hydrophilic and absorb moisture vapour and liquid water. Controlling the movement and distribution of water in the fabric is an inherent property of a cellulosic fibre.
In the intended applications, fabrics are expected to be unaffected by all activities that they are subjected to. This means they need to have high tear strength, high abrasion resistance and good resistance to snagging. Fabrics also need to retain their appearance over a prolonged period of use and care. Therefore fabrics need to be washable and have good washing stability, low shrinkage, good pilling performance, and good colour fastness to washing and light. It is common for organizations that equip workers with personal protective clothing to require that the clothing conforms tb the organisation's corporate colours. There are also many cases where the colour of a garment is important for its function such as black for riot police or high visibility yellow, orange or green for firefighters and industrial workers. Therefore it is highly desirable that fabrics used for these applications can be dyed easily to a wide range of colours and give good fastness performance.
This invention is a flame resistant fabric suitable for use in garments intended to protect workers in the metal industry and the utility industry from accidental exposure to flame, molten metal - except alumina - and electric arcs. The fabric produces garments which are comfortable to wear, have a minimal effect on the physiological performance of the wearer and have excellent physical properties,
Prior Art
Textile materials vary considerably in their ability to resist flame and hence protect underlying materials. Most fabrics made from natural fibres and from synthetic fibres will burn when exposed to flame. The rate of burn and ease of ignition are determined primarily by the chemical nature of the polymer from which the fibre is made and the construction of the fabric. Many polymers, such as cellulose, polyester and nylon will burn readily. The rate of burn is lower the heavier a fabric is. Wool is the most common natural fibre which has flame resistant properties to some degree - heavy weight wool fabrics will not burn readily and are used in firefighter's clothing historically.
Fabrics for protection against molten metal splash as used in the metal industry including welding application are often extremely heavy and stiff. Fabric weights are ranging from 330 to 600g/m2. They are made from materials such as flame resistant treated cotton.
Fabrics can be treated to make them flame resistant by applying an
appropriate chemical to the fabric. The first FR treated fabrics used inorganic salts such as aluminium hydroxide, antimony trioxide and borates' to make cotton fabrics flame resistant. These were effective but were non-durable to washing. Organic phosphorous containing compounds that are reacted onto the cotton either by grafting or network formation are more durable and are widely used. Two of the leading brand names are Proban® and Pyrovatex®. While these finishes are durable, they can be removed by harsh chemical treatments and the level of finish reduces with the number of washing cycles. The finish application has an adverse stiffening effect on the fabric. Fabrics of this type are in use for protection from flame, molten metal splash and electric arc.
When exposed to flame, molten metal or electric arcs, fabrics of this type will not burn, but become highly embrittled and may break open leaving the wearer's skin exposed to the hazard.
The protection properties of fabrics againstliquid Iron splashes are classified by a three-stage system: E1 characterizes the lowest resistance while E3 stands for the highest molten iron resistance. For an E3-fabric a fabric weight of at least 450g/m2 FR treated Cotton is needed. Common FR treated cotton fabrics of a fabric weight of 290g/m2 only shows E1 properties.
The first flame resistant man made fibres produced were made by the viscose process. A high viscosity liquid flame resistant additive was dispersed in the spinning solution prior to extrusion of the fibre. The liquid was trapped in the cellulose by physical means as very small bubbles. The result was effective as a flame resistant fibre, but the additive could be removed by repeated washing. The strength of the fibre is reduced in proportion to the amount of additive included. The additive was withdrawn from the market due to safety concerns and production of the fibre was discontinued.
An improved flame resistant, viscose fibre can be produced by using a solid pigment flame retardartt. Fibre of this type will be referred to as FR viscose. , The pigment is finely ground and mixed with the spinning solution prior to extrusion of the fibre. The result is a dispersion of the insoluble particulate additive in the fibre. The strength of the fibre is reduced in proportion to the amount of additive included. All of the cellulose in the fibre contains some of the additive and the additive cannot be removed by washing or normal fabric dyeing or finishing processes. Hence the result of the process is an inherently flame resistant fibre. A well-known fibre of this kind is Visil®, which contains silica pigment flame retardant.
A further improvement can be achieved by incorporating the solid pigment flame retardant in the spinning solution used to produce modal fibre. The modal process is a modified viscose process designed to produce a fibre with a higher strength and higher wet modulus than normal viscose. The resultant fibre containing the flame retardant pigment is inherently flame resistant. It is stronger than fibre produced by the viscose process and gives fabrics with : higher strength and better stability. Fibre of this type will be referred to for the purposes of this invention as "FR Modal" but note that the properties of the fibre do not conform to the BISFA (INTERNATIONAL BUREAU FOR THE STANDARDISATION OF MAN-MADE FIBRES) definition of modal fibre. Proven flame retardant pigments for this kind of fibres are organic
phosphorous compounds and a preferred pigment is Exolith® (2'-oxybis[5,5- dimethyl-I .S^-dioxaphosphorinan^^'disulfid).
FR Modal is used in 100% form in only a few applications in the field of apparel such as metallised fabrics or fabrics which are mixtures of two or more yarns. On its own its performance is inadequate in a number of respects compared to other products.
In the same way Lyocell fibres can be made flame resistant. Due to the different manufacturing conditions usually different pigments are suitable. Fibre of this type will be referred to as Lyocell FR.
An alternative approach to producing an FR fibre is to modify the polymer from which the fibre is made so that it is inherently flame resistant but can still be formed into a fibre. There are many examples of such fibres but the leading ones being used in personal protective clothing are meta-aramid, para-aramid, Polybenzimidazole (PBI), FR polyester and modacrylic.
Flame resistant fibres can often be used on their own to make fabrics which function well. They can also be used in blends with each other and with non flame resistant fibres to produce fabrics: Such blend fabrics can have properties which are a combination of the properties of the component fibres.
There are many flame resistant fabrics available in the market. The most widely used in personal protective clothing are (blend ratios are given in %w/w): Flame resistant treated 100% cotton; Flame resistant treated cotton / polyamide blend (typ 85/ 5); Flame resistant treated polyester / cotton blend (typ 50/50); Modacrylic / cotton blend (typ 55/45); Modacrylic / cotton / aramid blend (typ 25/25/50); Modacrylic 7 lyocell / aramid blend (typ 25/25/50); 100% meta-aramid; Meta-aramid / para-aramid blend (typ 80/20); Meta-aramid / para-aramid/Anti static blend (typ 93/5/2); Meta-aramid / FR Modal blend (typ 70/30). Meta-aramid / FR Modal blend (typ 50/50; Meta-aramid / FR Modal blend (typ 35/65)). Each of these fabrics has its merits and deficiencies, as can be seen from : Table 2 (see Example 2). The fabric selection process used by garment makers and specifiers is based on a judgement of the overall performance and the required level based on risk analysis. None of the fabrics provides all of the criteria of an ideal fabric listed in Table 2.
FR treated cotton and cotton blend fabrics give poor to medium performance, fair comfort, relatively easy processing and are the most affordable.
Modacrylic blends give fair performance but poor comfort and cost more. Aramid fabrics give good performance and washing performance but are not comfortable and are expensive. None of the fabrics currently available are rated as good for metal splash or for electric arc. Only the meta-aramid/FR Modal fabric is rated as good for break open behaviour.
Adding FR Modal to an aramid fabric improves its overall performance and reduces the cost.
Each of the currently available fabrics has deficiencies in one or more respects. No single fabric has given good all-round performance, protection, comfort, processability and care properties at a reasonable cost. This is the target of the invention.
Objective
The objective of this invention is to produce a fabric for use in personal protective clothing which resolves the deficiencies of the prior art described above. It should show excellent performance in terms of safety of the user, . especially in respect of metal splash protection, electric arc protection and break open behaviour. It should also be at lower cost and with better comfort and aesthetic properties than current products to ensure that garments made from it have all of the required performance for the intended applications.
Current products in the market perform well in protecting the user, but they are expensive, which means their use is limited. They are made from, at least in part, fibres with poor comfort and aesthetic properties and they can be difficult to produce because of poor dyeability. Currently used fabrics especially for the molten metal industry are stiff and heavy (fabric weights ranging from 330 to 600g/m2). For electrical utilities, insulation against electric arc as well as improved break open performance after electric arc exposure are important safety requirements. There was a need for a fabric which will deliver:
• Protection
o Inherently flame resistant for the life of the product
o Extremely lightweight fabrics providing maximum protection against liquid metal splash
o Improved break open after electric arc exposure
o Very good break open behaviour after flame exposure; the fabric remains soft and intact
o Cool to the touch immediately after exposure to flame o Very good insulation against heat and flame
β Mechanical Performance and Durability:
o High tear resistance. o Low Pilling
o Excellent abrasion properties.
* Physiological Performance:
o Good thermal properties giving more efficient cooling of the user,
o Improved physiological performance of the user
• Comfort:
o High and rapid moisture absorption
o Good short-term water absorption capacity
o Cool touch
® Processability
o Fabric can be piece dyed
o Wide range of colours achievable
o Fabric printable using vat or reactive dye systems
« Washing Performance
o Stable to washing
Low washing shrinkage
o Environment / Sustainability
o Fibres which are OKQTEX Standard 100
o Fibres which are highly sustainable
Description
The product of the invention is a flame resistant fabric for use in personal protective clothing which provides a high level of protection from flames and other sources of heat such as molten metal splash and electric arc, which is made from a yarn which is an intimate blend of FR cellulosic fibres with high temperature resistant polymer fibres and standard flammable synthetic fibres
The blend ratio of the yarn is preferably: from 65 to 90% FR cellulosic fibres, from 10 to 20 % high temperature resistant polymer fibres and from 10 to 20% standard synthetic fibres, more preferably from 65 to 75 % FR Modal , from 12,5 to 17,5 % high temperature resistant polymer fibres and from 12,5 to 17,5 % standard flammable synthetic fibres.
It is surprising that a fabric with this fibre content can give such exceptional performance. It is generally believed by those skilled in the art that a fabric; will have better flammability performance and give better protection the higher the content of aramid fibre. The fabric of the invention contains a high percentage of FR cellulosic fibre and yet performs better than currently available fabrics made using a high percentage of aramid fibre.
Anti static properties of the fabric can be achieved by adding 1 to 5% antistatic staple fibre to the blend, or by creating an antistatic grid by including in the fabric yarns consisting of the ground yarn twisted with antistatic continuous filament yarns. All fibres used in the blend can be dope dyed (spun dyed) 'fibres.
The FR cellulosic fibre of the yarn is a cellulosic fibre that has been made flame resistant by addition of an FR agent during or after fibre production.
The FR cellulosic fibres of the yarn are chosen from the group consisting of FR Modal, FR viscose and FR Lyocell. More specifically the FR cellulosic fibres of the yarn are FR Modal fibres. Fibres can be dope dyed (spun dyed) or dyed in flock, tops, yarn or fabric.
The high temperature resistant polymer fibres are chosen from the group consisting of para-aramid, meta-aramid , aromatic polyester (PES), PBI and blends of these fibres. Preferably the high temperature resistant polymer fibres are para-aramid fibres. Fibres can be dope dyed (spun dyed) or stock dyed as staple fibre or top dyed. The standard flammable synthetic fibres are chosen from the group consisting of polyamid 6 (PA6), polyamid 6 (PA6.6) and polyester (PES). Preferably the fibres are PA6 and especially preferred is a high-tenacity PA6 fibre. Fibres can be dope dyed (spun dyed) or stock dyed as staple fibre or dyed as tops, yarn or fabric.
More specifically the product of the invention is a fabric consisting of a yarn^ which is a blend of FR Modal, and a para-aramid or meta-aramid or a blend of the two aramids and flammable high tenacity PA6. The fabric may be Woven, knitted or produced with non-woven technologies.
The woven fabric has a warp and weft composed of the yarn according to the invention.
Even though the fabric includes a percentage of flammable standard synthetic fibres, the fabric has exceptional flammability and protective performance, !t will not burn, it does not break open when exposed to a flame and continues to provide a barrier to flame. Furthermore, the fabric provides a high level of molten iron ("metal splash") protection even at a low fabric weight, as well as superior electric arc protection. For good orders sake it should be mentioned that the fabric of the invention does not protect against molten alumina.
Each of the fibres in the blend may be dope dyed (i. e. spun dyed). This will produce a fabric with very high colour fastness. Only very expensive Aramids have been available as dope dyed fibres so far.
The exceptional flammability and protective performance of the fabric of the invention has previously only been possible with significantly heavier, much more expensive fabrics such as PBI, 100% aramid or Lenzing FR/meta- aramid, as well as heavy Modacrylic - or flame resistant treated cotton blends and inorganic based fibres.
All of this is achieved with a fabric that has a lower fabric weight, better protection and lower production cost than other fabrics with similar performance and the fabric is much more comfortable because of the high proportion of cellulosic fibres.
The yarn is produced from staple fibre by spinning the yarn using conventional techniques such as ring spinning, open end spinning, vortex spinning, worsted spinning, semi-worsted spinning or any of the variations on these used in the yarn spinning industry. The staple length of the fibres for the primary yarn may be between 35 mm up to 160 mm. Especially preferred are fibres with a staple length of between 75 and 90 mm. The staple length will need to be
appropriate to the spinning system selected. At least the FR cellulosic fibres in the yarn according to the invention should be of this staple length, but in a preferred embodiment of the invention all fibres in the yarn according to the invention should be of this staple length. The use of fibres with a staple length of between 75 and 90 mm provides for a high durability of even lightweight fabrics with a low pilling and high tenacity, tear strength and abrasion resistance. At the same time the yarns according to the invention and also the fabrics made of these yarns have a more plain;, less hairy appearance.
·
The linear density (= titre) of the fibres and filaments used in the fabric will be chosen to fit with the intended application. Generally it will be in the range commonly used for such textile applications. The linear density will depend on the yarn spinning system used for the yarn.
During the preparatory processes prior to spinning the FR Modal fibre, the high temperature resistant polymer fibre and the standard flammable synthetic fibres are blended together in the required proportions. The yarn according to the invention is an intimate blend of the three fibres with each of the fibres well dispersed throughout the final yarn. This blending can be done during opening of the fibres, during carding or during drawing of the sliver.
The blend ratio of the yarn according to the invention in an especially preferred embodiment is T2011/000448
70 % FR Modal ,
15% high temperature resistant polymer fibres and
5% standard synthetic fibres. Anti static properties of the fabric can be added by blending 1 to 5% antistatic fibre in or by creating an anti static grid in the fabric using yarns that are made by twisting the ground yarn (according to the invention) with antistatic
continuous filament yarns. The proportion of para-aramid fibre in the yarn may be up to 30%, but the cost of the fabric increases with increasing para-aramid content with no
appreciable increase in performance against the applicable standards.
One or more of the individual fibre components in the fabric are dope dyed, stock dyed or dyed tops or can be dyed in the yam or fabric. The high
temperature resistant polymer fibres can be either dope dyed or dyed in flock or tops state. By using 100% dope dyed fibres the fabric colour fastness will be improved while at the same time a cost saving on fabric dyeing can be achieved. The fabric weight, construction and weave of the woven fabric are selected to deliver a fabric of the style and properties required for the application. E.g. the fabric construction may be a plain weave, twill, hopsack, satin, sateen or any other weave which is appropriate to a protective clothing application. For knitted fabrics a plain jersey, pique or any other suitable fabric construction is possible. The fabric may be a lightweight (i. e. a weight per unit area of 100 to 150 g/m2) plain weave for shirting applications. It may be a medium weight (i. e. a weight per unit area of 150 to 230 g/m2) twill weave for trousers. It may also be a heavyweight (i. e. a weight per unit area of 230 to 350 g/m2) twill : weave for jackets and other outerwear. The basic principle of the invention can be incorporated in a wide variety of fabrics. It will work regardless of the weave or construction, provided the correct blends and arrangements of yarns are used. Only exceptionally lightweight fabrics (less than 100 g/m2) would not show the benefits of the invention. The fabric of the invention may aiso be produced using a nonwoven fabric production method. Clearly for a nonwoven process a yarn is not required but all what was said above about the nature, properties and treatment of the yarn fibres as well as for the blend ratios applies for the composition of such nonwovens as well. The fibre components are blended together and made into a nonwoven fabric without first spinning a yarn. An example of such a fabric is a needlefelt fabric where the individual fibre components are mixed together in a blending device and then carded, crosslaid and needled to give a fabric. Such a fabric is of use e. g. as an insulating liner in a garment or could be used to make simple garments such as aprons.'
Use of the invention
The product of this invention is intended to be used as one of the primary components of clothing for personal protection in situations where there is a risk of exposure to flame, electric arc and liquid metal splash. The fabric is used to make garments that cover the body of the user to protect the skin from exposure to flames or to other sources of heat such as metal splash - except alumina - and electric arc that would cause injury.
Garments are usually made by assembling cut shaped pieces of fabric by ; sewing them together. The product of this invention may be the sole fabric . used in making a garment or may be one component of a garment; the other components consisting of fabrics of different design and purpose. It may also be combined with other fabrics by laminating prior to cutting the shaped pieces for garment assembly.
The product of this invention may be used as a layer of fabric on the inside of a garment. It may be used as a layer on the outside of a garment or it may be used as an internal component between two or more other fabrics. It may also be used to provide more than one layer in the garment. For example it could be used as the inner layer of the garment and as the outer layer of the garment with a third layer of a flame resistant wadding between the inner and outer layers. The fabric of the invention may be used for the production of all types of garments where protection from flames is a primary purpose. It can be used for jackets, coats, trousers, shirts, polos, sweaters and jumpers, sweatshirts, T-shirts, socks, aprons, gloves and gauntlets, hoods for head protection other headwear and any other garment that may be worn for the purpose of protecting the wearer from flame and similar hazards. The fabric may also be used in other articles which are intended to provide protection of people or ; property from exposure to flame such as shoe and boot components, welding screens, fire curtains, tents, sleeping bags, tarpaulins and any other similar articles made in whole or in part from fabric.
Coloured fabrics for the intended applications are preferably achieved by using spun dyed fibres, by piece dyeing or by printing, but in general all dyeing techniques are applicable. Example 1
A twill weave fabric was woven from the following components:
· Yarn: A Nm 45/2 worsted spun yarn in which 70% of the fibre was 3.3 dtex Lenzing FR® (1/3 with 75 mm and 2/3 with 90 mm staple length), 5% of the fibre was 1.7 dtex 100 mm staple length para-aramid and 15% of the fibre was high tenacity PA6. Lenzing FR® is an FR modal fibre available from Lenzing AG, Austria, which is produced according to a modal process (see AT-A 1371/2009) and which contains Exolith® as an incorporated FR pigment. The three fibre components were blended together in drafting of the slivers during preparatory
processing. The fabric warp count was 30 threads per cm. The weft count was 26 threads per cm.
The resulting fabric had a mass per unit area of 260 g/m2 Flame protection:
The resulting fabric could not be ignited in normal atmospheric conditions. On exposure to flame directed at the surface of the fabric, the fabric charred but maintained its structure and continued to act as a barrier to flame. No holes were formed in the fabric. The fabric remained soft and flexible without any break open after flame exposure according to EN ISO 15025 procedure A (surface ignition). Furthermore no heat shrinkage of the fabric was observed when the flame was directed at the fabric surface and during the whole flaming time of 10 seconds.
Afterfiame and afterglow of the fabric when tested according to EN ISO 15025 procedure A were 0 seconds in the warp direction and 0 seconds in the weft direction. Protective garments - jackets and trousers - were assembled from the fabric and evaluated as follows.
Testing with an instrumented manikin
according to ISO 13506.3: Protective clothing against heat and flame— Test method for complete garments— Prediction of burn injury using an instrumented manikin. This test method characterizes the thermal protection provided by garments, based on the measurement of heat transfer to a full- size manikin exposed to a laboratory simulation of a fire with controlled heat flux density, duration and flame distribution. The heat transfer measurements can also be used to calculate the predicted skin burn injury resulting from the exposure. Garments made from the fabric according to the invention were compared with garments made from a 100% aramid fabric (Tables 1 and 2).
TabSe 1 - Bum prediction: Table 2 - Dimensional Change after flame exposure:
n/a*: after flame exposure the garment was too brittle for evaluation
The garment made from the fabric of the invention showed far less burns in comparison with 00% Aramid garments. After the flame exposure the garments were removed from the manikin to measure the size and shrinkage of the garment. Parts of the 00% Aramid garments were too brittle to measure - the jacket upper arm and the trouser thigh. The fabric of the invention remained intact in one piece. No severe damage was observed. The fabric remained flexible and did not break open.
Surprisingly, the fabric of the invention does not shrink during the flame exposure. In fact the opposite occurs - some parts of the garment increased in dimensions. The 100% Aramid garment show significant flame shrinkage.
In the visual evaluation of the test garments it can clearly be seen that the garment made from the fabric of the invention is creating a kind of extra protection cushion when exposed to flame. Metal spSash protection:
The fabric of the invention was tested according to ISO 9185 and
classification according to EN ISO 11612. Despite of it's relatively low fabric weight of 260 g/m2 the result was on the highest protection level which can be achieved: E3. For comparison: A typical fabric already used for iron metal splash protection has a fabric weight of 400 g/m2 and only shows a protection level E1. This test assesses the ability of the fabric to withstand a certain quantity of molten metal and how the metal interacts with the fabric. The best performing materials retain their structure and the metal does not adhere to the surface. Damage done to the fabric.is minimized.
Electric Arc protection:
. The fabric of the invention was tested according to EN ISO IEC 61482 1-2, 4kA and 7kA. The fabric passed with excellent values the required Stoll criteria for 4kA, and exhibited no break open of the fabric in a single layer, when tested to 7kA. The Stoll curve is a curve of thermal energy and time produced from data on human tissue tolerance to heat and used to predict the onset of second-degree burn injury (cited from EN ISO IEC 61482 1-2).. !VSec anica! Performance testing:
The tear test results tested according to ISO 13937-2 were as follows compared to some of the other products currently used in personal protective clothing in table 3: TabSe 3 - Fabric Performance Results
The fabric of the invention has a higher tear strength compared with most of the other materials on the market. Comfort testing: Results' according to Table 3 . Alam beta - Heat penetration coefficient:
The fabric was tested for its comfort properties. The Alambeta test measures the rate of transmission of body heat through the fabric. Fabrics with a high heat penetration coefficient feel cooler and this makes them more comfortable to wear. Referring to the results of Table 3 the fabric of the invention shows the highest heat penetration coefficient, resulting in the coolest fabric touch.
Short time water vapor absorption Fi:
The fabric was tested for short term water vapour absorption (Fi) according to
EN ISO 31092 using the human skin model apparatus. A high water vapour absorbency indicates the fabricis capable of positively managing the moisture in its environment. This helps to keep the body dry and cool. Referring to the results of Table 3 the fabric of the invention shows the highest short time ■ \
water vapor absorption, resulting in the best wearing comfort.
This can help to avoid the risk of heat stress and heat stroke and will improve the physiological performance of the wearer.
Colour fastness testing:
Due to the usage of 100% spundyed fibres, or quality dyeing procedures high colour fastness can be achieved, as colours never wash or wear out.
Example 2 The fabric of example 1 according to the invention was assessed subjectively and compared to commercially available fabrics used for Personal Protective Clothing. The results are given in Table 4, last column. In this table the scoring system is 1 to 3: 1 = poor, 3 = excellent. In every parameter judged, the fabric of example 1 was given the highest possible score. No other fabric assessed achieved the same high level on assessment. Tab!e 4 - Properties of commonly used Personal Protective Clothing Fabrics compared to example 1
MAC = Modacrylic

Claims

Claims What we claim is:
1. A flame resistant fabric for use in personal protective clothing which provides a high level of protection from flames and other sources of heat such as molten metal splash and electric arc, characterized in that it is made from an intimate blend of FR cellulosic fibres with high temperature resistant polymer fibres and standard synthetic fibres.
2. Fabric according to claim 1 , wherein the intimate blend is in the form of a yarn.
3. Fabric according to claim 2, wherein the blend ratio of the yarn is
preferably
- from 65 to 90% FR cellulosic fibres,
- from 10 to 20 % high temperature resistant polymer fibres and
- from 10 to 20% standard flammable synthetic fibres.
4. Fabric according to claim 2, wherein the blend ratio of the yarn is
preferably
- from 65 - to 75% FR cellulosic fibres,
- from 12,5 to 17,5% high temperature resistant polymer fibres and
- from 12,5 to 17,5% standard flammable synthetic fibres,
5. Fabric according to claim 2, wherein the FR cellulosic fibres of the yarn are staple fibres with a staple length of between 75 and 90 mm.
6. Fabric according to claim 2, wherein the FR cellulosic fibres of the yarn are cellulosic fibres that have been made flame resistant by addition of an FR agent during or after fibre production.
7. Fabric according to claim 2, wherein the FR cellulosic fibres of the yarn are chosen from the group consisting of FR Modal, FR viscose and FR Lyocell.
8. Fabric according to claim 7, wherein the FR cellulosic fibres of the yarn are FR Modal fibres.
9. Fabric according to claim 7, wherein the FR cellulosic fibres of the yarn can be a blend of different FR cellulosic fibres out of the group of FR Modal, FR Viscose and FR Lyocell.
10. Fabric according to claim 2, wherein the high temperature resistant polymer fibres are chosen from the group consisting of para-aramid, meta-aramid, aromatic PES, PBI and blends of these fibres.
11. Fabric according to claim 2, wherein the standard flammable synthetic fibres are selected from the group including PA6, PA6.6 and PES fibres.
12. Fabric according to claim 2 which has been made antistatic by the addition of 1 % to 5% of an antistatic staple fibre to the blend.
13. Fabric according to claim 2 which has been made antistatic by
incorporating a grid pattern of yarns consisting of the ground yam twisted with antistatic continuous filament yarn.
14. Fabric according to claim 2 wherein one or more of the individual fibre components has been dope dyed, or is stock dyed staple fibre or dyed tops, yam or fabric.
15. Fabric according to Claims 1 to 14 which is produced by weaving, knitting or a non woven fabric production method.
EP20110793645 2010-11-24 2011-11-07 Flame resistant fabric for protective clothing Not-in-force EP2643508B1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
ATA1953/2010A AT511288B1 (en) 2010-11-24 2010-11-24 Flame resistant fabric for protective clothing
PCT/AT2011/000448 WO2012068600A1 (en) 2010-11-24 2011-11-07 Flame resistant fabric for protective clothing

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EP2643508A1 true EP2643508A1 (en) 2013-10-02
EP2643508B1 EP2643508B1 (en) 2015-01-07

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US (1) US20130267140A1 (en)
EP (1) EP2643508B1 (en)
KR (1) KR20130131382A (en)
CN (1) CN103221595A (en)
AT (1) AT511288B1 (en)
TW (1) TW201237229A (en)
WO (1) WO2012068600A1 (en)

Families Citing this family (21)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20140026303A1 (en) * 2012-07-27 2014-01-30 E I Du Pont De Nemours And Company Fiber blends, yarns, fabrics, and garments for arc and flame protection
CA2879861C (en) 2012-07-27 2020-12-08 Drifire Llc Fiber blends for wash durable thermal and comfort properties
CN103668619B (en) * 2012-09-14 2017-06-09 美利肯公司 Yarn, textile material and the clothes containing it
AT513763B1 (en) * 2012-12-27 2016-06-15 Chemiefaser Lenzing Ag Flame retardant lyocell article that is dyed to provide good light and washfastness
EP2767180B1 (en) * 2013-02-18 2017-01-04 W.L. Gore & Associates GmbH Flame protective fabric structure
CN104674425A (en) * 2013-11-28 2015-06-03 杭州威垒特科技有限公司 Fabric capable of preventing metal splashing
CN103668696A (en) * 2013-12-27 2014-03-26 吴江市华宏纺织丝绸有限公司 High-temperature-resistant fiber fleece fabric
CA2953336C (en) 2014-07-15 2023-03-21 Drifire, Llc Lightweight, dual hazard fabrics
US20160060809A1 (en) * 2014-08-29 2016-03-03 Drifire, Llc Lightweight, arc-rated, dyeable fabrics
CN106192422A (en) * 2015-09-23 2016-12-07 南通金仕达超微阻燃材料有限公司 The production method of the low washing shrinkage anti pilling Modal wide cut woven fabric of excellent performance
CN105401288A (en) * 2015-10-30 2016-03-16 太仓市璜泾镇佳梦化纤厂 High-strength durable comfortable blend fiber
CN105586679A (en) * 2016-01-26 2016-05-18 安徽省无为天成纺织有限公司 Composite inflaming-retarding and high-temperature-resisting blended yarn for protective garment
TR201602591A2 (en) * 2016-02-29 2016-06-21 Kipas Mensucat Isletmeleri Anonim Sirketi PROTECTIVE WOVEN FABRIC AGAINST MELT METALS AND ELECTRIC ARKIN
CA2964708A1 (en) * 2016-04-22 2017-10-22 General Recycled Protective fabric and process of manufacturing same
EP3524720B1 (en) * 2016-10-05 2021-04-07 Toray Industries, Inc. Flame-resistant woven fabric
CA3039312A1 (en) * 2016-11-01 2018-05-11 Teijin Limited Fabric, method for manufacturing same, and fiber product
DE202017102561U1 (en) * 2017-05-02 2018-08-07 Rainer Schneider Yarn, twine, textile material of this yarn and / or twine and made-up product of this textile material
US11039692B2 (en) * 2018-04-09 2021-06-22 Pneuma Pure I.P. Limited Fire retardant cushioning devices
WO2020168437A1 (en) 2019-02-22 2020-08-27 Jess Black Inc. Fire-resistant double-faced fabric of knitted construction
CN110644114A (en) * 2019-10-22 2020-01-03 江苏阳光股份有限公司 Preparation method of heating and warm-keeping wool fabric
CN116411376B (en) * 2023-04-04 2024-03-22 山东省产品质量检验研究院 Comfortable flame-retardant arc-preventing fabric and preparation method and application thereof

Family Cites Families (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
ATA103182A (en) * 1982-03-15 1987-05-15 Zimmer Kg Taunus Textildruck FLAME RETARDANT TEXTILE AREA
US5766746A (en) * 1994-11-07 1998-06-16 Lenzing Aktiengesellschaft Flame retardant non-woven textile article
DE19617634A1 (en) * 1996-05-02 1997-11-06 Basf Ag Flame retardant fabric based on melamine resin fibers
US6057032A (en) * 1997-10-10 2000-05-02 Green; James R. Yarns suitable for durable light shade cotton/nylon clothing fabrics containing carbon doped antistatic fibers
GB2384249A (en) * 2002-01-17 2003-07-23 Tencel Ltd Dyeing & finishing of regenerated cellulose fabric with controlled fibrillation involving treatment with acid or acid donor then heat in gaseous atmosphere
US20040001978A1 (en) * 2002-07-01 2004-01-01 Yves Bader Molten metal resistant fabrics
US7168140B2 (en) * 2002-08-08 2007-01-30 Milliken & Company Flame resistant fabrics with improved aesthetics and comfort, and method of making same
US20050025962A1 (en) * 2003-07-28 2005-02-03 Reiyao Zhu Flame retardant fiber blends comprising flame retardant cellulosic fibers and fabrics and garments made therefrom
US20050032449A1 (en) * 2003-08-06 2005-02-10 Lovasic Susan L. Lightweight protective apparel
JP2008509297A (en) * 2004-08-06 2008-03-27 サザンミルズ インコーポレイテッド High visibility flame resistant cloth and method for producing the same
US20060292953A1 (en) * 2005-06-22 2006-12-28 Springfield Llc Flame-resistant fiber blend, yarn, and fabric, and method for making same
US10072365B2 (en) * 2007-07-17 2018-09-11 Invista North America S.A.R.L. Knit fabrics and base layer garments made therefrom with improved thermal protective properties
WO2009096444A1 (en) * 2008-01-30 2009-08-06 Kurashiki Boseki Kabushiki Kaisha Flame retardant processing method, and cellulosic fiber material imparted with flame retardancy
AT508653B1 (en) * 2009-11-02 2011-03-15 Chemiefaser Lenzing Ag FLAME-HOLDING FABRIC FOR A PROTECTIVE CLOTHING
US8209785B2 (en) * 2010-02-09 2012-07-03 International Textile Group, Inc. Flame resistant fabric made from a fiber blend
US8133584B2 (en) * 2010-04-08 2012-03-13 E.I. Du Pont De Nemours And Company Crystallized meta-aramid blends for flash fire and arc protection having improved comfort

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO2012068600A1 *

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Publication number Publication date
US20130267140A1 (en) 2013-10-10
AT511288A1 (en) 2012-10-15
AT511288B1 (en) 2013-01-15
WO2012068600A1 (en) 2012-05-31
CN103221595A (en) 2013-07-24
TW201237229A (en) 2012-09-16
KR20130131382A (en) 2013-12-03
EP2643508B1 (en) 2015-01-07

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