EP3030708B1 - Mit c6 basiertem perfluoroalkyl-polymer ausgerustetes abstandstextil und verfahren zur herstellung - Google Patents

Mit c6 basiertem perfluoroalkyl-polymer ausgerustetes abstandstextil und verfahren zur herstellung Download PDF

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Publication number
EP3030708B1
EP3030708B1 EP13747397.1A EP13747397A EP3030708B1 EP 3030708 B1 EP3030708 B1 EP 3030708B1 EP 13747397 A EP13747397 A EP 13747397A EP 3030708 B1 EP3030708 B1 EP 3030708B1
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EP
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Prior art keywords
spacer fabric
treating composition
treated
measurements
liquid treating
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English (en)
French (fr)
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EP3030708A1 (de
Inventor
Frank Jost
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Baldus Ausruestungsgesellschaft Mbh
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Baldus Ausruestungsgesellschaft Mbh
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Priority to PL13747397T priority Critical patent/PL3030708T3/pl
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    • 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
    • D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/244—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of halogenated hydrocarbons
    • D06M15/256—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of halogenated hydrocarbons containing fluorine
    • D—TEXTILES; PAPER
    • D03—WEAVING
    • D03D—WOVEN FABRICS; METHODS OF WEAVING; LOOMS
    • D03D11/00—Double or multi-ply fabrics not otherwise provided for
    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04B—KNITTING
    • D04B21/00—Warp knitting processes for the production of fabrics or articles not dependent on the use of particular machines; Fabrics or articles defined by such processes
    • D04B21/14—Fabrics characterised by the incorporation by knitting, in one or more thread, fleece, or fabric layers, of reinforcing, binding, or decorative threads; Fabrics incorporating small auxiliary elements, e.g. for decorative purposes
    • D04B21/16—Fabrics characterised by the incorporation by knitting, in one or more thread, fleece, or fabric layers, of reinforcing, binding, or decorative threads; Fabrics incorporating small auxiliary elements, e.g. for decorative purposes incorporating synthetic threads
    • 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
    • D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/263—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters thereof
    • D06M15/277—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters thereof containing fluorine
    • 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
    • D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/285—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acid amides or imides
    • D06M15/295—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acid amides or imides containing fluorine
    • 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
    • D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/327—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated alcohols or esters thereof
    • D06M15/33—Esters containing fluorine
    • 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
    • D06M15/564—Polyureas, polyurethanes or other polymers having ureide or urethane links; Precondensation products forming them
    • D06M15/576—Polyureas, polyurethanes or other polymers having ureide or urethane links; Precondensation products forming them containing fluorine
    • 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
    • D06M15/643—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicon in the main chain
    • D06M15/657—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicon in the main chain containing fluorine
    • 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
    • D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
    • D06M2101/16—Synthetic fibres, other than mineral fibres
    • D06M2101/30—Synthetic polymers consisting of macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M2101/32—Polyesters
    • 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
    • D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
    • D06M2101/16—Synthetic fibres, other than mineral fibres
    • D06M2101/30—Synthetic polymers consisting of macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M2101/34—Polyamides
    • 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
    • D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
    • D06M2200/10—Repellency against liquids
    • D06M2200/11—Oleophobic properties
    • 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
    • D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
    • D06M2200/30—Flame or heat resistance, fire retardancy properties
    • 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
    • D10B2403/00—Details of fabric structure established in the fabric forming process
    • D10B2403/02—Cross-sectional features
    • D10B2403/021—Lofty fabric with equidistantly spaced front and back plies, e.g. spacer fabrics
    • 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
    • D10B2505/00—Industrial
    • D10B2505/02—Reinforcing materials; Prepregs

Definitions

  • the present invention relates in general to treated spacer fabrics and a method of preparing such spacer fabrics and more particularly to a spacer fabric being treated for imparting the spacer fabric with at least one or all of the properties selected from good flame retardancy, good oil repellency, high spray rating and low volatile emissions. Furthermore, the invention relates to the use of a specific liquid treating composition for preparing a treated spacer fabric having at least one or all of the properties selected from good flame retardancy, good oil repellency, high spray rating and low volatile emissions.
  • Spacer fabrics are three-dimensional fabrics, which are available in different executions and material thicknesses. They provide excellent properties such as a low weight, durable elasticity, springiness and their climate effect. This material is used, for example, as automotive textile in climatic and ventilated seats, seat covers, head liners, instrument and door panels as well as in composite constructions or as consumer textile in mattresses and furniture or in technical clothing and shoes.
  • spacer fabrics are required to further provide specific properties like good oil repellency, high spray rating, good flame retardancy and low volatile emissions. Especially, good flame behavior and low volatile emissions are mandatory requirements for spacer fabrics when used in the automotive industry today. Furthermore, good oil repellency and high spray rating are desired requirements for such spacer fabrics because of their better processability in the automotive industry.
  • so-called C8 fluorocarbon polymers have been used as state-of-the-art treating material for imparting spacer fabrics used in the automotive industry with the required oil repellency and spray rating. To achieve the also required flame retardancy the spacer fabrics were and still are additionally treated with flame retardants.
  • PFOA is an abbreviation for Perfluorooctanoic Acid.
  • C8 telomer is a chemical compound that contains 8 carbon atoms and 17 fluorine atoms.
  • Many water and oil repellent products used for long term protection of textiles are based on C8 telomers.
  • EPA U.S. Environmental Protection Agency
  • Chemicals containing perfluoroalkyl sections are more expensive than e.g. wax emulsions or silicone applications.
  • US 7 552 604 B1 discloses the production of double needle bar spacer fabric suitable for applications such as transportation vehicles.
  • the spacers are made of polyester yarns and can be treated with a fluorochemical finish composition to impart stain water and/or oil resistance to the spacer.
  • WO 2012/147582 A2 discloses a method to treat a twill weave with a C6-perfluoroalkyl based polymer.
  • US 2011/257327 discloses the application to textiles of a water and oil repellent comprising C4-C6 perfluorinated polymer being low in bioaccumulation potential.
  • This invention is a method of preparing a treated spacer fabric according to claim 1, comprising the steps:
  • a "spacer fabric” as herein referred to comprises at least a first and second fabric layers that are arranged in an opposing back-to-back, spaced apart relationship with each other.
  • the first and second fabric layers are interconnected to each other with one or more spacer fibers that interconnect the first and second fabric layers and define a space between these layers.
  • the spacer fibers comprise a resilient material that is able to maintain the space between the fabric layers, while still permitting the layers to be reversibly compressed together. As a result, the spacer fabric provides a relatively light weight and flexible fabric.
  • the spacer fabric has a thickness in the range of 1.0 to 7 mm, more preferably in the range of 1.4 to 6 mm, and most preferably in the range of 1.6 to 5 mm.
  • the weight per unit area of the provided spacer fabric used for the preparation of the treated spacer fabric of the present invention is preferably in the range of 100 to 500 g/m 2 , more preferably in the range of 150 to 400 g/m 2 , and most preferably in the range of 200 to 350 g/m 2 .
  • the spacer fibers that interconnect the first and second fabric layers are preferably monofil fibers.
  • the spacer fabric of a thermoplastic polymer provided in step a) of the inventive method and used to prepare the treated spacer fabric is based on a thermoplastic polymer or at least mainly consists a thermoplastic polymer.
  • the thermoplastic polymer is preferably selected from the group consisting of polyester, polyamid and a combination thereof. Spacer fabrics made of polyester are particularly preferred. "Based on” means that the spacer fabric comprises the thermoplastic polymer, for example, as material for the first fabric layer, for the second fabric layer or for both. Alternatively, the spacer fabric comprises the thermoplastic polymer as material for the spacer fibers that interconnect the first and second fabric layers.
  • the spacer fabric can comprise the thermoplastic polymer as material for the spacer fibers and only one of the first fabric layer and the second fabric layer. "At least mainly consist of” means that the material the spacer fabric is made of consists of at least 50 % by weight of the thermoplastic polymer. Preferably, at least 90 % by weight, more preferably at least 95 % by weight or even 100 % by weight, of the spacer fabric is made of a thermoplastic polymer as defined above.
  • the treated spacer fabric prepared according to the present invention is particularly suitable for use in an automobile because of its good flame retardancy and low volatile emissions properties. Furthermore, the treated spacer fabric prepared according to the present invention is also particularly suitable for use in an automobile because of its high spray rating and/or good oil repellency properties.
  • the treated spacer fabric prepared according to the present invention has an acceptable flame retardancy measured according to FMVSS 302 (corresponds to DIN 75200).
  • FMVSS 302 the first side of the fabric is applied to a flame. It is measured the distance of burning, the time of burning and the velocity of burning in the machine direction as well as the cross direction. The same is measured on the second side of the fabric. Each of the measurements is repeated 3 times. "Acceptable” here means that at least five of the six measurements on the first and the second side in cross direction yield a velocity of burning of less than 100 mm/minute, preferably less than 85 mm/minute, most preferably less than 70 mm/minute.
  • the treated spacer fabric prepared according to the present invention has a total emission according to VDA 277 (5 hours, 120 °C) of less than 100 ⁇ gC/g, preferably less than 90 ⁇ gC/g.
  • the treated spacer fabric prepared according to the present invention typically has a fogging according to DIN 75201-B (16 hours, 100 °C) of less than 100 mg, preferably less than 90 mg, most preferably less than 80 mg.
  • the treated spacer fabric prepared according to the present invention typically has a smell according to VDA 270-2 (40 °C) of not worse than grade 3, preferably of grade 2, most preferably of grade 1.
  • the treated spacer fabric prepared according to the present invention typically has a emission of formaldehyde according to VDA 275 of less than 3.0 mg/kg, preferably less than 2.5 mg/kg, most preferably less than 2.0 mg/kg.
  • the treated spacer fabric prepared according to the present invention typically has a spraytest rating according to AATCC 22 of at least 70, preferably at least 75, most preferably at least 80.
  • the treated spacer fabric prepared according to the present invention typically has an oil repellency rating according to AATCC 118 of at least 4, preferably at least 5, most preferably at least 6.
  • the C6-perfluoralkyl based fluoropolymer(s) may additionally comprise a polymeric backbone bearing more than one groups selected from the perfluorohexyl tails and the perfluoroalkyl (CF 2 ) n -sections.
  • the polymeric backbone may additionally comprise one or more spacer groups between the polymeric backbone and one or more of the the perfluorohexyl tails and/or the perfluoroalkyl (CF 2 ) n -sections.
  • the polymeric backbone may additionally comprise one or more side groups which can bond via any kind of chemical or physical bond to the surface of a spacer fabric.
  • Preferred C6-perfluoralkyl based fluoropolymers used according to the invention are fluorocarbon derivatives comprising more than one perfluorohexyl tails and a polymeric backbone bearing the perfluorohexyl tails.
  • a "treated spacer fabric” as herein referred to means a spacer fabric which has been treated with any kind of substance, compositions or solutions.
  • the treating substances or compositions can be in the solid, pulverulent, liquid, viscous or gaseous state. Further, any kind of treatment is encompassed, e.g. dipping, immerging, spraying or the like. The only proviso is that an amount of such a substance or composition remains on or is adhered to the spacer fabric.
  • the substance can be adhered to the spacer fabric by any kind of chemical and/or physical bonding.
  • a "liquid treating composition” as herein referred to means an emulsion, a solution or any other kind of liquid composition which can be used to treat a spacer fabric.
  • the provided liquid treating composition used in the method of the invention has a concentration of the C6-perfluoralkyl based fluoropolymer(s) in the in the range of from 0.3 to 10 g/l, preferably in the range of from 0.4 to 8 g/l, and most preferably in the range of from 0.5 to 6 g/l. It is preferred that the liquid treating composition is an aqueous liquid treating composition.
  • the provided spacer fabric is preferably free of perfluorooctanoic acid (PFOA), perfluorooctanesulfonic acid (PFOS) and perfluorooctane sulfonate (PFOS).
  • PFOA perfluorooctanoic acid
  • PFOS perfluorooctanesulfonic acid
  • PFOS perfluorooctane sulfonate
  • the spacer fabric provided is free of perfluorooctanesulfonic acid, perfluorooctane sulfonate and perfluorooctanoic acid.
  • "Being ensured to be free of" perfluorooctanesulfonic acid, perfluorooctane sulfonate and perfluorooctanoic acid means here that it has been actively ensured by appropriate measures that the provided spacer fabric indeed comprises not more than 1 ppm, preferably not more than 100 ppb, most preferably not more than 10 ppb, of the sum of perfluorooctanoic acid, perfluorooctanesulfonic acid and perfluorooctane sulfonate, based on of the total weight of the spacer fabric.
  • An appropriate measure in this context can be a pre-washing step where the provided spacer fabric is washed prior to step c).
  • the provided spacer fabric can be prefixed prior to step c).
  • "Prefixing” means here that the provided spacer fabric is heated and, optionally, brought into uniform shape by, for example, stretching the spacer fabric. The heating may also lead to a reduction of any PFOA, PFOS and PFOS eventually present on the provided spacer fabric.
  • the liquid treating composition is preferably free of perfluorooctanesulfonic acid, perfluorooctane sulfonate and perfluorooctanoic acid.
  • the liquid treating composition comprises not more than 1 ppm, preferably not more than 100 ppb, most preferably not more than 10 ppb, of the sum of perfluorooctanoic acid, perfluorooctanesulfonic acid and perfluorooctane sulfonate, based on of the total weight of the liquid treating composition.
  • both the provided spacer fabric and the liquid treating composition are free of any C8-perfluoralkyl based fluoropolymers - due to the environmental problems discussed above.
  • step d) to remove excessive treating composition from the treated spacer fabric.
  • Excessive treating composition can be removed, for example, by squeezing out the excessive treating composition from the spacer fabric. Squeezing out can be performed, for example, by nip-rolling the spacer fabric between two rubber rolls. Other methods of removing excessive treating composition can also be used.
  • all of the removed treating composition - or at least a major part thereof - is separated from the bath containing the liquid treating composition which is used in step c) for treating the spacer fabric. This can be achieved, for example, by preventing at least a major part or all of the removed treating composition from flowing back to the bath containing the liquid treating composition.
  • a "major part” here means more than 40 % by weight, preferably more than 50 % by weight, even more preferably more than 60 % by weight, and most preferably more than 70 % by weight, of the removed treating composition.
  • the so-called "pick-up" is preferably in the range of 50 to 150 %, more preferably in the range of 60 to 100 %.
  • the "pick-up" as herein referred to is defined as the increase of weight of the wet treated spacer fabric after treatment with the treating composition and after removing excessive treating composition compared to the spacer fabric prior to the treatment. This means, if e.g. 100 gram provided spacer fabric have a weight of 150 gram after being treated with the treating composition and after removing of excessive treating composition the pick-up is 50%.
  • the excessive treating composition is removed from the spacer fabric by squeezing out between two rubber rolls.
  • the pressure between the two rubber rolls is preferably in the range of 1 to 8 bar, more preferably in the range of 3 to 6 bar.
  • the advantage of separating the removed treating composition from the bath containing the liquid treating composition is that fiber preparations washed out from the spacer fabric by excessive treating composition does not accumulate in the bath containing the liquid treating composition. This in turn prevents the spacer fabric immerged into the bath for treatment from being contaminated with the accumulated fiber preparations present in the bath. Contamination of the spacer fabric with accumulated fiber preparations present in the bath can be a problem because the properties selected from flame retardancy, oil repellency, spray rating and low volatile emissions can be negatively affected by the fiber preparations contamination, especially since such fiber preparations contamination is typically inhomogeneous or non-uniform.
  • Fiber preparations herein referred to are chemical substances not having an intended function at the final spacer fabric but which adhere to the provided spacer fabric as a result of the manufacture of the spacer fabric.
  • Typical fiber preparations are lubricants and static inhibitors.
  • the chemical substances behind these lubricants and static inhibitors are, for example, fats, waxes, oils and esters of phosphoric acid.
  • Excessive treating composition here means that amount or portion of treating composition which is absorbed from or adhere to the spacer fabric after the treated spacer fabric has left the immerging bath but which is not needed, e.g. for achieving the desired properties, such as good flame retardancy, good oil repellency, high spray rating and/or low volatile emissions, or which is just too much since it makes the treated spacer fabric too wet for adequate or sound further processing.
  • a spacer fabric in context of the present invention means that the spacer fabric is dried by means of, for example, warming or heating the spacer fabric, by blowing warm or cold air over or through the spacer fabric or by irradiating the spacer fabric with e.g. IR-radiation or the like.
  • the degree of "drying" or dryness is not critical and depends on the desired properties of or the demands on the final spacer fabric.
  • a spacer fabric in context of the present invention means that the treating composition adhered to the spacer fabric is fixed.
  • This fixing is a process where as a result of temperature and/or time and/or other causes the treating composition adhered to the spacer is hardened and/or aged and/or solidified and/or tempered and/or the like.
  • Fixing may also include a crosslinking process of the C6-perfluoralkyl based fluoropolymer(s) of the treating composition and/or a covalent binding process of the C6-perfluoralkyl based fluoropolymer(s) to the thermoplastic material of the spacer fabric.
  • step c) an optional step of pre-fixing the spacer fabric.
  • pre-fix a spacer fabric in context of the present invention means that the spacer fabric is brought into uniform shape by, for example, stretching and subsequently or at the same time heating the spacer fabric. Pre-fixing by means of heating can also be an alternative method to the optional pre-washing step of the provided spacer fabric mentioned above in context with removing of any PFOA, PFOS and PFOS eventually present on the provided spacer fabric.
  • the liquid treating composition used according to the present invention preferably comprises water as solvent and additionally one or more emulsifier(s) or surfactant(s).
  • emulsifier(s) or surfactant(s) non-ionic emulsifier/surfactants is/are preferred.
  • Polyoxyethylene glycol alkyl ethers and polyoxypropylene glycol alkyl ethers are particularly preferred.
  • liquid treating composition for example, alcohols like isopropanol as an auxiliary agent.
  • the liquid treating composition comprises the C6-perfluoralkyl based fluoropolymer(s), the emulsifier(s), isopropanol and the water.
  • the concentration of fiber preparations in the liquid treating composition in the bath is kept low as long as the treating step c) is performed. This means that it should be ensured - by appropriate measures - that the concentration of fiber preparations in the liquid treating composition in the bath is low, preferably as low as possible, when the spacer fabric is immerged into the bath of the liquid treating composition.
  • An "appropriate measure" for keeping the concentration of fiber preparations in the bath of liquid treating composition low can be, for example, ensuring that all or at least a major part of the removed treating composition is separated from the bath containing the liquid treating composition. The separation avoids accumulation of fiber preparations which can be washed out from the spacer fabric by excessive treating composition.
  • Another measure for keeping the concentration of fiber preparations low could be the dilution of "used" liquid treating composition with fresh and uncontaminated liquid treating composition or even - if a predetermined amount of fiber preparations contamination is reached - the substitution of "used" liquid treating composition with fresh and uncontaminated liquid treating composition.
  • the spacer fabric provided in step a) comprises fiber preparations in an amount as low as possible.
  • the provided spacer fabric is free of fiber preparations. Therefore, and in order to achieve best results with the present invention, it should be ensured - by appropriate measures - that the provided spacer fabric comprises fiber preparations in an amount as low as possible or is essentially free of fiber preparations, at least when entering the treating step c), i.e. when the spacer fabric is immerging into the bath of the liquid treating composition.
  • An appropriate measure in this context can be a pre-washing step where the provided spacer fabric is washed prior to step c).
  • the provided spacer fabric can be prefixed prior to step c). "Prefixing” means here that the provided spacer fabric is heated and, optionally, brought into uniform shape by, for example, stretching the spacer fabric.
  • the treated spacer fabrics prepared according to the present inventive method exhibit a good flame retardancy even if no additional flame retardants are used when treating the spacer fabrics.
  • no flame retardants are added to the provided liquid treating composition and/or to the provided spacer fabric and/or to the treated spacer fabric. It is particularly preferred that no flame retardants are added at all to the provided liquid treating composition and to the provided spacer fabric and to the treated spacer fabric.
  • “Flame retardants” in the sense of the present invention are the minerals, namely aluminium hydroxide, magnesium hydroxide, huntite and hydromagnesite, red phosphorus, and boron compounds; the organohalogen compounds, namely chlorendic acid derivatives and chlorinated paraffins, decabromodiphenyl ether, decabromodiphenyl ethane, brominated polystyrenes, brominated carbonate oligomers, brominated epoxy oligomers, tetrabromophthalic anyhydride, tetrabromobisphenol A and hexabromocyclododecane; the organophosphorus compounds, namely organophosphate, tris(2,3-dibromopropyl) phosphate, TPP, RDP, BPADP, tricresyl phosphate, phosphonates as DMMP and phosphinates.
  • the organohalogen compounds namely chlorendic acid derivatives and chlorinated
  • the present invention is also directed to a treated spacer fabric obtainable by the method described above.
  • the treated spacer fabric obtainable by the method described above comprises at least a spacer fabric and about 0.03 to about 1.0 % by weight, preferably about 0.04 to about 0.8 % by weight, and most preferably in the range of from about 0.05 to about 0.6 % by weight, of C6-perfluoralkyl based fluoropolymer(s), based on the weight of the spacer fabric.
  • the amount of C6-perfluoralkyl based fluoropolymer(s) can be determined according to the procedures described in DIN SPEC 1038:2010.
  • the person skilled in the art is able to identify and select those signals in the LC-MS (Liquid chromatography-mass spectrometry) measurements that origin from the C6-perfluoralkyl based fluoropolymer(s) and to calibrate the measurements to obtain correct results for the amount of C6-perfluoralkyl based fluoropolymer(s).
  • LC-MS Liquid chromatography-mass spectrometry
  • the spacer fabric obtainable by the method described above is practically free of perfluorooctanoic acid (PFOA), perfluorooctanesulfonic acid (PFOS) and perfluorooctane sulfonate (PFOS).
  • PFOA perfluorooctanoic acid
  • PFOS perfluorooctanesulfonic acid
  • PFOS perfluorooctane sulfonate
  • the spacer fabric comprises not more than 100 ppb, preferably not more than 10 ppb, most preferably not more than 1 ppb, of the sum of perfluorooctanoic acid, perfluorooctanesulfonic acid and perfluorooctane sulfonate, based on of the total weight of the spacer fabric.
  • the present invention is directed to any treated spacer fabric comprising at least a spacer fabric and one or more C6-perfluoralkyl based fluoropolymer(s), the treated spacer fabric being free of perfluorooctanesulfonic acid, perfluorooctane sulfonate and perfluorooctanoic acid and/or being free of any flame retardants.
  • the treated spacer fabric comprises 0.03 to 1.0 % by weight, preferably 0.04 to 0.8 % by weight, and most preferably in the range of from 0.05 to 0.6 % by weight, of the C6-perfluoralkyl based fluoropolymer(s) based on the weight of the spacer fabric.
  • Free of any flame retardants means here that the spacer fabric comprises less than 3 % by weight, preferably less than 1 % by weight, most preferably less than 0.1 % by weight, of the sum of all flame retardants falling under the above definition, based on of the total weight of the spacer fabric.
  • the treated spacer fabric of the invention has a velocity of burning (the most important criterion of flame retardancy according to FMVSS 302) of less than 100 mm/minute, preferably less than 85 mm/minute, most preferably less than 70 mm/minute, in at least five of six measurements in cross direction, three measurements on the first and three measurements on the second side, and has a total emission according to VDA 277 (5 hours, 120 °C) of less than 100 ⁇ gC/g, preferably less than 90 ⁇ gC/g.
  • the treated spacer fabric according to the invention has a spraytest rating according to AATCC 22 of at least 70, preferably at least 75, most preferably at least 80.
  • the treated spacer fabric according to the invention has an oil repellency rating according to AATCC 118 of at least 4, preferably at least 5, most preferably at least 6.
  • the treated spacer fabric according to the invention has a fogging according to DIN 75201-B (16 hours, 100 °C) of less than 100 mg, preferably less than 90 mg, most preferably less than 80 mg, and/or a smell according to VDA 270-2 (40 °C) of not worse than grade 3, preferably of grade 2, most preferably of grade 1, and/or a emission of formaldehyde according to VDA 275 of less than 3.0 mg/kg, preferably less than 2.5 mg/kg, most preferably less than 2.0 mg/kg.
  • a fogging according to DIN 75201-B (16 hours, 100 °C) of less than 100 mg, preferably less than 90 mg, most preferably less than 80 mg, and/or a smell according to VDA 270-2 (40 °C) of not worse than grade 3, preferably of grade 2, most preferably of grade 1, and/or a emission of formaldehyde according to VDA 275 of less than 3.0 mg/kg, preferably less than 2.5 mg/kg, most preferably less than 2.0 mg/
  • the present invention is also directed to the use according to claim 8 of a liquid treating composition
  • a liquid treating composition comprising one or more C6-perfluoralkyl based fluoropolymer(s) for preparing a treated spacer fabric of a thermoplastic material, preferably a treated spacer fabric as described above in more detail.
  • the liquid treating composition comprises the C6-perfluoralkyl based fluoropolymer(s) in a concentration range of from 0.3 to 10 g/l, preferably in the range of from 0.4 to 8 g/l, and most preferably in the range of from 0.5 to 6 g/l.
  • the liquid treating composition used as mentioned above preferably comprises water as solvent and additionally one or more emulsifier(s) or surfactant(s).
  • Figure 1 shows a flow chart with the typical and preferred method steps when preparing a treated spacer fabric according to the invention.
  • One or more of the steps of pre-fixing, removing, drying and fixing can be optional if not needed for achieving customized requirements.
  • the flame retardancy of the spacer fabrics has been measured according to FMVSS 302 (corresponds to DIN 75200).
  • the total emission of the spacer fabrics has been measured according to VDA 277 (5 hours, 120 °C).
  • the fogging of the spacer fabrics has been measured according to DIN 75201-B (16 hours, 100 °C).
  • the smell of the spacer fabrics has been measured according to VDA 270-2 (40 °C).
  • the emission of formaldehyde of the spacer fabrics has been measured according to VDA 275.
  • the spraytest rating of the spacer fabrics has been measured according to AATCC 22.
  • the oil repellency rating of the spacer fabrics has been measured according to AATCC 118.
  • the untreated raw spacer fabrics are conducted via rolls through a bath containing the treating composition at a speed of 6 m/min whereby each section of the spacer fabrics is in contact with the treating composition in the bath for about 3 to 5 seconds.
  • the bath containing the treating composition is heated to a temperature of 23 °C.
  • the treating composition is an aqueous emulsion containing about 2 gram per liter of a C6-perfluoralkyl based fluoropolymer (in form of BAYGARD EFN which is a liquid composition containing about 30 % by weight of the C6-perfluoralkyl based fluoropolymer, BAYGARD EFN is available from Tanatex Chemicals B.V., Netherlands).
  • the spacer fabrics are conducted through two stainless steel rolls having a separation distance of 0.2 mm for removing excessive treating composition from the spacer fabrics.
  • Discharge means are arranged below the rolls which separate the removed treating composition from the bath containing the liquid treating composition.
  • the treated spacer fabrics are dried with hot blowing air at a temperature of about 165 °C.
  • the spacer fabrics are conducted through a device fixing the treated spacer fabrics.
  • the final treated spacer fabrics have been analyzed. The results are summarized in table 1.

Landscapes

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

Claims (11)

  1. Verfahren zur Herstellung eines behandelten Abstandsgewirkes, umfassend die Schritte:
    a) Bereitstellen eines Abstandsgewirkes, bestehend aus einem thermoplastischen Polymer;
    b) Bereitstellen einer flüssigen Behandlungszusammensetzung, umfassend ein oder mehrere auf C6-Perfluoralkyl basierende Fluorpolymere und ein Lösungsmittel;
    c) Behandeln des Abstandsgewirkes durch Eintauchen des Abstandsgewirkes in ein Bad mit der flüssigen Behandlungszusammensetzung;
    d) Entfernen überschüssiger Behandlungszusammensetzung von dem behandelten Abstandsgewirke;
    e) Trocknen des behandelten Abstandsgewirkes; und
    f) Fixieren des behandelten Abstandsgewirkes,
    wobei die Konzentration des oder der auf C6-Perfluoralkyl basierenden Fluorpolymere in der bereitgestellten flüssigen Behandlungszusammensetzung im Bereich von 0,3 bis 10 g/l liegt, und wobei das behandelte Abstandsgewirke, erhalten nach dem Verfahrensschritt f), eine Abbrandgeschwindigkeit nach FMVSS 302 aufweist von kleiner als 100 mm/min in wenigstens fünf von sechs Messungen in der Querrichtung, drei Messungen an der ersten und drei Messungen an der zweiten Seite, und eine Gesamtemission nach VDA 277 aufweist von weniger als 100 µg C/g.
  2. Verfahren nach Anspruch 1, wobei das thermoplastische Polymer ausgewählt ist aus der Gruppe bestehend aus Polyester, Polyamid und einer Kombination davon.
  3. Verfahren nach einem oder mehreren der vorhergehenden Ansprüche, wobei das Lösungsmittel Wasser ist und die flüssige Behandlungszusammensetzung zusätzlich einen oder mehrere Emulgatoren umfasst.
  4. Verfahren nach einem oder mehreren der vorhergehenden Ansprüche, wobei der bereitgestellten flüssigen Behandlungszusammensetzung und/oder dem bereitgestellten Abstandsgewirke und/oder dem behandelten Abstandsgewirke keine Flammschutzmittel zugesetzt sind.
  5. Verfahren nach einem oder mehreren der vorhergehenden Ansprüche, wobei wenigstens ein Großteil der entfernten Behandlungszusammensetzung von dem Bad abgetrennt wird, das die flüssige Behandlungszusammensetzung enthält, welche in Schritt c) zur Behandlung des Abstandsgewirkes verwendet wird.
  6. Behandeltes Abstandsgewirke, umfassend wenigstens ein Abstandsgewirke und ein oder mehrere auf C6-Perfluoralkyl basierende Fluorpolymere, wobei das behandelte Abstandsgewirke frei ist von Perfluoroctansulfonsäure, Perfluoroctansulfonat und Perfluoroctansäure und/oder frei ist von jeglichem Flammschutzmittel, wobei das behandelte Abstandsgewirke eine Abbrandgeschwindigkeit nach FMVSS 302 aufweist von kleiner als 100 mm/min in wenigstens fünf von sechs Messungen in der Querrichtung, drei Messungen an der ersten und drei Messungen an der zweiten Seite, und eine Gesamtemission nach VDA 277 aufweist von weniger als 100 µg C/g.
  7. Behandeltes Abstandsgewirke nach Anspruch 6, wobei das Abstandsgewirke 0,03 bis 1,0 Gew.-% an dem oder den auf C6-Perfluoralkyl basierenden Fluorpolymeren umfasst, basierend auf dem Gewicht des Abstandsgewirkes.
  8. Verwendung einer flüssigen Behandlungszusammensetzung, umfassend ein oder mehrere auf C6-Perfluoralkyl basierende Fluorpolymere und ein Lösungsmittel zur Herstellung eines behandelten Abstandsgewirkes, bestehend aus einem thermoplastischen Polymer, wobei das behandelte Abstandsgewirke eine Abbrandgeschwindigkeit nach FMVSS 302 aufweist von kleiner als 100 mm/min in wenigstens fünf von sechs Messungen in der Querrichtung, drei Messungen an der ersten und drei Messungen an der zweiten Seite, und eine Gesamtemission nach VDA 277 von weniger als 100 µg C/g aufweist.
  9. Verwendung nach Anspruch 8, wobei das Lösungsmittel Wasser ist und die flüssige Behandlungszusammensetzung zusätzlich einen oder mehrere Emulgatoren umfasst.
  10. Verwendung nach Anspruch 8 oder 9, wobei das behandelte Abstandsgewirke nach AATCC 22 eine Sprühtest-Bewertung aufweist von wenigstens 70 und/oder nach AATCC 118 eine Bewertung bei der Ölabweisung von wenigstens 4 und/oder nach DIN 75201-B ein Fogging von weniger als 100 mg und/oder nach VDA 270-2 einen Geruch von nicht schlechter als Note 3 und/oder nach VDA 275 eine Formaldehyd-Emission von weniger als 3,0 mg/kg aufweist.
  11. Verwendung nach einem oder mehreren der Ansprüche 8 bis 10, wobei die flüssige Behandlungszusammensetzung das oder die auf C6-Perfluoralkyl basierenden Fluorpolymere in einem Konzentrationsbereich von 0,3 bis 10 g/l umfasst.
EP13747397.1A 2013-08-08 2013-08-08 Mit c6 basiertem perfluoroalkyl-polymer ausgerustetes abstandstextil und verfahren zur herstellung Active EP3030708B1 (de)

Priority Applications (1)

Application Number Priority Date Filing Date Title
PL13747397T PL3030708T3 (pl) 2013-08-08 2013-08-08 Tkanina dystansowa obrabiana polimerem perfluoroalkilowym na bazie C6 i sposób jej wytwarzania

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/EP2013/066661 WO2015018449A1 (en) 2013-08-08 2013-08-08 Spacer fabric treated with c6 based perfluoroalkyl polymer and method of preparing thereof

Publications (2)

Publication Number Publication Date
EP3030708A1 EP3030708A1 (de) 2016-06-15
EP3030708B1 true EP3030708B1 (de) 2019-10-23

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US (1) US20160194821A1 (de)
EP (1) EP3030708B1 (de)
ES (1) ES2774260T3 (de)
MX (1) MX369708B (de)
PL (1) PL3030708T3 (de)
WO (1) WO2015018449A1 (de)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2539474B (en) * 2015-06-17 2020-09-09 Traffi Safe Ltd Glove and treatment method
TWI723914B (zh) 2020-07-13 2021-04-01 財團法人紡織產業綜合研究所 抗污樹脂、抗污織物及其製造方法
TWI847009B (zh) 2021-01-28 2024-07-01 財團法人紡織產業綜合研究所 撥水樹脂、撥水織物及其製造方法

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DE102005019616A1 (de) * 2005-04-28 2006-11-02 Recaro Gmbh & Co.Kg Fahrzeugsitz mit Klimasystem
WO2007065456A1 (de) * 2005-12-06 2007-06-14 HÄNSEL VERBUNDTECHNIK GmbH Textiles flächengebilde und verfahren zu seiner herstellung sowie deren verwendung
JP5439743B2 (ja) * 2007-10-11 2014-03-12 ユニマテック株式会社 撥水撥油剤
US7552604B1 (en) * 2008-04-09 2009-06-30 Milliken & Company Double needle bar elastomeric spacer knit
US10544502B2 (en) * 2009-11-30 2020-01-28 Xefco Pty Ltd Functional composite garment materials
ES2617214T3 (es) * 2011-04-25 2017-06-15 Teijin Frontier Co., Ltd. Tejidos y producto textil

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US20160194821A1 (en) 2016-07-07
ES2774260T3 (es) 2020-07-20
WO2015018449A1 (en) 2015-02-12
MX2016001611A (es) 2017-01-05
PL3030708T3 (pl) 2020-05-18
MX369708B (es) 2019-11-19
EP3030708A1 (de) 2016-06-15

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