EP1396572A1 - Process for producing a water-repellent aramide fabric and use thereof - Google Patents

Process for producing a water-repellent aramide fabric and use thereof Download PDF

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Publication number
EP1396572A1
EP1396572A1 EP20020020025 EP02020025A EP1396572A1 EP 1396572 A1 EP1396572 A1 EP 1396572A1 EP 20020020025 EP20020020025 EP 20020020025 EP 02020025 A EP02020025 A EP 02020025A EP 1396572 A1 EP1396572 A1 EP 1396572A1
Authority
EP
European Patent Office
Prior art keywords
water
repellent
fabric
aramid
yarn
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
EP20020020025
Other languages
German (de)
French (fr)
Other versions
EP1396572B8 (en
EP1396572B1 (en
Inventor
Christian Kurt Böttger
Rüdiger Hartert
Kurt Rainer Stolze
Jan Jager
Henk Ven Van De
Peter Gerard Akker
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.)
Teijin Aramid GmbH
Original Assignee
Teijin Twaron GmbH
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority to AT02020025T priority Critical patent/ATE325217T1/en
Priority to ES02020025T priority patent/ES2258582T3/en
Priority to SI200230356T priority patent/SI1396572T1/en
Priority to DK02020025T priority patent/DK1396572T3/en
Priority to DE50206665T priority patent/DE50206665D1/en
Priority to EP20020020025 priority patent/EP1396572B8/en
Application filed by Teijin Twaron GmbH filed Critical Teijin Twaron GmbH
Priority to JP2003310003A priority patent/JP4614306B2/en
Priority to US10/656,188 priority patent/US7132131B2/en
Publication of EP1396572A1 publication Critical patent/EP1396572A1/en
Application granted granted Critical
Publication of EP1396572B1 publication Critical patent/EP1396572B1/en
Publication of EP1396572B8 publication Critical patent/EP1396572B8/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Classifications

    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F41—WEAPONS
    • F41H—ARMOUR; ARMOURED TURRETS; ARMOURED OR ARMED VEHICLES; MEANS OF ATTACK OR DEFENCE, e.g. CAMOUFLAGE, IN GENERAL
    • F41H5/00—Armour; Armour plates
    • F41H5/02—Plate construction
    • F41H5/04—Plate construction composed of more than one layer
    • F41H5/0471—Layered armour containing fibre- or fabric-reinforced layers
    • F41H5/0485—Layered armour containing fibre- or fabric-reinforced layers all the layers being only fibre- or fabric-reinforced layers
    • A—HUMAN NECESSITIES
    • A41—WEARING APPAREL
    • A41D—OUTERWEAR; PROTECTIVE GARMENTS; ACCESSORIES
    • A41D31/00—Materials specially adapted for outerwear
    • A41D31/04—Materials specially adapted for outerwear characterised by special function or use
    • A41D31/24—Resistant to mechanical stress, e.g. pierce-proof
    • 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
    • D06M23/00—Treatment of fibres, threads, yarns, fabrics or fibrous goods made from such materials, characterised by the process
    • 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
    • D06M2101/36—Aromatic 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
    • D06M2200/12—Hydrophobic properties
    • 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.]
    • Y10T442/20—Coated or impregnated woven, knit, or nonwoven fabric which is not [a] associated with another preformed layer or fiber layer or, [b] with respect to woven and knit, characterized, respectively, by a particular or differential weave or knit, wherein the coating or impregnation is neither a foamed material nor a free metal or alloy layer
    • Y10T442/2164—Coating or impregnation specified as water repellent
    • 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.]
    • Y10T442/20—Coated or impregnated woven, knit, or nonwoven fabric which is not [a] associated with another preformed layer or fiber layer or, [b] with respect to woven and knit, characterized, respectively, by a particular or differential weave or knit, wherein the coating or impregnation is neither a foamed material nor a free metal or alloy layer
    • Y10T442/2861—Coated or impregnated synthetic organic fiber fabric
    • Y10T442/2893—Coated or impregnated polyamide fiber fabric
    • Y10T442/2902—Aromatic polyamide fiber fabric

Definitions

  • the present invention relates to a method for producing a water-repellent finished aramid fabric and its use.
  • WO 95/04854 describes a method for plasma treatment that is antiballistically more effective Materials such as of aramids, in a first stage a plasma treatment with ⁇ 50% of an inorganic gas or mixture of inorganic Gases and in a second stage a plasma treatment with a hydrophobizing acting organic gas or with mixtures of such gases from the group of saturated hydrocarbons, unsaturated hydrocarbons, saturated fluorocarbons, unsaturated fluorocarbons, siloxanes or vinyl compounds optionally carried out in the presence of one or more inorganic gases becomes.
  • US 4,232,087 discloses the coating of aramid fibers and / or aramid fabrics (e.g. of Nomex fibers) with an aqueous dispersion of polytetrafluoroethylene particles and a water-soluble chromium coordination complex with a fluorine-substituted one Hydrocarbon compound that substituted amine and sulfonylamine Contains alkyl groups with ⁇ 6 carbon atoms.
  • the treated tissue will dried. After the fabric has dried, crosslinking is preferred performed by heat treatment.
  • WO 92/01108 describes the coating of aramid fibers with an aqueous Fluoropolymer dispersion applied to the fiber either in the wet or in the dry State is applied, preferably the not yet dried fiber is immersed in a coating bath with the fluoropolymer dispersion. Subsequently the coated fiber is dried, the coating on the Fiber surface is networked.
  • US 5 116 682 describes the production of anti-wicking and water-repellent heat resistant yarns such as from polyester yarns or from yarns Glass, nylon or aramid.
  • the yarn is made with a fluorocarbon emulsion or - Dispersion coated, dried and then crosslinked under heat.
  • Aramid fabrics are known to have a high antiballistic effect in the dry Status.
  • the antiballistic effect wears off considerably when the tissue is in the wet state. Therefore, aramid fabrics are often water-repellent equipped.
  • it has been shown to be water repellent in a known manner finished aramid fabrics still clearly in their antiballistic Reduce the protective effect when they are wet.
  • the object of the present invention is a method for the production to provide a water-repellent aramid fabric, that has a good antiballistic effect even when wet.
  • the antiballistic effect of the method according to the invention water-repellent aramid fabric at least when dry just as high and possibly even higher than that of a water-repellent in a known manner finished aramid fabric in the dry state.
  • the present invention also has the task of a method for Manufacture of a water-repellent aramid fabric available to provide, the antiballistic effect is good even in the dry state.
  • the method according to the invention surprisingly provides water-repellent Equipped aramid fabric, whose antiballistic effect is higher when wet is than in a known way of water-resistant aramid fabric when wet.
  • the method according to the invention surprisingly provides water-repellent equipped aramid fabric, its antiballistic effect when dry at least as high and even higher in some embodiments is than in a known way of water-resistant aramid fabric when dry.
  • the aramid yarn can, for example by unwinding the yarn from a bobbin, after which the yarn can be moistened with an agent that the pulling up of the water-repellent
  • step b) of the method according to the invention is the aramid yarn submitted in the spinning process after leaving the wash bath, the yarn in damp state and the moisture essentially consists of water and - each according to the efficiency of the previous wash - from more or less low Shares in sulfuric acid.
  • This embodiment of the invention Process causes in comparison to the aramid yarn to be run through anyway - Spinning process only requires a small additional effort and is therefore preferred.
  • the term “aramid yarn” means a yarn whose fiber-forming substance is a long-chain synthetic polyamide, wherein at least 85% of the amide bonds are directly linked to two aromatic rings are. It is particularly preferred in step a) of the process according to the invention as Aramid yarn submitted a yarn made of poly-p-phenylene terephthalamide, in particular a yarn available under the name Twaron® from Teijin Twaron, whose titer preferably in the range from 200 to 5000 dtex, particularly preferably in the range from 550 to 3360 dtex and preferably from 100 to 3000 filaments, especially preferably consists of 500 to 2000 filaments.
  • the term “yarn” means a linear one textile structure from the fiber-forming substance as defined above, such as e.g. Staple yarn, twisted staple yarn, twisted filament yarn, untwisted intertwined Yarn (also known as interlaced yarn) and preferably untwisted Filament yarn.
  • any agent can be used that repels water and that on the aramid yarn can be applied, preferably using an agent, the fluorine and Includes carbon atoms.
  • step b) of the method according to the invention as water-repellent Agent used an agent that a fluoropolymer and very particularly preferred comprises a blend of fluoroacrylate polymers, e.g. OLEOPHOBOL.RTM SM® from Ciba Specialty Chemicals Pfersee GmbH, Langweid, DE.
  • OLEOPHOBOL.RTM SM® from Ciba Specialty Chemicals Pfersee GmbH, Langweid, DE.
  • the water repellent may also contain an antistatic such as e.g. Leomin AN® from CLARIANT GmbH, Division Textile Leather Products, BU Textile Chemicals, Frankfurt Main, DE.
  • an antistatic such as e.g. Leomin AN® from CLARIANT GmbH, Division Textile Leather Products, BU Textile Chemicals, Frankfurt Main, DE.
  • the water-repellent additionally a lubricant, being a lubricant Mixture of a 1,3-dihydroxyalkyl-5,5-dialkyl hydantoin and an ester Oleic acid and ethylene oxide and in particular a mixture of a 1,3-dihydroxyethyl-5,5-dimethyl - hydantoin and an ester of 1 mol oleic acid and 17 Mole of ethylene oxide is preferred because it increases the formation of static deposits Prevent thread guide organs.
  • a lubricant being a lubricant Mixture of a 1,3-dihydroxyalkyl-5,5-dialkyl hydantoin and an ester Oleic acid and ethylene oxide and in particular a mixture of a 1,3-dihydroxyethyl-5,5-dimethyl - hydantoin and an ester of 1 mol oleic acid and 17 Mole of ethylene oxide is preferred because it increases the formation of static deposits Prevent thread
  • water-repellent can - provided it meets the criteria mentioned above - be used as a pure substance.
  • the water-repellent Agents in the form of a solution or a dispersion or, preferably, an aqueous one to apply emulsion to the aramid yarn, the water repellent in the aqueous emulsion preferably in a concentration in the range from 20 to 300 g / l is included.
  • the method according to the invention is suitable for all methods with which the water-repellent agent is uniform in the chosen formulation can be distributed on the yarn surface.
  • you can use the wording apply the water repellent as a thin film on a roller and pass the aramid yarn through the film.
  • the application preferably takes place in step b) of the method according to the invention by passing the aramid yarn over a roller that is immersed in a bath, which contains the aqueous emulsion of the water repellent, the Emulsion preferably has a temperature in the range of 15 to 35 ° C.
  • the drying of the aramid yarn in step c) of the process according to the invention is carried out carried out in a temperature and time range sufficient for the in Step b) resulting aramid yarn is not glued during the subsequent winding.
  • the parameter ranges for temperature and time of drying are directed according to the requirements of the chosen application method in step b) of the invention Process. If you apply the water-repellent By means of the aramid yarn e.g. in the aramid yarn spinning process after the If the wash bath has left, the areas for temperature and time are aligned the drying according to the spinning speed and the structural conditions of the Spinning plant.
  • the aramid yarn resulting in step b) becomes at one temperature in the range of 130 to 210 ° C and during a drying time in the range dried from 5 to 15 seconds, a very good drying result is achieved, which is why these areas are preferred.
  • the aramid yarn resulting in step c) in step d) a fabric, preferably in plain weave, is produced, in particular a fabric with a thread density in the warp and weft in the range from 3 to 20 threads / cm.
  • step e) of the method according to the invention the resultant in step d) Tissue heat treated, preferably until the tissue absorbs water sinks.
  • the areas of time required for the heat treatment are aligned and temperature essentially after the water-repellent applied in step b) Medium.
  • a heat treatment temperature is in the range of 120 to 200 ° C and a heat treatment time of 30 to 120 seconds are sufficient.
  • OLEOPHOBOL SM® from Ciba Specialty Chemicals is used as a water repellent Pfersee GmbH, Langweid am Lech, DE.
  • OLEOPHOBOL SM® is one aqueous emulsion
  • the fluoroacrylate polymers and nonionic / cationic surfactants comprises, the proportion of fluoroacrylate polymers 19.5% by weight and the fluorine proportion 5.3% by weight.
  • the finishing agent to be applied to the aramid yarn 74 parts by weight of demineralized water are introduced.
  • the finish obtained in this way is applied to Twaron® yarn of type 2000 (930 dtex f1000) from Teijin Twaron integrated in the spinning process. That’s what it’s about Aramid yarn after leaving the wash bath at a rate of 325 m / min over a rotating roller that dips into a bath, in which the finish prepared as described above. Then it goes through with the finishing aramid yarn provided a drying zone, in which the yarn at a Temperature of 170 ° C is dried for 10 seconds. Then the yarn is wound up.
  • the aramid yarn is then woven into a fabric with a plain weave (9.4 threads / cm in warp and weft, 180 g / m 2 ) (fabric construction I).
  • the fabric is exposed to a temperature of 170 ° C for 90 seconds.
  • the fabric then contains 0.01 g of water repellent / g fabric.
  • An aramid fabric of fabric construction I made of Twaron® yarn of type 2000 (930 dtex f1000) by Teijin Twaron is padded with a finishing, for its production 40 parts by weight of demineralized water and 60 parts by weight of OLEOPHOBOL SM® were added.
  • the aramid fabric is passed through a bath that produces the one just described Avivage contains, and after leaving the bath with a pair of rollers squeezed so that the liquor intake is 35 percent by weight.
  • Anschlie ⁇ end we expose the fabric to a temperature of 170 ° C for 90 seconds.
  • the fabric then contains 0.042 g of water repellent / g fabric.
  • Example 2 is carried out as Example 1, with the difference that the Twaron® yarn type 2000 from Teijin Twaron (930 dtex f1000) is used and a fabric with plain weave (10.5 threads / cm in warp and weft, 200 g) / m 2 ) is produced (fabric construction II). The fabric then contains 0.01 g of water repellent / g fabric.
  • Example 2 As in Example 1, the Twaron® yarn from Example 2 is described there Avivage applied and the yarn at a temperature of 170 ° C for 10 seconds exposed. The yarn treated in this way then becomes a woven fabric fabric construction II, which contains 0.01 g of water repellent / g Contains tissue.
  • a fabric of fabric construction II made from the Twaron® yarns from Example 2 is padded with the finish described there in Comparative Example 1 a.
  • the Tissue is exposed to a temperature of 170 ° C for 90 seconds. After that the fabric contains 0.042 g of water repellent / g fabric.
  • OLEOPHOBOL SL® from Ciba Specialty Chemicals is used as a water repellent Pfersee GmbH, Langweid am Lech, DE.
  • OLEOPHOBOL SL® is one aqueous emulsion
  • the fluoroacrylate polymers and nonionic / cationic surfactants comprises, the proportion of fluoroacrylate polymers 20.0% by weight and the fluorine proportion 5.6% by weight.
  • the finishing agent to be applied to the aramid yarn 73.25 parts by weight of demineralized water are introduced.
  • the finish obtained in this way is based on Twaron® yarn of type 2000 (930 dtex f1000) from Teijin Twaron integrated in the spinning process. That’s what it’s about Aramid yarn after leaving the wash bath at a rate of 325 m / min over a rotating roller that dips into a bath, in which the aqueous finish prepared as described above. Then it goes through the finishing aramid yarn has a drying zone, in which the Drying the yarn at a temperature of 170 ° C for 10 seconds. Then it will be the yarn wound up.
  • the aramid yarn is then woven into a fabric with a plain weave (9.4 threads / cm in warp and weft, 180 g / m 2 ) (fabric construction I).
  • the fabric is exposed to a temperature of 170 ° C for 90 seconds.
  • the fabric then contains 0.01 g of water repellent / g fabric.
  • the antiballistic effect was determined by measuring the v 50 value of a tissue package consisting of 15 tissues (example 1 and comparative example 1a) or 14 tissues (example 2 and comparative examples 2a and 2b) using the test method STANAG 2920 (1.1 g splitter).
  • the v 50 value determined in this way denotes the projectile speed at which half of the projectiles are held by the fabric package and at which the other half of the projectiles completely penetrates the fabric package.
  • the tissue package was conditioned in the ISO 139 normal climate, ie for 24 h at 20 ⁇ 2 ° C and 65 ⁇ 2% relative humidity.
  • the water-repellent effect was additionally with the irrigation test measured according to Bundesmann (ISO 9865).
  • the water absorption determined with it after 10 minutes is marked with an * in the following table.

Abstract

A method for the production of waterproofed woven aramid fabric involves (a) making aramid yarn, (b) applying a waterproofing agent (WA) to the yarn, (c) drying the treated yarn, (d) making this into woven fabric and (e) subjecting the fabric to heat treatment. An Independent claim is also included for waterproof aramid woven fabric obtained by this method.

Description

Die vorliegende Erfindung betrifft ein Verfahren zur Herstellung eines wasserabweisend ausgerüsteten Aramidgewebes und dessen Verwendung.The present invention relates to a method for producing a water-repellent finished aramid fabric and its use.

Wasserabweisend ausgerüstete Aramidfasern und -gewebe und Verfahren zu deren Herstellung sind bekannt.Water-repellent aramid fibers and fabrics and process for their Manufacturing are known.

WO 95/04854 beschreibt ein Verfahren zur Plasmabehandlung antiballistisch wirksamer Materialien wie z.B. von Aramiden, wobei in einer ersten Stufe eine Plasmabehandlung mit ≥ 50 % eines anorganischen Gases oder Gemisches anorganischer Gase und in einer zweiten Stufe eine Plasmabehandlung mit einem hydrophobierend wirkenden organischen Gas oder mit Mischungen solcher Gase aus der Gruppe der gesättigten Kohlenwasserstoffe, ungesättigten Kohlenwasserstoffe, gesättigten Fluorkohlenwasserstoffe, ungesättigten Fluorkohlenwasserstoffe, Siloxane oder Vinylverbindungen ggf. in Gegenwart eines oder mehrerer anorganischer Gase durchgeführt wird.WO 95/04854 describes a method for plasma treatment that is antiballistically more effective Materials such as of aramids, in a first stage a plasma treatment with ≥ 50% of an inorganic gas or mixture of inorganic Gases and in a second stage a plasma treatment with a hydrophobizing acting organic gas or with mixtures of such gases from the group of saturated hydrocarbons, unsaturated hydrocarbons, saturated fluorocarbons, unsaturated fluorocarbons, siloxanes or vinyl compounds optionally carried out in the presence of one or more inorganic gases becomes.

US 4 232 087 offenbart die Beschichtung von Aramidfasern und/oder Aramidgeweben (z.B. von Nomexfasern) mit einer wässrigen Dispersion von Polytetrafluorethylen-Partikeln und einem wasserlöslichen Chrom-Koordinationskomplex mit einer fluorsubstituierten Kohlenwasserstoffverbindung, die amin- und sulfonylaminsubstituierte Alkylgruppen mit ≥ 6 Kohlenstoffatomen enthält. Das behandelte Gewebe wird getrocknet. Nach dem Trocknen des Gewebes wird vorzugsweise eine Vernetzung durch Wärmebehandlung durchgeführt.US 4,232,087 discloses the coating of aramid fibers and / or aramid fabrics (e.g. of Nomex fibers) with an aqueous dispersion of polytetrafluoroethylene particles and a water-soluble chromium coordination complex with a fluorine-substituted one Hydrocarbon compound that substituted amine and sulfonylamine Contains alkyl groups with ≥ 6 carbon atoms. The treated tissue will dried. After the fabric has dried, crosslinking is preferred performed by heat treatment.

WO 92/01108 beschreibt die Beschichtung von Aramidfasern mit einer wässrigen Fluorpolymerdispersion, welche auf die Faser entweder im nassen oder im getrockneten Zustand aufgebracht wird, wobei vorzugsweise die noch nicht getrocknete Faser in ein Beschichtungsbad mit der Fluorpolymerdispersion eingetaucht wird. Anschließend wird die beschichtete Faser getrocknet, wobei die Beschichtung auf der Faseroberfläche vernetzt wird.WO 92/01108 describes the coating of aramid fibers with an aqueous Fluoropolymer dispersion applied to the fiber either in the wet or in the dry State is applied, preferably the not yet dried fiber is immersed in a coating bath with the fluoropolymer dispersion. Subsequently the coated fiber is dried, the coating on the Fiber surface is networked.

US 5 116 682 beschreibt die Herstellung von anti-wicking und wasserabweisenden wärmebeständigen Garnen, wie z.B. von Polyestergarnen oder von Garnen aus Glas, Nylon oder Aramid. Das Garn wird mit einer Fluorcarbonemulsion oder - dispersion beschichtet, getrocknet und anschließend unter Wärme vernetzt.US 5 116 682 describes the production of anti-wicking and water-repellent heat resistant yarns such as from polyester yarns or from yarns Glass, nylon or aramid. The yarn is made with a fluorocarbon emulsion or - Dispersion coated, dried and then crosslinked under heat.

Aramid-Gewebe zeigen bekanntlich eine hohe antiballistische Wirkung im trockenen Zustand. Jedoch lässt die antiballistische Wirkung erheblich nach, wenn das Gewebe im nassen Zustand vorliegt. Daher werden Aramidgewebe oftmals wasserabweisend ausgerüstet. Jedoch hat es sich gezeigt, dass die in bekannter Weise wasserabweisend ausgerüsteten Aramidgewebe immer noch deutlich in ihrer antiballistischen Schutzwirkung nachlassen, wenn sie im nassen Zustand vorliegen.Aramid fabrics are known to have a high antiballistic effect in the dry Status. However, the antiballistic effect wears off considerably when the tissue is in the wet state. Therefore, aramid fabrics are often water-repellent equipped. However, it has been shown to be water repellent in a known manner finished aramid fabrics still clearly in their antiballistic Reduce the protective effect when they are wet.

Daher stellt sich die vorliegende Erfindung die Aufgabe, ein Verfahren zur Herstellung eines wasserabweisend ausgerüsteten Aramidgewebes zur Verfügung zu stellen, das auch im nassen Zustand eine gute antiballistische Wirkung aufweist.Therefore, the object of the present invention is a method for the production to provide a water-repellent aramid fabric, that has a good antiballistic effect even when wet.

Ferner sollte die antiballistische Wirkung des mit dem erfindungsgemäßen Verfahren wasserabweisend ausgerüsteten Aramidgewebes im trockenen Zustand mindestens ebenso hoch und möglichst noch höher sein als die eines in bekannter Weise wasserabweisend ausgerüsteten Aramidgewebes im trockenen Zustand. Furthermore, the antiballistic effect of the method according to the invention water-repellent aramid fabric at least when dry just as high and possibly even higher than that of a water-repellent in a known manner finished aramid fabric in the dry state.

Daher stellt sich die vorliegende Erfindung ferner die Aufgabe, ein Verfahren zur Herstellung eines wasserabweisend ausgerüsteten Aramidgewebes zur Verfügung zu stellen, dessen antiballistische Wirkung auch im trockenen Zustand gut ist.Therefore, the present invention also has the task of a method for Manufacture of a water-repellent aramid fabric available to provide, the antiballistic effect is good even in the dry state.

Diese Aufgaben werden gelöst durch ein Verfahren zur Herstellung eines wasserabweisend ausgerüsteten Aramidgewebes umfassend die Schritte

  • a) Vorlegen eines Aramidgarns,
  • b) Applizieren eines wasserabweisenden Mittels auf das Aramidgarn,
  • c) Trocknen des in Schritt b) resultierenden Aramidgarns,
  • d) Herstellen eines Gewebes aus dem in Schritt c) resultierenden Aramidgarn und
  • e) Wärmebehandlung des Gewebes.
    • These tasks are solved by a method for producing a water-repellent aramid fabric comprising the steps
  • a) presenting an aramid yarn,
  • b) applying a water-repellent agent to the aramid yarn,
  • c) drying the aramid yarn resulting in step b),
  • d) producing a fabric from the aramid yarn resulting in step c) and
  • e) heat treatment of the fabric.

    • Das erfindungsgemäße Verfahren liefert überraschenderweise wasserabweisend ausgerüstete Aramidgewebe, deren antiballistische Wirkung im nassen Zustand höher ist als bei einem in bekannter Weise wasserabweisend ausgerüsteten Aramidgewebe im nassen Zustand.The method according to the invention surprisingly provides water-repellent Equipped aramid fabric, whose antiballistic effect is higher when wet is than in a known way of water-resistant aramid fabric when wet.

    Ferner liefert das erfindungsgemäße Verfahren überraschenderweise wasserabweisend ausgerüstete Aramidgewebe, deren antiballistische Wirkung im trockenen Zustand mindestens ebenso hoch und in einigen Ausführungsformen sogar noch höher ist als bei einem in bekannter Weise wasserabweisend ausgerüsteten Aramidgewebe im trockenen Zustand.Furthermore, the method according to the invention surprisingly provides water-repellent equipped aramid fabric, its antiballistic effect when dry at least as high and even higher in some embodiments is than in a known way of water-resistant aramid fabric when dry.

    In Schritt a) des erfindungsgemäßen Verfahrens kann das Aramidgarn beispielsweise durch Abwickeln des Garns von einer Spule vorgelegt werden, wonach das Garn mit einem Mittel befeuchtet werden kann, welches das Aufziehen des wasserabweisenden Mittels in Schritt b) des erfindungsgemäßen Verfahrens erleichtert. In einer anderen Ausführungsform des erfindungsgemäßen Verfahrens wird das Aramidgarn im Spinnprozess nach Verlassen des Waschbades vorgelegt, wobei das Garn im feuchten Zustand vorliegt und die Feuchte im Wesentlichen aus Wasser und - je nach der Effizienz der vorangegangen Wäsche - aus mehr oder weniger geringen Anteilen an Schwefelsäure besteht. Diese Ausführungsform des erfindungsgemäßen Verfahrens verursacht im Vergleich zum ohnehin zu durchlaufenden Aramidgarn - Spinnverfahren nur einen geringfügigen Mehraufwand und ist daher bevorzugt.In step a) of the method according to the invention, the aramid yarn can, for example by unwinding the yarn from a bobbin, after which the yarn can be moistened with an agent that the pulling up of the water-repellent By means of step b) of the method according to the invention. In a Another embodiment of the method according to the invention is the aramid yarn submitted in the spinning process after leaving the wash bath, the yarn in damp state and the moisture essentially consists of water and - each according to the efficiency of the previous wash - from more or less low Shares in sulfuric acid. This embodiment of the invention Process causes in comparison to the aramid yarn to be run through anyway - Spinning process only requires a small additional effort and is therefore preferred.

    Im Rahmen der vorliegenden Erfindung bedeutet der Begriff "Aramidgarn" ein Garn, dessen faserbildende Substanz ein langkettiges synthetisches Polyamid ist, worin mindestens 85 % der Amidbindungen direkt an zwei aromatische Ringe geknüpft sind. Besonders bevorzugt wird in Schritt a) des erfindungsgemäßen Verfahrens als Aramidgarn ein Garn aus Poly-p-phenylenterephthalamid vorgelegt, insbesondere ein unter der Bezeichnung Twaron® von Teijin Twaron erhältliches Garn, dessen Titer vorzugsweise im Bereich von 200 bis 5000 dtex, besonders bevorzugt im Bereich von 550 bis 3360 dtex liegt und das vorzugsweise aus 100 bis 3000 Filamenten, besonders bevorzugt aus 500 bis 2000 Filamenten besteht.In the context of the present invention, the term “aramid yarn” means a yarn whose fiber-forming substance is a long-chain synthetic polyamide, wherein at least 85% of the amide bonds are directly linked to two aromatic rings are. It is particularly preferred in step a) of the process according to the invention as Aramid yarn submitted a yarn made of poly-p-phenylene terephthalamide, in particular a yarn available under the name Twaron® from Teijin Twaron, whose titer preferably in the range from 200 to 5000 dtex, particularly preferably in the range from 550 to 3360 dtex and preferably from 100 to 3000 filaments, especially preferably consists of 500 to 2000 filaments.

    Der Begriff "Garn" bedeutet im Rahmen der vorliegenden Erfindung ein linienförmiges textiles Gebilde aus der wie vorstehend definierten faserbildenden Substanz, wie z.B. Stapelgarn, gezwirntes Stapelgarn, gezwirntes Filamentgarn, ungezwirntes verschlungenes Garn (auch als interlaced Garn bekannt) und vorzugsweise ungezwirntes Filamentgarn.In the context of the present invention, the term “yarn” means a linear one textile structure from the fiber-forming substance as defined above, such as e.g. Staple yarn, twisted staple yarn, twisted filament yarn, untwisted intertwined Yarn (also known as interlaced yarn) and preferably untwisted Filament yarn.

    Als wasserabweisendes Mittel ist in Schritt b) des erfindungsgemäßen Verfahrens im Prinzip jedes Mittel einsetzbar, das Wasser abweist und das auf das Aramidgarn aufgebracht werden kann, wobei vorzugsweise ein Mittel eingesetzt wird, das Fluorund Kohlenstoffatome umfaßt.As a water-repellent in step b) of the process according to the invention Principle any agent can be used that repels water and that on the aramid yarn can be applied, preferably using an agent, the fluorine and Includes carbon atoms.

    Insbesondere wird in Schritt b) des erfindungsgemäßen Verfahrens als wasserabweisendes Mittel ein Mittel eingesetzt, das ein Fluorpolymer und ganz besonders bevorzugt ein Gemisch aus Fluoracrylatpolymeren umfaßt, wie z.B. OLEOPHOBOL SM® von Ciba Spezialitätenchemie Pfersee GmbH, Langweid, DE. In particular, in step b) of the method according to the invention as water-repellent Agent used an agent that a fluoropolymer and very particularly preferred comprises a blend of fluoroacrylate polymers, e.g. OLEOPHOBOL.RTM SM® from Ciba Specialty Chemicals Pfersee GmbH, Langweid, DE.

    Ferner kann das wasserabweisende Mittel ein Antistatikum enthalten, wie z.B. Leomin AN® von CLARIANT GmbH, Division Textile Leather Products, BU Textile Chemicals, Frankfurt Main, DE.The water repellent may also contain an antistatic such as e.g. Leomin AN® from CLARIANT GmbH, Division Textile Leather Products, BU Textile Chemicals, Frankfurt Main, DE.

    In einer weiteren Ausführungsform des erfindungsgemäßen Verfahrens enthält das wasserabweisende Mittel zusätzlich ein Schmiermittel, wobei als Schmiermittel ein Gemisch aus einem 1,3-Dihydroxyalkyl-5,5-Dialkyl - Hydantoin und einem Ester aus Ölsäure und Ethylenoxid und insbesondere ein Gemisch aus einem 1,3-Dihydroxyethyl-5,5-Dimethyl - Hydantoin und einem Ester aus 1 Mol Ölsäure und 17 Mol Ethylenoxid bevorzugt ist, weil sich damit die Bildung von Ablagerungen an statischen Fadenführungsorganen verhindern läßt. Ein derartiges Gemisch ist unter der Bezeichnung Hymo 90 von Goulston Technologies, Inc, Monroe, NC, USA erhältlich.In a further embodiment of the method according to the invention, the water-repellent additionally a lubricant, being a lubricant Mixture of a 1,3-dihydroxyalkyl-5,5-dialkyl hydantoin and an ester Oleic acid and ethylene oxide and in particular a mixture of a 1,3-dihydroxyethyl-5,5-dimethyl - hydantoin and an ester of 1 mol oleic acid and 17 Mole of ethylene oxide is preferred because it increases the formation of static deposits Prevent thread guide organs. Such a mixture is under the Designation Hymo 90 available from Goulston Technologies, Inc, Monroe, NC, USA.

    Das in Schritt b) des erfindungsgemäßen Verfahrens auf das Aramidgarn applizierte wasserabweisende Mittel kann - sofern es die vorstehend genannten Kriterien erfüllt - als Reinsubstanz eingesetzt werden. Jedoch ist es wegen der einfacheren Dosierbarkeit einer gewünschten Menge an wasserabweisendem Mittel auf dem Garn vorteilhaft, in Schritt b) des erfindungsgemäßen Verfahrens das wasserabweisende Mittel in Form einer Lösung oder einer Dispersion oder vorzugsweise einer wässrigen Emulsion auf das Aramidgarn zu applizieren, wobei das wasserabweisende Mittel in der wässrigen Emulsion vorzugsweise in einer Konzentration im Bereich von 20 bis 300 g/l enthalten ist.The one applied to the aramid yarn in step b) of the method according to the invention water-repellent can - provided it meets the criteria mentioned above - be used as a pure substance. However, it is because of the easier dosing a desired amount of water repellent on the yarn is advantageous, in step b) of the method according to the invention the water-repellent Agents in the form of a solution or a dispersion or, preferably, an aqueous one To apply emulsion to the aramid yarn, the water repellent in the aqueous emulsion preferably in a concentration in the range from 20 to 300 g / l is included.

    Zum Applizieren des wasserabweisenden Mittels auf das Aramidgarn in Schritt b) des erfindungsgemäßen Verfahrens sind im Prinzip alle Verfahren geeignet, mit denen sich das wasserabweisende Mittel in der jeweils gewählten Formulierung gleichmäßig auf der Garnoberfläche verteilen läßt. Beispielsweise kann man die Formulierung des wasserabweisenden Mittels als dünnen Film auf eine Walze auftragen und das Aramidgarn durch den Film führen. Ferner kann man die Formulierung des wasserabweisenden Mittels auf das Aramidgarn sprühen. Auch kann man die Formulierung des wasserabweisenden Mittels mit einer Pumpe und mit einem Stift-, Schlitzoder Block-Applikator auf das Garn applizieren.To apply the water repellent to the aramid yarn in step b) In principle, the method according to the invention is suitable for all methods with which the water-repellent agent is uniform in the chosen formulation can be distributed on the yarn surface. For example, you can use the wording apply the water repellent as a thin film on a roller and pass the aramid yarn through the film. You can also use the water repellent formulation Spray on the aramid yarn. You can also use the wording of the water repellent with a pump and with a pin, slot or Apply the block applicator to the yarn.

    Vorzugsweise geschieht in Schritt b) des erfindungsgemäßen Verfahrens das Applizieren durch Führen des Aramidgarns über eine Walze, die in ein Bad eintaucht, welches die wässrige Emulsion des wasserabweisenden Mittels enthält, wobei die Emulsion vorzugsweise eine Temperatur im Bereich von 15 bis 35°C hat.The application preferably takes place in step b) of the method according to the invention by passing the aramid yarn over a roller that is immersed in a bath, which contains the aqueous emulsion of the water repellent, the Emulsion preferably has a temperature in the range of 15 to 35 ° C.

    Das Trocknen des Aramidgarns in Schritt c) des erfindungsgemäßen Verfahrens wird in einem Temperatur- und Zeitbereich durchgeführt, der ausreicht, damit das in Schritt b) resultierende Aramidgarn beim anschließenden Aufwickeln nicht verklebt. Zusätzlich richten sich die Parameterbereiche für Temperatur und Zeit der Trocknung nach den Erfordernissen des gewählten Applikationsverfahrens in Schritt b) des erfindungsgemäßen Verfahrens. Führt man das Applizieren des wasserabweisenden Mittels auf das Aramidgarn z.B. im Aramidgarn - Spinnprozess durch, nachdem das Garn das Waschbad verlassen hat, richten sich die Bereiche für Temperatur und Zeit der Trockung nach der Spinngeschwindigkeit und den baulichen Gegebenheiten der Spinnanlage. Wird dabei das in Schritt b) resultierende Aramidgarn bei einer Temperatur im Bereich von 130 bis 210 °C und während einer Trocknungszeit im Bereich von 5 bis 15 Sekunden getrocknet, wird ein sehr gutes Trocknungsergebnis erzielt, weshalb besagte Bereiche bevorzugt sind.The drying of the aramid yarn in step c) of the process according to the invention is carried out carried out in a temperature and time range sufficient for the in Step b) resulting aramid yarn is not glued during the subsequent winding. In addition, the parameter ranges for temperature and time of drying are directed according to the requirements of the chosen application method in step b) of the invention Process. If you apply the water-repellent By means of the aramid yarn e.g. in the aramid yarn spinning process after the If the wash bath has left, the areas for temperature and time are aligned the drying according to the spinning speed and the structural conditions of the Spinning plant. The aramid yarn resulting in step b) becomes at one temperature in the range of 130 to 210 ° C and during a drying time in the range dried from 5 to 15 seconds, a very good drying result is achieved, which is why these areas are preferred.

    Im erfindungsgemäßen Verfahren wird aus dem in Schritt c) resultierenden Aramidgarn in Schritt d) ein Gewebe, vorzugsweise in Leinwandbindung, hergestellt, insbesondere ein Gewebe mit einer Fadendichte in Kette und Schuß im Bereich von 3 bis 20 Fäden/cm.In the process according to the invention, the aramid yarn resulting in step c) in step d) a fabric, preferably in plain weave, is produced, in particular a fabric with a thread density in the warp and weft in the range from 3 to 20 threads / cm.

    In Schritt e) des erfindungsgemäßen Verfahrens wird das in Schritt d) resultierende Gewebe wärmebehandelt, vorzugsweise bis die Wasseraufnahme des Gewebes sinkt. Dabei richten sich die für die Wärmebehandlung benötigten Bereiche von Zeit und Temperatur im wesentlichen nach dem in Schritt b) applizierten wasserabweisenden Mittel. In vielen Fällen ist eine Wärmebehandlungstemperatur im Bereich von 120 bis 200 °C und eine Wäremebehandlungszeit von 30 bis 120 Sekunden ausreichend.In step e) of the method according to the invention, the resultant in step d) Tissue heat treated, preferably until the tissue absorbs water sinks. The areas of time required for the heat treatment are aligned and temperature essentially after the water-repellent applied in step b) Medium. In many cases, a heat treatment temperature is in the range of 120 to 200 ° C and a heat treatment time of 30 to 120 seconds are sufficient.

    Bei einem Anteil des wasserabweisenden Mittels von 0,001 bis 0,02 g an wasserabweisenden Mittel / g Gewebe und insbesondere von 0,006 bis 0,015 g an wasserabweisenden Mittel / g Gewebe nach Schritt e) des erfindungsgemäßen Verfahrens resultiert eine besonders hohe wasserabweisende Wirkung gepaart mit hoher antiballistischer Wirkung im trockenen und im nassen Zustand.With a proportion of water-repellent from 0.001 to 0.02 g of water-repellent Medium / g fabric and in particular from 0.006 to 0.015 g of water-repellent Average / g tissue after step e) of the method according to the invention results in a particularly high water-repellent effect combined with a high antiballistic Effect in dry and wet condition.

    Die der Erfindung zugrunde liegenden Aufgaben werden ferner gelöst durch ein gemäß dem erfindungsgemäßen Verfahren wasserabweisend ausgerüstetes Aramidgewebe, das sich - wie die folgenden Beispiele zeigen - vorteilhaft zur Herstellung von antiballistisch wirksamen Artikeln, wie z.B. von Schutzwesten und Helmen verwenden lässt.The objects underlying the invention are further achieved by an according aramid fabric made water-repellent by the method according to the invention, which - as the following examples show - is advantageous for production of antiballistically effective articles, e.g. of protective vests and helmets leaves.

    Beispiel 1example 1

    Als wasserabweisendes Mittel wird OLEOPHOBOL SM® von Ciba Spezialitätenchemie Pfersee GmbH, Langweid am Lech, DE, eingesetzt. OLEOPHOBOL SM® ist eine wässrige Emulsion, die Fluoracrylatpolymere und nichtionische/kationische Tenside umfaßt, wobei der Anteil an Fluoracrylatpolymeren 19,5 Gew.% und der Fluor-Anteil 5,3 Gew.% beträgt. Zur Herstellung der auf das Aramidgarn zu applizierenden Avivage werden 74 Gewichtsteile demineralisiertes Wasser vorgelegt. Dazu werden 25,5 Gewichtsteile OLEOPHOBOL SM® und 0,25 Gewichtsteile Leomin AN® von CLARIANT GmbH, Division Textile Leather Products, BU Textile Chemicals, Frankfurt Main, DE, hinzugefügt, so dass die Avivage 5,0 Gew.% an Fluoracrylatpolymeren enthält. OLEOPHOBOL SM® from Ciba Specialty Chemicals is used as a water repellent Pfersee GmbH, Langweid am Lech, DE. OLEOPHOBOL SM® is one aqueous emulsion, the fluoroacrylate polymers and nonionic / cationic surfactants comprises, the proportion of fluoroacrylate polymers 19.5% by weight and the fluorine proportion 5.3% by weight. For the production of the finishing agent to be applied to the aramid yarn 74 parts by weight of demineralized water are introduced. To do this 25.5 parts by weight of OLEOPHOBOL SM® and 0.25 parts by weight of Leomin AN® from CLARIANT GmbH, Textile Leather Products division, BU Textile Chemicals, Frankfurt Main, DE, added, so that the finish 5.0% by weight of fluoroacrylate polymers contains.

    Die in solcher Weise erhaltene Avivage wird auf Twaron® -Garn der Type 2000 (930 dtex f1000) von Teijin Twaron integriert im Spinnprozess appliziert. Dazu läuft das Aramidgarn nach dem Verlassen des Waschbades mit einer Geschwindigkeit von 325 m/min über eine sich drehende Walze, die in ein Bad eintaucht, worin sich die wie vorstehend beschrieben hergestellte Avivage befindet. Danach durchläuft das mit der Avivage versehene Aramidgarn eine Trocknungszone, worin das Garn bei einer Temperatur von 170 °C 10 Sekunden lang getrocknet wird. Dann wird das Garn aufgewickelt.The finish obtained in this way is applied to Twaron® yarn of type 2000 (930 dtex f1000) from Teijin Twaron integrated in the spinning process. That’s what it’s about Aramid yarn after leaving the wash bath at a rate of 325 m / min over a rotating roller that dips into a bath, in which the finish prepared as described above. Then it goes through with the finishing aramid yarn provided a drying zone, in which the yarn at a Temperature of 170 ° C is dried for 10 seconds. Then the yarn is wound up.

    Anschließend wird das Aramidgarn zu einem Gewebe mit Leinwandbindung (9,4 Fäden/cm in Kette und Schuss, 180 g/m2) verwebt (Gewebekonstruktion I).The aramid yarn is then woven into a fabric with a plain weave (9.4 threads / cm in warp and weft, 180 g / m 2 ) (fabric construction I).

    Schließlich wird das Gewebe 90 Sekunden lang einer Temperatur von 170 °C ausgesetzt. Danach enthält das Gewebe 0,01 g an wasserabweisendem Mittel / g Gewebe.Finally, the fabric is exposed to a temperature of 170 ° C for 90 seconds. The fabric then contains 0.01 g of water repellent / g fabric.

    Vergleichsbeispiel 1aComparative Example 1a

    Ein Aramidgewebe der Gewebekonstruktion I aus Twaron®-Garn der Type 2000 (930 dtex f1000) von Teijin Twaron wird mit einer Avivage foulardiert, zu deren Herstellung 40 Gewichtsteile demineralisiertes Wasser vorgelegt und 60 Gewichtsteile OLEOPHOBOL SM® hinzugefügt wurden.An aramid fabric of fabric construction I made of Twaron® yarn of type 2000 (930 dtex f1000) by Teijin Twaron is padded with a finishing, for its production 40 parts by weight of demineralized water and 60 parts by weight of OLEOPHOBOL SM® were added.

    Das Aramidgewebe wird durch ein Bad geführt, das die wie eben beschreiben hergestellte Avivage enthält, und nach dem Verlassen des Bades mit einem Walzenpaar so abgequetscht, dass die Flottenaufnahme 35 Gewichtsprozent beträgt. Anschlieβend wir das Gewebe 90 Sekunden lang einer Temperatur von 170 °C ausgesetzt. Danach enthält das Gewebe 0,042 g an wasserabweisendem Mittel / g Gewebe. The aramid fabric is passed through a bath that produces the one just described Avivage contains, and after leaving the bath with a pair of rollers squeezed so that the liquor intake is 35 percent by weight. Anschlieβend we expose the fabric to a temperature of 170 ° C for 90 seconds. The fabric then contains 0.042 g of water repellent / g fabric.

    Beispiel 2Example 2

    Beispiel 2 wird wie Beispiel 1 ausgeführt mit dem Unterschied, dass als Garn Twaron® -Garn der Type 2000 von Teijin Twaron (930 dtex f1000) eingesetzt wird und ein Gewebe mit Leinwandbindung (10,5 Fäden/cm in Kette und Schuss, 200 g/m2) hergestellt wird (Gewebekonstruktion II). Danach enthält das Gewebe 0,01 g an wasserabweisendem Mittel / g Gewebe.Example 2 is carried out as Example 1, with the difference that the Twaron® yarn type 2000 from Teijin Twaron (930 dtex f1000) is used and a fabric with plain weave (10.5 threads / cm in warp and weft, 200 g) / m 2 ) is produced (fabric construction II). The fabric then contains 0.01 g of water repellent / g fabric.

    Vergleichsbeispiel 2aComparative Example 2a

    Auf das Twaron®-Garn von Beispiel 2 wird wie in Beispiel 1 die dort beschriebene Avivage appliziert und das Garn 10 Sekunden lang einer Temperatur von 170 °C ausgesetzt. Danach wird aus dem in solcher Weise behandelten Garn ein Gewebe der Gewebekonstruktion II hergestellt, das 0,01 g an wasserabweisendem Mittel / g Gewebe enthält.As in Example 1, the Twaron® yarn from Example 2 is described there Avivage applied and the yarn at a temperature of 170 ° C for 10 seconds exposed. The yarn treated in this way then becomes a woven fabric fabric construction II, which contains 0.01 g of water repellent / g Contains tissue.

    Vergleichsbeispiel 2bComparative Example 2b

    Ein Gewebe der Gewebekonstruktion II aus den Twaron® -Garnen von Beispiel 2 wird wie im Vergleichsbeispiel 1 a mit der dort beschriebenen Avivage foulardiert. Das Gewebe wird 90 Sekunden lang einer Temperatur von 170 °C ausgesetzt. Danach enthält das Gewebe 0,042 g an wasserabweisendem Mittel / g Gewebe.A fabric of fabric construction II made from the Twaron® yarns from Example 2 is padded with the finish described there in Comparative Example 1 a. The Tissue is exposed to a temperature of 170 ° C for 90 seconds. After that the fabric contains 0.042 g of water repellent / g fabric.

    Beispiel 3Example 3

    Als wasserabweisendes Mittel wird OLEOPHOBOL SL® von Ciba Spezialitätenchemie Pfersee GmbH, Langweid am Lech, DE, eingesetzt. OLEOPHOBOL SL® ist eine wässrige Emulsion, die Fluoracrylatpolymere und nichtionische/kationische Tenside umfaßt, wobei der Anteil an Fluoracrylatpolymeren 20,0 Gew.% und der Fluor-Anteil 5,6 Gew.% beträgt. Zur Herstellung der auf das Aramidgarn zu applizierenden Avivage werden 73,25 Gewichtsteile demineralisiertes Wasser vorgelegt. Dazu werden 25 Gewichtsteile OLEOPHOBOL SL® , 0,25 Gewichtsteile Leomin AN® von CLARIANT GmbH, Division Textile Leather Products, BU Textile Chemicals, Frankfurt Main, DE, und 2,5 Gewichtsteile Hymo 90 von Goulston Technologies, Inc, Monroe, NC, USA hinzugefügt, so dass die Avivage 5,0 Gew.% an Fluoracrylatpolymeren enthält.OLEOPHOBOL SL® from Ciba Specialty Chemicals is used as a water repellent Pfersee GmbH, Langweid am Lech, DE. OLEOPHOBOL SL® is one aqueous emulsion, the fluoroacrylate polymers and nonionic / cationic surfactants comprises, the proportion of fluoroacrylate polymers 20.0% by weight and the fluorine proportion 5.6% by weight. For the production of the finishing agent to be applied to the aramid yarn 73.25 parts by weight of demineralized water are introduced. To do this 25 parts by weight of OLEOPHOBOL SL®, 0.25 parts by weight of Leomin AN® from CLARIANT GmbH, Textile Leather Products Division, BU Textile Chemicals, Frankfurt Main, DE, and 2.5 parts by weight Hymo 90 from Goulston Technologies, Inc, Monroe, NC, USA added so that the finish contains 5.0% by weight of fluoroacrylate polymers.

    Die in solcher Weise erhaltene Avivage wird auf Twaron®-Garn der Type 2000 (930 dtex f1000) von Teijin Twaron integriert im Spinnprozess appliziert. Dazu läuft das Aramidgarn nach dem Verlassen des Waschbades mit einer Geschwindigkeit von 325 m/min über eine sich drehende Walze, die in ein Bad eintaucht, worin sich die wie vorstehend beschrieben hergestellte wässrige Avivage befindet. Danach durchläuft das mit der Avivage versehene Aramidgarn eine Trocknungszone, worin das Garn bei einer Temperatur von 170 °C 10 Sekunden lang getrocknet wird. Dann wird das Garn aufgewickelt.The finish obtained in this way is based on Twaron® yarn of type 2000 (930 dtex f1000) from Teijin Twaron integrated in the spinning process. That’s what it’s about Aramid yarn after leaving the wash bath at a rate of 325 m / min over a rotating roller that dips into a bath, in which the aqueous finish prepared as described above. Then it goes through the finishing aramid yarn has a drying zone, in which the Drying the yarn at a temperature of 170 ° C for 10 seconds. Then it will be the yarn wound up.

    Anschließend wird das Aramidgarn zu einem Gewebe mit Leinwandbindung (9,4 Fäden/cm in Kette und Schuss, 180 g/m2) verwebt (Gewebekonstruktion I).The aramid yarn is then woven into a fabric with a plain weave (9.4 threads / cm in warp and weft, 180 g / m 2 ) (fabric construction I).

    Schließlich wird das Gewebe 90 Sekunden lang einer Temperatur von 170 °C ausgesetzt. Danach enthält das Gewebe 0,01 g an wasserabweisendem Mittel / g Gewebe. Finally, the fabric is exposed to a temperature of 170 ° C for 90 seconds. The fabric then contains 0.01 g of water repellent / g fabric.

    Testverfahrentest method Antiballistische WirkungAntiballistic effect

    Die antiballistische Wirkung wurde durch Messung des v50-Wertes eines Gewebepakets aus 15 Geweben (Beispiel 1 und Vergleichsbeispiel 1a) bzw. 14 Geweben (Beispiel 2 und Vergleichsbeispiele 2a und 2b) mit der Testmethode STANAG 2920 (1,1 g Splitter) bestimmt. Der damit ermittelte v50-Wert bezeichnet die Geschossgeschwindigkeit, bei welcher die Hälfte der Geschosse durch das Gewebepaket gehalten wird, und bei der die andere Hälfte der Geschosse das Gewebepaket vollständig durchschlägt.The antiballistic effect was determined by measuring the v 50 value of a tissue package consisting of 15 tissues (example 1 and comparative example 1a) or 14 tissues (example 2 and comparative examples 2a and 2b) using the test method STANAG 2920 (1.1 g splitter). The v 50 value determined in this way denotes the projectile speed at which half of the projectiles are held by the fabric package and at which the other half of the projectiles completely penetrates the fabric package.

    Vor der Messung von v50 im trockenen Zustand wurde das Gewebepaket im ISO 139 Normalklima, d.h. 24 h lang bei 20 ± 2 °C und 65 ± 2 % relativer Feuchte konditioniert.Before the measurement of v 50 in the dry state, the tissue package was conditioned in the ISO 139 normal climate, ie for 24 h at 20 ± 2 ° C and 65 ± 2% relative humidity.

    Vor der Messung von v50 im nassen Zustand wurde das Gewebepaket 1 h lang in Wasser getaucht und 3 Minuten abtropfen gelassen.Before the measurement of v 50 when wet, the tissue package was immersed in water for 1 hour and drained for 3 minutes.

    Wasserabweisende WirkungWater repellent effect

    Die wasserabweisende Wirkung wird durch Messung der Wasseraufnahme eines Gewebepakets aus 15 Geweben (Beispiel 1 und Vergleichsbeispiel 1a) bzw. 14 Geweben (Beispiel 2 und Vergleichsbeispiele 2a und 2b) gemessen. Dazu wird das trockene Gewebepaket gewogen (= w1), 1 h lang in Wasser getaucht, 3 Minuten abtropfen gelassen, nochmals gewogen (= w2) und die prozentuale Wasseraufnahme W gemäß W = [(w2/w1)-1] · 100 [%] berechnet. The water-repellent effect is measured by measuring the water absorption of a tissue package comprising 15 tissues (example 1 and comparative example 1a) or 14 tissues (example 2 and comparative examples 2a and 2b). For this purpose, the dry tissue package is weighed (= w 1 ), immersed in water for 1 h, drained for 3 minutes, weighed again (= w 2 ) and the percentage water absorption W according to W = [(w 2 / w 1 ) -1] · 100 [%] calculated.

    In Beispiel 3 wurde die wasserabweisende Wirkung zusätzlich mit der Beregnungsprüfung nach Bundesmann (ISO 9865) gemessen. Die damit bestimmte Wasseraufnahme nach 10 Minuten ist in der folgenden Tabelle mit einem * gekennzeichnet.In example 3, the water-repellent effect was additionally with the irrigation test measured according to Bundesmann (ISO 9865). The water absorption determined with it after 10 minutes is marked with an * in the following table.

    Die antiballistische und die wasserabweisende Wirkung der erfindungsgemäß wasserabweisend ausgerüsteten Gewebe (Beispiele 1 und 2) und der nicht erfindungsgemäß wasserabweisend ausgerüsteten Gewebe (Vergleichsbeispiele 1 a, 2a und 2b) sind in der folgenden Tabelle zusammengefasst.The antiballistic and the water-repellent effect of the water-repellent according to the invention finished fabrics (Examples 1 and 2) and not according to the invention water-repellent fabric (comparative examples 1 a, 2a and 2b) are summarized in the following table.

    Die Tabelle zeigt, das bei erfindungsgemäßer wasserabweisender Ausrüstung des Gewebes die v50-Werte

    • im nassen Zustand in jedem Fall höher und
    • im trockenen Zustand zumindest gleich hoch oder höher
    sind als bei nicht erfindungsgemäßer wasserabweisender Ausrüstung des Gewebes. Beispiel Gewebekonstruktion Aufbringen des wasserabweisenden Mittels v50 trocken m/s v50 naß m/s W % 1 I Garnbeschichtung Garntrocknung Herstellung des Gewebes Wärmebehandlung des Gewebes 500 477 21 1a I Gewebebeschichtung Wärmebehandlung des Gewebes 480 467 26,6 2 II Garnbeschichtung Garntrocknung Herstellung des Gewebes Wärmebehandlung des Gewebes 480 458 21 2a II Garnbeschichtung Garntrocknung Gewebeherstellung 480 383 27,7 2b II Gewebebeschichtung Wärmebehandlung des Gewebes 478 453 21,5 3 I Garnbeschichtung Garntrocknung Herstellung des Gewebes Wärmebehandlung des Gewebes 500 469 29,8
    22,2*         The table shows that when the fabric is water-repellent according to the invention, the v 50 values
    • in the wet state in any case higher and
    • in the dry state at least the same or higher
    are than in the case of water-repellent finishing of the fabric not according to the invention. example tissue engineering Applying the water repellent v 50 dry m / s v 50 wet m / s W% 1 I Yarn coating Yarn drying Fabric production Heat treatment of the fabric 500 477 21 1a I Fabric coating Heat treatment of the fabric 480 467 26.6 2 II Yarn coating Yarn drying Fabric production Heat treatment of the fabric 480 458 21 2a II Yarn coating Yarn drying Fabric manufacturing 480 383 27.7 2 B II Fabric coating Heat treatment of the fabric 478 453 21.5 3 I Yarn coating Yarn drying Fabric production Heat treatment of the fabric 500 469 29.8
    22.2 *

    Claims (19)

    Verfahren zur Herstellung eines wasserabweisend ausgerüsteten Aramidgewebes umfassend die Schritte a) Vorlegen eines Aramidgarns, b) Applizieren eines wasserabweisenden Mittels auf das Aramidgarn, c) Trocknen des in Schritt b) resultierenden Aramidgarns, d) Herstellen eines Gewebes aus dem in Schritt c) resultierenden Aramidgarn und e) Wärmebehandlung des Gewebes. A method for producing a water-repellent aramid fabric comprising the steps a) presenting an aramid yarn, b) applying a water-repellent agent to the aramid yarn, c) drying the aramid yarn resulting in step b), d) producing a fabric from the aramid yarn resulting in step c) and e) heat treatment of the fabric. Verfahren nach Anspruch 1, dadurch gekennzeichnet, dass in Schritt a) das Aramidgarn im Spinnprozess nach Verlassen des Waschbades vorgelegt wird.A method according to claim 1, characterized in that in step a) the aramid yarn is placed in the spinning process after leaving the wash bath. Verfahren nach Anspruch 1 oder 2, dadurch gekennzeichnet, dass in Schritt a) als Aramidgarn ein Garn aus Poly-p-phenylenterephthalamid vorgelegt wird.A method according to claim 1 or 2, characterized in that in step a) a yarn made of poly-p-phenylene terephthalamide is presented as aramid yarn. Verfahren nach einem oder mehreren der Ansprüche 1 bis 3, dadurch gekennzeichnet, dass in Schritt b) als wasserabweisendes Mittel ein Mittel eingesetzt wird, das Fluor- und Kohlenstoffatome umfaßt. Method according to one or more of claims 1 to 3, characterized in that in step b) an agent is used as the water-repellent agent which comprises fluorine and carbon atoms. Verfahren nach Anspruch 4, dadurch gekennzeichnet, dass in Schritt b) als wasserabweisendes Mittel ein Mittel eingesetzt wird, das ein Gemisch aus Fluoracrylatpolymeren umfaßt.A method according to claim 4, characterized in that an agent is used as the water-repellent agent in step b), which comprises a mixture of fluoroacrylate polymers. Verfahren nach Anspruch 5, dadurch gekennzeichnet, dass das wasserabweisende Mittel ein Antistatikum enthält.A method according to claim 5, characterized in that the water-repellent contains an antistatic. Verfahren nach Anspruch 5 oder 6, dadurch gekennzeichnet, dass das wasserabweisende Mittel ein Schmiermittel enthält.A method according to claim 5 or 6, characterized in that the water-repellent contains a lubricant. Verfahren nach einem oder mehreren der Ansprüche 1 bis 7, dadurch gekennzeichnet, dass in Schritt b) des erfindungsgemäßen Verfahrens das wasserabweisende Mittel in Form einer wässrigen Emulsion auf das Aramidgarn appliziert wird.Method according to one or more of claims 1 to 7, characterized in that in step b) of the method according to the invention the water-repellent is applied to the aramid yarn in the form of an aqueous emulsion. Verfahren nach Anspruch 8, dadurch gekennzeichnet, dass in Schritt b) das wasserabweisende Mittel in der wässrigen Emulsion in einer Konzentration im Bereich von 20 bis 300 g/l enthalten ist.A method according to claim 8, characterized in that in step b) the water-repellent is contained in the aqueous emulsion in a concentration in the range of 20 to 300 g / l. Verfahren nach einem oder mehreren der Ansprüche 1 bis 9, dadurch gekennzeichnet, dass in Schritt b) das Applizieren durch Führen des Aramidgarns über eine Walze geschieht, die in ein Bad eintaucht, welches die wässrige Emulsion des wasserabweisenden Mittels enthält.Method according to one or more of claims 1 to 9, characterized in that in step b) the application takes place by passing the aramid yarn over a roller which is immersed in a bath which contains the aqueous emulsion of the water-repellent agent. Verfahren nach Anspruch 10, dadurch gekennzeichnet, dass in Schritt b) die wässrige Emulsion eine Temperatur im Bereich von 15 bis 35 °C hat.A method according to claim 10, characterized in that in step b) the aqueous emulsion has a temperature in the range of 15 to 35 ° C. Verfahren nach einem oder mehreren der Ansprüche 1 bis 11, dadurch gekennzeichnet, dass in Schritt c) das in Schritt b) resultierende Aramidgarn bei einer Temperatur im Bereich von 130 bis 210 °C getrocknet wird. Method according to one or more of claims 1 to 11, characterized in that in step c) the aramid yarn resulting in step b) is dried at a temperature in the range from 130 to 210 ° C. Verfahren nach Anspruch 12, dadurch gekennzeichnet, dass in Schritt c) die Trocknungszeit des in Schritt b) resultierenden Aramidgarns im Bereich von 5 bis 15 Sekunden liegt.A method according to claim 12, characterized in that in step c) the drying time of the aramid yarn resulting in step b) is in the range of 5 to 15 seconds. Verfahren nach einem oder mehreren der Ansprüche 1 bis 13, dadurch gekennzeichnet, dass in Schritt d) ein Gewebe in Leinwandbindung hergestellt wird.Method according to one or more of claims 1 to 13, characterized in that a fabric is made in plain weave in step d). Verfahren nach einem oder mehreren der Ansprüche 1 bis 14, dadurch gekennzeichnet, dass in Schritt e) die Wärmebehandlungstemperatur im Bereich von 120 bis 200 °C liegt.Method according to one or more of claims 1 to 14, characterized in that in step e) the heat treatment temperature is in the range from 120 to 200 ° C. Verfahren nach Anspruch 15, dadurch gekennzeichnet, dass in Schritt e) die Wärmebehandlungszeit im Bereich von 30 bis 120 Sekunden liegt.A method according to claim 15, characterized in that in step e) the heat treatment time is in the range of 30 to 120 seconds. Verfahren nach einem oder mehreren der Ansprüche 1 bis 16, dadurch gekennzeichnet, dass nach Schritt e) das Gewebe 0,001 bis 0,02 g an wasserabweisendem Mittel / g Gewebe enthält.Method according to one or more of claims 1 to 16, characterized in that after step e) the fabric contains 0.001 to 0.02 g of water-repellent / g fabric. Wasserabweisend ausgerüstetes Aramidgewebe hergestellt nach einem oder mehreren der Ansprüche 1 bis 17.Water-repellent aramid fabric manufactured according to one or several of claims 1 to 17. Verwendung des wasserabweisend ausgerüsteten Aramidgewebes nach Anspruch 18 zur Herstellung von antiballistisch wirksamen Artikeln.Use of the water-repellent aramid fabric according to claim 18 for the production of antiballistically effective articles.
    EP20020020025 2002-09-06 2002-09-06 Process for producing a water-repellent aramide fabric and use thereof Expired - Lifetime EP1396572B8 (en)

    Priority Applications (8)

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    SI200230356T SI1396572T1 (en) 2002-09-06 2002-09-06 Process for producing a water-repellent aramide fabric and use thereof
    DK02020025T DK1396572T3 (en) 2002-09-06 2002-09-06 Process for the preparation of a water-repellent aramid fabric and its use
    DE50206665T DE50206665D1 (en) 2002-09-06 2002-09-06 Process for the preparation of a water repellent aramid fabric and its use
    EP20020020025 EP1396572B8 (en) 2002-09-06 2002-09-06 Process for producing a water-repellent aramide fabric and use thereof
    AT02020025T ATE325217T1 (en) 2002-09-06 2002-09-06 METHOD FOR PRODUCING A WATER-REPELLENT ARAMID FABRIC AND USE THEREOF
    ES02020025T ES2258582T3 (en) 2002-09-06 2002-09-06 PROCEDURE TO PRODUCE AN ARAMIDE FABRIC PROVIDED WITH A HYDROPHOBO PREPARATION AND ITS USE.
    JP2003310003A JP4614306B2 (en) 2002-09-06 2003-09-02 Method for producing hydrophobic finished aramid fabric and use thereof
    US10/656,188 US7132131B2 (en) 2002-09-06 2003-09-08 Method for producing a hydrophobically finished aramid fabric and use thereof

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    EP20020020025 EP1396572B8 (en) 2002-09-06 2002-09-06 Process for producing a water-repellent aramide fabric and use thereof

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    JP (1) JP4614306B2 (en)
    AT (1) ATE325217T1 (en)
    DE (1) DE50206665D1 (en)
    DK (1) DK1396572T3 (en)
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    US7132131B2 (en) 2006-11-07
    US20040142617A1 (en) 2004-07-22
    EP1396572B8 (en) 2006-08-16
    DK1396572T3 (en) 2006-08-21
    DE50206665D1 (en) 2006-06-08
    EP1396572B1 (en) 2006-05-03
    JP2004263360A (en) 2004-09-24
    ATE325217T1 (en) 2006-06-15
    ES2258582T3 (en) 2006-09-01
    SI1396572T1 (en) 2006-10-31

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