EP1396572B1 - 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
EP1396572B1
EP1396572B1 EP20020020025 EP02020025A EP1396572B1 EP 1396572 B1 EP1396572 B1 EP 1396572B1 EP 20020020025 EP20020020025 EP 20020020025 EP 02020025 A EP02020025 A EP 02020025A EP 1396572 B1 EP1396572 B1 EP 1396572B1
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EP
European Patent Office
Prior art keywords
water
fabric
aramid
yarn
repellent
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.)
Expired - Lifetime
Application number
EP20020020025
Other languages
German (de)
French (fr)
Other versions
EP1396572B8 (en
EP1396572A1 (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
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Filing date
Publication date
Priority to DK02020025T priority Critical patent/DK1396572T3/en
Priority to DE50206665T priority patent/DE50206665D1/en
Priority to AT02020025T priority patent/ATE325217T1/en
Priority to SI200230356T priority patent/SI1396572T1/en
Priority to EP20020020025 priority patent/EP1396572B8/en
Priority to ES02020025T priority patent/ES2258582T3/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 process for producing a water-repellent treated aramid fabric and its use.
  • WO 95/04854 describes a process for the plasma treatment of antiballistically active materials such as e.g. of aramids, wherein 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 organic gas or with mixtures of such gases from the group of saturated hydrocarbons, unsaturated hydrocarbons, saturated Fluorocarbons, unsaturated fluorocarbons, siloxanes or vinyl compounds is optionally carried out in the presence of one or more inorganic gases.
  • antiballistically active materials such as e.g. of aramids
  • US 4,232,087 discloses the coating of aramid fibers and / or aramid fabrics (eg, Nomex fibers) with an aqueous dispersion of polytetrafluoroethylene particles and a water soluble chromium coordination complex with a fluoro-substituted hydrocarbon compound containing amine and sulfonylamine substituted alkyl groups having ⁇ 6 carbon atoms.
  • the treated tissue becomes dried.
  • crosslinking is preferably carried out by heat treatment.
  • WO 92/01108 describes the coating of aramid fibers with an aqueous fluoropolymer dispersion which is applied to the fiber either in the wet or in the dried state, preferably the not yet dried fiber is immersed in a coating with the fluoropolymer dispersion. Subsequently, the coated fiber is dried, whereby the coating is crosslinked on the fiber surface.
  • US 5 116 682 describes the preparation of anti-wicking and water-repellent heat-resistant yarns, e.g. polyester yarns or yarns of glass, nylon or aramid.
  • the yarn is coated with a fluorocarbon emulsion or dispersion, dried and then crosslinked under heat.
  • Aramid fabrics are known to have a high antiballistic action in the dry state.
  • the antiballistic effect diminishes considerably when the tissue is in the wet state.
  • aramid fabrics are often rendered water repellent.
  • the aramid fabrics which have been rendered water-repellent in a known manner, still clearly lose their antiballistic protective effect when they are in the wet state.
  • the object of the present invention is to provide a process for producing a water-repellent treated aramid fabric which has a good antiballistic effect even when wet.
  • the antiballistic effect of the water-repellent finished aramid fabric in the dry state should be at least as high and possibly even higher than that of a water-repellent aramid fabric in a dry state in a known manner.
  • the present invention further has an object to provide a process for producing a water-repellent armed aramid fabric whose antiballistic effect is good even in the dry state.
  • the process according to the invention provides aramid fabrics which have been rendered water-repellent and whose antiballistic effect is higher in the wet state than in the wet state in a water-repellent treated aramid fabric in a known manner.
  • the process according to the invention surprisingly provides water-repellent treated aramid fabrics whose antiballistic action in the dry state is at least as high and in some embodiments even higher than in a dry-state-treated aramid fabric in a known manner.
  • the aramid yarn can be presented, for example, by unwinding the yarn from a spool, after which the yarn can be moistened with an agent which facilitates the application of the water-repellent in step b) of the process according to the invention.
  • the aramid yarn is presented in the spinning process after leaving the washing bath, wherein the yarn is in the wet state and the moisture consists essentially of water and - depending on the efficiency of the preceding laundry - more or less low Shares of sulfuric acid. This embodiment of the method according to the invention causes only a slight additional effort in comparison to the aramid yarn spinning process which is to be carried out anyway, and is therefore preferred.
  • the term "aramid yarn” means a yarn whose fiber-forming substance is a long-chain synthetic polyamide in which at least 85% of the amide bonds are attached directly to two aromatic rings.
  • the aramid yarn is a yarn of poly-p-phenylene terephthalamide presented, in particular a yarn sold under the name Twaron® Teijin Twaron whose titer preferably in the range of 200 to 5000 dtex, more preferably in the range from 550 to 3360 dtex and which preferably consists of 100 to 3000 filaments, particularly preferably from 500 to 2000 filaments.
  • bin in the context of the present invention means a linear textile structure of the fiber-forming substance as defined above, such as e.g. Staple yarn, twisted staple yarn, twisted filament yarn, untwisted entangled yarn (also known as interlaced yarn) and preferably untwisted filament yarn.
  • step b) of the process of the present invention there can be used, in principle, any agent which repels water and which can be applied to the aramid yarn, preferably using an agent comprising fluorine and carbon atoms.
  • a water-repelling agent which comprises a fluoropolymer and very particularly preferably a mixture of fluoroacrylate polymers, such as, for example, OLEOPHOBOL SM® from Ciba Spezialitätenchemie Pfersee GmbH, Langweid, DE.
  • the water-repellent agent may contain an antistatic agent, e.g. Leomin AN® from CLARIANT GmbH, Division Textile Leather Products, BU Textile Chemicals, Frankfurt Main, DE.
  • an antistatic agent e.g. Leomin AN® from CLARIANT GmbH, Division Textile Leather Products, BU Textile Chemicals, Frankfurt Main, DE.
  • the water-repellent additionally contains a lubricant, wherein as lubricant a mixture of a 1,3-dihydroxyalkyl-5,5-dialkyl-hydantoin and an ester of oleic acid and ethylene oxide and in particular a mixture of a 1, 3-dihydroxyethyl-5,5-dimethyl - hydantoin and an ester of 1 mole of oleic acid and 17 moles of ethylene oxide is preferred because it can prevent the formation of deposits on static thread guide members.
  • a lubricant a mixture of a 1,3-dihydroxyalkyl-5,5-dialkyl-hydantoin and an ester of oleic acid and ethylene oxide and in particular a mixture of a 1, 3-dihydroxyethyl-5,5-dimethyl - hydantoin and an ester of 1 mole of oleic acid and 17 moles of ethylene oxide is preferred because it can prevent the formation of deposits on static thread guide
  • the water-repellent agent applied to the aramid yarn in step b) of the process according to the invention can, if it satisfies the abovementioned criteria, be used as pure substance.
  • the water repellent in the form of a solution or a dispersion or preferably an aqueous emulsion is preferably contained in a concentration in the range of 20 to 300 g / l.
  • the water-repellent agent for the application of the water-repellent agent to the aramid yarn in step b) of the process according to the invention, in principle all processes are suitable with which the water-repellent agent can be uniformly distributed in the selected formulation on the yarn surface.
  • the formulation of the water repellent agent for example, one can apply the formulation of the water repellent agent as a thin film on a roller and lead the Aramidgarn through the film. Further, one can spray the formulation of the water repellent agent on the Aramidgarn.
  • you can use the wording Apply the water-repellent agent to the yarn with a pump and with a pen, slot or block applicator.
  • step b) of the process of the present invention the application is carried out by passing the aramid yarn over a roller immersed in a bath containing the water-repellent aqueous emulsion, the emulsion preferably having 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 in a temperature and time range which is sufficient so that the aramid yarn resulting in step b) does not stick together during subsequent winding.
  • the parameter ranges for temperature and time of the drying are based on the requirements of the selected application method in step b) of the method according to the invention.
  • a fabric preferably plain weave, is produced from the aramid yarn resulting from step c) in step d), in particular a fabric having a thread density in warp and weft in the range from 3 to 20 threads / cm.
  • step e) of the method according to the invention the tissue resulting in step d) is heat-treated, preferably until the water absorption of the tissue decreases.
  • the areas of time and temperature required for the heat treatment are essentially based on the water-repellent applied in step b) Medium. In many cases, a heat treatment temperature in the range of 120 to 200 ° C and a heat treatment time of 30 to 120 seconds is sufficient.
  • OLEOPHOBOL SM® As a water-repellent agent, OLEOPHOBOL SM® from Ciba Spezialitätenchemie Pfersee GmbH, Langweid am Lech, DE, is used. OLEOPHOBOL SM® is an aqueous emulsion comprising fluoroacrylate polymers and nonionic / cationic surfactants wherein the proportion of fluoroacrylate polymers is 19.5% by weight and the fluorine content is 5.3% by weight. To prepare the to be applied to the aramid yarn avivage 74 parts by weight of demineralized water are submitted.
  • the finishing agent obtained in this way is applied to Twaron® yarn of type 2000 (930 dtex f1000) by Teijin Twaron, integrated in the spinning process.
  • the aramid yarn after exiting the wash bath, passes at a speed of 325 m / min over a rotating roller immersed in a bath containing the lubricant prepared as described above. Thereafter, the coated aramid yarn passes through a drying zone wherein the yarn is dried at a temperature of 170 ° C for 10 seconds. Then the yarn is wound up.
  • the aramid yarn is woven into a fabric with 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. Thereafter, the fabric contains 0.01 g of water repellent / g fabric.
  • An aramid fabric of fabric construction 1 made of Twaron® yarn of the type 2000 (930 dtex f1000) from Teijin Twaron is padded with a finishing agent, for the preparation of which 40 parts by weight of demineralized water have been initially charged and 60 parts by weight of OLEOPHOBOL SM® have been added.
  • the aramid fabric is passed through a bath containing the finishing made as just described and, after leaving the bath, squeezed with a pair of rollers so that the liquor pickup is 35% by weight. Then we exposed the fabric to a temperature of 170 ° C for 90 seconds. Thereafter, the fabric contains 0.042 g of water repellent / g fabric.
  • Example 2 is carried out as Example 1 with the difference that Twaron® yarn type 2000 from Teijin Twaron (930 dtex f1000) is used as yarn and a plain weave fabric (10.5 threads / cm in warp and weft, 200 g / m 2 ) is produced (fabric construction II). Thereafter, the fabric contains 0.01 g of water repellent / g fabric.
  • Example 2 On the Twaron® yarn of Example 2 is applied as described in Example 1, the Avivage described therein and exposed the yarn for 10 seconds at a temperature of 170 ° C. Thereafter, a fabric of fabric construction II containing 0.01 g of water repellent / g fabric is prepared from the yarn thus treated.
  • a fabric of the fabric construction 11 from the Twaron® yarns of Example 2 is padded as described in Comparative Example 1 a with the Avivage described therein.
  • the fabric is exposed to a temperature of 170 ° C for 90 seconds. Thereafter, the fabric contains 0.042 g of water repellent / g fabric.
  • OLEOPHOBOL SL® from Ciba Spezialitätenchemie Pfersee GmbH, Langweid am Lech, DE, is used as the water-repellent agent.
  • OLEOPHOBOL SL® is an aqueous emulsion containing fluoroacrylate polymers and nonionic / cationic surfactants wherein the proportion of Fluoracrylatpolymeren 20.0 wt.% And the fluorine content is 5.6 wt.%.
  • OLEOPHOBOL SL® 25 parts by weight of OLEOPHOBOL SL®, 0.25 parts by weight of Leomin AN® from CLARIANT GmbH, Textile Leather Products Division, Textile Chemicals BU, Frankfurt Main, DE, and 2.5 parts by weight Hymo 90 from Goulston Technologies, Inc., Monroe, NC. USA, so that the finishing agent contains 5.0% by weight of fluoroacrylate polymers.
  • the finishing agent obtained in this way is applied to Twaron® yarn of type 2000 (930 dtex f1000) by Teijin Twaron, integrated in the spinning process.
  • the aramid yarn after exiting the wash bath, passes at a speed of 325 m / min. Over a rotating roller immersed in a bath containing the aqueous finishing agent prepared as described above. Thereafter, the coated aramid yarn passes through a drying zone wherein the yarn is dried at a temperature of 170 ° C for 10 seconds. Then the yarn is wound up.
  • the aramid yarn is woven into a fabric with plain weave (9.4 threads / cm in warp and weft, 180 g / m 2 ) (fabric construction 1).
  • the fabric is exposed to a temperature of 170 ° C for 90 seconds. Thereafter, the fabric contains 0.01 g of water repellent / g fabric.
  • the antiballistic effect was determined by measuring the V 50 value of a tissue pack of 15 tissues (Example 1 and Comparative Example 1a) or 14 tissues (Example 2 and Comparative Examples 2a and 2b) with the test method STANAG 2920 (1.1 g splitter).
  • the v 50 value thus determined indicates the projectile speed at which half of the projectiles are held by the fabric package and the other half of the projectiles completely penetrate the fabric package.
  • the fabric package was conditioned in the ISO 139 standard climate, ie for 24 hours at 20 ⁇ 2 ° C and 65 ⁇ 2% relative humidity.
  • the tissue packet Before measuring v 50 in the wet state, the tissue packet was immersed in water for 1 hour and allowed to drain for 3 minutes.
  • Example 3 the water repellency was additionally measured with the sprinkler test according to Bundesmann (ISO 9865). The water absorption after 10 minutes is marked with a * in the following table.

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

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 process for producing a water-repellent treated aramid fabric and its use.

Wasserabweisend ausgerüstete Aramidfasern und -gewebe und Verfahren zu deren Herstellung sind bekannt.Water repellent treated aramid fibers and fabrics and methods of making the same 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 process for the plasma treatment of antiballistically active materials such as e.g. of aramids, wherein 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 organic gas or with mixtures of such gases from the group of saturated hydrocarbons, unsaturated hydrocarbons, saturated Fluorocarbons, unsaturated fluorocarbons, siloxanes or vinyl compounds is optionally carried out in the presence of one or more inorganic gases.

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 (eg, Nomex fibers) with an aqueous dispersion of polytetrafluoroethylene particles and a water soluble chromium coordination complex with a fluoro-substituted hydrocarbon compound containing amine and sulfonylamine substituted alkyl groups having ≥ 6 carbon atoms. The treated tissue becomes dried. After drying the fabric, crosslinking is preferably carried out 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 which is applied to the fiber either in the wet or in the dried state, preferably the not yet dried fiber is immersed in a coating with the fluoropolymer dispersion. Subsequently, the coated fiber is dried, whereby the coating is crosslinked on the fiber surface.

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 preparation of anti-wicking and water-repellent heat-resistant yarns, e.g. polyester yarns or yarns of glass, nylon or aramid. The yarn is coated with a fluorocarbon emulsion or dispersion, 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 action in the dry state. However, the antiballistic effect diminishes considerably when the tissue is in the wet state. As a result, aramid fabrics are often rendered water repellent. However, it has been found that the aramid fabrics, which have been rendered water-repellent in a known manner, still clearly lose their antiballistic protective effect when they are in the wet state.

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 to provide a process for producing a water-repellent treated aramid fabric which 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 water-repellent finished aramid fabric in the dry state should be at least as high and possibly even higher than that of a water-repellent aramid fabric in a dry state in a known manner.

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 further has an object to provide a process for producing a water-repellent armed aramid fabric whose 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 objects are achieved by a process for producing a water-repellent treated aramid fabric comprising the steps
  • a) presentation of 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 tissue.

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.Surprisingly, the process according to the invention provides aramid fabrics which have been rendered water-repellent and whose antiballistic effect is higher in the wet state than in the wet state in a water-repellent treated aramid fabric in a known manner.

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 process according to the invention surprisingly provides water-repellent treated aramid fabrics whose antiballistic action in the dry state is at least as high and in some embodiments even higher than in a dry-state-treated aramid fabric in a known manner.

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 process according to the invention, the aramid yarn can be presented, for example, by unwinding the yarn from a spool, after which the yarn can be moistened with an agent which facilitates the application of the water-repellent in step b) of the process according to the invention. In another embodiment of the method according to the invention, the aramid yarn is presented in the spinning process after leaving the washing bath, wherein the yarn is in the wet state and the moisture consists essentially of water and - depending on the efficiency of the preceding laundry - more or less low Shares of sulfuric acid. This embodiment of the method according to the invention causes only a slight additional effort in comparison to the aramid yarn spinning process which is to be carried out anyway, 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 in which at least 85% of the amide bonds are attached directly to two aromatic rings. Particularly preferred in step a) of the process according to the invention as the aramid yarn is a yarn of poly-p-phenylene terephthalamide presented, in particular a yarn sold under the name Twaron® Teijin Twaron whose titer preferably in the range of 200 to 5000 dtex, more preferably in the range from 550 to 3360 dtex and which preferably consists of 100 to 3000 filaments, particularly preferably from 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.The term "yarn" in the context of the present invention means a linear textile structure of the fiber-forming substance as defined above, such as e.g. Staple yarn, twisted staple yarn, twisted filament yarn, untwisted entangled 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 Fluor- und Kohlenstoffatome umfaßt.As the water-repellent agent, in step b) of the process of the present invention, there can be used, in principle, any agent which repels water and which can be applied to the aramid yarn, preferably using an agent comprising fluorine and 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 process according to the invention a water-repelling agent is used which comprises a fluoropolymer and very particularly preferably a mixture of fluoroacrylate polymers, such as, for example, OLEOPHOBOL SM® from Ciba Spezialitätenchemie 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.Further, the water-repellent agent may contain an antistatic agent, 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 contains a lubricant, wherein as lubricant a mixture of a 1,3-dihydroxyalkyl-5,5-dialkyl-hydantoin and an ester of oleic acid and ethylene oxide and in particular a mixture of a 1, 3-dihydroxyethyl-5,5-dimethyl - hydantoin and an ester of 1 mole of oleic acid and 17 moles of ethylene oxide is preferred because it can prevent the formation of deposits on static thread guide members. Such a mixture is available under the name Hymo 90 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 water-repellent agent applied to the aramid yarn in step b) of the process according to the invention can, if it satisfies the abovementioned criteria, be used as pure substance. However, because of the ease of metering a desired amount of water repellent on the yarn, it is advantageous to apply the water repellent in the form of a solution or a dispersion or preferably an aqueous emulsion to the aramid yarn in step b) of the process of the invention, the water repellent in the aqueous emulsion is preferably contained in a concentration in the range of 20 to 300 g / l.

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-, Schlitz- oder Block-Applikator auf das Garn applizieren.For the application of the water-repellent agent to the aramid yarn in step b) of the process according to the invention, in principle all processes are suitable with which the water-repellent agent can be uniformly distributed in the selected formulation on the yarn surface. For example, one can apply the formulation of the water repellent agent as a thin film on a roller and lead the Aramidgarn through the film. Further, one can spray the formulation of the water repellent agent on the Aramidgarn. Also you can use the wording Apply the water-repellent agent to the yarn with a pump and with a pen, slot or block applicator.

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.Preferably, in step b) of the process of the present invention, the application is carried out by passing the aramid yarn over a roller immersed in a bath containing the water-repellent aqueous emulsion, the emulsion preferably having 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 in a temperature and time range which is sufficient so that the aramid yarn resulting in step b) does not stick together during subsequent winding. In addition, the parameter ranges for temperature and time of the drying are based on the requirements of the selected application method in step b) of the method according to the invention. By applying the water repellent agent to the aramid yarn, e.g. In the aramid yarn spinning process, after the yarn has left the washing bath, the temperature and drying time ranges are determined by the spinning speed and the structural conditions of the spinning plant. If the aramid yarn resulting from step b) is dried at a temperature in the range from 130 to 210 ° C. and during a drying time in the range from 5 to 15 seconds, a very good drying result is achieved, and therefore said ranges 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, a fabric, preferably plain weave, is produced from the aramid yarn resulting from step c) in step d), in particular a fabric having a thread density in 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 tissue resulting in step d) is heat-treated, preferably until the water absorption of the tissue decreases. The areas of time and temperature required for the heat treatment are essentially based on the water-repellent applied in step b) Medium. In many cases, a heat treatment temperature in the range of 120 to 200 ° C and a heat treatment time of 30 to 120 seconds is 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 the water-repellent agent of 0.001 to 0.02 g of water-repellent / g tissue and in particular 0.006 to 0.015 g of water-repellent / g tissue after step e) of the method according to the invention results in a particularly high water repellency coupled with 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 on which the invention is based are furthermore achieved by a water-repellent treated aramid fabric according to the invention which, as the following examples show, is advantageous for the production of antiballistically active articles, e.g. of protective vests and helmets.

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.As a water-repellent agent, OLEOPHOBOL SM® from Ciba Spezialitätenchemie Pfersee GmbH, Langweid am Lech, DE, is used. OLEOPHOBOL SM® is an aqueous emulsion comprising fluoroacrylate polymers and nonionic / cationic surfactants wherein the proportion of fluoroacrylate polymers is 19.5% by weight and the fluorine content is 5.3% by weight. To prepare the to be applied to the aramid yarn avivage 74 parts by weight of demineralized water are submitted. To this end, 25.5 parts by weight of OLEOPHOBOL SM® and 0.25 part by weight of Leomin AN® from CLARIANT GmbH, Division Textile Leather Products, BU Textile Chemicals, Frankfurt Main, DE, are added so that the finishing agent 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 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 finishing agent obtained in this way is applied to Twaron® yarn of type 2000 (930 dtex f1000) by Teijin Twaron, integrated in the spinning process. To do so, the aramid yarn, after exiting the wash bath, passes at a speed of 325 m / min over a rotating roller immersed in a bath containing the lubricant prepared as described above. Thereafter, the coated aramid yarn passes through a drying zone wherein the yarn is dried at a temperature of 170 ° C 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).Subsequently, the aramid yarn is woven into a fabric with 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. Thereafter, the fabric contains 0.01 g of water repellent / g fabric.

Vergleichsbeispiel 1aComparative Example 1a

Ein Aramidgewebe der Gewebekonstruktion 1 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 1 made of Twaron® yarn of the type 2000 (930 dtex f1000) from Teijin Twaron is padded with a finishing agent, for the preparation of which 40 parts by weight of demineralized water have been initially charged and 60 parts by weight of OLEOPHOBOL SM® have been 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. Anschließend 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 containing the finishing made as just described and, after leaving the bath, squeezed with a pair of rollers so that the liquor pickup is 35% by weight. Then we exposed the fabric to a temperature of 170 ° C for 90 seconds. Thereafter, the fabric 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 Twaron® yarn type 2000 from Teijin Twaron (930 dtex f1000) is used as yarn and a plain weave fabric (10.5 threads / cm in warp and weft, 200 g / m 2 ) is produced (fabric construction II). Thereafter, the fabric 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.On the Twaron® yarn of Example 2 is applied as described in Example 1, the Avivage described therein and exposed the yarn for 10 seconds at a temperature of 170 ° C. Thereafter, a fabric of fabric construction II containing 0.01 g of water repellent / g fabric is prepared from the yarn thus treated.

Vergleichsbeispiel 2bComparative Example 2b

Ein Gewebe der Gewebekonstruktion 11 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 the fabric construction 11 from the Twaron® yarns of Example 2 is padded as described in Comparative Example 1 a with the Avivage described therein. The fabric is exposed to a temperature of 170 ° C for 90 seconds. Thereafter, 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 Spezialitätenchemie Pfersee GmbH, Langweid am Lech, DE, is used as the water-repellent agent. OLEOPHOBOL SL® is an aqueous emulsion containing fluoroacrylate polymers and nonionic / cationic surfactants wherein the proportion of Fluoracrylatpolymeren 20.0 wt.% And the fluorine content is 5.6 wt.%. To prepare the to be applied to the aramid yarn Avivage 73.25 parts by weight of demineralized water are submitted. To this are added 25 parts by weight of OLEOPHOBOL SL®, 0.25 parts by weight of Leomin AN® from CLARIANT GmbH, Textile Leather Products Division, Textile Chemicals BU, Frankfurt Main, DE, and 2.5 parts by weight Hymo 90 from Goulston Technologies, Inc., Monroe, NC. USA, so that the finishing agent 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 finishing agent obtained in this way is applied to Twaron® yarn of type 2000 (930 dtex f1000) by Teijin Twaron, integrated in the spinning process. To do so, the aramid yarn, after exiting the wash bath, passes at a speed of 325 m / min. Over a rotating roller immersed in a bath containing the aqueous finishing agent prepared as described above. Thereafter, the coated aramid yarn passes through a drying zone wherein the yarn is dried at a temperature of 170 ° C 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 1).Subsequently, the aramid yarn is woven into a fabric with plain weave (9.4 threads / cm in warp and weft, 180 g / m 2 ) (fabric construction 1).

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. Thereafter, the fabric 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 pack of 15 tissues (Example 1 and Comparative Example 1a) or 14 tissues (Example 2 and Comparative Examples 2a and 2b) with the test method STANAG 2920 (1.1 g splitter). The v 50 value thus determined indicates the projectile speed at which half of the projectiles are held by the fabric package and the other half of the projectiles completely penetrate 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 fabric package was conditioned in the ISO 139 standard climate, ie for 24 hours 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 measuring v 50 in the wet state, the tissue packet was immersed in water for 1 hour and allowed to drain 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 = [ ( w 2 / w 1 ) − 1 ] ⋅ 100 [ % ]

Figure imgb0001
berechnet.The water-repellent effect is measured by measuring the water uptake of a tissue package of 15 tissues (Example 1 and Comparative Example 1a) or 14 tissues (Example 2 and Comparative Examples 2a and 2b). For this purpose, the dry fabric 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 [ % ]
Figure imgb0001
 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 repellency was additionally measured with the sprinkler test according to Bundesmann (ISO 9865). The water absorption after 10 minutes is marked with a * 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 1a, 2a und 2b) sind in der folgenden Tabelle zusammengefasst.The antiballistic and water-repellent action of the water-repellent treated fabrics according to the invention (Examples 1 and 2) and the fabrics not water-repellent treated according to the invention (Comparative Examples 1a, 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 V 50 trocken m/s V 50 naß m/s W % 1 I Garnbeschichtung Garntrocknung Herstellung des Gewebes Wärmebehandlung des Gewebes 500 477 21 1a l 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 in water-repellent finishing of the fabric according to the invention the v 50 values
  • in the wet state in each case higher and
  • in the dry state, at least equal to or higher
are as in non-inventive water-repellent finish of the fabric. example tissue engineering Apply the water-repellent agent V 50 dry m / s V 50 wet m / s W% 1 I Garnbeschichtung Garntrocknung Production of the fabric Heat treatment of the fabric 500 477 21 1a l Fabric coating Heat treatment of the fabric 480 467 26.6 2 II Garnbeschichtung Garntrocknung Production of the fabric Heat treatment of the fabric 480 458 21 2a II Garnbeschichtung Garntrocknung Tissue production 480 383 27.7 2 B II Fabric coating Heat treatment of the fabric 478 453 21.5 3 I Garnbeschichtung Garntrocknung Production of the fabric Heat treatment of the fabric 500 469 29.8 22.2 *

Claims (19)

  1. A method for producing a hydrophobically finished aramid fabric, comprising the steps
    a) provision of an aramid yarn,
    b) application of a water-repellent agent to the aramid yarn,
    c) drying of the aramid yarn resulting from step b),
    d) production of a fabric from the aramid yarn resulting from step c),
    e) heat treatment of the fabric.
  2. Method according to Claim 1, characterised in that in step a) the aramid yarn is provided in the spinning process after leaving the wash bath.
  3. Method according to Claim 1 or 2, characterised in that in step a) a yarn produced from poly(p-phenylene terephthalamide) is provided as the aramid yarn.
  4. Method according to one or more of Claims 1 to 3, characterised in that in step b) an agent comprising fluorine and carbon atoms is used as the water-repellent agent.
  5. Method according to Claim 4, characterised in that in step b) an agent comprising a mixture of fluoroacrylate polymers is used as the water-repellent agent.
  6. Method according to Claim 5, characterised in that the water-repellent agent contains an antistatic agent.
  7. Method according to Claim 5 or 6, characterised in that the water-repellent agent contains a lubricant.
  8. Method according to one or more of Claims 1 to 7, characterised in that in step b) of the method of the invention, the water-repellent agent is applied to the aramid yarn in the form of an aqueous emulsion.
  9. Method according to Claim 8, characterised in that in step b) the water-repellent agent is present in the aqueous emulsion in a concentration in the range of 20 - 300 g/l.
  10. Method according to one or more of Claims 1 to 9, characterised in that in step b) the application is effected by passing the aramid yarn over a roller immersed in a bath containing the aqueous emulsion of the water-repellent agent.
  11. Method according to Claim 10, characterised in that in step b) the aqueous emulsion has a temperature in the range of 15 - 35°C.
  12. Method according to one or more of Claims 1 to 11, characterised in that in step c) the aramid yarn resulting from step b) is dried at a temperature in the range of 130 - 210°C.
  13. Method according to Claim 12, characterised in that in step c) the drying time of the aramid yarn resulting from step b) lies in the range of 5 -15 seconds.
  14. Method according to one or more of Claims 1 to 13, characterised in that in step d) a plain weave fabric is produced.
  15. Method according to one or more of Claims 1 to 14, characterised in that in step e) the heat treatment is carried out in the temperature range of 120 - 200°C.
  16. Method according to Claim 15, characterised in that in step e) the heat treatment is carried out for a duration of 30 -120 seconds.
  17. Method according to one or more of Claims 1 to 16, characterised in that after step e) the fabric contains 0.001 - 0.02 g of water-repellent agent per g of fabric.
  18. Hydrophobically finished aramid fabric produced according to one or more of Claims 1 to 17.
  19. Use of the hydrophobically finished 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)

Application Number Priority Date Filing Date Title
AT02020025T ATE325217T1 (en) 2002-09-06 2002-09-06 METHOD FOR PRODUCING A WATER-REPELLENT ARAMID FABRIC AND USE THEREOF
SI200230356T SI1396572T1 (en) 2002-09-06 2002-09-06 Process for producing a water-repellent aramide fabric and use thereof
EP20020020025 EP1396572B8 (en) 2002-09-06 2002-09-06 Process for producing a water-repellent aramide 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.
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
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

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
EP20020020025 EP1396572B8 (en) 2002-09-06 2002-09-06 Process for producing a water-repellent aramide fabric and use thereof

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EP1396572A1 EP1396572A1 (en) 2004-03-10
EP1396572B1 true EP1396572B1 (en) 2006-05-03
EP1396572B8 EP1396572B8 (en) 2006-08-16

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EP (1) EP1396572B8 (en)
JP (1) JP4614306B2 (en)
AT (1) ATE325217T1 (en)
DE (1) DE50206665D1 (en)
DK (1) DK1396572T3 (en)
ES (1) ES2258582T3 (en)
SI (1) SI1396572T1 (en)

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JP2004263360A (en) 2004-09-24
EP1396572B8 (en) 2006-08-16
SI1396572T1 (en) 2006-10-31
US7132131B2 (en) 2006-11-07
JP4614306B2 (en) 2011-01-19
DK1396572T3 (en) 2006-08-21
US20040142617A1 (en) 2004-07-22
EP1396572A1 (en) 2004-03-10
ES2258582T3 (en) 2006-09-01
ATE325217T1 (en) 2006-06-15

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