EP3298191B1 - Surface textile à apprêt hydrophobe et son procédé de production - Google Patents

Surface textile à apprêt hydrophobe et son procédé de production Download PDF

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Publication number
EP3298191B1
EP3298191B1 EP16725795.5A EP16725795A EP3298191B1 EP 3298191 B1 EP3298191 B1 EP 3298191B1 EP 16725795 A EP16725795 A EP 16725795A EP 3298191 B1 EP3298191 B1 EP 3298191B1
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EP
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Prior art keywords
water
melting point
paraffin wax
component
repellent finish
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EP16725795.5A
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German (de)
English (en)
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EP3298191A1 (fr
Inventor
Rüdiger Hartert
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Teijin Aramid GmbH
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Teijin Aramid GmbH
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    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/02—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with hydrocarbons
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/10—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing oxygen
    • D06M13/224—Esters of carboxylic acids; Esters of carbonic acid
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/322—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen
    • D06M13/325—Amines
    • D06M13/328—Amines the amino group being bound to an acyclic or cycloaliphatic carbon atom
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/39—Aldehyde resins; Ketone resins; Polyacetals
    • D06M15/423—Amino-aldehyde resins
    • 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

Definitions

  • the present invention relates to a water-repellent textile fabric and a method for its production.
  • Water-repellent textile fabrics are known.
  • the patent specification DE 870 544 describes a process for producing a water-repellent finish on fiber materials, the fiber materials being treated with solutions of derivatives of methylolaminotriazines which contain at least one aliphatic radical with 4 C atoms and of other water-repellent compounds, such as paraffin, waxes, such as Beeswax, or fatty substances, for example esters of higher molecular weight fatty acids, such as montanic acid, treated in organic solvents, optionally with the addition of acidic or acid-releasing catalysts, and the fiber material treated in this way, optionally after removing the solvents, a heat treatment, preferably at 125 to 150 ° C, subjects.
  • a heat treatment preferably at 125 to 150 ° C, subjects.
  • paraffin according to " R ⁇ MPP CHEMIE LEXIKON ", 9th edition, volume 4 (1991), page 3216 a solid, semi-solid or liquid mixture of purified, saturated, aliphatic hydrocarbons.
  • a solid paraffin is hard paraffin, a solid crystalline mass with a solidification point on the rotating thermometer of 50-62 ° C.
  • semi-solid paraffin qualities with a melting point of 45-65 ° C names like soft paraffin are known, for those with a melting point of 38-60 ° C names like petrolatum are known.
  • the liquid paraffin forms are often added to the mineral oils and collectively referred to as paraffin oil or white oil . Some paraffin fractions are traded as waxes.
  • waxes refers to " R ⁇ MPP CHEMIE LEXIKON ", 9th edition, volume 6 (1992), page 4972 Substances that generally have the following properties: Kneadable at 20 ° C, solid to brittle hard, coarse to fine crystalline, melting above 40 ° C without decomposition;
  • beeswax refers to R ⁇ MPP CHEMIE LEXIKON ", 9th edition, volume 1 (1989), page 412 a wax obtained from the honeycomb honeycomb with a melting point of 61-68 ° C.
  • fatty substances denotes "fats” which according to " R ⁇ MPP CHEMIE LEXIKON ", 9th edition, volume (1990), page 1339 consist essentially of mixed glycerol esters of higher fatty acids.
  • Montanoic acid H 3 C- (CH 2 ) 26 -COOH
  • esters of montanic acid with higher molecular fatty acids have a melting point above 78 ° C.
  • a water-repellent finish is necessary in order to achieve the required protective effect, expressed by the v 50 value.
  • equipment which contains acrylate polymers which have perfluoroalkyl groups with the structure CF 3 - (CF 2 ) x -CF 2 - with x ⁇ 6.
  • Textile fabrics made from aramid fibers which are provided with a finish which comprises fluorine and carbon atoms, such as, for example, acrylate polymers with perfluoroalkyl groups of the structure CF 3 - (CF 2 ) x -CF 2 - with x ⁇ 6, show a high level Degree of water-repellent effect and thus the required ballistic protective effect.
  • a finish which comprises fluorine and carbon atoms such as, for example, acrylate polymers with perfluoroalkyl groups of the structure CF 3 - (CF 2 ) x -CF 2 - with x ⁇ 6, show a high level Degree of water-repellent effect and thus the required ballistic protective effect.
  • customers are increasingly demanding equipment that does not contain fluorine for textile fabrics made from aramid fibers.
  • the object of the present invention is to provide a textile fabric made from aramid fibers, the finish containing no fluorine, but being at least as water-repellent as the known finishings with acrylate polymers, the perfluoroalkyl groups with the structure CF. 3 - (CF 2 ) x -CF 2 - with x ⁇ 6, and wherein a fabric with such a water-repellent fabric made of aramid fibers shows at least the same antiballistic effect as a fabric made of aramid fibers that with the known equipment is equipped with acrylate polymers containing perfluoroalkyl groups with the structure CF 3 - (CF 2 ) x -CF 2 - with x ⁇ 6.
  • a textile fabric comprising aramid fibers for example a fabric consisting of aramid fibers, which has been treated with the water-repellent finish according to the invention, compared to a textile fabric comprising aramid fibers constructed in the same way, for example in comparison to a fabric from aramid fibers, but which has been treated with the known equipment which contains acrylate polymers which have perfluoroalkyl groups with the structure CF 3 - (CF 2 ) x -CF 2 - with x ⁇ 6, at least the same hydrophobizing effect (measured as water absorption according to DIN EN 29 865 (November 1993)) and the same v 50 values in dry and wet bombardment, although the water-repellent finish according to the invention preferably contains no fluorine, ie is preferably fluorine-free.
  • aramid fibers preferably means filament yarns which are made from aramides, ie from aromatic polyamides, in which at least 85% of the amide (-CO-NH-) bonds are bonded directly to two aromatic rings.
  • Aromatic polyamides which are particularly preferred for the present invention are p-aramides, in particular poly-p-phenylene terephthalamide, a homopolymer which results from the mol: mol polymerization of the monomers p-phenylene diamine and terephthalic acid dichloride.
  • the aramid fibers which comprise the textile fabric according to the invention are p-aramid fibers, in particular poly-p-phenylene terephthalamide fibers and particularly preferably poly-p-phenylene terephthalamide filament yarns, which are sold under the name TWARON® are available from Teijin Aramid GmbH (DE).
  • aramid fibers in particular aramid filament yarns, which consist of aromatic copolymers, in the production of which the monomers p-phenylenediamine and / or terephthalic acid dichloride have been partially or completely substituted by other aromatic diamines and / or dicarboxylic acid dichlorides.
  • the textile fabric contains 0.8 to 4.0% by weight of dry substance, based on its weight, more preferably 1.4 to 3.0% by weight of dry substance and very particularly preferably 1.6 to 2 , 3% by weight dry matter of the water-repellent finish.
  • dry substance means the sum of all substances contained in the water-repellent finish, which, after the textile fabric treated with the water-repellent finish has dried, reach a water content equal to the equilibrium moisture content of the fabric in the normal climate of DIN EN ISO 139 / A1 ( May 2008 ), ie at a temperature of 20.0 ⁇ 2.0 ° C and at a relative humidity of 65 ⁇ 4.0%, remain on and in the textile fabric.
  • the textile fabric is a woven fabric, knitted fabric, knitted fabric or a uniaxial or multiaxial scrim.
  • the term woven fabric encompasses all types of weave, e.g. Plain weave, satin weave, Panama weave, twill weave and the like.
  • the fabric preferably has a plain weave.
  • the woven fabric, the knitted fabric, the knitted fabric or the uniaxial or multiaxial scrim comprises fibers made of p-aramid.
  • Multifilament yarns and staple fiber yarns are available under the name TWARON® from Teijin Aramid GmbH, DE.
  • the water-repellent finish of the textile fabric according to the invention consists of a mixture of components A, B and C, it being particularly preferred that none of the components mentioned contains fluorine.
  • the water-repellent finish of the fabric according to the invention consists of an aqueous emulsion of components A, B and C, it being particularly preferred that none of the components mentioned and also none of the auxiliaries, such as e.g. Emulsifiers used to make the emulsion contains fluorine.
  • the reaction product which forms component A of the water-repellent finish was obtained from the reaction of an aliphatic carboxylic acid with a methylolmelamine, the aliphatic carboxylic acid having a structure of the formula CH 3 - (CH 2 ) n - Has COOH, where n is an integer in the range from 15 to 25, more preferably from 18 to 22, more preferably from 19 to 21 and very particularly preferably from 20 (behenic acid).
  • the reaction of the aliphatic carboxylic acid with the methylolmelamine is particularly preferably an esterification, so that the reaction product which forms component A of the water-repellent finish of the textile fabric according to the invention is an ester.
  • the methylolmelamine is a mono-, di-, tri-, tetra-, penta-, or hexamethylolmelamine.
  • the reaction product which forms component A of the water-repellent finish of the textile fabric according to the invention can be carried out at elevated temperature, e.g. crosslink in the range from approximately 150 to approximately 175 ° C., particularly preferably in the range from approximately 153 to approximately 172 ° C.
  • the crosslinking can be a crosslinking of the reaction product with itself and / or with reactive groups of fibers which form the textile fabric according to the invention, to which the water-repellent finish has been applied, and / or with any other constituents of the water-repellent finish which may be present.
  • the paraffin wax forming component B of the water-repellent finish has a melting point T B and the further paraffin wax of component C has a melting point T C2 , T C2 being less than T B.
  • the melting point T C2 of the further paraffin wax is 3 to 7 ° C, particularly preferably 4 to 6 ° C, and very particularly preferably 5 ° C lower than the melting point T B of the paraffin wax.
  • the paraffin wax contained in the water-repellent finish has a melting point T B in the range from 58 to 62 ° C.
  • the paraffin wax contained in the water-repellent finish particularly preferably has a melting point T B of approximately 60 ° C.
  • the further paraffin wax C2 contained in the water-repellent finish has a melting point T C2 in the range from 53 to 57 ° C.
  • the further paraffin wax C2 contained in the water-repellent finish particularly preferably has a melting point T C2 of approximately 55 ° C.
  • the ester wax C1 of component C can be prepared by esterifying a synthetic wax acid with a synthetic alcohol or by copolymerizing an olefin with an unsaturated ester.
  • the ester wax C1 contained in the water-repellent finish has a melting point T C1 in the range from 50 to 60 ° C., particularly preferably in the range from 53 to 57 ° C. and very particularly preferably from approx. 55 ° C.
  • the water-repellent finish comprises the mixture of components A, B and C, component C comprising the ester wax C1 and the further paraffin wax C2.
  • the paraffin wax forming component B of the water-repellent finish has a melting point T B and the further paraffin wax C2 of component C has a melting point T C2 , where T C2 is less than T B.
  • the equipment comprises an aqueous emulsion of components A, B and C and in particular an aqueous emulsion of components A, B, C1 and C2.
  • the water-repellent finish contains components A and B in a percentage by weight w A + B and component C in a percentage by weight w C , a ratio w A + B : w C in the range from 70:30 to 30:70, more preferably in the range from 60:40 to 40:60, and the ratio w A + B : w C being very particularly preferably 50:50.
  • components A and / or B of the water-repellent finish additionally contain at least one amine of the formula CH 3 - (CH 2 ) m -N (CH 3 ) 2 , where m is preferably an integer in the range from 12 to 20, more preferably in the range from 14 to 18.
  • m 15 (cetyldimethylamine) or 17 (Dimethylstearylamine).
  • a mixture of cetyldimethylamine and dimethylstearylamine is very particularly preferred.
  • component C of the water-repellent finish additionally contains a zirconium salt, acetic acid and isopropanol.
  • a textile fabric comprising aramid fibers for example a fabric consisting of aramid fibers
  • the masking step which is described in comparative example 1 of FIG This application is described, and which is necessary if a textile fabric comprising aramid fibers is to be treated with a water-repellent finish which contains acrylate polymers which contain perfluoroalkyl groups with the structure CF 3 - (CF 2 ) x -CF 2 - with x ⁇ 6.
  • a water-repellent finish which contains acrylate polymers which contain perfluoroalkyl groups with the structure CF 3 - (CF 2 ) x -CF 2 - with x ⁇ 6.
  • a first premix comprising components A and B can be used to prepare the mixture used in step b) of the process according to the invention.
  • the first premix is preferably an aqueous emulsion which preferably comprises 20 to 30% by weight, more preferably 23 to 27% by weight, and particularly preferably 25% by weight A + B.
  • a second premix can be used to produce the mixture used in step b) of the process according to the invention, which comprises component C, that is to say the ester wax C1 and possibly the further paraffin wax C2.
  • the second premix is preferably an aqueous emulsion which preferably comprises 25 to 35% by weight, more preferably 28 to 32% by weight, and particularly preferably 30% by weight of C.
  • the finished textile fabric in step c) of the finishing process according to the invention is preferably dried at a drying temperature in the range from 130 to 180 ° C., particularly preferably from 140 to 170 ° C., during a drying time, preferably in the range from 60 to 240 seconds, particularly preferably from 90 to 180 seconds.
  • the reaction product of component A of the water-repellent finishing is obtained by reacting an aliphatic carboxylic acid with a methylolmelamine, the aliphatic carboxylic acid having a structure of the formula CH 3 - (CH 2 ) n -COOH, in which n is a means integer in the range from 15 to 25.
  • the water-repellent is Finish an aqueous emulsion.
  • the water-repellent finish additionally contains at least one amine of the formula CH 3 - (CH 2 ) m -N (CH 3 ) 2 , where m is an integer in the range from 12 to 20.
  • the water-repellent finishing additionally contains a zirconium salt, acetic acid and isopropanol.
  • a poly-p-phenylene terephthalamide filament yarn (TWARON®, Type 2040, 930dtex f1000 t0) is equipped with Leomin OR (Clariant, DE) in its manufacturing process after washing and before drying.
  • the dried fiber contains 0.6 to 0.8% by weight of Leomin OR solids.
  • the yarn resulting from a) is processed into a fabric with L 1/1 weave with 10.5 threads per cm in warp and weft and with a weight per unit area of 200 g / m 2 .
  • the tissue resulting from step 24) of c) is passed through a bath at room temperature, which consists of water and, based on the water, 60 g / l Oleophobol SL, 30 g / l Oleophobol SM and 10 g / l Phobol XAN (all from Huntsman, DE).
  • the fabric is then squeezed, dried at 130 ° C for 75 seconds and heat treated at a temperature of 190 ° C for 95 seconds.
  • the fabric Based on its weight, the fabric contains the state of equilibrium moisture in the normal climate of DIN EN ISO 139 / A1 (May 2008), ie at a temperature of 20.0 ⁇ 2.0 ° C and a relative humidity of 65 ⁇ 4.0 % approx. 0.75% by weight of the dry substance contained in Oleophobol SL, Oleophobol SM and Phobol XAN as water-repellent finish.
  • the water absorption of the finished fabric measured according to DIN EN 29 865 (November 1993) is 4.5% by weight after 10 minutes and 11.5% by weight after 60 minutes (see Table 1).
  • a further 22 layers of the fabric resulting from d) are piled up to form a dry package.
  • the water absorption before wet bombardment is 30% by weight (see Table 1).
  • the package is then bombarded with 9mm DM 41 bullets and the v 50 value is determined.
  • the v 50 value of the package when wet is 414 ⁇ 6 m / s (see Table 1).
  • Another 14 layers of the fabric resulting from d) are piled up to form a package.
  • the package is shot with splinters of the 1.1g FSP type and the v 50 value is determined.
  • the v 50 value of the package when dry is 483 ⁇ 9 m / s (see Table 1).
  • a further 14 layers of the tissue resulting from d) are saturated with water and piled up to form a package.
  • the package comes with splinters from Shard type 1.1g FSP and determine the v 50 value.
  • the v 50 value of the package in the wet state is 468 ⁇ 11 m / s (see Table 1).
  • a poly-p-phenylene terephthalamide filament yarn (Twaron Type 2040, 930 dtex, f1000 t0) is produced as in step a) of Comparative Example 1.
  • a fabric is produced from the aramid yarn obtained in a) as in step b) of Comparative Example 1.
  • the fabric is prewashed as in step c) of comparative example 1 (see steps 1) to 5)), rinsed (see steps 6) to 10)), rinsed (see steps 11 ) to13)), but not masked. This means that the fabric is dried after step 13) as in step 24).
  • the dried fabric is passed through a bath which is at room temperature and which contains an aqueous, equally proportioned mixture of 100 g / l Repellan HY-N and 100 g / l Repellan-BD (both from Pulcra Chemicals GmbH, DE).
  • Repellan HY-N is supplied as a 25% by weight aqueous emulsion containing a paraffin wax with a melting point of approx. 60 ° C, a reaction product of behenic acid with a methylolmelamine and additionally dimethylstearylamine and cetyldimethylamine.
  • Repellan BD is supplied as a 30% by weight aqueous emulsion which contains a paraffin wax with a melting point of approx. 55 ° C, an ester wax with a similar melting point and additionally a zirconium salt, acetic acid and isopropanol.
  • the fabric After leaving the bath, the fabric is dried at 170 ° C for 120 seconds. Additional heat treatment is not necessary and therefore does not take place.
  • the fabric Based on its weight, the fabric contains 1.9% by weight of the dry substance contained in Repellan HY-N and Repellan BD as water-repellent finish.
  • the water absorption of the finished fabric measured according to DIN EN 29 865 (November 1993) is 2.6% by weight after 10 minutes and 4.7% by weight after 60 minutes (see Table 1).
  • a further 22 layers of the fabric treated with the water-repellent described in d) are piled up to form a dry package.
  • W (w before - w after ) / w calculated before ⁇ 100%, where w before is the weight of the tissue package before and w after is the weight of the tissue package after watering and draining.
  • the water absorption before wet bombardment is 15% by weight (see Table 1).
  • the package is then bombarded with 9mm DM 41 bullets and the v 50 value is determined.
  • the v 50 value of the package when wet is 422 ⁇ 18 m / s (see Table 1).
  • Another 14 layers of the fabric treated with the water-repellent agent according to the invention are piled up to form a package.
  • the package is shot with splinters of the 1.1g FSP type and the v 50 value is determined.
  • the v 50 value of the package when dry is 470 ⁇ 8 m / s (see Table 1).
  • a further 14 layers of the fabric treated with the water-repellent agent according to the invention are piled up to form a dry package.
  • W (W before - w after) / W before ⁇ 100% is calculated, where w before the weight of the tissue package prior to and after the weight of the tissue package, after washing and draining is.
  • the water absorption before wet bombardment is 15% by weight (see Table 1).
  • the package is then bombarded with splinters of type 1.1g FSP and the v 50 value is determined.
  • the v 50 value of the package in the wet state is 459 ⁇ 16 m / s (see Table 1).
  • Comparative example 2 is carried out as example 1, but with the difference that that in step d) the bath contains an aqueous 200 g / l emulsion of Repellan HY-N (from Pulcra Chemicals GmbH, DE).
  • Comparative example 3 is carried out as example 1, but with the difference that in step d) the bath contains an aqueous 200 g / l emulsion of Repellan BD (from Pulcra Chemicals GmbH, DE).
  • Table 1 shows that the fabrics finished with the equal proportion mixture of Repellan HY-N and Repellan BD have a significantly lower water absorption than the fabrics finished with the (Oleophobol SL + Oleophobol SM + Phobol XAN) mixture.
  • the fabrics finished with the equal proportion mixture of Repellan HY-N and Repellan BD show the same high v 50 values as those with the (Oleophobol SL + Oleophobol SM + Phobol XAN) mixture within the error range of the v 50 determination equipped tissue packages.
  • the synergistic effect of the above-mentioned hydrophobizing components is also noticeable in a higher antiballistic effect when bombarded with bullets of the 9mm DM 41 specification:
  • v 5 values of the tissue packages were not measured. However, it can be assumed that due to the poorer hydrophobization of these fabrics in comparison to the fabrics of Example 1, the v 50 values of these fabric packages are less than 422 ⁇ 18 [m / s].
  • a poly-p-phenylene terephthalamide filament yarn (Twaron Type 2040, 930 dtex, f1000 t0) is produced as in step a) of Comparative Example 1.
  • a fabric is produced from the aramid yarn obtained in a) as in step b) of Comparative Example 1.
  • the fabric is prewashed as in step c) of comparative example 1 (see steps 1) to 5)), post-washed (see steps 6) to 10)) and then - unlike in Comparative Example 1 - sprayed with water in 4 spray passages, but not masked.
  • the dried fabric is passed through a bath at room temperature, which contains an aqueous, equally proportioned mixture of 80 g / l Repellan HY-N and 80 g / l Repellan-BD (both from Pulcra Chemicals GmbH, DE) and a pH Has a value of 4.
  • the fabric which showed a liquor pick-up of 36% after leaving the bath, was dried at 150 ° C. for 240 seconds. Additional heat treatment is not necessary and therefore does not take place.
  • the fabric Based on its weight, the fabric contains 1.52% by weight of the dry substance contained in Repellan HY-N and Repellan BD as a water-repellent finish.
  • the water absorption of the finished fabric measured according to DIN EN 29 865 (November 1993) is 3.31% by weight after 10 minutes.
  • the beading effect measured according to DIN EN 29 865 (November 1993) reaches rating level 4 on a scale from 1 to 5 (see the reference photographs in Figure 1 of DIN EN 29 865 (November 1993).
  • the stiffness of the finished fabric measured according to ASTM D4032 - 08 is 22.3 N.
  • Comparative example 4 is carried out as in example 2, with the difference that in step d) the bath contains an aqueous 160 g / l emulsion of Repellan HY-N (from Pulcra Chemicals GmbH, DE).
  • the water absorption of the finished fabric measured according to DIN EN 29 865 (November 1993) is 5.69% by weight after 10 minutes.
  • the beading effect measured according to DIN EN 29 865 (November 1993) reaches rating level 4.
  • the stiffness of the finished fabric measured according to ASTM D4032-08 is 26.8 N.
  • Comparative example 5 is carried out as in example 2, with the difference that in step d) the bath contains an aqueous 160 g / l emulsion of Repellan BD (from Pulcra Chemicals GmbH, DE).
  • the water absorption of the finished fabric measured according to DIN EN 29 865 (November 1993) is 8.14% by weight after 10 minutes.
  • the beading effect measured according to DIN EN 29 865 (November 1993) reaches rating level 4-3.
  • the stiffness of the finished fabric measured according to ASTM D4032-08 is 22.8 N.
  • Example 2 The results of Example 2 and Comparative Examples 4 and 5 are shown in Table 2.
  • Example 3 is carried out like example 2, with the difference that in step d), the fabric is passed through a bath which contains an aqueous, uniform mixture of 60 g / l Repellan HY-N and 60 g / l Repellan-BD (both from Pulcra Chemicals GmbH, DE) contains.
  • the fabric Based on its weight, the fabric contains 1.14% by weight of the dry substance contained in Repellan HY-N and Repellan BD as a water-repellent finish.
  • the water absorption of the finished fabric measured according to DIN EN 29 865 (November 1993) is 3.53% by weight after 10 minutes.
  • the beading effect measured according to DIN EN 29 865 (November 1993) reaches rating level 4 on a scale from 1 to 5 (see the reference photographs in Figure 1 of DIN EN 29 865 (November 1993).
  • the stiffness of the finished fabric measured according to ASTM D4032 - 08 is 22.8 N.
  • Comparative example 6 is carried out as example 2, but with the difference that in step d) the bath contains an aqueous 120 g / l emulsion of Repellan HY-N (from Pulcra Chemicals GmbH, DE).
  • the water absorption of the finished fabric measured according to DIN EN 29 865 (November 1993) is 6.65% by weight after 10 minutes.
  • the beading effect measured according to DIN EN 29 865 (November 1993) reaches rating level 4-3.
  • the stiffness of the finished fabric measured according to ASTM D4032-08 is 22.4 N.
  • Comparative example 7 is carried out as in example 2, with the difference that in step d) the bath contains an aqueous 120 g / l emulsion of Repellan BD (from Pulcra Chemicals GmbH, DE).
  • the water absorption of the finished fabric measured according to DIN EN 29 865 (November 1993) is 10.8% by weight after 10 minutes.
  • the beading effect measured according to DIN EN 29 865 (November 1993) reaches rating level 4-3.
  • the stiffness of the finished fabric measured according to ASTM D4032-08 is 18.5 N.
  • the results of Example 3 and Comparative Examples 6 and 7 are shown in Table 2.
  • Example 4 is carried out like Example 2, with the difference that in step d), the fabric is passed through a bath which contains an aqueous, equally proportioned mixture of 40 g / l Repellan HY-N and 40 g / l Repellan-BD (both from Pulcra Chemicals GmbH, DE) contains.
  • the fabric Based on its weight, the fabric contains 0.76% by weight of the dry substance contained in Repellan HY-N and Repellan BD as a water-repellent finish.
  • the beading effect measured according to DIN EN 29 865 (November 1993) reaches rating level 4 on a scale from 1 to 5 (see the reference photographs in Figure 1 of DIN EN 29 865 (November 1993).
  • the stiffness of the finished fabric measured according to ASTM D4032 - 08 is 22.1 N.
  • Comparative example 8 is carried out as in example 2, with the difference that in step d) the bath contains an aqueous 80 g / l emulsion of Repellan HY-N (from Pulcra Chemicals GmbH, DE).
  • the water absorption of the finished fabric measured according to DIN EN 29 865 (November 1993) is 4.37% by weight after 10 minutes.
  • the beading effect measured according to DIN EN 29 865 (November 1993) reaches rating level 4.
  • the stiffness of the finished fabric measured according to ASTM D4032-08 is 19.4 N.
  • Comparative example 9 is carried out as in example 2, with the difference that in step d) the bath contains an aqueous 80 g / l emulsion of Repellan BD (from Pulcra Chemicals GmbH, DE).
  • the water absorption of the finished fabric measured according to DIN EN 29 865 (November 1993) is 10.8% by weight after 10 minutes.
  • the beading effect measured according to DIN EN 29 865 (November 1993) reaches rating level 4-3.
  • the stiffness of the finished fabric measured according to ASTM D4032-08 is 16.5 N.
  • Example 4 and Comparative Examples 8 and 9 are shown in Table 2. ⁇ b> Table 2 ⁇ /b> Example 2 Comparative Example 4 Comparative Example 5 Example 3 Comparative Example 6 Comparative Example 7 Example 4 Comparative Example 8 Comparative Example 9 Repellan HY-N [g / l] 80 160 0 60 120 0 40 80 0 Repellan BD [g / l] 80 0 160 60 0 120 40 0 80 H 2 O uptake of the tissue after 10 minutes [%] 3.31 5.69 8.14 3.53 6.65 10.8 5.70 4.37 10.8 Beading effect of the fabric 4th 4th 4-3 4th 4-3 4-3 4th 4th 4-3 Tissue stiffness [N] 22.3 26.8 22.8 22.8 22.4 18.5 22.1 19.4 16.5
  • example 2 shows that the fabric which was passed through a bath which contained an equal mixture of 80 g / l Repellan HY-N and 80 g / Repellan BD has a lower stiffness as the comparative fabrics of Comparative Examples 4 and 5 which were passed through a bath containing 160 g / l Repellan HY-N and 160 g / Repellan BD, respectively.

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

Claims (14)

  1. Surface textile comprenant des fibres d'aramide et apprêtée avec un apprêt hydrofuge, dans laquelle l'apprêt hydrofuge comprend un mélange d'un composant A, d'un composant B et d'un composant C, dans laquelle
    - le composant A est un produit de réaction d'un acide carboxylique aliphatique avec une méthylolmélamine,
    - le composant B est une cire de paraffine et
    - le composant C est une cire d'ester C1 et/ou une autre cire de paraffine C2 et la cire de paraffine formant le composant B de l'apprêt hydrofuge a un point de fusion TB et l'autre cire de paraffine C2 du composant C a un point de fusion TC2, dans laquelle TC2 est inférieur à TB.
  2. Surface textile selon la revendication 1, caractérisée en ce que la surface textile, rapportée à son poids, atteint 0,8 à 4,0 % en poids de matière sèche de l'apprêt hydrofuge.
  3. Surface textile selon la revendication 1 ou 2, caractérisée en ce que le produit de réaction, lequel forme le composant A de l'apprêt hydrofuge, a été obtenu à partir de la mise en réaction d'un acide carboxylique aliphatique avec une méthylolmélamine, dans laquelle l'acide carboxylique aliphatique a une structure de formule CH3-(CH2)n-COOH, dans laquelle n représente un nombre entier dans la plage de 15 à 25.
  4. Surface textile selon l'une ou plusieurs des revendications 1 à 3, caractérisée en ce que, dans l'apprêt hydrofuge, le point de fusion TC2 de l'autre cire de paraffine C2 contenue dans l'apprêt hydrofuge est de 3 à 7 °C inférieur au point de fusion TB de la cire de paraffine.
  5. Surface textile selon l'une ou plusieurs des revendications 1 à 4, caractérisée en ce que la cire de paraffine contenue dans l'apprêt hydrofuge a au moins un hydrocarbure saturé, qui a un point de fusion TB dans la plage de 55 à 65 °C, et l'autre cire de paraffine C2 est au moins un hydrocarbure saturé, qui a un point de fusion TC2 dans la plage de 50 à 60 °C.
  6. Surface textile selon l'une ou plusieurs des revendications 1 à 5, caractérisée en ce que la cire d'ester C1 contenue dans l'apprêt hydrofuge a un point de fusion TC1 dans la plage de 50 à 60 °C.
  7. Surface textile selon la revendication 1, caractérisée en ce que l'apprêt comprend une émulsion aqueuse des composants A, B et C.
  8. Surface textile selon l'une ou plusieurs des revendications 1 à 7, caractérisée en ce que l'apprêt contient les composants A et B dans un pourcentage en poids WA+B et le composant C dans un pourcentage en poids Wc, dans lequel un rapport WA+B : WC se situe dans la plage de 70 : 30 à 30 : 70.
  9. Procédé pour fabriquer une surface textile comprenant des fibres d'aramide, lequel comprend les étapes suivantes consistant à :
    a) fournir une surface textile comprenant des fibres d'aramide,
    b) apprêter la surface textile avec un apprêt hydrofuge formulée de manière aqueuse et
    c) sécher la surface textile apprêtée,
    caractérisé en ce que
    - l'apprêt utilisé à l'étape b) comprend un mélange d'un composant A, d'un composant B et d'un composant C, dans lequel
    - le composant A est un produit de réaction d'un acide carboxylique aliphatique avec une méthylolmélamine,
    - le composant B est une cire de paraffine et
    - le composant C est une cire d'ester C1 et/ou une autre cire de paraffine C2, et
    - la surface textile séchée résultante à l'étape c) n'est soumise à aucun traitement thermique supplémentaire et que la cire de paraffine formant le composant B de l'apprêt hydrofuge a un point de fusion TB et l'autre cire de paraffine C2 du composant C a un point de fusion TC2, dans lequel TC2 est inférieur à TB.
  10. Composition d'apprêt hydrofuge comprenant un mélange de
    - un produit de réaction d'un acide carboxylique aliphatique avec une méthylolmélamine et
    - un composant choisi dans le groupe constitué de
    (1) une combinaison d'une cire de paraffine, laquelle a un point de fusion de 55 à 65 °C, et une cire d'ester, laquelle a un point de fusion de 50 à 60 °C,
    (2) une combinaison d'une première cire de paraffine, laquelle a un point de fusion de 55 à 65 °C, et d'une seconde cire de paraffine, laquelle a un point de fusion de 50 à 60 °C, dans laquelle le point de fusion de la seconde cire de paraffine est de 3 à 7 °C inférieur au point de fusion de la première cire de paraffine, et
    (3) une combinaison d'une première cire de paraffine, laquelle a un point de fusion de 55 à 65 °C, d'une cire d'ester, laquelle a un point de fusion de 50 à 60 °C, et d'une seconde cire de paraffine, laquelle a un point de fusion de 50 à 60 °C, dans laquelle le point de fusion de la seconde cire de paraffine est de 3 à 7 °C inférieur au point de fusion de la première cire de paraffine.
  11. Composition d'apprêt hydrofuge selon la revendication 10, caractérisée en ce que le produit de réaction du composant A de l'apprêt hydrofuge est obtenu par mise en réaction d'un acide carboxylique aliphatique avec une méthylolmélamine, dans laquelle l'acide carboxylique aliphatique a une structure de formule CH3-(CH2)n-COOH, dans laquelle n représente un nombre entier dans la plage de 15 à 25.
  12. Composition d'apprêt hydrofuge selon l'une ou plusieurs des revendications 10 et 11, caractérisée en ce que l'apprêt hydrofuge est une émulsion aqueuse.
  13. Composition d'apprêt hydrofuge selon l'une ou plusieurs des revendications 10 à 12, caractérisée en ce que l'apprêt hydrofuge contient en plus au moins une amine de formule CH3-(CH2)m-N(CH3)2, dans laquelle m représente un nombre entier dans la plage de 12 à 20.
  14. Composition d'apprêt hydrofuge selon l'une ou plusieurs des revendications 10 à 13, caractérisée en ce que l'apprêt hydrofuge contient en plus un sel de zirconium, de l'acide acétique et de l'isopropanol.
EP16725795.5A 2015-05-18 2016-05-18 Surface textile à apprêt hydrophobe et son procédé de production Active EP3298191B1 (fr)

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EP15167957 2015-05-18
PCT/EP2016/061062 WO2016184877A1 (fr) 2015-05-18 2016-05-18 Surface textile à apprêt hydrophobe et son procédé de production

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EP (1) EP3298191B1 (fr)
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CN (1) CN107709654B (fr)
BR (1) BR112017024575B1 (fr)
CA (1) CA2986180C (fr)
CO (1) CO2017012572A2 (fr)
IL (1) IL255657B (fr)
MX (1) MX2017014669A (fr)
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CA3141479A1 (fr) 2019-05-24 2020-12-03 Southern Mills, Inc. Tissus finis ignifuges presentant un caractere hydrofuge et leurs procedes de fabrication

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CH278260A (de) 1949-08-11 1951-10-15 Ciba Geigy Beständige, konzentrierte, wässerige Emulsion.
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CH515379A (de) * 1969-01-27 1971-12-31 Ciba Geigy Ag Verwendung wässeriger Emulsionen zum dauerhaft Wasserabweisendmachen von Textilmaterialien
DE3939341A1 (de) * 1989-11-29 1991-06-06 Bayer Ag Hydrophobierungs- und oleophobierungsmittel
JP2508343B2 (ja) * 1990-02-21 1996-06-19 旭硝子株式会社 フッ素系撥水撥油剤組成物
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WO2003051629A1 (fr) * 2001-12-14 2003-06-26 Hiraoka & Co., Ltd. Feuille antisalissure impermeable a l'eau
EP1396572B8 (fr) * 2002-09-06 2006-08-16 Teijin Twaron GmbH Procédé de fabrication d'un tissu d'aramide hydrofuge et son utilisation
US7485588B2 (en) * 2003-01-10 2009-02-03 Yunzhang Wang Method for making textile substrates having layered finish structure for improving liquid repellency and stain release
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BR112017024575B1 (pt) 2022-09-20
CN107709654B (zh) 2021-03-16
EP3298191A1 (fr) 2018-03-28
CN107709654A (zh) 2018-02-16
BR112017024575A2 (pt) 2018-07-31
KR102536443B1 (ko) 2023-05-26
MX2017014669A (es) 2018-04-24
CO2017012572A2 (es) 2018-02-28
RU2017142543A3 (fr) 2019-06-20
KR20180008535A (ko) 2018-01-24
RU2017142543A (ru) 2019-06-18
ZA201708308B (en) 2018-11-28
US20160340825A1 (en) 2016-11-24
IL255657B (en) 2021-02-28
CA2986180A1 (fr) 2016-11-24
CA2986180C (fr) 2023-02-14
RU2707937C2 (ru) 2019-12-02
US10683606B2 (en) 2020-06-16
WO2016184877A1 (fr) 2016-11-24
IL255657A (en) 2018-01-31

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