EP3298191B1 - Textile sheet material having a water-repellent finish and method for producing said sheet material - Google Patents

Description

The present invention relates to a water-repellent textile fabric and a method for its production.

Water-repellent textile fabrics are known.

1. (a) ein Melamin-Derivat, worin alle 6 H-Atome der drei NH₂-Gruppen durch (CH₂OR)_x und (CH₂O₂CR¹)_y substituiert sind, worin R eine C₁-C₆ - Alkylgruppe, R¹ eine aliphatische Kohlenwasserstoffgruppe mit 11-23 C-Atomen, y eine ganze Zahl von 2 bis 5 bedeutet, und x+y = 6 ist,
2. (b) ein Wachs und
3. (c) ein Tensid der Formel R²N(R³)₂·HO₂CR⁴, worin
   R² eine C₁₂-C₁₈ - Alkylgruppe,
   R³ eine C₁-C₄ - Alkylgruppe und
   R⁴CO₂H eine Carbonsäure mit mindestens 1 C-Atom ist,
   und wobei das Salz R²N(R³)₂·HO₂CR⁴ maximal 25 C-Atome enthält.

The patent specification US 3,480,579 describes a solid water repellent composition comprising

1. (a) a melamine derivative in which all 6 H atoms of the three NH ₂ groups are substituted by (CH ₂ OR) _x and (CH ₂ O ₂ CR ¹ ) _y , in which R is a C ₁ -C ₆ alkyl group R ^{1 is} an aliphatic hydrocarbon group with 11-23 carbon atoms, y is an integer from 2 to 5 and x + y = 6,
2. (b) a wax and
3. (c) a surfactant of the formula R ² N (R ³ ) ₂ · HO ₂ CR ⁴ , wherein
   R ^{2 is} a C ₁₂ -C ₁₈ alkyl group,
   R ^{3 is} a C ₁ -C ₄ alkyl group and
   R ⁴ CO ₂ H is a carboxylic acid with at least 1 C atom,
   and wherein the salt R ² N (R ³ ) ₂ · HO ₂ CR ^{4 contains} a maximum of 25 carbon atoms.

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.

The term "paraffin" according to " RÖMPP 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. For 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. In the technical field, 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.

The term "waxes" refers to " RÖMPP 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; The term "beeswax" refers to RÖMPP CHEMIE LEXIKON ", 9th edition, volume 1 (1989), page 412 a wax obtained from the honeycomb honeycomb with a melting point of 61-68 ° C. Beeswax consists of cerin, a mixture of cerotinic acid (hexacosanoic acid; C ₂₅ H ₅₁ -COOH; melting point = 88 ° C) and melissic acid (tricotanoic acid; H ₃ C- (CH ₂ ) ₂₈ -COOH; melting point = 93.4-94 ° C) and from an ester mixture called myricin , consisting of about 70 esters of C ₁₆ to C ₃₆ acids and C ₂₄ to C ₃₆ alcohols.

The term "fatty substances" denotes "fats" which according to " RÖMPP 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) has a melting point of 78 ° C. Consequently, esters of montanic acid with higher molecular fatty acids have a melting point above 78 ° C.

1. i) Imprägnieren der Fasermaterialien in einem Imprägnierbad, wobei man als Imprägnierbad eine wässrige Emulsion verwendet, enthaltend auf
   • 10 Teile eines Kondensationsproduktes aus einem mit 2 Mol Stearinsäure veresterten, hochveretherten Methylolmelaminmethylether und Stearinsäurediglycerid
   • 10 Teile Paraffin und neben geringen Mengen eines Härtungskatalysators weiterhin noch
   • 18 Teile des Acetats des ternären basischen Kondensationsproduktes aus einem hochveretherten Methylolmelaminmethylether, Stearinsäure und Triethanolamin,
2. ii) Trocknen der imprägnierten Fasermaterialien und
3. iii) Härten der Kondensationsprodukte in üblicher Weise, d.h. durch eine Wärmebehandlung, z.B. bei 120 bis 150 °C während 5 bis 15 Minuten.

The layout font DE 1 017 133 describes a method for rendering fiber materials water repellent

1. i) Impregnation of the fiber materials in an impregnation bath, an aqueous emulsion containing is used as the impregnation bath
   • 10 parts of a condensation product from a highly etherified methylolmelamine methyl ether and stearic acid diglyceride esterified with 2 mol of stearic acid
   • 10 parts of paraffin and in addition to small amounts of a curing catalyst still
   • 18 parts of the acetate of the ternary basic condensation product from a highly etherified methylolmelamine methyl ether, stearic acid and triethanolamine,
2. ii) drying the impregnated fiber materials and
3. iii) hardening the condensation products in the usual way, ie by heat treatment, for example at 120 to 150 ° C. for 5 to 15 minutes.

In particular for textile fabrics made of aramid fibers that are to be used in ballistic applications, a water-repellent finish is necessary in order to achieve the required protective effect, expressed by the v ₅₀ value. For this purpose it is known to use equipment which contains acrylate polymers which have perfluoroalkyl groups with the structure CF ₃ - (CF ₂ ) _x -CF ₂ - with x ≥ 6.

1. a) Vorlegen eines Aramidgarns,
2. b) Applizieren eines wasserabweisenden, vorzugsweise Fluor- und Kohlenstoffatome umfassendes Mittels auf das Aramidgarn, wobei Acrylat-Polymere, die Perfluor-Alkylgruppen mit der Struktur CF₃-(CF₂)_x-CF₂- mit x ≥ 6 aufweisen, besonders bevorzugt sind,
3. c) Trocknen des in Schritt b) resultierenden Aramidgarns,
4. d) Herstellen eines Gewebes aus dem in Schritt c) resultierenden Aramidgarn und
5. e) Wärmebehandlung des Gewebes.

EP 1 396 572 A1 describes a method for producing a water-repellent aramid fabric comprising the steps

1. a) presenting an aramid yarn,
2. b) applying a water-repellent agent, preferably comprising fluorine and carbon atoms, to the aramid yarn, acrylate polymers which have perfluoroalkyl groups with the structure CF ₃ - (CF ₂ ) _x -CF ₂ - with x ≥ 6 being particularly preferred ,
3. c) drying the aramid yarn resulting in step b),
4. d) producing a fabric from the aramid yarn resulting in step c) and
5. e) heat treatment of the fabric.

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. For ecological reasons, however, customers are increasingly demanding equipment that does not contain fluorine for textile fabrics made from aramid fibers.

Therefore, 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.

• die Komponente A ein Reaktionsprodukt einer aliphatischen Carbonsäure mit einem Methylolmelamin,
• die Komponente B ein Paraffinwachs und
• die Komponente C ein Esterwachs C1 und/oder ein weiteres Paraffinwachs C2 ist und dass das die Komponente B der wasserabweisenden Ausrüstung bildende Paraffinwachs einen Schmelzpunkt T_B und das weitere Paraffinwachs C2 der Komponente C einen Schmelzpunkt T_C2 hat, wobei T_C2 kleiner ist als T_B.

This object is surprisingly achieved by a textile fabric comprising aramid fibers and equipped with a water-repellent finish, the water-repellent finish comprising a mixture of a component A, a component B and a component C, wherein

• component A is a reaction product of an aliphatic carboxylic acid with a methylolmelamine,
• component B is a paraffin wax and
• component C is an ester wax C1 and / or a further paraffin wax C2 and that 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.

Surprisingly, 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.

• die Komponente A ein Reaktionsprodukt einer aliphatischen Carbonsäure mit einem Methylolmelamin,
• die Komponente B ein Paraffinwachs und
• die Komponente C ein Esterwachs C1 und/oder ein weiteres Paraffinwachs C2 ist und dass das die Komponente B der wasserabweisenden Ausrüstung bildende Paraffinwachs einen Schmelzpunkt T_B und das weitere Paraffinwachs C2 der Komponente C einen Schmelzpunkt T_C2 hat, wobei T_C2 kleiner ist als T_B, signifikant größer ist als die hydrophobierende Wirkung eines textilen Flächengebildes mit einer Ausrüstung, die entweder nur die Komponenten A und B oder nur die Komponente C umfasst.

Furthermore, it was surprisingly found that the hydrophobizing, ie water-repellent effect of the textile fabric according to the invention with a finish comprising a mixture of a component A, a component B and a component C, wherein

• component A is a reaction product of an aliphatic carboxylic acid with a methylolmelamine,
• component B is a paraffin wax and
• component C is an ester wax C1 and / or a further paraffin wax C2 and that 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 , wherein T _{C2 is} smaller than T _B , is significantly greater than the hydrophobizing effect of a textile fabric equipment that comprises only components A and B or only component C.

• eines Reaktionsproduktes einer aliphatischen Carbonsäure mit einem Methylolmelamin
• mit einem Paraffinwachs und
• mit einem Esterwachs C1 und/oder einem weiteren Paraffinwachs C2, wobei dass das die Komponente B der wasserabweisenden Ausrüstung bildende Paraffinwachs einen Schmelzpunkt T_B und das weitere Paraffinwachs C2 der Komponente C einen Schmelzpunkt T_C2 hat und wobei T_C2 kleiner ist als T_B, sind selbst dem Erfinder unbekannt.

The reasons for the synergistic increase in the hydrophobization of the textile fabric according to the invention through the interaction

• a reaction product of an aliphatic carboxylic acid with a methylolmelamine
• with a paraffin wax and
• with an ester wax C1 and / or a further paraffin wax C2, wherein 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 and wherein T _{C2 is} less than T _B , are unknown even to the inventor.

In the context of the present invention, the term “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. Therefore, in a preferred embodiment of the present invention, 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). Also suitable for the textile fabric according to the invention are 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.

In a preferred embodiment of the textile fabric according to the invention, 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. The term "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.

In a further preferred embodiment of the textile fabric according to the invention, the textile fabric is a woven fabric, knitted fabric, knitted fabric or a uniaxial or multiaxial scrim. When the fabric according to the invention is a woven fabric, 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.

In a further preferred embodiment of the textile fabric according to the invention, the woven fabric, the knitted fabric, the knitted fabric or the uniaxial or multiaxial scrim comprises fibers made of p-aramid.

• in einer besonders bevorzugten Ausführungsform Multifilamentgarne sind, die ganz besonders bevorzugt aus Poly(p-phenylenterephthalamid) bestehen, und
• in einer weiteren besonders bevorzugten Ausführungsform Stapelfasergarne sind, die ganz besonders bevorzugt aus Poly(p-phenylenterephthalamid) bestehen.

In a particularly preferred embodiment of the textile fabric according to the invention, the woven fabric, the knitted fabric, the knitted fabric or the uniaxial or multiaxial scrim consists of fibers made of p-aramid, the fibers

• in a particularly preferred embodiment are multifilament yarns which very particularly preferably consist of poly (p-phenylene terephthalamide), and
• in a further particularly preferred embodiment, staple fiber yarns which are very particularly preferably made of poly (p-phenylene terephthalamide) consist.

The above Multifilament yarns and staple fiber yarns are available under the name TWARON® from Teijin Aramid GmbH, DE.

In a preferred embodiment, 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.

In a further preferred embodiment, 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.

In a further preferred embodiment of the fabric according to the invention, 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. Furthermore, it is particularly preferred if the methylolmelamine is a mono-, di-, tri-, tetra-, penta-, or hexamethylolmelamine.

In a further particularly preferred embodiment, 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.

In the textile fabric according to the invention, 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.

In a further preferred embodiment of the textile fabric according to the invention, 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.

• das weitere Paraffinwachs C2, das in der wasserabweisenden Ausrüstung enthalten ist, mindestens ein gesättigter Kohlenwasserstoff, der einen Schmelzpunkt T_C2 im Bereich von 50 bis 60 °C hat, wobei der mindestens eine gesättigte Kohlenwasserstoff vorzugsweise ein Alkan ist, z.B. Tetracosan (C₂₄H₅₀; T_C2 = 52 °C), Pentacosan (C₂₅H₅₂; T_C2 = 54 °C), Hexacosan (C₂₆H₅₄; T_C2 = 56,4 °C) oder Heptacosan (C₂₇H₅₆; T_C2 = 59,5 °C) oder ein Gemisch aus mindestens zwei der eben genannten Alkane, jedoch immer unter der Bedingung, dass T_C2 des weiteren Paraffinwachses C2 um 3 bis 7 °C, vorzugsweise um 3 bis 5 °C, noch bevorzugter um 4 bis 6 °C und besonders bevorzugt um 5 °C kleiner ist als der Schmelzpunkt T_B des Paraffinwachses.

In a further preferred embodiment of the textile fabric according to the invention, the paraffin wax which is contained in the water-repellent finish is at least one saturated hydrocarbon which has a melting point T _B in the range from 55 to 65 ° C., the at least one saturated hydrocarbon preferably at least is an alkane, for example hexacosan (C ₂₆ H ₅₄ ; T _B = 56.4 ° C), heptacosan (C ₂₇ H ₅₆ ; T _B = 59.5 ° C), octacosane (C ₂₈ H ₅₈ ; T _B = 64 , 5 ° C) or nonacosan (C ₂₉ H ₆₀ ; T _B = 63.7 ° C) or a mixture of at least two of the alkanes just mentioned, and

• the further paraffin wax C2, which is contained in the water-repellent finish, at least one saturated hydrocarbon which has a melting point T _C2 in the range from 50 to 60 ° C., the at least one saturated hydrocarbon preferably being an alkane, for example tetracosane (C ₂₄ H ₅₀ ; T _C2 = 52 ° C), pentacosan (C ₂₅ H ₅₂ ; T _C2 = 54 ° C), hexacosan (C ₂₆ H ₅₄ ; T _C2 = 56.4 ° C) or heptacosan (C ₂₇ H ₅₆ ; T _C2 = 59.5 ° C) or a mixture of at least two of the alkanes just mentioned, but always under the condition that T _{C2 of} the further paraffin wax C2 by 3 to 7 ° C, preferably by 3 to 5 ° C, more preferably by 4 to 6 ° C and particularly preferably 5 ° C lower than the melting point T _{B of} the paraffin wax.

In a particularly preferred embodiment of the textile fabric according to the invention, 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.

In a further particularly preferred embodiment of the textile fabric according to the invention, 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.

In a further preferred embodiment of the fabric according to the invention, 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.

In a further preferred embodiment of the textile fabric according to the invention, 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. , wherein 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. It is particularly preferred if 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.

In a further preferred embodiment of the textile fabric according to the invention, 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. The above-described synergistic increase in the hydrophobization of the textile fabric according to the invention occurs both with the same and with different proportions by weight of w _{A + B} and w _c , although it is preferred that the ratio w _{A + B} : w _C in the case of different proportions by weight Range is from 70:30 to 30:30.

In a further preferred embodiment of the textile fabric according to the invention, 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. For example, m = 15 (cetyldimethylamine) or 17 (Dimethylstearylamine). A mixture of cetyldimethylamine and dimethylstearylamine is very particularly preferred.

In a further preferred embodiment of the textile fabric according to the invention, component C of the water-repellent finish additionally contains a zirconium salt, acetic acid and isopropanol.

1. a) Vorlegen eines textilen Flächengebildes umfassend Aramidfasern, vorzugsweise bestehend aus Aramidfasern, insbesondere aus p-Aramidfasern,
2. b) Ausrüsten des textilen Flächengebildes mit einer wasserabweisenden, wässrig formulierten Ausrüstung und
3. c) Trocknen des ausgerüsteten textilen Flächengebildes,
   dadurch gekennzeichnet, dass
   • die in Schritt b) eingesetzte Ausrüstung eine Mischung einer Komponente A, einer Komponente B und einer Komponente C umfasst, wobei
     • die Komponente A ein Reaktionsprodukt einer aliphatischen Carbonsäure mit einem Methylolmelamin,
     • die Komponente B ein Paraffinwachs und
     • die Komponente C ein Esterwachs C1 und/oder ein weiteres Paraffinwachs C2 ist, und
   • das in Schritt c) resultierende getrocknete Flächengebilde keiner zusätzlichen Wärmebehandlung unterzogen wird und dass das die Komponente B der wasserabweisenden Ausrüstung bildende Paraffinwachs einen Schmelzpunkt T_B und das weitere Paraffinwachs C2 der Komponente C einen Schmelzpunkt T_C2 hat, wobei T_C2 kleiner ist als T_B.

The textile fabric according to the invention comprising aramid fibers, preferably consisting of aramid fibers, is produced by a method which comprises the following steps:

1. a) presentation of a textile fabric comprising aramid fibers, preferably consisting of aramid fibers, in particular of p-aramid fibers,
2. b) equipping the textile fabric with water-repellent, water-formulated equipment and
3. c) drying the finished textile fabric,
   characterized in that
   • the equipment used in step b) comprises a mixture of a component A, a component B and a component C, wherein
     • component A is a reaction product of an aliphatic carboxylic acid with a methylolmelamine,
     • component B is a paraffin wax and
     • component C is an ester wax C1 and / or a further paraffin wax C2, and
   • the dried sheet resulting in step c) is not subjected to any additional heat treatment and that 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 same applies to the terms “textile fabric”, “aramid fibers” and for components A, B and C, as has been said, what has already been explained for the textile fabric according to the invention.

Surprisingly, it was found that after the above Textile fabrics produced according to the present method already develop their full water-repellent effect after drying step c).

On the other hand, one with the in EP 1 396 572 A1 described equipment with acrylate polymers, which have perfluoroalkyl groups with the structure CF ₃ - (CF ₂ ) _x -CF ₂ - with x ≥ 6, treated textile fabric comprising aramid fibers, for example a fabric made of aramid fibers, according to the Drying an additional heat treatment. Only in this way are the perfluoroalkyl groups arranged in the side chain of the polymers erected, so that it is only in this erected conformation of the perfluoroalkyl groups that the full water-repellent effect is achieved. Even those in the patent DE 870 544 and in the layout DE 1 017 133 The processes described for producing a water-repellent finish on fiber materials require additional heat treatment after the fiber materials impregnated with the finish described there have dried.

When treating a fabric comprising aramid fibers, e.g. a fabric consisting of aramid fibers, with the water-repellent finish used according to the invention, however, the additional heat treatment described above is omitted, as a result of which the finishing of textile fabrics comprising aramid fibers, e.g. of fabrics made of aramid fibers, is simplified and cheaper.

Furthermore, in the preparation of 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. This makes finishing textile fabrics comprising aramid fibers, for example fabrics consisting of aramid fibers, even easier and cheaper. For the preferred embodiments of components A, B and C in the mixture which is used in step b) of the process according to the invention, the same applies analogously as was said in the description of the water-repellent finish used according to the invention.

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.

Furthermore, 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.

• einem Reaktionsprodukt einer aliphatischen Carbonsäure mit einem Methylolmelamin und
• einer Komponente ausgewählt aus der Gruppe bestehend aus
  1. (1) einer Kombination eines Paraffinwachses, welches einen Schmelzpunkt von 55 bis 65 °C hat, und eines Esterwachses, welches einen Schmelzpunkt von 50 bis 60 °C hat,
  2. (2) einer Kombination eines ersten Paraffinwachses, welches einen Schmelzpunkt von 55 bis 65 °C hat, und eines zweiten Paraffinwachses, welches einen Schmelzpunkt von 50 bis 60 °C hat, wobei der Schmelzpunkt des zweiten Paraffinwachses um 3 bis 7 °C kleiner ist als der Schmelzpunkt des ersten Paraffinwachses, und
  3. (3) einer Kombination eines ersten Paraffinwachses, welches einen Schmelzpunkt von 55 bis 65 °C hat, eines Esterwachses, welches einen Schmelzpunkt von 50 bis 60 °C hat, und eines zweiten Paraffinwachses, welches einen Schmelzpunkt von 50 bis 60 °C hat, wobei der Schmelzpunkt des zweiten Paraffinwachses um 3 bis 7 °C kleiner ist als der Schmelzpunkt des ersten Paraffinwachses.

The present invention also includes a water repellent finishing composition comprising a mixture of

• a reaction product of an aliphatic carboxylic acid with a methylolmelamine and
• a component selected from the group consisting of
  1. (1) a combination of a paraffin wax which has a melting point of 55 to 65 ° C and an ester wax which has a melting point of 50 to 60 ° C,
  2. (2) a combination of a first paraffin wax, which has a melting point of 55 to 65 ° C, and a second paraffin wax, which has a melting point of 50 to 60 ° C, the melting point of the second paraffin wax being 3 to 7 ° C lower than the melting point of the first paraffin wax, and
  3. (3) a combination of a first paraffin wax, which has a melting point of 55 to 65 ° C, an ester wax, which has a melting point of 50 to 60 ° C, and a second paraffin wax, which has a melting point of 50 to 60 ° C, wherein the melting point of the second paraffin wax is 3 to 7 ° C lower than the melting point of the first paraffin wax.

In a preferred embodiment of the water-repellent finishing composition according to the invention, 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.

In a further preferred embodiment of the water-repellent finishing composition according to the invention, the water-repellent is Finish an aqueous emulsion.

In a further preferred embodiment of the water-repellent finish composition according to the invention, 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.

In a further preferred embodiment of the water-repellent finishing composition according to the invention, the water-repellent finishing additionally contains a zirconium salt, acetic acid and isopropanol.

The invention is explained in more detail in the following (comparative) examples.

Comparative Example 1 a) Production of an aramid yarn

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.

b) Fabrication of a fabric

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 .

c) Preparation of the fabric for finishing with a water-repellent agent containing acrylate polymers with perfluoroalkyl groups with the structure CF ₃ - (CF ₂ ) _x -CF ₂ - with x ≥ 6

1. 1) Einbau des in Rollenform angelieferten Gewebes in einen Jigger;
2. 2) Füllen des Jiggers mit Frischwasser;
3. 3) Aufheizen des Frischwassers auf 80 °C;
4. 4) Vorwaschen in 2 Passagen, wobei jede Passage aus
   • 4₁) einem Abwickeln des Gewebes von der Rolle,
   • 4₂) Führen des Gewebes durch die Tensid/Wasser-Mischung,
   • 4₃) Aufwickeln des Gewebes auf einer weiteren Rolle,
   • 4₄) Abwickeln des Gewebes von der weiteren Rolle,
   • 4₅) Führen des Gewebes durch die Tensid/Wasser-Mischung und
   • 4₆) Aufwickeln des Gewebes auf der Rolle
     besteht;
5. 5) Ablassen des Waschwassers aus dem Jigger;
6. 6) Füllen des Jiggers mit Frischwasser;
7. 7) Aufheizen des Frischwassers auf 80 °C;
8. 8) Zugabe des Tensides Kieralon OLB conc. (Fa. BASF) in einer auf das Frischwasser bezogenen Konzentration von 1 g/l;
9. 9) Nachwaschen in 10 Passagen, wobei jede Passage aus den o.g. Schritten 4₁ bis 4₆ besteht.
10. 10) Ablassen des Waschwassers aus dem Jigger;
11. 11) Füllen des Jiggers mit Frischwasser;
12. 12) Aufheizen des Frischwassers auf 80 °C;
13. 13) Spülen in 3 Passagen, wobei jede Passage aus den den o.g. Schritten 4₁ bis 4₆ entsprechenden Schritten besteht;
14. 14) Ablassen des Spülwassers;
15. 15) Füllen des Jiggers mit Frischwasser;
16. 16) Aufheizen des Frischwassers auf 80 °C;
17. 17) Zugabe des Maskierungsmittels Erional RF (Fa. Huntsman, DE in einer auf das Frischwasser bezogenen Konzentration von 3g/l;
18. 18) 10 Maskierungspassagen, wobei jede Maskierungspassage aus den den o.g. Schritten 4₁ bis 4₆ entsprechenden Schritten besteht;
19. 19) Ablassen des maskierungsmittelhaltigen Wassers aus dem Jigger;
20. 20) Füllen des Jiggers mit Frischwasser;
21. 21) Aufheizen des Frischwassers auf 80 °C;
22. 22) Spülen in 4 Passagen, wobei jede Passage aus den den o.g. Schritten 4₁ bis 4₆ entsprechenden Schritten besteht;
23. 23) Ausbau der Rolle mit dem Gewebe aus dem Jigger;
24. 24) Durchlaufenlassen des Gewebes bei 170 °C durch einem Trockenofen mit einer Verweilzeit des Gewebes im Ofen von ca. 60 Sekunden;

The tissue resulting from b) is pre-washed in the steps described below (see steps 1) to 5)), washed (see steps 6) to 10)), rinsed (see steps 11) to 14)), masked and dried (see Steps 15) to 24)).

1. 1) Installation of the tissue supplied in roll form in a jigger;
2. 2) filling the jigger with fresh water;
3. 3) heating the fresh water to 80 ° C;
4. 4) Prewash in 2 passages, with each passage made up
   • 4 ₁ ) unwinding the fabric from the roll,
   • 4 ₂ ) guiding the fabric through the surfactant / water mixture,
   • 4 ₃ ) winding the fabric on another roll,
   • 4 ₄ ) unwinding the fabric from the further roll,
   • 4 ₅ ) Pass the fabric through the surfactant / water mixture and
   • 4 ₆ ) Wind up the fabric on the roll
     consists;
5. 5) draining the wash water from the jigger;
6. 6) filling the jigger with fresh water;
7. 7) heating the fresh water to 80 ° C;
8. 8) Add the Kieralon OLB conc. (From BASF) in a concentration of 1 g / l based on the fresh water;
9. 9) Rinse in 10 passages, each passage consisting of steps 4 ₁ to 4 ₆ above.
10. 10) draining the wash water from the jigger;
11. 11) filling the jigger with fresh water;
12. 12) heating the fresh water to 80 ° C;
13. 13) Rinsing in 3 passages, each passage consisting of the steps corresponding to steps 4 ₁ to 4 ₆ above;
14. 14) draining the rinse water;
15. 15) filling the jigger with fresh water;
16. 16) heating the fresh water to 80 ° C;
17. 17) Add the Erional RF masking agent (from Huntsman, DE in a concentration of 3 g / l based on the fresh water;
18. 18) 10 masking passages, each masking passage consisting of the steps corresponding to steps 4 ₁ to 4 ₆ above;
19. 19) draining the water containing the masking agent from the jigger;
20. 20) filling the jigger with fresh water;
21. 21) heating the fresh water to 80 ° C;
22. 22) Rinsing in 4 passages, each passage consisting of the steps corresponding to steps 4 ₁ to 4 ₆ above;
23. 23) removing the roll with the tissue from the jigger;
24. 24) passing the fabric through at 170 ° C. through a drying oven with a residence time of the fabric in the oven of approx. 60 seconds;

d) finishing the fabric with a water-repellent agent containing acrylate polymers with perfluoroalkyl groups with the structure CF ₃ - (CF ₂ ) _x -CF ₂ - with x ≥ 6

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.

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).

e) Antiballistic properties

22 layers of the fabric resulting from d) are piled up to form a package. The package is bombarded with 9mm DM 41 bullets and the v ₅₀ value determined. The v ₅₀ value of the package when dry is 474 ± 9 m / s (see Table 1).

A further 22 layers of the fabric resulting from d) are piled up to form a dry package. To determine the water absorption W of the dry tissue package, the tissue package is sewn, soaked for 1 hour and left to drain for 3 minutes while hanging. The packet of fabrics is weighed before and after the washing, and 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 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).

example 1 a) Production of an aramid yarn

A poly-p-phenylene terephthalamide filament yarn (Twaron Type 2040, 930 dtex, f1000 t0) is produced as in step a) of Comparative Example 1.

b) Fabrication of a fabric

A fabric is produced from the aramid yarn obtained in a) as in step b) of Comparative Example 1.

c) Preparation of the fabric for finishing the fabric with a water-repellent agent according to the invention

To prepare the fabric for finishing with a water-repellent agent according to the invention, 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).

d) finishing the fabric with a water-repellent agent containing a paraffin wax with a melting point of about 60 ° C, the reaction product of behenic acid with a methylolmelamine, a paraffin wax with a melting point of about 55 ° C and an ester wax with a similar melting point

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.

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.

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).

e) Antiballistic properties

22 layers of the fabric treated with the water-repellent agent according to the invention are piled up to form a package. The package is bombarded with 9mm DM 41 bullets and the v ₅₀ value determined. The v ₅₀ value of the package when dry is 475 ± 4 m / s (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. To determine the water absorption W of the dry tissue package, the tissue package is sewn, soaked for 1 hour and left to drain for 3 minutes while hanging. The tissue package is made before and after watering weighed and 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. To determine the water absorption W of the dry tissue package, the tissue package is sewn, soaked for 1 hour and left to drain for 3 minutes while hanging. The packet of fabrics is weighed before and after the washing, and 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

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

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).

• "H₂O-Aufnahme nach 10, bzw. 60 Min." die Wasseraufnahme des ausgerüsteten und trockenen Gewebes, die nach 10 bzw. 60 Minuten gemessen wurde,
• "v₅₀ (trocken)" der v₅₀-Wert des ausgerüsteten und trockenen Gewebepakets, d.h. des Gewebepakets im Zustand der Gleichgewichtsfeuchte bei einer Temperatur von 20 ± 2 °C und bei einer relativer Feuchte von 65,0 ± 4 %,
• "v₅₀ (nass)" der v₅₀-Wert des ausgerüsteten und mit Wasser gesättigten Gewebepakets,
• "9 mm DM 41" Kugel-Munition der Spezifikation 9 mm DM 41,
• "1,1 g FSP" Splitter-Munition der Spezifikation 1,1 g FSP und
• "H₂O-Aufnahme vor Nassbeschuss" die Wasseraufnahme des trockenen und ausgerüsteten Gewebepakets vor dem Nassbeschuss.

Tabelle 1 Vergleichsbeispiel 1: Beispiel 1: Vergleichsbeispiel 2: Vergleichsbeispiel 3: Oleophobol SL+ Oleophobol SM + Phobol XAN Repellan HY-N + Repellan BD Repellan HY-N Repellan BD H₂O-Aufnahme des Gewebes nach 10 Min. [%] 4,5 2,6 8,5 4,9 H₂O-Aufnahme des Gewebes nach 60 Min. [%] 11,5 4,7 10,8 9,6 v₅₀ (trocken) des Pakets mit 22 Geweben 9mm DM 41 [m/s] 474 ± 9 475 ± 4 469 ± 4 - H₂O-Aufnahme des Pakets mit 22 Geweben vor Nassbeschuss [%] 30 15 27 - v₅₀ (nass) des Pakets mit 22 Geweben 9mm DM 41 [m/s] 414 ± 6 422 ± 18 285 ± 16 - v₅₀ (trocken) des Pakets mit 14 Geweben 1,1 g FSP [m/s] 483 ± 9 470 ± 8 469 ± 12 - H₂O-Aufnahme des Pakets mit 14 Geweben vor Nassbeschuss [%] - 15 20 - v₅₀ (nass) des Pakets mit 14 Geweben 1,1 g FSP [m/s] 468 ± 11 459 ± 16 479 ± 8 - The results of Example 1 and Comparative Examples 1 to 3 are shown in Table 1. Mean

• "H ₂ O uptake after 10 or 60 minutes." the water absorption of the finished and dry tissue, which was measured after 10 or 60 minutes,
• "v ₅₀ (dry)" is the v ₅₀ value of the finished and dry tissue package, ie the tissue package in the state of equilibrium moisture at a temperature of 20 ± 2 ° C and a relative humidity of 65.0 ± 4%,
• "v ₅₀ (wet)" is the v ₅₀ value of the finished and water-saturated tissue package,
• "9 mm DM 41" bullet ammunition of the specification 9 mm DM 41,
• "1.1 g FSP" sliver ammunition of the specification 1.1 g FSP and
• "H ₂ O absorption before wet bombardment" means the water absorption of the dry and equipped fabric package before wet bombardment.

<b> Table </b> 1 Comparative Example 1: Example 1: Comparative Example 2: Comparative Example 3: Oleophobol SL + Oleophobol SM + Phobol XAN Repellan HY-N + Repellan BD Repellan HY-N Repellan BD H ₂ O uptake of the tissue after 10 min. [%] 4.5 2.6 8.5 4.9 H ₂ O uptake of the tissue after 60 min. [%] 11.5 4.7 10.8 9.6 v ₅₀ (dry) of the package with 22 fabrics 9mm DM 41 [m / s] 474 ± 9 475 ± 4 469 ± 4 - H ₂ O absorption of the package with 22 fabrics before wet bombardment [%] 30th 15 27 - v ₅₀ (wet) of the package with 22 fabrics 9mm DM 41 [m / s] 414 ± 6 422 ± 18 285 ± 16 - v ₅₀ (dry) of the package with 14 tissues 1.1 g FSP [m / s] 483 ± 9 470 ± 8 469 ± 12 - H ₂ O absorption of the package with 14 fabrics before wet bombardment [%] - 15 20th - v ₅₀ (wet) of the package with 14 tissues 1.1 g FSP [m / s] 468 ± 11 459 ± 16 479 ± 8 -

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. When layered into a fabric package, 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.

• schon bei der Vorbereitung des Gewebes für die Ausrüstung durch Wegfall der Maskierung
• und nach der Trocknung des ausgerüsteten Gewebes durch Wegfall einer weiteren Wärmebehandlung
  deutlich einfacher durchzuführen ist.

These results are all the more surprising when finishing the fabric with Repellan HY-N and Repellan BD

• already when preparing the fabric for the equipment by eliminating the masking
• and after the finished fabric has dried by eliminating further heat treatment
  is much easier to carry out.

The comparison of Example 1 with Comparative Example 2 shows that after 10 minutes the H ₂ O uptake of the fabric hydrophobicized with the aqueous, uniformly proportioned mixture of 100 g / l Repellan HY-N and 100 g / l Repellan BD is only 2.6% and thus 8.5: 2.6 = 3.3 times smaller than that of the fabric which has been hydrophobized with an aqueous 200 g / l Repellan HY-N emulsion.

The comparison of Example 1 with Comparative Example 3 shows that after 10 minutes the H ₂ O uptake of the tissue hydrophobicized with the aqueous, equally proportioned mixture of 100 g / l Repellan HY-N and 100 g / l Repellan BD is only 2.6% and thus 4.9: 2.6 = 1.9 times smaller than in the case of the fabric which was hydrophobized with an aqueous 200 g / l Repellan BD emulsion.

The comparison of Example 1 with Comparative Example 2 shows that after 60 minutes the H ₂ O uptake of the 100 g / l mixture with the aqueous component Repellan HY-N and 100 g / l Repellan BD hydrophobicized fabric is only 4.7% and is thus 10.8: 4.7 = 2.3 times smaller than the fabric that is made with an aqueous 200 g / l Repellan HY -N emulsion was made hydrophobic.

The comparison of Example 1 with Comparative Example 3 shows that after 60 minutes the H ₂ O uptake of the tissue hydrophobicized with the aqueous, equally proportioned mixture of 100 g / l Repellan HY-N and 100 g / l Repellan BD is only 4.7% and thus 9.6: 4.7 = 2.0 times smaller than that of the fabric which has been hydrophobized with an aqueous 200 g / l Repellan BD emulsion.

• das in Repellan HY-N enthaltene Paraffinwachs mit einem Schmelzpunkt von ca. 60 °C und das Reaktionsprodukt von Behensäure mit einem Methylolmelamin und
• das in Repellan BD enthaltenen Paraffinwachs mit einem Schmelzpunkt von ca. 55 °C und das Esterwachs mit ähnlichem Schmelzpunkt
  in synergistischer Weise einen Grad der Hydrophobierung bewirken, der signifikant größer ist als die Hydrophobierung, die durch die gleiche Menge von Repellan HY-N, bzw. von Repellan BD erzielt wird.

Thus, the comparison of the hydrophobization achieved in Example 1 with the hydrophobization achieved in Comparative Examples 2 and 3 shows that

• the paraffin wax contained in Repellan HY-N with a melting point of approx. 60 ° C and the reaction product of behenic acid with a methylolmelamine and
• the paraffin wax contained in Repellan BD with a melting point of approx. 55 ° C and the ester wax with a similar melting point
  effect in a synergistic manner a degree of hydrophobization which is significantly greater than the hydrophobization which is achieved by the same amount of Repellan HY-N or Repellan BD.

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: The tissue package hydrophobicized with the aqueous, equally proportioned mixture of 100 g / l Repellan HY-N and 100 g / l Repellan BD shows with v ₅₀ = 422 ± 18 [m / s] an antiballistic effect, which is (422: 285) = 1.5 greater than the antiballistic effect of the tissue package, which with an aqueous 200 g / l Repellan HY-N Emulsion was made hydrophobic. Furthermore, the water absorption before wet bombardment is 15% lower by a factor (27:15) = 1.8. Before bombardment with splinters Specification 1.1 g FSP, the water absorption is 15% lower by a factor (20:15) = 1.3.

The v ₅ values of the tissue packages, the tissues of which were hydrophobized with an aqueous 200 g / l Repellan BD emulsion, 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].

Example 2 a) Production of an aramid yarn

A poly-p-phenylene terephthalamide filament yarn (Twaron Type 2040, 930 dtex, f1000 t0) is produced as in step a) of Comparative Example 1.

b) Fabrication of a fabric

A fabric is produced from the aramid yarn obtained in a) as in step b) of Comparative Example 1.

c) Preparation of the fabric for finishing the fabric with a water-repellent agent according to the invention

To prepare the fabric for finishing with a water-repellent agent according to the invention, 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.

This means that the roll with the fabric after step 13) is removed as in step 23 and the fabric is dried as in step 24).

d) finishing the fabric with a water-repellent agent containing a paraffin wax with a melting point of about 60 ° C, the reaction product of behenic acid with a methylolmelamine, a paraffin wax with a melting point of about 55 ° C and an ester wax with a similar melting point

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.

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

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

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.

The results of Example 2 and Comparative Examples 4 and 5 are shown in Table 2.

Example 3

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.

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

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

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

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.

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 measured according to DIN EN 29 865 (November 1993) Water absorption of the finished fabric is 5.70% 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 22.1 N.

Comparative Example 8

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

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.

The results of 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

The comparison of Example 2 with Comparative Example 4 shows that after 10 minutes the H ₂ O uptake of the tissue hydrophobicized with the aqueous, equally proportioned mixture of 80 g / l Repellan HY-N and 80 g / l Repellan BD is only 3.31% and thus 5.69: 3.31 = 1.7 times smaller than in the case of the fabric which was hydrophobized with an aqueous 160 g / l Repellan HY-N emulsion.

The comparison of Example 2 with Comparative Example 5 shows that after 10 minutes the H ₂ O uptake of the fabric hydrophobicized with the aqueous, equally proportioned mixture of 80 g / l Repellan HY-N and 80 g / l Repellan BD is only 3.31% and thus 8.14: 3.31 = 2.5 times smaller than in the case of the fabric which was hydrophobized with an aqueous 160 g / l Repellan BD emulsion.

• das in Repellan HY-N enthaltene Paraffinwachs mit einem Schmelzpunkt von ca. 60 °C und das Reaktionsprodukt von Behensäure mit einem Methylolmelamin und
• das in Repellan BD enthaltenen Paraffinwachs mit einem Schmelzpunkt von ca. 55 °C und das Esterwachs mit ähnlichem Schmelzpunkt
  in synergistischer Weise einen Grad der Hydrophobierung bewirken, der signifikant größer ist als die Hydrophobierung, die durch die gleiche Menge von Repellan HY-N, bzw. von Repellan BD erzielt wird.

Thus, the comparison of the hydrophobization achieved in Example 2 with the hydrophobization achieved in Comparative Examples 4 and 5 shows that

• the paraffin wax contained in Repellan HY-N with a melting point of approx. 60 ° C and the reaction product of behenic acid with a methylolmelamine and
• the paraffin wax contained in Repellan BD with a melting point of approx. 55 ° C and the ester wax with a similar melting point
  effect in a synergistic manner a degree of hydrophobization which is significantly greater than the hydrophobization which is achieved by the same amount of Repellan HY-N or Repellan BD.

Furthermore, the comparison of example 2 with comparative examples 4 and 5 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.

The comparison of Example 3 with Comparative Example 6 shows that after 10 minutes the H ₂ O uptake of the tissue hydrophobicized with the aqueous, evenly proportioned mixture of 60 g / l Repellan HY-N and 60 g / l Repellan BD is only 3.53% and thus 6.65: 3.53 = 1.9 times smaller than the fabric that was hydrophobized with an aqueous 120 g / l Repellan HY-N emulsion.

The comparison of Example 3 with Comparative Example 7 shows that after 10 minutes the H ₂ O uptake of the fabric hydrophobicized with the aqueous, equally proportioned mixture of 60 g / l Repellan HY-N and 60 g / l Repellan BD is only 3.53% and thus 10.8: 3.53 = 3.1 times smaller than in the case of the fabric which was hydrophobized with an aqueous 120 g / l Repellan BD emulsion.

• das in Repellan HY-N enthaltene Paraffinwachs mit einem Schmelzpunkt von ca. 60 °C und das Reaktionsprodukt von Behensäure mit einem Methylolmelamin und
• das in Repellan BD enthaltenen Paraffinwachs mit einem Schmelzpunkt von ca. 55 °C und das Esterwachs mit ähnlichem Schmelzpunkt

in synergistischer Weise einen Grad der Hydrophobierung bewirken, der signifikant größer ist als die Hydrophobierung, die durch die gleiche Menge von Repellan HY-N, bzw. von Repellan BD erzielt wird.Thus, the comparison of the hydrophobization achieved in Example 3 with the hydrophobization achieved in Comparative Examples 6 and 7 shows that

• the paraffin wax contained in Repellan HY-N with a melting point of approx. 60 ° C and the reaction product of behenic acid with a methylolmelamine and
• the paraffin wax contained in Repellan BD with a melting point of approx. 55 ° C and the ester wax with a similar melting point

effect in a synergistic manner a degree of hydrophobization which is significantly greater than the hydrophobization which is achieved by the same amount of Repellan HY-N or Repellan BD.

Claims (14)

1. A textile fabric comprising aramid fibres and provided with a water-repellent finish, wherein the water-repellent finish comprises a mixture of a component A, a component B and a component C, wherein

   - component A is a reaction product of an aliphatic carboxylic acid with a methylolmelamine;

   - component B is a paraffin wax and

   - component C is an ester wax C1 and/or a further paraffin wax C2 and the paraffin wax forming the component B of the water-repellent finish has a melting point T_B and the further paraffin wax C2 of the component C has a melting point T_C2, where T_C2 is lower than T_B.
2. Textile fabric according to claim 1, characterised in that the textile fabric contains 0.8 to 4.0% by weight, in relation to its weight, of dry substance of the water-repellent finish.
3. Textile fabric according to claim 1 or 2, characterised in that the reaction product which constitutes component A of the water-repellent finish has been obtained from the reaction of an aliphatic carboxylic acid with a methylolmelamine, wherein the aliphatic carboxylic acid has a structure of the formula CH₃-(CH₂)_n-COOH wherein n is an integer in the range of 15 to 25.
4. Textile fabric according to one or more of claims 1 to 3, characterised in that in the water-repellent finish the melting point T_C2 of the paraffin wax C2 also contained in the water-repellent finish is 3 to 7°C lower than the melting point T_B of the paraffin wax.
5. Textile fabric according to one or more of claims 1 to 4, characterised in that the paraffin wax contained in the water-repellent finish is at least one saturated hydrocarbon which has a melting point T_B in the range of 55 to 65°C and the further paraffin wax C2 is at least one saturated hydrocarbon which has a melting point T_C2 in the range of 50 to 60°C.
6. Textile fabric according to one or more of claims 1 to 5, characterised in that the ester wax C1 contained in the water-repellent finish has a melting point T_C1 in the range of 50 to 60°C.
7. Textile fabric according to claim 1, characterised in that the finish comprises an aqueous emulsion of components A, B and C.
8. Textile fabric according to one or more of claims 1 to 7, characterised in that the finish comprises components A and B in a percentage by weight W_A+B and component C in a percentage by weight W_C, wherein a ratio W_A+B: W_C is in the range of 70:30 to 30:70.
9. Method for the production of a textile fabric comprising aramid fibres, which comprises the following steps:

   a) Provision of a textile fabric comprising aramid fibres;

   b) Finishing the textile fabric with a water-repellent, aqueously formulated finish and

   c) Drying the finished textile fabric,
   characterised in that

   - the finish used in step b) comprises a mixture of a component A, a component B and a component C; wherein

   - component A is a reaction product of an aliphatic carboxylic acid with a methylolmelamine,

   - component B is a paraffin wax and

   - component C is an ester wax C1 and/or a further paraffin wax C2, and

   - the dried fabric resulting in step c) is not subjected to any additional heat treatment and in that 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 lower than T_B.
10. A water-repellent finish composition comprising a mixture of

    - a reaction product of an aliphatic carboxylic acid with a methylolmelamine, and

    - a component selected from the group consisting of

    (1) a combination of a paraffin wax which has a melting point of 55 to 65°C and an ester wax which has a melting point of 50 to 60°C,

    (2) a combination of a first paraffin wax which has a melting point of 55 to 65°C and a second paraffin wax which has a melting point of 50 to 60°C, wherein the melting point of the second paraffin wax is 3 to 7°C lower than the melting point of the first paraffin wax, and

    (3) a combination of a first paraffin wax having a melting point of 55 to 65°C, an ester wax having a melting point of 50 to 60°C, and a second paraffin wax having a melting point of 50 to 60°C, wherein the melting point of the second paraffin wax is 3 to 7°C lower than the melting point of the first paraffin wax.
11. A water-repellent finish composition according to claim 10, characterised in that the reaction product of component A of the water repellent finish is obtained by reacting an aliphatic carboxylic acid with a methylolmelamine, wherein the aliphatic carboxylic acid has a structure of the formula CH₃-(CH₂)_n-COOH where n is an integer in the range of 15 to 25.
12. A water-repellent finish composition according to one or more of claims 10 and 11, characterised in that the water-repellent finish is an aqueous emulsion.
13. A water-repellent finish composition according to one or more of claims 10 to 12, characterised in that the water repellent finish additionally comprises at least one amine of the formula CH₃-(CH₂)_m-N(CH₃)₂ where m is an integer in the range of 12 to 20.
14. A water-repellent finish composition according to one or more of claims 10 to 13, characterised in that the water-repellent finish additionally comprises a zirconium salt, acetic acid and isopropanol.