EP0283556A2 - Process for the production of textile coverings coated with polyurethane, textile coverings coated with polyurethane and their use in producing breathing and water repellent finishes - Google Patents

Process for the production of textile coverings coated with polyurethane, textile coverings coated with polyurethane and their use in producing breathing and water repellent finishes Download PDF

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Publication number
EP0283556A2
EP0283556A2 EP87114169A EP87114169A EP0283556A2 EP 0283556 A2 EP0283556 A2 EP 0283556A2 EP 87114169 A EP87114169 A EP 87114169A EP 87114169 A EP87114169 A EP 87114169A EP 0283556 A2 EP0283556 A2 EP 0283556A2
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EP
European Patent Office
Prior art keywords
polyurethane
coated
dispersion
anionic
cationic
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP87114169A
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German (de)
French (fr)
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EP0283556A3 (en
EP0283556B1 (en
Inventor
Kurt Dr. Dahmen
Dolf Dr. Stockhausen
Karl-Heinz Stukenbrock
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Stockhausen GmbH and Co KG
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Chemische Fabrik Stockhausen GmbH
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Publication of EP0283556A3 publication Critical patent/EP0283556A3/en
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Publication of EP0283556B1 publication Critical patent/EP0283556B1/en
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Classifications

    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
    • D06N3/12—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins
    • D06N3/14—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins with polyurethanes
    • D06N3/141—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins with polyurethanes mixture of two or more polyurethanes in the same layer
    • A—HUMAN NECESSITIES
    • A41—WEARING APPAREL
    • A41D—OUTERWEAR; PROTECTIVE GARMENTS; ACCESSORIES
    • A41D31/00—Materials specially adapted for outerwear
    • A41D31/04—Materials specially adapted for outerwear characterised by special function or use
    • A41D31/10—Impermeable to liquids, e.g. waterproof; Liquid-repellent
    • A41D31/102—Waterproof and breathable
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/23907—Pile or nap type surface or component
    • Y10T428/2395—Nap type surface
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T442/00—Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
    • Y10T442/20—Coated or impregnated woven, knit, or nonwoven fabric which is not [a] associated with another preformed layer or fiber layer or, [b] with respect to woven and knit, characterized, respectively, by a particular or differential weave or knit, wherein the coating or impregnation is neither a foamed material nor a free metal or alloy layer
    • Y10T442/2041—Two or more non-extruded coatings or impregnations
    • Y10T442/2098—At least two coatings or impregnations of different chemical composition
    • Y10T442/2107—At least one coating or impregnation contains particulate material
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T442/00—Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
    • Y10T442/20—Coated or impregnated woven, knit, or nonwoven fabric which is not [a] associated with another preformed layer or fiber layer or, [b] with respect to woven and knit, characterized, respectively, by a particular or differential weave or knit, wherein the coating or impregnation is neither a foamed material nor a free metal or alloy layer
    • Y10T442/2213—Coating or impregnation is specified as weather proof, water vapor resistant, or moisture resistant
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T442/00—Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
    • Y10T442/20—Coated or impregnated woven, knit, or nonwoven fabric which is not [a] associated with another preformed layer or fiber layer or, [b] with respect to woven and knit, characterized, respectively, by a particular or differential weave or knit, wherein the coating or impregnation is neither a foamed material nor a free metal or alloy layer
    • Y10T442/2221—Coating or impregnation is specified as water proof
    • Y10T442/2246—Nitrogen containing
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T442/00—Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
    • Y10T442/30—Woven fabric [i.e., woven strand or strip material]
    • Y10T442/3325—Including a foamed layer or component
    • Y10T442/3366—Woven fabric is coated, impregnated, or autogenously bonded
    • Y10T442/3374—Coating or impregnation includes particulate material other than fiber

Definitions

  • the invention relates to a process for the production of polyurethane-coated textile fabrics, the use of polyurethane-coated textile fabrics and their use for the production of breathable and water-repellent finishing.
  • Fabrics are increasingly in demand for sports, leisure and rain protection clothing, which on the one hand are water and wind resistant on the outside, and on the other hand discharge water vapor from the inside to the outside.
  • the textiles provided are made hydrophobic. This gives good breathability and water repellency (water repellency), but not water resistance.
  • water repellency water repellency
  • several new developments have been presented to improve water resistance, for example in chemical fibers / textile industry, 36th / 88th. Volume, 1986, p. 66.
  • One possibility is the lamination of a carrier material with membranes or microporous foils based on hydrophilic copolyesters or polyurethanes, the porosity sometimes having to be created subsequently by fine perforation of the plastic sheets by means of electron beams.
  • Another possibility is to coat a support with solvent-containing polyurethanes to form a compact, microporous PU layer.
  • All of these processes have disadvantages in that solvent-based adhesives have to be used for the lamination and solvents have to be used for the coating, the processing of which increasingly poses problems with regard to costs, flammability, toxicity and pollution.
  • a fibrous, porous sheet material is impregnated with an aqueous, ionic dispersion of a polyurethane with covalently bound, solubilizing, ionizable groups and then coagulated with aqueous acid or alkali solutions.
  • the procedure requires working with large amounts of liquid, firstly during the coagulation itself, but then also when washing out and neutralizing the coagulant used; this means that a multitude of aggregates is required for this process, which are not available in most equipment factories.
  • a coagulation time of 5 minutes does not correspond to normal practical conditions because it makes rational production impossible.
  • the object of the invention is to improve the durability of the polyurethane layer applied to such a sheet material and thus to achieve a long-lasting water-tightness of the coated material, which also withstands cleaning and washing.
  • polyurethane dispersions which can be used for the process according to the invention are commercially available and are prepared by known processes, as described, for example, in DE-OS 29 31 044. They contain polyurethanes with ionic or ionizable groups which are covalently bonded to the main polymer chain and which disperse the polymer in water enable. If the solubilizing, covalently bonded groups are carboxyl or sulfonic acid groups or their salts, one speaks of anionic polyurethane dispersions. If the solubilizing group covalently bound to the polymer chain is an amino group or its salt, it is a cationic polyurethane dispersion.
  • Such dispersions often contain a solids content of between 10 and 60% by weight, usually between 30 and 50% by weight.
  • the viscosity of the commercially available, aqueous polyurethane dispersions can vary widely between 10 and 200,000 mPa.s.
  • Such process steps are familiar to the person skilled in the art of coating technology, and he can determine the correct selection according to the type and amount of the necessary viscosity regulators with a few preliminary tests.
  • the coating pastes are preferably adjusted to viscosities between 50,000 and 200,000 mPa.s.
  • the anionic and cationic polyurethane dispersions are used in a weight ratio of 1: 2 to 2: 1, preferably in a weight ratio of 1: 1, for the primer and topcoat according to the in-line two-coat technology.
  • Preference is given to amounts by weight of oppositely charged aqueous polyurethane dispersions such that the anionic and the cationic, covalently bonded, solubilizing groups are present in stoichiometrically equivalent amounts.
  • the procedure can be such that the anionic dispersion is spread onto the substrate as the first coat and then the cationic dispersion is applied, wet-on-wet, or vice versa, that the cationic polyurethane dispersion is used as the primer and the anionic dispersion is used as the top coat without intermediate drying .
  • Pre-coat and top coat can each be applied as a compact coat, e.g. according to the air knife method.
  • the top coat can be applied as a foam, e.g. with a roller squeegee.
  • the foam application gives the textile material thus finished a particularly soft and voluminous handle and a good textile fall.
  • the wet layers of anionic and cationic coating are selected in such a range that the finished material has a total dry layer of between 5 and 50 g / m2, preferably between 15 and 35 g / m2 .
  • the equipment on the units used in the coating technology is applied in the usual way Temperatures between 80 and 180 ° C, preferably between 120 - 140 ° C, dried and optionally slightly calendered while still warm.
  • the invention further relates to the textile fabrics manufactured by the process according to the invention and coated with polyurethane and their use for the production of breathable, water vapor-permeable, but water and wind repellent clothing or technical textiles, such as, for example Tarpaulins, or of leather substitutes.
  • the finished textiles can be sanded or sanded afterwards and thus give them a suede-like or suede-like appearance without worsening the other technical properties. In this way it is possible to produce leather substitutes.
  • a paste is prepared 100 parts by weight of an aqueous, cationic polyurethane dispersion with a solids content of 30% by weight and a viscosity of 50 mPa.s, prepared by a known process from a polypropylene glycol with a molecular weight of 1000 and a hydroxyl number of 112, from dicyclohexylmethane diisocyanate and N- Methyldiethanolamine as a solubilizing, cationic component and 5 parts by weight of a 50% aqueous solution of a nonionic thickener based on polyurethane (eg BORCHIGEL L 75).
  • a 50% aqueous solution of a nonionic thickener based on polyurethane eg BORCHIGEL L 75.
  • the paste has a viscosity of 60,000 mPa.s (Brookfield RVT, spindle 6/10 U min ⁇ 1).
  • the paste is applied to a commercially available polyester / cotton 66/33 cotton fabric using the air knife method coated with a basis weight of 160 g / m2 and results in a wet coating of 30 g / m2.
  • the pre-coated fabric is treated in a second coat with a paste of the following composition: 70 parts by weight of an aqueous, anionic polyurethane dispersion with a solids content of 40% by weight and a viscosity of 300 mPa.s, produced by a known process from a polyether polyol (propylene oxide / ethylene oxide adduct based on glycerol with a molecular weight of 4000) , from isophorone diisocyanate and dimethylolpropionic acid as a solubilizing, anionic component. 1 part by weight defoamer based on Mg stearate, 23 parts by weight of water and 6 parts by weight of thickener (BORCHIGEL L 75).
  • the wet coating for the second coat is 40 g / m2.
  • the coated fabric is then dried in an air drying cabinet at 90 ° C. for 2 minutes and then subjected to hydrophobization. For this purpose, it is immersed in a float composed of 40 g / l of a fluorocarbon resin emulsion, squeezed onto a 43% wet pad and dried and condensed in a drying cabinet at 170 ° C. for 4 minutes.
  • the fabric is then placed on a two-roll calender between a steel and calendered a plastic roller, the temperature of the steel roller 170 ° C, the pressure 150 kg / cm2 linear and the working speed 10 m / min.
  • the fabric thus finished has a total dry coating of 21 g / m2 of polyurethane. The measurement results are shown in the table.
  • aqueous, anionic polyurethane dispersion is applied as the first coat and an aqueous, cationic polyurethane dispersion as the second coat.
  • Pastes of the following composition are used for this:
  • an aqueous, anionic polyurethane dispersion with a solids content of 40% by weight and a viscosity of 40 mPa.s prepared by known processes from a linear, hydroxyl-containing polyester based on diethylene glycol and adipic acid with an OH number of 43 , from trimethyl-1, 6-hexamethylene diisocyanate and dimethylolpropionic acid as solubilizing anionic component, 1 part by weight of defoaming agent based on Ca stearate, 18 parts by weight of water 6 parts by weight of a 50% aqueous solution of a non-ionic thickener based on polyurethane (BORCHIGEL L 75).
  • the finished fabric has a total dry coating of polyurethane of 17 g / m2 and, after post-hydrophobization according to Example 1, gives the measurement values listed in the table.
  • a fabric as described in Example 1 was coated with a spreading paste of the following composition using the air knife method: 80 parts by weight of an aqueous, cationic polyurethane dispersion with a solids content of 30% by weight and a viscosity of 200 mPa.s, prepared by a known method from a Mixture of polyol components from polypropylene glycol with a molecular weight of 1000, trimethylolpropane and ethylene glycol, from dicyclohexylmethane diisocyanate and N-methyldiethanolamine as a solubilizing, cationic component, 2 parts by weight of stearate-based defoaming agent 5 parts by weight of thickener (BORCHIGEL L 75) 13 parts by weight of water
  • the wet coating for the primer was 60 g / m2, corresponding to a dry coating of 15 g / m2.
  • the fabric coated in this way was dried in a Benz laboratory dryer at 90 ° C. for 2 minutes and then slightly calendered while still warm.
  • the fabric prepared in this way was now hydrophobicized and recalendered as in Example 1. It has a total dry surface of 39 g / m2 and has the values listed in the table.
  • an aqueous, anionic polyurethane dispersion with a solids content of 40% by weight and a viscosity of 40 mPa.s prepared by known processes from a linear, hydroxyl-containing polyester based on diethylene glycol and adipic acid, with an OH number of 43, from trimethyl-1,6-hexamethylene diisocyanate and dimethylolpropionic acid as solubilizing anionic component, 1 part by weight of defoaming agent based on Ca stearate 18 parts by weight of water 6 parts by weight of a 50% aqueous solution of a nonionic thickener based on polyurethane.
  • the wet edition is 25 g / m2. After working up as in Example 1, the total dry coating of polyurethane is 16.5 g / m 2. The measurement results are listed in the table.
  • the cleaning is carried out on a B ⁇ WE R8 cleaning system in perchlorethylene with the addition of 2 g / l cleaning booster for 8 min and a reversing run with additional load.
  • the humidity above the fleet is 65% rel. Humidity. It is then rinsed in clear perchlorethylene for 3 min, spun and dried.

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

Abstract

Die Erfindung betrifft ein Verfahren zur Herstellung von mit Polyurethan beschichteten textilen Flächenge­bilden, bei dem das zu beschichtende Material mit zwei entgegengesetzt geladenen wässrigen, ionischen Dispersionen von Polyurethanen, die keine freie Isocy­anatgruppe mehr enthalten und kovalent gebundene löslichkeitsvermittelnde ionische Gruppen enthalten, beschichtet, getrocknet und gegebenenfalls hydropho­biert wird. Kationische und anionische Polyurethandis­persionen werden bevorzugt im Gewichtsverhältnis 1 : 1, in Zweistrich-Technik naß-in-naß auf das Tex­tilmaterial aufgebracht. Die Erfindung betrifft fer­ner so hergestellte textile Flächengebilde mit verbes­serter Wasserdichtigkeit und ihre Verwendung zur Herstellung von atmungsaktiver, wasserdampfdurchläs­siger, wasser- und windabweisender Kleidung, von technischen Textilien oder von Lederersatzprodukten. The invention relates to a process for the production of textile fabrics coated with polyurethane, in which the material to be coated is coated, dried and optionally with two oppositely charged aqueous, ionic dispersions of polyurethanes which no longer contain a free isocyanate group and contain covalently bound solubilizing ionic groups is made hydrophobic. Cationic and anionic polyurethane dispersions are preferably applied in a weight ratio of 1: 1 to the textile material using the two-line technique, wet-on-wet. The invention further relates to textile fabrics thus produced with improved waterproofness and their use for the manufacture of breathable, water vapor permeable, water and wind repellent clothing, technical textiles or leather replacement products.

Description

Die Erfindung betrifft ein Verfahren zur Herstellung mit Polyurethan beschichteter textiler Flächengebil­de, mit Polyurethan beschichtete textile Flächengebil­de und ihre Verwendung zur Herstellung atmungsaktiver und wasserabweisender Ausrüstungen.The invention relates to a process for the production of polyurethane-coated textile fabrics, the use of polyurethane-coated textile fabrics and their use for the production of breathable and water-repellent finishing.

Für Sport-, Freizeit- und Regenschutzkleidung sind zunehmend Gewebe gefragt, die einerseits außen was­ser- und windabweisend ausgerüstet sind, andererseits von innen nach außen Wasserdampf ableiten. Zu diesem Zweck werden die dafür vorgesehenen Textilien hydro­phobiert. Hierdurch erreicht man zwar gute Atmungsak­tivität und Wasserabweisung (Abperleffekt), aber keine Wasserdichtigkeit. Zur Verbesserung der Wasser- dichtigkeit wurden in den letzten Jahren mehrere Neuentwicklungen vorgestellt, wid sie z.B. in Chemie­fasern/Textilindustrie, 36./88. Jahrgang, 1986, S. 66 beschrieben sind. Eine Möglichkeit besteht in der Kaschierung eines Trägermaterials mit Membranen oder mikroporösen Folien auf Basis hydrophiler Copoly­ester oder Polyurethane, wobei z.T. die Porösität durch Feinperforierung der Kunststoffbahnen mittels Elektronenstrahlung nachträglich geschaffen werden muß. Eine weitere Möglichkeit besteht in der Beschich­tung eines Trägers mit lösungsmittelhaltigen Polyure­thanen unter Ausbildung einer kompakten, mikroporösen PU-Schicht. Allen diesen Verfahren haften Nachteile insofern an, daß bei der Kaschierung Lösungsmittelkle­ber und bei der Beschichtung Lösungsmittel verwendet werden müssen, deren Verarbeitung zunehmend Probleme hinsichtlich Kosten, Brennbarkeit, Toxizität und Umweltverschmutzung bereiten.Fabrics are increasingly in demand for sports, leisure and rain protection clothing, which on the one hand are water and wind resistant on the outside, and on the other hand discharge water vapor from the inside to the outside. For this purpose, the textiles provided are made hydrophobic. This gives good breathability and water repellency (water repellency), but not water resistance. In recent years, several new developments have been presented to improve water resistance, for example in chemical fibers / textile industry, 36th / 88th. Volume, 1986, p. 66. One possibility is the lamination of a carrier material with membranes or microporous foils based on hydrophilic copolyesters or polyurethanes, the porosity sometimes having to be created subsequently by fine perforation of the plastic sheets by means of electron beams. Another possibility is to coat a support with solvent-containing polyurethanes to form a compact, microporous PU layer. All of these processes have disadvantages in that solvent-based adhesives have to be used for the lamination and solvents have to be used for the coating, the processing of which increasingly poses problems with regard to costs, flammability, toxicity and pollution.

Es ist deshalb vorgeschlagen worden, die aufwendige Kaschierung oder die ökologisch bedenkliche Beschich­tung mit lösungsmittelhaltigen Polymeren durch eine Beschichtung mit wässrigen Dispersionen zu ersetzen.It has therefore been proposed to replace the complex lamination or the ecologically questionable coating with solvent-containing polymers by a coating with aqueous dispersions.

Ein solches Verfahren wird in der DE-PS 29 31 125 beschrieben. Nach diesem Verfahren wird ein faseri­ges, poröses Bahnenmaterial mit einer wässrigen, ionischen Dispersion eines Polyurethans mit kovalent gebundenen, löslichkeitsvermittelnden, ionisierbaren Gruppen imprägniert und anschließend mit wässrigen Säure- oder Laugenlösungen koaguliert. Die Verfahrens­weise bedingt das Arbeiten mit großen Flüssigkeits­mengen, einmal bei der Koagulation selbst, dann aber auch beim Auswaschen und Neutralisieren des verwende­ten Koagulans; das bedeutet, daß man für diesen Pro­zeß Aggregate in einer Vielzahl benötigt, wie sie in den meisten Ausrüstungsbetrieben nicht vorhanden sind. Weiterhin entspricht eine Koagulationsdauer von 5 Minuten nicht üblichen Praxisbedingungen, weil sie eine rationelle Fertigung unmöglich macht. Es hat sich außerdem als nachteilig erwiesen, daß ab bestimmten Schichtdicken, die für eine ausreichende , wasserdichte Beschichtung notwendig sind, Schwierig­keiten auftreten, eine durchgehende Koagulation des Polymeren zu erreichen. Weitere Nachteile des Verfah­rens nach DE-PS 29 31 125 sind, daß die koagulierten Teilchen von grober Struktur sind und nur eine gerin­ge mechanische Haftung untereinander und zum Substrat besitzen, so daß sie schon während der Koagulation zum Teil abgelöst werden und die Maschinen verschmut­zen. Auch beim fertig ausgerüsteten Textil wird die Beschichtung bei Reinigung und Wäsche zu einem großen Teil extrahiert oder abgelöst. Als besonders nachteilig wird ein Farbtonumschlag (Grauschleier) nach der Trocknung des berschichteten Bahnenmaterials angesehen.Such a method is described in DE-PS 29 31 125. According to this method, a fibrous, porous sheet material is impregnated with an aqueous, ionic dispersion of a polyurethane with covalently bound, solubilizing, ionizable groups and then coagulated with aqueous acid or alkali solutions. The procedure requires working with large amounts of liquid, firstly during the coagulation itself, but then also when washing out and neutralizing the coagulant used; this means that a multitude of aggregates is required for this process, which are not available in most equipment factories. Furthermore, a coagulation time of 5 minutes does not correspond to normal practical conditions because it makes rational production impossible. It has also proven to be disadvantageous that from certain layer thicknesses which are necessary for a sufficient, waterproof coating, difficulties arise in achieving continuous coagulation of the polymer. Further disadvantages of the process according to DE-PS 29 31 125 are that the coagulated particles are of a coarse structure and have only a low mechanical adhesion to one another and to the substrate, so that they are partially detached already during the coagulation and contaminate the machines. Even with finished textiles, the coating is largely extracted or removed during cleaning and washing. As special a color change (gray haze) after drying of the coated sheet material is considered disadvantageous.

Aufgabe der Erfindung ist es ,die Dauerhaftigkeit der auf einem solchen Bahenmaterial aufgebrachten Polyurethanschicht zu verbessern und damit eine lang­dauernde, auch Reinigung und Wäsche überstehende Waserdichtigkeit des beschichteten Materials zu erreichen.The object of the invention is to improve the durability of the polyurethane layer applied to such a sheet material and thus to achieve a long-lasting water-tightness of the coated material, which also withstands cleaning and washing.

Aufgabe der Erfindung ist es ferner, ein verbessertes Verfahren zur Beshichtung textiler Flächengebilde mit wässrigen Polyurethandispersionen bereitzustel­len, das mit geringeren Flüssigkeitsmengen auskommt und apparativ weniger aufwendig ist.It is also an object of the invention to provide an improved method for coating textile fabrics with aqueous polyurethane dispersions, which manages with smaller amounts of liquid and is less complex in terms of apparatus.

Diese Aufgabe wird gelöst durch die Merkmale des Kennzeichens von Anspruch 1. Hierbei wird in einfa­cher Weise, nämlich in einer bekannten und üblichen in-line-Zweistrichtechnik, wie sie z.B. bei der Be­schichtung mit PVC-Plastisolen angewendet wird, ein textiles Flächengebilde mit mindestens zwei wässrigen Polyurethandispersionen entgegengesetzter Ladung nacheinander naß-in-naß beschichtet, anschließend getrocknet und gegebenenfalls hydrophobiert.This object is achieved by the features of the characterizing part of claim 1. This is done in a simple manner, namely in a known and customary in-line two-stroke technique, such as that e.g. when coating with PVC plastisols, a textile fabric is coated with at least two aqueous polyurethane dispersions of opposite charge, successively wet-on-wet, then dried and, if appropriate, made hydrophobic.

Die für das erfindungsgemäße Verfahren anwendbaren Polyurethandispersionen sind handelsüblich und werden nach bekannten Verfahren hergestellt, wie z.B in der DE-OS 29 31 044 beschrieben. Sie enthalten Polyu­rethane mit an der Polymerhauptkette kovalent gebun­denen, ionischen bzw. ionisierbaren Gruppen, die die Dispergierung des Polymeren in Wasser ermöglichen. Handelt es sich bei den löslichkeitsver­mittelnden, kovalent gebundenen Gruppen um Carboxyl- bzw. Sulfonsäuregruppen bzw. deren Salze, spricht man von anionischen Polyurethandispersionen. Ist die solubilisierende, kovalent an die Polymerkette gebundene Gruppe eine Aminogruppe bzw. deren Salz, handelt es sich um eine kationische Polyurethandis­persion.The polyurethane dispersions which can be used for the process according to the invention are commercially available and are prepared by known processes, as described, for example, in DE-OS 29 31 044. They contain polyurethanes with ionic or ionizable groups which are covalently bonded to the main polymer chain and which disperse the polymer in water enable. If the solubilizing, covalently bonded groups are carboxyl or sulfonic acid groups or their salts, one speaks of anionic polyurethane dispersions. If the solubilizing group covalently bound to the polymer chain is an amino group or its salt, it is a cationic polyurethane dispersion.

Solche Dispersionen enthalten vielfach einen Fest­stoffanteil zwischen 10 und 60 Gew.-%, üblicherweise zwischen 30 und 50 Gew.-%. Die Viskosität der handels­üblichen, wässrigen Polyurethandispersionen kann in weiten Bereichen zwischen 10 und 200.000 mPa.s schwanken. Um die Viskosität einer Paste der angewen­deten Beschichtungstechnologie anzupassen, ist es vielfach notwendig, entweder die Viskosität der Dis­persion durch Verdünnen mit Wasser zu senken oder umgekehrt, durch Zugabe geeigneter, vorzugsweise handelsüblicher, nichtionogener Verdickungsmittel auf Polyurethanbasis, auf das gewünschte Maß anzuhe­ben. Solche Verfahrensschritte sind dem mit der Be­schichtungstechnologie vertrauten Fachmann geläufig, und er kann mit wenigen Vorversuchen die richtige Auswahl nach Art und Menge der notwendigen Viskosi­tätsregulatoren ermitteln. Auftretende Schaumprobleme können hierbei durch Zugabe geringer Mengen Entschäu­mungsmittel unterdrückt werden. Vorzugsweise werden die Beschichtungspasten auf Viskositäten zwischen 50.000 und 200.000 mPa.s eingestellt. Für Vorstrich und Deckstrich nach der in-line-Zweistrichtechnologie werden die anionische und kationische Polyurethandis­persion im Gewichtsverhältnis 1:2 bis 2:1, vorzugswei­se im Gewichtsverhältnis 1:1 eingesetzt. Besonders bevorzugt werden solche Gewichtsmengen an entgegenge­setzt geladenen wässrigen Polyurethandispersionen, daß die anionischen und die kationischen, kovalent gebundenen, löslichkeitsvermittelnden Gruppen in stöchiometrisch äquivalenten Mengen vorliegen.Such dispersions often contain a solids content of between 10 and 60% by weight, usually between 30 and 50% by weight. The viscosity of the commercially available, aqueous polyurethane dispersions can vary widely between 10 and 200,000 mPa.s. In order to adapt the viscosity of a paste to the coating technology used, it is often necessary to either lower the viscosity of the dispersion by diluting with water or vice versa, by adding suitable, preferably commercially available, nonionic polyurethane-based thickeners to the desired level. Such process steps are familiar to the person skilled in the art of coating technology, and he can determine the correct selection according to the type and amount of the necessary viscosity regulators with a few preliminary tests. Foaming problems can be suppressed by adding small amounts of defoaming agents. The coating pastes are preferably adjusted to viscosities between 50,000 and 200,000 mPa.s. The anionic and cationic polyurethane dispersions are used in a weight ratio of 1: 2 to 2: 1, preferably in a weight ratio of 1: 1, for the primer and topcoat according to the in-line two-coat technology. Especially Preference is given to amounts by weight of oppositely charged aqueous polyurethane dispersions such that the anionic and the cationic, covalently bonded, solubilizing groups are present in stoichiometrically equivalent amounts.

Erfindungsgemäß kann so verfahren werden, daß als erster Strich die anionische Dispersion auf das Sub­strat aufgestrichen und anschließend, naß-in-naß, die kationische Dispersion aufgebracht wird oder umgekehrt, daß als Vorstrich die kationische Polyure­thandispersion und als Deckstrich die anionische Dispersion ohne Zwischentrocknung verwendet wird.According to the invention, the procedure can be such that the anionic dispersion is spread onto the substrate as the first coat and then the cationic dispersion is applied, wet-on-wet, or vice versa, that the cationic polyurethane dispersion is used as the primer and the anionic dispersion is used as the top coat without intermediate drying .

Vorstrich und Deckstrich können hierbei jeweils als Kompaktstrich aufgetragen werden, z.B. nach der Luft­rakelmethode. In einer bevorzugten Ausführungsform kann aber auf den kompakten Vorstrich der Deckstrich als Schaum, z.B. mit einer Walzenrakel, aufgebracht werden. Der Schaumauftrag verleiht dem so ausgerüste­ten textilen Material einen besonders weichen und voluminösen Griff und einen guten textilen Fall.Pre-coat and top coat can each be applied as a compact coat, e.g. according to the air knife method. In a preferred embodiment, however, the top coat can be applied as a foam, e.g. with a roller squeegee. The foam application gives the textile material thus finished a particularly soft and voluminous handle and a good textile fall.

Unter Berücksichtigung der bereits genannten Gewichts­verhältnisse der anionischen und kationischen Disper­sionen zueinander werden die Naßauflagen an anioni­scher und kationischer Beschichtung in einem solchen Bereich ausgewählt, daß das ausgerüstete Material eine Gesamttrockenauflage zwischen 5 und 50 g/m², vorzugsweise zwischen 15 und 35 g/m², aufweist.Taking into account the weight ratios of the anionic and cationic dispersions to one another, the wet layers of anionic and cationic coating are selected in such a range that the finished material has a total dry layer of between 5 and 50 g / m², preferably between 15 and 35 g / m² .

Nach der naß-in-naß-Beschichtung des Trägermaterials wird die Ausrüstung auf den in der Beschichtungstech­nik verwendeten Aggregaten in üblicher Weise bei Temperaturen zwischen 80 und 180°C, bevorzugt zwi­schen 120 - 140°C, getrocknet und gegebenenfalls im noch warmen Zustand leicht kalandert.After the wet-on-wet coating of the carrier material, the equipment on the units used in the coating technology is applied in the usual way Temperatures between 80 and 180 ° C, preferably between 120 - 140 ° C, dried and optionally slightly calendered while still warm.

Es hat sich als vorteilhaft erwiesen, das mit Polyure­than beschichtete Material anschließend noch einer Hydrophobierung, vorzugsweise unter Verwendung einer Fluorcarbonharz- oder Silikonharzemulsion, zu unter­ziehen.
Die technischen Effekte der nach dem erfindungsgemä­ßen Verfahren ausgerüsteten textilen Materialien sind den nachfolgenden Beispielen zu entnehmen. Als besonders vorteilhaft gegenüber den bekannten Verfah­ren der Technik hat sich herausgestellt, daß eine ausgezeichnete Haftung der Beschichtung zum textilen Substrat gegeben ist, die sich in einer guten Wasch- und Reinigungsbeständigkeit widerspiegeln. Farbtonän­derungen unter Ausbildung eines Grauschleiers sind bei Produkten nach dem erfindungsgemäßen Verfahren nicht zu beobachten.
Weitere Vorteile des erfindungsgemäßen Verfahrens gegenüber dem Stand der Technik liegen darin, daß die in der Beschichtungstechnologie vorhandenen appa­rativen Einrichtungen ohne zusätzliche Aggregate und Investitionen benutzt werden können und zeitauf­wendige Spülvorgänge und hierdurch Abwasserbelastun­gen mit Spülwässern vermieden werden.It has proven to be advantageous to subsequently subject the material coated with polyurethane to hydrophobization, preferably using a fluorocarbon resin or silicone resin emulsion.
The technical effects of the textile materials finished by the process according to the invention can be seen from the examples below. It has been found to be particularly advantageous over the known methods of technology that the coating has excellent adhesion to the textile substrate, which is reflected in good resistance to washing and cleaning. Color changes with the formation of a gray haze are not observed in products using the process according to the invention.
Further advantages of the method according to the invention over the prior art are that the apparatuses available in the coating technology can be used without additional units and investments and time-consuming rinsing processes and thereby wastewater pollution with rinsing water are avoided.

Die Erfindung betrifft ferner die nach dem erfindungs­gemäßen Verfahren hergestellten und mit Polyurethan beschichteten, textilen Flächengebilde und ihre Ver­wendung zur Herstellung atmungsaktiver, wasserdampf­durchlässiger, jedoch wasser- und windabweisender Kleidung oder von technischen Textilien, wie z.B Zeltplanen, oder von Lederersatzprodukten. Die ausge­rüsteten Textilien kann man nachträglich schleifen oder schmirgeln und ihnen so ein verloursartiges bzw. ein verlourslederartiges Aussehen verleihen, ohne die sonstigen technischen Eigenschaften zu ver­schlechtern. Es ist auf diese Weise möglich, Lederer­satzstoffe zu erzeugen.The invention further relates to the textile fabrics manufactured by the process according to the invention and coated with polyurethane and their use for the production of breathable, water vapor-permeable, but water and wind repellent clothing or technical textiles, such as, for example Tarpaulins, or of leather substitutes. The finished textiles can be sanded or sanded afterwards and thus give them a suede-like or suede-like appearance without worsening the other technical properties. In this way it is possible to produce leather substitutes.

Beispiel 1:Example 1: Vorstrich:Primer:

Man bereitet eine Paste aus
100 Gew.-teilen einer wässrigen, kationischen Poly­urethandispersion mit einem Feststoff­gehalt von 30 Gew.-% und einer Visko­sität von 50 mPa.s, hergestellt nach bekanntem Verfahren aus einem Polypro­pylenglykol mit der Molmasse 1000 und einer Hydroxylzahl von 112, aus Dicyclohexylmethandiisocyanat und N-Methyldiethanolamin als löslich­keitsvermittelnde, kationische Kom­ponente und
5 Gew.-teilen einer 50 %igen wässrigen Lösung eines nichtionogenen Verdickungsmittels auf Polyurethanbasis (z.B. BORCHIGEL L 75).A paste is prepared
100 parts by weight of an aqueous, cationic polyurethane dispersion with a solids content of 30% by weight and a viscosity of 50 mPa.s, prepared by a known process from a polypropylene glycol with a molecular weight of 1000 and a hydroxyl number of 112, from dicyclohexylmethane diisocyanate and N- Methyldiethanolamine as a solubilizing, cationic component and
5 parts by weight of a 50% aqueous solution of a nonionic thickener based on polyurethane (eg BORCHIGEL L 75).

Die Paste hat eine Viskosität von 60.000 mPa.s (Brook­field RVT, Spindel 6 / 10 U min⁻¹). Die Paste wird nach der Luftrakelmethode auf ein handelsübli­ches Popelinegewebe aus Polyester/Baumwolle 66/33 mit einem Flächengewicht von 160 g/m² aufgestri­chen und ergibt eine Naßauflage von 30 g/m².The paste has a viscosity of 60,000 mPa.s (Brookfield RVT, spindle 6/10 U min⁻¹). The paste is applied to a commercially available polyester / cotton 66/33 cotton fabric using the air knife method coated with a basis weight of 160 g / m² and results in a wet coating of 30 g / m².

Deckstrich:Top line:

Ohne Zwischentrocknung behandelt man das so vorgestri­chene Gewebe in einem zweiten Strich mit einer Paste folgender Zusammensetzung:
70 Gew.-Teile einer wässrigen, anionischen Poly­urethandispersion mit einem Feststoff­gehalt von 40 Gew.-% und einer Visko­sität von 300 mPa.s, hergestellt nach bekanntem Verfahren aus einem Poly­etherpolyol (Propylenoxid/Ethylen­oxid-Addukt auf Basis Glycerin mit einer Molmasse von 4000), aus Isopho­rondiisocyanat und Dimethylolpropion­säure als löslichkeitsvermittelnde, anionische Komponente.
1 Gew.-Teil Entschäumungsmittel auf Mg-Stearatba­sis,
23 Gew.-Teile Wasser und
6 Gew.-Teile Verdickungsmittel (BORCHIGEL L 75).
Die Naßauflage für den zweiten Strich beträgt 40 g/m².Without intermediate drying, the pre-coated fabric is treated in a second coat with a paste of the following composition:
70 parts by weight of an aqueous, anionic polyurethane dispersion with a solids content of 40% by weight and a viscosity of 300 mPa.s, produced by a known process from a polyether polyol (propylene oxide / ethylene oxide adduct based on glycerol with a molecular weight of 4000) , from isophorone diisocyanate and dimethylolpropionic acid as a solubilizing, anionic component.
1 part by weight defoamer based on Mg stearate,
23 parts by weight of water and
6 parts by weight of thickener (BORCHIGEL L 75).
The wet coating for the second coat is 40 g / m².

Das beschichtete Gewebe wird nun im Lufttrocken­schrank bei 90°C 2 Minuten getrocknet und anschlie­ßend einer Hydrophobierung unterzogen. Hierzu wird es in einer Flotte aus 40 g/l einer Fluorcarbonharz­emulsion getaucht, auf 43 % Naßauflage abgequetscht und 4 Minuten bei 170°C im Trockenschrank getrocknet und kondensiert. Anschließend wird das Gewebe auf einem Zweiwalzenkalander zwischen einer Stahl- und einer Kunststoffwalze kalandert, wobei die Temperatur der Stahlwalze 170°C, der Druck 150 kg/cm² linear und die Arbeitsgeschwindigkeit 10 m/min betragen. Das so ausgerüstete Gewebe hat eine Gesamttrockenauflage von 21 g/m² an Polyurethan. Die Meßergebnisse sind in der Tabelle aufgeführt.The coated fabric is then dried in an air drying cabinet at 90 ° C. for 2 minutes and then subjected to hydrophobization. For this purpose, it is immersed in a float composed of 40 g / l of a fluorocarbon resin emulsion, squeezed onto a 43% wet pad and dried and condensed in a drying cabinet at 170 ° C. for 4 minutes. The fabric is then placed on a two-roll calender between a steel and calendered a plastic roller, the temperature of the steel roller 170 ° C, the pressure 150 kg / cm² linear and the working speed 10 m / min. The fabric thus finished has a total dry coating of 21 g / m² of polyurethane. The measurement results are shown in the table.

Beispiel 2:Example 2:

Nach der gleichen Verfahrensweise wie in Beispiel 1 beschrieben wird als erster Strich eine wässrige, anionische polyurethandispersion und als zweiter Strich eine wässrige, kationische Polyurethandispersi­on auf ein Gewebe aufgebracht. Hierzu werden Pasten folgender Zusammensetzung verwendet:Using the same procedure as described in Example 1, an aqueous, anionic polyurethane dispersion is applied as the first coat and an aqueous, cationic polyurethane dispersion as the second coat. Pastes of the following composition are used for this:

Vorstrich:Primer:

75 Gew.-Teile einer wässrigen, anionischen Poly­urethandispersion mit einem Feststoff­gehalt von 40 Gew.-% und einer Visko­sität von 40 mPa.s, hergestellt nach bekannten Verfahren aus einem linea­ren, hydroxylgruppenhaltigem Polye­ster auf Basis Diethylenglykol und Adipinsäure mit einer OH-Zahl von 43, aus Trimethyl-1, 6-hexamethylen­diisocyanat und Dimethylolpropion­säure als löslichkeitsvermittelnde, anionische Komponente,
1 Gew.-Teil Entschäumungsmittel auf Ca-Stearatba­sis 18 Gew.-Teile Wasser
6 Gew.-Teile einer 50 %igen wässrigen Lösung eines nichtionogenen Verdickungsmittels auf Polyurethanbasis (BORCHIGEL L 75).
Naßauflage : 30 g/m²75 parts by weight of an aqueous, anionic polyurethane dispersion with a solids content of 40% by weight and a viscosity of 40 mPa.s, prepared by known processes from a linear, hydroxyl-containing polyester based on diethylene glycol and adipic acid with an OH number of 43 , from trimethyl-1, 6-hexamethylene diisocyanate and dimethylolpropionic acid as solubilizing anionic component,
1 part by weight of defoaming agent based on Ca stearate, 18 parts by weight of water
6 parts by weight of a 50% aqueous solution of a non-ionic thickener based on polyurethane (BORCHIGEL L 75).
Wet pad: 30 g / m²

Deckstrich:Top line:

90 Gew.-Teile einer wässrigen, kationischen Poly­urethandispersion mit einem Feststoff­gehalt von 30 Gew.-% und einer Visko­sität von 50 mPa.s, hergestellt, wie in Beispiel 1 beschrieben.
4 Gew.-Teile einer wässrigen Verdickungsmittel­lösung auf Polyurethanbasis
Naßauflage: 30 g/m²90 parts by weight of an aqueous, cationic polyurethane dispersion with a solids content of 30% by weight and a viscosity of 50 mPa.s, prepared as described in Example 1.
4 parts by weight of an aqueous thickener solution based on polyurethane
Wet edition: 30 g / m²

Das fertig ausgerüstete Gewebe hat eine Gesamttrocke­nauflage an Polyurethan von 17 g/m² und liefert, nach einer Nachhydrophobierung gemäß Beispiel 1, die in der Tabelle aufgeführten Meßwerte.The finished fabric has a total dry coating of polyurethane of 17 g / m² and, after post-hydrophobization according to Example 1, gives the measurement values listed in the table.

Beispiel 3:Example 3:

Ein wie im Beispiel 1 beschriebenes Gewebe wurde im Luftrakelverfahren mit einer Streichpaste folgender Zusammensetzung gestrichen:
80 Gew.-Teile einer wässrigen, kationischen Polyurethandispersion mit einem Fest­stoffgehalt von 30 Gew.-% und einer Viskosität von 200 mPa.s, hergestellt nach bekanntem Verfahren aus einem Gemisch an Polyolkomponenten aus Polypropylenglykol einer Molmasse von 1000, Trimethylolpropan und Ethylen­glycol, aus Dicyclohexylmethandiiso­cyanat und N-Methyldiethanolamin als löslichkeitsvermittelnde, kationische Komponente,
2 Gew.-Teile Entschäumungsmittel auf Stearatbasis
5 Gew.-Teile Verdickungmittel (BORCHIGEL L 75)
13 Gew.-Teile WasserA fabric as described in Example 1 was coated with a spreading paste of the following composition using the air knife method:
80 parts by weight of an aqueous, cationic polyurethane dispersion with a solids content of 30% by weight and a viscosity of 200 mPa.s, prepared by a known method from a Mixture of polyol components from polypropylene glycol with a molecular weight of 1000, trimethylolpropane and ethylene glycol, from dicyclohexylmethane diisocyanate and N-methyldiethanolamine as a solubilizing, cationic component,
2 parts by weight of stearate-based defoaming agent
5 parts by weight of thickener (BORCHIGEL L 75)
13 parts by weight of water

Die Naßauflage für den Vorstrich betrug 60 g/m², entsprechend einer Trockenauflage von 15 g/m².The wet coating for the primer was 60 g / m², corresponding to a dry coating of 15 g / m².

Eine Mischung aus
95 Gew.-Teilen einer wässrigen, anionischen Polyure­thandispersion mit einem Feststoffge­gehalt von 40 Gew.-%, wie sie im Bei­spiel 1 verwendet worden ist,
2 Gew.-Teile Schaumhilfsmittel auf Basis eines Sulfosuccinamats
3 Gew.-Teile Schaumstabilisator auf Basis Ammoni­umstearat
wurde mit einem Mathis-Labormixer auf ein Schaumliter­gewicht von 250 g aufgeschäumt und im Walzenrakelver­fahren mit einer Schichtdicke von 0,25 mm auf die noch nasse Vorbeschichtung aufgetragen. Das so be­schichtete Gewebe wurde in einem Benz-Labortrockner bei 90°C 2 Minuten getrocknet und anschließend im noch warmen Zustand leicht kalandert. Das so vorberei­tete Gewebe wurde nun wie im Beispiel 1 hydrophobiert und nachkalandert.
Es hat eine Gesamttrockenauflage von 39 g/m² und weist die in der Tabelle aufgeführten Werte auf.A mix of
95 parts by weight of an aqueous, anionic polyurethane dispersion with a solids content of 40% by weight, as used in Example 1,
2 parts by weight of foam aid based on a sulfosuccinamate
3 parts by weight of foam stabilizer based on ammonium stearate
was foamed with a Mathis laboratory mixer to a foam liter weight of 250 g and applied with a layer thickness of 0.25 mm to the still wet precoating using the roller doctor method. The fabric coated in this way was dried in a Benz laboratory dryer at 90 ° C. for 2 minutes and then slightly calendered while still warm. The fabric prepared in this way was now hydrophobicized and recalendered as in Example 1.
It has a total dry surface of 39 g / m² and has the values listed in the table.

Beispiel 4:Example 4:

Analog Beispiel 1 werden folgende Pasten eingesetzt.The following pastes are used as in Example 1.

Vorstrich:Primer:

100 Gew.-Teile einer wässrigen, kationischen Poly­urethandispersion mit einem Feststoff­gehalt von 30 Gew.-% und einer Visko­sität von 50 mPa.s, hergestellt wie in Beispiel 1 beschrieben.
5 Gew.-Teile einer 50 %igen wässrigen Lösung eines nichtionogenen Verdickungsmittels auf Polyurethanbasis (z.B. BORCHIGEL L 75)
Die Naßauflage beträgt 30 g/m².100 parts by weight of an aqueous, cationic polyurethane dispersion with a solids content of 30% by weight and a viscosity of 50 mPa.s, prepared as described in Example 1.
5 parts by weight of a 50% aqueous solution of a nonionic thickener based on polyurethane (eg BORCHIGEL L 75)
The wet pad is 30 g / m².

Deckstrich:Top line:

75 Gew.-Teile einer wässrigen, anionischen Poly­urethandispersion mit einem Feststoff­gehalt von 40 Gew.-% und einer Visko­sität von 40 mPa.s, hergestellt nach bekannten Verfahren aus einem linea­ren, hydroxylgruppenhaltigen Polye­ster auf Basis Diethylenglykol und Adipinsäure, mit einer OH-Zahl von 43, aus Trimethyl-1,6-hexamethylen­diisocyanat und Dimethylolpropion­säure als löslichkeitsvermittelnde, anionische Komponente,
1 Gew.-Teil Entschäumungsmittel auf Ca-Stearatba­sis
18 Gew.-Teile Wasser
6 Gew.-Teile einer 50 %igen wässrigen Lösung eines nichtionogenen Verdickungsmittels auf Polyurethanbasis.
Die Naßauflage beträgt 25 g/m².
Nach Aufarbeitung wie in Beispiel 1 beträgt die Ge­samttrockenauflage an Polyurethan 16,5 g/m².
Die Meßergebnisse sind in der Tabelle aufgelistet.

Figure imgb0001
75 parts by weight of an aqueous, anionic polyurethane dispersion with a solids content of 40% by weight and a viscosity of 40 mPa.s, prepared by known processes from a linear, hydroxyl-containing polyester based on diethylene glycol and adipic acid, with an OH number of 43, from trimethyl-1,6-hexamethylene diisocyanate and dimethylolpropionic acid as solubilizing anionic component,
1 part by weight of defoaming agent based on Ca stearate
18 parts by weight of water
6 parts by weight of a 50% aqueous solution of a nonionic thickener based on polyurethane.
The wet edition is 25 g / m².
After working up as in Example 1, the total dry coating of polyurethane is 16.5 g / m 2.
The measurement results are listed in the table.
Figure imgb0001

Legende zur Tabelle:Legend for the table:

Zur Bestimmung der Meßwerte werden folgende Methoden angewendet:
Wassersäule nach DIN 53 886
Wasserdampfdurchlässigkeit nach DIN 53 333
Spraytest nach AATCC 22-1974The following methods are used to determine the measured values:
Water column according to DIN 53 886
Water vapor permeability according to DIN 53 333
Spray test according to AATCC 22-1974

Die Reinigung erfolgt auf einer BÖWE R8-Reinigungsan­lage in Perchlorethylen unter Zusatz von 2 g/l Reini­gungsverstärker während 8 min und reversierendem Lauf unter Beiladung. Die Feuchtigkeit oberhalb der Flotte beträgt 65 % rel. Luftfeuchte. Anschließend wird in klarem Perchlorethylen 3 min gespült, geschleudert und getrocknet.The cleaning is carried out on a BÖWE R8 cleaning system in perchlorethylene with the addition of 2 g / l cleaning booster for 8 min and a reversing run with additional load. The humidity above the fleet is 65% rel. Humidity. It is then rinsed in clear perchlorethylene for 3 min, spun and dried.

Claims (10)

1. Verfahren zur Herstellung eines mit Polyurethan beschichteten textilen Flächengebildes durch Naßbe­schichtung des textilen Materials mit einer wässri­gen, ionischen Dispersion eines keine freien Isocyca­natgruppen mehr enthaltenden Polyurethans mit kova­lent gebundenen, löslichkeitsvermittelnden, ionisier­baren Gruppen, und anschließender Trocknung des be­schichteten Materials sowie gegebenenfalls zusätzli­cher Hydrophobierung, dadurch gekennzeichnet, daß man entweder zuerst mit einer wässrigen, kationischen Dispersion eines Polyurethans mit kovalent gebunde­nen, löslichkeitsvermittelnden, kationischen Gruppen und danach mit einer wässrigen, anionischen Dispersi­on eines Polyurethans mit kovalent gebundenen, lös­lichkeitsvermittelnden, anionischen Gruppen oder zuerst mit einer wässrigen anionischen Dispersion eines Polyurethans mit kovalent gebundenen, löslich­keitsvermittelnden, anionischen Gruppen und danach mit einer wässrigen, kationischen Dispersion eines Polyurethans mit kovalent gebundenen löslichkeitsver­mittelnden kationischen Gruppen beschichtet.1. A process for producing a textile fabric coated with polyurethane by wet coating the textile material with an aqueous, ionic dispersion of a polyurethane containing no more free isocyanate groups with covalently bound, solubilizing, ionizable groups, and subsequent drying of the coated material and, if appropriate, additional hydrophobization, thereby characterized in that either with an aqueous, cationic dispersion of a polyurethane with covalently bound, solubilizing, cationic groups and then with an aqueous, anionic dispersion of a polyurethane with covalently bound, solubilizing, anionic groups, or first with an aqueous anionic dispersion of a polyurethane covalently bound, solubilizing, anionic groups and then with an aqueous, cationic dispersion of a polyurethane with covalently bound a solubilizing cationic groups coated. 2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß man die anionische und die kationische Dispersion in Gewichtsverhältnis 1 : 2 bis 2 : 1, bevorzugt im Gewichtsverhältnis 1 : 1 verwendet.2. The method according to claim 1, characterized in that one uses the anionic and the cationic dispersion in a weight ratio of 1: 2 to 2: 1, preferably in a weight ratio of 1: 1. 3. Verfahren nach einem der Ansprüche 1 bis 2, da­durch gekennzeichnet, daß man die kationische und die anionische Dispersion in solchen Mengen verwendet, daß die anionischen und kationischen, kovalent gebun­ denen, löslichkeitsvermittelnden Gruppen in stöchiome­trisch äquivalenten Mengen vorliegen.3. The method according to any one of claims 1 to 2, characterized in that one uses the cationic and the anionic dispersion in such amounts that the anionic and cationic, covalently bonded those, solubility-imparting groups are present in stoichiometrically equivalent amounts. 4. Verfahren nach einem der Ansprüche 1 bis 3, da­durch gekennzeichnet, daß man die anionische und die kationische Dispersion als kompakte Schicht aufträgt.4. The method according to any one of claims 1 to 3, characterized in that the anionic and the cationic dispersion are applied as a compact layer. 5. Verfahren nach einem der Ansprüche 1 bis 3, da­durch gekennzeichnet, daß man die erste Dispersion als kompakte Schicht und die zweite Dispersion als geschäumte Schicht aufträgt.5. The method according to any one of claims 1 to 3, characterized in that the first dispersion is applied as a compact layer and the second dispersion as a foamed layer. 6. Verfahren nach einem der Ansprüche 1 bis 5, da­durch gekennzeichnet, daß man Dispersionen mit einem Feststoffgehalt von 10 bis 60 Gew.-%, vorzugsweise von 20 bis 50 Gew.-% verwendet.6. The method according to any one of claims 1 to 5, characterized in that dispersions with a solids content of 10 to 60 wt .-%, preferably from 20 to 50 wt .-% are used. 7. Verfahren nach einem der Ansprüche 1 bis 6, da­durch gekennzeichnet, daß man Dispersionen einer Viskosität von 10 bis 200.000 mPa.s, vorzugsweise von 200 bis 100.000 mPa.s verwendet, deren Viskosität gegebenenfalls durch Verdünnung mit Wasser oder Zu­satz von Verdickungsmitteln eingestellt wird.7. The method according to any one of claims 1 to 6, characterized in that dispersions having a viscosity of 10 to 200,000 mPa.s, preferably from 200 to 100,000 mPa.s are used, the viscosity of which is optionally adjusted by dilution with water or the addition of thickeners . 8. Verfahren nach einem der Ansprüche 1 bis 7, da­durch gekennzeichnet, daß die Naßauflagen an anioni­scher und kationischer Beschichtung in einem Bereich ausgewählt sind, daß das getrocknete und gegebenen­falls hydrophobierte textile Material mit 5 bis 50 g/m² vorzugsweise 15 bis 35 g/m² Polyurethan beschich­tet ist.8. The method according to any one of claims 1 to 7, characterized in that the wet layers of anionic and cationic coating are selected in a range that the dried and optionally hydrophobicized textile material with 5 to 50 g / m², preferably 15 to 35 g / m² Polyurethane is coated. 9. Mit Polyurethan beschichtetes, textiles Flächenge­bilde, erhältlich nach dem Verfahren gemäß Ansprüchen 1 bis 8.9. Polyurethane-coated textile fabric, obtainable by the process according to claims 1 to 8. 10. Verwendung der mit Polyurethan beschichteten textilen Flächengebilde nach Anspruch 9 zur Herstel­lung atmungsaktiver, wasserdampfdurchlässiger, was­ser- und windabweisender Kleidung oder technischer Textilien oder von Lederersatzprodukten.10. Use of the textile fabric coated with polyurethane according to claim 9 for the production of breathable, water vapor permeable, water and wind repellent clothing or technical textiles or leather replacement products.
EP87114169A 1986-10-04 1987-09-29 Process for the production of textile coverings coated with polyurethane, textile coverings coated with polyurethane and their use in producing breathing and water repellent finishes Expired - Lifetime EP0283556B1 (en)

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DE19863633874 DE3633874A1 (en) 1986-10-04 1986-10-04 METHOD FOR THE PRODUCTION OF POLYURETHANE COATED TEXTILE SURFACES, POLYURETHANE COATED TEXTILE SURFACES AND THE USE THEREOF FOR THE PRODUCTION OF BREATHABLE AND WATER REPELLENT EQUIPMENT
DE3633874 1986-10-04

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CA1301566C (en) 1992-05-26
DE3633874C2 (en) 1988-10-13
DE3633874A1 (en) 1988-04-14
US4774131A (en) 1988-09-27
JPS6399376A (en) 1988-04-30
DE3779300D1 (en) 1992-06-25
EP0283556B1 (en) 1992-05-20

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