EP1283296B1 - Textile fabric with reduced soiling properties - Google Patents

Description

The invention relates to novel textile fabrics which have at least one applied to a flat textile support coating and which have a low soiling tendency and a very good self-cleaning effect.

Due to their fiber structure and the associated high surface area, textiles are particularly prone to staining. Their cleaning is often problematic and is not possible in many cases. In particular, technical textiles that are used outdoors, eg as tarpaulins, tarpaulins, awnings and the like, or as decorative textiles, for example, as textile wall coverings, screens, blinds, curtains or tablecloths are exposed to heavy pollution and can usually only with large Effort to be cleaned. To reduce their soiling tendency and to facilitate their cleaning, such textiles are often provided with a soil release finish or oleophobic finish. For this purpose, fluoroorganic compounds or fluoroorganic polymers (fluorocarbon waxes) are frequently used (see, for example, US Pat K. Fischer et al. "Textile Auxiliaries" Chap. 7 and 8.2.5 in Ullmann's Encyclopaedia of Industrial Chemistry, 5th ed. On CD-ROM , as well as to oleophobic equipment: D. Lämmermann, Melliand Textilber. 72 (1991) 949-954 ; D. Lämmermann, Melliand Textilber. 74 (1993) 883-889 ; M. Wilhelm, Int. Text. Bull. 39 (1993) 57-60 ; RE Wiltgen, Textilveredlung 21 (1986) 384-389 ; R. Kleber: "Modern Aspects of Textile Oleophobic Equipment," TPI Text. Prax. Int. 27 (1972) 499-503 , The textiles treated in this way have a lower dirt sensitivity to oils and fats. The soiling tendency to dust from the air and other particulate contamination can be improved in this way, however, only inadequate.

Textiles are often also provided with a hydrophobic finish to increase the water permeability of the fabric with respect to the use of the textiles in rainwear and sportswear, protective clothing, as tarpaulins, in tents, umbrellas, awnings, wallpapers, tablecloths or in other textile products, for which a waterproofness is desired to prevent. Waxes, fatty acid salts, quaternary ammonium compounds, silicone resins and fluorocarbon resins or mixtures thereof are frequently used for this purpose. Furthermore, it is known to provide textiles with polymer coatings in order to achieve increased water resistance and opacity. Water-repellent or coated textiles generally do not have a reduced soiling tendency.

Surfaces have been reported on several occasions, which on the one hand are not wetted by water and on which dirt particles show only slight adhesion. Such surfaces are also characterized by a self-cleaning effect, ie the dirt particles are rinsed by moving water, eg by dripping water droplets from the surface, leaving a more or less completely cleaned surface. This effect, as it is known from the leaves of the lotus plant, also called the lotus effect (see Barthlott et al., Biology in Our Time, 28, No. 5, 314-322 ).

The WO 96/04123 describes surfaces which have an artificial surface structure, which has elevations and depressions, wherein the structure is characterized in particular by the distance of 5 to 200 microns between the elevations and a height of the elevations of 5 to 100 microns. The surfaces are produced, for example, by applying Teflon powder to an area treated with adhesive or by embossing a structure onto a thermoplastically deformable hydrophobic material. Such surfaces are allegedly characterized by the fact that dust or other particulate contaminants can be rinsed off the surfaces by means of water and thus show a self-cleaning or lotus effect.

From the US 3,354,022 Similar surfaces are known. Again, the surface is prepared either by imprinting a structure or by applying hydrophobic particles, such as wax particles, to a hydrophobic surface.

In addition, a surface is described, which consists of wax-coated glass powder with a grain size of 3 to 12 microns.

From the JP 7328532-A For example, a coating process is known in which a finely divided material having a hydrophobic surface is applied to a moist lacquer and cured. In this case, water-repellent surfaces are obtained.

The WO 00/58410 describes a method of making stain resistant surfaces by applying a hydrophobic material to a surface from a solution, dispersion or emulsion, the hydrophobic material being selected to form a surface on self-assembly evaporation of the dissolving or dispersing agent Has elevations and depressions with a distance of 0.1 to 200 microns and a height of 0.1 to 100 microns and is also removable by detergents.

The methods described in the prior art for producing difficult-to-wet surfaces with a self-cleaning effect are either very expensive or do not lead to satisfactory results. The production of a structured surface by embossing is complicated and can be used economically only on flat surfaces. A treatment of textiles is not possible in this way. Surfaces in which a structuring is achieved by subsequent application of hydrophobic particles can often be poorly reproduced and have only a low mechanical stability. In addition, these procedures for textiles should also hardly be applicable. Textiles with a self-cleaning effect have not been described in the prior art.

The applicant's own investigations have shown that it is fundamentally possible to produce textiles with a self-cleaning effect by coating textile supports with finely divided powder preparations having a specific size distribution and fluorocarbon waxes. However, such equipment is mechanically unstable and, in particular, has only one low abrasion resistance. Conversely, the replacement of the fluorocarbon waxes by conventional binders, as commonly used to coat textiles, does not result in coatings that exhibit a self-cleaning effect.

The present invention is therefore based on the object to equip textiles in such a way that they show only a low soiling tendency and a high self-cleaning effect and do not lose this property even under mechanical stress. In addition, the coatings should be resistant to washing and cleaning. In particular, the coatings should be abrasion resistant.

This object is surprisingly achieved by coatings comprising at least 50% by weight of a finely divided material M which is not suitable for film formation, in which 80% by weight of the particles have a diameter in the range from 0.5 to 100 μm, and a sufficient amount of a polymeric binder as matrix-forming agent, if the matrix-forming binder contains at least one conventional polymeric binder as component i and at least one fluorocarbon polymer or a mixture thereof with a hydrocarbon wax as component ii, if the ratio of conventional binder to component ii is in the range of 1 : 2 to 100: 1.

• 50 bis 80 Gew.-%, bezogen auf das Gesamtgewicht der Beschichtung, wenigstens eines feinteiligen Materials M, worin 80 Gew.-% der Teilchen einen Durchmesser im Bereich von 0,5 bis 100 µm aufweisen und
• 20 bis 50 Gew.-%, bezogen auf das Gesamtgewicht der Beschichtung, eine Matrix, umfassend:
  1. i) als Komponente i wenigstens ein fluorfreies, konventionelles polymeres Bindemittel B,
  2. ii) als Komponente ii wenigstens ein fluororganisches Polymer FP oder eine Mischung davon mit einem hydrophoben Wachs, wobei der Fluorgehalt der Komponente ii wenigstens 1 Gew.-%, beträgt, und
  3. iii) gegebenenfalls Hilfsstoffe in einer Menge von bis zu 5 Gew.-%, bezogen auf die Matrix,

wobei das Gewichtsverhältnis von Komponente i zu Komponente ii im Bereich von 1:2 bis 100:1, vorzugsweise im Bereich von 1:1 bis 50:1 und insbesondere im Bereich von 2:1 bis 20:1 liegt.The present invention thus relates to textile fabrics comprising a flat textile support, and at least one coating applied to the support, which is composed of the following constituents:

• 50 to 80 wt .-%, based on the total weight of the coating, of at least one finely divided material M, wherein 80 wt .-% of the particles have a diameter in the range of 0.5 to 100 microns, and
• From 20 to 50% by weight, based on the total weight of the coating, of a matrix comprising:
  1. i) as component i at least one fluorine-free, conventional polymeric binder B,
  2. ii) as component ii, at least one fluoroorganic polymer FP or a mixture thereof with a hydrophobic wax, wherein the fluorine content of component ii is at least 1 wt .-%, and
  3. iii) optionally adjuvants in an amount of up to 5% by weight, based on the matrix,

wherein the weight ratio of component i to component ii is in the range from 1: 2 to 100: 1, preferably in the range from 1: 1 to 50: 1 and in particular in the range from 2: 1 to 20: 1.

As a particulate material, in principle, all materials can be used, whose particles meet the above criterion of the diameter and which largely retain their shape during the production of the coating, ie, do not melt or melt. At least 80% of the particles preferably have particle diameters in the range from 1 to 50 μm and in particular in the range from 1 to 20 μm. The average particle diameter (weight average, determined by the sieve curve) is generally below 50 μm, preferably in the range from 1 to 20 μm, in particular in the range from 1 to 10 μm and particularly preferably in the range from 2 to 8 μm. The particles preferably have a compact structure, ie a non-porous structure and in particular a spherical or ellipsoidal structure, wherein the ratio of maximum diameter to minimum diameter usually does not exceed a value of 3: 1. Their surface can be smooth or irregular. Examples of suitable materials may be organic in nature, eg potato starch, or inorganic, eg oxidic in nature. Examples of the latter are quartz flours and Quarzfeinstmehle such as those sold under the brands DORSILIT ^® and Micro DORSILIT ^® products of the company. Dorfner, Hirschau, Germany, glass beads and hollow glass spheres, such as those sold under the name Spheriglass ^® products of the company. Potters Ballotoni , Kirchheim-Bolanden, kaolin powder, eg the products marketed under the name KAOLINS from the company Dorfner, kieselguhr, eg the products sold under the names SEITZ Extra by the company SEITZ Filter Werke GmbH.

The proportion of finely divided material M in the coating is preferably 55 to 75 wt .-% and in particular 60 to 70 wt .-%, based on the total weight of the coating. As a result, an optimal soil repellency is achieved with sufficient strength of the coating. The coating of finely divided material M in the coatings according to the invention is preferably at least 10 g / m ^2, for example 10 to 150 g / m ² , in particular 20 to 100 g / m ² .

The coating thickness (overlay) is generally at least 10 g / m ² , preferably 10 to 200 g / m ² , in particular 15 to 150 g / m ² and particularly preferably 20 to 120 g / m ² . Higher volumes are usually not required but will not decrease the self-cleaning effect.

In principle, all essentially fluorine-free polymeric binders which are customarily used for coating textiles come into consideration as component i. The type of polymeric binder depends on the intended use of the fabric. If the sheet is to be flexible, it is preferable to choose uncrosslinked polymers or polymers having a low degree of crosslinking; If, on the other hand, one wishes to have a rather rigid shape, it is preferable to use polymers which are more crosslinkable than binder B.

It is preferred if the polymeric binder B in the formulation has a glass transition temperature T _G in the range of -40 to +100 ° C, preferably -30 to +60 ° C, especially -20 to +40 ° C. If polyurethanes are used as binders B, the glass transition temperature is preferably rather lower, for example in the range from -30 to + 40 ° C., in particular in the range from -20 to +20 ° C.

The proportion of component i (polymer and optionally crosslinker) is generally at least 10 wt .-%, preferably at least 15 wt .-% and in particular at least 20 wt .-%, for example 10 to 49.5 wt .-%, preferably 15 to 40 wt .-% and in particular 20 to 35 wt .-%, each based on the total weight of the coating.

As component i, preference is given to those binders B which are self-crosslinking. By this the skilled person understands polymer systems, preferably based on aqueous polymer dispersions, which undergo intramolecular and / or intermolecular crosslinking reactions during the drying of the coating. The crosslinking reactions are known to be effected by the polymers having either different functional groups which react with each other to form ionic or covalent bonds or by the binder comprising a polymer having functional groups and a low molecular weight or oligomeric crosslinker or a polyvalent metal salt the crosslinker has at least two functional groups which can react with the functional groups of the polymer. Examples of suitable reactive groups in polymers are carboxyl groups which react, for example, with hydroxyl, amino, epoxy or aziridine groups or with polyvalent metal ions such as Ca ²⁺ , Al ³⁺ , Mn ²⁺ , Zn ²⁺ ; Hydroxyl groups which react with carboxyl, isocyanate, epoxide, anhydride or aldehyde groups; Aldehyde or keto groups that react with amines or hydrazides; N-methylolamine, N-methylolamide and hydroxymethylamino groups which react with themselves; Isocyanate groups which may also be reversibly blocked (capped), for example with phenols, t-butanol, 1,3-diketones, malonates, cyclic amides such as caprolactam, nitriles, aldehydes or oximes, and which react with amino groups, OH groups and the like can. The theoretical crosslink density in the self-crosslinking binders, ie the molar number of crosslinking points which result from complete reaction of the reactive groups on the polymer and which corresponds to half of the functional groups on the polymer, is preferably in the range from 0.01 to 2 mol / mol. kg polymer and optionally crosslinker and in particular in the range of 0.1 to 1 mol / kg.

Examples of suitable crosslinkers are the di- or polyols mentioned below; primary or secondary diamines, preferably primary diamines, for example alkylenediamines such as hexamethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, N, N-bis [(aminopropyl) amino] ethane, 3,6-dioxaoctanediamine, 3,7-dioxanonandiamine, 3.6, 9-trioxaundecanediamine or Jeffamine, (4,4'-diaminodicyclohexyl) methane (4,4'-diamino-3,3-dimethyldicyclohexyl) methane; Amino alcohols like Ethanolamine, hydroxypropylamine; ethoxylated di- and oligoamines; Dihydrazides of aliphatic or aromatic dicarboxylic acids such as adipic dihydrazide; Dialdehydes such as glyoxal; partially or completely O-methylated melamines, as well as compounds or oligomers having on average 2 or more, preferably 3 or more isocyanate groups or reversibly blocked isocyanate groups. Self-crosslinking polymer dispersions which do not require external crosslinkers have, for example, OH groups in combination with carboxyl or anhydride groups, or N-methylolamide groups.

Preferably used as component i mixtures of a polymer having reactive groups, and a complementary crosslinking agent. In this case, the ratio of crosslinker to polymer is such that the molar ratio of the reactive groups in the polymer to the reactive groups in the crosslinker is usually in the range of 1:10 to 10: 1 and preferably in the range of 3: 1 to 1 : 3 is. Usually, the weight ratio of polymer to crosslinker is in the range of 100: 1 to 1: 1 and in particular in the range of 50: 1 to 5: 1.

Suitable polymers which are used as binder B in the coating of textiles are known to the person skilled in the art, for example from D. Distler "Aqueous Polymer Dispersions", Wiley-VCH, Weinheim, 1999, p. 171 et seq , and literature cited there.

• Acrylatharze (Reinacrylate);
• Styrolacrylate;
• Styrol/Butadien-Copolymerisate;
• Polyvinylester, insbesondere Polyvinylacetate;
• Vinylester-Olefin-Copolymere; sowie
• Vinylester-Acrylat-Copolymere.

Examples of suitable binders B are self-crosslinking or crosslinkable polymers based on ethylenically unsaturated monomers, such as:

• Acrylate resins (pure acrylates);
• styrene acrylates;
• Styrene / butadiene copolymers;
• Polyvinyl esters, in particular polyvinyl acetates;
• Vinylester-olefin copolymers; such as
• Vinylester-acrylate copolymers.

By acrylic resins, the expert means homopolymers or copolymers of acrylic and / or methacrylic acid esters, optionally with further ethylenically unsaturated comonomers, and optionally ethylenically unsaturated auxiliary monomers, for example ethylenically unsaturated mono- and dicarboxylic acids such as (meth) acrylic acid, itaconic acid, their amides such as (meth) acrylamide and N-methylol (meth) acrylamide, ethylenically unsaturated sulfonic acids such as vinylsulfonic acid, styrenesulfonic acid, (meth) acrylamido-2- methylpropanesulfonic acid or its ammonium, sodium or potassium salts, cationic or cationogenic monomers such as amino-C ₂ -C ₄ -alkyl (meth) acrylamide, N, N-di-C ₁ -C ₄ -alkylamino-C ₂ -C _4- alkyl (meth) acrylamides, N, N-di-C ₁ -C ₄ -alkylamino-C ₂ -C ₄ -alkyl (meth) acrylates and their quaternization products such as the methosulfates or methyl halides and / or hydroxyalkyl (meth) acrylates. Examples of (meth) acrylic esters are the C ₁ -C ₁₀ -alkyl esters, in particular the methyl, ethyl, propyl, n-butyl, tert-butyl and 2-ethylhexyl esters of acrylic and methacrylic acid. By styrene acrylates, the person skilled in the art accordingly understands copolymers of styrene with at least one ester of acrylic acid and / or methacrylic acid and optionally other monomers, for example the abovementioned auxiliary monomers. The term styrene-butadiene copolymers is understood by the person skilled in the art to mean copolymers of butadiene with styrene, which if appropriate contain in copolymerized form the abovementioned auxiliary monomers and / or, if appropriate, acrylonitrile and / or methacrylonitrile.

Polyvinyl esters are understood by the person skilled in the art to be the homopolymers and copolymers of vinyl esters of aliphatic C ₁ -C ₂₀ -monocarboxylic acids, in particular of vinyl acetate, optionally with further comonomers, for example vinyl propionate, vinyl butyrate, vinyl valerate, vinyl hexanoate and / or acrylonitrile, and optionally the abovementioned auxiliary monomers. Polyvinyl esters which contain copolymerized C ₂ -C ₆ -olefins, such as ethylene, are also referred to as vinyl ester-olefin copolymers. Polyvinyl esters which contain esters of monoethylenically unsaturated mono- and / or dicarboxylic acids in copolymerized form are termed vinyl ester acrylates.

Such copolymers are commercially available, for example in the form of aqueous polymer latices, for example under the names ACRONAL, STYROFAN, BUTOFAN (BASF AG), MOWILITH, MOWIPLUS, APPRETAN (Clariant), VINNAPAS, VINNOL (WACKER).

In a preferred embodiment of the invention, the polymeric binder B is a polyurethane, in particular a polyurethane with polyester structures (hereinafter polyester urethane). The polyurethane is preferably used in the form of an aqueous polyurethane dispersion. This is preferably a crosslinkable or self-crosslinking polyurethane.

Polyurethanes are known to be addition products of at least one isocyanate component comprising at least one diisocyanate and at least one polyol component comprising at least one diol. In addition, the isocyanate component also higher functional isocyanates, eg. B. Triisocyante or oligomeric isocyanates having on average more than 2 and preferably 3, 4 or more isocyanate groups include. The polyol component can also comprise higher-functionality polyols or oligomeric polyols having on average more than 2 OH groups, preferably 3, 4 and more OH groups.

Suitable diisocyanates are aromatic diisocyanates such as 2,4- and 2,6-toluene diisocyanate (TDI) and isomer mixtures thereof, tetramethylxylene diisocyanate (TMXDI), xylene diisocyanate (XDI), diphenylmethane-4,4'-diisocyanate (MDI), and aliphatic and cycloaliphatic diisocyanates such as dicyclohexylmethane-4,4'-diisocyanate (H ₁₂ MDI), tetramethylene diisocyanate, hexamethylene diisocyanate (HMDI), isophorone diisocyanate (IPDI), trimethylhexamethylene diisocyanate and mixtures thereof. Preferred diisocyanates are aliphatic or cycloaliphatic in nature. In particular, diisocyanates are of the general formula

OCN- (CH ₂ ) _n -NCO

with n = 2 to 8 and in particular 4 to 6 preferred. Preferred diisocyanates include hexamethylene diisocyanate (HMDI) and isophorone diisocyanate. Examples of higher functional isocyanates are triisocyanates such as triphenylmethane-4,4 ', 4 "-triisocyanate, the partial condensation products of the abovementioned diisocyanates such as the cyanurates and biurets of the abovementioned diisocyanates, and oligomers obtained by specific reaction of diisocyanates or of semi-blocked diisocyanates with polyols, which on average have more than 2 and preferably at least 3 OH groups per molecule are obtainable.

The proportion of the polyisocyanate component in the constituents which form the polyurethane is generally in the range from 5 to 60% by weight and in particular from 10 to 40% by weight. The proportion of diisocyanate, based on the weight of the polyisocyanate component is generally at least 60 wt .-% and in particular at least 80 wt .-%.

Suitable diols are glycols preferably having 2 to 25 carbon atoms. These include 1,2-ethanediol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,10-decanediol, diethylene glycol, 2,2, 4-trimethylpentanediol-1,5, 2,2-dimethylpropanediol-1,3, 1,4-dimethylolcyclohexane, 1,6-dimethylolcyclohexane, 2,2-bis (4-hydroxyphenyl) -propane (bisphenol A), 2,2 Bis (4-hydroxyphenyl) butane (bisphenol B) or 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane (bisphenol C).

Other possible constituents of the polyol component are trihydric and higher molecular weight, low molecular weight alcohols. They usually have 3 to 25, preferably 3 to 18 carbon atoms. These include glycerol, trimethylolethane, trimethylolpropane, erythritol, pentaerythritol, sorbitol and their alkoxylates.

The diols and higher polyols also include linear or branched oligomers and polymers which have at least 2, preferably arranged at their termini OH groups. Examples of these are polyester polyols, polycarbonate polyols and polyether polyols. Preferred among these are linear oligomers and polymers. The number average molecular weight of this component is preferably in the range of 500 to 20,000 daltons. The oligomeric component is preferably built up from aliphatic and / or cycloaliphatic building blocks.

The proportion of oligomeric polyols in the polyurethane-forming components is generally in the range of 10 to 95 wt .-%, preferably 20 to 95 wt .-% and in particular 25 to 85 wt .-% based on the total weight of the polyurethane forming components. The proportion of low molecular weight alcohols is in the Usually not more than 60 wt .-%, for example 1 to 60 wt .-%, and often up to 30 wt .-% or up to 20 wt .-%.

aufgebaut sind. In Formel I steht R für einen bivalenten organischen Rest, der in der Regel 2 bis 20 Kohlenstoffatome aufweist und durch ein oder mehrere z.B. 1, 2, 3 oder 4 nicht benachbarte Sauerstoffatome unterbrochen sein kann. R leitet sich vorzugsweise von einem aliphatischen oder cycloaliphatischen Diol ab. Derartige Polycarbonatpolyole werden üblicherweise als aliphatische Polycarbonatpolyole bezeichnet. Beispiele für geeignete aliphatische Diole sind lineare oder verzweigte Alkylenglykole mit 2 bis 20, vorzugsweise 2 bis 10 C-Atomen, z.B. lineare Alkylenglykole der Formel HO-(CH₂)_n-OH mit n = 2, 3, 4, 5, 6, 7 oder 8, vorzugsweise 3, 4, 5, 6 oder 7, Alkylsubstituierte α,ω-Alkandiole mit 3 bis 20 C-Atomen wie Propylenglykol, Neopentylglykol und dergleichen, Oligomere wie Di- Tri- und Tetraethylenglycol, Di-, Tri- und Tetrapropylenglykol, HO-((CH₂)₄O)_mH mit m = 2, 3, 4 oder 5, weiterhin cycloaliphatische Diole, z.B. Cylohexan-1,4-diol, 1,4-Bis(hydroxymethyl)cyclohexan oder 2,2-Bis(4-hydroxycyclohexyl)propan.
Das Polycarbonatpolyol kann auch eine oder mehrere, z.B. 1, 2 oder 3 Verzweigungstellen aufweisen, die sich von mehrwertigen Alkohlen, wie Glycerin, Trimethylolpropan, Pentaerythrit, oder von Zuckeralkoholen wie Sorbit ableiten. In Abhängigkeit von der Anzahl der Verzweigungsstellen und der Funktionalität des Alkohols weist das resultierende Polycarbonatpolyol eine Hydroxylfunktionalität > 2 auf.Polyetherols are understood as meaning both linear and branched polyethers which on average have at least 2, preferably at their termini, hydroxyl groups per molecule. Preference is given to aliphatic polyether polyols, ie polyether polyols which are composed of aliphatic and / or cycloaliphatic building blocks. As a rule, polyether polyols are obtained by polymerization of alkylene oxides having 2 to 4 carbon atoms, optionally with a starter. Examples of suitable alkylene oxide are ethylene oxide, 1,2-propylene oxide, 1,2- and 2,3-butylene oxide, in particular ethylene oxide and propylene oxide. As a starter molecule z. As water, low molecular weight di- or polyols, for example, the aforementioned glycols, oligomeric alcohols, polyetherols and polyesterols into consideration. Examples of suitable initiators are, in particular, ethanediol, 1,2- and 1,3-propanediol, bisphenol A, glycerol, trimethylolpropane, pentaerythritol and sorbitol. Polyether polyols having only two hydroxy end groups are obtained using difunctional initiators such as water, ethylene glycol, propylene glycol and bifunctional oligoalkylene oxides. Polyetherols are also accessible by cationic polymerization of cyclic ethers, such as tetrahydrofuran. Particularly preferred polyether polyols are polyether diols, among these particularly preferably polyethylene oxide, polypropylene oxide and random and block copolymers of ethylene oxide with propylene oxide. The degree of polymerization of the polyetherols is generally in the range from about 5 to 200. The number average molecular weight of the polyether sequence is in particular 500 to 5000 g / mol.
Polyester polyols are understood as meaning both linear and branched polyesters having at least two, preferably terminal, OH groups. Their molecular weight is in particular in the range of 800 to 20,000, especially in the range of 1,000 to 10,000 g / mol. Suitable polyesterols can be z. Example, by polycondensation of aliphatic, cycloaliphatic and aromatic di-, tri- and / or polycarboxylic acids or ester-forming derivatives such as anhydrides or chlorides with the aforementioned di- and / or polyols and / or polyetherols, the alcohol component used in excess is, ie the molar ratio of OH groups to acid groups is more than 1: 1, z. 1.1: 1 to 2: 1. Suitable carboxylic acids are, for. For example, aliphatic dicarboxylic acids having 2 to 20 carbon atoms, preferably 4 to 15 carbon atoms, for example succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, sebacic acid, dodecanedioic acid, cyclohexanedicarboxylic acid and aromatic dicarboxylic acids such as phthalic acid, terephthalic acid and isophthalic acid. Preference is given to polyester diols which are obtainable by condensation of dicarboxylic acids with diols. Polyester polyols can also be prepared by polycondensation of hydroxycarboxylic acids or lactones with the abovementioned di- or polyols. Suitable lactones are, for example, those having 3 to 20 carbon atoms, such as α, α-dimethyl-β-propiolactone, γ-butyrolactone and ε-caprolactone. Suitable hydroxycarboxylic acids are α-hydroxycarboxylic acids such as glycolic acid, lactic acid, hydroxybutyric acid, mandelic acid, which may also be in the form of their lactides or β-hydroxycarboxylic acids, γ-hydroxycarboxylic acids, δ-hydroxycarboxylic acids or ω-hydroxycarboxylic acids such as ω-valeric acid. Preference is given to aliphatic polyester polyols, ie the building blocks which form the polyester are selected from aliphatic and cycloaliphatic building blocks.
Polycarbonate polyols are understood as meaning those polycarbonates which have on average at least 2, for example 2, 3, 4 or 5, preferably hydroxyl groups per molecule and which are essentially more than 80% by weight, more preferably more than 90% by weight .-%, of repeating units of the general formula I.

are constructed. In formula I, R is a bivalent organic radical which generally has 2 to 20 carbon atoms and can be interrupted by one or more, for example, 1, 2, 3 or 4 non-adjacent oxygen atoms. R is preferably derived from an aliphatic or cycloaliphatic diol. Such polycarbonate polyols are commonly referred to as aliphatic polycarbonate polyols. Examples of suitable aliphatic diols are linear or branched alkylene glycols having 2 to 20, preferably 2 to 10, carbon atoms, for example linear alkylene glycols of the formula HO- (CH ₂ ) _n -OH where n = 2, 3, 4, 5, 6, 7 or 8, preferably 3, 4, 5, 6 or 7, alkyl-substituted α, ω-alkanediols having 3 to 20 carbon atoms such as propylene glycol, neopentyl glycol and the like, oligomers such as di-tri and tetraethylene glycol, di-, tri- and tetrapropylene glycol, HO - ((CH ₂ ) ₄ O) _m H with m = 2, 3, 4 or 5, furthermore cycloaliphatic diols, eg cyclohexane-1,4-diol, 1, 4-bis (hydroxymethyl) cyclohexane or 2,2-bis (4-hydroxycyclohexyl) propane.
The polycarbonate polyol may also have one or more, for example, 1, 2 or 3 branching points derived from polyhydric alcohols, such as glycerol, trimethylolpropane, pentaerythritol or sugar alcohols, such as sorbitol. Depending on the number of branching sites and the functionality of the alcohol, the resulting polycarbonate polyol has a hydroxyl functionality> 2.

Since the polyurethanes are preferably used in the form of an aqueous dispersion for producing the coating, they generally have polar functional groups, in particular ionogenic and / or ionic groups, such as carboxylic acid groups, sulfonic acid groups, phosphonic acid groups, phosphoric acid groups, the alkali metal and ammonium salts thereof, Amino groups, quaternary amino groups, and polyether groups. The introduction of these functional groups in the polyurethane is generally carried out by using appropriately substituted with anionic or anionogenic or cationic or cationogenic groups substituted compounds having at least two isocyanate-reactive groups, in the preparation of the polyurethanes. The proportion of such building blocks, based on the total amount of the polyurethane-forming components, is generally in the range of 0.1 to 25 wt .-%, preferably 0.5 to 20 wt .-%.

Suitable compounds having polar functional groups are, for example, anionically modified diols or polyols, such as the reaction products of dicarboxylic acids, which additionally have at least one phosphonic acid group, sulfonic acid group or sulfonate group, with the abovementioned diols. The dicarboxylic acid component includes, for example, sulfosuccinic acid, 4-sulfophthalic acid, 5-sulfoisophthalic acid, sulfoterephthalic acid, 4-sulfonaphthalene-2,7-dicarboxylic acid, 5- (4-sulfophenoxy) terephthalic acid, and the like corresponding salts. The anionically modified diols also include the diester diols of tri- or tetracarboxylic acids with the abovementioned diols. Examples of tri- or tetracarboxylic acids are 2-phosphonobutane-1,2-4-tricarboxylic acid, citric acid, 1,2,3-propanetricarboxylic acid, 1,3,5-benzenetricarboxylic acid (trimesic acid), 1,2,4-benzenetricarboxylic acid (trimellitic acid) , 1,2,4,5-Benzoltetracarboxylic acid (pyromellitic acid). The anionically functionalized diols also include linear or branched diols, which may be aliphatic, cycloaliphatic or aromatic and which carry an anionic functional group. Examples thereof are dimethylolpropionic acid (bis-2,2- (hydroxymethyl) propionic acid), 2-sulfo-1,4-butanediol, 2,5-dimethyl-3-sulfo-2,5-hexanediol and salts thereof, in particular their sodium and potassium salts. Suitable anionically modified compounds are furthermore correspondingly substituted amino alcohols and diamines, for example ethylenediamine-N-acetic acid, ethylenediamine-N-propionic acid, N- (sulfonatoethyl) ethylenediamine, their salts, in particular their sodium and potassium salts.

Suitable compounds having polar functional groups are furthermore cationically modified compounds. Cationogen is understood here and below to mean cationic groups and groups which can be converted into a cationic group by modification, eg protonation or alkylation (quaternization). Examples of these are cationically modified diols or polyols, cationically modified di- or polyamines and amino alcohols such as N, N-bis (hydroxy-C ₂ -C ₈ -alkyl) amines which have one or two further radicals on the nitrogen, for example an aryl radical, a C ₁ -C ₈ -alkyl radical or an aryl-C ₁ -C ₈ -alkyl radical, furthermore hydroxy-C ₂ -C ₈ -alkylpiperazine bis (hydroxy-C ₂ -C ₈ -alkyl) piperazine, N- (amino C ₂ -C ₈ alkyl) piperazines and N, N'-bis (amino-C ₂ -C ₈ alkyl) piperazines and their quaternization products.

The polyurethane may also have reactive functional groups that allow subsequent crosslinking of the polyurethane. These include the abovementioned reactive groups, in particular OH groups, carboxylate groups, blocked isocyanate groups, amino groups. Often you will use a polyurethane, that still has free OH groups as reactive groups. As a rule, the proportion of reactive functional groups is 0.1 to 2 mol / kg of polymer.

The introduction of the reactive groups can be carried out, for example, by reacting polyurethanes which have free or reversibly blocked isocyanate groups with compounds which have both an isocyanate-reactive functional group and another of the abovementioned reactive functional groups. It is likewise possible to prepare polyurethanes containing OH groups or isocyanate groups by selective condensation of polyol and polyisocyanate components which either contain higher-valent polyols in addition to the diols or higher-valent isocyanates in addition to the diisocyanates, so that an excess of OH groups is used in the preparation or an excess of isocyanate groups (or blocked isocyanate groups) based on the required stoichiometry is used. In a preferred embodiment of the invention, crosslinkable polyurethanes are used, in particular polyesterurethanes as binder B, which still have free OH groups.

The polyurethanes used as component i are known for the coating of textiles (see eg J. Hemmrich, Int. Text. Bull. 39, 1993, No.2, pp. 53-56 ; " Aqueous polyurethane coating systems "Chemiefasern / Textilind." 39 91 (1989) T149, T150 ; W. Schröer, Textilveredelung 22, 1987, pp. 459-467 ) and commercially available, for example under the trade names Alberdingk® the Fa. Alberdingk, Impranie ^® the Fa. BAYER AG, Permutex ^® the Fa. Steel, Waalwijk, Netherlands, the company BASF Aktiengesellschaft or can be prepared by known methods, such For example, in "production process for polyurethanes" in Houben-Weyl, "Methods of Organic Chemistry", Volume E 20 / Macromolecular Substances, p. 1587 . D. Dietrich et al., Angew. Chem. 82 (1970), p. 53 et seq. . Angew. Makrom. Chem. 76, 1972, 85 et seq. and Angew. Makrom. Chem. 98, 1981, 133-165 . Progress in Organic Coatings, 9, 1981, pp. 281-240 , respectively. Römpp Chemielexikon, 9th edition, volume 5, p. 3575 to be discribed.

In a particularly preferred embodiment, the binder B used is a mixture of a hydroxyl-containing polyurethane, in particular a polyether or polyester urethane, and an isocyanate crosslinker which has free or blocked isocyanate groups.

As component ii, in principle all fluoro-organic polymers and their mixtures with waxes are considered, as they are usually used for finishing textiles. The proportion of organic fluorine in the component ii according to the invention is at least 1 wt .-%, preferably at least 2 wt .-%, z. B. in the range of 2 to 25 wt .-%, in particular in the range of 2 to 15 wt .-%.

• m für 2 bis 10, vorzugsweise 3 bis 8 und n für 0 bis 5, vorzugsweise für 1, 2, 3 oder 4 stehen.

As a rule, the organofluorine fluorochemical FP contains, as the organofluorine constituent, fluorohydrocarbon groups of the formula I:

F ₃ C (CF ₂ ) _m (CH ₂ ) _n - (I)

wherein

• m is 2 to 10, preferably 3 to 8 and n is 0 to 5, preferably 1, 2, 3 or 4.

• m und n die bevorzugt angegebenen Bedeutungen aufweisen,
• X für ein Sauerstoffatom, oder eine Carboxylgruppe steht und
• R für eine ethylenisch ungesättigten Kohlenwasserstoffrest mit vorzugsweise 2 bis 8 C-Atomen und gegebenenfalls weiteren Heteroatomen steht.

The organofluorine polymers are generally homopolymers or copolymers of fluoroorganic monomers of the formula A:

F ₃ C (CF ₂ ) _m (CH ₂ ) _n -XR (A)

wherein

• m and n have the preferred meanings given,
• X represents an oxygen atom, or a carboxyl group, and
• R is an ethylenically unsaturated hydrocarbon radical having preferably 2 to 8 C atoms and optionally further heteroatoms.

In formula A, R is vinyl, allyl, methallyl and 1-propen-2-yl. In particular, XR is acryloxy or methacryloxy.

In addition to the monomers A, the fluoroorganic polymer may contain one or more, including various ethylenically unsaturated comonomers in copolymerized form. Usually, the comonomers comprise at least one electrically neutral, preferably water-insoluble or only slightly soluble comonomer B (solubility at 25 ° C. <1 g / l) and optionally one or more water-soluble, preferably ionic or ionizable monomers C.

The proportion of copolymerized monomers A in the total mass of the polymer FP is generally in the range of 1 to 50 wt .-%, preferably in the range of 5 to 40 wt .-% and in particular in the range of 10 to 30 wt .-%. The proportion of the monomers B is generally in the range of 50 to 99 wt .-%, preferably in the range of 60 to 95 wt .-% and in particular in the range of 70 to 90 wt .-%. The proportion of the monomers C is generally in the range of 0 to 20 wt .-%, preferably in the range of 0 to 10 wt .-% and in particular in the range of 0.1 to 8 wt .-%.

The monomers B include the esters of ethylenically unsaturated mono- and dicarboxylic acids such as acrylic acid, methacrylic acid, maleic acid, fumaric acid and itaconic acid, with C ₁ -C ₂₄ -alkanols, the vinyl and the allyl esters of saturated aliphatic C ₂ -C ₂₄ -carboxylic acids, Vinyl halides such as vinyl chloride, vinylidene chloride, vinylidene fluoride, 1-olefins such as ethylene, propene, 1-butene, isobutene, n-hexene and the like; and vinyl aromatic monomers such as styrene, α-methylstyrene and chlorostyrenes. Preferably, the monomers B comprise at least one monomer B1 with a C ₆ -C ₂₄ -hydrocarbon radical, for example a C ₆ -C ₂₄ -alkyl acrylate, a C ₆ -C ₂₄ -alkyl methacrylate and / or a vinyl-C ₇ -C ₂₄ -alkanoate , and optionally one or more thereof different monomers B2, for example one or more C ₁ -C ₅ -alkyl acrylates, C ₁ -C ₅ -alkyl methacrylates, vinyl-C ₂ -C ₆ -alkanoates, vinyl halides or vinylaromatic compounds. Preferred monomers B1 are the C ₆ -C ₂₄ -alkyl acrylates and C ₆ -C ₂₄ -alkyl methacrylates, such as lauryl (meth) acrylate and stearyl (meth) acrylate. Preferred monomer B2 are the vinyl halides. The monomers B1 usually constitute from 20 to 99% by weight and preferably from 40 to 90% by weight, and the monomers B2 from 0 to 50% by weight and preferably from 0 to 30% by weight.

The polymers FP are frequently used in the form of an aqueous dispersion and then contain polymerized ionic or ionic monomers C for their stabilization. Suitable monomers C may be anionic in nature, for example ethylenically unsaturated mono- and dicarboxylic acids such as (meth) acrylic acid, itaconic acid, ethylenically unsaturated sulfonic acids such as vinylsulfonic acid, styrenesulfonic acid, (meth) acrylamido-2-methylpropanesulfonic acid or their ammonium, sodium or potassium salts , as well as cationogenic or cationic nature such as amino-C ₂ -C ₄ -alkyl (meth) acrylamide, N, N-di-C ₁ -C ₄ -alkylamino-C ₂ -C ₄ -alkyl (meth) acrylamides, N , N-di-C ₁ -C ₄ -alkylamino-C ₂ -C ₄ -alkyl (meth) acrylates, or their reaction products with mineral acid such as hydrochloric acid or sulfuric acid and their reaction products with alkyl halides or alkyl sulfates. In addition to or instead of the polymer FP can also amides of the aforementioned ethylenically unsaturated carboxylic acids such as (meth) acrylamide and N-methylol (meth) acrylamide, or hydroxy-C ₂ -C ₄ alkyl esters of ethylenically unsaturated mono- or dicarboxylic acids, for example hydroxy-C ₂ -C ₄ alkyl (meth) acrylates in copolymerized form.

As a further component, component ii may also contain one or more hydrophobic waxes as extender, provided that the total content of organic fluorine does not fall below a value of 1% by weight, preferably 2% by weight.

As a rule, the hydrophobic waxes are substances whose films have a surface tension in the range from 20 to 50 mN / m (determined, for example, by the hanging drop method, see US Pat S. Wu, "Polymer Interface and Adhesion", Marcel Decker Inc., New York 1982, pp. 266-268 ). Examples include vegetable waxes, mineral waxes, petrochemical waxes, chemically modified waxes, z. As montan ester waxes, synthetic waxes, z. As polyethylene waxes, and polymers with long-chain alkyl groups (C ₁₀ -C ₃₀ ), z. Polybehenyl acrylates, polystearyl acrylates and the like. The proportion of wax in the component ii is often 10 to 90 wt .-%, the proportion of fluorine-organic polymer accordingly 10 to 90 wt .-%.

The coatings according to the invention can be designed so that the conventional polymer B and the component ii are distributed uniformly over the coating cross section. The component ii can also be arranged on a first basecoat, which is essentially composed of the finely divided material M and the fluorine-free polymeric binder B and optionally other conventional auxiliaries. A uniform distribution should also be understood to mean inhomogeneous distributions in which the different phases do not form layers. The type of arrangement of the coating results in the usual way by the nature of the coating method, as will be explained below.

The two-layer arrangement makes it possible to keep the proportion of component ii in the coating very low, for example in the range from 0.2 to 1% by weight, in particular from 0.5 to 1% by weight, without losing the self-cleaning effect , Of course, the proportion of component ii may also be above 1 wt .-%, for example in the range of 1 to 30 wt .-% and preferably in the range of 1 to 20 wt .-%. If the coating contains component ii in more or less homogeneous distribution, the proportion of component ii in the coating is preferably in the range from 1 to 30% by weight and in particular in the range from 2 to 20% by weight. Preference is given to those coatings in which the amount of component ii used per surface is at least 0.2 g / m ² , preferably at least 0.5 g / m ² and in particular at least 1 g / m ² , with generally no more runs than 40 g / m ² , in particular not more than 30 g / m ² and particularly preferably not more than 20 g / m ² are preferred for reasons of cost.

In addition to the abovementioned constituents, the coatings may contain customary additives such as are used in conventional coating compositions for textiles and which partly result from the substances used to produce the coatings and / or which are oriented in a known manner according to the intended use. These include colorants and auxiliaries, for example UV stabilizers, dispersing aids, surface-active substances, thickeners, defoamers, pH adjusters, flame retardants, antioxidants and preservatives. The Coatings may contain the abovementioned additives in the quantities customary for this purpose, without any loss in terms of the desired self-cleaning effect. In general, the total amount of the customary auxiliaries will not exceed a value of 10% by weight, preferably 5% by weight, based on the total weight of all the substances forming the coating.

Examples of colorants are inorganic and organic pigments and organic dyes. These are commercially available as a powder and as a solid or liquid pigment preparation. Typical inorganic pigments are titanium dioxide, barium sulfate, zinc oxide, iron oxides, carbon black, graphite. Typical organic color pigments such as Sepia, Cambogia, Kasseler Braun, Touidin red, Para red, Hansa Yellow, Indigo, Azo dyes, anthraquinoid and indigoid dyes. Optionally, pigment mixtures are used. The pigment should be as finely divided as possible. Preferably, the pigment particles have a particle size ≤ 5 microns. Since the colorants, if particulate, may have particle sizes in the ranges given for the component M, in these cases they are assigned to the component M. Coloring constituents which dissolve in the polymer matrix (dyes) are added to the customary auxiliaries and can be present in the coating in an amount of up to 20% by weight.

As flame retardants for the coating composition according to the invention, the halo- or phosphorus-containing compounds known to those skilled in the art, alumina hydrate, zinc borate, ammonium phosphates, antimony oxide, magnesium hydroxide and other conventional compounds or mixtures thereof can be used.

PH adjusting agents are the commonly used inorganic or organic, for example ammonia, alkali metal bases such as potassium and sodium hydroxide, sodium bicarbonate, sodium carbonate, potassium carbonate, potassium bicarbonate, alkaline earth metal bases such as calcium hydroxide, calcium oxide, magnesium hydroxide or magnesium carbonate, alkylamines such as ethylamine, diethylamine, Trimethylamine, triethylamine, triisopropylamine and mono-, di- and trialkanolamines such as ethanolamine, diethanolamine, aminomethylpropanol, Aminomethylpropanediol and trishydroxymethylaminomethane and mixtures thereof.

Suitable surface-active substances are the emulsifiers, polymer surfactants and protective colloids customarily used for the preparation of aqueous polymer dispersions. The emulsifiers may be amphoteric, neutral, anionic or cationic in nature. Suitable emulsifiers are known to those skilled in the art, for example from R. Heusch, "Emulsions" in Ullmann's Encyclopaedia of Industrial Chemistry, 5th ed. On CD-Rom, Chapter 7 , Examples of nonionic emulsifiers are alkoxylated fats and oils, e.g. Corn oil ethoxylates, castor oil ethoxylates, tallow fatty ethoxylates; Glycerol esters, e.g. B. glycerol monostearate; Fatty alcohol alkoxylates and oxo alcohol alkoxylates; Alkylphenol alkoxylates, e.g. B. isononylphenol ethoxylates; and sugar surfactants, e.g. B. sorbitan fatty acid esters (sorbitan monooleate, sorbitan tristearate), polyoxyethylene sorbitan fatty acid esters. In particular, fatty alcohol ethoxylates are used. Examples of suitable anionic emulsifiers are soaps, alkanesulfonates, olefinsulfonates, alkylarylsulfonates, alkylnaphthalenesulfonates, sulfosuccinates, alkyl sulfates and alkyl ether sulfates, alkylmethyl ester sulfonates and mixtures thereof, preferably in the form of the sodium salts. Examples of polymer surfactants are: block copolymers such as polyethylene oxide-block polypropylene oxide, polystyrene-block polyethylene oxide, and AB-comb polymers, eg polymethacrylic-comb-polyethylene oxide and copolymers of acrylic acid and maleic anhydride, in particular copolymers of acrylic acid and maleic anhydride, preferably in neutralized form, for. B. in the form of sodium or ammonium salts. Suitable protective colloids are, for example, cellulose ethers, such as carboxymethylcellulose, methylcellulose, hydroxyethylcellulose, gum arabic, polyvinyl alcohols and polyvinylpyrrolidone. The proportion of surface-active substances, based on the total weight of the polymer constituents of the coating, is generally in the range from 0 to 10 wt .-%, preferably 0.1 to 5 wt .-% based on the total weight of the preparation.

Suitable defoamers are, for example, higher alcohols, nonionic acetylene compounds, aliphatic hydrocarbons with non-ionic constituents and oligosiloxanes. As a rule, the amount of defoamer should be 5 to 20% by weight, for example 10% by weight of the surfactant fraction or 0.1 to 5% by weight, based on the total weight of the composition.

Suitable thickeners are in addition to the aforementioned protective colloids and gum arabic, gelatin, caseins, starch, alginates, polyethers, cellulose derivatives such as methyl, carboxymethylcellulose or hydroxyethyl u. Propyl cellulose, polyacrylic acid salts, such as the sodium salt or the ammonium salt of polyacrylic acid, hydrophobically modified polyurethanes (associative thickener) and inorganic thickeners such as silica, and mixtures thereof. The amount of thickening agent naturally depends on the desired rheology of the coating composition used for the coating and can therefore vary over a wide range. Usually, it is 0 to 5 wt .-%, based on the total weight of the composition.

Optionally, the coating additionally contains catalysts for the post-crosslinking, customary matting agents such as silica derivatives or customary water repellents.

The coatings according to the invention can be prepared according to the coating method customary for the coating of textiles by applying a coating composition containing the abovementioned constituents, in a manner known per se, to a flat, textile support, preferably in the amounts indicated above, and then the latter solidified wet coating solidified, z. B. by drying them. The preparation can also be carried out by first applying a first coating composition containing the finely divided material M and the binder B in the above proportions to a textile support, then drying the first layer and then applying a coating composition to the first-coated substrate apply and dry again. If the binder used is a crosslinkable or self-crosslinking binder as component i), the solidification also includes a so-called "condensation step", ie a crosslinking phase. Of the Condensation step or the crosslinking is usually triggered by heating the coated textile to a temperature above the crosslinking temperature of i). The crosslinking temperature is usually above 150 ° C and often above 160 ° C. The condensation step may coincide with the drying step and preferably takes place after the drying.

The term "flat textile carriers" or "textile fabrics" encompasses both woven and knitted fabrics produced from yarns and nonwoven nonwoven fabrics. In principle, all fiber materials commonly used for the production of textiles come into consideration as fiber materials. These include cotton, wool, hemp fiber, sisal fibers, flax, ramie, polyacrylonitrile, polyester fibers, polyamide fibers, viscose, silk, acetate fibers, triacetate fibers, aramid fibers, and the like. The coating compositions according to the invention are particularly suitable for textile fabrics based on fibers such as cotton, wool, polyester fibers, polyamide fibers and mixtures thereof.

• 50 bis 80 Gew.-%, bezogen auf den Feststoffgehalt der Zusammensetzung, wenigstens eines feinteiligen Materials, worin 80 Gew.-% der Teilchen einen Durchmesser im Bereich von 1 bis 100 µm aufweisen und
• 20 bis 50 Gew.-% , bezogen auf den Feststoffgehalt der Zusammensetzung, Matrix-Bestandteile, umfassend:
  1. i) als Komponente i wenigstens ein fluorfreies polymeres Bindemittel B, in Form einer wässrigen Dispersion und
  2. ii) als Komponente ii wenigstens ein fluororganisches Polymer FP oder eine Mischung davon mit einem hydrophoben Wachs, wobei der Fluorgehalt der Komponente ii wenigstens 1 Gew.-%, vorzugsweise wenigstens 2 Gew.-%, beträgt, in Form einer wässrigen Dispersion,
  3. iii) gegebenenfalls Hilfsstoffe in einer Menge von bis zu 10 Gew.-%, bezogen auf die Matrix,

wobei das Gewichtsverhältnis von Bindemittel B zu Komponente ii im Bereich von 1:2 bis 100:1 liegt.Advantageously, aqueous coating compositions are used to prepare the coatings according to the invention. As a result, unlike the processes of the prior art, larger amounts of organic solvents can be avoided. The invention therefore also relates to processes for the preparation of the coatings according to the invention, comprising the application of at least one aqueous coating composition to a textile support and subsequent drying of the application, which is characterized in that the aqueous coating composition contains:

• From 50 to 80% by weight, based on the solids content of the composition, of at least one finely divided material, wherein 80% by weight of the particles have a diameter in the range from 1 to 100 μm, and
• From 20 to 50% by weight, based on the solids content of the composition, of matrix constituents comprising:
  1. i) as component i at least one fluorine-free polymeric binder B, in the form of an aqueous dispersion and
  2. ii) as component ii at least one fluoro-organic polymer FP or a mixture thereof with a hydrophobic wax, wherein the fluorine content of component ii is at least 1 wt .-%, preferably at least 2 wt .-%, in the form of an aqueous dispersion,
  3. iii) optionally adjuvants in an amount of up to 10% by weight, based on the matrix,

wherein the weight ratio of binder B to component ii is in the range of 1: 2 to 100: 1.

• 50 bis 80 Gew.-%, bezogen auf den Feststoffgehalt der ersten Beschichtungszusammensetzung, wenigstens eines feinteiligen Materials, worin 80 Gew.-% der Teilchen einen Durchmesser im Bereich von 0,5 bis 100 µm aufweisen und
• 20 bis 50 Gew.-% , bezogen auf den Feststoffgehalt der Zusammensetzung, wenigstens ein fluorfreies polymeres Bindemittel B, in Form einer wässrigen Dispersion, sowie Wasser und gegebenenfalls bis 10 Gew.-% bezogen auf das Bindemittel B übliche Hilfsmittel,

enthält, auf einen textilen Träger aufbringt, gegebenenfalls anschließend den ersten Auftrag trocknet und dann hierauf eine zweite Beschichtungszusammensetzung, die

• wenigstens ein fluororganisches Polymer FP oder eine Mischung davon mit einem hydrophoben Wachs (Komponente ii) in Form einer wässrigen Dispersion enthält, wobei der Fluorgehalt wenigstens 1 Gew.-%, bezogen auf die Gesamtmenge an fluororganischem Polymer FP und gegebenenfalls dem Wachs, beträgt,

in einer Menge aufbringt, dass das Gewichtsverhältnis von Bindemittel B zu der Gesamtmenge an fluororganischem Polymer FP und gegebenenfalls dem Wachs im Bereich von 1:2 bis 100:1 liegt, und anschließend erneut trocknet. Auf diese Weise erhält man eine erfindungsgemäße Beschichtung, die eine erste Schicht, welche im Wesentlichen aus dem feinteiligen Material M und dem fluorfreien polymeren Bindemittel B aufgebaut ist und die wenigstens eine auf der ersten Schicht angeordnete zweite Schicht, welche im Wesentlichen aus der Komponente ii aufgebaut ist, umfasst. In allen Fällen kann sich an die Trocknung der oben beschriebene "Kondensationsschritt" anschließen.In a specific embodiment of the process according to the invention, the procedure is followed so as to successively produce a first aqueous coating composition which

• From 50 to 80% by weight, based on the solids content of the first coating composition, of at least one finely divided material, wherein 80% by weight of the particles have a diameter in the range from 0.5 to 100 μm, and
• 20 to 50 wt .-%, based on the solids content of the composition, at least one fluorine-free polymeric binder B, in the form of an aqueous dispersion, and water and optionally up to 10 wt .-% based on the binder B conventional auxiliaries,

is applied, applied to a textile support, if appropriate, then the first order is dried and then a second coating composition, the

• at least one fluoroorganic polymer FP or a mixture thereof with a hydrophobic wax (component ii) in the form of an aqueous dispersion, the fluorine content being at least 1% by weight, based on the total amount of fluorinated-organic polymer FP and optionally the wax,

in an amount that the weight ratio of binder B to the total amount of fluoro-organic polymer FP and optionally the wax in the range of 1: 2 to 100: 1, and then dried again. In this way, a coating according to the invention is obtained, which comprises a first layer which is essentially composed of the finely divided material M and the fluorine-free polymeric binder B and which has at least one second layer arranged on the first layer and essentially composed of the component ii is included. In all cases, the drying can be followed by the "condensation step" described above.

The aqueous coating compositions are novel and also the subject of the present invention. In addition to the constituents mentioned above, they naturally also contain an aqueous dispersing medium. They are prepared in a simple manner by mixing the individual components in conventional mixing devices.

An aqueous dispersing medium is understood here and below as meaning water and mixtures which contain at least 50% by volume, preferably at least 80% by volume, of water and a water-miscible organic solvent. Suitable solvents are ketones, for example acetone or methyl ethyl ketone, water-miscible ethers, for example tetrahydrofuran, dioxane, 1,2-priopanediol-1-n-propyl ether, 1,2-butanediol-1-methyl ether, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, diethylene glycol dimethyl ether, mono- or Polyalcohols such as methanol, ethanol, n-propanol, isopropanol, glycol, glycerol, propylene glycol or polyethylene glycol, and mixtures thereof. Preference is given to water-only dispersing medium (water content> 95% by volume).

The amount of dispersing medium is generally such that the resulting aqueous composition has a solids content of 10 to 90 wt .-%, preferably 20 to 80 wt .-%, most preferably 45 to 70 wt .-%.

Accordingly, component i, comprising at least one polymer and optionally a crosslinker, in the form of its aqueous dispersion, are used to prepare the compositions according to the invention. Polymer and dispersion can also be used as separate formulations for the preparation of the composition according to the invention become. The particle size of the polymer particles in such dispersions is generally in the range from 10 to 2000 nm, in particular in the range from 20 to 1500 nm.

Component ii will generally also be used as an aqueous dispersion or aqueous solution having a solids content of from 5 to 50% by weight. If a two-layer coating is desired, component ii can also be used as a dilute aqueous liquor having a solids content of from 1 to 10% by weight.

The coating compositions are applied to the usual methods for coating textiles, e.g. by spraying, rolling, printing, patting, knife-coating, brushing or padding. In particular, the coating compositions can be applied as a dilute liquor, after the addition of foaming agents as a foam or after the addition of thickeners as a paste. Spray methods are also possible and allow a very uniform application of the compositions of the invention.

The solids content of the coating composition of the invention in the spray process is generally in the range of 5 to 25 wt .-%. Preferably, the application is in the form of a liquor or paste, wherein the solids content of the composition is then preferably in the range of 15 to 90 wt .-%, in particular 25 to 80 wt .-%.

The application of the coating composition may be carried out as a direct coating, i. the fabric is coated directly with the coating composition, or by reverse or transfer coating.

Preferably, the coating compositions are applied as a paste or liquor in a direct process by knife coating, for example by air, blanket and roll doctoring. Also advantageous is the rotary screen coating, patting or reverse roll coater method. Upon successive application of the first and second coating compositions, the aqueous composition containing component ii is applied preferably by padding a dilute aqueous liquor of component ii.

Optionally, the aqueous coating compositions may be filtered prior to their application to the textile backing to remove agglomerates from the coating composition which would adversely affect the quality of the coating.

After application of the aqueous coating composition of the present invention, the aqueous dispersant is removed. The drying is then usually carried out under atmospheric pressure at temperatures above 100 ° C, preferably in the range of 130 to 200 ° C. The drying process usually takes 30 seconds to 5 minutes. But longer drying times are possible. With successive application of the first and the second coating, a drying step can take place after the application of the first coating and before the application of the component ii. The conditions for this are analogous to the conditions already described. The use of a self-crosslinking binder as component i) is preferably first drying below the crosslinking temperature of the binder, ie usually the temperatures up to 160 ° C, preferably to 150 ° C, perform to remove volatile components, and then crosslinking the binder (= condensation step) at temperatures above the crosslinking temperature, z. B. at temperatures in the range> 150 to 240 ° C, preferably> 160 to 200 ° C, trigger. Drying and condensation steps can also coincide. Drying time and duration of crosslinking are determined in a manner known per se according to the nature and quantity of the job and can be determined and optimized by the skilled person by means of routine experiments. In all cases, the drying can be carried out at a constant temperature (± 10 ° C). Preferably, however, it is progressive, ie with increasing temperature, for example starting with a temperature T ₁ ≦ 100 ° C, z. B. 70 to 100 ° C, and ending with a temperature T ₂ ≥ 130 ° C, z. B. 130 to 180 ° C or 120 to 150 ° C, depending on whether a separate condensation step should be carried out or not.

The textile fabrics coated according to the invention are not wetted by water or wetted only to a very small extent. Particulate contaminants such as soot, dust or even toner pigments adhere only moderately to the coated side of the fabric and can be rinsed with water as far as possible or completely without the use of detergents. The compositions of the invention are also abrasion resistant, i. rub-fast. In addition, they show excellent oleophobic properties. In addition, the coatings are wash-permanent, d. H. they do not lose the low soiling tendency and the self-cleaning effect even after repeated washing (eg with heavy-duty detergent at 60 ° C.).

The textile fabrics of the invention are thus suitable for the production of textile articles in which such properties are desired, for. As of textiles in rainwear and sportswear, protective clothing, for textile tarpaulins, for tents, umbrellas, awnings, textile wallpaper, tablecloths and the like.

The following examples are intended to illustrate the invention without, however, limiting it.

I. Feedstocks

• Polyurethane Dispersion PU1: Commercially available, 30% strength by weight, anionic, crosslinkable aqueous polyesterurethane dispersion having a glass transition temperature of -4 ° C.: ROTTA Coating BW 95871 from ROTTA GmbH in Mannheim.
• Polyurethane Dispersion PU2: Commercially available, 50% strength by weight, cationic, crosslinkable, aqueous polyesterurethane dispersion having a glass transition temperature of -2 ° C.: ROTTA Coating WS 80525 from ROTTA GmbH in Mannheim.
• Crosslinker: Commercially available 40% strength by weight aqueous dispersion of an isocyanate crosslinker having reversibly blocked isocyanate groups: ROTAL 444 from ROTTA GmbH.
• Fluorocarbon resin FP1: 30% strength by weight aqueous dispersion of a fluoropolymer with copolymerized monomers of the formula A with m = 7 to 8 and n = 2 with an organic fluorine content of about 11% by weight, based on the polymer constituents: DIPOLIT 481 the ROTTA GmbH in Mannheim.
• Fluorocarbon resin FP2: 30 wt .-% aqueous dispersion of a mixture of a fluoropolymer with copolymerized monomers of formula A with m = 7 to 8 and n = 2 and a paraffin wax extender with an organic fluorine content of about 1.6 wt .-%, based on the polymer constituents: DIPOLIT 470 of ROTTA GmbH in Mannheim.
• Quartz powder: Quarzfeinstmehl (Mikro-Dorsilit 110) from the company Dorfner, with the following particle size distribution: 8 wt .-%> 10 microns, 23 wt .-% in the range 6 - 10 microns, 22 wt .-% in the range 4 - 6 microns , 24 wt .-% in the range 2 - 4 microns and 23% of the particles is <2 microns. The weight-average particle size is 4.4 μm. Composition: 98.5% by weight of quartz, 1% by weight of feldspar and 0.5% by weight of residual constituents.
• Glass spheres: Glass spheres with a weight-average diameter of 3.5 to 7 μm (specification) in which 90% by weight of the glass spheres have a diameter in the range from 0.5 to 19.3 μm (according to DIN 4188).
• Thickener: 1 to 2% by weight aqueous hydroxyethyl cellulose solution.
• Preservative: Commercially available isothiazoline compound: Mergal K9N, Riedel de Hähn.
• Defoamer: 10% strength by weight aqueous silicone emulsion Antifoam RD from Dow Corning.

II. Compositions: Composition Z1 (according to the invention):

66 parts by weight of the aqueous polyurethane dispersion PU1 were mixed with 33 parts by weight of a 30 wt .-% fluorinated resin FP1 and 10 parts by weight of the commercial crosslinking agent with stirring at room temperature for 15 minutes. Then added with stirring 60 parts by weight of quartz powder and allowed to stir for 30 minutes. After addition of 0.5-1 parts by weight of thickener (aqueous hydroxyethyl cellulose solution) was adjusted with ammonia / water, the pH to 8 to 9 a. The viscosity of the composition was about 6000-7000 mPas. Finally, 0.5 parts by weight of commercially available preservative and 0.5-1 parts by weight of commercially available defoamer were added to the mixture. After a stirring time of 15 minutes, the mixture was homogeneous.

Composition Z2 (according to the invention):

50 parts by weight of a commercially available, crosslinkable aqueous 50 wt .-% polyurethane dispersion PU2 were mixed with 50 parts by weight of 30 wt .-% fluorocarbon resin FP1 15 min. At room temperature. 60 parts by weight of glass beads and 0.5-1 parts by weight of thickener were added thereto, and the pH was brought to 8-9 with ammonia / water. After a stirring time of 15 minutes, 0.5% by weight was added. Parts of preservative and 0.5 - 1 parts by weight defoamer mixed. The mixture was stirred until homogeneous (about 15 minutes). The viscosity was in the range of 6000-7000 mPas.

Composition Z3 (according to the invention):

Composition Z3 consists of a coating composition 1 and a liquor for fluorocarbon resin finish as coating composition 2.

60 parts by weight of quartz fine flour with 60 parts by weight of polyurethane dispersion PU2 while stirring at room temperature for 15 min. mixed. After addition of 0.5-1 parts by weight of thickener, the pH was adjusted to 8-9 with ammonia / water. The viscosity of the mixture was about 6000-7000 mPas. Finally, 0.5 parts by weight of preservative and 0.5-1 parts by weight of commercially available defoamer were added to the mixture. After a stirring time of 15 minutes, the mixture was homogeneous.

For the fleet of fluorocarbon resin equipment, the fluorocarbon resin FP1 diluted with water to 40 g / l was used.

Composition Z4 (according to the invention):

The composition Z4 consists of a first coating composition and a fluorocarbon resin finish as a second coating composition.

60 parts by weight Quarzfeinstmehl with 60 parts by weight polyurethane dispersion PU2 mixed with stirring at room temperature for 15 min. After addition of 0.5-1 parts by weight of thickener, the pH was adjusted to 8-9 with ammonia / water. The viscosity of the mixture was 6000-7000 mPas. Finally, 0.5 parts by weight of preservative and 0.5-1 parts by weight of commercially available defoamer were added to the mixture. After a stirring time of 15 minutes, the mixture was homogeneous.

For the fleet of fluorocarbon resin equipment, the fluorocarbon resin dispersion FP2 diluted with water to 40 g / l was used.

Composition ZV1 (comparison):

A coating composition was prepared analogously to composition Z2, but the addition of the 30% strength by weight fluorocarbon resin FP1 (DIPOLIT 481) was dispensed with and instead a mixture of 60 parts by weight of quartz fine flour and 60 parts by weight of the polyurethane Dispersion PU2 used.

Composition ZV2 (comparison):

Analogously to composition Z2, a coating composition was prepared, but omitting the addition of the polyurethane dispersion and instead mixing 60 parts by weight of glass beads with 100 parts by weight of the 30% strength by weight aqueous dispersion of the fluorocarbon resin FP1.

Composition ZV3 (comparison):

The comparative composition ZV3 is the 30% strength by weight aqueous dispersion of the fluorocarbon resin FP1 without further additives.

III. Application examples: Example 1:

After controlling the viscosity to be maintained at 6,000-7,000 mPas, the coating composition Z1 was applied to a cotton gauze fabric having a basis weight of 122 g / m ² as an one-coat coating with an air knife. The order was made in such an amount that a dry coating in an edition of about 100 g / m ² resulted. After applying the coating composition, it was dried for 2 minutes at 150 ° C.

Example 2:

In an analogous manner to Example 1, the composition Z2 au cotton Hämmerle product was applied with a basis weight of 122 g / m ² . This resulted in an edition of about 101 g / m ² .

Example 3:

First, the first coating composition of composition Z3 was applied analogously to Example 1 on cotton-Hämmele fabric having a basis weight of 122 g / m ² . The resulting Overlay in the first layer was about 100 g / m ² . Subsequently, the diluted Fluorcarbonharzflotte was padded and dried at -160 ° C for 2 minutes. The circulation of the fluorocarbon resin layer resulted at a liquor pickup of 100% to about 1.2 g / m ² .

Example 4:

Analogously to Example 3, the first coating composition of Z3 was applied to cotton-hammock fabric having a basis weight of 122 g / m ² . The resulting overlay was 100 g / m ² . However, the fluorocarbon resin liquor was padded as undiluted, 30 wt .-% dispersion and dried for 2 minutes at 160 ° C. The circulation of the fluorocarbon resin layer resulted in a liquor pickup of 100% to about 30 g / m ² .

Example 5:

The coating composition of Z4 was applied analogously to Example 3 on cotton-Hämmele fabric having a basis weight of 122 g / m ² . The resulting overlay in the first layer was about 100 g / m ² . The circulation of fluorocarbon resin / extender layer resulted at a liquor pickup of 100% to about 1.5 g / m ² .

Example 6:

A polyamide fabric treated with a fluorocarbon resin (basis weight 135 g / m ² (fluorocarbon resin 0.4 to 0.6 g / m ² ) was first coated with the first coating composition of Z 3 as in Example 3. The resulting coating was 43 g / m ² . Subsequently, the diluted fluorocarbon resin liquor was padded, and the coating of the fluorocarbon resin layer was about 1.2 g / m ² .

Comparative Example 1

In an analogous manner to Example 1, the composition ZV1 was applied to cotton-hammock fabric having a basis weight of 122 g / m ² . This resulted in a circulation of about 100 g / m ² .

Comparative Example 2:

In an analogous manner to Example 1, the composition ZV2 was applied to cotton hemp products with a basis weight of 122 g / m ² . This resulted in a circulation of about 100 g / m ² .

Comparative Example 3

The composition of the ZV3 equipment was padded on cotton hemp ware at a basis weight of 122 g / m ² . At a liquor pick-up of 100% resulted in a circulation of fluorocarbon resin of about 24 g / m ² .

IV. Application Testing: Hydrophobicity:

Spray test DIN 53888 (grades 0 to 100 = best)

oleophobia:

Oil value AATCC 118/1983 (grades 0 to 8 = best)

Soiling and cleaning (3M dry soil test) :

Stain test: 3M dry soiling test with toner Inspection Cleaning: Rinse the sample strip with 5 ml of water spray. The grading is done by visual assessment of the sample (0% = white = best, 100% = black).

Abrasion resistance:

Exam:

Scrub test (1000 tours, 1 kg load)

Device:

FLEXOMETER TYPE SCRUBB, DIN NFG37110 or SNV 18498

rub fastness

Prüfung:

DIN 54021 (Crockmeter, Noten 1 bis 5 = bestes)

Die Prüfung wird an angefärbten beschichteten Mustern (1% Helizarin-Blau BT in der Beschichtungspaste) durchgeführt.

Exam:

DIN 54021 (Crockmeter, grades 1 to 5 = best)

The test is carried out on stained coated samples (1% Helizarin Blue BT in the coating paste).

The results of the performance test for Examples 1-5 and Comparative Examples 1-3 are given in Table 1.

The coated according to Example 6 fabric was soiled with commercial graphite oil by applying graphite oil on the coated side of the fabric, then loaded the soiled side for 4 h with 1 kg and the dirt for a further 16 h act. For purposes of comparison, the uncoated but fluorocarbon resin treated fabric was similarly soiled.

Both samples were then washed in a household wash (Miele WFK 2801 normal program 60 ° C) with a heavy duty detergent (Burti, 280 ml for normal soiled laundry). The sample according to the invention was completely cleanable, while the uncoated comparative sample had heavy stains after washing. To demonstrate the washing permanence, the sample according to the invention was washed a further three times in the manner described above and again soiled with graphite oil in the manner described above. Another wash in the manner described above resulted in a complete cleaning of the sample without the appearance of dirt residues. Table 1: Example spray test oil rating soiling Cleaning (residual dirt) Scrub Test rub fastness 1 100 7 60% 0% good, abrasion 30% 3 2 100 7 70% 10% good, abrasion 10% 3 3 100 6.7 60% 5% good, abrasion 30% 3 4 100 7 70% 5% good, abrasion 10% 3 5 100 6 60% 10% good, abrasion 30% V1 50 0 50% 20% medium, abrasion 40% 3 V2 100 7 60% 0% bad, abrasion 90% V3 100 6 80% 60%

Claims (14)

1. A textile fabric comprising a sheetlike textile support and at least one coating applied atop the support and constructed from:

   - 50% to 80% by weight, based on the total weight of the coating, of at least one finely divided material M wherein 80% by weight of the particles have a diameter in the range from 0.5 to 100 µm, and

   - 20% to 50% by weight, based on the total weight of the coating, of a matrix comprising:

   i) as component i, at least one fluorine-free, conventional polymeric binder B,

   ii) as component ii), at least one fluorochemical polymer FP or a mixture thereof with a hydrophobic wax, the fluorine content of said component ii being at least 1% by weight,

   iii) if appropriate, auxiliary materials in an amount up to 10% by weight, based on the matrix,

   the weight ratio of component i to component ii being in the range from 1:2 to 100:1.
2. A textile fabric according to claim 1, wherein the coating is at least 10 g/m² thick.
3. A textile fabric according to claim 1 or 2, wherein the coating contains said component ii in an add-on of at least 0.2 g/m².
4. A textile fabric according to any one of the preceding claims, wherein the coating contains the finely divided material M in an amount of at least 10 g/m².
5. A textile fabric according to claim 1 or 2, wherein the coating contains said component i in an amount of at least 15% by weight, based on the total weight of the coating.
6. A textile fabric according to any one of the preceding claims, wherein the fluorine-free polymeric binder B has a glass transition temperature in the range from -40 to +100°C.
7. A textile fabric according to any one of the preceding claims, wherein the fluorine-free polymeric binder B is a polyurethane resin.
8. A textile fabric according to any one of the preceding claims, wherein the fluorochemical constituent of the fluorochemical polymer FP comprises fluorohydrocarbyl groups of the formula I:
   
           F₃C(CF₂)_m(CH₂)_n-     (I)
   
   where m is from 2 to 10 and n is from 0 to 5.
9. A textile fabric according to any one of the preceding claims, wherein the coating comprises a first layer constructed from the finely divided material M and the fluorine-free polymeric binder B and at least one second layer disposed atop the first layer and constructed from component ii.
10. A textile fabric according to claim 9, wherein the second layer has an add-on of at lest 0.2 g/m².
11. A process for producing a textile fabric according to any one of claims 1 to 10, comprising applying at least one aqueous coating composition atop a textile support and subsequently drying the applied material, characterized in that the aqueous coating composition contains:

    - 50% to 80% by weight, based on the solids content of the composition, of at least one finely divided material wherein 80% by weight of the particles have a diameter in the range from 0.5 to 100 µm, and

    - 20% to 50% by weight, based on the solids content of the composition, of matrix constituents comprising:

    i) as component i, at least one fluorine-free polymeric binder B,

    ii) as component ii, at least one fluorochemical polymer FP or a mixture thereof with a hydrophobic wax, the fluorine content of said component ii being at least 1% by weight, in the form of an aqueous dispersion,

    iii) if appropriate, auxiliary materials in an amount of up to 10% by weight, based on the matrix,

    the weight ratio of binder B to component ii being in the range from 1:2 to 1:100.
12. A process for producing a textile fabric according to claim 9 or 10 by successively applying a first aqueous coating composition to a textile support, if appropriate subsequently drying the first applied material and applying a second coating composition and subsequently drying again, characterized in that the first coating composition contains:

    - 50% to 80% by weight, based on the solids content of the coating composition, of at least one finely divided material wherein 80% by weight of the particles have a diameter in the range from 0.5 to 100 µm, and

    - 20% to 50% by weight, based on the solids content of the composition, of at least one fluorine-free polymeric binder B, in the form of an aqueous dispersion, and also water and if appropriate customary auxiliaries in an amount up to 10% by weight, based on said binder B,

    and the second coating composition contains at least one fluorochemical polymer FP or a mixture thereof with a hydrophobic wax (component ii) in the form of an aqueous dispersion, the fluorine content being at least 1% by weight, based on the total amount of fluorochemical polymer FP and, if appropriate, the wax,
    the first and second coating compositions being applied in such a quantitative ratio that the weight ratio of binder B to the total amount of fluorochemical polymer FP and, if appropriate, the wax is in the range from 1:2 to 100:1.
13. A coating composition containing:

    - 50% to 80% by weight, based on the total weight of the coating, of at least one finely divided material wherein 80% by weight of the particles have a diameter in the range from 0.5 to 100 µm, and

    - 20% to 50% by weight, based on the total weight of the coating, of polymeric constituents comprising:

    i) as component i, at least one fluorine-free polymeric binder B, in the form of an aqueous dispersion and

    ii) as component ii, at least one fluorochemical polymer FP or a mixture thereof with a hydrophobic wax, the fluorine content of said component ii being at least 1% by weight, in the form of an aqueous dispersion

    iii) and also water and, if appropriate, conventional auxiliary materials in an amount up to 10% by weight, based on the binder B,

    the weight ratio of binder B to component ii being in the range from 1:2 to 100:1.
14. A coating composition in the form of a 2-component composition comprising:

    a) a first aqueous coating composition containing

    - 50% to 80% by weight, based on the solids content of the first coating composition, of at least one finely divided material wherein 80% by weight of the particles have a diameter in the range from 0.5 to 100 µm, and

    - 20% to 50% by weight, based on the solids content of the composition, of at least one fluorine-free polymeric binder B, in the form of an aqueous dispersion, and also water and, if appropriate, up to 10% by weight, based on said binder B, of customary auxiliaries and

    b) a second aqueous coating composition containing at least one fluorochemical polymer FP or a mixture thereof with a hydrophobic wax in the form of an aqueous dispersion, the fluorine content being at least 1% by weight, based on the total amount of fluorochemical polymer FP and, if appropriate, the wax, the quantitative ratio of first and second coating compositions ensuring a weight ratio of binder B to the total amount of fluorochemical polymer FP and, if appropriate, the wax in the range from 1:2 to 100:1.