EP1283296A1 - Textile fabric with reduced soiling properties - Google Patents

Abstract

Flax structured textiles of low soiling tendency and good self-cleaning power which are not lost under mechanical loads can be achieved by the use of coatings containing at least 50 wt.% of finely divided particles unsuitable for film formation of a material (M), in which 80 wt.% of the particles are of diameter 0.5-100 micro m, and sufficient polymer binder as matrix builder. Flax structured textiles including a flax textile carrier and at least one coating on the carrier from (wt.%) at least one finely divided material (M) (50-80) in which 80 wt.% of the particles have a diameter of 0.5-100 micro m, and a matrix (20-50) including: (I) at least one fluorine-free conventional polymer binder (B); (II) at least one fluoroorganic polymer (FP) or a mixture of this with a hydrophobic wax, where the F content of component (II) is at least 1 wt.%; and (III) optionally adjuvants in amount up to 10 wt.% relative to the matrix, and the weight ratio of component (I) to component (II) is 1:2 to 100:1. Independent claims are included for: (1) a process for preparation of the textile material including application of at least one aqueous coating composition to a textile carrier and drying of the carrier, where the aqueous coating composition contains (wt.%) at least one finely divided material (50-80) in which 80 wt.% of the particles are of diameter 0.5-100 micro m and a matrix component (20-50 wt.%) including: (i) F-free polymer binder (B) in aqueous dispersion; (ii) a fluoroorganic polymer or a mixture of this with a wax , where the F-content of component (ii) is less than 1 wt. % as an aqueous dispersion; and (iii) optionally adjuvants in amount up to 10 wt.% on the matrix, where the weight ratio of binder (B) to component (ii) is 1:2 to 100:1; (2) a coating composition containing (wt.%) at least one finely divided material (50-80) in which 80% of the particles are of diameter 0.5-100 micro m, and a polymer component including: (a) at least one F-free polymer binder (B), in the form of an aqueous dispersion; (b) at least one fluoroorganic polymer (FT) or a mixture of this with a hydrophobic wax, where the F-content of component (b) is at least 1 wt.%, in the form of an aqueous dispersion; and (c) water and optionally up to 10 wt.% of binder (B), and conventional adjuvants, where the weight ratio of binder (B) to component (b) is 1:2 to 100:1; and (3) a two-component coating composition including a first aqueous coating composition containing at least one finely divided material in which 80 wt.% of the particles are of diameter 0.5-100 micro m, at least one F-free polymer binder (B) as an aqueous dispersion, water, and up 10 wt.% of adjuvants relative to binder (B).

Description

The invention relates to novel textile fabrics that at least one attached to a flat textile carrier Have coating and a low tendency to soiling and have a very good self-cleaning effect.

Textiles are particularly prone to soiling due to their fiber structure and the associated high surface area. Cleaning them is often problematic and in many cases is not possible. In particular, technical textiles that are used outdoors, e.g. as tent sheets, tarpaulins, awnings and the like, or as decorative textiles, e.g. as textile wall coverings, blinds, roller blinds, curtains or tablecloths, are exposed to heavy soiling and can usually only be cleaned with a large amount Effort to be cleaned. To reduce their tendency to soiling and to facilitate their cleaning, such textiles are often provided with a soil release finish or an oleophobic finish. To this end, fluorine organic compounds or fluoro-organic polymers (fluorocarbon waxes) are often used (see, eg, K. Fischer et al. "Textile Auxiliaries" chap. 7 and 8.2.5 ^th ed in Ullmann's Encyclopedia of Industrial Chemistry, 5th on CD-ROM , and for 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 Finishing," TPI Text. Prax. Int . 27 (1972) 499-503 Treated textiles are less sensitive to oils and fats, but the tendency to soiling against airborne dust and other particulate contaminants can only be insufficiently improved in this way.

Textiles are also often given a hydrophobic finish, to the water permeability of the fabric in terms of Use of textiles in rain and sports clothing, protective clothing, as tarpaulin, in tents, umbrellas, awnings, wallpaper, Tablecloths or other textile products for which a waterproofness is desired to prevent. For this purpose often waxes, fatty acid salts, quaternary ammonium compounds, Silicone resins and fluorocarbon resins or mixtures thereof are used. It is also known to provide textiles with polymer coatings, to achieve increased waterproofness and opacity. Hydrophobized or coated textiles usually have no reduced tendency to soiling.

There have been various reports of surfaces, on the one hand not be wetted by water and on which dirt particles only have little liability. Such surfaces stand out also by a self-cleaning effect, i.e. the dirt particles are caused by moving water, e.g. due to droplets of water rinsed off the surface, being a more or less completely cleaned surface remains. This effect will since it is known from the leaves of the lotus plant, also known as the lotus effect referred to (see Barthlott et al., Biology in our time, 28, No. 5, 314-322).

WO 96/04123 describes surfaces that have an artificial surface structure own, which has elevations and depressions, the structure in particular by the distance from 5 to 200 µm between the surveys and a height of the surveys of 5 up to 100 µm is characterized. The surfaces are manufactured for example by applying Teflon powder to one with Adhesive treated surface or by stamping a structure on it a thermoplastic deformable hydrophobic material. such Surfaces are said to be characterized by the fact that dust or other particulate contaminants from the surfaces by means of Water can be rinsed off and therefore a self-cleaning or show lotus effect.

Similar surfaces are known from US 3,354,022. Here too the surface is produced either by stamping a structure or by applying hydrophobic particles, for example of wax particles on a hydrophobic surface.

It also describes a surface that is made with wax coated glass powder with a grain size of 3 to 12 µm consists.

A coating method is known from JP 7328532-A, in which a finely divided material with a hydrophobic surface apply a wet varnish and harden it. Here are preserve water-repellent surfaces.

WO 00/58410 describes a method for producing dirt-repellent Surfaces, where one from a solution, dispersion or Emulsion applies a hydrophobic material to a surface, wherein the hydrophobic material is selected such that it evaporates of the solvent or dispersant under self-organization forms a surface, the elevations and depressions with a Has a distance of 0.1 to 200 microns and a height of 0.1 to 100 microns and can also be detached by detergents.

The manufacturing methods described in the prior art difficult to wet surfaces with self-cleaning effect are either very complex or do not lead to satisfactory results. The creation of a structured surface by embossing processes is complex and can only be economical with flat surfaces be used. Treatment of textiles is on not possible this way. Surfaces on which a structuring achieved by the subsequent application of hydrophobic particles are often difficult to reproduce and have only one low mechanical stability. These procedures are also likely can hardly be used for textiles. 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 is possible by coating textile supports with Preparations from finely divided powders, which have a special Have size distribution, and fluorocarbon wax, textiles with to produce a self-cleaning effect. Such equipment However, they are mechanically unstable and in particular only have one low abrasion resistance. Conversely, the replacement of the fluorocarbon waxes through conventional binders, such as those used for coating of textiles usually used, not too Coatings that show a self-cleaning effect.

The present invention is therefore based on the object of textiles to be equipped in such a way that they have a low tendency to become soiled and show a high self-cleaning effect and do not lose this property even under mechanical stress. In addition, the coatings should be washable and cleanable his. In particular, the coatings should be resistant to abrasion.

Surprisingly, this object is achieved by coatings, which is at least 50% by weight of a finely divided, for film formation unsuitable material M, in which 80% by weight of the particles have a Have diameters in the range of 0.5 to 100 microns, and a sufficient amount of a polymeric binder as a matrix former included when the binder forming the matrix is at least one conventional polymeric binder as component i and at least a fluorocarbon polymer or a mixture thereof with one Contains hydrocarbon wax as component ii if the ratio from conventional binder to component ii in Range is 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:
• i) als Komponente i wenigstens ein fluorfreies, konventionelles polymeres Bindemittel B,
• 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
• 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 carrier, and at least one coating applied to the carrier, which is composed of the following components:

• 50 to 80% by weight, based on the total weight of the coating, of at least one finely divided material M, in which 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 fluoroorganic polymer FP or a mixture thereof with a hydrophobic wax, the fluorine content of component ii being at least 1% by weight, and
• iii) optionally auxiliary substances 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.

In principle, all materials can be used as particulate material are used, whose particles meet the above criterion of diameter and their shape during the production of the coating largely retained, i.e. that do not melt or melt. At least 80% of the particles preferably have a particle diameter in Range from 1 to 50 µm and especially in the range from 1 to 20 µm on. The average particle diameter (weight average, determined via Sieve line) is usually below 50 microns, preferably in Range from 1 to 20 µm, especially in the range from 1 to 10 µm and particularly preferably in the range from 2 to 8 μm. The particles point preferably a compact structure, i.e. 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 3: 1. Your surface can be smooth or irregular in shape. examples for suitable materials can be both organic in nature, e.g. Potato starch, or more inorganic, e.g. be oxidic in nature. Examples of the latter are quartz flours and quartz flours, e.g. those marketed under the Dorsilit® and Mikro-Dorsilit® brands Products from Dorfner, Hirschau, Germany, glass balls and Hollow glass spheres, e.g. those marketed under the name Spheriglas® Products from Potters-Ballotoni, Kirchheim-Bolanden, Kaolin powder, e.g. those sold under the name KAOLINS Products from Dorfner, diatomaceous earth, e.g. the under the designations SEITZ Extra distributed by SEITZ Filter Werke GmbH Products.

The proportion of the finely divided material M in the coating is preferably 55 to 75% by weight and in particular 60 to 70% by weight, based on the total weight of the coating. In this way, optimal dirt repellency is achieved while the coating is sufficiently strong. The amount 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 . Larger runs are generally not necessary, but do not lead to a decrease in the self-cleaning effect.

Basically, all essentially fluorine-free come as component i polymeric binder into consideration, which is usually used for Coating of textiles can be used. The type of polymer The binder depends on the intended use of the fabric. Provided the fabric is flexible should, preferably choose uncrosslinked polymers or polymers a low degree of crosslinking; if you want one instead rigid shape, so you are preferably more cross-linkable Use polymers as binder B.

It is preferred if the polymeric binder B in the preparation has a glass transition temperature T _G in the range from -40 to +100 ° C, preferably -30 to +60 ° C, in particular -20 to +40 ° C. If polyurethanes are used as binder 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 crosslinking agent) is usually at least 10% by weight, preferably at least 15% and especially at least 20%, e.g. 10 to 49.5% by weight, preferably 15 to 40% by weight and in particular 20 to 35% by weight, based on the total weight of the coating.

Compounds B which are self-crosslinking are preferred as component i. The person skilled in the art understands this to mean polymer systems, preferably based on aqueous polymer dispersions, which undergo intra- and / or intermolecular crosslinking reactions when the coating dries. The crosslinking reactions are known to be effected in that the polymers either have different functional groups which react with one another to form ionic or covalent bonds, or in that the binder comprises a polymer with functional groups and a low-molecular or oligomeric crosslinker or a polyvalent metal salt, where the crosslinker has at least two functional groups which can react with the functional groups of the polymer. Suitable reactive groups in polymers are, for example, 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, epoxy, anhydride or aldehyde groups; Aldehyde or keto groups that react with amines or hydrazides; N-methylolamine, N-methylolamide and hydroxymethylamino groups that react with themselves; Isocyanate groups, which can also be reversibly blocked (blocked), for example with phenols, t-butanol, 1,3-diketones, malonic esters, cyclic amides such as caprolactam, nitriles, aldehydes or oximes, and which react with amino groups, OH groups and the like can. The theoretical crosslinking density in the self-crosslinking binders, ie the molar number of crosslinking points which arise on 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 / kg of polymer and optionally crosslinker and in particular in the range from 0.1 to 1 mol / kg.

Examples of suitable crosslinkers are the di- or polyols; primary or secondary diamines, preferably primary Diamines, e.g. Alkylene diamines such as hexamethylene diamine, diethylene triamine, Triethylene tetramine, tetraethylene pentamine, N, N-bis [(aminopropyl) amino] ethane, 3,6-Dioxaoctanediamine, 3,7-Dioxanonanediamine, 3,6,9-Trioxaundecanediamine or Jeffamine, (4,4'-diaminodicyclohexyl) methane (4,4'-diamino-3,3-dimethyldicyclohexyl) methane; Amino alcohols such as Ethanolamine, hydroxypropylamine; ethoxylated di- and oligoamines; Dihydrazides of aliphatic or aromatic dicarboxylic acids such as adipic; Dialdehydes such as glyoxal; partially or completely O-methylated melamines, as well as compounds or oligomers, which have an average of 2 or more, preferably 3 or more isocyanate groups or have reversibly blocked isocyanate groups. self- Polymer dispersions that do not require external crosslinkers, indicate e.g. OH groups in combination with carboxyl or Anhydride groups, or N-methylolamide groups.

Mixtures of a polymer which are preferred as component i Has reactive groups, and a complementary crosslinker used. In this case the quantity ratio of crosslinker to polymer dimensioned so that the molar ratio of the reactive groups in the polymer to the reactive groups in the crosslinker usually in Range from 1:10 to 10: 1 and preferably in the range from 3: 1 to 1: 3 lies. The weight ratio of polymer is usually too Crosslinkers in the range from 100: 1 to 1: 1 and in particular in the range from 50: 1 to 5: 1.

Suitable polymers which are used as binder B in the coating of Textiles used are known to the person skilled in the art, e.g. from D. Distler "Aqueous Polymer Dispersions", Wiley-VCH, Weinheim, 1999, Pp. 171 ff. 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, especially polyvinyl acetates;
• Vinylester-olefin copolymers; such as
• Vinylester-acrylate copolymers.

The skilled person understands acrylic resins as homo- 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 their 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 methosulphates 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. Accordingly, the person skilled in the art understands styrene acrylates as copolymers of styrene with at least one ester of acrylic acid and / or methacrylic acid and optionally further monomers, for example the aforementioned auxiliary monomers. The term “styrene-butadiene copolymers” is understood by the person skilled in the art to mean copolymers of butadiene with styrene, which may contain the above-mentioned auxiliary monomers and / or optionally acrylonitrile and / or methacrylonitrile in copolymerized form.

Polyvinyl esters are understood by those skilled in the art to mean the homo- 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, if appropriate, the auxiliary monomers mentioned above. Polyvinyl esters which contain C ₂ -C ₆ olefins such as ethylene in copolymerized form are also referred to as vinyl ester-olefin copolymers. Polyvinyl esters which contain polymerized esters of monoethylenically unsaturated mono- and / or dicarboxylic acids are referred to as vinyl ester acrylates.

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

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

As is known, polyurethanes are addition products of at least an isocyanate component which comprises at least one diisocyanate, and at least one polyol component containing at least one diol includes. In addition, the isocyanate component can also be more functional Isocyanates, e.g. B. triisocyanates or oligomeric isocyanates, those on average more than 2 and preferably 3, 4 or more Have isocyanate groups. The polyol component can also higher functional polyols or oligomeric polyols with an average of more than 2 OH groups, preferably 3, 4 and more OH groups.

Suitable diisocyanates are aromatic diisocyanates such as 2,4- and 2,6-tolylene diisocyanate (TDI) and isomer mixtures thereof, tetramethylxylene diisocyanate (TMXDI), xylene diisocyanate (XDI), diphenylmethane-4,4'-diisocyanate (MDI), and aliphatic and cycloaliphatic diisocyanates such as dicylohexylmethane-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 biureths of the abovementioned diisocyanates, and oligomers which are produced by the targeted reaction of diisocyanates or semi-blocked diisocyanates with polyols, which have on average more than 2 and preferably at least 3 OH groups per molecule are available.

The proportion of the polyisocyanate component in the components which forming the polyurethane is usually in the range of 5 to 60 % By weight and in particular 10 to 40% by weight. The proportion of diisocyanate, based on the weight of the polyisocyanate component is in the Usually at least 60% by weight and in particular at least 80% by weight.

Suitable diols are glycols with preferably 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 components of the polyol component are trivalent (Triols) and higher-quality, low-molecular alcohols. They point in usually 3 to 25, preferably 3 to 18 carbon atoms. These include glycerin, trimethylolethane, trimethylolpropane, Erythritol, pentaerythritol, sorbitol and their alkoxylates.

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

The proportion of oligomeric polyols in those forming the polyurethane Components are generally in the range from 10 to 95% by weight, preferably 20 to 95% by weight and in particular 25 to 85% by weight based on the total weight of the components forming the polyurethane. The proportion of low molecular weight alcohols is in the Usually not more than 60% by weight, e.g. 1 to 60% by weight, and often up to 30% by weight or up to 20% by weight.

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 to mean both linear and branched polyethers which have an average of at least 2 hydroxyl groups, preferably arranged on their termini, per molecule. Aliphatic polyether polyols, ie polyether polyols which are composed of aliphatic and / or cycloaliphatic building blocks, are preferred. As a rule, polyether polyols are obtained by polymerizing alkylene oxides having 2 to 4 carbon atoms, optionally with a starter. Examples of alkylene oxide include ethylene oxide, 1,2-propylene oxide, 1,2- and 2,3-butylene oxide, in particular ethylene oxide and propylene oxide. As a starter molecule come z. B. water, low molecular weight diols or polyols, for example the aforementioned glycols, oligomeric alcohols, polyetherols and polyesterols. Examples of suitable starters are in particular ethanediol, 1,2- and 1,3-propanediol, bisphenol A, glycerol, trimethylolpropane, pentaerythritol and sorbitol. Polyether polyols with only two hydroxyl end groups are obtained when difunctional starters such as water, ethylene glycol, propylene glycol and bifunctional oligoalkylene oxides are used. Polyetherols are also accessible by cationic polymerization of cyclic ethers such as tetrahydrofuran. Particularly preferred polyether polyols are polyether diols, including 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 both linear and branched polyesters with at least two, preferably terminal OH groups. Their molecular weight is in particular in the range from 800 to 20,000, especially in the range from 1,000 to 10,000 g / mol. Suitable polyesterols can e.g. B. by polycondensation of aliphatic, cycloaliphatic and aromatic di-, tri- and / or polycarboxylic acids or ester-forming derivatives such as anhydrides or chlorides with the above-mentioned di- and / or polyols and / or polyetherols, the alcohol component being used in excess is, ie the molar ratio of OH groups to acid groups is more than 1: 1, z. B. 1.1: 1 to 2: 1. Suitable carboxylic acids are e.g. B. 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. Preferred are polyester diols which can be obtained by condensing dicarboxylic acids with diols. Polyester polyols can also be produced by polycondensation of hydroxycarboxylic acids or lactones with the di- or polyols mentioned above. Suitable lactones are, for example, those with 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. Aliphatic polyester polyols are preferred, ie the building blocks which form the polyester are selected from aliphatic and cycloaliphatic building blocks.
Polycarbonate polyols are understood to be those polycarbonates which have on average at least 2, for example 2, 3, 4 or 5, preferably hydroxyl groups arranged on their termini per molecule and which essentially, generally to more than 80% by weight, preferably more than 90% by weight .-%, from repeating units of the general formula I.

are set up. In formula I, R represents a divalent 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 usually 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 with 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, for example cyclohexane-1,4-diol, 1,4-bis (hydroxymethyl) cyclohexane or 2, 2-bis (4-hydroxycyclohexyl) propane.
The polycarbonate polyol can also have one or more, for example 1, 2 or 3, branching points which are derived from polyhydric alcohols, such as glycerol, trimethylolpropane, pentaerythritol, or from sugar alcohols, such as sorbitol. Depending on the number of branching points and the functionality of the alcohol, the resulting polycarbonate polyol has a hydroxyl functionality> 2.

Since the polyurethanes for producing the coating are preferred in Are used in the form of an aqueous dispersion, they have in the Rule polar functional groups, especially 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. The introduction of these functional groups into the Polyurethane is usually made using accordingly anionic or anionogenic or cationic or cationogenic Groups of substituted compounds that are at least two opposite Have isocyanate reactive groups in the manufacture of the polyurethanes. The proportion of such building blocks, based on the total quantity of the components forming the polyurethane is usually in the range of 0.1 to 25% by weight, preferably 0.5 to 20% by weight.

Suitable compounds with 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 Have phosphonic acid group, sulfonic acid group or sulfonate group, with the diols mentioned above. The dicarboxylic acid component includes e.g. Sulfosuccinic acid, 4-sulfophthalic acid, 5-sulfoisophthalic acid, Sulfoterephthalic acid, 4-sulphonaphthalene-2,7-dicarboxylic acid, 5- (4-sulfophenoxy) terephthalic acid and the corresponding salts. Anionically modified diols include also the diester diols of tri- or tetracarboxylic acids with the previous ones called diols. Coming as tri- or tetracarboxylic acids for example 2-phosphonobutane-1,2-4-tricarboxylic acid, citric acid, 1,2,3-propane tricarboxylic acid, 1,3,5-benzene tricarboxylic acid (trimesic acid), 1,2,4-benzenetricarboxylic acid (trimellitic acid), 1,2,4,5-benzenetetracarboxylic acid (Pyromellitic acid). To the anionically functionalized Diols continue to count linear or branched diols can be aliphatic, cycloaliphatic or aromatic and the carry an anionic functional group. examples for this are Dimethylolpropionic acid (bis-2,2- (hydroxymethyl) propionic acid), 2-sulfo-1,4-butanediol, 2,5-dimethyl-3-sulfo-2,5-hexanediol and their Salts, especially their sodium and potassium salts. suitable Anionically modified compounds are still corresponding substituted amino alcohols and diamines, e.g. Ethylenediamine-N-acetic acid, Ethylenediamine-N-propionic acid, N- (sulfonatoethyl) ethylenediamine, their salts, especially their sodium and Potassium salts.

Suitable compounds with polar functional groups are furthermore cationogenically modified compounds. Here and below, cationogenic means cationic groups and groups which can be converted into a cationic group by modification, for example protonation or alkylation (quaternization). Examples of these are cationically modified di- or polyols, cationogenically modified di- or polyamines and amino alcohols such as N, N-bis (hydroxy-C ₂ -C ₈ -alkyl) amines which contain one or two further radicals on the nitrogen, for example an aryl radical, may have a C ₁ -C ₈ -alkyl radical or an aryl-C ₁ -C ₈ -alkyl radical, furthermore hydroxy-C ₂ -C ₈ alkylpiperazines bis (hydroxy-C ₂ -C ₈ -alkyl) piperazines, 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 can also reactive functional groups have, which allow a subsequent crosslinking of the polyurethane. These include the reactive groups mentioned above, especially OH groups, carboxylate groups, blocked isocyanate groups, Amino groups. Often you will use a polyurethane that still has free OH groups as reactive groups. In the As a rule, the proportion of reactive functional groups is 0.1 to 2 mol / kg polymer.

The introduction of the reactive groups can, for example, by Implementation of polyurethanes that blocked free or reversibly Have isocyanate groups with compounds that are both opposite to each other Isocyanate groups reactive functional group as well have further reactive functional groups mentioned above, respectively. It is also possible to use OH groups or isocyanate groups containing polyurethanes through targeted condensation of Manufacture polyol with polyisocyanate components, either in addition to the diols higher polyols or in addition to the diisocyanates contain higher-quality isocyanates, so that in the manufacture of a Excess OH groups or excess isocyanate groups (or on masked isocyanate groups) based on the required Stoichiometry is used. In a preferred embodiment The invention uses crosslinkable polyurethanes, in particular Polyester urethanes as binders B, which still have free OH groups exhibit.

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

In a particularly preferred embodiment, are used as binders B a mixture of a hydroxyl-containing polyurethane, in particular a polyether or polyester urethane, and an isocyanate crosslinker that contains free or blocked isocyanate groups has used.

Basically, all fluoroorganic polymers come as component ii and their mixtures with waxes, as is customary be used to finish textiles. The share of Organic fluorine in component ii is included according to the invention at least 1% by weight, preferably at least 2% by weight, e.g. B. in Range of 2 to 25 wt .-%, especially in the range of 2 to 15% by weight.

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 fluoroorganic polymer FP has fluorocarbon groups of the formula I as an organofluorine component: F ₃ C (CF ₂ ) _m (CH ₂ ) _n - 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 fluoroorganic polymers are usually homo- or copolymers of organofluorine monomers of the formula A: F ₃ C (CF ₂ ) _m (CH ₂ ) _n -XR wherein

m and n have the preferred meanings,

X represents an oxygen atom or a carboxyl group and

R represents an ethylenically unsaturated hydrocarbon radical with preferably 2 to 8 carbon atoms and optionally further heteroatoms.

In formula A, R represents vinyl, allyl, methallyl and 1-propen-2-yl. In particular, X-R stands for acryloxy or methacryloxy.

In addition to the monomers A, the fluoroorganic polymer can be one or several, of which different ethylenically unsaturated comonomers polymerized included. Usually, the comonomers include at least one electrically neutral, preferably not in water or only partially 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 polymerized monomers A in the total mass of the Polymer FP is generally in the range from 1 to 50% by weight, preferably in the range from 5 to 40% by weight and in particular in the Range from 10 to 30% by weight. The proportion of the monomers B is in the Usually in the range of 50 to 99% by weight, preferably in the range of 60 to 95% by weight and in particular in the range from 70 to 90% by weight. The proportion of the monomers C is generally in the range from 0 to 20 % By weight, preferably in the range from 0 to 10% by weight and in particular in the range of 0.1 to 8% by weight.

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 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 chlorostyrene. The monomers B preferably comprise at least one monomer B1 having 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 monomers B2 different therefrom, 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 vinyl aromatic 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 generally make up 20 to 99% by weight and preferably 40 to 90% by weight and the monomers B2 0 to 50% by weight and preferably 0 to 30% by weight.

The FP polymers are frequently used in the form of an aqueous dispersion and then contain ionized or ionic monomers C polymerized in to stabilize them. Suitable monomers C can be both 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 , and also cationogenic or cationic in 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 or instead, 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 Polymerized ₂ -C ₄ alkyl (meth) acrylates.

As a further component, component ii can also be a or contain several hydrophobic waxes as extenders, provided the total content of organic fluorine a value of 1% by weight, preferably 2% by weight, not less.

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 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, e.g. B. Montanester waxes, synthetic waxes, e.g. B. polyethylene waxes, and polymers with long-chain alkyl groups (C ₁₀ -C ₃₀ ), for. B. polybehenyl acrylates, polystearyl acrylates and the like. The proportion of wax in component ii is frequently 10 to 90% by weight, and the proportion of organofluorine polymer accordingly is 10 to 90% by weight.

The coatings according to the invention can be designed that the conventional polymer B and component ii evenly are distributed over the coating cross section. Component ii can also be arranged on a first base coating, which in the Essentially from the fine-particle material M and the fluorine-free one polymeric binder B and optionally other conventional auxiliaries is constructed. Under an even distribution also inhomogeneous distributions are understood, in which the different Phases do not form layers. The type of arrangement the coating results in the usual way from the type of Coating process, as 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 0.5 to 1% by weight, without the self-cleaning effect being lost , The proportion of component ii can of course also be above 1% by weight, for example in the range from 1 to 30% by weight and preferably in the range from 1 to 20% by weight. If the coating contains component ii in a 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. Preferred coatings are those in which the amount of component ii used per area 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 , as a rule no more than requirements 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 aforementioned components, the coatings can Contain customary additives, as in conventional coating compositions be used for textiles and the z.T. from the materials used to produce the coatings arise and / or in a known manner according to the application judge. These include colorants and auxiliaries e.g. UV stabilizers, Dispersing agents, surface-active substances, Thickeners, defoamers, agents for adjusting the pH value, Flame retardants, antioxidants and preservatives. The Coatings can contain the aforementioned additives in this usual quantities included, without sacrificing the desired self-cleaning effect comes. As a rule, the Total amount of the usual auxiliaries a value of 10% by weight, preferably 5% by weight, based on the total weight of all the Coating substances, do not exceed.

Examples of colorants are inorganic and organic pigments as well as organic dyes. These are commercially available as powders as well available as a solid or liquid pigment preparation. typical inorganic pigments are titanium dioxide, barium sulfate, zinc oxide, Iron oxides, soot, graphite. Typical organic color pigments such as Sepia, gummy, Kasseler Braun, Touidin red, Pararot, Hansa yellow, Indigo, azo dyes, anthraquinone and indigoid dyes contain. If necessary, pigment mixtures are used. The pigment should be as fine as possible. Preferably they have Pigment particles a particle size ≤ 5 microns. Because the colorants, provided particulate, particle sizes in the for component M specified areas, they will in these cases added to component M. Coloring components that are in solve the polymer matrix (dyes), are the usual tools attributed and can in an amount of up to 20 wt .-%, in the coating.

As a flame retardant for the coating composition according to the invention can contain the halogen or phosphorus known to the expert Compounds, aluminum oxide hydrate, zinc borate, ammonium phosphates, Antimony oxide, magnesium hydroxide and other common ones Compounds or mixtures thereof are used.

Means for adjusting the pH are those which are usually used inorganic or organic, for example ammonia, Alkali metal bases such as potassium and sodium hydroxide, sodium hydrogen carbonate, Sodium carbonate, potassium carbonate, potassium hydrogen carbonate, 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 as well as mixtures thereof.

Suitable surface-active substances are the emulsifiers, polymer surfactants and protective colloids usually used for the preparation of aqueous polymer dispersions. The emulsifiers can be amphoteric, neutral, anionic or cationic in nature. Suitable emulsifiers are known to those skilled in the art, for example, 5 ^th ed from R. Heusch, "Emulsiones" in Ullmann's Encyclopedia of Industrial Chemistry. On CD-Rom, Chapter 7. Examples of nonionic emulsifiers are alkoxylated fats and Oils, e.g. B. corn oil ethoxylates, castor oil ethoxylates, tallow fat 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, alkyl methyl 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, for example 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, e.g. B. in the form of the sodium or ammonium salts. Suitable protective colloids are, for example, cellulose ethers, such as carboxymethyl cellulose, methyl cellulose, hydroxyethyl cellulose, gum arabic, polyvinyl alcohols and polyvinyl pyrrolidone. The proportion of surface-active substances, based on the total weight of the polymer components of the coating, is generally in the range from 0 to 10% by weight, preferably 0.1 to 5% by weight, based on the total weight of the preparation.

Suitable defoamers are, for example, higher alcohols, nonionic Acetylene compounds, aliphatic hydrocarbons with non-ionic components and oligosiloxanes. Usually the amount of defoamer should be about 5 to 20% by weight, e.g. about 10 % By weight of the surfactant fraction or 0.1 to 5% by weight, based on the Make up the total weight of the composition.

In addition to the protective colloids mentioned above, suitable thickeners are also Gum arabic, gelatin, casein, starch, alginates, polyether, Cellulose derivatives such as methyl, carboxymethyl cellulose or hydroxyethyl u. Propyl cellulose, polyacrylic acid salts, such as the sodium salt or the ammonium salt of polyacrylic acid, hydrophobically modified Polyurethanes (associative thickeners) and inorganic thickeners such as silica, and mixtures thereof. The amount of thickener naturally depends on the desired rheology of the coating composition used for coating from and can therefore fluctuate over a wide range. Usually lies it at 0 to 5 wt .-%, based on the total weight of the composition.

The coating may also contain catalysts for post-crosslinking, conventional matting agents such as silica derivatives or conventional water repellents.

The coatings of the invention can according to the Coating of textiles produced using conventional coating processes by making a coating composition which contains the above-mentioned components in a manner known per se on a flat, textile carrier, preferably in the above applied amounts and then the resulting moist coating solidified, e.g. B. by drying them. you can also proceed to the production so that you first a first Coating composition comprising the finely divided material M and Contains binder B in the proportions given above, onto a textile carrier, then the first order dries and then a coating composition on the applies the first coated carrier and dries again. Unless as Binder is a crosslinkable or self-crosslinking binder Component i) is used, the solidification also includes one so-called "condensation step", d. H. a networking phase. The Condensation step or crosslinking is usually done by Heating the coated textile to a temperature above the Crosslinking temperature triggered by i). The crosslinking temperature is usually above 150 ° C and often above 160 ° C. The The condensation step can coincide with the drying step and is preferably done after drying.

The term "flat textile carrier" or "textile fabric" includes both fabrics and knitted fabrics made from yarn as well as non-woven nonwovens made of fibers (nonwovens). As Basically all fiber materials come for the production of Textiles usually used fiber materials into consideration. 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 of the invention are particularly suitable for textile fabrics based on fibers such as cotton, wool, Polyester fibers, polyamide fibers and their mixtures.

• 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:
• i) als Komponente i wenigstens ein fluorfreies polymeres Bindemittel B, in Form einer wässrigen Dispersion und
• 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,
• 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.Aqueous coating compositions are advantageously used to produce the coatings according to the invention. In this way, in contrast to the methods of the prior art, larger amounts of organic solvents can be avoided. The invention therefore also relates to processes for the production 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:

• 50 to 80% by weight, based on the solids content of the composition, of at least one finely divided material, in which 80% by weight of the particles have a diameter in the range from 1 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, in the form of an aqueous dispersion and
• ii) as component ii at least one fluoroorganic polymer FP or a mixture thereof with a hydrophobic wax, the fluorine content of component ii being at least 1% by weight, preferably at least 2% by weight, in the form of an aqueous dispersion,
• iii) optionally auxiliaries 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 from 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 special embodiment of the method according to the invention, one proceeds in such a way that a first aqueous coating composition, which

• 50 to 80% by weight, based on the solids content of the first coating composition, of at least one finely divided material, in which 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 water and optionally up to 10% by weight, based on binder B, of conventional auxiliaries,

contains, applies to a textile carrier, optionally subsequently drying the first application and then a second coating composition thereon, the

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

The aqueous coating compositions are new and also Subject of the present invention. They contain in addition to the above constituents mentioned, of course, also an aqueous dispersion medium. They are produced in a simple manner by mixing of the individual components in the usual mixing devices.

An aqueous dispersion medium is understood here and in Following water and mixtures, the at least 50 vol .-%, preferably at least 80% by volume of water and an organic miscible with water Contain solvents. Suitable solvents ketones, for example acetone or methyl ethyl ketone, miscible with water Ethers, for example tetrahydrofuran, dioxane, 1,2-propanediol-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, glycerin, propylene glycol or polyethylene glycol, as well Mixtures of these. Water is preferably the sole dispersing medium (Water content> 95 vol.%).

The amount of dispersing medium is usually measured so that the resulting aqueous composition has a solids content of 10 to 90 wt .-%, preferably about 20 to 80 wt .-%, very particularly preferably has about 45 to 70 wt .-%.

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

Component ii is usually also used as an aqueous dispersion or aqueous solution with a solids content of 5 to 50 % By weight are used. Provided a two-layer coating if desired, component ii can also be diluted aqueous Use liquor with a solids content of 1 to 10% by weight.

The coating compositions are applied to the processes customary for coating textiles, e.g. by Spraying, rolling, printing, splashing, knife coating, brushing or padding. In particular, the coating compositions can be used as diluted liquor, after adding foaming agents as foam or after Adding thickeners can be applied as a paste. spraying are also possible and allow a very even Application of the compositions according to the invention.

The solids content of the coating composition according to the invention the spraying process is usually in the range from 5 to 25% by weight. Application in the form of a liquor or is preferred Paste, the solids content of the composition then preferably in the range from 15 to 90% by weight, in particular 25 to 80% by weight lies.

The coating composition can be applied as a direct coating, i.e. the textile fabric is directly with the Coated coating composition, or by reverse or Transfer coating is done.

The coating compositions are preferably applied as a paste or fleet in a direct process by knife coating, for example by air, blanket and roller doctor blades. That is also advantageous Rotary screen printing coating, splashing or reverse roll coater processes. With successive application of the first and the second coating composition is applied aqueous, second component containing component ii preferably by padding a dilute aqueous liquor component ii.

If necessary, one can use the aqueous coating compositions Filter to agglomerates before applying to the textile support to remove from the coating composition that the quality would adversely affect the coating.

After the aqueous coating composition of the invention has been applied, the aqueous dispersant is removed. The drying then generally takes place under normal pressure at temperatures above 100 ° C., preferably in the range from about 130 to 200 ° C. The drying process usually takes 30 seconds to 5 minutes. Longer drying times are also possible. If the first and the second coating are applied successively, a drying step can take place after the application of the first coating and before the application of 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 carried out first by drying below the crosslinking temperature of the binder, ie generally the temperatures up to 160 ° C., preferably up to 150 ° C., in order to remove volatile constituents, and then crosslinking the binder (= condensation step) at temperatures above the crosslinking temperature, e.g. B. at temperatures in the range> 150 to 240 ° C, preferably> 160 to 200 ° C, trigger. The drying and condensation steps can also coincide. The drying time and crosslinking time depend in a manner known per se on the type and amount of the application and can be determined and optimized by the person skilled in the art by means of routine experiments. In all cases, drying can take place at a constant temperature (± 10 ° C). However, it is preferably carried out progressively, ie with increasing temperature, for example starting with a temperature T ₁ 100 100 ° C., for. 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 is to be carried out or not.

The textile fabrics coated according to the invention are manufactured by Water is not or only slightly wetted. particulate Soiling such as soot, dust or even toner pigments adhere leave only moderately on the coated side of the fabrics 5 as far as possible with water without the use of detergents or rinse completely. The compositions of the invention are also abrasion resistant, i.e. rub-fast. They also show excellent oleophobic properties. In addition, the coatings are wash-resistant, d. H. they lose the low tendency to soiling and the Self-cleaning effect even after repeated washing (e.g. with a full detergent at 60 ° C) not.

The textile fabrics according to the invention are therefore suitable for Manufacture of textile articles with such properties are desired, e.g. B. of textiles in rain and sports clothing, Protective clothing, for textile tarpaulins, for tents, Umbrellas, awnings, textile wallpapers, tablecloths and the like.

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

I. Input materials

Polyurethane dispersion PU1: commercially available, 30% by weight anionic, crosslinkable aqueous polyester urethane dispersion with a glass transition temperature of -4 ° C: ROTTA Coating BW 95871 ROTTA GmbH in Mannheim.

Polyurethane dispersion PU2: commercial, 50 wt .-%, cationic, crosslinkable, aqueous polyester urethane dispersion with a glass transition temperature of -2 ° C: ROTTA Coating WS 80525 from ROTTA GmbH in Mannheim.

Crosslinker: Commercially available 40% by weight aqueous dispersion of a Isocyanate crosslinker with reversibly blocked isocyanate groups: ROTAL 444 from ROTTA GmbH.

Fluorocarbon resin FP1: 30 wt .-% aqueous dispersion of one Fluoropolymers with copolymerized monomers of the formula A with m = 7 to 8 and n = 2 with a proportion of organic fluorine of about 11% by weight, based on the polymer components: DIPOLIT 481 ROTTA GmbH in Mannheim.

Fluorocarbon resin FP2: 30% by weight 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 % By weight, based on the polymer components: DIPOLIT 470 der ROTTA GmbH in Mannheim.

Quartz flour: fine quartz flour (micro-Dorsilit 110) from Dorfner, with the following grain size distribution: 8% by weight> 10 µm, 23% by weight in the range 6 - 10 µm, 22% by weight in the range 4 - 6 µm, 24% by weight in the range 2 - 4 µm and 23% of the particles is <2 µm. The weight average grain size is 4.4 µm. Composition: 98.5 % By weight quartz, 1% by weight feldspar and 0.5% by weight residual components.

Glass balls: glass balls with a weight average diameter from about 3.5 to 7 µm (specification) wherein 90% by weight of the Glass spheres have a diameter in the range from 0.5 to 19.3 µm have (according to DIN 4188).

Thickener: 1 to 2% by weight aqueous hydroxyethyl cellulose solution.

Preservative: Commercial isothiazoline compound: Mergal K9N, from Riedel de Hähn.

Defoamer: 10% 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 with 33 parts by weight of a 30 wt .-% fluorocarbon resin FP1 and 10 parts by weight of the commercially available crosslinker with stirring Room temperature mixed for 15 minutes. Then you added with stirring, 60 parts by weight of quartz powder was added and left for 30 minutes stirred. After adding 0.5 - 1 part by weight of thickener (aqueous Hydroxyethyl cellulose solution) was made with ammonia / water adjust the pH to 8 to 9. The viscosity of the composition was about 6000 - 7000 mPas. Finally, that was Mixture 0.5 parts by weight of a commercially available preservative and 0.5 - 1 part by weight of commercially available defoamers added. To After stirring for 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 with 50 parts by weight of the 30% by weight fluorocarbon resin FP1 for 15 minutes Mixed room temperature. 60 parts by weight were added with stirring Glass balls and 0.5-1 parts by weight of thickener and prepared with ammonia / water to pH 8 to 9. After a subsequent stirring time of 15 minutes, 0.5 part by weight of preservative and 0.5 - 1 part by weight of defoamer added. The mixture was used until Homogeneity stirred (approx. 15 minutes). The viscosity was Range from 6000 - 7000 mPas.

Composition Z3 (according to the invention):

The composition Z3 consists of a Coating composition 1 and a liquor for Fluorocarbon resin finish as a coating composition 2.

60 parts by weight of quartz powder with 60 parts by weight of polyurethane dispersion PU2 with stirring at room temperature for 15 min. mixed. After adding 0.5-1 part by weight of thickener the pH is adjusted to 8 to 9 with ammonia / water. The The viscosity of the mixture was approximately 6000-7000 mPas. Finally, 0.5 parts by weight of preservative was added to the mixture and 0.5-1 parts by weight of commercially available defoamers added. After a stirring time of 15 minutes it was Mixture homogeneous.

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

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 of quartz powder with 60 parts by weight of polyurethane dispersion PU2 with stirring at room temperature for 15 min. mixed. After adding 0.5-1 part by weight of thickener the pH is adjusted to 8 to 9 with ammonia / water. The The viscosity of the mixture was approximately 6000-7000 mPas. Finally the mixture became 0.5 parts by weight Preservative and 0.5 - 1 parts by weight commercially available Defoamer added. After stirring for 15 minutes the mixture was homogeneous.

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

Composition ZV1 (comparison):

A coating composition was prepared analogously to composition Z2 forth, but one on the addition of the 30% by weight fluorocarbon resin FP1 (DIPOLIT 481) and instead, a mixture of 60 parts by weight of quartz powder and 60 parts by weight of the polyurethane dispersion PU2 used.

Composition ZV2 (comparison):

Analogous to composition Z2, a Coating composition forth, but with the The addition of the polyurethane dispersion was dispensed with and instead 60 parts by weight of glass balls with 100 parts by weight of the 30 wt .-% aqueous dispersion of the fluorocarbon resin FP1 mixed.

Composition ZV3 (comparison):

The comparison composition ZV3 is the 30% by weight aqueous dispersion of the fluorocarbon resin FP1 without other additives.

III. Application examples: Example 1:

After checking the viscosity to be maintained of 6000-7000 mPas, the coating composition Z1 was applied to a cotton-Hämmerle product with a basis weight of 122 g / m ² as a one-coat coating with an air knife. The application was carried out in an amount such that a dry coating resulted in a print run of approximately 100 g / m ² . After the coating composition had been applied, the mixture was dried at 150 ° C. for 2 minutes.

Example 2:

In a manner analogous to Example 1, the composition Z2 was applied from cotton hammers with a basis weight of 122 g / m ² . This resulted in a print run of approximately 101 g / m ² .

Example 3:

First of all, the first coating composition of composition Z3 was applied analogously to Example 1 on cotton piles with a basis weight of 122 g / m ² . The resulting overlay in the first layer was approximately 100 g / m ² . The diluted fluorocarbon resin liquor was then padded and dried at 160 ° C. for 2 minutes. The coating of the fluorocarbon resin layer was approximately 1.2 g / m ² with a liquor absorption of 100%.

Example 4:

Analogously to Example 3, the first coating composition of Z3 was applied to cotton piles with a basis weight of 122 g / m ² . The resulting edition was 100 g / m ² . However, the fluorocarbon resin liquor was padded as an undiluted, 30% by weight dispersion and dried at 160 ° C. for 2 minutes. The coating of the fluorocarbon resin layer was approximately 30 g / m ² with a liquor absorption of 100%.

Example 5:

The coating composition of Z4 was applied in a manner analogous to Example 3 on cotton piles with a basis weight of 122 g / m ² . The resulting overlay in the first layer was approximately 100 g / m ² . The coating of fluorocarbon resin / extender layer resulted in a liquor absorption of 100% at approx. 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 Z3 analogously to Example 3. The resulting application was 43 g / m ² . The diluted fluorocarbon resin liquor was then padded in. The coating of the fluorocarbon resin layer was approximately 1.2 g / m ² .

Comparative Example 1:

In a manner analogous to Example 1, the composition ZV1 was applied to cotton piles with a basis weight of 122 g / m ² . This resulted in a print run of approx. 100 g / m ² .

Comparative Example 2:

In a manner analogous to Example 1, the composition ZV2 was applied to cotton hammock fabric with a weight per unit area of 122 g / m ² . This resulted in a print run of approx. 100 g / m ² .

Comparative Example 3:

The composition of the equipment ZV3 was padded onto cotton-haemele goods with a basis weight of 122 g / m ² . With a liquor absorption of 100%, a fluorocarbon resin coating of about 24 g / m ² resulted.

IV. Application test: 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 soiling test) :

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

Abrasion resistance:

Exam:

Scrub test (1000 tours, 1 kg load)

Device:

FLEXOMETRE TYPE SCRUBB, DIN NFG37110 or SNV 18498

rub fastness

Exam:

DIN 54021 (crock meter, grades 1 to 5 = best)

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

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

The fabric coated according to Example 6 was made with commercially available Soiled graphite oil by putting graphite oil on the coated Side of the fabric, then the soiled side for 4 hours loaded with 1 kg and allowed the dirt to act for a further 16 h. For comparison purposes, the uncoated but with fluorocarbon resin treated tissues soiled in the same way.

Then both samples were washed in a household wash (Miele WFK 2801; normal program 60 ° C) with a full detergent (Burti, 280 ml for normally soiled laundry). The sample according to the invention was able to be cleaned completely, while the uncoated comparison sample had severe dirt 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. Further washing in the manner described above led to a complete cleaning of the sample without any dirt residues being visible.

Claims (14)

Textile fabric comprising a flat textile support and at least one coating applied to the support, which is composed of: 50 to 80% by weight, based on the total weight of the coating, of at least one finely divided material M, in which 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 fluoroorganic polymer FP or a mixture thereof with a hydrophobic wax, the fluorine content of component ii being at least 1% by weight, iii) optionally auxiliaries in an amount of up to 10% 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. Textile fabric according to claim 1, wherein the coating has a thickness of at least 10 g / m ² . Textile fabric according to claim 1 or 2, wherein the coating contains component ii in a coating of at least 0.2 g / m ² . Textile fabric according to one of the preceding claims, wherein the coating contains the finely divided material M in an amount of at least 10 g / m ² . Textile fabric according to claim 1 or 2, wherein the Coating component i in an amount of at least 15 % By weight, based on the total weight of the coating. Textile fabric according to one of the preceding claims, wherein the fluorine-free polymeric binder B a Glass transition temperature in the range of -40 to + 100 ° C. Textile fabric according to one of the preceding claims, wherein the fluorine-free polymeric binder B is a polyurethane resin is. Textile fabric according to one of the preceding claims, wherein the fluoroorganic polymer FP as an organofluorine component contains fluorohydrocarbon groups of the formula I: F ₃ C (CF ₂ ) _m (CH ₂ ) _n - wherein m is 2 to 10 and n is 0 to 5. Textile fabric according to one of the preceding claims, wherein the coating is a first layer that consists essentially of the fine-particle material M and the fluorine-free polymer Binder B is built, and at least one on the first Layer arranged second layer, which consists essentially of the Component ii is built includes. Textile fabric according to claim 9, wherein the second layer has a coverage of at least 0.2 g / m ² . Method for producing a textile fabric according to one of claims 1 to 10, comprising applying at least one aqueous coating composition to a textile carrier and then drying the application, 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, in which 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, in the form of an aqueous dispersion and ii) as component ii at least one fluoroorganic polymer FP or a mixture thereof with a hydrophobic wax, the fluorine content of component ii being at least 1% by weight, in the form of an aqueous dispersion, iii) optionally auxiliaries 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 from 1: 2 to 100: 1. Method for producing a textile fabric according to claim 9 or 10, by successively applying a first aqueous coating composition to a textile carrier, optionally subsequently drying the first application and applying a second coating composition and then drying again, characterized in that the first coating composition contains: 50 to 80% by weight, based on the solids content of the first coating composition, of at least one finely divided material, in which 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 conventional auxiliaries in an amount of up to 10% by weight, based on the binder B, and the second coating composition contains 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 is at least 1% by weight, based on the total amount of fluoroorganic polymer FP and optionally the wax,
wherein the first and second coating compositions are applied in an amount ratio such that the weight ratio of binder B to the total amount of fluoroorganic polymer FP and optionally the wax is in the range from 1: 2 to 100: 1. Coating composition containing: 50 to 80% by weight, based on the total weight of the coating, of at least one finely divided material, in which 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 components, 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 fluoroorganic polymer FP or a mixture thereof with a hydrophobic wax,
wherein the fluorine content of component ii is at least 1% by weight, in the form of an aqueous dispersion, iii) and water and optionally up to 10% by weight, based on binder B, of conventional auxiliaries, wherein the weight ratio of binder B to component ii is in the range from 1: 2 to 100: 1. A coating composition in the form of a two-component composition comprising: a) a first aqueous coating composition, the 50 to 80% by weight, based on the solids content of the first coating composition, of at least one finely divided material, in which 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 binder B, conventional auxiliaries and b) a second aqueous coating composition which contains at least one fluoroorganic polymer FP or a mixture thereof with a hydrophobic wax in the form of an aqueous dispersion, the fluorine content at least 1% by weight, based on the total amount of organofluorine polymer FP and optionally the wax , the ratio of the first and second coating compositions ensuring a weight ratio of binder B to the total amount of organofluorine polymer FP and optionally the wax, in the range from 1: 2 to 100: 1.