EP1283296B1 - Structure textile plane avec une faible tendance à l'encrassement - Google Patents

Structure textile plane avec une faible tendance à l'encrassement Download PDF

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Publication number
EP1283296B1
EP1283296B1 EP02017662A EP02017662A EP1283296B1 EP 1283296 B1 EP1283296 B1 EP 1283296B1 EP 02017662 A EP02017662 A EP 02017662A EP 02017662 A EP02017662 A EP 02017662A EP 1283296 B1 EP1283296 B1 EP 1283296B1
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Prior art keywords
weight
coating
component
range
fluorine
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EP02017662A
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German (de)
English (en)
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EP1283296A1 (fr
Inventor
Wolfgang Ritter
Jürgen Delhey
Inge Knerr
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Dystar Textilfarben GmbH and Co Deutschland KG
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Dystar Textilfarben GmbH and Co Deutschland KG
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Classifications

    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
    • D06N3/12—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins
    • D06N3/14—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins with polyurethanes
    • D06N3/142—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins with polyurethanes mixture of polyurethanes with other resins in the same layer
    • D06N3/144—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins with polyurethanes mixture of polyurethanes with other resins in the same layer with polyurethane and polymerisation products, e.g. acrylics, PVC
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B08—CLEANING
    • B08B—CLEANING IN GENERAL; PREVENTION OF FOULING IN GENERAL
    • B08B17/00—Methods preventing fouling
    • B08B17/02—Preventing deposition of fouling or of dust
    • B08B17/06—Preventing deposition of fouling or of dust by giving articles subject to fouling a special shape or arrangement
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B08—CLEANING
    • B08B—CLEANING IN GENERAL; PREVENTION OF FOULING IN GENERAL
    • B08B17/00—Methods preventing fouling
    • B08B17/02—Preventing deposition of fouling or of dust
    • B08B17/06—Preventing deposition of fouling or of dust by giving articles subject to fouling a special shape or arrangement
    • B08B17/065—Preventing deposition of fouling or of dust by giving articles subject to fouling a special shape or arrangement the surface having a microscopic surface pattern to achieve the same effect as a lotus flower
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
    • D06M11/77—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with silicon or compounds thereof
    • D06M11/79—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with silicon or compounds thereof with silicon dioxide, silicic acids or their salts
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/244—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of halogenated hydrocarbons
    • D06M15/256—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of halogenated hydrocarbons containing fluorine
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/263—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters thereof
    • D06M15/277—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters thereof containing fluorine
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/564—Polyureas, polyurethanes or other polymers having ureide or urethane links; Precondensation products forming them
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M23/00—Treatment of fibres, threads, yarns, fabrics or fibrous goods made from such materials, characterised by the process
    • D06M23/08—Processes in which the treating agent is applied in powder or granular form
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
    • D06N3/0056—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the compounding ingredients of the macro-molecular coating
    • D06N3/0063—Inorganic compounding ingredients, e.g. metals, carbon fibres, Na2CO3, metal layers; Post-treatment with inorganic compounds
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
    • D06N3/04—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D06N3/047—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds with fluoropolymers
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
    • D06N3/18—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with two layers of different macromolecular materials
    • D06N3/183—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with two layers of different macromolecular materials the layers are one next to the other

Definitions

  • 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.
  • textiles 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.
  • 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.
  • such textiles are often provided with a soil release finish or oleophobic finish.
  • fluoroorganic compounds or fluoroorganic polymers fluorocarbon waxes
  • 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.
  • 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.
  • the surface is prepared either by imprinting a structure or by applying hydrophobic particles, such as wax particles, to a hydrophobic surface.
  • a surface which consists of wax-coated glass powder with a grain size of 3 to 12 microns.
  • 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 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.
  • the coatings should be resistant to washing and cleaning.
  • 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 ⁇ m, 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.
  • the particles 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 ⁇ m and in particular in the range from 1 to 20 ⁇ m.
  • the average particle diameter (weight average, determined by the sieve curve) is generally below 50 ⁇ m, preferably in the range from 1 to 20 ⁇ m, in particular in the range from 1 to 10 ⁇ m and particularly preferably in the range from 2 to 8 ⁇ m.
  • 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.
  • 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.
  • 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 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.
  • polymeric binder 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.
  • 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 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.
  • binders B which are self-crosslinking.
  • 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.
  • 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.
  • carboxyl groups which react, for example, with hydroxyl, amino, epoxy or azir
  • 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.
  • 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; Dia
  • 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.
  • 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.
  • 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
  • (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.
  • 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.
  • 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).
  • 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.
  • 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.
  • aromatic diisocyanates such as 2,4- and 2,6-toluene diisocyanate (TDI) and isomer mixtures thereof
  • TMXDI tetramethylx
  • diisocyanates are aliphatic or cycloaliphatic in nature.
  • Preferred diisocyanates include hexamethylene diisocyanate (HMDI) and isophorone diisocyanate.
  • 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).
  • polystyrene resin 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 .-%.
  • 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.
  • 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.
  • a starter molecule z.
  • low molecular weight di- or polyols for example, the aforementioned glycols, oligomeric alcohols, polyetherols and polyesterols into consideration.
  • 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.
  • Suitable polyesterols can be z.
  • Suitable carboxylic acids are, for.
  • 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.
  • 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 ⁇ , ⁇ -dimethyl- ⁇ -propiolactone, ⁇ -butyrolactone and ⁇ -caprolactone.
  • Suitable hydroxycarboxylic acids are ⁇ -hydroxycarboxylic acids such as glycolic acid, lactic acid, hydroxybutyric acid, mandelic acid, which may also be in the form of their lactides or ⁇ -hydroxycarboxylic acids, ⁇ -hydroxycarboxylic acids, ⁇ -hydroxycarboxylic acids or ⁇ -hydroxycarboxylic acids such as ⁇ -valeric acid.
  • aliphatic polyester polyols 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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
  • 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.
  • 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.
  • 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.
  • 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 .-%.
  • R is vinyl, allyl, methallyl and 1-propen-2-yl.
  • XR is acryloxy or methacryloxy.
  • the fluoroorganic polymer may contain one or more, including various ethylenically unsaturated comonomers in copolymerized form.
  • 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, ⁇ -methylstyrene and chlorostyrenes.
  • 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 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.
  • 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
  • different monomers B2 for example one or more C 1 -C 5 -alky
  • 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 -alkyla
  • 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.
  • carboxylic acids such as (meth) acrylamide and N-methylol (meth) acrylamide
  • 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.
  • 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.
  • 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.
  • 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 ,
  • 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 .-%.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • pigment mixtures are used.
  • the pigment should be as finely divided as possible.
  • the pigment particles have a particle size ⁇ 5 microns.
  • 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 are added to the customary auxiliaries and can be present in the coating in an amount of up to 20% by weight.
  • 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.
  • 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, Tri
  • 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.
  • fatty alcohol ethoxylates are used.
  • 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.
  • 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 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.
  • 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.
  • the coating additionally contains catalysts for the post-crosslinking, customary matting agents such as silica derivatives or customary water repellents.
  • 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.
  • the solidification also includes a so-called "condensation step", ie a crosslinking phase.
  • 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.
  • flat textile carriers or "textile fabrics” encompasses both woven and knitted fabrics produced from yarns and nonwoven nonwoven fabrics.
  • fiber materials 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.
  • 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.
  • 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 .-%.
  • 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.
  • 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 .-%.
  • 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.
  • 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.
  • the aqueous composition containing component ii is applied preferably by padding a dilute aqueous liquor of component ii.
  • 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.
  • 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.
  • 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 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.
  • 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.
  • protective clothing for textile tarpaulins, for tents, umbrellas, awnings, textile wallpaper, tablecloths and the like.
  • compositions II. Compositions:
  • Composition Z1 (according to the invention):
  • aqueous polyurethane dispersion PU1 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.
  • thickener aqueous hydroxyethyl cellulose solution
  • Composition Z2 (according to the invention):
  • 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.
  • 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.
  • 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.
  • fluorocarbon resin FP1 DIPOLIT 481
  • composition ZV2 (comparison):
  • composition Z2 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.
  • 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.
  • 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 .
  • 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 .
  • 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 .
  • 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 .
  • 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 .
  • 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 .
  • 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 .
  • 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 .
  • 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 .
  • composition of the ZV3 equipment was padded on cotton hemp ware at a basis weight of 122 g / m 2 .
  • a liquor pick-up of 100% resulted in a circulation of fluorocarbon resin of about 24 g / m 2 .
  • 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.
  • the uncoated but fluorocarbon resin treated fabric was similarly soiled.
  • 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%

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Claims (14)

  1. Structure textile plane comprenant un support textile plat et au moins un revêtement ajouté au support, composé de :
    - 50 à 80% en poids, sur base du poids total du revêtement, d'au moins une matière finement dispersée M, dans laquelle 80% en poids des particules présentent un diamètre compris dans la plage de 0,5 à 100 µm, et
    - 20 à 50% en poids, sur base du poids total du revêtement, d'une matrice, comprenant :
    i) comme composant i au moins un liant polymère B classique sans fluor,
    ii) comme composant ii au moins un polymère FP organofluoré ou un mélange de celui-ci avec une cire hydrophobe, la teneur en fluor du composant ii étant d'au moins 1% en poids,
    iii)le cas échéant des adjuvants dans une quantité de 10% en poids maximum, sur base de la matrice,
    le rapport pondéral du composant i au composant ii se situant entre 1:2 et 100:1.
  2. Structure textile plane selon la revendication 1, dans laquelle le revêtement présente une épaisseur d'au moins 10 g/m2.
  3. Structure textile plane selon la revendication 1 ou 2, dans laquelle le revêtement contient le composant ii dans une couche d'au moins 0,2 g/m2.
  4. Structure textile plane selon l'une des revendications précédentes, dans laquelle le revêtement contient la matière finement dispersée M dans une quantité d'au moins 10 g/m2.
  5. Structure textile plane selon la revendication 1 ou 2, dans laquelle le revêtement contient le composant i dans une quantité d'au moins 15% en poids, sur base du poids total du revêtement.
  6. Structure textile plane selon l'une des revendications précédentes, dans laquelle le liant polymère B sans fluor présente une température de transition vitreuse comprise entre -40 et +100°C.
  7. Structure textile plane selon l'une des revendications précédentes, dans laquelle le liant polymère B sans fluor est une résine de polyuréthanne.
  8. Structure textile plane selon l'une des revendications précédentes, dans laquelle le polymère FP organofluoré présente comme constituant organofluoré des groupes fluorohydrocarbonés de formule I

            F3C(CF2)m(CH2)n-     (I)

    dans laquelle m vaut 2 à 10 et n vaut de 0 à 5.
  9. Structure textile plane selon l'une des revendications précédentes, dans laquelle le revêtement comporte une première couche constituée de la matière M finement dispersée et du liant polymère B sans fluor et au moins une deuxième couche agencée sur la première couche constituée du composant ii.
  10. Structure textile plane selon la revendication 9, dans laquelle la deuxième couche présente une couche-support d'au moins 0,2 g/m2.
  11. Procédé de fabrication d'une structure textile plane selon l'une des revendications 1 à 10, comportant l'application d'au moins une composition aqueuse de revêtement sur un support textile et le séchage consécutif de l'enduit, caractérisé en ce que la composition aqueuse de revêtement contient :
    - de 50 à 80% en poids, sur base de la teneur en solides de la composition, d'au moins une matière finement dispersée, dans laquelle 80% en poids des particules présentent un diamètre compris dans la plage de 0,5 à 100 µm, et
    - de 20 à 50% en poids, sur base de la teneur en solides de la composition, de constituants de matrice, comprenant :
    i) comme composant i au moins un liant polymère B sans fluor, sous forme d'une dispersion aqueuse et
    ii) comme composant ii au moins un polymère FP organofluoré ou un mélange de celui-ci avec une cire hydrophobe, la teneur en fluor du composant ii étant d'au moins 1% en poids, sous forme d'une dispersion aqueuse,
    iii)le cas échéant des adjuvants dans une quantité de 10% en poids maximum, sur base de la matrice,
    le rapport pondéral du liant B au composant ii étant situé entre 1:2 et 100:1.
  12. Procédé de fabrication d'une structure textile plane selon la revendication 9 ou 10, par application successive d'une première composition de revêtement aqueuse sur un support textile, séchage consécutif éventuel du premier enduit et application d'une deuxième composition de revêtement et nouveau séchage consécutif, caractérisé en ce que la première composition de revêtement contient :
    - de 50 à 80% en poids, sur base de la teneur en solides de la première composition de revêtement, d'au moins une matière finement dispersée, dans laquelle 80% en poids des particules présentent un diamètre compris dans la plage de 0,5 à 100 µm, et
    - de 20 à 50% en poids, sur base de la teneur en solides de la composition, d'au moins un liant polymère B sans fluor, sous forme d'une dispersion aqueuse, ainsi que de l'eau et le cas échéant des adjuvants habituels, dans une quantité de 10% en poids maximum, sur base du liant B,
    et la deuxième composition de revêtement contient au moins un polymère FP organofluoré ou un mélange de celui-ci avec une cire hydrophobe (composant ii) sous forme d'une dispersion aqueuse, la teneur en fluor étant d'au moins 1% en poids, sur base de la quantité totale de polymère FP organofluoré, et le cas échéant de la cire,
    la première et la deuxième composition de revêtement étant appliquées dans un rapport quantitatif de telle sorte que le rapport pondéral du liant B à la quantité totale de polymère FP organofluoré et éventuellement de cire soit situé dans la plage de 1:2 à 100:1.
  13. Composition de revêtement contenant :
    - de 50 à 80% en poids, sur base du poids total du revêtement, d'au moins une matière finement dispersée, dans laquelle 80% en poids des particules présentent un diamètre compris dans la plage de 0,5 à 100 µm, et
    - de 20 à 50% en poids, sur base du poids total du revêtement, de constituants polymères, comprenant :
    i) comme composant i au moins un liant polymère B sans fluor, sous forme d'une dispersion aqueuse et
    ii) comme composant ii au moins un polymère FP organofluoré ou un mélange de celui-ci avec une cire hydrophobe, la teneur en fluor du composant ii étant d'au moins 1% en poids, sous forme d'une dispersion aqueuse,
    iii)ainsi que de l'eau et éventuellement jusqu'à 10% en poids, sur base du liant B, d'adjuvants habituels,
    le rapport pondéral du liant B au composant ii étant situé entre 1:2 et 100:1.
  14. Composition de revêtement sous forme d'une composition à 2 composants, comportant :
    a) une première composition de revêtement aqueuse qui contient :
    - 50 à 80% en poids, sur base de la teneur en solides de la première composition de revêtement, d'au moins une matière finement dispersée, dans laquelle 80% en poids des particules présentent un diamètre compris dans la plage de 0,5 à 100 µm, et
    - 20 à 50% en poids, sur base de la teneur en solides de la composition, d'au moins un liant polymère B sans fluor, sous forme d'une dispersion aqueuse, ainsi que de l'eau et le cas échéant jusqu'à 10% en poids, sur base du liant B, d'adjuvants habituels, et
    b) une deuxième composition aqueuse de revêtement qui contient au moins un polymère FP organofluoré ou un mélange de celui-ci avec une cire hydrophobe sous forme d'une dispersion aqueuse, la teneur en fluor étant d'au moins 1% en poids, sur base de la quantité totale de polymère FP organofluoré et éventuellement de cire, le rapport quantitatif de la première composition de revêtement à la deuxième composition de revêtement garantissant un rapport pondéral du liant B à la quantité totale de polymère FP organofluoré et éventuellement de cire, dans la plage de 1:2 à 100:1.
EP02017662A 2001-08-08 2002-08-06 Structure textile plane avec une faible tendance à l'encrassement Expired - Lifetime EP1283296B1 (fr)

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EP01119123 2001-08-08
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US7727289B2 (en) 2005-06-07 2010-06-01 S.C. Johnson & Son, Inc. Composition for application to a surface
US7763083B2 (en) 2005-06-07 2010-07-27 S.C. Johnson & Son, Inc. Composition for application to a surface
US7776108B2 (en) 2005-06-07 2010-08-17 S.C. Johnson & Son, Inc. Composition for application to a surface
US7829146B2 (en) 2005-06-07 2010-11-09 S.C. Johnson & Son, Inc. Method of neutralizing a stain on a surface
US7906172B2 (en) 2005-09-16 2011-03-15 Basf Aktiengesellschaft Method for coating surfaces and suitable particles therefor
US8061269B2 (en) 2008-05-14 2011-11-22 S.C. Johnson & Son, Inc. Multilayer stencils for applying a design to a surface
US8557758B2 (en) 2005-06-07 2013-10-15 S.C. Johnson & Son, Inc. Devices for applying a colorant to a surface
US20210087350A1 (en) * 2019-09-23 2021-03-25 Eastman Kodak Company Light-blocking articles from foamed composition containing solid polymeric particles

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US20070197111A1 (en) * 2004-05-19 2007-08-23 Basf Aktiengesellschaft Method for finishing absorbent materials
DE102004038218A1 (de) * 2004-08-05 2006-03-16 Basf Ag Verfahren zur Ausrüstung von saugfähigen Materialien
DE102004062739A1 (de) * 2004-12-27 2006-07-06 Degussa Ag Selbstreinigende Oberflächen mit durch hydrophobe Partikel gebildeten Erhebungen, mit verbesserter mechanischer Festigkeit
US8846154B2 (en) 2005-06-07 2014-09-30 S.C. Johnson & Son, Inc. Carpet décor and setting solution compositions
DE102009029153A1 (de) * 2009-09-03 2011-03-17 Evonik Degussa Gmbh Waschpermanente Wandbeläge
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US8795780B2 (en) * 2011-08-04 2014-08-05 Soon Kie JUNG Textile fabric sheet having stain and liquid resistance and the preparation method thereof
US11851583B2 (en) 2016-07-19 2023-12-26 Evonik Operations Gmbh Process for producing porous polyurethane coatings using polyol ester additives

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US7727289B2 (en) 2005-06-07 2010-06-01 S.C. Johnson & Son, Inc. Composition for application to a surface
US7763083B2 (en) 2005-06-07 2010-07-27 S.C. Johnson & Son, Inc. Composition for application to a surface
US7776108B2 (en) 2005-06-07 2010-08-17 S.C. Johnson & Son, Inc. Composition for application to a surface
US7829146B2 (en) 2005-06-07 2010-11-09 S.C. Johnson & Son, Inc. Method of neutralizing a stain on a surface
US8048517B2 (en) 2005-06-07 2011-11-01 S.C. Johnson & Son, Inc. Composition for application to a surface
US8557758B2 (en) 2005-06-07 2013-10-15 S.C. Johnson & Son, Inc. Devices for applying a colorant to a surface
US8734533B2 (en) 2005-06-07 2014-05-27 S.C. Johnson & Son, Inc. Composition for application to a surface
US7906172B2 (en) 2005-09-16 2011-03-15 Basf Aktiengesellschaft Method for coating surfaces and suitable particles therefor
US8061269B2 (en) 2008-05-14 2011-11-22 S.C. Johnson & Son, Inc. Multilayer stencils for applying a design to a surface
US20210087350A1 (en) * 2019-09-23 2021-03-25 Eastman Kodak Company Light-blocking articles from foamed composition containing solid polymeric particles
US11932744B2 (en) * 2019-09-23 2024-03-19 Eastman Kodak Company Light-blocking articles from foamed composition containing solid polymeric particles

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