EP1379725B1 - Flat textile structures with self-cleaning and water-repellent surfaces - Google Patents

Flat textile structures with self-cleaning and water-repellent surfaces Download PDF

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Publication number
EP1379725B1
EP1379725B1 EP02704724A EP02704724A EP1379725B1 EP 1379725 B1 EP1379725 B1 EP 1379725B1 EP 02704724 A EP02704724 A EP 02704724A EP 02704724 A EP02704724 A EP 02704724A EP 1379725 B1 EP1379725 B1 EP 1379725B1
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EP
European Patent Office
Prior art keywords
particles
base material
textile fabric
fabric according
textile
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Expired - Lifetime
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EP02704724A
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German (de)
French (fr)
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EP1379725A1 (en
Inventor
Markus Oles
Edwin Nun
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Evonik Operations GmbH
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Degussa GmbH
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    • 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
    • D06M23/10—Processes in which the treating agent is dissolved or dispersed in organic solvents; Processes for the recovery of organic solvents thereof
    • 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
    • D06M11/32—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 oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond
    • D06M11/36—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 oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond with oxides, hydroxides or mixed oxides; with salts derived from anions with an amphoteric element-oxygen bond
    • D06M11/45—Oxides or hydroxides of elements of Groups 3 or 13 of the Periodic Table; Aluminates
    • 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
    • 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
    • D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
    • D06M2200/10—Repellency against liquids
    • D06M2200/12—Hydrophobic properties
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T442/00—Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
    • Y10T442/20—Coated or impregnated woven, knit, or nonwoven fabric which is not [a] associated with another preformed layer or fiber layer or, [b] with respect to woven and knit, characterized, respectively, by a particular or differential weave or knit, wherein the coating or impregnation is neither a foamed material nor a free metal or alloy layer
    • Y10T442/2164—Coating or impregnation specified as water repellent
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T442/00—Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
    • Y10T442/20—Coated or impregnated woven, knit, or nonwoven fabric which is not [a] associated with another preformed layer or fiber layer or, [b] with respect to woven and knit, characterized, respectively, by a particular or differential weave or knit, wherein the coating or impregnation is neither a foamed material nor a free metal or alloy layer
    • Y10T442/2213—Coating or impregnation is specified as weather proof, water vapor resistant, or moisture resistant
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T442/00—Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
    • Y10T442/20—Coated or impregnated woven, knit, or nonwoven fabric which is not [a] associated with another preformed layer or fiber layer or, [b] with respect to woven and knit, characterized, respectively, by a particular or differential weave or knit, wherein the coating or impregnation is neither a foamed material nor a free metal or alloy layer
    • Y10T442/2279—Coating or impregnation improves soil repellency, soil release, or anti- soil redeposition qualities of fabric
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T442/00—Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
    • Y10T442/20—Coated or impregnated woven, knit, or nonwoven fabric which is not [a] associated with another preformed layer or fiber layer or, [b] with respect to woven and knit, characterized, respectively, by a particular or differential weave or knit, wherein the coating or impregnation is neither a foamed material nor a free metal or alloy layer
    • Y10T442/2762—Coated or impregnated natural fiber fabric [e.g., cotton, wool, silk, linen, etc.]
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T442/00—Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
    • Y10T442/20—Coated or impregnated woven, knit, or nonwoven fabric which is not [a] associated with another preformed layer or fiber layer or, [b] with respect to woven and knit, characterized, respectively, by a particular or differential weave or knit, wherein the coating or impregnation is neither a foamed material nor a free metal or alloy layer
    • Y10T442/2861—Coated or impregnated synthetic organic fiber fabric
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T442/00—Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
    • Y10T442/20—Coated or impregnated woven, knit, or nonwoven fabric which is not [a] associated with another preformed layer or fiber layer or, [b] with respect to woven and knit, characterized, respectively, by a particular or differential weave or knit, wherein the coating or impregnation is neither a foamed material nor a free metal or alloy layer
    • Y10T442/2926—Coated or impregnated inorganic fiber fabric

Definitions

  • the present invention relates to textile fabrics with self-cleaning and water-repellent surface.
  • Prior art is according to EP 0 933 388, that for such self-cleaning surfaces, an aspect ratio of> 1 and a surface energy of less than 20 mN / m is required.
  • the aspect ratio is defined as the quotient of height to width of the structure.
  • the aforementioned criteria are realized in nature, for example in the lotus leaf.
  • the surface of the plant formed from a hydrophobic waxy material has elevations which are a few microns apart. Water droplets are essentially only in contact with these tips. Such water-repellent surfaces are widely described in the literature.
  • CH-PS-268 258 describes a process in which structured surfaces are produced by applying powders such as kaolin, talc, clay or silica gel.
  • the powders are fixed on the surface by oils and resins based on organosilicon compounds (Examples 1 to 6).
  • EP 0 909 747 teaches a method for producing a self-cleaning surface.
  • the surface has hydrophobic elevations with a height of 5 to 200 microns.
  • Such a surface is prepared by applying a dispersion of powder particles and an inert material in a siloxane solution and then curing. The structure-forming particles are thus fixed by an auxiliary medium on the substrate.
  • WO 00/58410 comes to the conclusion that it is technically possible to surfaces of Artificially self-cleaning objects.
  • the surface structures of elevations and depressions required for this purpose have a spacing between the elevations of the surface structures in the range from 0.1 to 200 ⁇ m and a height of the elevation in the range from 0.1 to 100 ⁇ m.
  • the materials used for this purpose must consist of hydrophobic polymers or permanently hydrophobized material. Dissolution of the particles from the carrier matrix must be prevented.
  • hydrophobic materials such as perfluorinated polymers
  • hydrophobic surfaces are known.
  • a further development of these surfaces is to structure the surfaces in the ⁇ m range to the nm range.
  • US Pat. No. 5,599,489 discloses a method in which a surface can be provided in a particularly repellent manner by bombardment with particles of a corresponding size and subsequent perfluorination.
  • Another method is described by H. Saito et al. in "Service Coatings International", 4, 1997, p.168 ff.
  • particles of fluoropolymers are applied to metal surfaces, wherein a greatly reduced wettability of the surfaces thus produced to water was shown with a significantly reduced tendency to icing.
  • WO 00/58410 describes the structures and claims the formation thereof by spraying hydrophobic alcohols such as nonacosan-10-ol or alkanediols such as nonacosan-5,10-diol.
  • hydrophobic alcohols such as nonacosan-10-ol or alkanediols such as nonacosan-5,10-diol.
  • a disadvantage of this is the poor stability of the self-cleaning surfaces, since detergents lead to the dissolution of the structure.
  • the object of the present invention was to find textile fabrics which have very good water-repellent and self-cleaning surfaces, these properties having to be maintained in daily use of the articles produced from these textile fabrics and the textile fabrics being formed by a process which does not involve a great deal of technical complexity Effort is to be performed, can be produced.
  • the attachment of particles by adhesive and the like should be eliminated in view of the properties of the fabrics in use.
  • Another object of the invention is the use of these textile fabrics with self-cleaning and water-repellent surface for the production of textile articles.
  • the textile base material A may be formed by a variety of common polymers, such as.
  • base material are natural materials from plant parts selected from cotton, kapok, flax, hemp, jute, sisal and coconut, from hair dressings of animals, silk or mineral origin. Blended fabrics of natural and artificial materials are also suitable.
  • the base material A to be used according to the invention is explained in more detail below by way of example.
  • the production of textile finished product is usually made of polymer threads that were produced by spinning.
  • Garn u Piece goods are subjected in the course of their processing various mechanical and chemical processing processes, eg. B. combing, weighting, impregnation, Krumpfok- u. Crease resistant equipment, mercerization, dyeing and printing, metallization, texturing, etc., which are intended to improve od. Modification of the natural properties of the fibers with a view to later use. Criteria according to which the utility value of a finished textile product is assessed by suitable textile testing methods are u. a .: resistance to tensile and bursting forces as well as to abrasion, wrinkle recovery in dry and wet condition and associated with the wash-and-wear behavior, resistance z.
  • Polymer fabric / textiles ie the base material A in the sense of the invention, can be produced from different fibers.
  • thermoplastic fibers such as PET, PA66, PE or PP
  • Fibers are usually traded under protected brand names, examples being Perlon®, Diolen®, Trevira®, Orleon®, but also trivial names such as acrylic fibers, polyester fibers, olefin fibers, aramid fibers, etc. are common.
  • the particles used are those which comprise at least one material selected from Have silicates, minerals, metal oxides, metal powders, silicas, pigments or polymers.
  • particles are used which have a particle diameter of 0.02 to 100 microns, more preferably from 0.1 to 50 microns and most preferably from 0.1 to 30 microns.
  • particles which are composed of primary particles to form agglomerates or aggregates of a size of 0.2-100 ⁇ m are also suitable.
  • the particles are bonded to the surface of the polymer fibers in such a way that they have spacings between 0 and 10 particle diameters.
  • the particles on the base material A do not have to be very close to one another. Rather, it is possible that the base material A is only partially occupied with particles and free surfaces of 2 - 3 diameter of the particles are possible.
  • the wetting of solids can be described by the contact angle, which forms a water droplet with the surface.
  • a contact angle of 0 degrees means a complete wetting of the surface.
  • the measurement of the contact angle of fibers is usually done by the Wilhelmy method. The thread is wetted by a liquid and the force with which the fiber is pulled into the liquid due to the surface tension is measured. The higher the contact angle, the worse the surface can be wetted.
  • the aspect ratio is defined as the quotient of height to width of the structure of the surface.
  • the textile surfaces according to the invention have high contact angles and a high aspect ratio of the elevations. It may be advantageous if the particles used have a structured surface. Preferably, particles which have an irregular fine structure in the nanometer range on the surface are used. The use of such particles is new and the subject of a separate patent application (internal reference: EM 010098).
  • particles in particular as particles, which have an irregular fine structure in the Having nanometer region on the surface, preferably those particles are used which have at least one compound selected from fumed silica, precipitated silicas, alumina, silica, fumed and / or doped silicates or powdered polymers. It may be advantageous if the particles used have hydrophobic properties.
  • the hydrophobic properties of the particles may be inherent in the material of the particles used. But it can also be used hydrophobized particles which have hydrophobic properties after a suitable treatment, such as. Example, a treatment with at least one compound from the group of alkylsilanes, fluoroalkylsilanes or disilazanes.
  • the particles are provided with hydrophobic properties after bonding to the base material A.
  • the particles are preferably provided by a treatment with at least one of the group of alkylsilanes, fluoroalkylsilanes or disilazanes having hydrophobic properties.
  • the particles used can come from different areas. For example, it may be silicates, doped silicates, minerals, metal oxides, alumina, silicic acids or fumed silicates, aerosils or powdery polymers such. Spray-dried and agglomerated emulsions or cryogenic PTFE. Suitable particle systems are, in particular, hydrophobized pyrogenic silicas, so-called aerosils. In addition to the structure, a hydrophobicity is needed to generate the self-cleaning surfaces.
  • the particles used may themselves be hydrophobic, such as the PTFE.
  • the particles may be hydrophobic, such as, for example, the Aerosil VPR 411 or Aerosil R 8200. However, they can also be subsequently rendered hydrophobic.
  • the particles are rendered hydrophobic before application or after application.
  • Aeroperl 90/30 Sipemat Silica 350, alumina C, zirconium silicate, vanadium-doped or Aeroperl P 25/20.
  • the hydrophobization is carried out expediently by treatment with perfluoroalkylsilane and subsequent heat treatment.
  • solvents for the respective base materials A are suitable as solvents.
  • a list of polymers can be found, for example, in Polymer Handbook, Second Edition; J. Brandrup, E.H. Always good; John Wiley & Sons Publishing, New York - London - Sydney - Toronto, 1975, in Chapter IV, Solvents and Non-Solvents for Polymers.
  • Suitable solvents are in principle suitable compounds from the group of alcohols, glycols, ethers, glycol ethers, ketones, esters, amides, nitro compounds, halogenated hydrocarbons, aliphatic and aromatic hydrocarbons or a mixture of one or more of these compounds in question, such as.
  • the solvent used at temperatures of - 30 to 300 ° C can be used.
  • the temperature of the solvent is limited by its boiling point and by the Tg of the base material A.
  • the solvent comprising the particles is heated to a temperature of from 25 to 100 ° C., preferably to a temperature of from 50 to 85 ° C., prior to application to the polymer surface.
  • the invention likewise relates to the use of the textile fabrics for the production of articles with a self-cleaning and water-repellent surface, in particular for the production of items of clothing which are exposed to high levels of contamination by dirt and water, such.
  • the object is also the use for the production of carpets, sewing threads, ropes, wall hangings, textiles, wallpaper, clothing, tents, decorative curtains, stage curtains, seams.
  • a polyester fabric, fiber diameter ⁇ 20 microns, is drawn into a heated to 50 ° C DMSO bath with a 1% Aerosil R 8200 suspension. The residence time of the tissue in the solution is 10 seconds. Before the tissue is rolled up, the tissue is passed over a heat source to allow evaporation of the solvent. Table 1 gives the static contact angles measured on the fabric before and after application of the particles.
  • FIGS. 1 and 2 show SEM images of an untreated polyester fabric.
  • FIGS. 3 and 4 show SEM images of a polyester fabric treated with Aerosil R8200. Table 1: Static contact angle before and after application of the particulate systems contact angle polyester fabric 140 Polyester fabric + particles 150-160

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Dispersion Chemistry (AREA)
  • Chemical Or Physical Treatment Of Fibers (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
  • Laminated Bodies (AREA)
  • Cleaning Implements For Floors, Carpets, Furniture, Walls, And The Like (AREA)

Abstract

Textile fabrics having a self cleaning and water repellent surface, constructed from A) at least one synthetic and/or natural textile base material and B) an artificial, at least partly hydrophobic surface having elevations and depressions comprising particles securely bonded to said base material A without adhesives, resins or coatings, obtained by treating said base material A with at least one solvent containing said particles in undissolved form and removing said solvent to leave at least a portion of said particles securely bonded to the surface of said base material A.

Description

Die vorliegende Erfindung betrifft textile Flächengebilde mit selbstreinigender und wasserabweisender Oberfläche.The present invention relates to textile fabrics with self-cleaning and water-repellent surface.

Es ist bekannt, dass zum Erzielen einer guten Selbstreinigung einer Oberfläche die Oberfläche neben einer sehr hydrophoben Oberfläche auch eine gewisse Rauhigkeit aufweisen muss. Eine geeignete Kombination aus Struktur und Hydrophobie macht es möglich, dass schon geringe Mengen bewegten Wassers auf der Oberfläche haftende Schmutzpartikel mitnehmen und die Oberfläche reinigen (WO 96/04123; US-P 3,354,022).It is known that in order to achieve a good self-cleaning of a surface, the surface must also have a certain roughness in addition to a very hydrophobic surface. A suitable combination of structure and hydrophobicity makes it possible for even small amounts of moving water to take along adhering dirt particles on the surface and to clean the surface (WO 96/04123, US Pat. No. 3,354,022).

Stand der Technik ist gemäß EP 0 933 388, dass für solche selbstreinigenden Oberflächen ein Aspektverhältnis von > 1 und eine Oberflächenenergie von weniger als 20 mN/m erforderlich ist. Das Aspektverhältnis ist hierbei definiert als der Quotient von Höhe zur Breite der Struktur. Vorgenannte Kriterien sind in der Natur, beispielsweise im Lotusblatt, realisiert. Die aus einem hydrophoben wachsartigen Material gebildete Oberfläche der Pflanze weist Erhebungen auf, die einige µm voneinander entfernt sind. Wassertropfen kommen im Wesentlichen nur mit diesen Spitzen in Berührung. Solche wasserabstoßenden Oberflächen werden in der Literatur vielfach beschrieben.Prior art is according to EP 0 933 388, that for such self-cleaning surfaces, an aspect ratio of> 1 and a surface energy of less than 20 mN / m is required. The aspect ratio is defined as the quotient of height to width of the structure. The aforementioned criteria are realized in nature, for example in the lotus leaf. The surface of the plant formed from a hydrophobic waxy material has elevations which are a few microns apart. Water droplets are essentially only in contact with these tips. Such water-repellent surfaces are widely described in the literature.

CH-PS-268 258 beschreibt ein Verfahren, bei dem durch Aufbringen von Pulvern wie Kaolin, Talkum, Ton oder Silicagel strukturierte Oberflächen erzeugt werden. Die Pulver werden durch Öle und Harze auf Basis von Organosiliziumverbindungen auf der Oberfläche fixiert (Beispiele 1 bis 6).CH-PS-268 258 describes a process in which structured surfaces are produced by applying powders such as kaolin, talc, clay or silica gel. The powders are fixed on the surface by oils and resins based on organosilicon compounds (Examples 1 to 6).

EP 0 909 747 lehrt ein Verfahren zur Erzeugung einer selbstreinigenden Oberfläche. Die Oberfläche weist hydrophobe Erhebungen mit einer Höhe von 5 bis 200 µm auf. Hergestellt wird eine derartige Oberfläche durch Aufbringen einer Dispersion von Pulverpartikeln und einem inerten Material in einer Siloxan-Lösung und anschließendem Aushärten. Die strukturbildenden Partikel werden also durch ein Hilfsmedium am Substrat fixiert. WO 00/58410 kommt zu dem Ergebnis, dass es technisch möglich ist, Oberflächen von Gegenständen künstlich selbstreinigend zu machen. Die hierfür nötigen Oberflächenstrukturen aus Erhebungen und Vertiefungen haben einen Abstand zwischen den Erhebungen der Oberflächenstrukturen im Bereich von 0,1 bis 200 µm und eine Höhe der Erhebung im Bereich 0,1 bis 100 µm. Die hierfür verwendeten Materialien müssen aus hydrophoben Polymeren oder dauerhaft hydrophobiertem Material bestehen. Ein Lösen der Teilchen aus der Trägermatrix muss verhindert werden.EP 0 909 747 teaches a method for producing a self-cleaning surface. The surface has hydrophobic elevations with a height of 5 to 200 microns. Such a surface is prepared by applying a dispersion of powder particles and an inert material in a siloxane solution and then curing. The structure-forming particles are thus fixed by an auxiliary medium on the substrate. WO 00/58410 comes to the conclusion that it is technically possible to surfaces of Artificially self-cleaning objects. The surface structures of elevations and depressions required for this purpose have a spacing between the elevations of the surface structures in the range from 0.1 to 200 μm and a height of the elevation in the range from 0.1 to 100 μm. The materials used for this purpose must consist of hydrophobic polymers or permanently hydrophobized material. Dissolution of the particles from the carrier matrix must be prevented.

Der Einsatz von hydrophoben Materialien, wie perfluorierten Polymeren, zur Herstellung von hydrophoben Oberflächen ist bekannt. Eine Weiterentwicklung dieser Oberflächen besteht darin, die Oberflächen im µm-Bereich bis nm-Bereich zu strukturieren. US PS 5,599,489 offenbart ein Verfahren, bei dem eine Oberfläche durch Beschuss mit Partikeln einer entsprechenden Größe und anschließender Perfluorierung besonders abweisend ausgestattet werden kann. Ein anderes Verfahren beschreibt H. Saito et al. in "Service Coatings International", 4, 1997, S.168 ff. Hier werden Partikel aus Fluorpolymeren auf Metalloberflächen aufgebracht, wobei eine stark erniedrigte Benetzbarkeit der so erzeugten Oberflächen gegenüber Wasser mit einer erheblich reduzierten Vereisungsneigung dargestellt wurde.The use of hydrophobic materials, such as perfluorinated polymers, for the production of hydrophobic surfaces is known. A further development of these surfaces is to structure the surfaces in the μm range to the nm range. US Pat. No. 5,599,489 discloses a method in which a surface can be provided in a particularly repellent manner by bombardment with particles of a corresponding size and subsequent perfluorination. Another method is described by H. Saito et al. in "Service Coatings International", 4, 1997, p.168 ff. Here, particles of fluoropolymers are applied to metal surfaces, wherein a greatly reduced wettability of the surfaces thus produced to water was shown with a significantly reduced tendency to icing.

Das Prinzip ist der Natur entlehnt. Kleine Kontaktflächen erniedrigen die Van-der Waal's Wechselwirkung, die für die Haftung an ebenen Oberflächen mit niedriger Oberflächenenergie verantwortlich ist. Beispielsweise sind die Blätter der Lotuspflanze mit Erhebungen aus einem Wachs versehen, die die Kontaktfläche zu Wasser herabsetzen. WO 00/58410 beschreibt die Strukturen und beansprucht die Ausbildung selbiger durch Aufsprühen von hydrophoben Alkoholen, wie Nonacosan-10-ol oder Alkandiolen, wie Nonacosan-5,10-diol. Nachteilig hieran ist die mangelhafte Stabilität der selbstreinigenden Oberflächen, da Detergenzien zur Auflösung der Struktur führen.The principle is borrowed from nature. Small contact areas lower Van der Waal's interaction, which accounts for adhesion to low surface energy planar surfaces. For example, the leaves of the lotus plant are provided with elevations of a wax, which reduce the contact area to water. WO 00/58410 describes the structures and claims the formation thereof by spraying hydrophobic alcohols such as nonacosan-10-ol or alkanediols such as nonacosan-5,10-diol. A disadvantage of this is the poor stability of the self-cleaning surfaces, since detergents lead to the dissolution of the structure.

Verfahren zur Herstellung dieser strukturierten Oberflächen sind ebenfalls bekannt. Neben der detailgetreuen Abformung dieser Strukturen durch eine Masterstruktur im Spritzguss oder Prägeverfahren sind auch Verfahren bekannt, die das Aufbringen von Partikeln auf eine Oberfläche nutzen (US 5 599 489).Methods for producing these structured surfaces are also known. In addition to the detailed reproduction of these structures by a master structure in the injection molding or embossing process, methods are known which use the application of particles on a surface (US 5,599,489).

Gemeinsam ist aber, dass das selbstreinigende Verhalten von Oberflächen durch ein sehr hohes Aspektverhältnis beschrieben wird. Hohe Aspektverhältnisse sind technisch nur sehr schwer realisierbar und besitzen eine geringe mechanische Stabilität.What is common is that the self-cleaning behavior of surfaces is described by a very high aspect ratio. High aspect ratios are technically very difficult to implement and have low mechanical stability.

Aufgabe der vorliegenden Erfindung war es, textile Flächengebilde zu finden, die sehr gute wasserabweisende und selbstreinigende Oberflächen aufweisen, wobei diese Eigenschaften im täglichen Gebrauch der hergestellten Gegenstände aus diesen textilen Flächengebilden erhalten bleiben müssen und wobei die textilen Flächengebilde durch ein Verfahren, welches ohne großen technischen Aufwand durchzuführen ist, herstellbar sind. Auf das Befestigen von Partikeln durch Klebstoff und dergleichen sollte im Hinblick auf die Eigenschaften der textilen Flächengebilde im Gebrauch verzichtet werden können. Es bestand auch die Aufgabe, textile Flächengebilde mit selbstreinigender und wasserabweisender Oberfläche zu finden, die ein hohes Aspektverhältnis der Erhebungen, einen hohen Randwinkel mit Wasser und über ein nicht-prägendes Verfahren in textile Flächengebilde eingebracht werden können.The object of the present invention was to find textile fabrics which have very good water-repellent and self-cleaning surfaces, these properties having to be maintained in daily use of the articles produced from these textile fabrics and the textile fabrics being formed by a process which does not involve a great deal of technical complexity Effort is to be performed, can be produced. The attachment of particles by adhesive and the like should be eliminated in view of the properties of the fabrics in use. It was also the object to find textile fabrics with self-cleaning and water-repellent surface, which can be introduced into textile fabrics a high aspect ratio of the surveys, a high contact angle with water and a non-embossing process.

Überraschenderweise wurde gefunden, dass es möglich ist, Partikel mit der Oberfläche von textilen Flächengebilden dauerhaft zu verbinden. Durch Behandlung der textilen Flächengebilde mit Partikeln und Lösemittel konnte die gestellte Aufgabe gelöst werden. Nach dem Entfernen des Lösungsmittels sind die Partikeln fest mit den textilen Flächengebilden verbunden, ohne dass das Gewebe zerstört wurde.Surprisingly, it has been found that it is possible to permanently bond particles to the surface of textile fabrics. By treating the textile fabrics with particles and solvents, the task could be solved. After removal of the solvent, the particles are firmly bonded to the fabrics without destroying the fabric.

Gegenstand der Erfindung sind textile Flächengebilde mit selbstreinigender und wasserabweisender Oberfläche, aufgebaut aus

  • A) mindestens einem synthetischen und/oder natürlichen textilen Basismaterial und
  • B) einer künstlichen, mindestens teilweise hydrophoben Oberfläche mit Erhebungen und Vertiefungen aus Partikeln, die ohne Klebstoffe, Harze oder Lacke mit dem Basismaterial A fest verbunden sind,
erhalten durch Behandlung des Basismaterials A mit zumindest einem Lösemittel für das Basismaterial A, welches die Partikel, ausgewählt aus Silikaten, Mineralien, Metalloxiden, Metallpulvern, Kieselsäuren, Pigmenten oder Polymeren, ungelöst enthält, und Entfernen des Lösemittels, wobei zumindest ein Teil der Partikel mit der Oberfläche des Basismaterials A fest verbunden werden.The invention relates to textile fabrics with self-cleaning and water-repellent surface, constructed from
  • A) at least one synthetic and / or natural textile base material and
  • B) an artificial, at least partially hydrophobic surface with elevations and depressions of particles which are firmly bonded to the base material A without adhesives, resins or lacquers,
obtained by treating the base material A with at least one solvent for the base material A, which contains the particles, selected from silicates, minerals, metal oxides, metal powders, silicas, pigments or polymers, undissolved, and removing the Solvent, wherein at least a part of the particles with the surface of the base material A are firmly connected.

Weiterer Gegenstand der Erfindung ist die Verwendung dieser textilen Flächengebilde mit selbstreinigender und wasserabweisender Oberfläche zur Herstellung von textilen Gegenständen.Another object of the invention is the use of these textile fabrics with self-cleaning and water-repellent surface for the production of textile articles.

Es hat sich gezeigt, dass die erfindungsgemäßen textilen Flächengebilde mit selbstreinigender und wasserabweisender Oberfläche und die daraus hergestellten Textilien durchaus auch mit Wasser mit Detergenzien in Berührung kommen dürfen. Die selbstreinigenden Eigenschaften der Oberflächen gehen dabei nicht verloren. Voraussetzung hierfür ist allerdings, dass die Detergenzien wieder vollständig ausgewaschen werden und eine hydrophobe Oberfläche vorliegt.It has been found that the textile fabrics according to the invention with a self-cleaning and water-repellent surface and the textiles produced therefrom may well come into contact with detergents with water. The self-cleaning properties of the surfaces are not lost. The prerequisite for this, however, is that the detergents are completely washed out again and a hydrophobic surface is present.

Das textile Basismaterial A kann durch die verschiedensten gebräuchlichen Polymere gebildet sein, wie z. B. aus Polycarbonaten, Poly(meth)acrylaten, Polyamiden, PVC, Polyethylenen, Polypropylenen, Polystyrolen, Polyestern, Polyethersulfonen oder Polyalkylenterpthalaten, sowie deren Gemische oder Copolymere.The textile base material A may be formed by a variety of common polymers, such as. Example of polycarbonates, poly (meth) acrylates, polyamides, PVC, polyethylenes, polypropylenes, polystyrenes, polyesters, polyethersulfones or Polyalkylenterpthalaten, and mixtures thereof or copolymers.

Als Basismaterial eignen sich auch natürliche Materialien aus Pflanzenteilen ausgewählt aus Baumwolle, Kapok, Flachs, Hanf, Jute, Sisal und Kokos, aus Haarkleidern von Tieren, aus Seide oder mineralischen Ursprung. Mischgewebe aus natürlichen und künstlichen Materialien sind ebenfalls geeignet.Also suitable as the base material are natural materials from plant parts selected from cotton, kapok, flax, hemp, jute, sisal and coconut, from hair dressings of animals, silk or mineral origin. Blended fabrics of natural and artificial materials are also suitable.

Das erfindungsgemäß einzusetzende Basismaterial A wird im Folgenden beispielhaft näher erläutert.The base material A to be used according to the invention is explained in more detail below by way of example.

Die Herstellung von textiler Fertigware erfolgt in der Regel aus Polymerfäden, die im Spinnverfahren hergestellt wurden.The production of textile finished product is usually made of polymer threads that were produced by spinning.

Aus den Fasern und Garnen werden textile Flächengebilde erzeugt. Hierbei können folgende Verfahren verwandt werden:From the fibers and yarns textile fabrics are produced. The following procedures can be used:

Weben: Zu diesen Webwaren gehören Gewebe, Teppiche und Bobinets die durch ihrer klassische Gewebebindung von Kett- u. Schussfäden charakterisiert sind.
Wirken und Stricken: Hierbei entstehen Maschenwaren wie z. B. Pullover.
Klöppeln: Hier entstehen die sogenannten Spitze.
Nadeln: Hier entstehen Filze, Nadelfilz- und Nadelflorteppiche, die zusammen mit den Vliesstoffen zu den Textilverbundstoffen zu rechnen sind.Weaving: Woven fabrics, carpets and bobinets are part of this weaving weave, thanks to their classic woven weave of warp and weft. Weft threads are characterized.
Knitting and knitting: this results in knitwear such. B. sweater.
Lace: Here arise the so-called tip.
Needles: This produces felts, needlefelt and needlefelt carpets, which, together with the nonwovens, can be expected to form the textile composites.

Garn- u. Stückwaren werden im Verlauf ihrer Verarbeitung diversen mechanischen und chemischen Veredlungsprozessen unterworfen, z. B. Kämmen, Beschwerung, Imprägnierung, Krumpffrei- u. Knitterfestausrüstung, Mercerisation, Färben und Bedrucken, Metallisierung, Texturierung usw., die der Verbesserung od. Modifizierung der natürlichen Eigenschaften der Fasern im Hinblick auf die spätere Verwendung dienen sollen. Kriterien, nach denen der Gebrauchswert einer textilen Fertigware durch geeignete Textilprüfungsmethoden beurteilt wird, sind u. a.: Festigkeit gegenüber Zug- und Berstkräften sowie gegen Scheuereinwirkung, Knittererholung in trockenem und nassem Zustand und damit verbunden das Wash-and-Wear-Verhalten, Widerstandsfähigkeit z. B. gegen elektrostatischer Aufladung, Entflammbarkeit oder Regeneinwirkung, Chlor-Retention, Anschmutzverhalten, Luftdurchlässigkeit, Gewebedichte, Filz- u. Krumpffreiheit, Quellfähigkeit, Hydrophilie, Hydrophobie u. Oleophobie, Glanz, Griff, Wasch-, Schweiß- u. Farbechtheit, Resistenz gegen mikrobielle Zerstörung. usw.Garn u. Piece goods are subjected in the course of their processing various mechanical and chemical processing processes, eg. B. combing, weighting, impregnation, Krumpffrei- u. Crease resistant equipment, mercerization, dyeing and printing, metallization, texturing, etc., which are intended to improve od. Modification of the natural properties of the fibers with a view to later use. Criteria according to which the utility value of a finished textile product is assessed by suitable textile testing methods are u. a .: resistance to tensile and bursting forces as well as to abrasion, wrinkle recovery in dry and wet condition and associated with the wash-and-wear behavior, resistance z. As against electrostatic charge, flammability or rain, chlorine retention, soiling, air permeability, fabric density, felt u. Shrinkage, swelling, hydrophilicity, hydrophobicity and the like Oleophobia, gloss, handle, washing, welding u. Color fastness, resistance to microbial destruction. etc.

Polymergewebe / Textilien, also das Basismaterial A im Sinne der Erfindung, können aus verschiedene Fasern hergestellt werden. Für die meistern Fasern aus thermoplastischen Kunststoffen, wie PET, PA66, PE oder PP, sind die oben genannten Verfahren geeignet. Fasern werden meist mit geschützten Markennamen gehandelt, Beispiele sind Perlon® , Diolen® , Trevira® , Orleon® , aber auch Trivialnamen wie Acrylfasern, Polyesterfasern, Olefinfasern, Aramidfasem usw., sind gebräuchlich.Polymer fabric / textiles, ie the base material A in the sense of the invention, can be produced from different fibers. For the most advanced thermoplastic fibers, such as PET, PA66, PE or PP, the above-mentioned methods are suitable. Fibers are usually traded under protected brand names, examples being Perlon®, Diolen®, Trevira®, Orleon®, but also trivial names such as acrylic fibers, polyester fibers, olefin fibers, aramid fibers, etc. are common.

Als Partikel werden solche eingesetzt, die zumindest ein Material, ausgewählt aus Silikaten, Mineralien, Metalloxiden, Metallpulvern, Kieselsäuren, Pigmenten oder Polymeren aufweisen. Vorzugsweise werden Partikel eingesetzt, die einen Partikeldurchmesser von 0,02 bis 100 µm, besonders bevorzugt von 0,1 bis 50 µm und ganz besonders bevorzugt von 0,1 bis 30 µm aufweisen. Geeignet sind aber auch Partikel, die sich aus Primärteilchen zu Agglomeraten oder Aggregaten mit einer Größe von 0,2-100 µm zusammenlagern.The particles used are those which comprise at least one material selected from Have silicates, minerals, metal oxides, metal powders, silicas, pigments or polymers. Preferably, particles are used which have a particle diameter of 0.02 to 100 microns, more preferably from 0.1 to 50 microns and most preferably from 0.1 to 30 microns. However, particles which are composed of primary particles to form agglomerates or aggregates of a size of 0.2-100 μm are also suitable.

Im Allgemeinen sind die Partikel derart an der Oberfläche der Polymerfasern gebunden, dass sie untereinander Abstände von 0 - 10 Partikeldurchmesser aufweisen.In general, the particles are bonded to the surface of the polymer fibers in such a way that they have spacings between 0 and 10 particle diameters.

Überraschenderweise wurde bei den erfindungsgemäßen textilen Flächengebilde gefunden, dass die Partikel auf dem Basismaterial A nicht sehr eng beieinander liegen müssen. Vielmehr ist es möglich, dass das Basismaterial A nur punktuell mit Partikeln belegt ist und freie Flächen von 2 - 3 Durchmesser der Partikel möglich sind.Surprisingly, it has been found in the textile fabrics according to the invention that the particles on the base material A do not have to be very close to one another. Rather, it is possible that the base material A is only partially occupied with particles and free surfaces of 2 - 3 diameter of the particles are possible.

Die Benetzung von Festkörpern lässt sich durch den Randwinkel, den ein Wassertropfen mit der Oberfläche bildet, beschreiben. Ein Randwinkel von 0 Grad bedeutet dabei eine vollständige Benetzung der Oberfläche. Die Messung des Randwinkel an Fasern erfolgt in der Regel nach der Wilhelmy Methode. Dabei wird der Faden von einer Flüssigkeit benetzt und die Kraft, mit der die Faser aufgrund der Oberflächenspannung in die Flüssigkeit gezogen wird, gemessen. Je höher der Randwinkel ist, um so schlechter kann die Oberfläche benetzt werden. Das Aspektverhältnis ist definiert als der Quotient von Höhe zur Breite der Struktur der Oberfläche.The wetting of solids can be described by the contact angle, which forms a water droplet with the surface. A contact angle of 0 degrees means a complete wetting of the surface. The measurement of the contact angle of fibers is usually done by the Wilhelmy method. The thread is wetted by a liquid and the force with which the fiber is pulled into the liquid due to the surface tension is measured. The higher the contact angle, the worse the surface can be wetted. The aspect ratio is defined as the quotient of height to width of the structure of the surface.

Die erfindungsgemäßen textilen Flächen weisen hohe Randwinkel und ein hohes Aspektverhältnis der Erhebungen auf.
Es kann vorteilhaft sein, wenn die eingesetzten Partikel eine strukturierte Oberfläche haben. Vorzugsweise werden Partikel, die eine unregelmäßige Feinstruktur im Nanometerbereich auf der Oberfläche aufweisen, eingesetzt. Die Verwendung derartiger Partikel ist neu und Gegenstand einer gesonderten Patentanmeldung (internes Aktenzeichen: EM 010098).The textile surfaces according to the invention have high contact angles and a high aspect ratio of the elevations.
It may be advantageous if the particles used have a structured surface. Preferably, particles which have an irregular fine structure in the nanometer range on the surface are used. The use of such particles is new and the subject of a separate patent application (internal reference: EM 010098).

Als Partikel, insbesondere als Partikel, die eine unregelmäßige Feinstruktur im Nanometerbereich an der Oberfläche aufweisen, werden vorzugsweise solche Partikel eingesetzt, die zumindest eine Verbindung, ausgewählt aus pyrogener Kieselsäure, Fällungskieselsäuren, Aluminiumoxid, Siliziumdioxid, pyrogenen und/oder dotierten Silikaten oder pulverförmige Polymeren aufweisen. Es kann vorteilhaft sein, wenn die eingesetzten Partikel hydrophobe Eigenschaften aufweisen.As particles, in particular as particles, which have an irregular fine structure in the Having nanometer region on the surface, preferably those particles are used which have at least one compound selected from fumed silica, precipitated silicas, alumina, silica, fumed and / or doped silicates or powdered polymers. It may be advantageous if the particles used have hydrophobic properties.

Die hydrophoben Eigenschaften der Partikel können durch das verwendete Material der Partikel inhärent vorhanden sein. Es können aber auch hydrophobierte Partikel eingesetzt werden, die nach einer geeigneten Behandlung hydrophobe Eigenschaften aufweisen, wie z. B. eine Behandlung mit zumindest einer Verbindung aus der Gruppe der Alkylsilane, der Fluoralkylsilane oder der Disilazane.The hydrophobic properties of the particles may be inherent in the material of the particles used. But it can also be used hydrophobized particles which have hydrophobic properties after a suitable treatment, such as. Example, a treatment with at least one compound from the group of alkylsilanes, fluoroalkylsilanes or disilazanes.

Ebenso ist es im Rahmen der Erfindung möglich, dass die Partikel nach dem Verbinden mit dem Basismaterial A mit hydrophoben Eigenschaften ausgestattet werden. Auch in diesem Fall werden die Partikel vorzugsweise durch eine Behandlung mit zumindest einer Verbindung aus der Gruppe der Alkylsilane, der Fluoralkylsilane oder der Disilazane mit hydrophoben Eigenschaften ausgestattet.Likewise, it is possible within the scope of the invention for the particles to be provided with hydrophobic properties after bonding to the base material A. Also in this case, the particles are preferably provided by a treatment with at least one of the group of alkylsilanes, fluoroalkylsilanes or disilazanes having hydrophobic properties.

Im Folgenden werden die bevorzugt eingesetzten Partikel näher erläutert.In the following, the preferred used particles are explained in more detail.

Die eingesetzten Partikel können aus unterschiedlichen Bereichen kommen. Beispielsweise können es Silikate sein, dotierte Silikate, Mineralien, Metalloxide, Aluminiumoxid, Kieselsäuren oder pyrogene Silikate, Aerosile oder pulverförmige Polymere, wie z. B. sprühgetrocknete und agglomerierte Emulsionen oder cryogemahlenes PTFE. Als Partikelsysteme eignen sich im Besonderen hydrophobierte pyrogene Kieselsäuren, sogenannte Aerosile. Zur Generierung der selbstreinigenden Oberflächen ist neben der Struktur auch eine Hydrophobie nötig. Die eingesetzten Partikel können selbst hydrophob sein, wie beispielsweise das PTFE. Die Partikel können hydrophob ausgerüstet sein, wie beispielsweise das Aerosil VPR 411 oder Aerosil R 8200. Sie können aber auch nachträglich hydrophobiert werden. Hierbei ist es unwesentlich, ob die Partikel vor dem Auftragen oder nach dem Auftragen hydrophobiert werden. Diese, beispielsweise für Aeroperl 90/30, Sipemat Kieselsäure 350, Aluminiumoxid C, Zirkonsilikat, vanadiumdotiert oder Aeroperl P 25/20. Zur letzteren erfolgt die Hydrophobierung zweckmäßig durch Behandlung mit Perfluoralkylsilan und anschließender Temperung.The particles used can come from different areas. For example, it may be silicates, doped silicates, minerals, metal oxides, alumina, silicic acids or fumed silicates, aerosils or powdery polymers such. Spray-dried and agglomerated emulsions or cryogenic PTFE. Suitable particle systems are, in particular, hydrophobized pyrogenic silicas, so-called aerosils. In addition to the structure, a hydrophobicity is needed to generate the self-cleaning surfaces. The particles used may themselves be hydrophobic, such as the PTFE. The particles may be hydrophobic, such as, for example, the Aerosil VPR 411 or Aerosil R 8200. However, they can also be subsequently rendered hydrophobic. It is immaterial whether the particles are rendered hydrophobic before application or after application. These, for example for Aeroperl 90/30, Sipemat Silica 350, alumina C, zirconium silicate, vanadium-doped or Aeroperl P 25/20. For the latter, the hydrophobization is carried out expediently by treatment with perfluoroalkylsilane and subsequent heat treatment.

Als Lösemittel eignen sich prinzipiell alle Lösemittel für die jeweiligen Basismaterialien A. Eine Auflistung für Polymere findet sich beispielsweise in Polymer Handbook, Second Edition; J. Brandrup, E.H. Immergut; John Wiley & Sons Verlag, New York - London - Sydney - Toronto, 1975, im Kapitel IV, Solvents and Non-Solvents for Polymers.In principle, all solvents for the respective base materials A are suitable as solvents. A list of polymers can be found, for example, in Polymer Handbook, Second Edition; J. Brandrup, E.H. Always good; John Wiley & Sons Publishing, New York - London - Sydney - Toronto, 1975, in Chapter IV, Solvents and Non-Solvents for Polymers.

Als Lösemittel kommen prinzipiell geeignete Verbindung aus der Gruppe der Alkohole, der Glykole, der Ether, der Glykolether, der Ketone, der Ester, der Amide, der Nitro-Verbindungen, der Halogenkohlenwasserstoffe, der aliphatischen und aromatischen Kohlenwasserstoffe oder eine Mischung von einer oder mehrerer dieser Verbindungen in Frage, wie z. B. Methanol, Ethanol, Propanol, Butanol, Octanol, Cyclohexanol, Phenol, Kresol, Ethylenglykol, Diethylenglykol, Diethylether, Dibutylether, Anisol, Dioxan, Dioxolan, Tetrahydrofuran, Monoethylenglykolether, Diethylenglykolether, Triethylenglykolether, Polyethylenglykolether, Aceton, Butanon, Cyclohexanon, Ethylacetat, Butylacetat, Iso-Amylacetat, Ethylhexylacetat, Glykolester, Dimethylformamid, Pyridin, N-Methylpyrrolidon, N-Methylcaprolacton, Acetonitril, Schwefelkohlenstoff, Dimethylsulfoxid, Sulfolan, Nitrobenzol, Dichlormethan, Chloroform, Tetrachlormethan, Trichlorethen, Tetrachlorethen, 1,2-Dichlorethan, Chlorphenol, Chlorfluorkohlenwasserstoffe, Benzine, Petrolether, Cyclohexan, Methylcyclohexan, Decalin, Tetralin, Terpene, Benzol, Toluol oder Xylol oder geeignete Mischungen.Suitable solvents are in principle suitable compounds from the group of alcohols, glycols, ethers, glycol ethers, ketones, esters, amides, nitro compounds, halogenated hydrocarbons, aliphatic and aromatic hydrocarbons or a mixture of one or more of these compounds in question, such as. Methanol, ethanol, propanol, butanol, octanol, cyclohexanol, phenol, cresol, ethylene glycol, diethylene glycol, diethyl ether, dibutyl ether, anisole, dioxane, dioxolane, tetrahydrofuran, monoethylene glycol ether, diethylene glycol ether, triethylene glycol ether, polyethylene glycol ether, acetone, butanone, cyclohexanone, ethyl acetate, Butyl acetate, iso-amyl acetate, ethylhexyl acetate, glycol esters, dimethylformamide, pyridine, N-methylpyrrolidone, N-methylcaprolactone, acetonitrile, carbon disulfide, dimethyl sulfoxide, sulfolane, nitrobenzene, dichloromethane, chloroform, carbon tetrachloride, trichloroethene, tetrachloroethene, 1,2-dichloroethane, chlorophenol, Chlorofluorocarbons, gasolines, petroleum ethers, cyclohexane, methylcyclohexane, decalin, tetralin, terpenes, benzene, toluene or xylene or suitable mixtures.

Prinzipiell kann das verwendete Lösemittel bei Temperaturen von - 30 bis 300 °C eingesetzt werden. Allgemein wird die Temperatur des Lösemittels durch seinen Siedepunkt und durch den Tg des Basismaterials A limitiert.In principle, the solvent used at temperatures of - 30 to 300 ° C can be used. Generally, the temperature of the solvent is limited by its boiling point and by the Tg of the base material A.

In einer besonders bevorzugten Ausführungsart der Erfindung wird das Lösemittel, welches die Partikel aufweist, vor dem Aufbringen auf die Polymeroberfläche auf eine Temperatur von 25 bis 100 °C, vorzugsweise auf eine Temperatur von 50 bis 85 °C, erwärmt.In a particularly preferred embodiment of the invention, the solvent comprising the particles is heated to a temperature of from 25 to 100 ° C., preferably to a temperature of from 50 to 85 ° C., prior to application to the polymer surface.

Ebenfalls Gegenstand der Erfindung ist die Verwendung der textilen Flächengebilde zur Herstellung von Gegenständen mit einer selbstreinigenden und wasserabweisenden Oberfläche, insbesondere zur Herstellung von Bekleidungsstücken, die hohen Belastungen durch Schmutz und Wasser ausgesetzt sind, wie z. B. für den Skisport, Alpinsport, Motorsport, Motorradsport, Motocrosssport, Segelsport, Textilien für den Freizeitbereich sowie technische Textilien wie Zelte, Markisen, Regenschirme, Tischdecken und Kabrio-Verdecke. Gegenstand ist ebenfalls die Verwendung zur Herstellung von Teppichen, Nähgarnen, Seilen, Wandbehängen, Textilien, Tapeten, Bekleidungsstücken, Zelten, Dekor-Vorhängen, Bühnen-Vorhängen, Nähten.The invention likewise relates to the use of the textile fabrics for the production of articles with a self-cleaning and water-repellent surface, in particular for the production of items of clothing which are exposed to high levels of contamination by dirt and water, such. B. for skiing, alpine sports, motor sports, motorcycle racing, motocross sports, yachting, textiles for the leisure sector and technical textiles such as tents, awnings, umbrellas, tablecloths and convertible tops. The object is also the use for the production of carpets, sewing threads, ropes, wall hangings, textiles, wallpaper, clothing, tents, decorative curtains, stage curtains, seams.

Durch das folgende Beispiel wird die Erfindung näher erläutert.The following example explains the invention in more detail.

Anweindungsbeispiel 1:Connection example 1:

Ein Polyestergewebe, Faserdurchmesser Ø 20 µm, wird in ein auf 50 °C erhitztes DMSO Bad mit einer 1 %igen Aerosil R 8200-Suspension gezogen. Die Verweildauer des Gewebes in der Lösung beträgt 10 Sekunden. Vor dem Aufrollen des Gewebes wird das Gewebe über eine Wärmequelle geführt, um ein Abdampfen des Lösungsmittels zu ermöglichen. Tabelle 1 gibt die am Gewebe gemessenen statischen Randwinkel vor und nach dem Aufbringen der Partikel wieder. Die Figuren Fig. 1 und Fig. 2 zeigen REM-Bilder eines unbehandelten Polyestergewebes. Die Figuren Fig. 3 und Fig. 4 zeigen REM-Bilder eines mit Aerosil R8200 behandelten Polyestergewebes. Tabelle 1: Statischer Randwinkel vor und nach dem Aufbringen der partikulären Systeme Randwinkel Polyestergewebe 140 Polyestergewebe + Partikel 150-160 A polyester fabric, fiber diameter Ø 20 microns, is drawn into a heated to 50 ° C DMSO bath with a 1% Aerosil R 8200 suspension. The residence time of the tissue in the solution is 10 seconds. Before the tissue is rolled up, the tissue is passed over a heat source to allow evaporation of the solvent. Table 1 gives the static contact angles measured on the fabric before and after application of the particles. FIGS. 1 and 2 show SEM images of an untreated polyester fabric. FIGS. 3 and 4 show SEM images of a polyester fabric treated with Aerosil R8200. Table 1: Static contact angle before and after application of the particulate systems contact angle polyester fabric 140 Polyester fabric + particles 150-160

Claims (20)

  1. A textile fabric having a self cleaning and water repellent surface, constructed from
    A) at least one synthetic and/or natural textile base material and
    B) an artificial, at least partly hydrophobic surface having elevations and depressions comprising particles securely bonded to the base material A without adhesives, resins or coatings,
    obtained by treating the base material A with at least one solvent for the base material A, containing the particles, selected from silicates, minerals, metal oxides, metal powders, silicas, pigments and polymers, in undissolved form and removing the solvent to leave at least a portion of the particles securely bonded to the surface of the base material A.
  2. A textile fabric according to claim 1, characterized in that the particles are suspended in the solvent.
  3. A textile fabric according to either or both of claims 1 and 2, characterized in that the textile base material A comprises a polymeric woven based on polycarbonates, poly(meth)acrylates, polyamides, PVC, polyethylenes, polypropylenes, polystyrenes, polyesters, polyether sulphones or polyalkylene terephthalates and also a blend or copolymer thereof.
  4. A textile fabric according to either or both of claims 1 and 2, characterized in that the textile base material A comprises a natural material composed of plant parts selected from cotton, kapok, flax, hemp, jute, sisal, hair coats of animals, silk, of mineral origin or a blend of natural and artificial materials.
  5. A textile fabric according to one or more of claims 1 to 4, characterized in that the solvent is at least one compound from the group of the alcohols, the glycols, the ethers, the glycol ethers, the ketones, the esters, the amides, the nitro compounds, the (hydro)halocarbons, the aliphatic and aromatic hydrocarbons or mixtures that is suitable as a solvent for the corresponding base material A.
  6. A textile fabric according to claim 5, characterized in that the solvent is at least one compound selected from methanol, ethanol, propanol, butanol, octanol, cyclohexanol, phenol, cresol, ethylene glycol, diethylene glycol, diethyl ether, dibutyl ether, anisole, dioxane, dioxolane, tetrahydrofuran, monoethylene glycol ether, diethylene glycol ether, triethylene glycol ether, polyethylene glycol ether, acetone, butanone, cyclohexanone, ethyl acetate, butyl acetate, isoamyl acetate, ethylhexyl acetate, glycol esters, dimethylformamide, pyridine, N-methylpyrrolidone, N-methylcaprolactone, acetonitrile, carbon disulphide, dimethyl sulphoxide, sulpholane, nitrobenzene, dichloromethane, chloroform, tetrachloromethane, trichloroethene, tetrachloroethene, 1,2-dichloroethane, chlorophenol, (hydro)chlorofluorocarbons, petroleum spirits, petroleum ethers, cyclohexane, methylcyclohexane, decalin, tetralin, terpenes, benzene, toluene and xylene or mixtures that is suitable as a solvent for the corresponding base material A.
  7. A textile fabric according to one or more of claims 1 to 6, characterized in that the solvent which contains the particles has a temperature of from -30°C to 300°C and preferably of from 25 to 100°C before application to the base material A.
  8. A textile fabric according to claim 7, characterized in that the solvent which comprises the particles is heated to a temperature of from 50 to 85°C before the application to the base material A.
  9. A textile fabric according to one or more of claims 1 to 8, characterized in that it includes particles having an average particle diameter of from 0.02 to 100 µm.
  10. A textile fabric according to one or more of claims 1 to 9, characterized in that it includes particles having an average particle diameter of from 0.1 to 30 µm.
  11. A textile fabric according to one or more of claims 1 to 10, characterized in that it includes particles having an irregular fine structure in the nanometre range on the surface.
  12. A textile fabric according to one or more of claims 1 to 11, characterized in that it includes particles selected from pyrogenic silicas, precipitated silicas, aluminium oxide, silicon dioxide, doped silicates, pyrogenic silicates and pulverulent polymers.
  13. A textile fabric according to one or more of claims 1 to 12, characterized in that the particles have hydrophobic properties.
  14. A textile fabric according to one or more of claims 1 to 12, characterized in that the particles have hydrophobic properties due to a treatment with a suitable compound.
  15. A textile fabric according to claim 14, characterized in that the particles are provided with hydrophobic properties before or after bonding to the base material A.
  16. A textile fabric according to either or both of claims 14 and 15, characterized in that the particles are provided with hydrophobic properties by a treatment with at least one compound from the group of the alkylsilanes, fluoroalkylsilanes and disilazanes.
  17. A textile fabric according to either or both of claims 14 and 15, characterized in that the individual particles on the base material A are spaced 0 - 10 particle diameters and especially 2 - 3 particle diameters apart.
  18. The use of a textile fabric according to one or more of claims 1 to 17 for manufacturing a textile article having a self cleaning and water repellent surface.
  19. The use according to claim 18 for manufacturing a garment exposed to high levels of soil and water, especially for ski sports, alpine sports, motor sports, motorcycle sports, motocross sports, sailing sports, a textile for the leisure sector and also an industrial textile such as a tent, an awning or blind, an umbrella, a tablecloth or a cabriolet cover.
  20. The use according to claim 18 for manufacturing a carpet, a sewing thread, a rope, a wallhanging, a textile, a wallpaper, a garment, a tent, a decorative curtain, a theatre curtain or stitching.
EP02704724A 2001-04-12 2002-02-26 Flat textile structures with self-cleaning and water-repellent surfaces Expired - Lifetime EP1379725B1 (en)

Applications Claiming Priority (3)

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DE10118346A DE10118346A1 (en) 2001-04-12 2001-04-12 Self-cleaning, water-repellent textiles, used e.g. for tents, sports clothing and carpets, made by impregnating textile material with a suspension of hydrophobic particles and then removing the solvent
DE10118346 2001-04-12
PCT/EP2002/002013 WO2002084016A1 (en) 2001-04-12 2002-02-26 Flat textile structures with self-cleaning and water-repellent surfaces

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EP (1) EP1379725B1 (en)
AT (1) ATE339545T1 (en)
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DE (2) DE10118346A1 (en)
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US8629070B2 (en) 2014-01-14
DE50208141D1 (en) 2006-10-26
EP1379725A1 (en) 2004-01-14
ATE339545T1 (en) 2006-10-15
US20040154106A1 (en) 2004-08-12
CA2443743A1 (en) 2002-10-24
DE10118346A1 (en) 2002-10-17
ES2272672T3 (en) 2007-05-01
WO2002084016A1 (en) 2002-10-24

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