EP1249280B2 - Surfaces auto-nettoyantes avec des structures hydrophobes et procédé pour leur réalisation - Google Patents

Surfaces auto-nettoyantes avec des structures hydrophobes et procédé pour leur réalisation Download PDF

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Publication number
EP1249280B2
EP1249280B2 EP02003960A EP02003960A EP1249280B2 EP 1249280 B2 EP1249280 B2 EP 1249280B2 EP 02003960 A EP02003960 A EP 02003960A EP 02003960 A EP02003960 A EP 02003960A EP 1249280 B2 EP1249280 B2 EP 1249280B2
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EP
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Prior art keywords
particles
self
process according
carrier
hydrophobic
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German (de)
English (en)
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EP1249280A2 (fr
EP1249280A3 (fr
EP1249280B1 (fr
Inventor
Edwin Dr. Nun
Markus Dr. Oles
Bernhard Dr. Schleich
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Evonik Operations GmbH
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Evonik Degussa GmbH
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D5/00—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures
    • B05D5/08—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures to obtain an anti-friction or anti-adhesive surface
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D5/00—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures
    • B05D5/08—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures to obtain an anti-friction or anti-adhesive surface
    • B05D5/083—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures to obtain an anti-friction or anti-adhesive surface involving the use of fluoropolymers
    • 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
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S977/00—Nanotechnology
    • Y10S977/70—Nanostructure
    • Y10S977/773—Nanoparticle, i.e. structure having three dimensions of 100 nm or less
    • 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
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S977/00—Nanotechnology
    • Y10S977/70—Nanostructure
    • Y10S977/778—Nanostructure within specified host or matrix material, e.g. nanocomposite films
    • Y10S977/786—Fluidic host/matrix containing nanomaterials
    • Y10S977/787—Viscous fluid host/matrix containing nanomaterials
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
    • Y10T428/24355—Continuous and nonuniform or irregular surface on layer or component [e.g., roofing, etc.]
    • Y10T428/24372—Particulate matter
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
    • Y10T428/24355—Continuous and nonuniform or irregular surface on layer or component [e.g., roofing, etc.]
    • Y10T428/24372—Particulate matter
    • Y10T428/2438—Coated
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
    • Y10T428/24355—Continuous and nonuniform or irregular surface on layer or component [e.g., roofing, etc.]
    • Y10T428/24372—Particulate matter
    • Y10T428/2438—Coated
    • Y10T428/24388—Silicon containing coating
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
    • Y10T428/24355—Continuous and nonuniform or irregular surface on layer or component [e.g., roofing, etc.]
    • Y10T428/24372—Particulate matter
    • Y10T428/24405—Polymer or resin [e.g., natural or synthetic rubber, 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
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
    • Y10T428/24355—Continuous and nonuniform or irregular surface on layer or component [e.g., roofing, etc.]
    • Y10T428/24372—Particulate matter
    • Y10T428/24413—Metal or metal compound
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
    • Y10T428/24355—Continuous and nonuniform or irregular surface on layer or component [e.g., roofing, etc.]
    • Y10T428/24372—Particulate matter
    • Y10T428/24421—Silicon containing
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/25—Web or sheet containing structurally defined element or component and including a second component containing structurally defined particles
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/25—Web or sheet containing structurally defined element or component and including a second component containing structurally defined particles
    • Y10T428/254—Polymeric or resinous material
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/25—Web or sheet containing structurally defined element or component and including a second component containing structurally defined particles
    • Y10T428/256—Heavy metal or aluminum or compound thereof
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/25—Web or sheet containing structurally defined element or component and including a second component containing structurally defined particles
    • Y10T428/259—Silicic material
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/26—Web or sheet containing structurally defined element or component, the element or component having a specified physical dimension

Definitions

  • the present invention relates to self-cleaning surfaces and methods for their production.
  • Articles having extremely difficult to wet surfaces have a number of economically important features.
  • the economically most important feature is the self-cleaning effect of difficult-to-wet surfaces, since the cleaning of surfaces is time consuming and costly.
  • Self-cleaning surfaces are therefore of the highest economic interest.
  • Adhesive mechanisms are usually conditioned by interfacial energy parameters between the two contacting surfaces. As a rule, the systems try to lower their free surface energy. If the free interfacial energies between two components are inherently very low, it can generally be assumed that the adhesion between these two components is weak. Important here is the relative lowering of the free surface energy. For pairings with high and low interfacial energy, the possibilities of interactions are very often important.
  • 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.
  • U.S. Patent 5,599,489 discloses a method in which a surface can be rendered particularly resistant by bombardment with particles of a corresponding size and subsequent perfluorination.
  • particles of fluoropolymers are applied to metal surfaces, wherein a greatly reduced wettability of the surfaces thus generated to water found with a significantly reduced tendency to icing has been.
  • WO 00/58410 describes the structures and claims the formation thereof by spraying hydrophobic alcohols such as nonakosan-10-ol or alkanediols such as nonakosan-5,10-diol.
  • hydrophobic alcohols such as nonakosan-10-ol or alkanediols such as nonakosan-5,10-diol.
  • the disadvantage here is the lack of stability of the self-cleaning surfaces, since detergents lead to the replacement of the structure.
  • EP 1 040 874 A2 describes the imprinting of microstructures and claims the use of such structures in analytics (microfluidics). A disadvantage of these structures is the insufficient mechanical stability.
  • EP 0 934 865 A2 describes a water repellant product and its preparation wherein the debris repellent surface is prepared by applying a film to the surface to be treated comprising fine particles of metal oxide and the hydrolyzate of a metal alkoxide or chelate. To solidify this film, the substrate to which the film has been applied must be sintered at temperatures above 400 ° C. The method can therefore only be used for substrates which are stable even at temperatures above 400 ° C.
  • WO 00/39 239 it is described a process for producing a surface with ultraphobic properties in which one coated with Ni (OH) 2 - particles, optionally coated with a primer and then provided with a hydrophobic and / or oleophobic coating.
  • the object of the present invention was to provide particularly well self-cleaning surfaces with structures in the nanometer range, as well as a simple method for producing such self-cleaning surfaces.
  • an object of the present invention to provide a method for producing self-cleaning surfaces, in which the coated material must be exposed to only low chemical or physical loads.
  • the subject of the present invention is therefore a self-cleaning surface which has an artificial, at least partially hydrophobic surface structure of elevations and depressions wherein the elevations and depressions are formed by means of a carrier on the surface fixed particles, which is characterized in that the particles have a fissured structure with elevations and / or depressions in the nanometer range.
  • the present invention also provides a process for the production of self-cleaning surfaces, in which a suitable, at least partially hydrophobic surface structure is provided by fixing particles by means of a carrier on a surface, which is characterized in that particles, the rugged structures with elevations and / or depressions in the nanometer range can be used.
  • a further advantage of the method according to the invention is that scratch-sensitive surfaces during application of the particles are not damaged by particles present in the carrier since the use of paints and subsequent application of the particles to the carrier already protect the scratch-sensitive surface by the carrier.
  • the self-cleaning surface according to the invention which has an artificial, at least partially hydrophobic surface structure of elevations and depressions, wherein the elevations and depressions are formed by particles fixed on the surface by means of a carrier, is characterized in that the particles have a rugged structure with elevations and or pits in the nanometer range aur mars.
  • the elevations have on average a height of 20 to 500 nm, particularly preferably of 50 to 200 nm.
  • the spacing of the elevations or depressions on the particles is preferably less than 500 nm, very particularly preferably less than 200 nm.
  • the rugged structures with elevations and / or pits in the nanometer range can be e.g. cavities, pores, grooves, peaks and / or spikes are formed.
  • the particles themselves have an average size of less than 50 .mu.m, preferably of less than 30 .mu.m and most preferably of less than 20 .mu.m.
  • the particles have a BET surface area of 50 to 600 square meters per gram. Most preferably, the particles have a BET surface area of 50 to 200 m 2 / g.
  • the particles comprise at least one material selected from silicates, doped silicates, minerals, metal oxides, silicas, polymers and silica-coated metal powders.
  • Aerosil R 974 preferably having a particle size of 1 ⁇ m or pulverulent polymers, such as, for example, cryogenically ground or spray-dried polytetrafluoroethylene (PTFE) or perfluorinated copolymers or copolymers with tetrafluoroethylene, on.
  • PTFE polytetrafluoroethylene
  • the particles preferably also have hydrophobic properties in addition to the fissured structures in order to generate the self-cleaning surfaces.
  • the particles themselves may be hydrophobic, e.g. PTFE-containing particles, or the particles used may have been rendered hydrophobic.
  • the hydrophobing of the particles can be carried out in a manner known to those skilled in the art.
  • Typical hydrophobized particles are e.g. Fine powders such as Aerosil-R 8200 (Degussa AG), which are available for purchase.
  • the preferably used silicic acids preferably have a dibutyl phthalate adsorption, based on DIN 53 601, of between 100 and 350 ml / 100 g, preferably values between 250 and 350 ml / 100 g.
  • the particles are fixed to the surface by means of a carrier.
  • the self-cleaning surface can be generated.
  • the support is a lacquer cured by means of thermal energy and / or light energy, a two-component lacquer system or another reactive lacquer system, wherein the curing preferably takes place by polymerization or crosslinking.
  • the cured lacquer particularly preferably comprises polymers and / or copolymers of mono- and / or polyunsaturated acrylates and / or methacrylates.
  • the mixing ratios can be varied within wide limits. It is also possible that the cured lacquer compounds having functional groups, such as hydroxyl groups, epoxide groups, amine groups, or fluorine-containing compounds, such as perfluorinated esters of acrylic acid.
  • lacquer and hydrophobic particles such as Aerosil R 8200 by means of N- [2- (acryloyloxy) ethyl] -N-ethylperfluoroctan-1-sulfonklamid be coordinated.
  • lacquers not only lacquers based on acrylic resin can be used, but also lacquers based on polyurethane or lacquers which have polyurethane acrylates or silicone acrylates.
  • the self-cleaning surfaces according to the invention have an unrolling angle of less than 20 °, particularly preferably less than 10 °, the unrolling angle being defined such that a drop of water applied from a 1 cm height rolls onto a plane surface resting on an inclined plane.
  • the advancing angle and the retreating angle are above 140 °, preferably above 150 ° and have a hysteresis of less than 15 °, preferably less than 10 °. Because the surfaces according to the invention have an advancing and retreating angle above at least 140 °, preferably above 150 °, particularly good self-cleaning surfaces become accessible.
  • the self-cleaning surfaces are semitransparent.
  • the surfaces according to the invention can be contact-transparent, that is to say that after the creation of a surface according to the invention on a labeled object, this inscription, depending on the size of the writing, can still be read.
  • the self-cleaning surfaces according to the invention are preferably produced by the process according to the invention for producing these surfaces.
  • This inventive method for producing self-cleaning surfaces in which a suitable, at least partially hydrophobic surface structure is created by fixing particles by means of a carrier on a surface, is characterized in that particles, the rugged structures with elevations and / or depressions in the nanometer range have to be used.
  • those particles which comprise at least one material selected from silicates, doped silicates, minerals, metal oxides, silicic acids or polymers are used.
  • the particles very particularly preferably have pyrogenic silicates or silicic acids, in particular aerosils, minerals such as magadiite Al 2 O 3 , SiO 2 , TiO 2 , ZrO 2 with Zn powder coated with Aerosil R 974 or pulverulent polymers, such as, for example, cryogenically ground or spray-dried polytetrafluoroethylene (PTFE).
  • PTFE polytetrafluoroethylene
  • Particles having a BET surface area of 50 to 600 m 2 / g are used. Very particular preference is given to using particles which have a BET surface area of from 50 to 200 m 2 / g.
  • the particles preferably also have hydrophobic properties in addition to the fissured structures in order to generate the self-cleaning surfaces.
  • the particles themselves may be hydrophobic, e.g. PTFE-containing particles, or the particles used may have been rendered hydrophobic.
  • the hydrophobing of the particles can be carried out in a manner known to those skilled in the art.
  • Typical hydrophobized particles are e.g. Fine powders such as Aerosil R 974 or Aerosil-R 8200 (Degussa AG), which are available for purchase.
  • the application of the curable substance may e.g. by spraying, knife coating, painting or spraying done.
  • the curable substance is applied in a thickness of 1 to 100 microns, preferably in a thickness of 5 to 50 microns.
  • the viscosity of the curable substance it may be advantageous to allow the substance to harden or to dry before the particles are applied.
  • the viscosity of the curable substance is chosen so that the applied particles can at least partially sink into the curable substance, but the curable substance or the particles applied to it no longer run when the surface is placed vertically.
  • the application of the particles can be carried out by conventional methods such as spraying or powdering.
  • the application of the particles can be effected by spraying using an electrostatic spray gun.
  • excess particles that is to say particles which do not adhere to the curable substance, can be removed from the surface by shaking, brushing or blowing off. These particles can be collected and reused.
  • the curable substance used may be a lacquer which comprises at least mixtures of mono- and / or polyunsaturated acrylates and / or methacrylates.
  • the mixing ratios can be varied within wide limits. Particular preference is given to using a lacquer curable by means of thermal or chemical energy and / or light energy.
  • a lacquer or a lacquer system is selected which has hydrophobic properties if the particles used have hydrophobic properties.
  • a lacquer is selected which has hydrophilic properties when the particles used have hydrophilic properties.
  • the mixtures used as lacquer have compounds with functional groups, such as, for example, hydroxyl groups, epoxide groups, amine groups or fluorine-containing compounds, for example perfluorinated esters of acrylic acid.
  • functional groups such as, for example, hydroxyl groups, epoxide groups, amine groups or fluorine-containing compounds, for example perfluorinated esters of acrylic acid.
  • hydrophobic particles such as Aerosil VPR 411 using N- [2- (acryloyloxy) ethyl] -N-ethylperfluoroctan-1-sulfonic acid amide matched become.
  • curable substances not only acrylic resin-based paints can be used, but also polyurethane-based paints, or polyurethane acrylates or silicone acrylates. It is likewise possible to use two-component coating systems or other reactive coating systems as curable substances.
  • the fixing of the particles on the carrier takes place by hardening of the carrier, this being done, depending on the paint system used, preferably by thermal and / or chemical energy and / or light energy.
  • the hardening of the support triggered by chemical or thermal energy and / or light energy, may be e.g. by polymerization or crosslinking of the components of the paints or paint systems.
  • the carrier is particularly preferably cured by light energy, and the carrier is most preferably polymerized by the light of an Hg medium-pressure lamp in the UV range.
  • the curing of the support takes place under an inert gas atmosphere, most preferably under a nitrogen atmosphere.
  • the curable substance is cured within 0.1 to 10 minutes, preferably within 1 to 5 minutes after application of the particles.
  • particles which have hydrophobic properties and / or which have hydrophobic properties by treatment with at least one compound from the group of alkylsilanes, alkyldisilazanes or perfluoroalkylsilanes.
  • the hydrophobization of particles is known and may be e.g. in the series Pigments, number 18, the Degussa AG be read.
  • the particles of the treated surface are treated by treatment with at least one compound selected from the group consisting of alkylsilanes, perfluoroalkylsilanes, e.g. available from Sivento GmbH, are equipped with hydrophobic properties.
  • the treatment is carried out by subjecting the particle-bearing surface to be hydrophobicized to a solution containing a hydrophobing reagent, such as e.g. Alkylsilane has, is dipped, excess hydrophobing reagent is drained and the surface is annealed at the highest possible temperature.
  • a hydrophobing reagent such as e.g. Alkylsilane has
  • the process according to at least one of claims 8 to 17 can be used excellently for producing self-cleaning surfaces on planar or non-planar objects, in particular on non-planar objects. This is only possible to a limited extent with the conventional methods. In particular, by methods in which prefabricated films are applied to a surface or in processes in which a structure is to be created by embossing, are non-planar objects, such as. Sculptures, not or only partially accessible. Naturally, however, the process according to the invention can also be used to produce self-cleaning surfaces on objects with planar surfaces, such as e.g. Greenhouses or public transport.
  • the use of the method according to the invention for the production of self-cleaning surfaces on greenhouses has advantages since the method self-cleaning surfaces e.g. can also be produced on transparent materials such as glass or Plexiglas® and the self-cleaning surface can be formed at least as transparent that sufficient sunlight can penetrate through the equipped with a self-cleaning surface transparent surface for the growth of the plants in the greenhouse.
  • greenhouses having a surface according to the invention according to one of claims 1 to 7, can be operated with longer cleaning intervals.
  • the method of the invention may also be used to make self-cleaning surfaces on non-rigid surfaces of articles, such as e.g. Umbrellas or other surfaces that are kept flexible.
  • the method according to the invention can be used according to at least one of claims 8 to 17, for the production of self-cleaning surfaces on flexible or inflexible walls in the sanitary area.
  • Such walls can e.g. Partitions in public toilets, walls of shower cubicles, swimming pools or saunas, but also shower curtains (flexible wall) be.
  • Fig. 1 shows a SEM image of the aluminum oxide aluminum oxides C (Degussa AG).
  • Fig. 2 shows a SEM image of the surface of particles of silica Sipernat FK 350 (Degussa AG) on a support.
  • the support was cured at a wavelength of 308 nm under nitrogen. After curing the backing, excess Aerosil VPR 411 was brushed off. The characterization of the surface was initially visual and is logged with +++. +++ means, water droplets are almost completely formed. The roll-off angle was 2.4 °. Progressive and retreatment angles greater than 150 ° each were measured. The associated hysteresis is below 10 °.
  • Example 1 The experiment of Example 1 was repeated, wherein particles of aluminum oxide C (Degussa AG), an aluminum oxide having a BET surface area of 100 m 2 / g, were sprayed electrostatically. After curing of the carrier according to Example 1 and scrubbing of excess particles, the cured, brushed plate for hydrophobing in a formulation of Tridecafluoroctyltriethoxysilane in ethanol (Dynasilan 8262, Sivento GmbH) was immersed. After draining off excess Dynasilan 8262, the plate was annealed at a temperature of 80 ° C. The surface is rated ++, ie the shape of the water droplets is not ideal, the rolling angle is below 20 °.
  • Aluminum oxide C Degussa AG
  • BET surface area 100 m 2 / g
  • Silica acid Sipernat 350 from Degussa AG is sprinkled onto the support-treated plate from Example 1. After a penetration time of 5 minutes, the treated plate is cured under nitrogen in UV light at 308 nm. Excess particles are brushed off again and the plate is then immersed again in Dynasilan 8262 and then annealed at 80 ° C. The surface is classified as +++.
  • Example 1 The experiment of Example 1 is repeated, but instead of Aerosil VPR 411 Aerosil R 8200 (Degussa AG), which uses a BET surface area of 200 ⁇ 25 m 2 / g.
  • the assessment of the surface is +++.
  • the roll angle has been determined to be 1.3 °.
  • progression and retraction angles were measured, each of which exceeded 150 °.
  • the associated hysteresis is below 10 °.
  • the rolling angle was 0.5 °. Progressive and retreatment angles greater than 150 ° each were measured. The associated hysteresis is below 10 °.
  • Example 1 On the dried support of Example 1 applied in a thickness of 200 ⁇ is a suspension of 10 wt .-% spray-dried fumed silica, Aeroperl 90 / 30Degussa AG, a silica having a BET surface area of 90 m 2 / g, in ethanol, knife.
  • the surface After curing in UV light and treatment with the hydrophobing agent Dynasilan 8262, the surface is evaluated only with +, ie, the droplet forms poorly and sticks to high angles of inclination at the surface.
  • the poor cleaning effect is due to the smearing of the fissured structures. This is probably done by dissolving monomers of the not yet cured paint system in ethanol. The ethanol vaporizes before curing and the monomers remain in the fissured structures where they also harden during the hardening process, thereby greasing and filling the fissured structures. In this way, the self-cleaning effect deteriorates significantly.

Landscapes

  • Paints Or Removers (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)
  • Cleaning Implements For Floors, Carpets, Furniture, Walls, And The Like (AREA)
  • Laminated Bodies (AREA)
  • Treatments Of Macromolecular Shaped Articles (AREA)
  • Cleaning Or Drying Semiconductors (AREA)

Claims (19)

  1. Surface auto-nettoyante constituée d'une structure superficielle artificielle, au moins partiellement hydrophobe, la structure superficielle étant formée par des particules fixées sur la surface au moyen d'un support durci,
    caractérisée en ce que
    les particules comportent une structure fissurée avec des saillies et/ou creux dans le domaine du nanomètre sous la forme de cavités, de pores, de cannelures, de pointes et/ou de dentelures et une surface BET de 50 à 600 m2/g.
  2. Surface auto-nettoyante selon la revendication 1,
    caractérisée en ce que
    le support est un vernis durci au moyen d'énergie thermique ou chimique ou encore d'énergie lumineuse.
  3. Surface auto-nettoyante selon l'une des revendications 1 ou 2,
    caractérisée en ce que
    le vernis durci comporte des mélanges d'acrylates et/ou de méthacrylates mono- et/ou poly- insaturés, ou encore du polyuréthane.
  4. Surface auto-nettoyante selon au moins une des revendications 1 à 3,
    caractérisée en ce que
    les particules présentent une taille moyenne inférieure à 50 µm.
  5. Surface auto-nettoyante selon la revendication 4,
    caractérisée en ce que
    les particules présentent une taille moyenne inférieure à 30 µm.
  6. Surface auto-nettoyante selon au moins une des revendications 1 à 5,
    caractérisée en ce que
    les particules sont constituées d'un matériau sélectionné parmi les substances suivantes : silicates, silicates dopés, minéraux, oxydes métalliques, acides siliciques, polymères et poudres métalliques.
  7. Surface auto-nettoyante selon la revendication 6,
    caractérisée en ce que
    les particules présentent des propriétés hydrophobes.
  8. Procédé de production de surfaces auto-nettoyantes, selon lequel une structure superficielle appropriée, au moins partiellement hydrophobe, est créée par fixation de particules au moyen d'un support sur une surface,
    caractérisé par
    les étapes suivantes :
    a) mise en place d'une substance durcissable comme support sur une surface,
    b) mise en place de particules, comportant une structure fissurée avec des saillies et/ou creux dans le domaine du nanomètre sous la forme de cavités, de pores, de cannelures, de pointes et/ou de dentelures et une surface BET de 50 à 600 m2/g, sur le support,
    c) fixation des particules par durcissement du support.
  9. Procédé selon la revendication 8,
    caractérisé en ce qu'
    on utilise au moins un matériau sélectionné parmi les substances suivantes : silicates, silicates dopés, minéraux, oxydes métalliques, acides siliciques, poudres métalliques ou polymères.
  10. Procédé selon la revendication 9,
    caractérisé en ce que
    le durcissement du support s'effectue au moyen d'énergie thermique ou chimique et/ou d'énergie lumineuse.
  11. Procédé selon la revendication 9 ou 10,
    caractérisé en ce que
    comme substance durcissable on utilise un vernis qui comporte au moins des mélanges d'acrylates et/ou de méthacrylates insaturés une fois ou plusieurs fois et/ou des polyuréthanes et/ou des acrylates de silicone et/ ou des acrylates d'uréthane.
  12. Procédé selon la revendication 11,
    caractérisé en ce que
    comme substance durcissable on sélectionne un vernis qui présente des propriétés hydrophobes lorsque les particules utilisées présentent des propriétés hydrophobes, et qui présente des propriétés hydrophiles lorsque les particules utilisées présentent des propriétés hydrophiles.
  13. Procédé selon au moins une des revendications 8 à 12,
    caractérisé en ce qu'
    on utilise des particules présentant des propriétés hydrophobes.
  14. Procédé selon au moins une des revendications 8 à 13,
    caractérisé en ce qu'
    on utilise des particules qui, par traitement à l'aide d'au moins un composé du groupe formé par les alkylsilanes, les perfluoralkylsilanes ou les alkyldisilazanes, présentent des propriétés hydrophobes.
  15. Procédé selon au moins une des revendications 8 à 14,
    caractérisé en ce que
    les particules, après fixation sur le support, sont pourvues de propriétés hydrophobes.
  16. Procédé selon là des revendication 15,
    caractérisé en ce que
    par traitement à l'aide d'au moins un composé du groupe formé par les alkylsilanes, les perfluoralkylsilanes ou les alkyldisilazanes, les particules sont pourvues de propriétés hydrophobes.
  17. Utilisation du procédé selon au moins une des revendication 8 à 16, pour la production de surfaces auto-nettoyantes sur des objets planaires ou non planaires.
  18. Utilisation du procédé selon au moins une des revendication 8 à 16, pour la production de surfaces auto-nettoyantes sur des surfaces non rigides d'objets.
  19. Utilisation du procédé selon au moins une des revendication 8 à 16, pour la production de surfaces auto-nettoyantes sur des parois flexibles ou rigides dans le domaine sanitaire.
EP02003960A 2001-04-12 2002-02-22 Surfaces auto-nettoyantes avec des structures hydrophobes et procédé pour leur réalisation Expired - Lifetime EP1249280B2 (fr)

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DE10118352A DE10118352A1 (de) 2001-04-12 2001-04-12 Selbstreinigende Oberflächen durch hydrophobe Strukturen und Verfahren zu deren Herstellung

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US20020150724A1 (en) 2002-10-17
JP2002346469A (ja) 2002-12-03
EP1249280A2 (fr) 2002-10-16
EP1249280A3 (fr) 2003-01-02
DE50208229D1 (de) 2006-11-09
US6858284B2 (en) 2005-02-22
ES2271131T3 (es) 2007-04-16
ES2271131T5 (es) 2009-10-30
EP1249280B1 (fr) 2006-09-27
CA2381134A1 (fr) 2002-10-12
DE10118352A1 (de) 2002-10-17
ATE340654T1 (de) 2006-10-15

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