EP1249280A2 - 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
EP1249280A2
EP1249280A2 EP02003960A EP02003960A EP1249280A2 EP 1249280 A2 EP1249280 A2 EP 1249280A2 EP 02003960 A EP02003960 A EP 02003960A EP 02003960 A EP02003960 A EP 02003960A EP 1249280 A2 EP1249280 A2 EP 1249280A2
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EP
European Patent Office
Prior art keywords
particles
self
carrier
cleaning
hydrophobic
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EP02003960A
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German (de)
English (en)
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EP1249280A3 (fr
EP1249280B2 (fr
EP1249280B1 (fr
Inventor
Edwin Dr. Nun
Markus Dr. Oles
Bernhard Dr. Schleich
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Evonik Operations GmbH
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Creavis Gesellschaft fuer Technologie und Innovation mbH
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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
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    • 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
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    • 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.
  • Objects with extremely difficult to wet surfaces have a number of economical ones significant features.
  • the most economically significant feature is the self-cleaning effect of difficult to wet surfaces, because the cleaning of Surface is time and cost intensive.
  • Self-cleaning surfaces are therefore of the highest quality economic interest.
  • Detention mechanisms are usually through interfacial energy parameters between the two surfaces in contact.
  • the systems try to lower their free interface energy. Lie the free interface energies between two components are inherently very low, So it can generally be assumed that the liability between these two Components is weak.
  • the relative lowering of the free is important Interfacial energy. For pairings with a high and a low interfacial energy the possibilities of interactions are very 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 Process in which a surface is bombarded with particles of an appropriate size and subsequent perfluorination can be made particularly repellent.
  • Another Methods describe H. Saito et al in "Service Coatings International" 4, 1997, p. 168 ff.
  • particles of fluoropolymers are applied to metal surfaces, with a strong reduced wettability of the surfaces thus produced against water with a considerably reduced tendency to icing was found.
  • US Pat. Nos. 3,354,022 and WO 96/04123 describe further methods for lowering the Wettability of objects due to topological changes in the surfaces described.
  • artificial elevations or depressions with a height of approx. 5 up to 1 000 ⁇ m and a distance of approx. 5 to 500 ⁇ m on hydrophobic or after Structuring applied hydrophobic materials.
  • Surfaces of this type lead to a rapid drop formation, the rolling drops absorbing dirt particles and thus clean the surface.
  • EP 1 040 874 A2 describes the stamping of microstructures and claims them Use of such structures in analysis (microfluidics). A disadvantage of these structures is the insufficient mechanical stability.
  • JP 11171592 describes a water-repellent product and its production, the dirt-repellent surface is produced by a film on the treating surface is applied, the fine particles of metal oxide and the hydrolyzate a metal alkoxide or chelate. To solidify this film, the substrate, to which the film was applied are sintered at temperatures above 400 ° C. The method can therefore only be used for substrates that are also at temperatures above of 400 ° C are stable.
  • the object of the present invention was to provide particularly good self-cleaning Surfaces with structures in the nanometer range, as well as a simple process for Manufacture of such self-cleaning surfaces.
  • the present invention therefore relates to a self-cleaning surface which has a artificial, at least partially hydrophobic surface structure from surveys and Has depressions, the elevations and depressions by means of a carrier fixed surface particles are formed, which is characterized in that the Particles a fissured structure with elevations and / or depressions in the nanometer range exhibit.
  • the present invention also relates to a method for producing self-cleaning surfaces where a suitable, at least partially hydrophobic Surface structure by fixing particles on a surface using a carrier is created, which is characterized in that particles, the jagged structures with elevations and / or depressions in the nanometer range can be used.
  • Self-cleaning surfaces are accessible through the method according to the invention Show particles with a jagged structure.
  • particles which have a rugged structure surfaces are easily accessible that up to are structured in the nanometer range.
  • To maintain this structure in the nanometer range it is necessary that the particles do not pass through the carrier with which they are on the surface are fixed, are wetted, otherwise the structure in the nano range would be lost.
  • Another advantage of the method according to the invention is that it is scratch-sensitive Surfaces when applying the particles are not caused by particles present in the carrier is damaged because when using paints and then applying the Particles on the carrier, the scratch-sensitive surface is already protected by the carrier.
  • the self-cleaning surface according to the invention which is an artificial, at least partially Has hydrophobic surface structure of elevations and depressions, the Elevations and depressions by particles fixed on the surface by means of a carrier are characterized in that the particles have a jagged structure Show elevations and / or depressions in the nanometer range.
  • the Increases on average a height of 20 to 500 nm, particularly preferably from 50 to 200 nm on.
  • the distance between the elevations or depressions on the particles is preferably less than 500 nm, very particularly preferably less than 200 nm.
  • the jagged structures with elevations and / or depressions in the nanometer range can e.g. over cavities, pores, grooves, tips and / or peaks are formed.
  • the Particles themselves have an average size of less than 50 ⁇ m, preferably of smaller size 30 ⁇ m and very particularly preferably from less than 20 ⁇ m.
  • the particles preferably have a BET surface area of 50 to 600 square meters per gram. Very particularly preferably the particles have a BET surface area of 50 to 200 m 2 / g.
  • the particles preferably have at least one material selected from silicates, doped silicates, minerals, metal oxides, silicas, polymers and metal powders coated with silicic acid.
  • the particles very particularly preferably have pyrogenic silicas or precipitated silicas, in particular aerosils, Al 2 O 3 , SiO 2 , TiO 2 , ZrO 2 , zinc powder coated with Aerosil R974, preferably with a particle size of 1 ⁇ m or powdery polymers, such as cryogenically ground or spray-dried polytetrafluoroethylene (PTFE) or perfluorinated copolymers or copolymers with tetrafluoroethylene.
  • PTFE polytetrafluoroethylene
  • the particles for generating the self-cleaning surfaces preferably have in addition to the rugged structures also have hydrophobic properties.
  • the particles can themselves be hydrophobic, e.g. Particles containing PTFE, or the particles used can have been made hydrophobic.
  • the hydrophobicization of the particles can be done by a person skilled in the art known way.
  • Typical hydrophobized particles are e.g. Very fine powder like Aerosil-R 8200 (Degussa AG), which can be purchased.
  • the preferably used silicas preferably have a dibutyl phthalate adsorbtion, 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 to generate.
  • the carrier is a lacquer hardened by means of thermal energy and / or light energy Two-component paint system or another reactive paint system, the curing preferably carried out by polymerization or crosslinking.
  • the mixing ratios can be in wide limits can be varied. It is also possible that the hardened paint connections with functional groups, e.g. Hydroxy groups, epoxy groups, amine groups, or fluorine-containing compounds, e.g. perfluorinated esters of acrylic acid.
  • Varnishes are not just varnishes Acrylic resin base can be used, but also varnishes based on polyurethane or varnishes that Have polyurethane acrylates or silicone acrylates.
  • the self-cleaning surfaces according to the invention have a roll angle of less 20 °, particularly preferably less than 10 °, the roll angle being defined such that one from 1 cm height on a flat surface resting on an inclined plane Water drops roll off.
  • the progression angle and the retreat angle are above 140 °, preferably above 150 ° and have a hysteresis of less than 15 °, preferably less 10 ° on. Because the surfaces according to the invention have a progressive and Have retraction angles above at least 140 °, preferably above 150 °, particularly good self-cleaning surfaces become accessible.
  • the self-cleaning surfaces are semi-transparent.
  • the surfaces according to the invention can be contact-transparent, that is to say after Creating a surface according to the invention on a labeled object Lettering, depending on the size of the font, is still legible.
  • the self-cleaning surfaces according to the invention are preferably by Process according to the invention for producing these surfaces.
  • This Process according to the invention for producing self-cleaning surfaces in which a suitable, at least partially hydrophobic surface structure by fixing particles is created on a surface by means of a carrier, characterized in that Particles, the fissured structures with elevations and / or depressions in the Have nanometer range, are used.
  • Those particles which have at least one material selected from silicates, doped silicates, minerals, metal oxides, silicas or polymers are preferably used.
  • the particles very particularly preferably have pyrogenic silicates or silicas, in particular aerosils, minerals such as magadiite Al 2 O 3 , SiO 2 , TiO 2 , ZrO 2, Zn powder coated with Aerosil R 974 or powdery polymers, such as, for example, cryogenically ground or spray-dried polytetrafluoroethylene (PTFE).
  • Particles with a BET surface area of 50 to 600 m 2 / g are particularly preferably used. Particles which have a BET surface area of 50 to 200 m 2 / g are very particularly preferably used.
  • the particles for generating the self-cleaning surfaces preferably have in addition to the rugged structures also have hydrophobic properties.
  • the particles can themselves be hydrophobic, e.g. Particles containing PTFE, or the particles used can have been made hydrophobic.
  • the hydrophobicization of the particles can be done by a person skilled in the art known way.
  • Typical hydrophobized particles are e.g. Very fine powder like Aerosil R 974 or Aerosil-R 8200 (Degussa AG), which can be purchased.
  • the curable substance can e.g. by spraying, knife coating, spreading or spraying.
  • the curable substance is in a thickness of 1 to 100 microns, preferably applied in a thickness of 5 to 50 microns.
  • the viscosity of the curable substance it may be advantageous to apply the substance before applying the particles to harden or let dry.
  • the viscosity of the curable substance will be like this chosen that the applied particles sink at least partially into the curable substance but the curable substance or the particles applied to it no longer run, when the surface is placed vertically.
  • the particles can be applied by conventional methods such as spraying or powdering respectively.
  • the particles can be applied by spraying using an electrostatic spray gun. After applying the particles you can excess particles, i.e. particles that do not adhere to the hardenable substance, by shaking, Brushing or blowing off the surface. These particles can be collected and be used again.
  • a varnish can be used as the carrier, which at least mixtures of simple and / or has polyunsaturated acrylates and / or methacrylates become.
  • the mixing ratios can be varied within wide limits.
  • a curable by means of thermal or chemical energy and / or light energy is preferred Paint used.
  • a varnish or a varnish system is selected as the curable substance, the hydrophobic Has properties if the particles used have hydrophobic properties. Conversely, a varnish with hydrophilic properties is selected as the curable substance if the particles used have hydrophilic properties.
  • the mixtures used as paint have compounds with functional groups, e.g. Hydroxy groups, epoxy groups, amine groups or fluorine-containing compounds, e.g. perfluorinated esters of acrylic acid.
  • functional groups e.g. Hydroxy groups, epoxy groups, amine groups or fluorine-containing compounds, e.g. perfluorinated esters of acrylic acid.
  • hydrophobic particles such as Aerosil VPR 411 matched to one another by means of N- [2- (acryloyloxy) ethyl] -N-ethylperfluorooctane-1-sulfonamide become.
  • two-component paint systems or other reactive paint systems can be used.
  • the particles are fixed on the carrier by hardening the carrier according to the paint system used, preferably by thermal and / or chemical energy and / or light energy takes place.
  • Hardening of the carrier triggered by chemical or thermal energy and / or light energy, e.g. by polymerization or crosslinking the Components of the paints or paint systems are made.
  • the curable substance is preferably applied within 0.1 to 10 minutes, preferably hardened within 1 to 5 minutes after application of the particles.
  • particles to use which have hydrophobic properties and / or by treatment with at least one compound from the group of alkylsilanes, alkyldisilazanes or Perfluoroalkylsilanes have hydrophobic properties.
  • the hydrophobization of particles is known and can e.g. in the Pigments series, number 18, by Degussa AG be looked up.
  • the particles of the treated Surface by treatment with at least one compound from the group of Alkylsilanes, the perfluoroalkylsilanes, e.g. are available from Sivento GmbH with hydrophobic properties.
  • the treatment is preferably carried out in that the particle-containing surface that is to be hydrophobicized into a Solution containing a water repellent such as e.g. Has alkylsilanes, is immersed, Excess water repellent is drained and the surface at a annealed as high as possible.
  • the maximum applicable temperature is by the Softening temperatures of carrier or substrate limited.
  • the inventive method according to at least one of claims 8 to 17 can excellent for producing self-cleaning surfaces on planar or non-planar Objects, especially on non-planar objects. This is with the conventional methods only possible to a limited extent. In particular about procedures at where prefabricated films are applied to a surface or in processes in which a structure to be created by embossing are non-planar objects, such as Sculptures, not or only partially accessible.
  • the invention can Process for the production of self-cleaning surfaces on objects with planar surfaces, e.g. Greenhouses or public transport become.
  • the use of the method according to the invention for the production of Self-cleaning surfaces on greenhouses have advantages because of the process self-cleaning surfaces e.g.
  • the method according to the invention can also be used to produce self-cleaning Surfaces on non-rigid surfaces of objects, such as e.g. Umbrellas or other surfaces that are kept flexible.
  • objects such as e.g. Umbrellas or other surfaces that are kept flexible.
  • inventive method according to at least one of claims 8 to 17, for Production of self-cleaning surfaces on flexible or inflexible walls in the Sanitary area can be used.
  • Such walls can e.g. Partitions in public Toilets, walls of shower cubicles, swimming pools or saunas, but also shower curtains (flexible wall).
  • 1 and 2 are scanning electron microscopic (SEM) images of as Structured particles used reproduced.
  • FIG. 2 shows an SEM image of the surface of particles of silica Sipernat FK 350 (Degussa AG) on a carrier.
  • the support was at a wavelength of 308 nm under nitrogen hardened. After the carrier had hardened, excess Aerosil VPR 411 was brushed off. The surface was initially characterized visually and is logged with +++. +++ means that water drops form almost completely. The roll angle was 2.4 °. The advancing and retreating angles were measured to be greater than 150 ° each. The associated Hysteresis is below 10 °.
  • Example 2 The experiment from Example 1 was repeated, particles of aluminum oxide C (Degussa AG), an aluminum oxide with a BET surface area of 100 m 2 / g, being sprayed on electrostatically.
  • the carrier had cured in accordance with Example 1 and excess particles had been brushed off
  • the hardened, brushed plate was immersed in a formulation of tridecafluorooctyltriethoxysilane in ethanol (Dynasilan 8262, Sivento GmbH) to make it hydrophobic.
  • the plate After draining excess Dynasilan 8262, the plate was annealed at a temperature of 80 ° C. The surface is classified with ++, which means that the shape of the water drops is not ideal, the roll angle is below 20 °.
  • Silica Sipernat 350 is added to the plate from Example 1 treated with the support Degussa AG spread. After 5 minutes of penetration, the treated plate under nitrogen in UV light hardened at 308 nm. Excess particles are brushed off and the The plate is then again immersed in Dynasilan 8262 and then at 80 ° C annealed The surface is classified with +++.
  • Aerosil VPR 411 Aerosil R 8200 (Degussa AG) is used, which has a BET surface area of 200 ⁇ 25 m 2 / g.
  • the evaluation of the surface is +++.
  • the roll angle has been determined to be 1.3 °.
  • Progress and retreat angles were also measured, each of which was greater than 150 °.
  • the associated hysteresis is below 10 °.
  • Example 2 The varnish from Example 1, which had already been mixed with the UV hardener, was added 10 wt .-% (based on the total weight of the paint mixture) 2- (N-ethylperfluorooctanesulfonamido) ethyl acrylate added. This mixture was at least 60 again stirred for min. This mixture was used as a carrier on a 2 mm thick PMMA plate in a 50 ⁇ m thickness applied. The layer was dried for 5 minutes. Then were as particles hydrophobicized, pyrogenic silica Aerosil VPR 411 (Degussa AG) by means of a electrostatic spray gun sprayed on. After 3 minutes the support became at one wavelength hardened from 308 nm under nitrogen. After the carrier hardened, excess became Aerosil VPR 411 brushed. The surface was initially characterized visually and is logged with +++. +++ means that water drops form almost completely.
  • the roll angle was 0.5 °. Progress and retreat angles were measured at each greater than 150 °. The associated hysteresis is below 10 °.
  • the bad cleaning effect is due to the smearing of the jagged structures due. This is probably not done by dissolving monomers of the yet hardened paint system in ethanol. Before curing, the ethanol and the evaporates Monomers remain in the jagged structures in which they harden during the process also harden, whereby the jagged structures are smeared or filled. 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)
  • Treatments Of Macromolecular Shaped Articles (AREA)
  • Cleaning Or Drying Semiconductors (AREA)
  • Laminated Bodies (AREA)
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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CN111484723A (zh) * 2020-05-14 2020-08-04 上海金山锦湖日丽塑料有限公司 一种自清洁阻燃pc树脂及其制备方法
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CN111484723B (zh) * 2020-05-14 2022-09-16 上海金山锦湖日丽塑料有限公司 一种自清洁阻燃pc树脂及其制备方法
CN111763100A (zh) * 2020-06-10 2020-10-13 大理大学 一种天然青石自清洁表面的制备方法
CN111763100B (zh) * 2020-06-10 2021-10-26 大理大学 一种天然青石自清洁表面的制备方法

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EP1249280A3 (fr) 2003-01-02
US20020150724A1 (en) 2002-10-17
ATE340654T1 (de) 2006-10-15
CA2381134A1 (fr) 2002-10-12
EP1249280B2 (fr) 2009-07-01
JP2002346469A (ja) 2002-12-03
DE50208229D1 (de) 2006-11-09
ES2271131T3 (es) 2007-04-16
DE10118352A1 (de) 2002-10-17
US6858284B2 (en) 2005-02-22
EP1249280B1 (fr) 2006-09-27

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