EP1249280B1 - Self-cleaning surfaces with hydrophobic structures and process for making them - Google Patents
Self-cleaning surfaces with hydrophobic structures and process for making them Download PDFInfo
- Publication number
- EP1249280B1 EP1249280B1 EP02003960A EP02003960A EP1249280B1 EP 1249280 B1 EP1249280 B1 EP 1249280B1 EP 02003960 A EP02003960 A EP 02003960A EP 02003960 A EP02003960 A EP 02003960A EP 1249280 B1 EP1249280 B1 EP 1249280B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- particles
- self
- process according
- carrier
- hydrophobic
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
Images
Classifications
-
- 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.
- 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., Service Coatings International 4, 1997, p. 168 et seq.
- particles of fluoropolymers are applied to metal surfaces, whereby a markedly reduced wettability of the surfaces thus produced to water has been determined with a considerably reduced tendency to freeze.
- U.S. Patent Nos. 3,354,022 and WO 96/04123 disclose further methods of reducing the wettability of articles by surface topological changes.
- artificial elevations or depressions with a height of about 5 to 1000 microns and a distance of about 5 to 500 microns are applied to hydrophobic or hydrophobized after structuring materials.
- Surfaces of this type lead to rapid droplet formation, whereby the rolling drops absorb dirt particles and thus clean the surface.
- 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 embossing of microstructures and claims the use of such structures in analytics (microfluidics).
- a disadvantage of these structures is the insufficient mechanical stability.
- JP 11171592 describes a water-repellent product and its preparation in which the soil-repellent surface is produced 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.
- 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 describes a process for producing a surface with ultraphobic properties, in which one is coated with Ni (OH) 2 particles, if appropriate coated with an adhesion promoter 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 present invention is therefore a self-cleaning surface having an artificial, at least partially hydrophobic surface structure of elevations and depressions, wherein the elevations and depressions are formed by fixed by means of a carrier on the surface particles, which is characterized in that the particles have a rugged 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 preferably have a BET surface area of from 50 to 600 square meters per gram. Most preferably, the particles have a BET surface area of from 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.
- the particles have fumed silicas or precipitated silicas, in particular aerosils, Al 2 O 3 , SiO 2 , TiO 2 , ZrO 2 , coated with Aerosil R974 zinc powder, preferably with a particle size of 1 micron or powdery polymers, such as 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 in wide limits are varied. 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 support 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 Particular preference is given to using particles having a BET surface area of 50 to 600 m 2 / g. 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 can be done for example by spraying, knife coating, brushing or spraying.
- 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 at least partially sink into the curable substance However, 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 hardenable 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 with hydrophobic properties after fixing on the support may also be advantageous to provide the particles with hydrophobic properties after fixing on the support.
- This can be done, for example, by providing the particles of the treated surface with hydrophobic properties by treatment with at least one compound from the group of the alkylsilanes, the perfluoroalkylsilanes, which can for example be obtained from Sivento GmbH.
- the treatment is carried out in that the surface having particles which is to be rendered hydrophobic is immersed in a solution comprising a hydrophobing reagent such as alkylsilanes, excess hydrophobing agent is drained off and the surface is dripped off annealed as high as possible.
- the maximum applicable temperature is limited by the softening temperatures of the carrier or substrate.
- 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 screens or other surfaces which 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 may be, for example, partitions in public toilets, walls of shower cubicles, swimming pools or saunas, but also shower curtains (flexible wall).
- SEM Scattered electron micrographs
- 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.
- the cured, brushed plate for hydrophobing was dipped in a formulation of tridecafluorooctyltriethoxysilane in ethanol (Dynasilan 8262, Sivento GmbH). 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 °.
- 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)
- Treatments Of Macromolecular Shaped Articles (AREA)
- Cleaning Or Drying Semiconductors (AREA)
- Laminated Bodies (AREA)
Abstract
Description
Die vorliegende Erfindung betrifft selbstreinigende Oberflächen und Verfahren zu deren Herstellung.The present invention relates to self-cleaning surfaces and methods for their production.
Gegenstände mit extrem schwer benetzbaren Oberflächen weisen eine Reihe von wirtschaftlich bedeutsamen Merkmalen auf. Das wirtschaftlich bedeutendste Merkmal ist dabei die selbstreinigende Wirkung von schwerbenetzbaren Oberflächen, da die Reinigung von Oberflächen zeit- und kostenintensiv ist. Selbstreinigende Oberflächen sind somit von höchstem wirtschaftlichen Interesse. Haftmechanismen werden in der Regel durch grenzflächenenergetische Parameter zwischen den beiden sich berührenden Oberflächen bedingt. In der Regel versuchen dabei die Systeme ihre freie Grenzflächenenergie zu erniedrigen. Liegen die freien Grenzflächenenergien zwischen zwei Komponenten von sich aus schon sehr niedrig, so kann allgemein davon ausgegangen werden, dass die Haftung zwischen diesen beiden Komponenten schwach ausgeprägt ist. Wichtig ist dabei die relative Erniedrigung der freien Grenzflächenenergie. Bei Paarungen mit einer hohen und einer niedrigen Grenzflächenenergie kommt es sehr oft auf die Möglichkeiten der Wechselwirkungen an. So ist beispielsweise beim Aufbringen von Wasser auf eine hydrophobe Oberfläche nicht möglich, eine merkliche Erniedrigung der Grenzflächenenergie herbeizuführen. Dies ist daran erkennbar, dass die Benetzung schlecht ist. Aufgebrachtes Wasser bildet Tropfen mit sehr hohem Kontaktwinkel. Perfluorierte Kohlenwasserstoffe, z.B. Polytetrafluorethylen, haben sehr niedrige Grenzflächenenergie. Auf solchen Oberflächen haften kaum irgendwelche Komponenten bzw. auf solchen Oberflächen abgelagerte Komponenten können sehr leicht wieder entfernt werden.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. For example, when water is applied to a hydrophobic surface, it is not possible to bring about a marked lowering of the interfacial energy. This is evident from the fact that the wetting is bad. Applied water forms drops with a very high contact angle. Perfluorinated hydrocarbons, e.g. Polytetrafluoroethylene, have very low interfacial energy. Hardly any components adhere to such surfaces or components deposited on such surfaces can be removed very easily.
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 beschreiben 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 festgestellt 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., Service Coatings International 4, 1997, p. 168 et seq. Here For example, particles of fluoropolymers are applied to metal surfaces, whereby a markedly reduced wettability of the surfaces thus produced to water has been determined with a considerably reduced tendency to freeze.
In US-PS 3 354 022 und WO 96/04123 sind weitere Verfahren zur Erniedrigung der Benetzbarkeit von Gegenständen durch topologische Veränderungen der Oberflächen beschrieben. Hier werden künstliche Erhebungen bzw. Vertiefungen mit einer Höhe von ca. 5 bis 1 000 µm und einem Abstand von ca. 5 bis 500 µm auf hydrophobe oder nach der Strukturierung hydrophobierte Werkstoffe aufgebracht. Oberflächen dieser Art führen zu einer schnellen Tropfenbildung, wobei die abrollenden Tropfen Schmutzteilchen aufnehmen und somit die Oberfläche reinigen.U.S. Patent Nos. 3,354,022 and WO 96/04123 disclose further methods of reducing the wettability of articles by surface topological changes. Here, artificial elevations or depressions with a height of about 5 to 1000 microns and a distance of about 5 to 500 microns are applied to hydrophobic or hydrophobized after structuring materials. Surfaces of this type lead to rapid droplet formation, whereby the rolling drops absorb dirt particles and thus clean the surface.
Dieses 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 Lotus-Pflanze 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 Nonakosan-10-ol, oder Alkandiolen, wie Nonakosan-5,10-diol. Nachteilig hieran ist die mangelhafte Stabilität der selbstreinigenden Oberflächen, da Detergentien zur Ablösung der Struktur führen.This principle is borrowed from nature. Small contact areas lower the van der Waals interaction, which is responsible 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 with water. 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. The disadvantage here is the lack of stability of the self-cleaning surfaces, since detergents lead to the replacement of the structure.
Eine weitere Methode, leicht reinigbare Oberflächen zu erzeugen, ist in DE 199 17 367 A1 beschrieben. Überzüge auf Basis fluorhaltiger Kondensate sind aber nicht selbstreinigend. Die Kontaktfläche zwischen Wasser und Oberfläche ist zwar reduziert, jedoch nicht in ausreichendem Maße.Another method for producing easily cleanable surfaces is described in DE 199 17 367 A1. However, coatings based on fluorine-containing condensates are not self-cleaning. The contact surface between water and surface is indeed reduced, but not sufficiently.
EP 1 040 874 A2 beschreibt das Abprägen von Mikrostrukturen und beansprucht die Verwendung solcher Strukturen in der Analytik (Mikrofluidik). Nachteilig an diesen Strukturen ist die ungenügende mechanische Stabilität.EP 1 040 874 A2 describes the embossing of microstructures and claims the use of such structures in analytics (microfluidics). A disadvantage of these structures is the insufficient mechanical stability.
In JP 11171592 wird ein Wasser abweisendes Produkt und dessen Herstellung beschrieben, wobei die Schmutz abweisende Oberfläche dadurch hergestellt wird, dass ein Film auf die zu behandelnde Oberfläche aufgetragen wird, der feine Partikel aus Metalloxid und das Hydrolysat eines Metallalkoxids oder - chelats aufweist. Zur Verfestigung dieses Films muss das Substrat, auf welches der Film aufgebracht wurde, bei Temperaturen oberhalb 400 °C gesintert werden. Das Verfahren ist deshalb nur für Substrate einsetzbar, welche auch bei Temperaturen oberhalb von 400 °C stabil sind.JP 11171592 describes a water-repellent product and its preparation in which the soil-repellent surface is produced 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.
In WO 00/39 239, wird es ein Verfahren zur Herstellung einer Oberfläche mit ultraphoben Eigenschaften beschrieben, bei dem eine mit Ni(OH)2 - Partikeln beschichtet, gegebenfalls mit einem Haftvermittler überzogen und anschließend mit einem Hydrophoben und/oder oleophoben Überzug versehen wird.WO 00/39 239 describes a process for producing a surface with ultraphobic properties, in which one is coated with Ni (OH) 2 particles, if appropriate coated with an adhesion promoter and then provided with a hydrophobic and / or oleophobic coating ,
Aufgabe der vorliegenden Erfindung war die Bereitstellung von besonders gut selbstreinigenden Oberflächen mit Strukturen im Nanometerbereich, sowie ein einfaches Verfahren zur Herstellung solcher selbstreinigenden Oberflächen.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.
Außerdem war Aufgabe der vorliegenden Erfindung ein Verfahren zur Herstellung von selbstreinigenden Oberflächen bereitzustellen, bei denen das beschichtete Material nur geringen chemischen oder physikalischen Belastungen ausgesetzt werden muss.In addition, 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.
Gegenstand der vorliegenden Erfindung ist deshalb eine selbstreinigende Oberfläche, die eine künstliche, zumindest teilweise hydrophobe Oberflächenstruktur aus Erhebungen und Vertiefungen aufweist, wobei die Erhebungen und Vertiefungen durch mittels eines Trägers auf der Oberfläche fixierten Partikel gebildet werden, welche dadurch gekennzeichnet ist, dass die Partikel eine zerklüftete Struktur mit Erhebungen und/oder Vertiefungen im Nanometerbereich aufweisen.The present invention is therefore a self-cleaning surface having an artificial, at least partially hydrophobic surface structure of elevations and depressions, wherein the elevations and depressions are formed by fixed by means of a carrier on the surface particles, which is characterized in that the particles have a rugged structure with elevations and / or depressions in the nanometer range.
Ebenfalls ist Gegenstand der vorliegenden Erfindung ein Verfahren zur Herstellung von selbstreinigenden Oberflächen, bei dem eine geeignete, zumindest teilweise hydrophobe Oberflächenstruktur durch Fixieren von Partikeln mittels eines Trägers auf einer Oberfläche geschaffen wird, welches dadurch gekennzeichnet ist, dass Partikel, die zerklüftete Strukturen mit Erhebungen und/oder Vertiefungen im Nanometerbereich aufweisen, eingesetzt werden.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.
Durch das erfindungsgemäße Verfahren sind selbstreinigende Oberflächen zugänglich, die Partikel mit einer zerklüfteten Struktur aurweisen. Durch die Verwendung von Partikeln, welche eine zerklüftete Struktur aufweisen, werden auf einfache Weise Oberflächen zugänglich, die bis in den Nanometerbereich strukturiert sind. Um diese Struktur im Nanometerbereich zu erhalten ist es notwendig, dass die Partikel nicht durch den Träger, mit welchem sie an der Oberfläche fixiert sind, benetzt sind, da sonst die Struktur im Nanobereich verloren gehen würde.By the method according to the invention self-cleaning surfaces are accessible, the aurweisen particles with a fissured structure. By the use of particles, which Having a rugged structure, surfaces are easily accessible, which are structured to the nanometer range. In order to maintain this structure in the nanometer range, it is necessary that the particles are not wetted by the carrier with which they are fixed to the surface, otherwise the structure would be lost in the nano range.
Ein weiterer Vorteil des erfindungsgemäßen Verfahrens besteht darin, dass kratzempfindliche Oberflächen beim Auftragen der Partikel nicht durch in dem Träger vorhandenen Partikeln beschädigt wird, da bei der Verwendung von Lacken und anschließendem Aufbringen der Partikel auf den Träger die kratzempfindliche Oberfläche bereits durch den Träger geschützt ist.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.
Im nachfolgenden werden Substanzen, die zur Fixierung von Partikeln auf einer Oberfläche eingesetzt werden, als Träger bezeichnet.In the following, substances which are used for fixing particles on a surface are referred to as carriers.
Die erfindungsgemäße selbstreinigende Oberfläche, die eine künstliche, zumindest teilweise hydrophobe Oberflächenstruktur aus Erhebungen und Vertiefungen aufweist, wobei die Erhebungen und Vertiefungen durch mittels eines Trägers auf der Oberfläche fixierten Partikel gebildet werden, zeichnet sich dadurch aus, dass die Partikel eine zerklüftete Struktur mit Erhebungen und/oder Vertiefungen im Nanometerbereich aurweisen. Vorzugsweise weisen die Erhöhungen im Mittel eine Höhe von 20 bis 500 nm, besonders bevorzugt von 50 bis 200 nm auf. Der Abstand der Erhöhungen bzw. Vertiefungen auf den Partikeln beträgt vorzugsweise weniger als 500 nm, ganz besonders bevorzugt weniger als 200 nm.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 aurweisen. 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.
Die zerklüfteten Strukturen mit Erhebungen und/oder Vertiefungen im Nanometerbereich können z.B. über Hohlräume, Poren, Riefen, Spitzen und/oder Zacken gebildet werden. Die Partikel selbst weisen eine durchschnittliche Größe von kleiner 50 µm, vorzugsweise von kleiner 30 µm und ganz besonders bevorzugt von kleiner 20 µm auf.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.
Bevorzugt weisen die Partikel eine BET-Oberfläche von 50 bis 600 Quadratmeter pro Gramm auf Ganz besonders bevorzugt weisen die Partikel eine BET-Oberfläche von 50 bis 200 m2/g auf.The particles preferably have a BET surface area of from 50 to 600 square meters per gram. Most preferably, the particles have a BET surface area of from 50 to 200 m 2 / g.
Als strukturbildende Partikel können verschiedenste Verbindungen aus vielen Bereichen der Chemie eingesetzt werden. Vorzugsweise weisen die Partikel zumindest ein Material, ausgewählt aus Silikaten, dotierten Silikaten, Mineralien, Metalloxiden, Kieselsäuren, Polymeren und mit Kieselsäure beschichteten Metallpulvern, auf. Ganz besonders bevorzugt weisen die Partikel pyrogene Kieselsäuren oder Fällungskieselsäuren, insbesondere Aerosile, Al2O3, SiO2, TiO2, ZrO2, mit Aerosil R974 ummanteltes Zinkpulver, vorzugsweise mit einer Teilchengrößen von 1 µm oder pulverförmige Polymere, wie z.B. kryogen gemahlenes oder sprühgetrocknetes Polytetrafluorethylen (PTFE) oder perfluorierte Copolymere bzw. Copolymere mit Tetrafluorethylen, auf.As structure-forming particles, a wide variety of compounds from many areas of chemistry can be used. Preferably, the particles comprise at least one material selected from silicates, doped silicates, minerals, metal oxides, silicas, polymers and silica-coated metal powders. Most preferably, the particles have fumed silicas or precipitated silicas, in particular aerosils, Al 2 O 3 , SiO 2 , TiO 2 , ZrO 2 , coated with Aerosil R974 zinc powder, preferably with a particle size of 1 micron or powdery polymers, such as cryogenically ground or spray-dried polytetrafluoroethylene (PTFE) or perfluorinated copolymers or copolymers with tetrafluoroethylene, on.
Vorzugsweise weisen die Partikel zur Generierung der selbstreinigenden Oberflächen neben den zerklüfteten Strukturen auch hydrophobe Eigenschaften auf. Die Partikel können selbst hydrophob sein, wie z.B. PTFE aufweisende Partikel, oder die eingesetzten Partikel können hydrophobiert worden sein. Das Hydrophobieren der Partikel kann auf eine dem Fachmann bekannte Weise erfolgen. Typische hydrophobierte Partikel sind z.B. Feinstpulver wie Aerosil-R 8200 (Degussa AG), die käuflich zu erwerben sind.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.
Die vorzugsweise verwendeten Kieselsäuren weisen vorzugsweise eine Dibutylphthalat-Adsorbption, angelehnt an DIN 53 601, von zwischen 100 und 350 ml/100 g, bevorzugt Werte zwischen 250 und 350 ml/100 g.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.
Die Partikel werden an der Oberfläche mittels eines Trägers fixiert. Durch Auftrag der Partikel auf die Oberfläche in einer dicht gepackten Schicht, lässt sich die selbstreinigende Oberfläche generieren.The particles are fixed to the surface by means of a carrier. By applying the particles to the surface in a tightly packed layer, the self-cleaning surface can be generated.
In einer bevorzugten Ausführungsart der erfindungsgemäßen selbstreinigenden Oberfläche ist der Träger ein mittels thermischer Energie und/oder Lichtenergie gehärteter Lack, ein Zweikomponenten-Lacksystem oder ein anderes reaktives Lacksystem, wobei die Härtung vorzugsweise durch Polymerisation oder Vernetzung erfolgt. Besonders bevorzugt weist der gehärtete Lack Polymerisate und/oder Copolymerisate aus einfach und/oder mehrfach ungesättigten Acrylaten und/oder Methacrylaten auf. Die Mischungsverhältnisse können in weiten Grenzen variiert werden. Ebenso ist es möglich, dass der gehärtete Lack Verbindungen mit funktionellen Gruppen, wie z.B. Hydroxy-Gruppen, Epoxid-Gruppen, Amin-Gruppen, oder fluorhaltige Verbindungen, wie z.B. perfluorierte Ester der Acrylsäure, aufweist. Dies ist insbesondere dann vorteilhaft, wenn die Verträglichkeit von Lack und hydrophoben Partikeln wie beispielsweise von Aerosil R 8200 mittels N-[2-(Acryloyloxy)-ethyl]-N-ethylperfluoroctan-1-sulfonsäureamid aufeinander abgestimmt werden. Als Lacke sind nicht nur Lacke auf Acrylharz-Basis einsetzbar, sondern auch Lacke auf Polyurethan-Basis oder aber Lacke, die Polyurethanacrylate oder Siliconacrylate aufweisen.In a preferred embodiment of the self-cleaning surface according to the invention, 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 in wide limits are varied. 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. This is particularly advantageous when the compatibility of lacquer and hydrophobic particles such as Aerosil R 8200 by means of N- [2- (acryloyloxy) ethyl] -N-ethylperfluoroctan-1-sulfonsäureamid be coordinated. As 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.
Die erfindungsgemäßen selbstreinigenden Oberflächen weisen eine Abrollwinkel von kleiner 20°, besonders bevorzugt kleiner 10° auf, wobei der Abrollwinkel so definiert ist, dass ein aus 1 cm Höhe auf eine auf einer schiefen Ebene ruhenden planen Oberfläche aufgebrachter Wassertropfen abrollt. Die Fortschreitwinkel und die Rückzugswinkel liegen oberhalb von 140°, bevorzugt oberhalb von 150° und weisen eine Hysterese von kleiner 15°, vorzugsweise kleiner 10° auf. Dadurch, dass die erfindungsgemäßen Oberflächen einen Fortschreit- und Rückzugswinkel oberhalb von zumindest 140°, vorzugsweise oberhalb von 150° aufweisen, werden besonders gute selbstreinigende Oberflächen zugänglich.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.
Je nach verwendetem Lacksystem und je nach Größe und Material der eingesetzten Partikel kann erreicht werden, dass die selbstreinigenden Oberflächen semitransparent sind. Insbesondere können die erfindungsgemäßen Oberflächen kontakttransparent sein, dass heißt das nach Erstellen einer erfindungsgemäßen Oberfläche auf einem beschrifteten Gegenstand diese Beschriftung, in Abhängigkeit von der Größe der Schrift, weiterhin lesbar ist.Depending on the paint system used and the size and material of the particles used, it can be achieved that the self-cleaning surfaces are semitransparent. In particular, 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.
Die erfindungsgemäßen selbstreinigenden Oberflächen werden vorzugsweise durch das erfindungsgemäße Verfahren zur Herstellung dieser Oberflächen hergestellt. Diese erfindungsgemäße Verfahren zur Herstellung von selbstreinigenden Oberflächen, bei dem eine geeignete, zumindest teilweise hydrophobe Oberflächenstruktur durch Fixieren von Partikeln mittels eines Trägers auf einer Oberfläche geschaffen wird, zeichnet sich dadurch aus, dass Partikel, die zerklüftete Strukturen mit Erhebungen und/oder Vertiefungen im Nanometerbereich aufweisen, eingesetzt werden.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 support on a surface, is characterized in that particles, the rugged structures with elevations and / or depressions in the nanometer range have to be used.
Vorzugsweise werden solche Partikel, die zumindest ein Material, ausgewählt aus Silikaten, dotierten Silikaten, Mineralien, Metalloxiden, Kieselsäuren oder Polymeren aufweisen, eingesetzt. Ganz besonders bevorzugt weisen die Partikel pyrogene Silikate oder Kieselsäuren, insbesondere Aerosile, Mineralien wie Magadiit Al2O3, SiO2, TiO2, ZrO2 mit Aerosil R 974 ummanteltes Zn-Pulver oder pulverförmige Polymere, wie z.B. kryogen gemahlenes oder sprühgetrocknet Polytetrafluorethylen (PTFE), auf.Preferably, 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).
Besonders bevorzugt werden Partikel mit einer BET-Oberfläche von 50 bis 600 m2/g eingesetzt. Ganz besonders bevorzugt werden Partikel eingesetzt, die eine BET-Oberfläche von 50 bis 200 m2/g aufweisen.Particular preference is given to using particles having a BET surface area of 50 to 600 m 2 / g. Very particular preference is given to using particles which have a BET surface area of from 50 to 200 m 2 / g.
Vorzugsweise weisen die Partikel zur Generierung der selbstreinigenden Oberflächen neben den zerklüfteten Strukturen auch hydrophobe Eigenschaften auf. Die Partikel können selbst hydrophob sein, wie z.B. PTFE aufweisende Partikel, oder die eingesetzten Partikel können hydrophobiert worden sein. Das Hydrophobieren der Partikel kann auf eine dem Fachmann bekannte Weise erfolgen. Typische hydrophobierte Partikel sind z.B. Feinstpulver wie Aerosil R 974 oder Aerosil-R 8200 (Degussa AG), die käuflich zu erwerben sind.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.
Das erfindungsgemäße Verfahren weist vorzugsweise die Schritte
- a) Aufbringen einer härtbaren Substanz als Träger auf eine Oberfläche,
- b) Aufbringen von Partikeln, die zerklüftete Strukturen aufweisen, auf den Träger und
- c) Fixieren der Partikel durch Härten des Trägers,
- a) applying a curable substance as a carrier to a surface,
- b) applying particles having fissured structures to the support and
- c) fixing the particles by hardening the carrier,
Das Aufbringen der härtbaren Substanz kann z.B. durch Aufsprühen, Aufrakeln, Aufstreichen oder Aufspritzen erfolgen. Vorzugsweise wird die härtbare Substanz in einer Dicke von 1 bis 100 µm, vorzugsweise in einer Dicke von 5 bis 50 µm aufgebracht. Je nach Viskosität der härtbaren Substanz kann es vorteilhaft sein, die Substanz vor dem Aufbringen der Partikel anhärten bzw. antrocknen zu lassen. Idealerweise wird die Viskosität der härtbaren Substanz so gewählt, dass die aufgebrachten Partikel zumindest teilweise in die härtbare Substanz einsinken können, die härtbare Substanz bzw. die auf ihr aufgebrachten Partikel aber nicht mehr verlaufen, wenn die Oberfläche senkrecht gestellt wird.The application of the curable substance can be done for example by spraying, knife coating, brushing or spraying. Preferably, the curable substance is applied in a thickness of 1 to 100 microns, preferably in a thickness of 5 to 50 microns. Depending on the viscosity of the curable substance, it may be advantageous to allow the substance to harden or to dry before the particles are applied. Ideally, the viscosity of the curable substance is chosen so that the applied particles at least partially sink into the curable substance However, the curable substance or the particles applied to it no longer run when the surface is placed vertically.
Das Aufbringen der Partikel kann durch gängige Verfahren wie Aufsprühen oder Bepudern erfolgen. Insbesondere kann das Aufbringen der Partikel durch Aufsprühen unter Verwendung einer elektrostatischen Sprühpistole erfolgen. Nach dem Aufbringen der Partikel können überschüssige Partikel, also Partikel die nicht an der härtbaren Substanz haften, durch Schütteln, Abbürsten oder Abblasen von der Oberfläche entfernt werden. Diese Partikel können gesammelt und wieder eingesetzt werden.The application of the particles can be carried out by conventional methods such as spraying or powdering. In particular, the application of the particles can be effected by spraying using an electrostatic spray gun. After the particles have been applied, excess particles, that is to say particles which do not adhere to the hardenable substance, can be removed from the surface by shaking, brushing or blowing off. These particles can be collected and reused.
Als härtbare Substanz kann als Träger ein Lack, der zumindest Mischungen aus einfach und/oder mehrfach ungesättigten Acrylaten und/oder Methacrylaten aufweist, eingesetzt werden. Die Mischungsverhältnisse können in weiten Grenzen variiert werden. Besonders bevorzugt wird ein mittels thermischer oder chemischer Energie und/oder Lichtenergie härtbarer Lack eingesetzt.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.
Als härtbare Substanz wird ein Lack oder ein Lacksystem ausgewählt, die hydrophobe Eigenschaften aufweist, wenn die eingesetzten Partikel hydrophobe Eigenschaften aufweisen. Umgekehrt wird als härtbare Substanz ein Lack ausgewählt der hydrophile Eigenschaften aufweist, wenn die eingesetzten Partikel hydrophile Eigenschaften aufweisen.As curable substance, a lacquer or a lacquer system is selected which has hydrophobic properties if the particles used have hydrophobic properties. Conversely, as a curable substance, a lacquer is selected which has hydrophilic properties when the particles used have hydrophilic properties.
Es kann vorteilhaft sein, wenn die als Lack eingesetzten Mischungen Verbindungen mit funktionellen Gruppen, wie z.B. Hydroxy-Gruppen, Epoxid-Gruppen, Amin-Gruppenoder fluorhaltige Verbindungen, wie z.B. perfluorierte Ester der Acrylsäure, aufweist. Dies ist insbesondere dann vorteilhaft, wenn die Verträglichkeit (in Bezug auf die hydrophoben Eigenschaften) von Lack und hydrophoben Partikeln wie beispielsweise von Aerosil VPR 411 mittels N-[2-(Acryloyloxy)-ethyl]-N-ethylperfluoroctan-1-sulfonsäureamid aufeinander abgestimmt werden. Als härtbare Substanzen können nicht nur Lacke auf Acrylharz-Basis eingesetzt werden, sondern auch Lacke auf Polyurethan-Basis, oder aber Polyurethanacrylate oder Siliconacrylate. Ebenfalls sind als härtbare Substanzen Zweikomponentenlacksysteme oder andere reaktive Lacksysteme einsetzbar.It may be advantageous if 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. This is particularly advantageous if the compatibility (with respect to the hydrophobic properties) of lacquer and hydrophobic particles such as Aerosil VPR 411 using N- [2- (acryloyloxy) ethyl] -N-ethylperfluoroctan-1-sulfonic acid amide matched become. As 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.
Das Fixieren der Partikel auf dem Träger erfolgt durch Härten des Trägers, wobei dieses, je nach verwendetem Lacksystem, vorzugsweise durch thermische und/oder chemische Energie und/oder Lichtenergie erfolgt. Das Härten des Trägers, ausgelöst durch chemische oder thermische Energie und/oder Lichtenergie, kann z.B. durch Polymerisation oder Vernetzung der Bestandteile der Lacke bzw. Lacksysteme erfolgen. Besonders bevorzugt erfolgt das Härten des Trägers durch Lichtenergie und ganz besonders bevorzugt erfolgt das Polymerisieren des Trägers durch Licht einer Hg-Mitteldrucklampe im UV-Bereich. Vorzugsweise erfolgt das Härten des Trägers unter einer Inertgas-Atmosphäre, ganz besonders bevorzugt unter einer Stickstoffatmosphäre.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. Preferably, the curing of the support takes place under an inert gas atmosphere, most preferably under a nitrogen atmosphere.
Je nach Dicke der aufgebrachten härtbaren Substanz und Durchmesser der verwendeten Partikel kann es notwendig sein, die Zeit, die zwischen Aufbringen der Partikel und Härten der härtbaren Substanz verstreicht, zu begrenzen, um ein vollständiges Eintauchen der Partikel in die härtbare Substanz zu vermeiden. Vorzugsweise wird die härtbare Substanz innerhalb von 0,1 bis 10 min, vorzugsweise innerhalb von 1 bis 5 min nach dem Aufbringen der Partikel gehärtet.Depending on the thickness of the applied curable substance and the diameter of the particles used, it may be necessary to limit the time that elapses between application of the particles and curing of the curable substance in order to avoid complete immersion of the particles in the curable substance. Preferably, the curable substance is cured within 0.1 to 10 minutes, preferably within 1 to 5 minutes after application of the particles.
Bei der Durchführung des erfindungsgemäßen Verfahrens kann es vorteilhaft sein, Partikel einzusetzen, die hydrophobe Eigenschaften aufweisen und/oder die durch eine Behandlung mit zumindest einer Verbindung aus der Gruppe der Alkylsilane, Alkyldisilazane oder Perfluoralkylsilane, hydrophobe Eigenschaften aufweisen. Die Hydrophobierung von Partikeln ist bekannt und kann z.B. in der Schriftenreihe Pigmente, Nummer 18, der Degussa AG nachgelesen werden.When carrying out the process according to the invention, it may be advantageous to use 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.
Es kann ebenso vorteilhaft sein, die Partikel nach dem Fixieren auf dem Träger mit hydrophoben Eigenschaften auszustatten. Dies kann z.B. dadurch erfolgen, dass die Partikel der behandelten Oberfläche durch eine Behandlung mit zumindest einer Verbindung aus der Gruppe der Alkylsilane, der Perfluoralkylsilane, die z.B. bei der Sivento GmbH zu beziehen sind, mit hydrophoben Eigenschaften ausgestattet werden. Vorzugsweise erfolgt die Behandlung dadurch, dass die Partikel aufweisende Oberfläche, die hydrophobiert werden soll, in eine Lösung, die ein Hydrophobierungsreagenz wie z.B. Alkylsilane aufweist, getaucht wird, überschüssiges Hydrophobierungsreagenz abgetropft wird und die Oberfläche bei einer möglichst hohen Temperatur getempert. Die maximal anwendbare Temperatur ist durch die Erweichungstemperaturen von Träger oder Substrat limitiert.It may also be advantageous to provide the particles with hydrophobic properties after fixing on the support. This can be done, for example, by providing the particles of the treated surface with hydrophobic properties by treatment with at least one compound from the group of the alkylsilanes, the perfluoroalkylsilanes, which can for example be obtained from Sivento GmbH. Preferably, the treatment is carried out in that the surface having particles which is to be rendered hydrophobic is immersed in a solution comprising a hydrophobing reagent such as alkylsilanes, excess hydrophobing agent is drained off and the surface is dripped off annealed as high as possible. The maximum applicable temperature is limited by the softening temperatures of the carrier or substrate.
Das erfindungsgemäße Verfahren gemäß zumindest einem der Ansprüche 8 bis 17 kann hervorragend zur Herstellung von selbstreinigenden Oberflächen auf planaren oder nichtplanaren Gegenständen, insbesondere auf nichtplanaren Gegenständen verwendet werden. Dies ist mit den herkömmlichen Verfahren nur eingeschränkt möglich. Insbesondere über Verfahren, bei denen vorgefertigte Filme auf eine Oberfläche aufgebracht werden oder bei Verfahren, bei denen eine Struktur durch Prägen erstellt werden soll, sind nichtplanare Gegenstände, wie z.B. Skulpturen, nicht oder nur eingeschränkt zugänglich. Naturgemäße kann das erfindungsgemäße Verfahren aber auch zur Herstellung von selbstreinigenden Oberflächen auf Gegenständen mit planaren Oberflächen, wie z.B. Gewächshäusern oder öffentlichen Verkehrsmitteln verwendet werden. Insbesondere die Anwendung des erfindungsgemäßen Verfahrens zur Herstellung von selbstreinigenden Oberflächen an Gewächshäusern weist Vorteile auf, da mit dem Verfahren selbstreinigende Oberflächen z.B. auch auf transparenten Materialien wie Glas oder Plexiglas® hergestellt werden können und die selbstreinigende Oberfläche zumindest soweit transparent ausgebildet werden kann, dass für das Wachstum der Pflanzen im Gewächshaus genügend Sonnenlicht durch die mit einer selbstreinigenden Oberfläche ausgerüstete transparente Oberfläche dringen kann. Im Gegensatz zu herkömmlichen Gewächshäusern, die regelmäßig von Laub-, Staub-, Kalk- und biologischem Material, wie z.B. Algen, gereinigt werden müssen, können Gewächshäuser, die eine erfindungsgemäße Oberfläche gemäß einem der Ansprüche 1 bis 7, aufweisen, mit längeren Reinigungsintervallen betrieben werden.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. In particular, 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. In contrast to conventional greenhouses, which are regularly harvested from deciduous, dust, lime and biological material, e.g. Algae to be cleaned, greenhouses having a surface according to the invention according to one of claims 1 to 7, can be operated with longer cleaning intervals.
Das erfindungsgemäße Verfahrens kann außerdem zur Herstellung von selbstreinigenden Oberflächen auf nicht starren Oberflächen von Gegenständen, verwendet werden, wie z.B. Schirmen oder anderen Oberflächen die flexibel gehalten sind. Ganz besonders bevorzugt kann das erfindungsgemäße Verfahren gemäß zumindest einem der Ansprüche 8 bis 17, zur Herstellung selbstreinigender Oberflächen auf flexiblen oder unflexiblen Wänden im Sanitärbereich verwendet werden. Solche Wände können z.B. Trennwände in öffentlichen Toiletten, Wände von Duschkabinen, Schwimmbädern oder Saunen, aber auch Duschvorhänge (flexible Wand) sein.The method of the invention may also be used to make self-cleaning surfaces on non-rigid surfaces of articles, such as screens or other surfaces which are kept flexible. Very particularly preferably, 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 may be, for example, partitions in public toilets, walls of shower cubicles, swimming pools or saunas, but also shower curtains (flexible wall).
In den Fig. 1 und 2 sind Rasterelektronenmikroskopische- (REM-) Aufnahmen von als Strukturbildnern eingesetzten Partikeln wiedergegeben.Scattered electron micrographs (SEM) of particles used as structuring agents are reproduced in FIGS. 1 and 2.
Fig. 1 zeigt eine REM-Aufnahme des Aluminiumoxids Aluminiumoxide C (Degussa AG).1 shows a SEM image of the aluminum oxide aluminum oxides C (Degussa AG).
Fig. 2 zeigt eine REM-Aufnahme der Oberfläche von Partikeln der Kieselsäure Sipernat FK 350 (Degussa AG) auf einem Träger.2 shows a SEM image of the surface of particles of the silica Sipernat FK 350 (Degussa AG) on a carrier.
Die nachfolgenden Beispiele sollen die erfindungsgemäßen Oberflächen bzw. das Verfahren zur Herstellung der Oberflächen näher erläutern, ohne dass die Erfindung auf diese Ausführungsarten beschränkt sein soll.The following examples are intended to explain the surfaces according to the invention or the method for producing the surfaces, without the invention being restricted to these embodiments.
20 Gew.-% Methylmethacrylat, 20 Gew.-% Pentaeritrittetraacrylat und 60 Gew.-% Hexandioldimethacrylat wurden miteinander vermischt. Bezogen auf diese Mischung werden 14 Gew.-% Plex 4092 F, ein acrylisches Copolymerisat der Röhm GmbH und 2 Gew.-% UV-Härter Darokur 1173 zugesetzt und mindestens 60 min lang gerührt. Diese Mischung wurde als Träger auf eine 2 mm dicken PMMA-Platte in einer Dicke von 50 µm aufgetragen. Die Schicht wurde für 5 min angetrocknet. Anschließend wurden als Partikel hydrophobierte, pyrogene Kieselsäure Aerosil VPR 411 (Degussa AG) mittels einer elektrostatischen Sprühpistole aufgesprüht. Nach 3 min wurde der Träger bei einer Wellenlänge von 308 nm unter Stickstoff gehärtet. Nach dem Härten des Trägers wurde überschüssiges Aerosil VPR 411 abgebürstet. Die Charakterisierung der Oberfläche erfolgte anfänglich visuell und ist mit +++ protokolliert. +++ bedeutet, Wassertropfen bilden sich nahezu vollständig aus. Der Abrollwinkel betrug 2,4°. Gemessen wurden Fortschreit- und Rückzugswinkel zu jeweils größer als 150°. Die zugehörige Hysterese liegt unterhalb von 10°.20% by weight of methyl methacrylate, 20% by weight of pentaerythritol tetraacrylate and 60% by weight of hexanediol dimethacrylate were mixed together. Based on this mixture, 14% by weight Plex 4092 F, an acrylic copolymer from Röhm GmbH and 2% by weight Darokur 1173 UV curing agent are added and the mixture is stirred for at least 60 minutes. This mixture was applied as a support to a 2 mm thick PMMA sheet in a thickness of 50 microns. The layer was dried for 5 minutes. Subsequently, hydrophobic fumed silica Aerosil VPR 411 (Degussa AG) was sprayed on as particles by means of an electrostatic spray gun. After 3 minutes, 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 °.
Der Versuch aus Beispiel 1 wurde wiederholt, wobei Partikel aus Aluminiumoxid C (Degussa AG), ein Aluminiumoxid mit einer BET-Oberfläche von 100 m2/g, elektrostatisch aufgesprüht wurden. Nach erfolgter Härtung des Trägers gemäß Beispiel 1 und Abbürsten überschüssiger Partikel, wurde die gehärtete, abgebürstete Platte zum Hydrophobieren in eine Formulierung von Tridecafluoroctyltriethoxysilan in Ethanol (Dynasilan 8262, Sivento GmbH) getaucht. Nach Abtropfen von überschüssigem Dynasilan 8262 wurde die Platte bei einer Temperatur von 80 °C getempert. Die Oberfläche wird mit ++ eingestuft, d.h., die Ausformung der Wassertropfen ist nicht ideal, der Abrollwinkel liegt unterhalb von 20°.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 brushing excess Particles, the cured, brushed plate for hydrophobing was dipped in a formulation of tridecafluorooctyltriethoxysilane in ethanol (Dynasilan 8262, Sivento GmbH). 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 °.
Auf die mit dem Träger behandelte Platte aus Beispiel 1 wird Kieselsäure Sipernat 350 der Degussa AG gestreut. Nach 5 min Eindringzeit wird die behandelte Platte unter Stickstoff im UV-Licht bei 308 nm gehärtet. Überschüssige Partikel werden wiederum abgebürstet und die Platte wird anschließend wiederum in Dynasilan 8262 getaucht und anschließend bei 80 °C getempert Die Oberfläche wird mit +++ eingestuft.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 +++.
Der Versuch aus Beispiel 1 wird wiederholt, aber an Stelle von Aerosil VPR 411 wird Aerosil R 8200 (Degussa AG), welches eine BET-Oberfläche von 200 ± 25 m2/g eingesetzt. Die Beurteilung der Oberfläche ist +++. Der Abrollwinkel ist zu 1,3° bestimmt worden. Gemessen wurden außerdem Fortschreit- und Rückzugswinkel, die jeweils größer als 150° betrugen. Die zugehörige Hysterese liegt unterhalb von 10°.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 °. In addition, progression and retraction angles were measured, each of which exceeded 150 °. The associated hysteresis is below 10 °.
Dem Lack aus Beispiel 1, der mit dem UV-Härter bereits vermischt wurde, wurden zusätzlich 10 Gew.-% (bezogen auf das Gesamtgewicht der Lackmischung) 2-(N-Ethylperfluoroctansulfonamido)-ethylacrylat zugesetzt. Auch dieses Gemisch wurde wieder mindestens 60 min lang gerührt. Diese Mischung wurde als Träger auf eine 2 mm dicken PMMA-Platte in einer Dicke von 50 µm aufgetragen. Die Schicht wurde für 5 min angetrocknet. Anschließend wurden als Partikel hydrophobierte, pyrogene Kieselsäure Aerosil VPR 411 (Degussa AG) mittels einer elektrostatischen Sprühpistole aufgesprüht. Nach 3 min wurde der Träger bei einer Wellenlänge von 308 nm unter Stickstoff gehärtet. Nach dem Härten des Trägers wurde überschüssiges Aerosil VPR 411 abgebürstet. Die Charakterisierung der Oberfläche erfolgte anfänglich visuell und ist mit +++ protokolliert. +++ bedeutet, Wassertropfen bilden sich nahezu vollständig aus.In addition, 10% by weight (based on the total weight of the coating mixture) of 2- (N-ethylperfluorooctanesulfonamido) -ethyl acrylate was added to the paint from Example 1 which had already been mixed with the UV curing agent. This mixture was stirred again for at least 60 minutes. This mixture was applied as a support to a 2 mm thick PMMA sheet in a thickness of 50 microns. The layer was dried for 5 minutes. Subsequently, hydrophobic fumed silica Aerosil VPR 411 (Degussa AG) was sprayed on as particles by means of an electrostatic spray gun. After 3 minutes, 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.
Der Abrollwinkel betrug 0,5°. Gemessen wurden Fortschreit- und Rückzugswinkel zu jeweils größer als 150°. Die zugehörige Hysterese liegt unterhalb von 10°.The rolling angle was 0.5 °. Progressive and retreatment angles greater than 150 ° each were measured. The associated hysteresis is below 10 °.
Auf den angetrockneten Träger aus Beispiel 1 aufgetragen in einer Dicke von 200 µ wird eine Suspension von 10 Gew.-% sprühgetrocknete pyrogene Kieselsäure, Aeroperl 90/30Degussa AG, eine Kieselsäure mit einer BET-Oberfläche von 90 m2/g, in Ethanol, aufgerakelt. Nach Härtung im UV-Licht und Behandlung mit dem Hydrophobierungsmittel Dynasilan 8262 wird die Oberfläche nur mit + beurteilt, d.h., der Tropfen bildet sich schlecht aus und klebt bis zu hohen Neigungswinkeln an der Oberfläche.On the dried support of Example 1 applied in a thickness of 200 μ 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. 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.
Der schlechte Reinigungseffekt ist auf das Zuschmieren der zerklüfteten Strukturen zurückzuführen. Dies geschieht vermutlich durch Lösen von Monomeren des noch nicht gehärteten Lacksystems in Ethanol. Vor dem Härten verdampft das Ethanol und die Monomeren bleiben in den zerklüfteten Strukturen zurück, in der sie beim Vorgang des Härtens ebenfalls aushärten, wodurch die zerklüfteten Strukturen zugeschmiert bzw. ausgefüllt werden. Auf diese Weise verschlechtert sich der Selbstreinigungseffekt deutlich.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.
Claims (19)
- A self-cleaning surface comprising an artificial, at least to some extent hydrophobic, surface structure which is formed by particles secured on the surface by means of a cured carrier,
characterized in that
the particles have a BET surface area of from 50 to 600 m2/g. - A self-cleaning surface according to claim 1,
characterized in that
the carrier is a surface coating cured by thermal or chemical energy or by the energy present in light. - A self-cleaning surface according to either of claims 1 and 2,
characterized in that
the cured surface coating comprises a mixture made from a mono- and/or polyunsaturated acrylate and/or methacrylate, or polyurethane. - A self-cleaning surface according to at least one of claims 1 to 3,
characterized in that
the particles have an average size of less than 50 µm. - A self-cleaning surface according to claim 4,
characterized in that
the particles have an average size of less than 30 µm. - A self-cleaning surface according to at least one of claims 1 to 5,
characterized in that
the particles have been selected from at least one material selected from a silicate, doped silicate, mineral, metal oxide, silica, polymer and metal powder. - A self-cleaning surface according to claim 6,
characterized in that
the particles have hydrophobic properties. - A process for producing a self-cleaning surface by producing a suitable, at least to some extent hydrophobic, surface structure by securing particles by means of a carrier on a surface,
characterized in that it comprises the steps ofa) applying a curable substance as carrier to a surface,b) applying, to the carrier, particles which have a BET surface area of from 50 to 600 m2/g, andc) curing the carrier to secure the particles. - A process according to claim 8,
characterized in that
use is made of particles which comprise at least one material selected from a silicate, doped silicate, mineral, metal oxide, silica, metal powder, and polymer. - A process according to claim 9,
characterized in that
the curing of the carrier takes place via thermal or chemical energy and/or the energy present in light. - A process according to claim 9 or 10,
characterized in that
the curable substance used comprises a surface coating which at least comprises a mixture made from singly and/or multiply unsaturated acrylates and/or methacrylates, and/or comprises polyurethanes and/or silicone acrylates and/or urethane acrylates. - A process according to claim 11,
characterized in that
the curable substance selected comprises a surface coating which has hydrophobic properties if the particles used have hydrophobic properties, and the curable substance selected comprises a surface coating which has hydrophilic properties if the particles used have hydrophilic properties. - A process according to at least one of claims 8 to 12,
characterized in that
the particles used comprise particles having hydrophobic properties. - A process according to at least one of claims 8 to 13,
characterized in that
the particles used comprise particles which have hydrophobic properties as a result of treatment with at least one compound selected from the group consisting of the alkylsilanes, perfluoroalkylsilanes and alkyldisilazanes. - A process according to at least one of claims 8 to 14,
characterized in that
the particles are equipped with hydrophobic properties after securing to the carrier. - A process according to claim 15,
characterized in that
the particles are given hydrophobic properties by treatment with at least one compound selected from the group consisting of the alkylsilanes, perfluoroalkylsilanes and alkyldisilazanes. - The use of a process according to at least one of claims 8 to 16, for producing a self-cleaning surface on a planar or nonplanar object.
- The use of a process according to at least one of claims 8 to 16, for producing a self-cleaning surface on a non-rigid surface of an object.
- The use of a process according to at least one of claims 8 to 16, for producing a self-cleaning surface on a flexible or inflexible partition in the sanitary sector.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE10118352 | 2001-04-12 | ||
DE10118352A DE10118352A1 (en) | 2001-04-12 | 2001-04-12 | Self-cleaning surfaces through hydrophobic structures and processes for their production |
Publications (4)
Publication Number | Publication Date |
---|---|
EP1249280A2 EP1249280A2 (en) | 2002-10-16 |
EP1249280A3 EP1249280A3 (en) | 2003-01-02 |
EP1249280B1 true EP1249280B1 (en) | 2006-09-27 |
EP1249280B2 EP1249280B2 (en) | 2009-07-01 |
Family
ID=7681415
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP02003960A Expired - Lifetime EP1249280B2 (en) | 2001-04-12 | 2002-02-22 | Self-cleaning surfaces with hydrophobic structures and process for making them |
Country Status (7)
Country | Link |
---|---|
US (1) | US6858284B2 (en) |
EP (1) | EP1249280B2 (en) |
JP (1) | JP2002346469A (en) |
AT (1) | ATE340654T1 (en) |
CA (1) | CA2381134A1 (en) |
DE (2) | DE10118352A1 (en) |
ES (1) | ES2271131T5 (en) |
Families Citing this family (101)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE10118345A1 (en) * | 2001-04-12 | 2002-10-17 | Creavis Tech & Innovation Gmbh | Properties of structure formers for self-cleaning surfaces and the production of the same |
DE10118346A1 (en) * | 2001-04-12 | 2002-10-17 | Creavis Tech & Innovation Gmbh | 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 |
DE10118351A1 (en) * | 2001-04-12 | 2002-10-17 | Creavis Tech & Innovation Gmbh | Self-cleaning surfaces through hydrophobic structures and processes for their production |
DE10118352A1 (en) * | 2001-04-12 | 2002-10-17 | Creavis Tech & Innovation Gmbh | Self-cleaning surfaces through hydrophobic structures and processes for their production |
DE10134477A1 (en) | 2001-07-16 | 2003-02-06 | Creavis Tech & Innovation Gmbh | Self-cleaning surfaces through hydrophobic structures and processes for their production |
DE10159767A1 (en) * | 2001-12-05 | 2003-06-18 | Degussa | Process for the manufacture of articles with anti-allergic surfaces |
DE10205007A1 (en) * | 2002-02-07 | 2003-08-21 | Creavis Tech & Innovation Gmbh | Process for the production of protective layers with dirt and water repellent properties |
DE10210668A1 (en) * | 2002-03-12 | 2003-09-25 | Creavis Tech & Innovation Gmbh | Device manufactured by injection molding, for storing liquids and processes for the production of this device |
DE10210674A1 (en) * | 2002-03-12 | 2003-10-02 | Creavis Tech & Innovation Gmbh | Surface extrudates with self-cleaning properties and process for producing such extrudates |
DE10210673A1 (en) * | 2002-03-12 | 2003-09-25 | Creavis Tech & Innovation Gmbh | Injection molded body with self-cleaning properties and method for producing such injection molded body |
DE10210667A1 (en) * | 2002-03-12 | 2003-09-25 | Creavis Tech & Innovation Gmbh | Production of web products with self-cleaning surfaces by means of a calendering process, web products themselves and the use of these |
DE10210671A1 (en) * | 2002-03-12 | 2003-09-25 | Creavis Tech & Innovation Gmbh | Mold release agent which has hydrophobic, nanoscale particles and use of these mold release agents |
GB0206930D0 (en) | 2002-03-23 | 2002-05-08 | Univ Durham | Method and apparatus for the formation of hydrophobic surfaces |
DE10231757A1 (en) | 2002-07-13 | 2004-01-22 | Creavis Gesellschaft Für Technologie Und Innovation Mbh | Process for the preparation of a surfactant-free suspension on an aqueous basis of nanostructured, hydrophobic particles and their use |
DE10233830A1 (en) * | 2002-07-25 | 2004-02-12 | Creavis Gesellschaft Für Technologie Und Innovation Mbh | Method for preparation of self cleaning surfaces by application and fixing of particles to the surface useful for production of films, shaped parts, objects subjected to high dirt and water loads, especially in outdoor sports |
DE10233831A1 (en) * | 2002-07-25 | 2004-02-12 | Creavis Gesellschaft Für Technologie Und Innovation Mbh | A process for preparation of structured surfaces with a carrier layer coated with nano particles useful for preparation of structured surfaces or films |
DE10242560A1 (en) * | 2002-09-13 | 2004-03-25 | Creavis Gesellschaft Für Technologie Und Innovation Mbh | Process for preparation of self-cleaning surfaces on coated flat textile structures useful for cladding technical textiles and structures obtained from these and production of raincoats and safety clothing with signaling effect |
US7196043B2 (en) * | 2002-10-23 | 2007-03-27 | S. C. Johnson & Son, Inc. | Process and composition for producing self-cleaning surfaces from aqueous systems |
DE10250328A1 (en) * | 2002-10-29 | 2004-05-13 | Creavis Gesellschaft Für Technologie Und Innovation Mbh | Production of suspensions of hydrophobic oxide particles |
DE10308379A1 (en) * | 2003-02-27 | 2004-09-09 | Creavis Gesellschaft Für Technologie Und Innovation Mbh | Dispersion of water in hydrophobic oxides for the production of hydrophobic nanostructured surfaces |
DE10315128A1 (en) * | 2003-04-03 | 2004-10-14 | Creavis Gesellschaft Für Technologie Und Innovation Mbh | Process for suppressing mold formation using hydrophobic substances and an anti-mold agent for parts of buildings |
ES2275039T3 (en) * | 2003-04-24 | 2007-06-01 | Goldschmidt Gmbh | PROCEDURE FOR THE PRODUCTION OF REMOVABLE LAMINAR COATINGS, DIRTY AND WATER REPELLENTS. |
DE10321851A1 (en) * | 2003-05-15 | 2004-12-02 | Creavis Gesellschaft Für Technologie Und Innovation Mbh | Use of particles hydrophobized with fluorosilanes for the production of self-cleaning surfaces with lipophobic, oleophobic, lactophobic and hydrophobic properties |
DE10325863A1 (en) * | 2003-06-06 | 2005-01-05 | Infineon Technologies Ag | A method of manufacturing an integrated fingerprint sensor and sensor circuitry and injection assembly |
TW200526406A (en) * | 2003-10-10 | 2005-08-16 | Inventqjaya Sdn Bhd | Self-cleaning window structure |
DE10356752A1 (en) * | 2003-12-04 | 2005-06-30 | Roche Diagnostics Gmbh | Coated test elements |
US8974590B2 (en) | 2003-12-18 | 2015-03-10 | The Armor All/Stp Products Company | Treatments and kits for creating renewable surface protective coatings |
US8034173B2 (en) * | 2003-12-18 | 2011-10-11 | Evonik Degussa Gmbh | Processing compositions and method of forming the same |
US7828889B2 (en) * | 2003-12-18 | 2010-11-09 | The Clorox Company | Treatments and kits for creating transparent renewable surface protective coatings |
US20110018249A1 (en) * | 2004-02-16 | 2011-01-27 | Horst Sonnendorfer | Shopping cart or transport container, and production method |
US9016221B2 (en) * | 2004-02-17 | 2015-04-28 | University Of Florida Research Foundation, Inc. | Surface topographies for non-toxic bioadhesion control |
US7650848B2 (en) * | 2004-02-17 | 2010-01-26 | University Of Florida Research Foundation, Inc. | Surface topographies for non-toxic bioadhesion control |
US7213309B2 (en) | 2004-02-24 | 2007-05-08 | Yunzhang Wang | Treated textile substrate and method for making a textile substrate |
DE102004036073A1 (en) * | 2004-07-24 | 2006-02-16 | Degussa Ag | Process for sealing natural stones |
DE102004046232A1 (en) * | 2004-09-22 | 2006-04-06 | Sew-Eurodrive Gmbh & Co. Kg | Drive component e.g. electric motor, for drive mechanism, has housing including cooling device with cooling fingers and fins, and self-cleaning surface having oleophobic and hydrophobic particles and rugged structure to provide lotus effect |
US20060094320A1 (en) * | 2004-11-02 | 2006-05-04 | Kimberly-Clark Worldwide, Inc. | Gradient nanofiber materials and methods for making same |
US7390760B1 (en) | 2004-11-02 | 2008-06-24 | Kimberly-Clark Worldwide, Inc. | Composite nanofiber materials and methods for making same |
DE102004062740A1 (en) * | 2004-12-27 | 2006-07-13 | Degussa Ag | Process for increasing the water-tightness of textile fabrics, textile fabrics treated in this way and their use |
DE102004062739A1 (en) * | 2004-12-27 | 2006-07-06 | Degussa Ag | Self-cleaning surfaces with protrusions formed by hydrophobic particles, with improved mechanical strength |
DE102004062743A1 (en) * | 2004-12-27 | 2006-07-06 | Degussa Ag | Process for increasing the water-tightness of textile fabrics, textile fabrics treated in this way and their use |
DE102004062742A1 (en) * | 2004-12-27 | 2006-07-06 | Degussa Ag | Textile substrates with self-cleaning properties (lotus effect) |
GB2421727B (en) * | 2004-12-30 | 2007-11-14 | Ind Tech Res Inst | Method for forming coating material and the material formed thereby |
DE102005017384A1 (en) * | 2005-04-14 | 2006-10-19 | Ropimex R. Opel Gmbh | Disinfectants with germicidal properties, methods of preparation and use |
WO2006116424A2 (en) * | 2005-04-26 | 2006-11-02 | Nanosys, Inc. | Paintable nanofiber coatings |
US7772393B2 (en) | 2005-06-13 | 2010-08-10 | Innovative Surface Technologies, Inc. | Photochemical crosslinkers for polymer coatings and substrate tie-layer |
US20080233356A1 (en) * | 2005-09-12 | 2008-09-25 | Perlen Converting Ag | Method for the Application of a Structured Coating Upon a Smooth Surface |
WO2007070714A2 (en) * | 2005-12-15 | 2007-06-21 | Ashland Licensing And Intellectual Property Llc | Spray wax composition |
DE102006001641A1 (en) * | 2006-01-11 | 2007-07-12 | Degussa Gmbh | Coating substrate, particularly wall paper, comprises e.g. applying composition containing inorganic compound comprising metal/half metal, silane-containg coating, coating containing biocidal and/or anti-microbial substances, and drying |
US20090018249A1 (en) * | 2006-01-30 | 2009-01-15 | Subbareddy Kanagasabapathy | Hydrophobic self-cleaning coating compositions |
US20080221263A1 (en) * | 2006-08-31 | 2008-09-11 | Subbareddy Kanagasabapathy | Coating compositions for producing transparent super-hydrophobic surfaces |
US8258206B2 (en) | 2006-01-30 | 2012-09-04 | Ashland Licensing And Intellectual Property, Llc | Hydrophobic coating compositions for drag reduction |
US20080221009A1 (en) * | 2006-01-30 | 2008-09-11 | Subbareddy Kanagasabapathy | Hydrophobic self-cleaning coating compositions |
EP1844863A1 (en) * | 2006-04-12 | 2007-10-17 | General Electric Company | Article having a surface with low wettability and its method of making |
IL175477A (en) * | 2006-05-08 | 2013-09-30 | Efraim Kfir | Assembly for lifting the sinus membrane for use in dental implant surgery |
DE102006027480A1 (en) * | 2006-06-14 | 2008-01-10 | Evonik Degussa Gmbh | Scratch and abrasion resistant coatings on polymeric surfaces |
DE102006054158A1 (en) * | 2006-11-16 | 2008-05-21 | Wacker Chemie Ag | Ultrahydrophobic coatings |
GB0624729D0 (en) * | 2006-12-12 | 2007-01-17 | Univ Leeds | Reversible micelles and applications for their use |
US20080145631A1 (en) * | 2006-12-19 | 2008-06-19 | General Electric Company | Articles having antifouling surfaces and methods for making |
FR2910315B1 (en) * | 2006-12-20 | 2010-04-02 | Oreal | COSMETIC COMPOSITION WITH HYDROPHOBIC FILM |
WO2008075282A2 (en) * | 2006-12-20 | 2008-06-26 | L'oreal | Cosmetic kit for providing a hydrophobic film |
TWI384039B (en) * | 2006-12-27 | 2013-02-01 | Ind Tech Res Inst | Method of fabricating transparent hydrophobic self-cleaning coating material and coating material and transparent coating made therefrom |
DE102007009590A1 (en) * | 2007-02-26 | 2008-08-28 | Evonik Degussa Gmbh | Shiny and scratch-resistant nail polish by adding sol-gel systems |
DE102007009589A1 (en) * | 2007-02-26 | 2008-08-28 | Evonik Degussa Gmbh | Shiny and scratch-resistant nail polish by addition of silanes |
US7943234B2 (en) * | 2007-02-27 | 2011-05-17 | Innovative Surface Technology, Inc. | Nanotextured super or ultra hydrophobic coatings |
DE102007012924A1 (en) | 2007-03-19 | 2008-09-25 | Robert Bosch Gmbh | Wiper rubber and process for its preparation |
US7732497B2 (en) * | 2007-04-02 | 2010-06-08 | The Clorox Company | Colloidal particles for lotus effect |
US20080250978A1 (en) * | 2007-04-13 | 2008-10-16 | Baumgart Richard J | Hydrophobic self-cleaning coating composition |
EP2011630A1 (en) * | 2007-07-03 | 2009-01-07 | F. Hoffmann-La Roche AG | Method for manufacturing an analytical element |
US20090064894A1 (en) * | 2007-09-05 | 2009-03-12 | Ashland Licensing And Intellectual Property Llc | Water based hydrophobic self-cleaning coating compositions |
US20100247862A1 (en) * | 2007-11-19 | 2010-09-30 | E.I. Dupont De Nemours And Company | Treated plastic surfaces having improved cleaning properties |
US8153834B2 (en) * | 2007-12-05 | 2012-04-10 | E.I. Dupont De Nemours And Company | Surface modified inorganic particles |
US7878056B2 (en) * | 2007-12-19 | 2011-02-01 | Siargo Ltd. | Micromachined thermal mass flow sensor with self-cleaning capability and methods of making the same |
US8870839B2 (en) * | 2008-04-22 | 2014-10-28 | The Procter & Gamble Company | Disposable article including a nanostructure forming material |
US11786036B2 (en) | 2008-06-27 | 2023-10-17 | Ssw Advanced Technologies, Llc | Spill containing refrigerator shelf assembly |
US8286561B2 (en) | 2008-06-27 | 2012-10-16 | Ssw Holding Company, Inc. | Spill containing refrigerator shelf assembly |
US20100028604A1 (en) * | 2008-08-01 | 2010-02-04 | The Ohio State University | Hierarchical structures for superhydrophobic surfaces and methods of making |
ES2654377T3 (en) | 2008-10-07 | 2018-02-13 | Ross Technology Corporation | Spill resistant surfaces with hydrophobic and oleophobic boundaries |
EP2364224A4 (en) * | 2008-11-11 | 2017-12-27 | University of Florida Research Foundation, Inc. | Method of patterning a surface and articles comprising the same |
US8691983B2 (en) * | 2009-03-03 | 2014-04-08 | Innovative Surface Technologies, Inc. | Brush polymer coating by in situ polymerization from photoreactive surface |
US8147607B2 (en) * | 2009-10-26 | 2012-04-03 | Ashland Licensing And Intellectual Property Llc | Hydrophobic self-cleaning coating compositions |
US9074778B2 (en) | 2009-11-04 | 2015-07-07 | Ssw Holding Company, Inc. | Cooking appliance surfaces having spill containment pattern |
US20110118686A1 (en) * | 2009-11-13 | 2011-05-19 | The Procter & Gamble Company | Substrate with adherence for feces and menses |
EP2547832A4 (en) * | 2010-03-15 | 2016-03-16 | Ross Technology Corp | Plunger and methods of producing hydrophobic surfaces |
US8443483B2 (en) * | 2010-08-30 | 2013-05-21 | GM Global Technology Operations LLC | Wiper blade for vehicle window wiper |
WO2012115986A1 (en) | 2011-02-21 | 2012-08-30 | Ross Technology Corporation | Superhydrophobic and oleophobic coatings with low voc binder systems |
US9937655B2 (en) | 2011-06-15 | 2018-04-10 | University Of Florida Research Foundation, Inc. | Method of manufacturing catheter for antimicrobial control |
GB201111439D0 (en) | 2011-07-04 | 2011-08-17 | Syngenta Ltd | Formulation |
DE102011085428A1 (en) | 2011-10-28 | 2013-05-02 | Schott Ag | shelf |
WO2013090939A1 (en) | 2011-12-15 | 2013-06-20 | Ross Technology Corporation | Composition and coating for superhydrophobic performance |
DE102012201899A1 (en) * | 2012-02-09 | 2013-09-19 | Robert Bosch Gmbh | Wiper rubber with surface structuring and highly hydrophobic coating |
EP2859053B1 (en) * | 2012-06-08 | 2019-12-25 | University Of Houston | Self-cleaning coatings and methods for making same |
MX2015000119A (en) | 2012-06-25 | 2015-04-14 | Ross Technology Corp | Elastomeric coatings having hydrophobic and/or oleophobic properties. |
DE102012022757A1 (en) | 2012-11-22 | 2013-01-24 | Sew-Eurodrive Gmbh & Co. Kg | Drive component such as gear box used in industrial apparatus, has gear housing with specific wall thickness that is provided with surface portion having periodic waveform |
WO2014097309A1 (en) | 2012-12-17 | 2014-06-26 | Asian Paints Ltd. | Stimuli responsive self cleaning coating |
US10072241B2 (en) | 2013-03-13 | 2018-09-11 | Innovative Surface Technologies, Inc. | Conical devices for three-dimensional aggregate(s) of eukaryotic cells |
US11566148B2 (en) | 2016-05-10 | 2023-01-31 | The Australian National University | Interpenetrating polymer networks |
CN106675305A (en) * | 2016-12-28 | 2017-05-17 | 华南理工大学 | Self-repairable ultraviolet-curing polyacrylate-polysiloxane-white carbon black superhydrophobic coating and preparation method thereof |
JP6333454B1 (en) * | 2017-08-18 | 2018-05-30 | 株式会社フェクト | Method for forming water / oil repellent coating and water / oil repellent coating |
CN111545432A (en) * | 2020-05-11 | 2020-08-18 | 中国工程物理研究院化工材料研究所 | Preparation method of high-stability lyophobic surface |
CN111484723B (en) * | 2020-05-14 | 2022-09-16 | 上海金山锦湖日丽塑料有限公司 | Self-cleaning flame-retardant PC resin and preparation method thereof |
CN111763100B (en) * | 2020-06-10 | 2021-10-26 | 大理大学 | Preparation method of natural bluestone self-cleaning surface |
Family Cites Families (18)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3354022A (en) | 1964-03-31 | 1967-11-21 | Du Pont | Water-repellant surface |
US5432000A (en) † | 1989-03-20 | 1995-07-11 | Weyerhaeuser Company | Binder coated discontinuous fibers with adhered particulate materials |
US5141915A (en) * | 1991-02-25 | 1992-08-25 | Minnesota Mining And Manufacturing Company | Dye thermal transfer sheet with anti-stick coating |
DE4238380B4 (en) * | 1992-11-13 | 2004-02-19 | Merck Patent Gmbh | Process for coating substrate materials with a glossy coating |
KR940018419A (en) | 1993-01-18 | 1994-08-18 | 이마무라 가즈수케 | Fluorine-containing polymer molded article having improved water repellency and cleaning jig prepared therefrom |
WO1996004123A1 (en) | 1994-07-29 | 1996-02-15 | Wilhelm Barthlott | Self-cleaning surfaces of objects and process for producing same |
DE19860139C1 (en) * | 1998-12-24 | 2000-07-06 | Bayer Ag | Process for producing an ultraphobic surface based on nickel hydroxide, ultraphobic surface and their use |
YU67701A (en) | 1999-03-25 | 2003-08-29 | Wilhelm Barthlott | Method of producing self-cleaning detachable surfaces |
DE19914007A1 (en) | 1999-03-29 | 2000-10-05 | Creavis Tech & Innovation Gmbh | Structured liquid-repellent surfaces with locally defined liquid-wetting parts |
DE19917367A1 (en) | 1999-04-16 | 2000-10-19 | Inst Neue Mat Gemein Gmbh | Production of easy-to-clean coatings on substrates e.g. metal, plastics, glass or textiles, comprises applying fluorinated condensate-forming composition and drying at room temperature |
ATE339568T1 (en) * | 1999-05-26 | 2006-10-15 | Basf Corp | METAL ROOF SHINGLE STOCK AND METHOD FOR PRODUCING THEREOF |
DE10015855A1 (en) * | 2000-03-30 | 2001-10-11 | Basf Ag | Application of the lotus effect in process engineering |
DE10022246A1 (en) * | 2000-05-08 | 2001-11-15 | Basf Ag | Coating agent for the production of difficult to wet surfaces |
JP2004525754A (en) * | 2001-01-12 | 2004-08-26 | ビーエーエスエフ アクチェンゲゼルシャフト | Surface dirt prevention treatment method |
DE10118351A1 (en) * | 2001-04-12 | 2002-10-17 | Creavis Tech & Innovation Gmbh | Self-cleaning surfaces through hydrophobic structures and processes for their production |
DE10118349A1 (en) * | 2001-04-12 | 2002-10-17 | Creavis Tech & Innovation Gmbh | Self-cleaning surfaces through hydrophobic structures and processes for their production |
DE10118345A1 (en) * | 2001-04-12 | 2002-10-17 | Creavis Tech & Innovation Gmbh | Properties of structure formers for self-cleaning surfaces and the production of the same |
DE10118352A1 (en) * | 2001-04-12 | 2002-10-17 | Creavis Tech & Innovation Gmbh | Self-cleaning surfaces through hydrophobic structures and processes for their production |
-
2001
- 2001-04-12 DE DE10118352A patent/DE10118352A1/en not_active Ceased
-
2002
- 2002-02-22 ES ES02003960T patent/ES2271131T5/en not_active Expired - Lifetime
- 2002-02-22 DE DE50208229T patent/DE50208229D1/en not_active Expired - Fee Related
- 2002-02-22 AT AT02003960T patent/ATE340654T1/en not_active IP Right Cessation
- 2002-02-22 EP EP02003960A patent/EP1249280B2/en not_active Expired - Lifetime
- 2002-04-09 US US10/118,258 patent/US6858284B2/en not_active Expired - Fee Related
- 2002-04-09 JP JP2002106941A patent/JP2002346469A/en active Pending
- 2002-04-10 CA CA002381134A patent/CA2381134A1/en not_active Abandoned
Also Published As
Publication number | Publication date |
---|---|
EP1249280B2 (en) | 2009-07-01 |
ATE340654T1 (en) | 2006-10-15 |
CA2381134A1 (en) | 2002-10-12 |
US6858284B2 (en) | 2005-02-22 |
DE50208229D1 (en) | 2006-11-09 |
US20020150724A1 (en) | 2002-10-17 |
EP1249280A2 (en) | 2002-10-16 |
EP1249280A3 (en) | 2003-01-02 |
ES2271131T3 (en) | 2007-04-16 |
DE10118352A1 (en) | 2002-10-17 |
JP2002346469A (en) | 2002-12-03 |
ES2271131T5 (en) | 2009-10-30 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
EP1249280B1 (en) | Self-cleaning surfaces with hydrophobic structures and process for making them | |
EP1283076B1 (en) | Self cleaning surfaces due to hydrophobic structures and method for the preparation thereof | |
EP1249281B1 (en) | Self-cleaning surface with hydrophobic structure and process for making it | |
EP1249467B1 (en) | Self-cleaning surfaces due to hydrophobic structure and process for the preparation thereof | |
EP1317967B1 (en) | Diffusely reflecting surface and process for making it | |
EP1674535A1 (en) | Self cleaning surfaces having a surface structure made up of hydrophobic structural particles and wax particles | |
EP1472011B1 (en) | Method for the production of protective layers with dirt and water repelling properties | |
EP1283077A1 (en) | Obtaining a Lotus effect by preventing microbial growth on self-cleaning surfaces | |
EP1249468A2 (en) | Self-cleaning surfaces by hydrophobic structures and process for preparation | |
EP1171529A1 (en) | Method of producing self-cleaning detachable surfaces | |
WO2003013827A1 (en) | Structured surfaces that show a lotus effect | |
DE10210027A1 (en) | Hydrophilic surfaces | |
DE10231757A1 (en) | Process for the preparation of a surfactant-free suspension on an aqueous basis of nanostructured, hydrophobic particles and their use | |
EP1318165A1 (en) | Light-scattering materials having a self-cleaning surface | |
DE10134362A1 (en) | Structured hydrophobic surfaces, used to produce e.g. containers, pipettes, comprise projections which are parallel and linear, and which have a saw tooth shape | |
WO2003013748A1 (en) | Achieving a lotus effect by preventing microbial growth after damage to the self-cleaning surface | |
WO2004014575A1 (en) | Method for powder coating surfaces in order to produce the lotus effect | |
DE10233831A1 (en) | A process for preparation of structured surfaces with a carrier layer coated with nano particles useful for preparation of structured surfaces or films | |
DE102013218380A1 (en) | Self-generating textured surfaces with self-cleaning properties and a process for producing these surfaces |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
17P | Request for examination filed |
Effective date: 20020222 |
|
AK | Designated contracting states |
Kind code of ref document: A2 Designated state(s): AT BE CH CY DE DK ES FI FR GB GR IE IT LI LU MC NL PT SE TR |
|
AX | Request for extension of the european patent |
Free format text: AL;LT;LV;MK;RO;SI |
|
PUAL | Search report despatched |
Free format text: ORIGINAL CODE: 0009013 |
|
AK | Designated contracting states |
Kind code of ref document: A3 Designated state(s): AT BE CH CY DE DK ES FI FR GB GR IE IT LI LU MC NL PT SE TR |
|
AX | Request for extension of the european patent |
Free format text: AL;LT;LV;MK;RO;SI |
|
17Q | First examination report despatched |
Effective date: 20030407 |
|
AKX | Designation fees paid |
Designated state(s): AT BE CH CY DE DK ES FI FR GB GR IE IT LI LU MC NL PT SE TR |
|
RAP1 | Party data changed (applicant data changed or rights of an application transferred) |
Owner name: DEGUSSA AG |
|
GRAP | Despatch of communication of intention to grant a patent |
Free format text: ORIGINAL CODE: EPIDOSNIGR1 |
|
GRAS | Grant fee paid |
Free format text: ORIGINAL CODE: EPIDOSNIGR3 |
|
GRAA | (expected) grant |
Free format text: ORIGINAL CODE: 0009210 |
|
AK | Designated contracting states |
Kind code of ref document: B1 Designated state(s): AT BE CH CY DE DK ES FI FR GB GR IE IT LI LU MC NL PT SE TR |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: IE Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20060927 Ref country code: FI Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20060927 Ref country code: IT Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT;WARNING: LAPSES OF ITALIAN PATENTS WITH EFFECTIVE DATE BEFORE 2007 MAY HAVE OCCURRED AT ANY TIME BEFORE 2007. THE CORRECT EFFECTIVE DATE MAY BE DIFFERENT FROM THE ONE RECORDED. Effective date: 20060927 |
|
REG | Reference to a national code |
Ref country code: GB Ref legal event code: FG4D Free format text: NOT ENGLISH |
|
REG | Reference to a national code |
Ref country code: CH Ref legal event code: EP Ref country code: CH Ref legal event code: NV Representative=s name: SCHMAUDER & PARTNER AG PATENTANWALTSBUERO |
|
REG | Reference to a national code |
Ref country code: IE Ref legal event code: FG4D Free format text: LANGUAGE OF EP DOCUMENT: GERMAN |
|
REF | Corresponds to: |
Ref document number: 50208229 Country of ref document: DE Date of ref document: 20061109 Kind code of ref document: P |
|
GBT | Gb: translation of ep patent filed (gb section 77(6)(a)/1977) |
Effective date: 20061102 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: DK Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20061227 Ref country code: SE Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20061227 |
|
RAP2 | Party data changed (patent owner data changed or rights of a patent transferred) |
Owner name: DEGUSSA GMBH |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: MC Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20070228 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: PT Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20070313 |
|
ET | Fr: translation filed | ||
REG | Reference to a national code |
Ref country code: ES Ref legal event code: FG2A Ref document number: 2271131 Country of ref document: ES Kind code of ref document: T3 |
|
REG | Reference to a national code |
Ref country code: IE Ref legal event code: FD4D |
|
NLT2 | Nl: modifications (of names), taken from the european patent patent bulletin |
Owner name: DEGUSSA GMBH Effective date: 20070221 |
|
PLBI | Opposition filed |
Free format text: ORIGINAL CODE: 0009260 |
|
PLAX | Notice of opposition and request to file observation + time limit sent |
Free format text: ORIGINAL CODE: EPIDOSNOBS2 |
|
26 | Opposition filed |
Opponent name: BASF AKTIENGESELLSCHAFT Effective date: 20070627 |
|
NLR1 | Nl: opposition has been filed with the epo |
Opponent name: BASF AKTIENGESELLSCHAFT |
|
RAP2 | Party data changed (patent owner data changed or rights of a patent transferred) |
Owner name: EVONIK DEGUSSA GMBH |
|
PLBB | Reply of patent proprietor to notice(s) of opposition received |
Free format text: ORIGINAL CODE: EPIDOSNOBS3 |
|
NLT2 | Nl: modifications (of names), taken from the european patent patent bulletin |
Owner name: EVONIK DEGUSSA GMBH Effective date: 20071107 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: GR Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20061228 |
|
PLAB | Opposition data, opponent's data or that of the opponent's representative modified |
Free format text: ORIGINAL CODE: 0009299OPPO |
|
RAP2 | Party data changed (patent owner data changed or rights of a patent transferred) |
Owner name: EVONIK DEGUSSA GMBH |
|
NLT2 | Nl: modifications (of names), taken from the european patent patent bulletin |
Owner name: EVONIK DEGUSSA GMBH Effective date: 20080806 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: AT Payment date: 20090218 Year of fee payment: 8 Ref country code: ES Payment date: 20090219 Year of fee payment: 8 Ref country code: LU Payment date: 20090216 Year of fee payment: 8 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: DE Payment date: 20090219 Year of fee payment: 8 Ref country code: NL Payment date: 20090217 Year of fee payment: 8 |
|
PUAH | Patent maintained in amended form |
Free format text: ORIGINAL CODE: 0009272 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: PATENT MAINTAINED AS AMENDED |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: CH Payment date: 20090217 Year of fee payment: 8 Ref country code: GB Payment date: 20090219 Year of fee payment: 8 |
|
27A | Patent maintained in amended form |
Effective date: 20090701 |
|
AK | Designated contracting states |
Kind code of ref document: B2 Designated state(s): AT BE CH CY DE DK ES FI FR GB GR IE IT LI LU MC NL PT SE TR |
|
REG | Reference to a national code |
Ref country code: CH Ref legal event code: AEN Free format text: AUFRECHTERHALTUNG DES PATENTES IN GEAENDERTER FORM |
|
REG | Reference to a national code |
Ref country code: CH Ref legal event code: PCAR Free format text: SCHMAUDER & PARTNER AG PATENT- UND MARKENANWAELTE VSP;ZWAENGIWEG 7;8038 ZUERICH (CH) |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: CY Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20060927 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: IT Payment date: 20090223 Year of fee payment: 8 |
|
NLR2 | Nl: decision of opposition |
Effective date: 20090701 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: TR Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20060927 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: BE Payment date: 20090408 Year of fee payment: 8 |
|
NLR3 | Nl: receipt of modified translations in the netherlands language after an opposition procedure | ||
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: FR Payment date: 20090213 Year of fee payment: 8 |
|
REG | Reference to a national code |
Ref country code: ES Ref legal event code: DC2A Date of ref document: 20090818 Kind code of ref document: T5 |
|
REG | Reference to a national code |
Ref country code: FR Ref legal event code: CD Ref country code: FR Ref legal event code: CA |
|
REG | Reference to a national code |
Ref country code: NL Ref legal event code: TD Effective date: 20100223 Ref country code: NL Ref legal event code: SD Effective date: 20100223 |
|
BERE | Be: lapsed |
Owner name: EVONIK DEGUSSA G.M.B.H. Effective date: 20100228 |
|
REG | Reference to a national code |
Ref country code: NL Ref legal event code: V1 Effective date: 20100901 |
|
REG | Reference to a national code |
Ref country code: CH Ref legal event code: PL |
|
GBPC | Gb: european patent ceased through non-payment of renewal fee |
Effective date: 20100222 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: LI Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20100228 Ref country code: CH Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20100228 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: AT Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20100222 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: NL Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20100901 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: DE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20100901 Ref country code: BE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20100228 |
|
REG | Reference to a national code |
Ref country code: ES Ref legal event code: FD2A Effective date: 20110323 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: GB Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20100222 Ref country code: IT Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20100222 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: ES Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20110310 |
|
REG | Reference to a national code |
Ref country code: FR Ref legal event code: ST Effective date: 20110729 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: ES Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20100223 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: FR Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20100301 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: LU Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20100222 |