EP1249281A2 - Self-cleaning surface with hydrophobic structure and process for making it - Google Patents
Self-cleaning surface with hydrophobic structure and process for making it Download PDFInfo
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- EP1249281A2 EP1249281A2 EP02004703A EP02004703A EP1249281A2 EP 1249281 A2 EP1249281 A2 EP 1249281A2 EP 02004703 A EP02004703 A EP 02004703A EP 02004703 A EP02004703 A EP 02004703A EP 1249281 A2 EP1249281 A2 EP 1249281A2
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- Prior art keywords
- particles
- self
- depressions
- elevations
- cleaning
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D5/00—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures
- B05D5/08—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures to obtain an anti-friction or anti-adhesive surface
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D5/00—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures
- B05D5/08—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures to obtain an anti-friction or anti-adhesive surface
- 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
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- 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.]
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- 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
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- 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
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- 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
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- 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.]
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- 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
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- 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
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- 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
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- 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
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- 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
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- 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
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- Y10T428/254—Polymeric or resinous material
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- 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
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- Y10T428/256—Heavy metal or aluminum or compound thereof
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- 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
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- Y10T428/25—Web or sheet containing structurally defined element or component and including a second component containing structurally defined particles
- Y10T428/259—Silicic material
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- 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 structured particles and the use thereof for self-cleaning surfaces and processes for their manufacture.
- Objects with extremely difficult to wet surfaces have a number of economical ones significant features.
- the most economically significant feature is the self-cleaning effect of difficult to wet surfaces, because the cleaning of Surface is time and cost intensive.
- Self-cleaning surfaces are therefore of the highest quality economic interest.
- Detention mechanisms are usually through interfacial energy parameters between the two surfaces in contact.
- the systems try to lower their free interface energy. Lie the free interface energies between two components are inherently very low, So it can generally be assumed that the liability between these two Components is weak.
- the relative lowering of the free is important Interfacial energy. For pairings with a high and a low interfacial energy the possibilities of interactions are very important.
- hydrophobic materials such as perfluorinated polymers
- hydrophobic surfaces are known.
- a further development of these surfaces is to structure the surfaces in the ⁇ m range to the nm range.
- US Patent 5,599,489 discloses a Process in which a surface is bombarded with particles of an appropriate size and subsequent perfluorination can be made particularly repellent.
- Another Methods describe H. Saito et al in "Service Coatings International" 4, 1997, p. 168 ff.
- particles of fluoropolymers are applied to metal surfaces, with a strong reduced wettability of the surfaces thus produced against water with a considerably reduced tendency to icing was found.
- US Pat. Nos. 3,354,022 and WO 96/04123 describe further methods for lowering the Wettability of objects due to topological changes in the surfaces described.
- artificial elevations or depressions with a height of approx. 5 up to 1 000 ⁇ m and a distance of approx. 5 to 500 ⁇ m on hydrophobic or after Structuring applied hydrophobic materials.
- Surfaces of this type lead to a rapid drop formation, the rolling drops absorbing dirt particles and thus clean the surface.
- EP 1 040 874 A2 describes the stamping of microstructures and claims them Use of such structures in analysis (microfluidics). A disadvantage of these structures is the insufficient mechanical stability.
- JP 11171592 describes a water-repellent product and its production, the dirt-repellent surface is produced by a film on the treating surface is applied, the fine particles of metal oxide and the hydrolyzate a metal alkoxide or chelate. To solidify this film, the substrate, to which the film was applied are sintered at temperatures above 400 ° C. The method can therefore only be used for substrates that are also at temperatures above of 400 ° C are stable.
- the object of the present invention was to provide particularly good self-cleaning Surfaces with structures in the nanometer range, as well as a simple process for Manufacture of such self-cleaning surfaces.
- the present invention therefore relates to a self-cleaning surface which has a artificial, at least partially hydrophobic surface structure from surveys and Has depressions, the elevations and depressions through on the surface fixed particles are formed, which is characterized in that the particles a have fissured structure with elevations and / or depressions in the nanometer range.
- the present invention also relates to a method for producing self-cleaning surfaces where a suitable, at least partially hydrophobic Surface structure is created by fixing particles on a surface, which is characterized in that particles, the jagged structures with elevations and / or Have depressions in the nanometer range can be used.
- Self-cleaning surfaces are accessible through the method according to the invention Particles with a fissured structure. By using particles which have a rugged structure, surfaces are easily accessible that up to are structured in the nanometer range. In contrast to conventional methods that Use the smallest possible particles to achieve the cleaning effect in the The method according to the invention uses particles which themselves have a structure in the nanometer range have, which is why the particle size itself is less critical, since the distance between the surveys is determined not only by the particle size but also by the nanoscale structure.
- the self-cleaning surface according to the invention which is an artificial, at least partially Has hydrophobic surface structure of elevations and depressions, the Elevations and depressions are formed by particles fixed on the surface, is characterized in that the particles have a jagged structure with elevations and / or Have depressions in the nanometer range.
- the elevations and / or preferably have Wells on average a height of 20 to 500 nm, particularly preferably from 20 to 200 nm on.
- the distance between the elevations or depressions on the particles is preferably less than 500 nm, very particularly preferably less than 200 nm.
- the jagged structures with elevations and / or depressions in the nanometer range can e.g. over cavities, pores, grooves, tips and / or peaks are formed.
- the Particles themselves have an average size of less than 50 ⁇ m, preferably of smaller size 30 ⁇ m and very particularly preferably from less than 20 ⁇ m.
- the particles on the surface preferably have distances of 0-10 particle diameters, in particular 2-3 Particle diameter.
- the particles can be particles in the sense of DIN 53 206.
- the structure of such Particles can be spherical, strictly spherical, moderately aggregated, almost spherical, extremely strong be agglomerated or porous agglomerated.
- the preferred size of the agglomerates or Aggregate is between 20 nm and 100 ⁇ m, particularly preferably between 0.2 and 30 ⁇ m.
- the particles preferably have a BET surface area of 20 to 1000 square meters per gram.
- the particles very particularly preferably have a BET surface area of 50 to 200 m 2 / g.
- the particles preferably have at least one material selected from silicates, doped silicates, minerals, metal oxides, silicas, polymers and metal powders coated with silicic acid.
- the particles very particularly preferably have pyrogenic silicas or precipitated silicas, in particular aerosils, Al 2 O 3 , SiO 2 , TiO 2 , ZrO 2, zinc powder coated with Aerosil R974, preferably with a particle size of 0.2 to 30 ⁇ m or powdery polymers such as eg cryogenically ground or spray-dried polytetrafluoroethylene (PTFE) or perfluorinated copolymers or copolymers with tetrafluoroethylene.
- PTFE polytetrafluoroethylene
- the particles for generating the self-cleaning surfaces preferably have in addition to the rugged structures also have hydrophobic properties.
- the particles can themselves be hydrophobic, e.g. Particles containing PTFE, or the particles used can have been made hydrophobic.
- the hydrophobicization of the particles can be done by a person skilled in the art known way.
- Typical hydrophobized particles are e.g. Very fine powder like Aerosil-R 8200 (Degussa AG), which can be purchased.
- the preferably used silicas preferably have a dibutyl phthalate adsorbtion, based on DIN 53 601, of between 100 and 350 ml / 100 g, preferably values between 250 and 350 ml / 100 g.
- the particles are fixed on the surface.
- the fixing can be done by a person skilled in the art known manner in a chemical or physical (mechanical).
- the self-cleaning can Generate surface.
- the self-cleaning surfaces according to the invention have a roll angle of less than 20 °, particularly preferably less than 10 °, the roll angle being defined such that one of the first cm height on a flat surface resting on an inclined plane Water drops roll off.
- the progression angle and the retreat angle are above 140 °, preferably above 150 ° and have a hysteresis of less than 15 °, preferably less 10 ° on that the surfaces according to the invention have a progressive and Have retraction angles above at least 140 °, preferably above 150 °, particularly good self-cleaning surfaces become accessible.
- the self-cleaning surfaces are semi-transparent.
- the surfaces according to the invention can be contact-transparent, that is to say after Creating a surface according to the invention on a labeled object Lettering, depending on the size of the font, is still legible.
- the self-cleaning surfaces according to the invention are preferably by Method according to the invention according to one of claims 9 to 16 for the production of this Surfaces.
- This inventive method for producing self-cleaning surfaces where a suitable, at least partially hydrophobic Surface structure is created by fixing particles on the surface is characterized by the fact that, as described above, particles with fissured structures Have elevations and / or depressions in the nanometer range can be used.
- particles which have at least one material selected from silicates or doped silicates, minerals, metal oxides, pyrogenic silicas or precipitated silicas or polymers are preferably used.
- the particles very particularly preferably comprise silicates, pyrogenic silicas or precipitated silicas, in particular aerosils, minerals such as magadiite Al 2 O 3 , SiO 2 , TiO 2 , ZrO 2 Zn powder coated with Aerosil R 974 or powdery polymers, such as cryogenically ground or spray-dried Polytetrafluoroethylene (PTFE).
- PTFE Polytetrafluoroethylene
- Particles with a BET surface area of 50 to 600 m 2 / g are particularly preferably used. Particles which have a BET surface area of 50 to 200 m 2 / g are very particularly preferably used.
- the particles for generating the self-cleaning surfaces preferably have in addition to the rugged structures also have hydrophobic properties.
- the particles can themselves be hydrophobic, e.g. Particles containing PTFE, or the particles used can have been made hydrophobic.
- the hydrophobicization of the particles can be done by a person skilled in the art known way.
- Typical hydrophobized particles are e.g. Very fine powder like Aerosil R 974 or Aerosil-R 8200 (Degussa AG), which can be purchased.
- the particles can be fixed on the surface in a manner known to those skilled in the art Done chemically or physically.
- a chemical method of fixation e.g. the Use of a fixative can be used.
- fixatives Adhesives, adhesion promoters or paints in question. The person skilled in the art will find more Fixing agents or chemical fixing methods.
- particles to use which have hydrophobic properties and / or by treatment with at least one compound from the group of alkylsilanes, alkyldisilazanes, paraffins, waxes, Fluoroalkylsilanes, fatty acid esters, functionalized long chain alkane derivatives or Perfluoroalkylsilanes have hydrophobic properties.
- the hydrophobization of particles is well known and can e.g. in the series Pigments, number 18, Degussa AG can be read.
- the particles of the treated Surface by treatment with at least one compound from the group of Alkylsilanes e.g. are available from Sivento GmbH, alkyl disilazanes, paraffins, Waxes, fluoroalkylsilanes, fatty acid esters, functionalized long-chain alkane derivatives or Perfluoroalkylsilanes, with hydrophobic properties.
- the treatment in that the particle-containing surface that is hydrophobized in a solution containing a water repellent such as e.g.
- the maximum Applicable temperature is due to the softening temperatures of the substrate or substrate limited.
- the inventive method according to at least one of claims 9 to 16 can excellent for producing self-cleaning surfaces on planar or non-planar Objects, especially on non-planar objects. This is with the conventional methods only possible to a limited extent. In particular about procedures at where prefabricated films are applied to a surface or in processes in which a structure to be created by embossing are non-planar objects, such as Sculptures, not or only partially accessible.
- the invention can Process for the production of self-cleaning surfaces on objects with planar surfaces, e.g. Greenhouses or public transport become.
- the use of the method according to the invention for the production of Self-cleaning surfaces on greenhouses have advantages because of the process self-cleaning surfaces e.g.
- the method according to the invention can also be used to produce self-cleaning Surfaces on non-rigid surfaces of objects, such as e.g. Umbrellas or other surfaces that are kept flexible.
- objects such as e.g. Umbrellas or other surfaces that are kept flexible.
- inventive method according to at least one of claims 9 to 16 for Production of self-cleaning surfaces on flexible or inflexible walls in the Sanitary area can be used.
- Such walls can e.g. Partitions in public Toilets, walls of shower cubicles, swimming pools or saunas, but also shower curtains (flexible wall).
- the present invention also relates to particles which have a fissured structure with elevations and / or depressions in the nanometer range, and for Production of surfaces according to one of claims 1 to 8 are suitable.
- these particles Preferably have elevations and / or depressions with an average height of 20 to 500 nm, preferably from 20 to 200 nm.
- the distance is preferably Elevations and / or depressions on the particle less than 500 nm, preferably less than 200 nm.
- the particles according to the invention can e.g. from at least one material selected from silicates, doped silicates, minerals, metal oxides, pyrogenic or Precipitated silicas, polymers and metal powders can be selected.
- the particles can be particles in the sense of DIN 53 206.
- the structure of such Particles can be spherical, strictly spherical, moderately aggregated, almost spherical, extremely strong be agglomerated or porous agglomerated.
- the preferred size of the agglomerates or Aggregate is between 20 nm and 100 ⁇ m, particularly preferably between 0.2 and 30 ⁇ m.
- the support was at a wavelength of 308 nm under nitrogen hardened. After the carrier had hardened, excess Aerosil VPR 411 was brushed off. The surface was initially characterized visually and is logged with +++. +++ means that water drops form almost completely. The roll angle was 2.4 °. The advancing and retreating angles were measured to be greater than 150 ° each. The associated Hysteresis is below 10 °.
- Example 2 The experiment from Example 1 was repeated, particles of aluminum oxide C (Degussa AG), an aluminum oxide with a BET surface area of 100 m 2 / g, being sprayed on electrostatically.
- the carrier had cured in accordance with Example 1 and excess particles had been brushed off
- the hardened, brushed plate was immersed in a formulation of tridecafluorooctyltriethoxysilane in ethanol (Dynasilan 8262, Sivento GmbH) to make it hydrophobic.
- the plate After draining excess Dynasilan 8262, the plate was annealed at a temperature of 80 ° C. The surface is classified with ++, which means that the shape of the water drops is not ideal, the roll angle is below 20 °.
- Silica Sipernat 350 is added to the plate from Example 1 treated with the support Degussa AG spread. After 5 minutes of penetration, the treated plate under nitrogen in UV light hardened at 308 nm. Excess particles are brushed off and the The plate is then again immersed in Dynasilan 8262 and then at 80 ° C annealed. The surface is rated +++.
- Aerosil VPR 411 Aerosil R 8200 (Degussa AG) is used, which has a BET surface area of 200 ⁇ 25 m 2 / g.
- the evaluation of the surface is +++.
- the roll angle has been determined to be 1.3 °.
- Progress and retreat angles were also measured, each of which was greater than 150 °.
- the associated hysteresis is below 10 °.
- Example 2 The varnish from Example 1, which had already been mixed with the UV hardener, was added 10 wt .-% (based on the total weight of the paint mixture) 2- (N-ethylperfluorooctanesulfonamido) ethyl acrylate added. This mixture was again stirred for at least 60 min. This mixture was supported on a 2 mm thick PMMA plate applied in a thickness of 50 microns. The layer was left for 5 min dry. Then hydrophobicized, pyrogenic silica Aerosil as particles VPR 411 (Degussa AG) sprayed on using an electrostatic spray gun. After 3 min the carrier was cured at 308 nm wavelength under nitrogen.
- VPR 411 Degussa AG
- Aerosil VPR 411 After hardening excess Aerosil VPR 411 was brushed off the carrier. The characterization of the The surface was initially visual and is logged with +++. +++ means Drops of water form almost completely. The roll angle was 0.5 °. Measured progression and retreat angles were each greater than 150 °. The associated hysteresis is below 10 °.
Abstract
Description
Die vorliegende Erfindung betrifft strukturierte Partikel und die Verwendung selbiger für selbstreinigende Oberflächen und Verfahren zu deren Herstellung.The present invention relates to structured particles and the use thereof for self-cleaning surfaces and processes for their manufacture.
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.Objects with extremely difficult to wet surfaces have a number of economical ones significant features. The most economically significant feature is the self-cleaning effect of difficult to wet surfaces, because the cleaning of Surface is time and cost intensive. Self-cleaning surfaces are therefore of the highest quality economic interest. Detention mechanisms are usually through interfacial energy parameters between the two surfaces in contact. As a rule, the systems try to lower their free interface energy. Lie the free interface energies between two components are inherently very low, So it can generally be assumed that the liability between these two Components is weak. The relative lowering of the free is important Interfacial energy. For pairings with a high and a low interfacial energy the possibilities of interactions are very important. For example, at It is not possible to apply water to a hydrophobic surface, a noticeable one To bring about a reduction in the interfacial energy. This can be seen 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 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 are known. A further development of these surfaces is to structure the surfaces in the µm range to the nm range. US Patent 5,599,489 discloses a Process in which a surface is bombarded with particles of an appropriate size and subsequent perfluorination can be made particularly repellent. Another Methods describe H. Saito et al in "Service Coatings International" 4, 1997, p. 168 ff. Here particles of fluoropolymers are applied to metal surfaces, with a strong reduced wettability of the surfaces thus produced against water with a considerably reduced tendency to icing was found.
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.US Pat. Nos. 3,354,022 and WO 96/04123 describe further methods for lowering the Wettability of objects due to topological changes in the surfaces described. Here artificial elevations or depressions with a height of approx. 5 up to 1 000 µm and a distance of approx. 5 to 500 µm on hydrophobic or after Structuring applied hydrophobic materials. Surfaces of this type lead to a rapid drop formation, the rolling drops absorbing dirt particles and thus clean the surface.
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 decrease the van der Waal's interaction, for adhesion to flat surfaces with low surface energy responsible for. For example, the leaves of the lotus plant are raised from one Apply wax that will reduce the contact area to water. WO 00/58410 describes the Structures and claims the formation of the same by spraying on hydrophobic Alcohols, such as nonakosan-10-ol, or alkane diols, such as nonakosan-5,10-diol. adversely this is due to the poor stability of the self-cleaning surfaces, as detergents are used Detach the structure.
Eine weitere Methode, leicht reinigbare Oberflächen zu erzeugen, ist in DE 19917367 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 of producing easily cleanable surfaces is described in DE 19917367 A1 described. However, coatings based on fluorine-containing condensates are not self-cleaning. The Contact area between water and surface is reduced, but not in sufficient measure.
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 stamping of microstructures and claims them Use of such structures in analysis (microfluidics). A disadvantage of these structures is the insufficient mechanical stability.
Selbstwiederholende oder selbstähnlicheStrukturen von Oberflächen werden beispielsweise von Marie E. Turner in Advanced Materials, 2001, 13, No. 3, Seite 180 ff. beschrieben.Self-repeating or self-similar structures of surfaces are described, for example, by Marie E. Turner in Advanced Materials, 2001, 13, no. 3, page 180 ff.
In JP 11171592 wird ein wasserabweisendes Produkt und dessen Herstellung beschrieben, wobei die schmutzabweisende 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 production, the dirt-repellent surface is produced by a film on the treating surface is applied, the fine particles of metal oxide and the hydrolyzate a metal alkoxide or chelate. To solidify this film, the substrate, to which the film was applied are sintered at temperatures above 400 ° C. The method can therefore only be used for substrates that are also at temperatures above of 400 ° C are stable.
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 good self-cleaning Surfaces with structures in the nanometer range, as well as a simple process for Manufacture of such self-cleaning surfaces.
Überraschenderweise wurde gefunden, dass selbstreinigende Oberflächen besonders einfach erhalten werden können, wenn Partikel, die eine nanoskalige Struktur aufweisen eingesetzt werden.Surprisingly, it has been found that self-cleaning surfaces are particularly simple can be obtained if particles that have a nanoscale structure are used become.
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 auf der Oberfläche fixierte Partikel gebildet werden, welche dadurch gekennzeichnet ist, dass die Partikel eine zerklüftete Struktur mit Erhebungen und/oder Vertiefungen im Nanometerbereich aufweisen.The present invention therefore relates to a self-cleaning surface which has a artificial, at least partially hydrophobic surface structure from surveys and Has depressions, the elevations and depressions through on the surface fixed particles are formed, which is characterized in that the particles a have fissured 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 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 relates to a method for producing self-cleaning surfaces where a suitable, at least partially hydrophobic Surface structure is created by fixing particles on a surface, which is characterized in that particles, the jagged structures with elevations and / or Have depressions in the nanometer range can be used.
Durch das erfindungsgemäße Verfahren sind selbstreinigende Oberflächen zugänglich, die Partikel mit einer zerklüfteten Struktur aufweisen. Durch die Verwendung von Partikeln, welche eine zerklüftete Struktur aufweisen, werden auf einfache Weise Oberflächen zugänglich, die bis in den Nanometerbereich strukturiert sind. Im Gegensatz zu herkömmlichen Verfahren, die möglichst kleine Partikel einsetzen, um den Reinigungseffekt zu erzielen, werden in dem erfindungsgemäßen Verfahren Partikel eingesetzt, die selbst eine Struktur im Nanometerbereich aufweisen, weshalb die Partikelgröße selbst weniger kritisch ist, da der Abstand der Erhebungen nicht allein durch die Partikelgröße sondern auch durch die nanoskalige Struktur bestimmt wird.Self-cleaning surfaces are accessible through the method according to the invention Particles with a fissured structure. By using particles which have a rugged structure, surfaces are easily accessible that up to are structured in the nanometer range. In contrast to conventional methods that Use the smallest possible particles to achieve the cleaning effect in the The method according to the invention uses particles which themselves have a structure in the nanometer range have, which is why the particle size itself is less critical, since the distance between the surveys is determined not only by the particle size but also by the nanoscale structure.
Die erfindungsgemäße selbstreinigende Oberfläche, die eine künstliche, zumindest teilweise hydrophobe Oberflächenstruktur aus Erhebungen und Vertiefungen aufweist, wobei die Erhebungen und Vertiefungen durch auf der Oberfläche fixierten Partikel gebildet werden, zeichnet sich dadurch aus, dass die Partikel eine zerklüftete Struktur mit Erhebungen und/oder Vertiefungen im Nanometerbereich aufweisen. Vorzugsweise weisen die Erhöhungen und/oder Vertiefungen im Mittel eine Höhe von 20 bis 500 nm, besonders bevorzugt von 20 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 is an artificial, at least partially Has hydrophobic surface structure of elevations and depressions, the Elevations and depressions are formed by particles fixed on the surface, is characterized in that the particles have a jagged structure with elevations and / or Have depressions in the nanometer range. The elevations and / or preferably have Wells on average a height of 20 to 500 nm, particularly preferably from 20 to 200 nm on. The distance between the elevations or depressions on the particles is preferably less than 500 nm, very particularly preferably less than 200 nm.
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. Die Partikel auf der Oberfläche weisen vorzugsweise Abstände von 0 - 10 Partikeldurchmessern, insbesondere von 2 - 3 Partikeldurchmesser auf.The jagged structures with elevations and / or depressions in the nanometer range can e.g. over cavities, pores, grooves, tips and / or peaks are formed. The Particles themselves have an average size of less than 50 μm, preferably of smaller size 30 µm and very particularly preferably from less than 20 µm. The particles on the surface preferably have distances of 0-10 particle diameters, in particular 2-3 Particle diameter.
Die Partikel können Teilchen im Sinne von DIN 53 206 sein. Partikel oder Teilchen gemäß dieser Norm können Einzelteilchen aber auch Aggregate oder Agglomerate sein, wobei gemäß DIN 53 206 unter Aggregaten flächig oder kantenförmig aneinander gelagerte Primärteilchen (Partikel) und unter Agglomeraten punktförmig aneinandergelagerte Primärteilchen (Partikel) verstanden werden. Als Partikel können auch solche eingesetzt werden, die sich aus Primärteilchen zu Agglomeraten oder Aggregaten zusammenlagern. Die Struktur solcher Partikel kann sphärisch, streng sphärisch, mäßig aggregiert, nahezu sphärisch, äußerst stark agglomeriert oder porös agglomeriert sein. Die bevorzugte Größe der Agglomerate bzw. Aggregate liegt zwischen 20 nm und 100 µm, besonders bevorzugt zwischen 0,2 und 30 µm.The particles can be particles in the sense of DIN 53 206. Particles or particles according to According to this standard, individual particles can also be aggregates or agglomerates DIN 53 206 under aggregates of flat or edged primary particles (Particles) and primary particles (particles) which are clustered together under agglomerates be understood. Particles which are composed of Store primary particles together to form agglomerates or aggregates. The structure of such Particles can be spherical, strictly spherical, moderately aggregated, almost spherical, extremely strong be agglomerated or porous agglomerated. The preferred size of the agglomerates or Aggregate is between 20 nm and 100 µm, particularly preferably between 0.2 and 30 µm.
Bevorzugt weisen die Partikel eine BET-Oberfläche von 20 bis 1000 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 20 to 1000 square meters per gram. The particles very particularly preferably have a BET surface area of 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 0,2 bis 30 µm oder pulverförmige Polymere, wie z.B. kryogen gemahlenes oder sprühgetrocknetes Polytetrafluorethylen (PTFE) oder perfluorierte Copolymere bzw. Copolymere mit Tetrafluorethylen, auf.A wide variety of compounds from many areas of chemistry can be used as structure-forming particles. The particles preferably have at least one material selected from silicates, doped silicates, minerals, metal oxides, silicas, polymers and metal powders coated with silicic acid. The particles very particularly preferably have pyrogenic silicas or precipitated silicas, in particular aerosils, Al 2 O 3 , SiO 2 , TiO 2 , ZrO 2, zinc powder coated with Aerosil R974, preferably with a particle size of 0.2 to 30 μm or powdery polymers such as eg cryogenically ground or spray-dried polytetrafluoroethylene (PTFE) or perfluorinated copolymers or copolymers with tetrafluoroethylene.
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 for generating the self-cleaning surfaces preferably have in addition to the rugged structures also have hydrophobic properties. The particles can themselves be hydrophobic, e.g. Particles containing PTFE, or the particles used can have been made hydrophobic. The hydrophobicization of the particles can be done by a person skilled in the art known way. Typical hydrophobized particles are e.g. Very fine powder like Aerosil-R 8200 (Degussa AG), which can be purchased.
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 silicas preferably have a dibutyl phthalate adsorbtion, based on DIN 53 601, of between 100 and 350 ml / 100 g, preferably values between 250 and 350 ml / 100 g.
Die Partikel werden an der Oberfläche fixiert. Das Fixieren kann auf eine dem Fachmann bekannte Weise auf chemisch oder physikalisch (mechanisch) erfolgen. Durch Auftrag der Partikel auf die Oberfläche in einer dicht gepackten Schicht, läßt sich die selbstreinigende Oberfläche generieren.The particles are fixed on the surface. The fixing can be done by a person skilled in the art known manner in a chemical or physical (mechanical). By order of the Particles on the surface in a tightly packed layer, the self-cleaning can Generate surface.
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 a roll angle of less than 20 °, particularly preferably less than 10 °, the roll angle being defined such that one of the first cm height on a flat surface resting on an inclined plane Water drops roll off. The progression angle and the retreat angle are above 140 °, preferably above 150 ° and have a hysteresis of less than 15 °, preferably less 10 ° on that the surfaces according to the invention have a progressive and Have retraction angles above at least 140 °, preferably above 150 °, particularly good self-cleaning surfaces become accessible.
Je nach verwendeter Oberfläche 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 surface used and the size and material of the particles used, can achieved that the self-cleaning surfaces are semi-transparent. In particular the surfaces according to the invention can be contact-transparent, that is to say after Creating a surface according to the invention on a labeled object Lettering, depending on the size of the font, is still legible.
Die erfindungsgemäßen selbstreinigenden Oberflächen werden vorzugsweise durch das erfindungsgemäße Verfahren gemäß einem der Ansprüche 9 bis 16 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 auf der Oberfläche geschaffen wird, zeichnet sich dadurch aus, dass wie oben beschriebene Partikel, die zerklüftete Strukturen mit Erhebungen und/oder Vertiefungen im Nanometerbereich aufweisen, eingesetzt werden.The self-cleaning surfaces according to the invention are preferably by Method according to the invention according to one of claims 9 to 16 for the production of this Surfaces. This inventive method for producing self-cleaning surfaces where a suitable, at least partially hydrophobic Surface structure is created by fixing particles on the surface is characterized by the fact that, as described above, particles with fissured structures Have elevations and / or depressions in the nanometer range can be used.
Vorzugsweise werden solche Partikel, die zumindest ein Material, ausgewählt aus Silikaten oder dotierten Silikaten, Mineralien, Metalloxiden, pyrogenen Kieselsäuren oder Fällungskieselsäuren oder Polymeren aufweisen, eingesetzt. Ganz besonders bevorzugt weisen die Partikel Silikate, pyrogene Kieselsäuren oder Fällungskieselsäuren, 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.Those particles which have at least one material selected from silicates or doped silicates, minerals, metal oxides, pyrogenic silicas or precipitated silicas or polymers are preferably used. The particles very particularly preferably comprise silicates, pyrogenic silicas or precipitated silicas, in particular aerosils, minerals such as magadiite Al 2 O 3 , SiO 2 , TiO 2 , ZrO 2 Zn powder coated with Aerosil R 974 or powdery polymers, such as 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.Particles with a BET surface area of 50 to 600 m 2 / g are particularly preferably used. Particles which have a BET surface area of 50 to 200 m 2 / g are very particularly preferably used.
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 for generating the self-cleaning surfaces preferably have in addition to the rugged structures also have hydrophobic properties. The particles can themselves be hydrophobic, e.g. Particles containing PTFE, or the particles used can have been made hydrophobic. The hydrophobicization of the particles can be done by a person skilled in the art known way. Typical hydrophobized particles are e.g. Very fine powder like Aerosil R 974 or Aerosil-R 8200 (Degussa AG), which can be purchased.
Das Fixieren der Partikel auf der Oberfläche kann auf eine dem Fachmann bekannte Art und Weise chemisch oder physikalisch erfolgen. Als chemische Methode der Fixierung kann z.B. die Verwendung eines Fixiermittels eingesetzt werden. Als Fixiermittel kommen verschiedene Klebstoffe, Haftvermittler oder Lacke in Frage. Dem Fachmann ergeben sich weitere Fixiermittel oder chemische Fixiermethoden.The particles can be fixed on the surface in a manner known to those skilled in the art Done chemically or physically. As a chemical method of fixation e.g. the Use of a fixative can be used. Various come as fixatives Adhesives, adhesion promoters or paints in question. The person skilled in the art will find more Fixing agents or chemical fixing methods.
Als physikalische Methode kann z.B. das Auf- bzw. Eindrücken der Partikel in die Oberfläche eingesetzt werden. Der Fachmann erkennt leicht andere geeignete physikalische Methoden zur Fixierung von Partikeln mit der Oberfläche, beispielsweise das Zusammensintern von Partikeln untereinander bzw. der Partikel an ein feinpulveriges Trägermaterial.As a physical method e.g. the pushing or pushing of the particles into the surface be used. Those skilled in the art will readily recognize other suitable physical methods Fixing particles to the surface, for example sintering particles together with each other or the particles on a finely powdered carrier material.
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, Paraffine, Wachse, Fluoralkylsilane, Fettsäureester, funktionalisierten langkettige Alkanderivate oder Perfluoralkylsilane, hydrophobe Eigenschaften aufweisen. Die Hydrophobierung von Partikeln ist allgemein bekannt und kann z.B. in der Schriftenreihe Pigmente, Nummer 18, der Degussa AG nachgelesen werden.When carrying out the method according to the invention, it can be advantageous to use particles to use, which have hydrophobic properties and / or by treatment with at least one compound from the group of alkylsilanes, alkyldisilazanes, paraffins, waxes, Fluoroalkylsilanes, fatty acid esters, functionalized long chain alkane derivatives or Perfluoroalkylsilanes have hydrophobic properties. The hydrophobization of particles is well known and can e.g. in the series Pigments, number 18, Degussa AG can 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, die z.B. bei der Sivento GmbH zu beziehen sind, Alkyldisilazane, Paraffine, Wachse, Fluoralkylsilane, Fettsäureester, funktionalisierten langkettige Alkanderivate oder Perfluoralkylsilane, 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 Behandlung kann aber auch durch Besprühen der selbstreinigenden Oberfläche mit einem ein Hydrophobierungsreagenz aufweisenden Medium und anschließende Temperung, erfolgen. Eine solche Behandlung ist z.B. für die Behandlung von Stahlträgern oder anderen schweren oder sperrigen Gegenständen bevorzugt. Die maximal anwendbare Temperatur ist durch die Erweichungstemperaturen von Träger oder Substrat limitiert.It may also be advantageous to hydrophobicize the particles after they have been fixed on the support Equip properties. This can e.g. in that the particles of the treated Surface by treatment with at least one compound from the group of Alkylsilanes e.g. are available from Sivento GmbH, alkyl disilazanes, paraffins, Waxes, fluoroalkylsilanes, fatty acid esters, functionalized long-chain alkane derivatives or Perfluoroalkylsilanes, with hydrophobic properties. Preferably done the treatment in that the particle-containing surface that is hydrophobized in a solution containing a water repellent such as e.g. Has alkylsilanes, dipped is, excess hydrophobing reagent is drained and the surface at a annealed as high as possible. Treatment can also be by spraying the self-cleaning surface with a medium containing a hydrophobicizing reagent and subsequent annealing. Such treatment is e.g. for the treatment preferred by steel beams or other heavy or bulky items. The maximum Applicable temperature is due to the softening temperatures of the substrate or substrate limited.
Sowohl bei der Hydrophobierung als auch bei der Fixierung der Partikel auf der Oberfläche muss darauf geachtet werden, dass die zerklüftete Struktur der Partikel im Nanometerbereich erhalten bleibt, damit der Selbstreinigungseffekt der Oberfläche erzielt wird.Both when hydrophobing and when fixing the particles to the surface care must be taken to ensure that the jagged structure of the particles is in the nanometer range is retained so that the self-cleaning effect of the surface is achieved.
Das erfindungsgemäße Verfahren gemäß zumindest einem der Ansprüche 9 bis 16 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 unter anderem 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 8, aufweisen, mit längeren Reinigungsintervallen betrieben werden.The inventive method according to at least one of claims 9 to 16 can excellent for producing self-cleaning surfaces on planar or non-planar Objects, especially on non-planar objects. This is with the conventional methods only possible to a limited extent. In particular about procedures at where prefabricated films are applied to a surface or in processes in which a structure to be created by embossing are non-planar objects, such as Sculptures, not or only partially accessible. Naturally, the invention can Process for the production of self-cleaning surfaces on objects with planar surfaces, e.g. Greenhouses or public transport become. In particular, the use of the method according to the invention for the production of Self-cleaning surfaces on greenhouses have advantages because of the process self-cleaning surfaces e.g. also on transparent materials such as glass or Plexiglas® can be produced and the self-cleaning surface at least as far as transparent can be trained enough for the growth of plants in the greenhouse Sunlight through the transparent with a self-cleaning surface Surface can penetrate. Unlike traditional greenhouses that are regular including leaf, dust, lime and biological material such as Algae, cleaned must be greenhouses that have a surface according to the invention according to a of claims 1 to 8, operate 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 9 bis 16, 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 according to the invention can also be used to produce self-cleaning Surfaces on non-rigid surfaces of objects, such as e.g. Umbrellas or other surfaces that are kept flexible. Can very particularly preferably the inventive method according to at least one of claims 9 to 16 for Production of self-cleaning surfaces on flexible or inflexible walls in the Sanitary area can be used. Such walls can e.g. Partitions in public Toilets, walls of shower cubicles, swimming pools or saunas, but also shower curtains (flexible wall).
Gegenstand der vorliegenden Erfindung sind außerdem Partikel, die eine zerklüftete Struktur mit Erhebungen und/oder Vertiefungen im Nanometerbereich aufweisen, und die zur Herstellung von Oberflächen gemäß einem der Ansprüche 1 bis 8 geeignet sind. Vorzugsweise weisen diese Partikel Erhebungen und/oder Vertiefungen mit im Mittel einer Höhe von 20 bis 500 nm, vorzugsweise von 20 bis 200 nm auf. Vorzugsweise beträgt der Abstand der Erhebungen und/oder Vertiefungen auf dem Partikel weniger als 500 nm, vorzugsweise weniger als 200 nm. Die erfindungsgemäßen Partikel können z.B. aus zumindest einem Material, ausgewählt aus Silikaten, dotierten Silikaten, Mineralien, Metalloxiden, pyrogenen- oder Fällungskieselsäuren, Polymeren und Metallpulvern ausgewählt sein. The present invention also relates to particles which have a fissured structure with elevations and / or depressions in the nanometer range, and for Production of surfaces according to one of claims 1 to 8 are suitable. Preferably these particles have elevations and / or depressions with an average height of 20 to 500 nm, preferably from 20 to 200 nm. The distance is preferably Elevations and / or depressions on the particle less than 500 nm, preferably less than 200 nm. The particles according to the invention can e.g. from at least one material selected from silicates, doped silicates, minerals, metal oxides, pyrogenic or Precipitated silicas, polymers and metal powders can be selected.
Die Partikel können Teilchen im Sinne von DIN 53 206 sein. Partikel oder Teilchen gemäß dieser Norm können Einzelteilchen aber auch Aggregate oder Agglomeratesein, wobei gemäß DIN 53 206 unter Aggregaten flächig oder kantenförmig aneinander gelagerte Primärteilchen (Partikel) und unter Agglomeraten punktförmig aneinandergelagerte Primärteilchen (Partikel) verstanden werden. Als Partikel können auch solche eingesetzt werden, die sich aus Primärteilchen zu Agglomeraten oder Aggregaten zusammenlagern. Die Struktur solcher Partikel kann sphärisch, streng sphärisch, mäßig aggregiert, nahezu sphärisch, äußerst stark agglomeriert oder porös agglomeriert sein. Die bevorzugte Größe der Agglomerate bzw. Aggregate liegt zwischen 20 nm und 100 µm, besonders bevorzugt zwischen 0,2 und 30 µm.The particles can be particles in the sense of DIN 53 206. Particles or particles according to According to this standard, individual particles can also be aggregates or agglomerates, whereby according to DIN 53 206 under aggregates of flat or edged primary particles (Particles) and primary particles (particles) which are clustered together under agglomerates be understood. Particles which are composed of Store primary particles together to form agglomerates or aggregates. The structure of such Particles can be spherical, strictly spherical, moderately aggregated, almost spherical, extremely strong be agglomerated or porous agglomerated. The preferred size of the agglomerates or Aggregate is between 20 nm and 100 µm, particularly preferably between 0.2 and 30 µm.
In den Fig. 1 und 2 sind Rasterelektronenmikroskopische- (REM-) Aufnahmen von als Strukturbildnern eingesetzten Partikeln wiedergegeben.
- Fig. 1
- zeigt eine REM-Aufnahme des Aluminiumoxids Aluminiumoxide C (Degussa AG).
- Fig. 2
- zeigt eine REM-Aufnahme der Oberfläche von Partikeln der Kieselsäure Sipernat FK 350 (Degussa AG) auf einem Träger.
- Fig. 1
- shows a SEM image of the aluminum oxide aluminum oxide C (Degussa AG).
- Fig. 2
- shows a SEM image of the surface of particles of silica Sipernat FK 350 (Degussa AG) on a support.
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 illustrate the surfaces according to the invention and the process for Explain the manufacture of the surfaces in more detail without the invention being limited to them Types of execution should be limited.
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 methyl methacrylate, 20% by weight pentaeritrite tetraacrylate and 60% by weight Hexanediol dimethacrylate was mixed together. Based on this mixture, 14 % By weight of Plex 4092 F, an acrylic copolymer from Röhm GmbH and 2% by weight of UV hardener Darokur 1173 added and stirred for at least 60 min. This mixture was called Carrier applied to a 2 mm thick PMMA plate in a thickness of 50 microns. The layer was dried for 5 min. The particles were then rendered hydrophobic, pyrogenic Aerosil VPR 411 silica (Degussa AG) using an electrostatic spray gun sprayed. After 3 min, the support was at a wavelength of 308 nm under nitrogen hardened. After the carrier had hardened, excess Aerosil VPR 411 was brushed off. The surface was initially characterized visually and is logged with +++. +++ means that water drops form almost completely. The roll angle was 2.4 °. The advancing and retreating angles were measured to be greater than 150 ° each. The associated Hysteresis is below 10 °.
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 from Example 1 was repeated, particles of aluminum oxide C (Degussa AG), an aluminum oxide with a BET surface area of 100 m 2 / g, being sprayed on electrostatically. After the carrier had cured in accordance with Example 1 and excess particles had been brushed off, the hardened, brushed plate was immersed in a formulation of tridecafluorooctyltriethoxysilane in ethanol (Dynasilan 8262, Sivento GmbH) to make it hydrophobic. After draining excess Dynasilan 8262, the plate was annealed at a temperature of 80 ° C. The surface is classified with ++, which means that the shape of the water drops is not ideal, the roll angle is below 20 °.
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 Sipernat 350 is added to the plate from Example 1 treated with the support Degussa AG spread. After 5 minutes of penetration, the treated plate under nitrogen in UV light hardened at 308 nm. Excess particles are brushed off and the The plate is then again immersed in Dynasilan 8262 and then at 80 ° C annealed. The surface is rated +++.
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 from Example 1 is repeated, but instead of Aerosil VPR 411, Aerosil R 8200 (Degussa AG) is used, which has a BET surface area of 200 ± 25 m 2 / g. The evaluation of the surface is +++. The roll angle has been determined to be 1.3 °. Progress and retreat angles were also measured, each of which was greater than 150 °. The associated hysteresis is below 10 °.
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. Der Abrollwinkel betrug 0,5°. Gemessen wurden Fortschreit- und Rückzugswinkel zu jeweils größer als 150°. Die zugehörige Hysterese liegt unterhalb von 10°.The varnish from Example 1, which had already been mixed with the UV hardener, was added 10 wt .-% (based on the total weight of the paint mixture) 2- (N-ethylperfluorooctanesulfonamido) ethyl acrylate added. This mixture was again stirred for at least 60 min. This mixture was supported on a 2 mm thick PMMA plate applied in a thickness of 50 microns. The layer was left for 5 min dry. Then hydrophobicized, pyrogenic silica Aerosil as particles VPR 411 (Degussa AG) sprayed on using an electrostatic spray gun. After 3 min the carrier was cured at 308 nm wavelength under nitrogen. After hardening excess Aerosil VPR 411 was brushed off the carrier. The characterization of the The surface was initially visual and is logged with +++. +++ means Drops of water form almost completely. The roll angle was 0.5 °. Measured progression and retreat angles were each greater than 150 °. The associated hysteresis is below 10 °.
Claims (22)
dadurch gekennzeichnet, dass die Partikel eine zerklüftete Struktur mit Erhebungen und/oder Vertiefungen im Nanometerbereich aufweisen.Self-cleaning surface which has an artificial, at least partially hydrophobic surface structure made up of elevations and depressions, the elevations and depressions being formed by particles fixed on the surface,
characterized in that the particles have a jagged structure with elevations and / or depressions in the nanometer range.
dadurch gekennzeichnet, dass die Partikel eine durchschnittliche Größe von kleiner 50 µm aufweisen.Self-cleaning surface according to claim 1,
characterized in that the particles have an average size of less than 50 microns.
dadurch gekennzeichnet, dass die Partikel eine durchschnittliche Größe von kleiner 30 µm aufweisen.Self-cleaning surface according to one of claims 1 or 2,
characterized in that the particles have an average size of less than 30 microns.
dadurch gekennzeichnet, dass die Partikel aus zumindest einem Material, ausgewählt aus Silikaten, dotierten Silikaten, Mineralien, Metalloxiden, pyrogenen- oder Fällungskieselsäuren, Polymeren und Metallpulvern ausgewählt sind.Self-cleaning surface according to at least one of Claims 1 to 3,
characterized in that the particles are selected from at least one material selected from silicates, doped silicates, minerals, metal oxides, pyrogenic or precipitated silicas, polymers and metal powders.
dadurch gekennzeichnet, dass die Partikel hydrophobe Eigenschaften aufweisen.Self-cleaning surface according to at least one of Claims 1 to 4,
characterized in that the particles have hydrophobic properties.
dadurch gekennzeichnet, dass die einzelnen Partikel auf der Oberfläche Abstände von 0 -10 Partikeldurchmesser, insbesondere von 2 - 3 Partikeldurchmesser, aufweisen. Self-cleaning surface according to at least one of claims 1 to 5,
characterized in that the individual particles on the surface have distances of 0-10 particle diameter, in particular of 2-3 particle diameter.
dadurch gekennzeichnet, dass die Erhöhungen und/oder Vertiefungen im Mittel eine Höhe von 20 bis 500 nm, vorzugsweise von 20 bis 200 nm aurweisen.Self-cleaning surface according to claim 6,
characterized in that the elevations and / or depressions have an average height of 20 to 500 nm, preferably 20 to 200 nm.
dadurch gekennzeichnet, dass der Abstand der Erhöhungen bzw. Vertiefungen auf den Partikeln weniger als 500 nm, vorzugsweise weniger als 200 nm beträgt.Self-cleaning surface according to one of claims 1 to 7,
characterized in that the distance between the elevations or depressions on the particles is less than 500 nm, preferably less than 200 nm.
dadurch gekennzeichnet, dass Partikel, die zerklüftete Strukturen mit Erhebungen und/oder Vertiefungen im Nanometerbereich aufweisen, eingesetzt werden.Process for producing self-cleaning surfaces, in which a suitable, at least partially hydrophobic surface structure is created by fixing particles on a surface using a carrier,
characterized in that particles are used which have jagged structures with elevations and / or depressions in the nanometer range.
dadurch gekennzeichnet, dass Partikel, die zumindest ein Material, ausgewählt aus Silikaten oder dotierten Silikaten, Mineralien, Metalloxiden, Pyrogenen- oder Fällungskieselsäuren, Metallpulvern oder Polymeren aufweisen, eingesetzt werden.Method according to claim 9,
characterized in that particles are used which have at least one material selected from silicates or doped silicates, minerals, metal oxides, pyrogenic or precipitated silicas, metal powders or polymers.
dadurch gekennzeichnet, dass die Partikel durch chemische oder physikalische Methoden auf der Oberfläche fixiert werden.A method according to claim 9 or 10,
characterized in that the particles are fixed on the surface by chemical or physical methods.
dadurch gekennzeichnet, dass das Fixieren der Partikel chemisch unter Verwendung eines Fixiermittels oder physikalisch durch Eindrücken der Partikel in die Oberfläche oder durch Zusammensintem der Partikel untereinander beziehungsweise der Partikel an ein feinpulvriges Trägermaterial erfolgt.A method according to claim 11,
characterized in that the fixing of the particles takes place chemically using a fixing agent or physically by pressing the particles into the surface or by intermeshing the particles with one another or the particles on a finely powdered carrier material.
dadurch gekennzeichnet, dass Partikel eingesetzt werden, die hydrophobe Eigenschaften aufweisen.Method according to at least one of claims 9 to 12,
characterized in that particles are used which have hydrophobic properties.
dadurch gekennzeichnet, dass Partikel eingesetzt werden, die durch eine Behandlung mit zumindest einer Verbindung aus der Gruppe der Alkylsilane, Perfluoralkylsilane, Alkyldisilazane, Fluoralkylsilane, Disalazane, Wachse, Paraffine, Fettsäureester oder funktionalisierten langkettige Alkanderivate, hydrophobe Eigenschaften aufweisen.Method according to at least one of claims 9 to 13,
characterized in that particles are used which, by treatment with at least one compound from the group of alkylsilanes, perfluoroalkylsilanes, alkyldisilazanes, fluoroalkylsilanes, disalazanes, waxes, paraffins, fatty acid esters or functionalized long-chain alkane derivatives, have hydrophobic properties.
dadurch gekennzeichnet, dass die Partikel nach dem Fixieren auf der Oberfläche mit hydrophoben Eigenschaften ausgestattet werden.Method according to at least one of claims 9 to 12,
characterized in that the particles are provided with hydrophobic properties after being fixed on the surface.
dadurch gekennzeichnet, dass die Partikel durch eine Behandlung mit zumindest einer Verbindung aus der Gruppe der Alkylsilane, Perfluoralkylsilane, Alkyldisilazane, Fluoralkylsilane, Wachse, Paraffine, Fettsäureester oder funktionalisierten langkettige Alkanderivate oder Fluoralkanderivaten, mit hydrophoben Eigenschaften ausgestattet werden.A method according to claim 15,
characterized in that the particles are provided with hydrophobic properties by treatment with at least one compound from the group of alkylsilanes, perfluoroalkylsilanes, alkyldisilazanes, fluoroalkylsilanes, waxes, paraffins, fatty acid esters or functionalized long-chain alkane derivatives or fluoroalkane derivatives.
dadurch gekennzeichnet, dass die Erhebungen und/oder Vertiefungen im Mittel eine Höhe von 20 bis 500 nm, vorzugsweise von 20 bis 200 nm aufweisen.Particles according to claim 19,
characterized in that the elevations and / or depressions have an average height of 20 to 500 nm, preferably 20 to 200 nm.
dadurch gekennzeichnet, dass die Erhebungen und/oder Vertiefungen auf dem Partikel einen Abstand von weniger als 500 nm, vorzugsweise weniger als 200 nm aufweisen.Particles according to claim 19 or 20,
characterized in that the elevations and / or depressions on the particle are at a distance of less than 500 nm, preferably less than 200 nm.
dadurch gekennzeichnet, dass die Partikel aus zumindest einem Material, ausgewählt aus Silikaten, dotierten Silikaten, Mineralien, Metalloxiden, Kieselsäuren, Polymeren und Metallpulvern ausgewählt sind.Particles according to at least one of claims 19 to 21,
characterized in that the particles are selected from at least one material selected from silicates, doped silicates, minerals, metal oxides, silicas, polymers and metal powders.
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DE10118345A DE10118345A1 (en) | 2001-04-12 | 2001-04-12 | Properties of structure formers for self-cleaning surfaces and the production of the same |
DE10118345 | 2001-04-12 |
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EP (1) | EP1249281B1 (en) |
JP (1) | JP4102583B2 (en) |
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Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
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WO2004014574A2 (en) * | 2002-07-25 | 2004-02-19 | Creavis Gesellschaft Für Technologie Und Innovation Mbh | Method for producing structured surfaces |
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Cited By (10)
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WO2004014574A2 (en) * | 2002-07-25 | 2004-02-19 | Creavis Gesellschaft Für Technologie Und Innovation Mbh | Method for producing structured surfaces |
WO2004014574A3 (en) * | 2002-07-25 | 2004-06-03 | Creavis Tech & Innovation Gmbh | Method for producing structured surfaces |
WO2005105324A1 (en) * | 2004-04-02 | 2005-11-10 | Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. | Device with a scratch-resistant technical surface, which has optimized wetting properties, and method for producing this device |
DE102005037338A1 (en) * | 2005-08-04 | 2007-02-08 | Starnberger Beschichtungen Gmbh | Producing a nonstick coating on a substrate comprises applying a primer coat having inclusions, applying a top coat and heat-treating the top coat |
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EP1968753A4 (en) * | 2005-12-21 | 2011-04-20 | 3M Innovative Properties Co | Process for preparing a superhydrophobic coating |
WO2007092746A2 (en) * | 2006-02-03 | 2007-08-16 | Ut-Battelle, Llc | Transparent articles having hydrophobic or super-hydrophobic surfaces |
WO2007092746A3 (en) * | 2006-02-03 | 2007-10-11 | Ut Battelle Llc | Transparent articles having hydrophobic or super-hydrophobic surfaces |
EP2007692A1 (en) * | 2006-03-27 | 2008-12-31 | Beneq Oy | Hydrophobic glass surface |
EP2007692A4 (en) * | 2006-03-27 | 2012-10-24 | Beneq Oy | Hydrophobic glass surface |
Also Published As
Publication number | Publication date |
---|---|
ES2286169T3 (en) | 2007-12-01 |
EP1249281B1 (en) | 2007-05-16 |
EP1249281A3 (en) | 2003-01-02 |
CA2381747A1 (en) | 2002-10-12 |
JP4102583B2 (en) | 2008-06-18 |
JP2002346470A (en) | 2002-12-03 |
DE10118345A1 (en) | 2002-10-17 |
DK1249281T3 (en) | 2007-09-10 |
DE50210148D1 (en) | 2007-06-28 |
ATE362404T1 (en) | 2007-06-15 |
US20020150726A1 (en) | 2002-10-17 |
US6811856B2 (en) | 2004-11-02 |
CA2381747C (en) | 2012-01-24 |
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