EP1249280A2 - 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
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- EP1249280A2 EP1249280A2 EP02003960A EP02003960A EP1249280A2 EP 1249280 A2 EP1249280 A2 EP 1249280A2 EP 02003960 A EP02003960 A EP 02003960A EP 02003960 A EP02003960 A EP 02003960A EP 1249280 A2 EP1249280 A2 EP 1249280A2
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- Prior art keywords
- particles
- self
- carrier
- cleaning
- hydrophobic
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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
- 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
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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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- 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
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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
- Y10T428/24—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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- Y10T428/2438—Coated
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- Y10T428/24355—Continuous and nonuniform or irregular surface on layer or component [e.g., roofing, etc.]
- Y10T428/24372—Particulate matter
- Y10T428/24405—Polymer or resin [e.g., natural or synthetic rubber, etc.]
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Definitions
- the present invention relates to self-cleaning surfaces and methods for their Production.
- Objects with extremely difficult to wet surfaces have a number of economical ones significant features.
- the most economically significant feature is the self-cleaning effect of difficult to wet surfaces, because the cleaning of Surface is time and cost intensive.
- Self-cleaning surfaces are therefore of the highest quality economic interest.
- Detention mechanisms are usually through interfacial energy parameters between the two surfaces in contact.
- the systems try to lower their free interface energy. Lie the free interface energies between two components are inherently very low, So it can generally be assumed that the liability between these two Components is weak.
- the relative lowering of the free is important Interfacial energy. For pairings with a high and a low interfacial energy the possibilities of interactions are very important.
- hydrophobic materials such as perfluorinated polymers
- hydrophobic surfaces are known.
- a further development of these surfaces is to structure the surfaces in the ⁇ m range to the nm range.
- U.S. Patent 5,599,489 discloses a Process in which a surface is bombarded with particles of an appropriate size and subsequent perfluorination can be made particularly repellent.
- Another Methods describe H. Saito et al in "Service Coatings International" 4, 1997, p. 168 ff.
- particles of fluoropolymers are applied to metal surfaces, with a strong reduced wettability of the surfaces thus produced against water with a considerably reduced tendency to icing was found.
- US Pat. Nos. 3,354,022 and WO 96/04123 describe further methods for lowering the Wettability of objects due to topological changes in the surfaces described.
- artificial elevations or depressions with a height of approx. 5 up to 1 000 ⁇ m and a distance of approx. 5 to 500 ⁇ m on hydrophobic or after Structuring applied hydrophobic materials.
- Surfaces of this type lead to a rapid drop formation, the rolling drops absorbing dirt particles and thus clean the surface.
- EP 1 040 874 A2 describes the stamping of microstructures and claims them Use of such structures in analysis (microfluidics). A disadvantage of these structures is the insufficient mechanical stability.
- JP 11171592 describes a water-repellent product and its production, the dirt-repellent surface is produced by a film on the treating surface is applied, the fine particles of metal oxide and the hydrolyzate a metal alkoxide or chelate. To solidify this film, the substrate, to which the film was applied are sintered at temperatures above 400 ° C. The method can therefore only be used for substrates that are also at temperatures above of 400 ° C are stable.
- the object of the present invention was to provide particularly good self-cleaning Surfaces with structures in the nanometer range, as well as a simple process for Manufacture of such self-cleaning surfaces.
- the present invention therefore relates to a self-cleaning surface which has a artificial, at least partially hydrophobic surface structure from surveys and Has depressions, the elevations and depressions by means of a carrier fixed surface particles are formed, which is characterized in that the Particles a fissured structure with elevations and / or depressions in the nanometer range exhibit.
- the present invention also relates to a method for producing self-cleaning surfaces where a suitable, at least partially hydrophobic Surface structure by fixing particles on a surface using a carrier is created, which is characterized in that particles, the jagged structures with elevations and / or depressions in the nanometer range can be used.
- Self-cleaning surfaces are accessible through the method according to the invention Show particles with a jagged structure.
- particles which have a rugged structure surfaces are easily accessible that up to are structured in the nanometer range.
- To maintain this structure in the nanometer range it is necessary that the particles do not pass through the carrier with which they are on the surface are fixed, are wetted, otherwise the structure in the nano range would be lost.
- Another advantage of the method according to the invention is that it is scratch-sensitive Surfaces when applying the particles are not caused by particles present in the carrier is damaged because when using paints and then applying the Particles on the carrier, the scratch-sensitive surface is already protected by the carrier.
- the self-cleaning surface according to the invention which is an artificial, at least partially Has hydrophobic surface structure of elevations and depressions, the Elevations and depressions by particles fixed on the surface by means of a carrier are characterized in that the particles have a jagged structure Show elevations and / or depressions in the nanometer range.
- the Increases on average a height of 20 to 500 nm, particularly preferably from 50 to 200 nm on.
- the distance between the elevations or depressions on the particles is preferably less than 500 nm, very particularly preferably less than 200 nm.
- the jagged structures with elevations and / or depressions in the nanometer range can e.g. over cavities, pores, grooves, tips and / or peaks are formed.
- the Particles themselves have an average size of less than 50 ⁇ m, preferably of smaller size 30 ⁇ m and very particularly preferably from less than 20 ⁇ m.
- the particles preferably have a BET surface area of 50 to 600 square meters per gram. Very particularly preferably the particles have a BET surface area of 50 to 200 m 2 / g.
- the particles preferably have at least one material selected from silicates, doped silicates, minerals, metal oxides, silicas, polymers and metal powders coated with silicic acid.
- the particles very particularly preferably have pyrogenic silicas or precipitated silicas, in particular aerosils, Al 2 O 3 , SiO 2 , TiO 2 , ZrO 2 , zinc powder coated with Aerosil R974, preferably with a particle size of 1 ⁇ m or powdery polymers, such as cryogenically ground or spray-dried polytetrafluoroethylene (PTFE) or perfluorinated copolymers or copolymers with tetrafluoroethylene.
- PTFE polytetrafluoroethylene
- the particles for generating the self-cleaning surfaces preferably have in addition to the rugged structures also have hydrophobic properties.
- the particles can themselves be hydrophobic, e.g. Particles containing PTFE, or the particles used can have been made hydrophobic.
- the hydrophobicization of the particles can be done by a person skilled in the art known way.
- Typical hydrophobized particles are e.g. Very fine powder like Aerosil-R 8200 (Degussa AG), which can be purchased.
- the preferably used silicas preferably have a dibutyl phthalate adsorbtion, based on DIN 53 601, of between 100 and 350 ml / 100 g, preferably values between 250 and 350 ml / 100 g.
- the particles are fixed to the surface by means of a carrier.
- the self-cleaning surface can be to generate.
- the carrier is a lacquer hardened by means of thermal energy and / or light energy Two-component paint system or another reactive paint system, the curing preferably carried out by polymerization or crosslinking.
- the mixing ratios can be in wide limits can be varied. It is also possible that the hardened paint connections with functional groups, e.g. Hydroxy groups, epoxy groups, amine groups, or fluorine-containing compounds, e.g. perfluorinated esters of acrylic acid.
- Varnishes are not just varnishes Acrylic resin base can be used, but also varnishes based on polyurethane or varnishes that Have polyurethane acrylates or silicone acrylates.
- the self-cleaning surfaces according to the invention have a roll angle of less 20 °, particularly preferably less than 10 °, the roll angle being defined such that one from 1 cm height on a flat surface resting on an inclined plane Water drops roll off.
- the progression angle and the retreat angle are above 140 °, preferably above 150 ° and have a hysteresis of less than 15 °, preferably less 10 ° on. Because the surfaces according to the invention have a progressive and Have retraction angles above at least 140 °, preferably above 150 °, particularly good self-cleaning surfaces become accessible.
- the self-cleaning surfaces are semi-transparent.
- the surfaces according to the invention can be contact-transparent, that is to say after Creating a surface according to the invention on a labeled object Lettering, depending on the size of the font, is still legible.
- the self-cleaning surfaces according to the invention are preferably by Process according to the invention for producing these surfaces.
- This Process according to the invention for producing self-cleaning surfaces in which a suitable, at least partially hydrophobic surface structure by fixing particles is created on a surface by means of a carrier, characterized in that Particles, the fissured structures with elevations and / or depressions in the Have nanometer range, are used.
- Those particles which have at least one material selected from silicates, doped silicates, minerals, metal oxides, silicas or polymers are preferably used.
- the particles very particularly preferably have pyrogenic silicates or silicas, in particular aerosils, minerals such as magadiite Al 2 O 3 , SiO 2 , TiO 2 , ZrO 2, Zn powder coated with Aerosil R 974 or powdery polymers, such as, for example, cryogenically ground or spray-dried polytetrafluoroethylene (PTFE).
- Particles with a BET surface area of 50 to 600 m 2 / g are particularly preferably used. Particles which have a BET surface area of 50 to 200 m 2 / g are very particularly preferably used.
- the particles for generating the self-cleaning surfaces preferably have in addition to the rugged structures also have hydrophobic properties.
- the particles can themselves be hydrophobic, e.g. Particles containing PTFE, or the particles used can have been made hydrophobic.
- the hydrophobicization of the particles can be done by a person skilled in the art known way.
- Typical hydrophobized particles are e.g. Very fine powder like Aerosil R 974 or Aerosil-R 8200 (Degussa AG), which can be purchased.
- the curable substance can e.g. by spraying, knife coating, spreading or spraying.
- the curable substance is in a thickness of 1 to 100 microns, preferably applied in a thickness of 5 to 50 microns.
- the viscosity of the curable substance it may be advantageous to apply the substance before applying the particles to harden or let dry.
- the viscosity of the curable substance will be like this chosen that the applied particles sink at least partially into the curable substance but the curable substance or the particles applied to it no longer run, when the surface is placed vertically.
- the particles can be applied by conventional methods such as spraying or powdering respectively.
- the particles can be applied by spraying using an electrostatic spray gun. After applying the particles you can excess particles, i.e. particles that do not adhere to the hardenable substance, by shaking, Brushing or blowing off the surface. These particles can be collected and be used again.
- a varnish can be used as the carrier, which at least mixtures of simple and / or has polyunsaturated acrylates and / or methacrylates become.
- the mixing ratios can be varied within wide limits.
- a curable by means of thermal or chemical energy and / or light energy is preferred Paint used.
- a varnish or a varnish system is selected as the curable substance, the hydrophobic Has properties if the particles used have hydrophobic properties. Conversely, a varnish with hydrophilic properties is selected as the curable substance if the particles used have hydrophilic properties.
- the mixtures used as paint have compounds with functional groups, e.g. Hydroxy groups, epoxy groups, amine groups or fluorine-containing compounds, e.g. perfluorinated esters of acrylic acid.
- functional groups e.g. Hydroxy groups, epoxy groups, amine groups or fluorine-containing compounds, e.g. perfluorinated esters of acrylic acid.
- hydrophobic particles such as Aerosil VPR 411 matched to one another by means of N- [2- (acryloyloxy) ethyl] -N-ethylperfluorooctane-1-sulfonamide become.
- two-component paint systems or other reactive paint systems can be used.
- the particles are fixed on the carrier by hardening the carrier according to the paint system used, preferably by thermal and / or chemical energy and / or light energy takes place.
- Hardening of the carrier triggered by chemical or thermal energy and / or light energy, e.g. by polymerization or crosslinking the Components of the paints or paint systems are made.
- the curable substance is preferably applied within 0.1 to 10 minutes, preferably hardened within 1 to 5 minutes after application of the particles.
- particles to use which have hydrophobic properties and / or by treatment with at least one compound from the group of alkylsilanes, alkyldisilazanes or Perfluoroalkylsilanes have hydrophobic properties.
- the hydrophobization of particles is known and can e.g. in the Pigments series, number 18, by Degussa AG be looked up.
- the particles of the treated Surface by treatment with at least one compound from the group of Alkylsilanes, the perfluoroalkylsilanes, e.g. are available from Sivento GmbH with hydrophobic properties.
- the treatment is preferably carried out in that the particle-containing surface that is to be hydrophobicized into a Solution containing a water repellent such as e.g. Has alkylsilanes, is immersed, Excess water repellent is drained and the surface at a annealed as high as possible.
- the maximum applicable temperature is by the Softening temperatures of carrier or substrate limited.
- the inventive method according to at least one of claims 8 to 17 can excellent for producing self-cleaning surfaces on planar or non-planar Objects, especially on non-planar objects. This is with the conventional methods only possible to a limited extent. In particular about procedures at where prefabricated films are applied to a surface or in processes in which a structure to be created by embossing are non-planar objects, such as Sculptures, not or only partially accessible.
- the invention can Process for the production of self-cleaning surfaces on objects with planar surfaces, e.g. Greenhouses or public transport become.
- the use of the method according to the invention for the production of Self-cleaning surfaces on greenhouses have advantages because of the process self-cleaning surfaces e.g.
- the method according to the invention can also be used to produce self-cleaning Surfaces on non-rigid surfaces of objects, such as e.g. Umbrellas or other surfaces that are kept flexible.
- objects such as e.g. Umbrellas or other surfaces that are kept flexible.
- inventive method according to at least one of claims 8 to 17, for Production of self-cleaning surfaces on flexible or inflexible walls in the Sanitary area can be used.
- Such walls can e.g. Partitions in public Toilets, walls of shower cubicles, swimming pools or saunas, but also shower curtains (flexible wall).
- 1 and 2 are scanning electron microscopic (SEM) images of as Structured particles used reproduced.
- FIG. 2 shows an SEM image of the surface of particles of silica Sipernat FK 350 (Degussa AG) on a carrier.
- the support was at a wavelength of 308 nm under nitrogen hardened. After the carrier had hardened, excess Aerosil VPR 411 was brushed off. The surface was initially characterized visually and is logged with +++. +++ means that water drops form almost completely. The roll angle was 2.4 °. The advancing and retreating angles were measured to be greater than 150 ° each. The associated Hysteresis is below 10 °.
- Example 2 The experiment from Example 1 was repeated, particles of aluminum oxide C (Degussa AG), an aluminum oxide with a BET surface area of 100 m 2 / g, being sprayed on electrostatically.
- the carrier had cured in accordance with Example 1 and excess particles had been brushed off
- the hardened, brushed plate was immersed in a formulation of tridecafluorooctyltriethoxysilane in ethanol (Dynasilan 8262, Sivento GmbH) to make it hydrophobic.
- the plate After draining excess Dynasilan 8262, the plate was annealed at a temperature of 80 ° C. The surface is classified with ++, which means that the shape of the water drops is not ideal, the roll angle is below 20 °.
- Silica Sipernat 350 is added to the plate from Example 1 treated with the support Degussa AG spread. After 5 minutes of penetration, the treated plate under nitrogen in UV light hardened at 308 nm. Excess particles are brushed off and the The plate is then again immersed in Dynasilan 8262 and then at 80 ° C annealed The surface is classified with +++.
- Aerosil VPR 411 Aerosil R 8200 (Degussa AG) is used, which has a BET surface area of 200 ⁇ 25 m 2 / g.
- the evaluation of the surface is +++.
- the roll angle has been determined to be 1.3 °.
- Progress and retreat angles were also measured, each of which was greater than 150 °.
- the associated hysteresis is below 10 °.
- Example 2 The varnish from Example 1, which had already been mixed with the UV hardener, was added 10 wt .-% (based on the total weight of the paint mixture) 2- (N-ethylperfluorooctanesulfonamido) ethyl acrylate added. This mixture was at least 60 again stirred for min. This mixture was used as a carrier on a 2 mm thick PMMA plate in a 50 ⁇ m thickness applied. The layer was dried for 5 minutes. Then were as particles hydrophobicized, pyrogenic silica Aerosil VPR 411 (Degussa AG) by means of a electrostatic spray gun sprayed on. After 3 minutes the support became at one wavelength hardened from 308 nm under nitrogen. After the carrier hardened, excess became Aerosil VPR 411 brushed. The surface was initially characterized visually and is logged with +++. +++ means that water drops form almost completely.
- the roll angle was 0.5 °. Progress and retreat angles were measured at each greater than 150 °. The associated hysteresis is below 10 °.
- the bad cleaning effect is due to the smearing of the jagged structures due. This is probably not done by dissolving monomers of the yet hardened paint system in ethanol. Before curing, the ethanol and the evaporates Monomers remain in the jagged structures in which they harden during the process also harden, whereby the jagged structures are smeared or filled. In this way, the self-cleaning effect deteriorates significantly.
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.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. U.S. Patent 5,599,489 discloses a Process in which a surface is bombarded with particles of an appropriate size and subsequent perfluorination can be made particularly repellent. Another Methods describe H. Saito et al in "Service Coatings International" 4, 1997, p. 168 ff. 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 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 of producing easily cleanable surfaces is described in DE 199 17 367 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.
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 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.
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.It was also an object of the present invention to produce a process for to provide self-cleaning surfaces in which the coated material is only slight exposed to chemical or physical stress.
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 therefore relates to a self-cleaning surface which has a artificial, at least partially hydrophobic surface structure from surveys and Has depressions, the elevations and depressions by means of a carrier fixed surface particles are formed, which is characterized in that the Particles a fissured structure with elevations and / or depressions in the nanometer range exhibit.
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 relates to a method for producing self-cleaning surfaces where a suitable, at least partially hydrophobic Surface structure by fixing particles on a surface using a carrier is created, which is characterized in that particles, the jagged structures with elevations and / or depressions in the nanometer range can be used.
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.Self-cleaning surfaces are accessible through the method according to the invention Show particles with a jagged structure. By using particles which have a rugged structure, surfaces are easily accessible that up to are structured in the nanometer range. To maintain this structure in the nanometer range it is necessary that the particles do not pass through the carrier with which they are on the surface are fixed, are wetted, otherwise the structure in the nano range would be lost.
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.Another advantage of the method according to the invention is that it is scratch-sensitive Surfaces when applying the particles are not caused by particles present in the carrier is damaged because when using paints and then applying the Particles on the carrier, the scratch-sensitive surface is already protected by the carrier.
Im nachfolgenden werden Substanzen, die zur Fixierung von Partikeln auf einer Oberfläche eingesetzt werden, als Träger bezeichnet.The following are substances used to fix particles on a surface are used, 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 is an artificial, at least partially Has hydrophobic surface structure of elevations and depressions, the Elevations and depressions by particles fixed on the surface by means of a carrier are characterized in that the particles have a jagged structure Show elevations and / or depressions in the nanometer range. Preferably, the Increases on average a height of 20 to 500 nm, particularly preferably from 50 to 200 nm on. The distance between the elevations or depressions on the particles is preferably less than 500 nm, very particularly preferably less than 200 nm.
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 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.
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 50 to 600 square meters per gram. Very particularly preferably the particles 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 1 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 1 μm or powdery polymers, such as 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 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 on the surface in a tightly packed layer, the self-cleaning surface can be to generate.
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 carrier is a lacquer hardened by means of thermal energy and / or light energy Two-component paint system or another reactive paint system, the curing preferably carried out by polymerization or crosslinking. The hardened lacquer polymers and / or copolymers of single and / or multiple unsaturated acrylates and / or methacrylates. The mixing ratios can be in wide limits can be varied. It is also possible that the hardened paint connections with functional groups, e.g. Hydroxy groups, epoxy groups, amine groups, or fluorine-containing compounds, e.g. perfluorinated esters of acrylic acid. This is particularly advantageous if the compatibility of paint and hydrophobic particles such as Aerosil R 8200 using N- [2- (acryloyloxy) ethyl] -N-ethylperfluorooctane-1-sulfonic acid amide be coordinated. Varnishes are not just varnishes Acrylic resin base can be used, but also varnishes based on polyurethane or varnishes that Have polyurethane acrylates or silicone acrylates.
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 20 °, particularly preferably less than 10 °, the roll angle being defined such that one from 1 cm height on a flat surface resting on an inclined plane Water drops roll off. The progression angle and the retreat angle are above 140 °, preferably above 150 ° and have a hysteresis of less than 15 °, preferably less 10 ° on. Because the surfaces according to the invention have a progressive and Have retraction angles above at least 140 °, preferably above 150 °, particularly good self-cleaning surfaces become accessible.
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 can be 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 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 by Process according to the invention for producing these surfaces. This Process according to the invention for producing self-cleaning surfaces, in which a suitable, at least partially hydrophobic surface structure by fixing particles is created on a surface by means of a carrier, characterized in that Particles, the fissured structures with elevations and / or depressions in the Have nanometer range, are used.
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.Those particles which have at least one material selected from silicates, doped silicates, minerals, metal oxides, silicas or polymers are preferably used. The particles very particularly preferably have pyrogenic silicates or silicas, in particular aerosils, minerals such as magadiite Al 2 O 3 , SiO 2 , TiO 2 , ZrO 2, Zn powder coated with Aerosil R 974 or powdery polymers, such as, for example, cryogenically ground or spray-dried polytetrafluoroethylene ( PTFE).
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 erfindungsgemäße Verfahren weist vorzugsweise die Schritte
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.Application of the curable substance can e.g. by spraying, knife coating, spreading or spraying. Preferably, the curable substance is in a thickness of 1 to 100 microns, preferably applied in a thickness of 5 to 50 microns. Depending on the viscosity of the curable substance, it may be advantageous to apply the substance before applying the particles to harden or let dry. Ideally, the viscosity of the curable substance will be like this chosen that the applied particles sink at least partially into the curable substance but the curable substance or the particles applied to it no longer run, when the surface is placed vertically.
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 particles can be applied by conventional methods such as spraying or powdering respectively. In particular, the particles can be applied by spraying using an electrostatic spray gun. After applying the particles you can excess particles, i.e. particles that do not adhere to the hardenable substance, by shaking, Brushing or blowing off the surface. These particles can be collected and be used again.
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.As a curable substance, a varnish can be used as the carrier, which at least mixtures of simple and / or has polyunsaturated acrylates and / or methacrylates become. The mixing ratios can be varied within wide limits. Especially a curable by means of thermal or chemical energy and / or light energy is preferred Paint used.
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.A varnish or a varnish system is selected as the curable substance, the hydrophobic Has properties if the particles used have hydrophobic properties. Conversely, a varnish with hydrophilic properties is selected as the curable substance if the particles used have hydrophilic properties.
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 can be advantageous if the mixtures used as paint have compounds with functional groups, e.g. Hydroxy groups, epoxy groups, amine groups or fluorine-containing compounds, e.g. perfluorinated esters of acrylic acid. This is particularly advantageous if the tolerance (in relation to the hydrophobic Properties) of paint and hydrophobic particles such as Aerosil VPR 411 matched to one another by means of N- [2- (acryloyloxy) ethyl] -N-ethylperfluorooctane-1-sulfonamide become. It is not only acrylic resin-based paints that can be used as curable substances but also polyurethane-based paints, or polyurethane acrylates or Silicone acrylates. Also available as curable substances are two-component paint systems or other reactive paint systems can be used.
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 particles are fixed on the carrier by hardening the carrier according to the paint system used, preferably by thermal and / or chemical energy and / or light energy takes place. Hardening of the carrier, triggered by chemical or thermal energy and / or light energy, e.g. by polymerization or crosslinking the Components of the paints or paint systems are made. The hardening of the Carrier by light energy and very particularly preferably the polymerization of Carrier by light from an Hg medium pressure lamp in the UV range. This is preferably done Hardening the carrier under an inert gas atmosphere, very particularly preferably under one 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 curable substance applied and the diameter of the particles used it may be necessary to specify the time between application of the particles and hardening of the hardenable Substance passes, limit to a complete immersion of the particles in the hardenable Avoid substance. The curable substance is preferably applied within 0.1 to 10 minutes, preferably hardened 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 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 or Perfluoroalkylsilanes have hydrophobic properties. The hydrophobization of particles is known and can e.g. in the Pigments series, number 18, by Degussa AG be looked up.
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 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, the perfluoroalkylsilanes, e.g. are available from Sivento GmbH with hydrophobic properties. The treatment is preferably carried out in that the particle-containing surface that is to be hydrophobicized into a Solution containing a water repellent such as e.g. Has alkylsilanes, is immersed, Excess water repellent is drained and the surface at a annealed as high as possible. The maximum applicable temperature is by the Softening temperatures of carrier or substrate limited.
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 inventive method according to at least one of claims 8 to 17 can excellent for producing self-cleaning surfaces on planar or non-planar Objects, especially on non-planar objects. This is with the conventional methods only possible to a limited extent. In particular about procedures at where prefabricated films are applied to a surface or in processes in which a structure to be created by embossing are non-planar objects, such as Sculptures, not or only partially accessible. 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 of foliage, dust, lime and biological material, e.g. Algae that need to be cleaned can greenhouses that have 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 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 8 to 17, for Production of self-cleaning surfaces on flexible or inflexible walls in the Sanitary area can be used. Such walls can e.g. Partitions in public Toilets, walls of shower cubicles, swimming pools or saunas, but also shower curtains (flexible wall).
In den Fig. 1 und 2 sind Rasterelektronenmikroskopische- (REM-) Aufnahmen von als Strukturbildnern eingesetzten Partikeln wiedergegeben.1 and 2 are scanning electron microscopic (SEM) images of as Structured particles used reproduced.
Fig. 1 zeigt eine REM-Aufnahme des Aluminiumoxids Aluminiumoxide C (Degussa AG).1 shows a SEM image of the aluminum oxide aluminum oxide 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 an SEM image of the surface of particles of 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 illustrate the surfaces according to the invention and the process for Explain the manufacture of the surfaces in more detail without the invention being based on these embodiments 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. Be related to 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 classified with +++.
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. The varnish from Example 1, which had already been mixed with the UV hardener, was added 10 wt .-% (based on the total weight of the paint mixture) 2- (N-ethylperfluorooctanesulfonamido) ethyl acrylate added. This mixture was at least 60 again stirred for min. This mixture was used as a carrier on a 2 mm thick PMMA plate in a 50 µm thickness applied. The layer was dried for 5 minutes. Then were as particles hydrophobicized, pyrogenic silica Aerosil VPR 411 (Degussa AG) by means of a electrostatic spray gun sprayed on. After 3 minutes the support became at one wavelength hardened from 308 nm under nitrogen. After the carrier hardened, excess became Aerosil VPR 411 brushed. The surface was initially characterized visually and is logged with +++. +++ means that water drops form almost completely.
Der Abrollwinkel betrug 0,5°. Gemessen wurden Fortschreit- und Rückzugswinkel zu jeweils größer als 150°. Die zugehörige Hysterese liegt unterhalb von 10°.The roll angle was 0.5 °. Progress and retreat angles were measured at each greater than 150 °. 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.A suspension of 10% by weight of spray-dried pyrogenic silica, Aeroperl 90/30 Degussa AG, a silica with a BET surface area of 90 m 2 / g, in ethanol, is applied to the dried support from Example 1 in a thickness of 200 μ. knife. After curing in UV light and treatment with the hydrophobizing agent Dynasilan 8262, the surface is only rated with +, ie the drop forms poorly and sticks to the surface up to high angles of inclination.
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 bad cleaning effect is due to the smearing of the jagged structures due. This is probably not done by dissolving monomers of the yet hardened paint system in ethanol. Before curing, the ethanol and the evaporates Monomers remain in the jagged structures in which they harden during the process also harden, whereby the jagged structures are smeared or filled. In this way, the self-cleaning effect deteriorates significantly.
Claims (20)
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 of elevations and depressions, the elevations and depressions being formed by particles fixed on the surface by means of a carrier,
characterized in that the particles have a jagged structure with elevations and / or depressions in the nanometer range.
dadurch gekennzeichnet, dass der Träger ein mittels thermischer oder chemischer Energie oder Lichtenergie gehärteter Lack ist.Self-cleaning surface according to claim 1,
characterized in that the carrier is a lacquer hardened by means of thermal or chemical energy or light energy.
dadurch gekennzeichnet, dass der gehärtete Lack Mischungen aus einfach und/oder mehrfach ungesättigten Acrylaten und/oder Methacrylaten oder Polyurethan aufweist.Self-cleaning surface according to one of claims 1 or 2,
characterized in that the hardened lacquer has mixtures of mono- and / or polyunsaturated acrylates and / or methacrylates or polyurethane.
dadurch gekennzeichnet, dass die Partikel eine durchschnittliche Größe von kleiner 50 µm aufweisen.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 microns.
dadurch gekennzeichnet, dass die Partikel eine durchschnittliche Größe von kleiner 30 µm aufweisen.Self-cleaning surface according to claim 4,
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, Kieselsäuren, Polymeren und Metallpulvern ausgewählt sind.Self-cleaning surface according to at least one of claims 1 to 5,
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.
dadurch gekennzeichnet, dass die Partikel hydrophobe Eigenschaften aurweisen.Self-cleaning surface according to claim 6,
characterized in that the particles have hydrophobic properties.
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, dotierten Silikaten, Mineralien, Metalloxiden, Kieselsäuren, Metallpulvern oder Polymeren aufweisen, eingesetzt werden.A method according to claim 8,
characterized in that particles which have at least one material selected from silicates, doped silicates, minerals, metal oxides, silicas, metal powders or polymers are used.
dadurch gekennzeichnet, dass es die Schritte
aufweist.
characterized in that it is the steps
having.
dadurch gekennzeichnet, dass das Härten des Trägers durch thermische oder chemische Energie und/oder Lichtenergie erfolgt.A method according to claim 10,
characterized in that the hardening of the carrier is carried out by thermal or chemical energy and / or light energy.
dadurch gekennzeichnet, dass als härtbare Substanz ein Lack der zumindest Mischungen aus einfach und/oder mehrfach ungesättigten Acrylaten und/oder Methacrylaten und/oder Polyurethane und/oder Silikonacrylate und/oder Urethanacrylate aufweist, eingesetzt wird.A method according to claim 10 or 11,
characterized in that a varnish which comprises at least mixtures of mono- and / or polyunsaturated acrylates and / or methacrylates and / or polyurethanes and / or silicone acrylates and / or urethane acrylates is used as the curable substance.
dadurch gekennzeichnet, dass als härtbare Substanz ein Lack ausgewählt wird der hydrophobe Eigenschaften aufweist, wenn die eingesetzten Partikel hydrophobe Eigenschaften aufweist und als härtbare Substanz ein Lack ausgewählt wird der hydrophile Eigenschaften aufweist, wenn die eingesetzten Partikel hydrophile Eigenschaften aufweist.Method according to claim 12,
characterized in that a varnish is selected as the curable substance which has hydrophobic properties when the particles used have hydrophobic properties and a varnish is selected as the curable substance which has hydrophilic properties when the particles used have hydrophilic properties.
dadurch gekennzeichnet, dass Partikel eingesetzt werden, die hydrophobe Eigenschaften aufweisen.Method according to at least one of claims 8 to 13,
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 oder Alkyldisilazane , hydrophobe Eigenschaften aufweisen.Method according to at least one of claims 8 to 14,
characterized in that particles are used which, by treatment with at least one compound from the group of alkylsilanes, perfluoroalkylsilanes or alkyldisilazanes, have hydrophobic properties.
dadurch gekennzeichnet, dass die Partikel nach dem Fixieren auf dem Träger mit hydrophoben Eigenschaften ausgestattet werden. Method according to at least one of claims 8 to 15,
characterized in that the particles are provided with hydrophobic properties after being fixed on the support.
dadurch gekennzeichnet, dass die Partikel durch eine Behandlung mit zumindest einer Verbindung aus der Gruppe der Alkylsilane, Perfluoralkylsilane oder Alkyldisilazane, mit hydrophoben Eigenschaften ausgestattet werden.A method according to claim 16,
characterized in that the particles are provided with hydrophobic properties by treatment with at least one compound from the group of alkylsilanes, perfluoroalkylsilanes or alkyldisilazanes.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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DE10118352A DE10118352A1 (en) | 2001-04-12 | 2001-04-12 | Self-cleaning surfaces through hydrophobic structures and processes for their production |
DE10118352 | 2001-04-12 |
Publications (4)
Publication Number | Publication Date |
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EP1249280A2 true EP1249280A2 (en) | 2002-10-16 |
EP1249280A3 EP1249280A3 (en) | 2003-01-02 |
EP1249280B1 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) |
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Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5432000A (en) † | 1989-03-20 | 1995-07-11 | Weyerhaeuser Company | Binder coated discontinuous fibers with adhered particulate materials |
WO2000039239A1 (en) * | 1998-12-24 | 2000-07-06 | Sunyx Surface Nanotechnologies Gmbh | Method for producing an ultraphobic surface based on nickel hydroxide, ultraphobic surface and the use thereof |
WO2000071834A2 (en) * | 1999-05-26 | 2000-11-30 | Basf Corporation | Metal roofing shingle stock and method for making it |
WO2002055446A1 (en) † | 2001-01-12 | 2002-07-18 | Basf Aktiengesellschaft | Method for rendering surfaces resistant to soiling |
Family Cites Families (14)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3354022A (en) | 1964-03-31 | 1967-11-21 | Du Pont | Water-repellant surface |
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 |
US6660363B1 (en) | 1994-07-29 | 2003-12-09 | Wilhelm Barthlott | Self-cleaning surfaces of objects and process for producing same |
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 |
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 |
DE10118349A1 (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 |
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 |
DE10118351A1 (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 DE DE50208229T patent/DE50208229D1/en not_active Expired - Fee Related
- 2002-02-22 ES ES02003960T patent/ES2271131T5/en not_active Expired - Lifetime
- 2002-02-22 EP EP02003960A patent/EP1249280B2/en not_active Expired - Lifetime
- 2002-02-22 AT AT02003960T patent/ATE340654T1/en not_active IP Right Cessation
- 2002-04-09 JP JP2002106941A patent/JP2002346469A/en active Pending
- 2002-04-09 US US10/118,258 patent/US6858284B2/en not_active Expired - Fee Related
- 2002-04-10 CA CA002381134A patent/CA2381134A1/en not_active Abandoned
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5432000A (en) † | 1989-03-20 | 1995-07-11 | Weyerhaeuser Company | Binder coated discontinuous fibers with adhered particulate materials |
WO2000039239A1 (en) * | 1998-12-24 | 2000-07-06 | Sunyx Surface Nanotechnologies Gmbh | Method for producing an ultraphobic surface based on nickel hydroxide, ultraphobic surface and the use thereof |
WO2000071834A2 (en) * | 1999-05-26 | 2000-11-30 | Basf Corporation | Metal roofing shingle stock and method for making it |
WO2002055446A1 (en) † | 2001-01-12 | 2002-07-18 | Basf Aktiengesellschaft | Method for rendering surfaces resistant to soiling |
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EP1283076A2 (en) * | 2001-07-16 | 2003-02-12 | Creavis Gesellschaft für Technologie und Innovation mbH | Self cleaning surfaces due to hydrophobic structures and method for the preparation thereof |
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CN111763100A (en) * | 2020-06-10 | 2020-10-13 | 大理大学 | Preparation method of natural bluestone self-cleaning surface |
CN111763100B (en) * | 2020-06-10 | 2021-10-26 | 大理大学 | Preparation method of natural bluestone self-cleaning surface |
Also Published As
Publication number | Publication date |
---|---|
ES2271131T5 (en) | 2009-10-30 |
DE10118352A1 (en) | 2002-10-17 |
US20020150724A1 (en) | 2002-10-17 |
US6858284B2 (en) | 2005-02-22 |
ATE340654T1 (en) | 2006-10-15 |
EP1249280B1 (en) | 2006-09-27 |
CA2381134A1 (en) | 2002-10-12 |
JP2002346469A (en) | 2002-12-03 |
EP1249280A3 (en) | 2003-01-02 |
ES2271131T3 (en) | 2007-04-16 |
DE50208229D1 (en) | 2006-11-09 |
EP1249280B2 (en) | 2009-07-01 |
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