WO2003013748A1

WO2003013748A1 - Achieving a lotus effect by preventing microbial growth after damage to the self-cleaning surface

Info

Publication number: WO2003013748A1
Application number: PCT/EP2002/007213
Authority: WO
Inventors: Edwin Nun; Markus Oles; Peter Ottersbach
Original assignee: Creavis Gesellschaft Für Technologie Und Innovation Mbh
Priority date: 2001-08-10
Filing date: 2002-06-29
Publication date: 2003-02-20
Also published as: DE10139572A1

Abstract

The invention relates to self-cleaning surfaces that, after having been damaged, have antimicrobial properties in the very areas that have been damaged. The invention also relates to a method for producing such self-cleaning surfaces. The economic importance of articles provided with self-cleaning surfaces is increasing. The aim of the invention is therefore to provide a simple method for producing self-cleaning surfaces that, after having been damaged, have antimicrobial properties in the very areas that have been damaged. This aim is achieved by incorporating antimicrobial polymers into the coating or paint systems for fixating structurizers for producing self-cleaning surfaces. In this manner, the antimicrobial polymers are stably incorporated into a self-cleaning surface and become effective after damages to the surfaces.

Description

Maintaining the lotus effect by preventing microbial growth after damage to the self-cleaning surface

The present invention relates to self-cleaning surfaces which are given an antimicrobial treatment using reactive formulations.

Objects with extremely difficult to wet surfaces, so-called lotus effect surfaces, have a number of economically important features, in particular such surfaces are self-cleaning. Cleaning surfaces is time-consuming and costly. Self-cleaning surfaces are therefore of the highest economic interest. Adhesion mechanisms are usually caused by interfacial energy parameters between the two touching surfaces. As a rule, the systems try to lower their free interface energy. If the free interface energies between two components are themselves very low, it can generally be assumed that the adhesion between these two components is weak. What is important here is the relative reduction in the free interface energy. In pairings with a high and a low interfacial energy, the possibility of interactions is very important. For example, when water is applied to a hydrophobic surface, it is not possible to bring about a noticeable reduction in the interfacial energy. This can be seen from the fact that the wetting is poor. Applied water forms drops with very large contact angles. Perfluorinated hydrocarbons, e.g. B. polytetrafluoroethylene, have a very low interfacial energy. Hardly any components adhere to such surfaces, or components deposited on such surfaces can be removed very easily.

The use of hydrophobic materials, such as perfluorinated polymers, for the production of hydrophobic surfaces is known. A further development of these surfaces consists in structuring the surfaces in the μm range to the nm range. US Pat. No. 5,599,489 discloses a method in which a surface can be roughened by bombardment with particles of a corresponding size and can be given a particularly repellent finish by subsequent perfluorination. Another method is described by H. Saito et al in "Service Coatings International" 4, 1997, p. 168 ff. Here, particles of fluoropolymers are applied to metal surfaces, with a greatly reduced wettability of the surfaces thus produced against water with a considerably reduced tendency to icing.

US Pat. Nos. 3,354,022 and WO 96/04123 describe further methods for reducing the wettability of objects by topological changes in the surfaces. Here, artificial elevations or depressions with a height of approx. 5 to 1,000 μm and a distance of approx. 5 to 500 μm are applied to hydrophobic or hydrophobicized materials after structuring. Surfaces of this type lead to rapid drop formation, the rolling drops picking up dirt particles and thus cleaning the surface.

This principle is borrowed from nature. Small contact areas reduce the van der Waal's interaction, which is responsible for the adhesion to flat surfaces with low surface energy. For example, the leaves of the lotus plant are provided with raised areas made of wax, which reduce the contact area with water. WO 00/58410 describes the structures and claims the formation thereof by spraying on hydrophobic alcohols, such as nonakosan-10-ol, or alkanediols, such as nonakosan-5,10-diol. The disadvantage here is the poor mechanical stability of the self-cleaning surfaces and the fact that detergents lead to the detachment of the structure.

Another method of producing easily cleanable surfaces is described in DE 19917367 AI. However, coatings based on fluorine-containing condensates are not self-cleaning. The contact area between water and surface is reduced, but not to a sufficient extent.

EP 1 040 874 A2 describes the stamping of microstructures and claims the use of such structures in analysis (microfluidics). The disadvantage of these structures is the insufficient mechanical stability. Despite excellent self-cleaning surfaces, the colonization and spread of bacteria on surfaces, e.g. B. of pipes and containers or packaging possible, especially if there is damage to the self-cleaning surface. Colonization with microorganisms is highly undesirable because it makes self-cleaning difficult, if not completely suppressed. Mucus layers are often formed, which can extremely increase the microbial populations, e.g. B. subsequently affect water, beverage and food qualities and can even lead to spoilage of the goods and damage to the health of consumers.

Bacteria must be kept away from all areas of life where hygiene is important. This affects furniture and device surfaces as well as partitioning devices to protect the privacy, as well as wall and boundary surfaces in the sanitary area.

Device surfaces of furniture and textiles against bacteria are currently being treated as necessary or as a precautionary measure with chemicals or other solutions and mixtures that act as a disinfectant to a greater or lesser extent and have a massive antimicrobial effect. Such chemical agents have a non-specific effect, are often themselves toxic or irritating and can form degradation products which are harmful to health. Often, intolerances also appear in people who are appropriately sensitized.

Despite water-repellent surfaces, algae on the outer surfaces of buildings that are equipped with such water-repellent plastic surfaces sometimes occur. In addition to the undesirable visual impression, the function of corresponding components can also be reduced under certain circumstances. In this context, e.g. B. to think of algae growth of photovoltaic functional areas. In addition, the water-repellent or self-cleaning effect is lost with increasing algae growth.

Another form of microbial contamination, for which there is still no technically satisfactory solution, is the contamination of surfaces by fungi. So z. B. the infestation of joints and walls in damp rooms with AspergiUus niger in addition to the impaired visual appearance, also a serious one health-related aspect, since many people are allergic to the substances released by fungi, which can lead to severe chronic respiratory diseases.

The object of the present invention was therefore to provide self-cleaning surfaces and a process for their production which do not lose their self-cleaning effect as a result of adhering bacteria, algae or fungi.

Surprisingly, it was found that self-cleaning surfaces, which consist of a carrier material and a particulate system, the carrier material having antimicrobial properties, are covered with bacteria, algae or fungi much more slowly than conventional self-cleaning surfaces after damage to the self-cleaning surface, for example by scratches.

The subject of the present invention is therefore a surface according to claim 1, which has an artificial surface structure of elevations and depressions, which has self-cleaning properties, which is characterized in that the surface has a carrier system with antimicrobial properties.

The present invention also relates to a method according to claim 8 for the production of surfaces according to at least one of claims 1 to 7 which have self-cleaning properties, which is characterized in that at least one material which has antimicrobial properties is used in the production of the surfaces ,

The surfaces of the invention have the advantage that adhesion and spread of biological contaminants, such as. B. bacteria, fungi and algae is significantly slowed down and thus the self-cleaning properties of the surfaces are effectively retained for longer. This is particularly the case when the self-cleaning layer z. B. has been damaged by scratches, since the antimicrobial properties of the carrier system work particularly well at the damaged area. In the following, the terms antimicrobial and microbicidal are to be understood to mean one and the same property.

From European patent application EP 0 862 858 it is known that copolymers of tertiary butylaminoethyl methacrylate, a methacrylic acid ester with a secondary amino function, have inherent microbicidal properties. In the examples, this copolymer is called Amina T 100.

Without the addition of a microbicidal active ingredient, these polymers have so-called contact microbicidity. We are aware of a large number of contact microbicidal polymers from the following patent applications: DE 10024270, DE 10022406, PCT / EP 00/06501, DE 10014726, DE 10008177. These polymers contain no low molecular weight constituents. The antimicrobial properties are due to the contact of bacteria with the surface.

The surface according to the invention is described below by way of example, without the invention being restricted to these examples.

The present invention relates to a surface which has an artificial surface structure of elevations and depressions which has self-cleaning properties, the surface being characterized in that the surface has a carrier system with antimicrobial properties. In particular, the surface has at least partially antimicrobial properties after damage to the surface structure.

To achieve the self-cleaning effect, it is advantageous if the elevations of the surface structure are at a distance of 50 nm to 200 μm, preferably 500 nm to 100 μm and very particularly preferably 0.1 to 20 μm. It is also advantageous if the elevations of the surface structure have a height of 50 nm to 100,000 nm, preferably 50 to 50,000 nm and very particularly preferably 100 nm to 30,000 nm.

The elevations can be structures applied to the surface or through between Indentations that have been made in the surface are elevations. The indentations can be introduced into the surface in particular by embossing or molding structures into the carrier system.

In a particularly preferred embodiment of the surface according to the invention, the elevations and depressions are formed in that the surface has particles applied to it, which are preferably fixed by the carrier system.

Particles which can be used are particles which comprise at least one material selected from silicates, doped or pyrogenic silicates, minerals, metal oxides, silicas. Have metals or polymers. Preferably particles are used which have a particle diameter of 0.02 to 100 μm, particularly preferably from 0.1 to 50 μm and very particularly preferably from 0.3 to 30 μm. The surface structures according to the invention have the individual particles on the surface at intervals of 0-10 particle diameter, in particular of 0-3 particle diameter.

The surfaces according to the invention preferably have particles which have hydrophobic properties. The hydrophobic properties of the particles may be inherent due to the material used for the particles. However, hydrophobized particles can also be used, which, for. B. by treatment with at least one compound from the group of alkylsilanes, perfluoroalkylsilanes, paraffins, waxes, fatty acid esters, functionalized long-chain alkane derivatives or alkyldisilazanes, have hydrophobic properties.

The particles may also be present as aggregates or agglomerates, wherein, according to DIN 53 206, aggregates surface or kantenfbrmig each bearing (primary) particles and ^{agglomerates'} RMIG each mounted primary punktfb (particles) are understood. As particles it is also possible to use particles which aggregate from primary particles to form agglomerates or aggregates with a size of 0.2-100 μm. It can be advantageous if the particles used have a structured surface. Particles which have an irregular fine structure in the nanometer range on the surface are preferably used. The fine structure of the particles is preferably a jagged structure with elevations and / or depressions in the nanometer range. The elevations preferably have an average height of 20 to 500 nm, particularly preferably 50 to 200 nm. The distance between the elevations or depressions on the particles is preferably less than 500 nm, very particularly preferably less than 200 nm. B. craters, crack-like notches, notches, gaps, holes and cavities support the effective structure of the particles in relation to the self-cleaning effect.

As particles, in particular as particles which have an irregular fine structure in the nanometer range on the surface, those particles are preferably used which have at least one compound selected from pyrogenic silica, aluminum oxide, silicon oxide, mixed oxides, pyrogenic silicates or powdered polymers or powdered metals. It can be advantageous if the particles used have hydrophobic properties. Particularly suitable particles are, inter alia, hydrophobicized, pyrogenic silicas, so-called Aerosile ^® .

The surface according to the invention very particularly preferably has particles which are fixed on the surface by means of a carrier system. The known adhesive or lacquer systems can be used as the basis for the carrier system with antimicrobial properties. Such carrier systems are e.g. B. hot melt adhesive, which have at least one compound selected from the ethylene / ethyl acrylate copolymers, ethylene / vinyl acetate copolymers, polyamides, polyether sulfones, polyisobutenes or polyvinyl butyrals, or lacquers which contain at least mixtures of mono- and / or polyunsaturated acrylates and / or methacrylates and / or have polyurethanes.

For this purpose, the carrier system, which has antimicrobial properties, has at least one antimicrobial polymer which is selected from at least one monomer from methacrylic acid-2-tert-butylaminoethyl ester, methacrylic acid-2-diethylamino ethyl ester, methacrylic acid-2-diethylaminomethyl ester, acrylic acid-2-tert-butylaminoethyl ester, acrylic acid-3-dimethylaminopropyl ester, acrylic acid 2-diethylaminoethyl ester, acrylic acid-2-dimethylaminoethyl ester, dimethylaminopropyl methacrylamide, diethylamino-propyl-methacrylamide, acrylic acid -dimethylaminopropylamide, 2-methacryloyloxyethyltrimethyl-ammonium methosulfate, methacrylic acid-2-diethylaminoethyl ester, 2-methacryloyloxyethyltrimethylammonium chloride, 3-methacryloylaminopropyltrimethylammonium chloride, 2-meth-acryloyloxyethyltrimethylammonium-4-methyl-ammonoyl-methyl-2-methyloylmoyl-methyl-2-methyloylmoylmethyl-2-methyloylmoylmethyl-2-methyl-ammonoyl-methyl-2-methyl-ammonoyl-methyl-2-methyl-ammonoyl-methyl-2-methyl-ammonoyl-methyl-2-methyl-ammonoyl-methyl-2-methyl-ammonoyl-methyl-2-methoxy-4-yl -Acryl- amido-2-methyl-l-propanesulfonic acid, 2-diethylaminoethyl vinyl ether or 3-aminopropyl vinyl ether was prepared.

The carrier system, which has a polymer with antimicrobial properties, preferably has an antimicrobial polymer content of from 0.01 to 25% by weight, particularly preferably from 0.1 to 13% by weight and very particularly preferably from 6 to 10% by weight. -%, based on the polymerizable carrier system.

The surface according to the invention can have at least one surface of a shaped body made of a material selected from polymers such as, for. B. polyamides, polyurethanes, polyether block amides, polyester amides, polyvinyl chloride, polyolefins, polysilicones, polysiloxanes, polymethyl methacrylates or polyterephthalates, as well as metals, woods, leather, fibers, fabrics, glasses or ceramics. The list of polymeric materials is exemplary and is not limited to these. If the shaped body is a shaped body made of polymer, it can be advantageous if this shaped body, and thus the surface, has a polymer with antimicrobial properties.

The surfaces according to the invention are preferably produced using a method according to the invention for producing surfaces with an artificial surface structure which have self-cleaning properties, which is characterized in that at least one material which has antimicrobial properties is used as the carrier system in the production of the surfaces. The surface structure, which has elevations or depressions, can itself be produced on the surface on which a carrier system is applied. This can e.g. B. by embossing a negative form in the carrier system and subsequent hardening of the carrier system, or by applying and fixing particles on the surface. The particles can be applied and fixed on the surface in a manner known to the person skilled in the art. The use of a carrier system is used as the chemical method of fixation. Various adhesives, adhesion promoters or lacquers, to which antimicrobial polymers have preferably been added, can be used as the carrier system. Additional support systems or chemical fixing methods are apparent to the person skilled in the art.

The application of the particles to the surface to produce the surface structure can e.g. B. be carried out so that the carrier system, which can be a curable substance and contains antimicrobial polymer, is applied by spraying, knife coating, brushing or spraying onto a surface. The curable substance is preferably applied in a thickness of 1 to 200 μm, preferably in a thickness of 5 to 75 μm. Depending on the viscosity of the curable substance, it may be advantageous to allow the substance to harden before the particles are applied. Ideally, the viscosity of the curable substance is selected so that the particles applied can at least partially sink into the curable substance, but the curable substance or the particles applied to it no longer run when the surface is placed vertically.

In this embodiment, the particles themselves can be applied by spraying. In particular, the particles can be applied by spraying using an electrostatic spray gun. After the particles have been applied, excess particles, that is to say particles which do not adhere to the curable substance, can be removed from the surface by shaking, brushing or blowing off. These particles can be collected and reused.

In this embodiment of the method according to the invention, the particles are fixed on the surface by hardening the carrier system, this preferably being done by thermal energy and / or light energy. The carrier system is particularly preferably hardened by light energy. The carrier is preferably hardened under an inert gas atmosphere, very particularly preferably under a nitrogen atmosphere.

In particular, antimicrobial, UV-curable, thermally curable or air-curing coating systems can serve as carrier systems. Coating systems include paint-like mixtures of monounsaturated acrylates or methacrylates with polyunsaturated acrylates or methacrylates, but also mixtures of the polyunsaturated acrylates or methacrylates with one another. Urethane-based paint systems are also considered coating systems. The mixing ratios can be varied within wide limits. Depending on the structure-forming component to be added later, further functional groups such as hydroxyl groups, ethoxy groups, amines, ketones, isocyanates or the like, but also fluorine-containing monomers or inert filler components, such as polymers soluble in a monomer mixture, can be added. The additional functionality mainly serves the better connection of the structure formers. Pure acrylic dispersions and powder coating systems can also be used as carrier systems.

Surprisingly, it was found that, in particular, the carrier systems for the production of self-cleaning surfaces can be equipped with antimicrobial agents in a simple manner by adding a reactive mixture of the carrier system from different

Monomers, initiators and possibly other additives add a defined amount of antimicrobial polymer. It has proven to be advantageous here that antimicrobial polymers, and not, for example, the monomer or monomers used to produce this antimicrobial polymer, are used in the reactive mixture, since effective antimicrobial finishing can only be achieved by this procedure. After the reactive mixture has reacted (hardened), by means of which the particles are fixed, a carrier system is obtained which has an antimicrobial polymer and therefore itself has antimicrobial properties.

The carrier system used preferably has an antimicrobial polymer content from 0.01 to 25% by weight, particularly preferably from 0.1 to 13% by weight and very particularly preferably from 6 to 10% by weight, based on the carrier system.

Particles which can be used are particles which comprise at least one material selected from silicates, doped or pyrogenic silicates, minerals, metal oxides, mixed metal oxides, silicas. Have metals or polymers. Preferably particles are used which have a particle diameter of 0.02 to 100 μm, particularly preferably from 0.2 to 50 μm and very particularly preferably from 0.3 to 30 μm.

It can be advantageous if particles are used which have hydrophobic properties. The hydrophobic properties of the particles may be inherent due to the material used for the particles. However, hydrophobized particles can also be used, which, for. B. by treatment with at least one compound from the group of alkylsilanes, perfluoroalkylsilanes, paraffins, waxes, fatty acid esters, functionalized long-chain alkane derivatives or alkyldisilazanes, have hydrophobic properties.

The particles can also be in the form of aggregates or agglomerates, in accordance with DIN 53 206 being understood as aggregates of flat or edged primary particles (particles) and agglomerates of punctiform primary particles (particles). As particles it is also possible to use particles which aggregate from primary particles to form agglomerates or aggregates with a size of 0.2-100 μm.

It can be advantageous if the particles used have a structured surface. Particles which have an irregular fine structure in the nanometer range on the surface are preferably used. The fine structure of the particles is preferably a jagged structure with elevations and / or depressions in the nanometer range. The elevations preferably have an average height of 20 to 500 nm, particularly preferably 50 to 200 nm. The distance between the elevations or depressions on the particles is preferably less than 500 nm, very particularly preferably less than 200 nm. These wells, such as. B. craters, crack-like notches, notches, gaps, holes and cavities support the effective structure of the particles in relation to the self-cleaning effect.

Those particles which have at least one material selected from silicates or doped silicates, minerals, metal oxides, mixed metal oxides, pyrogenic silicas or precipitated silicas or polymers are preferably used. The particles very particularly preferably have silicates, pyrogenic silicas or precipitated silicas, in particular aerosils, minerals such as magadiite, Al ₂ O ₃ , SiO ₂ , TiO ₂ , ZrO ₂ and Zn powder coated with Aerosil R 974 or powdery polymers such as e.g. B. cryogenically ground or spray dried polytetrafluoroethylene (PTFE).

Particles with a BET surface area of 50 to 600 m / g are particularly preferably used. Particles with a BET surface area of 50 to 200 m Ig are very particularly preferably used.

The particles for generating the self-cleaning surfaces preferably also have hydrophobic properties in addition to the jagged structures. The particles themselves can be hydrophobic, e.g. B. PTFE-containing particles, or the particles used may have been made hydrophobic. The particles can be made hydrophobic in a manner known to the person skilled in the art. Typical hydrophobized particles are e.g. B. Very fine powder such as Aerosil R 974 or Aerosil-R 8200 (Degussa AG), which are commercially available.

To produce the carrier systems according to the invention, the carrier system used in the method according to the invention must have the antimicrobial material. Polymers which have been prepared from nitrogen- or phosphorus-functionalized monomers are preferably used as antibacterial materials. Particularly preferred antibacterial materials are those polymers which consist of at least one of the monomers selected from 2-tert-butylaminoethyl methacrylate, 2-diethylaminoethyl methacrylate, 2-diethylaminomethyl methacrylate, 2-tert.-butylaminoethyl acrylate , 3-dimethylaminopropyl acrylic acid, 2-diethylaminoethyl acrylic acid esters, 2-dimethylaminoethyl acrylate, dimethylaminopropyl methacrylamide, diethylaminopropylmethacrylamide, 3-dimethylaminopropylamide, 2-methacryloyloxyethyltrimethylammonium methosulfate, 2-diethylaminoethyl methacrylate, 2-methacryloyloxyethyltrimethylethylmethyl chloride, 2-methoxyammonylammonyl methoxyl ammonium chloride, Acryloyloxyethyl-4-benzoyl-dimethylammonium bromide, 2-methacryloyloxyethyl-4-benzoyldimethylammonium bromide, 2-acrylamido-2-methyl-l-propanesulfonic acid, 2-diethylaminoethyl vinyl ether, 3-amino propyl vinyl ether have been prepared.

It can be advantageous if the particles used also have at least partially antibacterial materials. Such particles can e.g. B. consist of polymers with antimicrobial properties, or coated with such polymers but also other antimicrobial materials.

The method according to the invention can be used excellently for the production of self-cleaning surfaces on planar or non-planar objects, in particular on non-planar objects which have antimicrobial properties after the particle layer has been damaged. This is only possible to a limited extent with the conventional methods. In particular, via processes in which prefabricated films are applied to a surface or in processes in which a structure is to be created by embossing, non-planar objects, such as, for. B. sculptures, not or only partially accessible. Naturally, the method according to the invention can also be used to produce self-cleaning surfaces on objects with planar surfaces, such as, for. B. greenhouses or public transport. In particular, the use of the method according to the invention for the production of self-cleaning surfaces on greenhouses has advantages, since with the method self-cleaning surfaces z. B. can also be produced on transparent materials such as glass or plexiglass and the self-cleaning surface can be made at least sufficiently transparent that sufficient sunlight can penetrate through the transparent surface provided with a self-cleaning surface for the growth of the plants in the greenhouse. In contrast to conventional greenhouses, which are regularly used by Foliage, dust, lime and biological material, such as. B. algae, must be cleaned, greenhouses that have a surface according to the invention according to one of claims 1 to 8, can be operated with longer cleaning intervals.

The present invention also relates to the use of the self-cleaning surfaces produced according to the invention for the production of products having antimicrobial surfaces after damage to the same and the products thus produced as such. Such products are preferably based on polymers such as. B. polyamides, polyurethanes, polyether block amides, polyester amides, polyvinyl chloride, polyolefins, polysilicones, polysiloxanes, polymethyl methacrylates or polyterephthalates as well as metals, woods, leather, fibers, fabrics, glasses and ceramics which have surfaces coated with compounds or polymer formulations and structuring agents according to the invention. The list of polymeric materials is exemplary and is not limited to the above.

Products of this type containing antimicrobial active carrier systems are, for example, and in particular components of air conditioning systems, coated pipes, semi-finished products, roofs, bathrooms and toilet articles, kitchen articles, components of sanitary facilities, components of animal cages and dwellings as well as materials of so-called textile construction.

The self-cleaning coatings with antimicrobial carrier systems can be used wherever there is a lack of bacteria, algae and / or fungi, i.e. H. microbicidal surfaces and surfaces with non-stick properties. Examples of uses for the surfaces according to the invention can be found in the following

areas:

Marine: port facilities, buoys, drilling platforms

House: roofing, walls, facades, greenhouses, sun protection, garden fences,

Wood protection, awnings, textile construction Sanitary: Public sanitary facilities such. B. toilets, bathrooms, shower curtains,

Toiletries, sauna, swimming pool, hospital facilities, facilities of Medical practices and physiotherapy treatment centers.

Food: kitchen, kitchen items

Machine parts: bioreactors, solar systems,

Utility articles: public transport, truck tarpaulins, animal cages,

The test results from Examples 1 to 3 and the comparative example are shown graphically in FIGS. 1 to 4. WSH mean water of standardized hardness and 2 x 2 denotes the specimen size in cm. 1 to 4 shows the reduction in the number of bacteria in log stages compared to the hardness standardized by water. Number of nuclei per unit volume and N _° Number of germs in the water sample after the respective contact time: where N mean.

1 shows the test results of the comparative example. It is easy to see that there are no factors that negatively affect microbial growth.

FIG. 2 shows the test results of Example 1. It can be clearly seen that intact, self-cleaning surfaces have only marginal antimicrobial behavior.

3 shows the test results of Example 2. It can be clearly seen that slight damage to the self-cleaning surface brings about the beginning of antimicrobial properties.

4 shows the test results of Example 3. It can be clearly seen that the antimicrobial effects increase with increasing destruction of the self-cleaning surface.

The following examples are intended to explain the surfaces according to the invention in more detail, without the invention being restricted to these embodiments.

Comparative example

20% methyl methacrylate, 20% pentaerythritol tetraacrylate and 60% hexanediol dimethacrylate are mixed together. Based on this mixture, 14% Plex 4092 F (Plexiglas, Röhm company) and 2% Darocur 1173, a UV hardener, are added and at least 60 min. touched. This mixture is drawn onto a 2 mm thick PMMA plate 50 μm thick and the layer 5 min. let dry. Then a silica (Aerosil R8200, Degussa AG) is sprinkled on and 3 min. later hardened with a wavelength of 308 nm under nitrogen. Excess Aerosil R8200 is brushed off. The characterization of the surfaces is visual and is recorded with +++, which means that water drops form almost completely and the roll angle is below 10 °. The assessment of the microbicidal activity against the test germ Staphylococcus aureus at 30 ° C in water of standardized hardness is indicated with a non-existent reduction in the bacterial count.

example 1

20% methyl methacrylate, 20% pentaerythritol tetraacrylate and 60% hexanediol dimethacrylate are mixed together. Based on this mixture, 4% Plex 4092 F (Röhm), 2% Darocur 1173 (UV hardener) and 10% Amina T100 are mixed in as previously described. The mixture is at least 60 min. long stirred, drawn on a 2 mm PMMA plate to 50 microns thick and 5 min. let dry. Then sprinkle with Aerosil R8200 and 3 min. later hardened at a wavelength of 308 nm under nitrogen. Excess Aerosil R8200 is brushed off. The surface is characterized visually and is recorded with +++, which means that water drops form almost completely and the roll angle is below 10 °. A 2 x 2 cm piece is sawn out of a plate treated in this way and the microbicidal activity has been tested. The test area was brought into contact with the structured side of the test solution and the bacterial count was determined as a function of time. The assessment of the microbicidal activity against the test germ Staphylococcus aureus at 30 ° C in water of standardized hardness is given with only 0.31 log steps.

Example 2 Analogously to Example 1, the monomers are mixed and the coating is carried out. However, the surface is slightly scratched so that the antimicrobial coating layer (the Carrier system) has contact with the nutrient fluid. The assessment of the microbicidal activity against the test germ Staphylococcus aureus at 30 ° C in water of standardized hardness is given with only 0.40 log steps.

Example 3

Analogously to Example 1, the monomers are mixed and the coating is carried out. However, the surface is scored more so that the antimicrobial coating layer (the carrier system) is in contact with the nutrient fluid. The assessment of the microbicidal activity against the test germ Staphylococcus aureus at 30 ° C in water of standardized hardness is given as 0.90 log steps.

From the examples and the associated figures FIGS. 1 to 4 it can be seen that the antimicrobial effect increases with increasing damage to the surface. The desired effect, namely the reduction in the occurrence of germs on self-cleaning surfaces, in particular on damaged self-cleaning surfaces, was achieved by the surface according to the invention.

Claims

claims:

1. Surface with an artificial surface structure of elevations and depressions, which has self-cleaning properties, characterized in that the surface structure has a carrier system with antimicrobial properties.

2. Surface according to claim 1, characterized in that the surface has particles.

3. Surface according to claim 2, characterized in that the surface has particles which are fixed on the surface by means of the carrier system.

4. Surface according to at least one of claims 1 to 3, characterized in that the carrier system have at least one antimicrobial polymer which is selected from at least one monomer from 2-tert-butylaminoethyl methacrylate, 2-diethylaminoethyl methacrylate, methacrylic acid, 2-diethylamino-methyl ester, acrylic acid-2-tert-butylaminoethyl ester, acrylic acid-3-dimethylaminopropyl ester, acrylic acid-2-diethylaminoethyl ester, acrylic acid-2-dimethylaminoethyl ester, dimethylaminopropyl methacrylamide, diethylaminopropyl methacrylamide, acrylic acid-3-dimethylaminopropyloylmethyl methoxy amide, 2 .

Methacrylic acid-2-diethylaminoethyl ester, 2-Methacryloyloxyethyltrimethylammonium- chloride, 3 -Methacryloylaminopropyltrimethylammonium chloride, 2-methacryloyloxy ethyl trimethyl ammonium chloride, 2-acryloyloxyethyl 4-benzoyldimethylammoniumbromid, 2- methacryloyloxyethyl benzoyldimethylammoniumbromid-4, 2-acrylamido-2-methyl- 1-propanesulfonic acid, 2-diethylaminoethyl vinyl ether or 3-aminopropyl vinyl ether was produced.

5. Surface according to claim 4, characterized in that the carrier system has an antimicrobial polymer content of 0.01 to

25 wt .-%, based on the carrier system.

6. Surface according to at least one of claims 1 to 5, characterized in that the surface of at least one surface of a shaped body made of a material selected from the polymers, in particular the polyamides, polyurethanes, polyether block amides, polyester amides, polyvinyl chloride, polyolefins, polysilicones, polysiloxanes, Polymethyl methacrylates or polyterephthalates as well as metals, woods, leather, fibers, fabrics, glasses or ceramics.

7. A process for the production of surfaces with an artificial surface structure according to at least one of claims 1 to 6, which have self-cleaning properties, characterized in that in the production of the surfaces at least one material is used as a carrier system which has antimicrobial properties.

8. The method according to claim 7, characterized in that a surface structure having elevations or depressions on the

Surface is made itself.

9. The method according to claim 8, characterized in that the surface structure by applying and fixing particles on the

Surface is generated.

10. The method according to claim 9, characterized in that a carrier system is used for fixing.

11. The method according to claim 9 or 10, characterized in that the particles have a material selected from silicates, doped silicates, minerals, metal oxides, silicas or polymers.

12. The method according to at least one of claims 9 to 11, characterized in that the particles have an average particle diameter of 0.05 to 30 microns.

13. The method according to at least one of claims 9 to 12, characterized in that the particles have an irregular fine structure in the nanometer range on the surface.

14. The method according to at least one of claims 8 to 13, characterized in that the particles and the carrier system have antimicrobial material.

15. The method according to at least one of claims 8 to 14, characterized in that a polymer is used as the antimicrobial material, which is selected from at least one monomer selected from methacrylic acid-2-tert-butylaminoethyl ester, methacrylic acid-2-diethylaminoethyl ester, methacrylic acid 2-diethylaminomethyl ester, acrylic acid-2-tert-butylaminoethyl ester, acrylic acid-3-dimethylaminopropyl ester, acrylic acid 2-diethylaminoethyl ester, acrylic acid-2-dimethylaminoethyl ester, dimethylaminopropyl methacrylamide, diethylaminopropyl methacrylamide, acrylic acid 3-dimethylaminopropylmethylamidyllmethyloxyethylmidllmethylamidyllmethylamidyllmethylamidylmethyllamidylmethyllamidylmethyllamidylmethyllamidylmethylamidylmethylamidylmethylamidylmethylamidylmethylamidylmethylamidylamidylmethylamidylmethylamidylmethylamidylmethylamine , Methacrylic acid-2-diethyl- aminoethyl ester, 2-methacryloyloxyethyltrimethylammonium chloride, 3-methacryloylaminopropyltrimethylammonium chloride, 2-methacryloyloxyethyltrimethylammonium chloride, 2-acryloyloxyethyl-4-benzoyldimethylammonium bromide, 2-methacryloyloxyethyl-4-benzoyldimethylammoniumsulfonylamidido, 2-methylammonium bromide, 2-methacrylate, 2-Diethylaminoethyl vinyl ether or 3-aminopropyl vinyl ether was produced.

16. Use of surfaces according to at least one of claims 1 to 8 for finishing surfaces in port facilities, buoys, drilling platforms, roofing, walls, facades, greenhouses, sun protection, garden fences, wood protection,

Awnings, textile construction, public sanitary facilities, bathrooms, shower curtains, toiletries, saunas, swimming pools, hospital facilities, medical practice and physiotherapy treatment center facilities, kitchens, kitchen items, bioreactors, solar systems, public transport, truck tarpaulins or animal cages.

17. Products with self-cleaning surfaces that have antimicrobial properties if the self-cleaning surfaces are damaged.