DE10205784A1 - Repair resin for improving surfaces having self-cleaning properties, a surface structure with hills, and suspended structure forming particles useful for the repair damaged surfaces, especially those having mechanical damage - Google Patents

Abstract

A novel repair resin for improving surfaces has self-cleaning properties, a surface structure with hills, at least one compound which can be cured to give a polymer, and suspended structure forming particles. Independent claims are also included for the following: (1) a process for preparation of the resin by production of a liquid to paste mixture containing at least one compound which can be cured to give a polymer and structure forming particles; and (2) an object with self-cleaning properties with a self-cleaning surface improved by the resin.

Description

The invention relates to repair resins for the repair of self-cleaning surfaces as well a process for producing these repair resins.

Various processes for treating surfaces are from surface technology known to make these surfaces dirt and water repellent. So z. B. known that to achieve good self-cleaning of a surface, the surface next to one very hydrophobic surface must also have a certain roughness. A suitable one A combination of structure and hydrophobicity makes it possible that even small amounts Take dirt particles adhering to the surface of moving water and remove them Clean the surface (WO 96/04123; US 3 354 022).

State of the art with regard to these surfaces is according to EP 0 933 388 that for such self-cleaning surfaces have an aspect ratio of> 1 and a surface energy of less than 20 mN / m is required. The aspect ratio is defined here as the Quotient of medium height to the medium width of the structure. The above criteria are in nature, for example in the lotus leaf. The one from a hydrophobic waxy Material-formed surface of the plant has elevations that are a few µm apart are removed. Water drops essentially only come into contact with these tips. Such water-repellent surfaces are widely described in the literature.

CH-PS-268 258 describes a process in which, by applying powders such as kaolin, Talc, clay or silica gel structured surfaces can be created. The powders will fixed on the surface by oils and resins based on organosilicon compounds (Examples 1 to 6).

EP 0 909 747 teaches a method for producing a self-cleaning surface. The Surface has hydrophobic elevations with a height of 5 to 200 µm. Manufactured is such a surface by applying a dispersion of powder particles and an inert material in a siloxane solution and then curing. The structure-forming particles are thus fixed to the substrate by an auxiliary medium.

WO 00/58410 comes to the conclusion that it is technically possible to produce surfaces of Make objects artificially self-cleaning. The surface structures required for this from surveys and depressions have a distance between the surveys of Surface structures in the range from 0.1 to 200 µm and an elevation in the Range 0.1 to 100 µm. The materials used for this must be made of hydrophobic Polymers or permanently hydrophobic material. A swelling of the particles the carrier matrix must be prevented. WO 00/58410 describes the structures and claims the formation of the same by spraying on hydrophobic alcohols, such as Nonacosan-10-ol or alkane diols, such as Nonacosan-5,10-diol. The disadvantage here is that poor stability of the self-cleaning surfaces because detergents dissolve the Structure lead.

The use of hydrophobic materials, such as perfluorinated polymers, for the production of hydrophobic surfaces are known. There is a further development of these surfaces in structuring the surfaces in the µm range to the nm range. U.S. Patent 5,599,489 discloses a method in which a surface is bombarded with particles appropriate size and subsequent perfluorination especially repellent can be. Another method describes H. Saito et al. in "Service Coatings International ", 4, 1997, 5.168 ff. Here are particles made of fluoropolymers Metal surfaces applied, with a greatly reduced wettability of the so produced Surfaces compared to water with a significantly reduced tendency to freeze has been.

JP 11171592 describes a water-repellent product and its production, wherein the dirt-repellent surface is produced by a film on the treating surface is applied, the fine particles of metal oxide and that Has hydrolyzate of a metal alkoxide or a metal chelate. To solidify this Films must have the substrate to which the film was applied at temperatures above of 400 ° C are sintered. This method can therefore only be used for substrates which can withstand temperatures above 400 ° C.

By means of all these processes, self-cleaning surfaces are accessible, which more or are less sensitive to mechanical stress. Too high mechanical stress leads to damage to the self-cleaning surfaces. A Repair of these surfaces is not planned so far, so if damaged of the self-cleaning surfaces they had to be completely re-treated or even had to be replaced.

The object of the present invention was to provide a way to repair damaged to provide self-cleaning surfaces.

Surprisingly, it was found that it is possible to easily repair resins manufacture a repair of the surfaces while restoring the enable self-cleaning properties by the repair resin structure-forming Particles are added.

The present invention therefore relates to repair resins for the repair of Surfaces with self-cleaning properties, the surface structures with elevations have, which are characterized in that the repair resins at least one have a polymer-curable compound and structure-forming particles suspended.

The present invention also relates to a method for producing Repair resin according to the invention, which is characterized in that a liquid Mixture containing at least one compound curable into a polymer and structure-forming Has particles is generated.

The present invention also relates to self-cleaning articles Properties which are characterized in that they are combined with an inventive Repair resin has repaired self-cleaning surfaces.

The present invention also relates to a method for repairing damaged self-cleaning surfaces, which is characterized in that a repair resin according to the invention is applied to the damaged surface, this Repair resin then hardens and thereby a hardened repair resin surface is generated, the surveys from structure-forming particles and self-cleaning Has properties.

The repair resin according to the invention makes repairs to self-cleaning Surfaces possible that have particles with a jagged structure without the entire surface needs to be equipped with new self-cleaning. Very advantageous proves the fact that surfaces with almost any geometry are high can be repaired self-cleaning. Even inner surfaces can be repaired as long as they are accessible to the repair resin.

Particularly good touch-up resins generally have the same material as a base, like the surface to be repaired. The simple way of making the Repair resin according to the invention, it is possible to repair resins based on various To provide plastic or polymer materials, which is why for many different self-cleaning surfaces, a repair resin can be provided, which same material as the surface as a base or at least one material that has similar chemical or physical properties or resistance.

The invention is described below by way of example, without referring to these embodiments to be limited.

The repair resins according to the invention for repairing surfaces with self-cleaning properties that have surface structures with elevations, are characterized in that the repair resins are at least one curable to a polymer Have compound and structure-forming particles suspended. When using the Repair resin, the particles are integrated directly into the repair resin surface.

Due to the elevations at least partially present due to the structure-forming particles on the repaired surface ensures that these surface areas are difficult are wettable or self-cleaning.

As a compound curable to a polymer, the repair resin can contain at least one monomer and / or an oligomer of polymers selected from the polycarbonates, Poly (meth) acrylates, polyamides, PVC, polyethylenes, polypropylenes, aliphatic linear, cyclic or branched polyalkenes, polystyrenes, polyesters, unsaturated Polyester resins, polyether sulfones, polyacrylonitrile or polyalkylene terephthalates and their mixtures or copolymers.

It is also possible that the repair resin as a polymer-curable compound at least one polymer dissolved in a solvent selected from polycarbonates, Poly (meth) acrylates, polyamides, PVC, polyethylenes, polypropylenes, aliphatic linear, cyclic or branched polyalkenes, polystyrenes, polyesters, unsaturated Polyester resins, polyether sulfones, polyacrylonitrile or polyalkylene terephthalates and their mixtures or copolymers.

It is also possible for the repair resin to be both undissolved polymers or in one Has solvent-dissolved polymers and oligomers and or monomers. The polymer Oligomer and / or monomer can be based on or based on the same polymeric compound different.

The repair resin can be chemically or thermally curable. Instructs the repair resin as only a dissolved polymer as a compound curable to a polymer, so the Hardening of the resin by evaporation of the solvent. This kind of hardening can be done by Supply of thermal energy can be accelerated, the temperature chosen so must be that the solvent evaporates better, but the polymer does not melts. Has the repair resin as a polymer curable compound monomers and / or oligomers of a polymer, the curing is usually carried out by Polymer formation reaction, i.e. polymerization, polyaddition or polycondensation. The Curing by polymer formation reaction can be chemical, thermal or by means of light energy be initiated. Chemical initiation can be carried out using conventional initiators. The Repair resin can already contain the hardener and / or the initiator if the actual one Polymerization reaction is initiated only by light or heat. Cures through Polyreaction directly when the hardener and / or initiator comes into contact with a polymer hardenable connection, the hardener / initiator must be used until the repair resin is used these are kept separately. For example, the polymerization of Styrene, so this is the monomer added to the repair resin, at elevated temperatures start with cyclohexanone peroxide. In the presence of cobalt salts, the Start temperature lowered to the room temperature range. A cobalt salt (co-octoate) can be added to the styrene, but not the peroxide. Detailed tables about Composition, mixing ratios, properties and reaction conditions are in standard polymer chemistry works, e.g. B. Hans Batzer, Polymers, Georg Thieme Verlag Stuttgart, New York, 1984. In this context it can be advantageous if the repair resin if it consists of two or more components that are mixed when the resin is used for curing must have, the structure-forming particles suspended in all components.

The repair resin is preferably liquid, the viscosity of the liquid Repair resin can be very different depending on the application and that Repair resin can be adjusted from thin to pasty. Preferably that Repair resin for the purpose of adjusting the viscosity in addition to the polymer and / or Oligomers and monomers have a solvent for these polymers and / or oligomers, which ensures that the repair resin is used in a desired processable state remains.

In particular, the repair resin has a solvent when it is in one Has solvent-dissolved polymer. The solvent can be used for the corresponding one Suitable polymer, monomer and / or oligomer as solvent. It can be advantageous if the corresponding monomer is used as a solvent for a polymer becomes. The repair resin preferably has solvents selected from the group of alcohols, glycols, ethers, glycol ethers, ketones, esters, amides, nitro Compounds, halogenated hydrocarbons, aliphatic and aromatic Hydrocarbons or mixtures thereof. This is particularly preferred Repair resin as solvent at least one compound selected from methanol, ethanol, Propanol, butanol, octanol, cyclohexanol, phenol, cresol, ethylene glycol, diethylene glycol, Diethyl ether, dibutyl ether, anisole, dioxane, dioxolane, tetrahydrofuran, Monoethylene glycol ether, diethylene glycol ether, triethylene glycol ether, Polyethylene glycol ether, acetone, butanone, cyclohexanone, ethyl acetate, butyl acetate, iso- Amylacetate, ethylhexyl acetate, glycol ester, dimethylformamide, pyridine, N-methylpyrrolidone, N-methylcaprolactone, acetonitrile, carbon disulfide, dimethyl sulfoxide, sulfolane, Nitrobenzene, dichloromethane, chloroform, carbon tetrachloride, trichlorethylene, carbon tetrachloride, 1,2-dichloroethane, chlorophenol, chlorofluorocarbons, petrol, petroleum ether, Cyclohexane, methylcyclohexane, decalin, tetralin, terpenes, benzene, toluene or xylene or Mixtures on.

The content of solvent in the repair resin according to the invention can be largely can be varied. If the repair resin is a resin that is one in one has solvent-dissolved polymer, the weight ratio of polymer to Solvents preferably from 1 to 0.001 to 1 to 0.2, preferably from 1 to 0.005 to 1 to 0.05.

The structure-forming particles present in the repair resin, which the elevations on the form self-cleaning surface of the repaired surfaces are preferred selected from silicates, minerals, metal oxides, metal powders, silicas, pigments or polymers, very particularly preferably from pyrogenic silicas, precipitated silicas, Aluminum oxide, silicon oxide, doped silicates, pyrogenic mixed oxides or powdered polymers.

The particles preferably have a particle diameter of 0.02 to 100 μm, particularly preferably from 0.1 to 50 μm and very particularly preferably from 0.1 to 30 μm. It can particles with diameters of less than 500 nm can also be used. But are suitable also particles that form primary particles into agglomerates or aggregates of one size store from 0.2 to 100 µm together. Such agglomerates or aggregates have one Substructuring, the substructure usually having an aspect ratio> 1, preferred even greater than 1.5.

As particles which are to form the elevations of the repaired structured surface, the repair resin preferably has those which have an irregular fine structure in the nanometer range on the surface. The particles with the irregular fine structure preferably have elevations with an aspect ratio of greater than 1, particularly preferably greater than 1.5. The aspect ratio is in turn defined as the quotient from the maximum height to the maximum width of the survey. In Fig. 1, the difference between the elevations formed by the particles and the elevations formed by the fine structure is illustrated schematically. The figure shows on the plastic surface K a plastic coating M which has particles P (only one particle is shown to simplify the illustration). The elevation formed by the particle itself has an aspect ratio of approx. 0.71, calculated as the quotient from the maximum height of the particle mil, which is 5, since only the part of the particle that contributes to the elevation protrudes from the plastic coating M, and the maximum width mB, which is 7 in relation to it. A selected elevation of the elevations E, which are present on the particles due to the fine structure of the particles, has an aspect ratio of 2.5, calculated as a quotient from the maximum height of the elevation mH ′, which is 2.5 and the maximum width mB ', which is 1 in proportion.

The repair resin preferably has as particles, in particular as particles, the one have irregular fine structure in the nanometer range on the surface, at least a compound selected from pyrogenic silica, precipitated silica, Aluminum oxide, silicon dioxide, pyrogenic mixed oxides and / or doped silicates or powder Polymers.

It can also be advantageous if the particles have hydrophobic properties. The wettability of the surface, especially in., Is affected by the hydrophobicity of the particles Reduced in terms of water, making the self-cleaning properties clear be improved. The hydrophobic properties can be attributed to the material properties of the materials present on the surfaces of the particles themselves or on one Treat the particles with a suitable compound. The particles can before the production of the repair resin or after the curing of the repair resin hydrophobic properties.

For hydrophobizing the particles or the surface of the hardened repair resin can the particles or the surface z. B. with a compound from the group of Alkylsilanes, fluoroalkylsilanes or disilazanes are treated.

The very particularly preferred particles are explained in more detail below. The Particles used can come from different areas. For example it can be silicates, doped silicates, minerals, metal oxides, aluminum oxide, Silicas or pyrogenic silicates, aerosils or powdered polymers, such as. B. spray-dried and agglomerated emulsions or cryomilled PTFE. As Particle systems are particularly suitable for hydrophobicized pyrogenic silicas, so-called Aerosile®. To generate the self-cleaning surfaces is next to the Hydrophobicity is also necessary for the structure. The particles used can themselves be hydrophobic such as PTFE. The particles can be made hydrophobic, such as for example the Aerosil VPR 411® or Aerosil R 8200®. But you can too are subsequently hydrophobized. It is immaterial whether the particles are in front of the Apply or become hydrophobic after application. This, for example for Aeroperl 90 / 30®, Sipernat Kieselsäure 350®, aluminum oxide C®, zirconium silicate, vanadium-doped or Aeroperl P 25 / 20®. For the latter, the hydrophobization is expediently carried out by treatment with perfluoroalkylsilane and subsequent tempering.

The repair resin preferably has a proportion of particles of 1 to 75% by weight, preferably from 5 to 50% by weight and very particularly preferably from 10 to 40% by weight. If the proportion of the particles is greater than 75% by weight, the repair resin is no longer liquid or pasty enough or cracks appear when processing the repair resin. With shares of less than 1% by weight it may happen that the repair resins are no longer sufficient Have particles to generate surfaces with intervals of the bumps are necessary to create self-cleaning properties.

The repair resin of the invention can be made so that the duration of the Processability can be varied within certain limits. The workability is in particular on the original viscosity and thus on the proportion of solvent from which Viscosity of the monomers and / or oligomers and the amount of dissolved polymer dependent and can be adjusted accordingly by changing the concentrations. ever after whether a solvent is used in the repair resin, which has a high or low vapor pressure at processing temperature is the duration of the Processability correspondingly shorter or longer. After applying to the depending on the repair surface, the time taken for the repair resin to harden Composition of the repair resin preferably up to a maximum of 12 hours. The curing time is preferably from 10 seconds to 6 hours and completely particularly preferably from 2 minutes to 4 hours.

The repair resin of the invention can be used to repair damaged self-cleaning Surfaces are used. There are objects with self-cleaning Properties or surfaces obtained with a repair resin according to the invention have repaired self-cleaning surfaces. The damage can only be one Damage to the structures responsible for the self-cleaning properties. In this case, the repair resin is preferably a very low viscosity polymer solution and / or oligomer solution with structure-forming particles, which is a very thin Coating the damaged surface without significantly changing the dimension allows. The repair resin can also be used as a filler, if major damage to the self-cleaning surfaces, which also extends into the Carrier material can reach in, exist and a change (restoration) the dimension of the body having the self-cleaning surfaces necessary or is desirable.

The method according to the invention for repairing damaged self-cleaning surfaces, is characterized in that a repair resin according to the invention on the damaged Surface is applied, this repair resin then hardens and thereby a cured repair resin surface is generated, the bumps from structure-forming Has particles and self-cleaning properties. The application of the repair resin can be done by spraying, brushing, knife coating or spreading. It can be beneficial be if after applying the repair resin and before curing the Repair resin on the uncured repair resin structure-forming particles are applied, and the repair resin is then cured. The additional Application of structure-forming particles can, for. B. by spraying, e.g. B. with a Spray gun done.

The repair resin according to the invention can be used to repair a wide variety of self-cleaning agents Surfaces are used. Such self-cleaning surfaces can e.g. B. on embossed metals, plastics or ceramics based on or with structuring particles based on coated metals, plastics or ceramics. The repair resins according to the invention are preferably used to repair self-cleaning surfaces based on polymers.

Such self-cleaning surfaces can e.g. B. polymers selected from polycarbonates, Poly (meth) acrylates, polyamides, PVC, polystyrenes, polyesters, polyether sulfones, aliphatic linear, cyclic or branched polyalkenes, polyacrylonitrile or Polyalkylene terephthalates, poly (trifluoroethylene), poly (vinylidene fluoride), Poly (chlorotrifluoroethylene), poly (hexafluoropropylene), poly (3,3,4,4,5,5,5-heptafluoro-1- penten) poly (fluoroalkyl methacrylate), poly (vinyl perfluoroalkyl ether) or other polymers Poly (ethylene), poly (propylene), poly (isobutene), and poly (4-methyl-1-pentene), polynorbones as Have homo- or copolymer. The self-cleaning ones are very particularly preferred surfaces to be repaired as material for the surface poly (ethylene), poly (propylene) or poly (vinylidene fluoride).

The best results are achieved when using self-cleaning polymer-based surfaces be repaired a repair resin according to the invention, which on the same polymer is based like the self-cleaning surface.

The repair resin according to the invention is therefore preferred for the repair of self-cleaning plastic surfaces based on polymers based on polycarbonates, Poly (meth) acrylates, polyamides, PVC, polyethylenes, polypropylenes, polystyrenes, Polyesters, unsaturated polyester resins, polyether sulfones, aliphatic linear, cyclic or branched polyalkenes, polyacrylonitrile or polyalkylene terephthalates, as well as their mixtures or copolymers.

The surfaces repaired with the repair resin using the method according to the invention with self-cleaning properties preferably have surveys with a medium Height of 50 nm to 25 microns and an average distance of 50 nm to 25 microns, preferably with an average height of 50 nm to 25 µm and / or an average distance of 50 nm up to 25 µm and very particularly preferably with an average height of 50 nm to 4 µm and / or an average distance of 50 nm to 4 µm. Point very particularly preferably Surfaces that have been treated with the repair resin according to the invention with an average height of 0.25 to 1 µm and an average distance of 0.25 to 1 µm. In the sense of the present invention, the Understand the distance from the highest survey of one survey to the next highest survey. If an elevation is in the form of a cone, the tip of the cone represents the highest elevation of the elevation. If the elevation is a cuboid, the top one Area of the cuboid represents the highest elevation of the elevation.

The particles that are firmly attached to the surface of the repair resin are preferably with at least 5 to 90%, preferably with 10 to 90%, particularly preferably with 30 to 80% and very particularly preferably with 30 to 50% of their surface with the Surface of the repair resin connected. In this way it is achieved that the firm connected particles are very durable with the surface of the resin.

The wetting of solids can be determined by the contact angle that a drop of water has of the surface. A contact angle of 0 degrees means one complete wetting of the surface. The wetting angle on fibers is measured in the Usually according to the Wilhelmy method. The thread is wetted by a liquid and the force with which the fiber is pulled into the liquid due to the surface tension is being measured. The higher the contact angle, the worse the surface can be wetted become. Poor wetting leads to structuring at the same time good self-cleaning properties, since such surfaces are easily affected by moving water are to be cleaned. The aspect ratio is defined as the quotient of the height to the width of the Structure of the surface.

The surfaces obtained with the repair resin according to the invention with self-cleaning and water-repellent properties have a high aspect ratio of the surveys. The elevations of the surfaces according to the invention which are formed by the particles preferably have an aspect ratio of greater than 0.3, preferably from 0.3 to 0.9 and particularly preferably from 0.5 to 0.8. The aspect ratio is defined as the ratio of the medium height to the medium width of the surveys. In the case of a spherical particle that looks out of the surface formed by the repair resin with 70% of its diameter, an aspect ratio of 0.7 results from the quotient of the average height (70%) and average width (100%). If a repair resin is used which has particles that have an irregular fine structure in the nanometer range on the surface, the aspect ratios of the surface can be increased to greater than 1, preferably greater than 1.5, if the elevations on the particles with the irregular fine structure have an aspect ratio of greater than 1, particularly preferably greater than 1.5. The aspect ratio is in turn defined as the quotient from the maximum height to the maximum width of the elevation (cf. FIG. 1).

The repair resin can be on the inner and / or outer surfaces of molded articles or Objects are used. To repair poorly accessible inner surfaces it may be advantageous to provide low viscosity repair resins which can run into cavities. Moldings which can have polymers as well Solid polymer or as a polymer hollow body. The moldings can likewise be those made of plastic or metal or wood Shaped bodies of all types are formed.

The repair resin according to the invention is preferably according to the invention Process for producing repair resin, which is characterized by that a liquid mixture containing at least one polymer curable compound as well as structure-forming particles which are preferably insoluble in the mixture becomes. The particles are preferably dispersed or suspended in the repair resin. The liquid mixture is preferably a dispersion or suspension. The liquid mixture can have very different viscosities. Under a liquid mixture in the Present invention both a low viscosity mixture and a pasty mixture Roger that.

It may be advantageous to produce a mixture that is curable as a polymer Compound at least one monomer and / or an oligomer of a polymer selected from the polycarbonates, poly (meth) acrylates, polyamides, PVC, polyethylenes, polypropylenes, aliphatic linear or branched polyalkenes, cyclic polyalkenes, polystyrenes, Polyesters, unsaturated polyester resins, polyether sulfones, polyacrylonitrile or Polyalkylene terephthalates, as well as their mixtures or copolymers.

It can be just as advantageous if a mixture is generated which is considered to be a polymer curable compound at least one polymer dissolved in a solvent selected from the Polycarbonates, poly (meth) acrylates, polyamides, PVC, polyethylenes, polypropylenes, aliphatic linear or branched polyalkenes, cyclic polyalkenes, polystyrenes, Polyesters, unsaturated polyester resins, polyether sulfones, polyacrylonitrile or Has polyalkylene terephthalates and their mixtures or copolymers.

It is also possible to create a mixture that is both a monomer and a Has oligomer and / or a polymer. These connections can be made on a and based on the same polymer or based on different polymers.

In particular, it can be advantageous that in a suspension obtained by suspending structure-forming particles generated in a solution of a polymer in a solvent will, monomers and / or oligomers are dissolved.

By adding oligomers and / or polymers to the mixture or suspension z. B. the viscosity and the compatibility of the mixture / suspension with the repairing surface to be set. Depending on the type of surface to be repaired it may be necessary for the mixture to have reactive monomers that have a chemical Form a bond with the surface to be repaired. The monomers and / or Oligomers can also serve as solvents for the polymer or the swell or dissolve the repairing surface, resulting in better adhesion of the Repair resin can come to the surface to be repaired.

A solvent can be added to the mixtures. For the preparation of the mixtures it may be advantageous to dissolve the polymer, oligomers and / or monomers Solve this in a solvent to generate the structure-forming particles be suspended or dispersed.

At least one solvent can be used as the solvent for the corresponding polymer, monomer and / or oligomer suitable compound from the group of alcohols, the glycols, the Ethers, the glycol ethers, the ketones, the esters, the amides, the nitro compounds, the Halogenated hydrocarbons, the aliphatic and aromatic hydrocarbons or Mixtures of these are used. At least one is preferably used as the solvent Solvent suitable compound for the corresponding polymers selected from methanol, Ethanol, propanol, butanol, octanol, cyclohexanol, phenol, cresol, ethylene glycol, Diethylene glycol, diethyl ether, dibutyl ether, anisole, dioxane, dioxolane, tetrahydrofuran, Monoethylene glycol ether, diethylene glycol ether, triethylene glycol ether, Polyethylene glycol ether, acetone, butanone, cyclohexanone, ethyl acetate, butyl acetate, iso- Amylacetate, ethylhexyl acetate, glycol ester, dimethylformamide, pyridine, N-methylpyrrolidone, N-methylcaprolactone, acetonitrile, carbon disulfide, dimethyl sulfoxide, sulfolane, Nitrobenzene, dichloromethane, chloroform, carbon tetrachloride, trichlorethylene, carbon tetrachloride, 1,2-dichloroethane, chlorophenol, chlorofluorocarbons, petrol, petroleum ether, Cyclohexane, methylcyclohexane, decalin, tetralin, terpenes, benzene, toluene or xylene or Mixtures of these are used.

It may be advantageous if the solvent has a temperature during the preparation of the solution from -30 ° C to 150 ° C, preferably 25 to 100 ° C and very particularly preferably from 25 to 49 ° C, from 50 to 85 ° C or from 86 to 100 ° C.

Depending on the monomer, oligomer or polymer present in the mixture, it may be necessary to add a hardener or initiator to the mixture. Initiators can e.g. B. be those that trigger a necessary for curing the polyreaction by z. B. by electromagnetic radiation, such as. B. activated UV radiation and trigger the polyreaction. It is not necessary to add hardeners or initiators if the mixture contains a dissolved polymer which hardens by evaporation of the solvent and thus fixes the particles on the surface to be repaired. It is also not necessary to add hardeners or initiators if the repair resin hardens due to the presence of substances in the ambient air. Such substances can e.g. B. atmospheric oxygen or water from the air humidity. An example of such repair resins is e.g. B. a cyanoacrylic acid ester, as is known from the superglue, which has particles suspended and which hardens by atmospheric oxygen. Table 1 below gives an example of possible repair resin compositions, without the invention being restricted to these. Table 1 Possible repair resin mixtures

The percentages by weight for initiator and accelerator relate to the total of the polymer / monomer or solvent mixture. The proportion of particles in the repair resin can be varied in the ranges mentioned and is preferably from 1 to 50% by weight based on the repair resin.

The particles are preferred for producing the repair resin according to the invention used such that at least one material selected from silicates, minerals, Have metal oxides, metal powders, silicas, pigments 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 0.1 to 30 μm exhibit. Particles with diameters of less than 500 nm can also be used become. However, particles which form primary particles to form agglomerates or are also suitable Store aggregates with a size of 0.2-100 µm.

Preference is given to particles, in particular particles, which have an irregular fine structure have in the nanometer range on the surface, such particles used that at least a compound selected from pyrogenic silica, precipitated silica, Aluminum oxide, silicon dioxide, pyrogenic mixed oxides and / or doped silicates or have powdered polymers.

The particles preferably have hydrophobic properties, the hydrophobic properties Properties on the material properties of those present on the surfaces of the particles Materials themselves can go back or by treating the particles with a suitable connection can be obtained. The particles can be before or after Connect to the surface with hydrophobic properties.

To make the particles hydrophobic before they are introduced into the repair resin or after The repair resin can be cured with a compound from the group of Alkylsilanes, fluoroalkylsilanes or disilazanes are treated.

The particles preferably used are explained in more detail below. The particles used can come from different areas. For example it can be silicates, doped silicates, minerals, metal oxides, aluminum oxide, Silicas or pyrogenic silicates, aerosils or powdered polymers, such as. B. spray-dried and agglomerated emulsions or cryomilled PTFE. As Particle systems are particularly suitable for hydrophobicized pyrogenic silicas, so-called aerosils. To generate the self-cleaning surfaces is next to the Hydrophobicity is also necessary for the structure. The particles used can themselves be hydrophobic such as PTFE. The particles can be made hydrophobic, such as for example the Aerosil VPR 411 or Aerosil R 8200. But you can also retrofit be made hydrophobic. It is immaterial whether the particles are applied before or be hydrophobicized after application. This, for example for Aeroperl 90/30, Sipernat Silicic acid 350, aluminum oxide C, zirconium silicate, vanadium-doped or Aeroperl P 25/20. For the latter, the water repellency is expediently carried out by treatment with Perfluoroalkylsilane and subsequent annealing.

The repair resin produced according to the invention preferably has a low viscosity that allows the resin to be repaired even in hard to reach places Objects, e.g. B. for repairing self-cleaning surfaces inside narrow-necked vessels, can be used.

The process according to the invention is described using the following example, without the invention being restricted to this exemplary embodiment.

example

10 g of polyester resin Vestopal 400®, an approx. 65% by weight solution of medium reactive unsaturated polyester resin based on dicidol in styrene was 1: 1 (weight ratio) mixed with monomeric styrene. Then, based on the polyester, 2% by weight Cyclonox 11® (cyclohexanone peroxide) and 1% by weight cobalt octoate added. Likewise based on the polyester was 5 wt .-% in a fluidized bed jet mill from Gritt freed Aerosil R 8200® mixed in intensively. The mixture was applied as a coating a PMMA plate was doctored and hardened at room temperature. Then the self-cleaning properties of this surface assessed. Drops of water roll from this The surface completely disappears even at a slight angle of inclination. An exact determination, at the angle at which water rolls off did not occur.

The surface previously produced was partially mechanically scratched and scraped off. The the same solution as described above was dripped on and the damaged areas were filled in. After hardening, the surface was again homogeneous in appearance and homogeneous in Rolling behavior against water.

Claims (26)

1. Repair resin for repairing surfaces with self-cleaning properties, which have surface structures with elevations, characterized in that the repair resin has at least one compound curable to form a polymer and structure-forming particles suspended. 2. repair resin according to claim 1, characterized, that it is at least one monomer and / or a compound curable to a polymer Oligomer of polymers selected from the polycarbonates, poly (meth) acrylates, Polyamides, PVC, polyethylenes, polypropylenes, aliphatic linear, cyclic or branched polyalkenes, polystyrenes, polyesters, unsaturated polyester resins, Polyether sulfones, polyacrylonitrile or polyalkylene terephthalates, and mixtures thereof or copolymers. 3. repair resin according to claim 1 or 2, characterized, that it is at least one in a solvent as a compound curable to a polymer dissolved polymer selected from polycarbonates, poly (meth) acrylates, polyamides, PVC, polyethylenes, polypropylenes, aliphatic linear, cyclic or branched polyalkenes, polystyrenes, polyesters, unsaturated polyester resins, Polyether sulfones, polyacrylonitrile or polyalkylene terephthalates, and mixtures thereof or copolymers. 4. Repair resin according to one of claims 1 to 3, characterized, that it is chemically or thermally curable. 5. Repair resin according to one of claims 1 to 4, characterized, that the structure-forming particles have an irregular fine structure in the nanometer range have on the surface. 6. repair resin according to at least one of claims 1 to 5, characterized, that there are particles selected from silicates, minerals, metal oxides, metal powders, Silicas, pigments or polymers. 7. repair resin according to at least one of claims 1 to 6, characterized, that there are particles selected from pyrogenic silicas, precipitated silicas, Aluminum oxide, silicon oxide, doped silicates, pyrogenic mixed oxides or has powdery polymers. 8. repair resin according to at least one of claims 1 to 7, characterized, that the particles have hydrophobic properties. 9. repair resin according to at least one of claims 1 to 8, characterized, that the repair resin is a solvent selected from methanol, ethanol, propanol, Butanol, octanol, cyclohexanol, phenol, cresol, ethylene glycol, diethylene glycol, Diethyl ether, dibutyl ether, anisole, dioxane, dioxolane, tetrahydrofuran, Monoethylene glycol ether, diethylene glycol ether, triethylene glycol ether, polyethylene glycol ether, acetone, Butanone, cyclohexanone, ethyl acetate, butyl acetate, iso-amyl acetate, ethyl hexyl acetate, Glycol esters, dimethylformamide, pyridine, N-methylpyrrolidone, N-methylcaprolactone, Acetonitrile, carbon disulfide, dimethyl sulfoxide, sulfolane, nitrobenzene, Dichloromethane, chloroform, carbon tetrachloride, trichlorethylene, carbon tetrachloride, 1,2-dichloroethane, chlorophenol, chlorofluorocarbons, petrol, petroleum ether, cyclohexane, Methylcyclohexane, decalin, tetralin, terpenes, benzene, toluene or xylene or Mixtures thereof. 10. A method for producing repair resin according to one of claims 1 to 9, characterized, that a liquid to pasty mixture that has at least one curable to a polymer Connection and structure-forming particles is produced. 11. The method according to claim 10, characterized, that a mixture is created which is a polymer curable compound at least one monomer and / or an oligomer of a polymer selected from the Polycarbonates, poly (meth) acrylates, polyamides, PVC, polyethylenes, polypropylenes, aliphatic linear or branched polyalkenes, cyclic polyalkenes, Polystyrenes, polyesters, unsaturated polyester resins, polyether sulfones, Polyacrylonitrile or polyalkylene terephthalates, and their mixtures or copolymers. 12. The method according to claim 10 or 11, characterized, that a mixture is created which is a polymer curable compound at least one polymer dissolved in a solvent selected from the polycarbonates, Poly (meth) acrylates, polyamides, PVC, polyethylenes, polypropylenes, aliphatic linear or branched polyalkenes, cyclic polyalkenes, polystyrenes, Polyesters, unsaturated polyester resins, polyether sulfones, polyacrylonitrile or Has polyalkylene terephthalates and their mixtures or copolymers. 13. The method according to at least one of claims 10 to 12, characterized, that in a suspension made by mixing a solution of a polymer in one Solvent and structure-forming particles are generated, monomers and / or oligomers be solved. 14. The method according to claim 12 or 13, characterized, that as a solvent at least one as a solvent for the corresponding monomer, Polymer and / or oligomer suitable compound from the group of alcohols, the Glycols, the ethers, the glycol ethers, the ketones, the esters, the amides, the nitro Compounds, halogenated hydrocarbons, aliphatic and aromatic Hydrocarbons or mixtures thereof is used. 15. A method for producing repair resin according to one of claims 10 to 14, characterized, that a hardener or initiator is added to the mixture. 16. The method according to at least one of claims 10 to 15, characterized, that particles with an average particle diameter of 0.02 to 100 µm be used. 17. The method according to claim 16, characterized, that particles with an average particle diameter of 0.1 to 30 µm be used. 18. The method according to at least one of claims 10 to 17, characterized, that particles selected from silicates, minerals, metal oxides, metal powders, Silicas, pigments or polymers. 19. The method according to at least one of claims 10 to 18, characterized, that the particles have hydrophobic properties. 20. The method according to claim 19, characterized, that the particles are hydrophobic by treatment with a suitable compound Have properties. 21. item with self-cleaning properties, characterized, that he repaired with a repair resin according to one of claims 1 to 9 has self-cleaning surfaces. 22. Process for repairing damaged self-cleaning surfaces, characterized, that a repair resin according to one of claims 1 to 9 on the damaged Surface is applied, this repair resin then hardens and thereby a cured repair resin surface is generated, the bumps structure-forming particles and self-cleaning properties. 23. The method according to claim 22, characterized, that after applying the repair resin and before curing the Repair resin on the uncured repair resin structure-forming particles are applied, and the repair resin is then cured. 24. The method according to claim 22 or 23, characterized, that the surveys have an average height of 50 nm to 25 µm and an average Have a distance of 50 nm to 25 µm. 25. The method according to claim 24, characterized, that the surveys have an average height of 50 nm to 4 µm and / or an average Have a distance of 50 nm to 4 µm. 26. The method according to any one of claims 22 to 25, characterized, that the structure-forming particles have hydrophobic properties.