DE10249453A1 - Production of structured hydrophobic surfaces, e.g. antireflective glass or plastic surfaces, comprises depositing a polyhedral oligomeric silicon-oxygen cluster compound on a surface - Google Patents

Abstract

Production of structured hydrophobic surfaces with elevations and depressions comprises depositing a polyhedral oligomeric silicon-oxygen cluster compound on a surface to form the elevations. Independent claims are also included for: (1) a structured hydrophobic surface with elevations and depressions, where the elevations are formed from polyhedral oligomeric silicon-oxygen clusters; (2) antireflective glass and plastic surfaces having a surface as above; (3) a wash-resistant coating with hydrophobic and self-cleaning properties produced by the process of (1).

Description

The present invention relates to a structured surface with elevations and Wells as well as a method for producing such surfaces and their use of these surfaces.

Structured surfaces with elevations and depressions are common today used. The structure of the surface results in a certain roughness, which for various applications is beneficial.

An area of application for structured surfaces is e.g. B. anti-reflective glass surfaces or plastic. These are of considerable importance because they reflect light that occurs when Disrupt or prevent seeing or perceiving images. Usually such anti-reflective surfaces by evaporating z. B. oxidic compounds on a Surface created. Anti-reflective surfaces are used e.g. B. in displays, optical Devices, e.g. B. microscopes or cameras, painted surfaces, as well as in buildings, Greenhouses, viewing panels and any type of surface used in the Solar energy use can be used (solar cells, photovoltaics, etc.).

The scratch and abrasion resistance is also ensured by structuring surfaces, especially with plastic surfaces in general, especially with lacquer and Ink films, positively influenced. The due to mechanical action Plastics (eg on scratches made of "Plexiglas®" made of polymethacrylate) lead not only to a visual impairment, but also to a reduction the translucency. This becomes particularly clear with plastic glasses (windows of all Type, glasses etc.).

Last but not least, self-cleaning properties are also important because not only that the environment is protected, but because the entire cleaning effort is reduced and Surfactants can be saved. For example, the one that occurs in nature shows Lotus plant the so-called lotus effect, which leads to solid dirt particles such. B. be completely washed off by rainwater. This effect is also based on one structured surface.

For some time now, efforts have been made to use these self-cleaning properties to artificially recreate. This is how EP 0 772 514 describes this effect. According to the state of the Technology is particularly beneficial if nano or micro structures are on the surface are generated and the surface simultaneously has hydrophobic properties (EP 0 933 388 A2). The structured surfaces are created by application particulate systems or by imprinting structures on the surfaces.

A lack of water repellency on surfaces of any kind leads to the fact that Weathering and subsequent drying residues remain and thus water can damage the subsurface. The structured self-cleaning surfaces therefore often have hydrophobic properties. This Hydrophobic properties are mostly generated by the fact that the particulate systems or the structured surfaces with at least one compound from the group of Alkylsilanes, fluoroalkylsilanes or disilazanes are treated. Dealing with These compounds pose some dangers as these substances are volatile, flammable and are lovely. As a rule, such surfaces do not provide abrasion and scratch resistance are also applied subsequently, which means an additional step.

The object of the present invention was therefore to provide structured, hydrophobic surfaces to provide, in the production of no compound from the group of alkylsilanes, the Fluoroalkylsilane or the Disilazane must be used. In addition, the manufacture of the surfaces can be easily and inexpensively.

Surprisingly, the task was solved by the fact that for the production of structured surfaces polyhedral oligomeric silicon-oxygen cluster compounds are used, the polyhedral oligomeric silicon-oxygen cluster units Bring hydrophobic properties to the surface and at the same time as particles for one provide appropriate structuring from surveys and in-depths.

The present invention therefore relates to structured, hydrophobic surfaces with elevations and depressions, which are characterized in that the surface has at least polyhedral oligomeric silicon-oxygen cluster units, which at least partially form the surveys.

The present invention also relates to a method for producing Surfaces according to the invention, which is characterized in that on the surface a polyhedral oligomeric silicon-oxygen cluster compound applied and fixed becomes.

The present invention also relates to the use of the The inventive method for producing films or films with antiblocking properties, for Manufacture of anti-reflective glass or plastic surfaces or for the production of self-cleaning glass or plastic surfaces.

The present invention also relates to anti-reflective glass or Plastic surfaces, which are characterized in that they have a surface according to the invention exhibit. This invention furthermore relates to a washable coating with hydrophobic and self-cleaning properties obtainable according to the invention Method.

The surfaces according to the invention have the advantage that no light and heat rays are reflected and so light and heat are fully utilized. The procedure for the production of these surfaces has the advantage that it is particularly simple because the polyhedral oligomeric silicon-oxygen cluster compounds due to the Incompatibility with the carrier material migrate to the surface and there, as it were Spacers can act (anti-blocking properties). The anti-reflective properties are achieved by forming an uneven nanostructure on the surface that prevents reflection.

A particular advantage of the surfaces according to the invention, the polyhedral oligomers Have silicon-oxygen cluster units is that the polyhedral oligomeric silicon-oxygen cluster compounds due to their molecular character a uniform and defined molecular weight and therefore a defined size exhibit. This makes it possible in a simple manner to use structured surfaces Surveys - and thus corresponding in-depth studies - to a certain height to generate. In particular, nano and micro structures can be created using polyhedral oligomeric silicon-oxygen cluster compounds are generated.

Due to the predominantly spherical shape of the polyhedral oligomeric silicon Oxygen cluster units the height of the distance between the surveys is predetermined, when the polyhedral oligomeric silicon-oxygen cluster units are in a densest two-dimensional packing are arranged. The structured surfaces can have self-cleaning properties, which means that the surface has a high Can have contact angle with water, which is why moving water from such Rolls surfaces and soak up and rinse off dirt particles from the surface can (lotus effect).

The polyhedral oligomeric silicon-oxygen cluster units are also thermal highly stable (up to several hundred degrees Celsius) and have a "cage-like" structure, which makes them very stable. Due to the cage structure of the polyhedral oligomeric silicon-oxygen cluster units are also few functional groups necessary for the connection of the molecules, because with one group an entire "cage" can be connected. Furthermore, the physical and chemical Properties of the polyhedral oligomeric silicon-oxygen cluster units simple to adjust. So z. B. their polarity can be set specifically via the radicals R and X. Around to enlarge the molecule, dendrimer structures or hyperbranched Structures are used.

Under a polyhedral oligomeric silicon-oxygen cluster compound preferably understood the two classes of compounds of silasesquioxanes and spherosilicates.

Silasesquioxanes are oligomeric or polymeric substances whose fully condensed representatives have the general formula (SiO _3/2 R) _n , where n ≥ 4 and the radical R can be a hydrogen atom, but usually represents an organic radical. The smallest structure of a silasesquioxane is the tetrahedron. Voronkov and Lavrent'yev (Top. Curr. Chem. 102 (1982), 199-236) describe the synthesis of fully condensed and incompletely condensed oligomeric silasesquioxanes by hydrolytic condensation of trifunctional RSiY ₃ precursors, where R is a hydrocarbon residue and Y is one hydrolyzable group, e.g. B. chloride, alkoxide or siloxide. Lichtenhan et al. describe the base-catalyzed preparation of oligomeric silasesquioxanes (WO 01/10871). Silasesquioxanes of the formula R ₈ Si ₈ O ₁₂ (with the same or different hydrocarbon radicals R) can be base-catalyzed to functionalized, incompletely condensed silasesquioxanes, such as, for. B. R ₇ Si ₇ O ₉ (OH) ₃ or also R ₈ Si ₈ O ₁₁ (OH) ₂ and R ₈ Si ₈ O ₁₀ (OH) ₄ (Chem. Commun. (1999), 2309-10; Polym. Mater. Sci. Eng. 82 (2000), 301-2; WO 01/10871) and thus serve as the parent compound for a large number of different incompletely condensed and functionalized silasesquioxanes. In particular, the silasesquioxanes (trisilanols) of the formula R ₇ Si ₇ O ₉ (OH) ₃ can be converted into appropriately modified oligomeric silasesquioxanes by reaction with functionalized, monomeric silanes (corner capping).

Oligomeric spherosilicates have a similar structure to the oligomeric silasesquioxanes. They also have a "cage-like" structure. In contrast to the silasesquioxanes, due to their production method, the silicon atoms at the corners of a spherosilicate are connected to another oxygen atom, which in turn is further substituted. Oligomeric spherosilicates can be prepared by silylating suitable silicate precursors (D. Hoebbel, W. Wieker, Z. Anorg. Allg. Chem. 384 (1971), 43-52; PA Agaskar, Colloids Surf. 63 (1992), 131- 8; PG Harrison, R. Kannengiesser, CJ Hall, J. Main Group Met. Chem. 20 (1997), 137-141; R. Weidner, Zeller, B. Deubzer, V. Frey, Ger. Offen. (1990) , DE 38 37 397). For example, a spherosilicate can be synthesized from a silicate precursor, which in turn is accessible via the reaction of Si (OEt) ₄ with choline silicate or through the reaction of waste products from the rice harvest with tetramethylammonium hydroxide (RM Laine, I. Hasegawa, C. Brick , J. Kampf, Abstracts of Papers, 222nd ACS National Meeting, Chicago, IL, United States, August 26-30, 2001, MTLS-018).

The surface according to the invention and a method for its production are described in Described by way of example below, without the invention being based on these embodiments should be limited.

The hydrophobic surfaces structured according to the invention with elevations and Wells are characterized by the fact that the surface is polyhedral oligomeric Silicon-oxygen cluster units, which at least partially the surveys form or cause. Correspondingly, the depressions arise between the surveys. These surfaces preferably have self-cleaning properties. These will achieved in that the surfaces of the invention structures from surveys and Have depressions and preferably hydrophobic properties. The structures have preferably distances between the surveys less than 200 microns, preferably less than 20 microns and distances of 5 μm to 0.05 μm are particularly preferred. The height of the surveys is determined by the Particle size determined and is preferably less than 30 microns, preferably less than 20 microns and very particularly preferably from 5 to 0.05 μm. The surveys themselves preferably show the Shape of spheres or almost spherical objects on or the shape of parts of a Ball if the particles are anchored in the surface instead of on the surface. The polyhedral oligomeric silicon-oxygen cluster units can be the polyhedral oligomeric silicon-oxygen cluster compound itself or chemically bound polyhedral oligomeric silicon-oxygen cluster compounds, i.e. H. that the polyhedral oligomeric silicon-oxygen cluster compounds chemically and / or physically with the Surface can be connected.

The polyhedral oligomeric silicon-oxygen cluster units preferably have one Molecular weight greater than 400 g / mol, preferably from 700 to 3000 g / mol, particularly preferred from 800 to 1500 g / mol. It is both possible to make several molecules into one larger one Condense molecule, e.g. B. via spacers and / or functional groups, as well Homo- and copolymerize molecules or by chemical reaction on a larger one Fix molecule or polymer (grafting). For example, polyhedral oligomers Silicon-oxygen cluster compounds connected to polymers via hydrosilylation become.

The polyhedral oligomeric silicon-oxygen cluster units can e.g. B. on a polyhedral oligomeric silicon-oxygen cluster compound of the formula

[(R _a X _b SiO _1.5 ) _m (R _c X _d SiO) _n (R _e X _f Si ₂ O _2.5 ) _o (R _g X _h Si ₂ O ₂ ) _p ]

based, with a, b, c = 0-1; d = 1-2; e, f, g = 0-3; h = 1-4; m + n + o + p ≥ 4; a + b = 1; c + d = 2; e + f = 3 and g + h = 4, R = hydrogen atom, alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl, heteroaryl group or polymer unit, which are each substituted or unsubstituted or further functionalized polyhedral oligomeric silicon-oxygen cluster units which are connected via a polymer unit or a bridge unit, X = oxy-, hydroxy-, alkoxy-, carboxy-, silyl-, alkylsilyl-, alkoxysilyl-, siloxy-, alkylsiloxy-, alkoxysiloxy-, silylalkyl- , Alkoxysilylalkyl, alkylsilylalkyl, halogen, epoxy, ester, fluoroalkyl, isocyanate, blocked isocyanate, acrylate, methacrylate, nitrile, amino, phosphine group or at least one such group of type X substituents from Type R, where the R type substituents are the same or different and the X type substituents are the same or different.

In a special embodiment of the surface according to the invention, the polyhedral oligomeric silicon-oxygen cluster units on polyhedral oligomers Silicon-oxygen cluster compounds that have functional groups.

The polyhedral oligomeric silicon-oxygen cluster units are preferably based on an oligomeric silasesquioxane compound of the formula

[(R _a X _b SiO _1.5 ) _m (R _c X _d SiO) _n ],

with a, b, c = 0-1; d = 1-2; m + n ≥ 4; a + b = 1; c + d = 2;
R = hydrogen atom, substituted or unsubstituted alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl, heteroaryl and X = oxy, hydroxyl, alkoxy, carboxy, silyl, alkylsilyl, Alkoxysilyl, siloxy, alkylsiloxy, alkoxysiloxy, silylalkyl, alkoxysilylalkyl, alkylsilylalkyl, halogen, epoxy, ester, fluoroalkyl, isocyanate, acrylate, methacrylate, nitrile, amino or phosphine group or such substituted or unsubstituted alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl or heteroaryl radicals having such groups, the radicals R being the same or different and the radicals X likewise being the same or different.

Preferred polyhedral oligomeric silicon-oxygen cluster units are based on silasesquioxanes which have a structure selected from
[(RSiO _1.5 ) _n ] _z (= homoleptic structure),
[(RSiO _{i, 5} ) _m (RXSiO _1.0 ) _n ] (= functionalized homoleptic structure),
[(RSiO _1.5 ) _m (R'SiO _1.5 ) _n ] _z (= heteroleptic structure) and
[(RSiO _1.5 ) _m (R'XSiO _1.0 ) _n ] _z (= functionalized heteroleptic structure)
with m + n = z and z ≥ 4, where z corresponds to the number of Si atoms in the skeleton structure of the oligomeric silasesquioxane, R and R 'each represent a hydrogen atom, a substituted or unsubstituted, functionalized or unfunctionalized alkyl, cycloalkyl, alkenyl -, Cycloalkenyl, alkynyl, cycloalkynyl, aryl or heteroaryl and X is an oxy, hydroxyl, alkoxy, carboxy, silyl, alkylsilyl, alkoxysilyl, alkoxysilylalkyl, siloxy, alkylsiloxy, alkoxysiloxy -, Halogen, isocyanate, nitrile, amino or phosphine group, with the proviso that the radicals R are the same or different, the radicals R 'are the same or different and the radicals X are also the same or different.

The surface according to the invention very particularly preferably has polyhedral oligomeric silicon-oxygen cluster units which are based on a functionalized silasesquioxane such as, for. B. Structure 2


are based, with X = oxy, hydroxy, alkoxy, carboxy, silyl, alkylsilyl, alkoxysilyl, siloxy, alkylsiloxy, alkoxysiloxy, silylalkyl, alkoxysilylalkyl, alkylsilylalkyl, halogen, epoxy, Ester, fluoroalkyl, isocyanate, acrylate, methacrylate, nitrile, amino or phosphine group or an alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl or heteroaryl radical, with at least one of these groups is functionalized and R = hydrogen atom, substituted or unsubstituted alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl, heteroaryl or all or part of a group X, where the groups X and / or R can be the same or different. The surface itself usually does not have the compound according to structure 5, but a compound derived from the compound, which is chemically bonded to other constituents of the surface via the radical X. Particularly preferred silasesquioxane units are based on polyhedral oligomeric silicon-oxygen cluster compounds of structure 2 with R = i-butyl.

The surfaces according to the invention can also preferably be polyhedral oligomers Have silicon-oxygen cluster units that are based on polyhedral oligomeric silicon Oxygen cluster compounds are based that have at least one alkoxysilylalkyl group and / or at least one alkoxysilyl group and at least one vinyl group contain. These groups ensure particularly good adhesion of the polyhedral oligomeric silicon-oxygen cluster unit reached on the surface. The Surfaces according to the invention can be polyhedral oligomeric silicon-oxygen cluster units contain, which are based on polyhedral oligomeric silicon-oxygen cluster compounds, which have at least one alkoxysilylalkyl group. Preferably, these have Surfaces based on polyhedral oligomeric silicon-oxygen cluster units polyhedral oligomeric silicon-oxygen cluster compounds based at least have a free hydroxyl or amino group.

As polyhedral oligomeric silicon-oxygen cluster units, the surfaces according to the invention can also have at least one completely condensed silasesquioxane of the formula R ₈ Si ₈ O ₁₂ with the structure 1,


wherein the radicals R are identical or different and represent a hydrogen atom or a substituted or unsubstituted alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl, heteroaryl radical.

Likewise, the surfaces according to the invention can also have polyhedral oligomeric silicon-oxygen cluster units which are based on an incompletely condensed silasesquioxane. Structures 3, 4 or 5 show examples of an incompletely condensed silasesquioxane, the incompletely condensed silasesquioxanes not being restricted exclusively to these structures.

The radicals R are the same or different and represent a hydrogen atom or one substituted or unsubstituted alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, Cycloalkynyl, aryl, heteroaryl radical.

In particular, it can be advantageous if the polyhedral oligomeric silicon-oxygen cluster units are based, at least on oligomeric silasesquioxanes, which, for example, by reacting incompletely condensed silasesquioxanes. B. the structure 3, 4 and 5 with monomeric functionalized silanes of the formula Y ₃ Si-X ¹ , Y ₂ SiX ¹ X ² and / or YSiX ¹ X ² X ³ can be obtained, the group Y being a leaving group with Y = alkoxy -, carboxy, halogen, silyloxy or amino group, the group X an oxy, hydroxyl, alkoxy, carboxy, silyl, alkylsilyl, alkoxysilyl, siloxy, alkylsiloxy, alkoxysiloxy, silylalkyl, Alkoxysilylalkyl, alkylsilylalkyl, halogen, epoxy, ester, fluoroalkyl, isocyanate, acrylate, methacrylate, nitrile, amino or phosphine group, the groups X ¹ , X ² and X ^{3 being the} same or different and the radicals R are the same or different and represent a hydrogen atom or a substituted or unsubstituted alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl, heteroaryl radical.

In a further embodiment of the surface according to the invention, the polyhedral oligomeric silicon-oxygen cluster units on an oligomeric Spherosilicate.

It can be advantageous if the surface according to the invention is polyhedral oligomeric Has silicon-oxygen cluster units, which have a molecular size of 0.1 to 500 nm, preferably from 1 to 50 nm and particularly preferably from 5 to 25 nm.

These polyhedral oligomers likewise preferably have Silicon-oxygen cluster units preferably have a molecular weight of 700 to 3000 g / mol, particularly preferably of 1000 to 2500 and very particularly preferably from 1250 to 1750 g / mol.

As already stated, due to their molecular character they are polyhedral oligomeric silicon-oxygen cluster units a uniform and defined Molecular weight and therefore a defined size. They are highly thermally stable and have a "cage-like" structure. Their polarity can not only be targeted via the radicals R and / or X. can be set, but you can also use functional groups on a Surface to be anchored. To make the molecule bigger, for example Dendrimer structures or hyperbranched structures can be used. That combination of hydrophobicity, molecular size and functionality means that wash-resistant hydrophobic nano to microstructures on one surface can be.

In the case of molecules of approximately 1 nm in size, the nanostructure usually only occurs in bulk itself, ie. H. for example, when the polyhedral oligomeric silicon-oxygen cluster compound in molten state. In solution they often form through loose storage some molecules to a larger unit, usually aggregates, from approx. 30 to 60 nm Size. In some cases, this aggregate formation also reaches sizes of 100 nm and about that. The aggregate formation is generally a question of compatibility with the respective Solvent system. In this case, good tolerance means that the polyhedral oligomeric silicon-oxygen cluster compound clearly soluble in the solvent in question is. This is usually the case with ethers and cyclic ethers, such as. B. tetrahydrofuran, Hydrocarbons such as B. hexane, or chlorinated hydrocarbons, such as. B. Chloroform. If the polyhedral oligomers are incompatible In contrast, silicon-oxygen cluster connection with the solvent system frequently occurs Aggregate formation. It is therefore to be avoided that by choosing incompatible systems, such as B. acetone or acetonitrile, agglomerates of over 50 microns, which ultimately to a rough surface. The intolerance problems mentioned exist of course only if a clear solution of a polyhedral oligomeric silicon Oxygen cluster compound an incompatible solvent system is added. It is on the other hand, very possible, finely ground powder of a polyhedral oligomer Disperse silicon-oxygen cluster compound in acetone without a Aggregate formation can be observed.

The surface according to the invention can be the surface of an object itself or but the surface of a coating that polyhedral oligomeric silicon Has oxygen cluster units.

The coating can be made entirely of polyhedral oligomeric silicon Oxygen cluster units consist of mixtures of polyhedral oligomers Have silicon-oxygen cluster units, additives and / or a matrix. Such a Matrix coating, e.g. B. on an organic basis, can be a paint system that the polyhedral oligomeric silicon-oxygen cluster compound and optionally additives contains, and which is applied to a surface.

Depending on the composition and / or type of coating, the coating can be a have different thickness. Coatings containing only the polyhedral oligomers Silicon-oxygen cluster units preferably have a thickness of less 150 µm, particularly preferably less than 50 µm and very particularly preferably less than 5 µm. Coatings that additionally have a carrier or matrix material can also be used in the mentioned layer thicknesses are present. But they can also have a greater thickness. Such coatings preferably have a thickness of less than 1000 μm, preferably less 700 µm and particularly preferably less than 250 µm.

If the surface according to the invention is the surface of a coating which has a mixture, then in a special embodiment of the surface according to the invention the surface preferably has a coating which
from 0.1 to 30 parts by weight of a polyhedral oligomeric silicon-oxygen cluster compound,
from 0 to 30 parts by weight of at least one additive and
from 40 to 99.9 parts by weight of an inorganic and / or organic matrix.

The surface very particularly preferably has a coating that
from 0.1 to 15 parts by weight of a polyhedral oligomeric silicon-oxygen cluster compound,
from 0 to 15 parts by weight of at least one additive and
from 70 to 99.9 parts by weight of an inorganic or organic matrix.

The additives can e.g. B. hydrophobic or hydrophobized particles selected from the micronized silica gels or silica gels, pyrogenic silicas, precipitated silicas, Metal oxides, minerals, bentonites and the micronized waxes. Especially silicates, pyrogenic silicas, precipitated silicas, for example Aerosil®, Silcron®, Santocel® and Syloid® types, which are available from Degussa, Glidden, Monsanto and Grace are offered to be present in the coating. Most notably preferred additives in the coating are pyrogenic silicates or silicas, in particular Aerosile®, aluminum oxide, silicon dioxide, titanium dioxide, zirconium dioxide or Mixtures of these products as well as zinc powder coated with Aerosil® are available. Even hydrophobicizing or hydrophobicized very fine powders such as Aerosil® R 972 and R 974 or Aerosil® R 8200 (Degussa) can be used as additives. Likewise, as Additives in the coating of the surface of the invention micronized waxes from Polyolefin, Fischer-Tropsch, amide wax, micro wax and PTFE type (Polytetrafluoroethylene) or their mixtures, which are on the market in sizes below 30 µm, below 20 µm, below 10 µm (measured with the CILAS 715 laser granulometer) will be present. The additives preferably have a particle size of 0.0001 to 20 µm, preferably from 0.1 to 10 µm and very particularly preferably from 4 to 0.5 µm. The Additives can also be compounds that are not in the form of particles. In particular Additives can also be compounds that have antimicrobial properties, e.g. B. antimicrobial polymers, such as. B. the AMINA® grades from Degussa AG. It is of course, it is also possible that these polymers or compounds are also in particulate form of the coating.

It may be advantageous if the coating is an organic matrix, such as. B. a Coating system. This matrix preferably contains at least one thermoplastic, elastomeric or thermosetting plastic. The organic matrix can be used as plastics a plastic selected from polyethylene, polypropylene, polyester, copolyester, Polycarbonate, polyamide, copolyamide, polyurethane, polyacrylate, polymethacrylate, Polymethacrylate copolymer, polysiloxane, polysilane, polytetrafluoroethylene, phenolic resin, Polyoxomethylene, epoxy resin, polyvinyl chloride, vinyl chloride copolymer, polystyrene, Copolymers of styrene, ABS polymer, alkyd resin, unsaturated polyester resin, Nitrocellulose resin and rubber. Connections can also be made in the matrix be present that have antimicrobial properties, such as. B. antimicrobial acting polymers, such as. B. the AMINA® grades from Degussa AG.

If the coatings are mixtures of polyhedral oligomers Silicon-oxygen cluster compounds with coating systems have these mixtures preferably from 1 to 70% by weight, preferably from 10 to 60% by weight and particularly preferably from 25 to 50% by weight of polyhedral oligomers Silicon-oxygen cluster compounds. The rest of this mixture can be a conventional paint system. Suitable coating systems and thus organic matrix materials used in printing inks and Varnishes commonly used are hydrocarbon resins, polyamide resins, Alkyd resins, maleate resins, polyacrylates, urea resins, polyterpene resins, ketone Aldehyde resins, epoxy resins, phenolic resins, polyesters and polyurethane systems, Cellulose derivatives, rosin-based resins, shellac and dammar, and all of derivatives derived from the aforementioned resins. Coatings made from powder coatings are also available possible. When the solid polyhedral oligomeric silicon-oxygen cluster compounds are sufficiently fine (i.e. below 10 µm) as e.g. B. when grinding with a Jetmill or jet mill is the case (Thomsen, Farbe und Lack 80, No. 4, 1974, 306-310; DE 35 33 436 and EP 0 324 077, as well as Jansen, Coating 4/89 133-145 and 5/89 172-174), they can also be applied electrostatically together with a powder coating as a carrier.

The coating can, as I said, for. B. also an ink or paint film or Be painting. In the case of a printing ink, the layer thickness is depending on the process (offset, Gravure, flexo or screen printing) usually from 3 to 40 µm. When painting with airless Devices or compressed air guns usually have a layer thickness of 50 to 400 µm, while coatings up to 1000 µm thick can be used.

The coating of the surface according to the invention can, for. B. on an inorganic or be applied organic material. The coating is preferably on one Material made of glass, ceramic, plastic, metal, mineral building material, textile fabric or fibers applied. The fibers, especially the textile fibers, can be natural or be of artificial origin. Textile fabrics can e.g. B. fabrics, knitted fabrics, mats, Be fleeces or nets. The surface according to the invention can be both the surface of a be individual fiber as well as the surface of a fabric made from this fiber.

As already mentioned, it is also possible for the surfaces according to the invention to be present directly on an object. This can e.g. B. be the case when the entire item
from 0.1 to 30 parts by weight of a polyhedral oligomeric silicon-oxygen cluster compound,
from 0 to 30 parts by weight of at least one additive and
from 40 to 99.9 parts by weight of an inorganic and / or organic matrix.

In this case too, it is preferred if the object
from 0.1 to 15 parts by weight of a polyhedral oligomeric silicon-oxygen cluster compound,
from 0 to 15 parts by weight of at least one additive and
from 70 to 99.9 parts by weight of an inorganic or organic matrix.

As additives and matrix materials, these objects can include the aforementioned Have connections.

The surfaces according to the invention have the advantage that, depending on the design of the Surface self-cleaning properties and / or scratch-resistant, dyeable and / or can be resistant to abrasion.

The surfaces of the invention are preferably in accordance with the invention Process for the production of surfaces according to the invention, which thereby is characterized in that a polyhedral oligomeric silicon Oxygen cluster connection is applied and fixed.

In a first method variant, a coating is produced on the surface, which has polyhedral oligomeric silicon-oxygen cluster units.

In a special embodiment of the method according to the invention, the coating is produced by applying a mixture having at least one polyhedral oligomeric silicon-oxygen cluster compound to the surface and then fixing the polyhedral oligomeric silicon-oxygen cluster units. The application can e.g. B. by spraying, spraying, brushing or knife application of a liquid or solid mixture, preferably a liquid mixture. The polyhedral oligomeric silicon-oxygen cluster compound or the mixture can be fixed chemically or physically. With a physical fixation z. B. Adhesion or attraction forces. In chemical fixation, covalent bonds form between the polyhedral oligomeric silicon-oxygen cluster compound and the surface or else a matrix material which itself is either chemically or physically fixed to the surface. The chemical fixation can e.g. B. initiated by radiation, temperature or chemically. The covalent bond is usually formed by reacting a functional group X of the polyhedral oligomeric silicon-oxygen cluster compound with a functional group of the surface or of the matrix material. Various chemical reactions or reaction mechanisms come into question for the formation of the covalent bond, such as. B. esterification reactions (hydroxyl group and carboxylic acid (derivative) group), hydrosilylation reaction (addition of an SiH group to alkanes or alkenes), urethane formation (hydroxyl group and isocyanate group), urea formation (amine group and isocyanate group), amino alcohol formation (epoxy group and Amino group) or formation of hydroxyethers (epoxy group and alcohol). In FIGS. 5 and 6 are shown one possible physical or chemical fixing a potential.

Cover or coating

The mixture used for coating can be in addition to the polyhedral oligomers Silicon-oxygen cluster compounds, depending on the application, very different substances contain. If coatings are to be created that only contain polyhedral oligomeric silicon Oxygen cluster units or predominantly polyhedral oligomers Having silicon-oxygen cluster units, mixtures of polyhedral oligomers are preferably Silicon-oxygen cluster compounds in liquid carriers or mixtures of polyhedral oligomeric silicon-oxygen cluster compounds used with carrier gas. The mixtures with liquid carriers are preferably sprayed on or painted. The mixtures with the carrier gas are preferably sprayed on. As liquid carriers are suitable for organic solvents and water. When using Water as a carrier must have functional groups of the polyhedral oligomeric silicon Oxygen cluster compound that can react with the water, such as. B. isocyanate Groups that are blocked, e.g. B. with caprolactam. Suitable organic solvents are especially all arias of aliphates, such as. B. pentane, hexane, octane, nonane, decane, etc., Cycloaliphatics such as As cyclohexane, cycloheptane, cyclooctane etc., white spirit, crystal oils and mineral oils of all kinds (e.g. K 21® and K 30® from Shell AG), cyclic and acyclic alkyl ethers such as e.g. B. tetrahydrofuran, halogenated hydrocarbons, such as. B. Chloroform, aromatics such as B. toluene, and halogenated aromatics, such as. B. Trifluorotoluene. Solvents are preferred which are light at room temperature are volatile.

The mixture used for the overlay coating preferably contains from 0.1 to 99.9% by weight of the polyhedral oligomeric silicon-oxygen cluster compound, in particular from 5.0 to 95% by weight, particularly preferably from 10 to 60% by weight of the polyhedral oligomeric silicon-oxygen cluster compound. The rest of the amount is either an organic solvent in which the polyhedral oligomeric silicon Oxygen cluster compound is dissolved or dispersed or a propellant or carrier gas and / or an additive. In the case of organic solvent systems as blowing agents, the proportion is polyhedral oligomeric silicon-oxygen cluster compound in wt .-% rather relative low, the proportion of polyhedral oligomeric silicon Oxygen cluster compound in wt .-% be relatively high.

Suitable propellants or carrier gases are all commercially available gases such as for example propane and butane, dimethyl ether, fluorinated hydrocarbons and Nitrogen, nitrous oxide, air or carbon dioxide gas.

The coating is applied either by brushing on or by Spraying, e.g. B. via "airless devices" or compressed air guns at a pressure of 2 to 20 bar and nozzles with a diameter of 0.2 to 1.0 mm in diameter. Likewise spraying is possible. For this one uses z. B. spray cans with a pressure of 1.2 to 10 bar and nozzles with a diameter of 0.2 to 1.0 mm in diameter.

In the case of organic solvents as blowing agents, one dissolves or disperses e.g. B. from 0.1 to 30% by weight, preferably from 2 to 15% by weight, of the polyhedral oligomeric silicon Oxygen cluster compound in a suitable solvent, e.g. B. aliphatics, cycloaliphatics, cyclic and acyclic ethers or halogenated hydrocarbons, and sprays, it sprays or spreads on the surface to be treated. The connection is made either purely physical, or - which is cheaper - the polyhedral oligomeric silicon Oxygen cluster compound is anchored to the surface by chemical reaction. This chemical fixation can either be physical, e.g. B. by radiation, Temperature, or unblocking of the reactive units or chemically by suitable Additives are initiated. The chemical connection of the polyhedral oligomeric silicon Oxygen cluster connection takes place in this case, for. B. over oxygen or Stickstofftbrücken.

Depending on the surface to be treated, one chooses for chemical bonding corresponding to polyhedral oligomeric silicon-oxygen cluster compounds functionalized polyhedral oligomeric silicon-oxygen cluster compounds. So z. B. on surfaces containing free amino, imino, hydroxyl or carboxy groups polyhedral oligomeric silicon-oxygen cluster compounds are fixed, which, for. B. Have isocyanate or epoxy groups. For fixing the polyhedral oligomers Silicon-oxygen cluster compounds become the isocyanate groups or epoxy groups reacted with the hydroxyl groups or amino groups on the surface. Conversely, epoxy, isocyanate or alkoxysilylalkyl groups Surfaces with polyhedral oligomeric silicon-oxygen cluster compounds coated, which have free hydroxyl, carboxy or amino groups. at Plastic surfaces without reactive groups, such as. B. polyolefins can whose surface by known methods, such as. B. "Flame" or "Corona discharge", hydroxyl or carboxy groups are generated and these for the Anchoring of polyhedral oligomeric silicon-oxygen cluster connections become.

If polyhedral oligomeric silicon-oxygen cluster compounds are to be applied to glass or to mineral substances such as plasters, it is advantageous if the polyhedral oligomeric silicon-oxygen cluster compound has a group capable of adhering to glass or to mineral substances such as plasters. Such groups are e.g. B. -Si (OR) ₃ or -Si (X) ₃ , where X represents a halogen or a hydrogen or an alkyl group. In addition to the hydrophobic effect, the "anti-graffiti effect", which permanently prevents spray damage, should be emphasized. It is also possible to anchor the polyhedral oligomeric silicon-oxygen cluster compounds directly onto textile fibers and finished textiles.

In particular in this embodiment of the method according to the invention, the Surface on which the coating is applied from fibers be composed. Such surfaces can e.g. B. fabrics, knitted fabrics, nonwovens, nets or represent mats. The fibers can be of natural origin or on plastic or Glass base exist.

In addition to the polyhedral oligomeric silicon-oxygen cluster compounds, the Mixtures also have additives. The structure-forming additives are e.g. B. Hydrophobic or hydrophobic particles selected from the micronized silica gels or silica gels, fumed silicas, precipitated silicas, metal oxides, minerals, Bentonite and the micronized waxes. Particularly preferred additives Silicates, pyrogenic silicas, precipitated silicas, for example Aerosil®-, Silcron®-, Santocel® and Syloid® types offered by Degussa, Glidden, Monsanto and Grace will be present in the mixture. Are very particularly preferred as additives in the Coating pyrogenic silicates or silicas, in particular Aerosile®, aluminum oxide, Silicon dioxide, titanium dioxide, zirconium dioxide or mixtures of these products and with Aerosil® coated zinc powder available. Also hydrophobic or hydrophobized fine powders such as Aerosil® R 972 and R 974 or Aerosil® R 8200 (Degussa) are suitable as additives. The particles mentioned preferably have a medium one Particle size from 0.0001 to 20 µm, preferably from 0.1 to 10 µm and particularly preferred from 0.5 to 2 µm.

Likewise, micronized waxes from polyolefin, Fischer- Tropsch, amide wax, micro wax and PTFE type (polytetrafluoroethylene) or mixtures these waxes, which are on the market in sizes below 30 µm, below 20 µm, below 10 µm (measured with the 715 laser granulometer from CILAS) are offered, to be available. The proportion of additive in the mixture used for the coating can preferably based on the proportion of the polyhedral oligomeric silicon Oxygen cluster compound from 0 to 100 wt .-%, particularly preferably it is from 0 to 60% by weight, very particularly preferably from 0 to 20% by weight.

matrix coating

In this coating variant, a mixture is applied to a surface that preferably in addition to the polyhedral oligomeric silicon-oxygen cluster compound has at least one organic and / or one inorganic matrix material. It can be advantageous if the mixture also has one or more additives.

Preferred mixtures have
from 0.1 to 30 parts by weight of a polyhedral oligomeric silicon-oxygen cluster compound,
from 0 to 30 parts by weight of at least one additive and
from 40 to 99.9 parts by weight of an inorganic and / or organic matrix.

Very particularly preferred mixtures have
from 0.1 to 15 parts by weight of a polyhedral oligomeric silicon-oxygen cluster compound,
from 0 to 15 parts by weight of at least one additive and
from 70 to 99.9 parts by weight of an inorganic or organic matrix.

The additives present in the mixture can e.g. B. hydrophobic or hydrophobic Particles selected from the micronized silica gels or silica gels, pyrogenic Silicas, precipitated silicas, metal oxides, minerals, bentonites and the micronized waxes. Particularly preferred additives are silicates, pyrogens Silicas, precipitated silicas, for example Aerosil®, Silcron®, Santocel® and Syloid® grades, which are offered by Degussa, Glidden, Monsanto and Grace, in the Coating may be present. Additives in the mixture are very particularly preferred pyrogenic silicates or silicas, in particular aerosils, aluminum oxide, silicon dioxide, Titanium dioxide, zirconium dioxide or mixtures of these products as well as with Aerosil coated zinc powder available. Also hydrophobic or hydrophobic Very fine powders such as Aerosil® R 972 and R 974 or Aerosil® R 8200 (Degussa) come as Additives into consideration. The particles mentioned preferably have an average particle size from 0.0001 to 20 µm, preferably from 0.1 to 10 µm and particularly preferably from 0.5 to 2 µm.

Likewise, micronized waxes from polyolefin, Fischer- Tropsch, amide wax, micro wax and PTFE type (polytetrafluoroethylene) or their Mixtures that are on the market in sizes below 30 µm, below 20 µm, below 10 µm (measured with the 715 laser granulometer from CILAS) are offered, to be available.

The additives can also be compounds that are not in the form of particles. In particular Additives can also be compounds which have antimicrobial properties, such as z. B. antimicrobial polymers such. B. the AMINA® grades from Degussa AG. It is of course, it is also possible that these polymers or compounds are also in particulate form of the mixture.

The mixture according to the invention particularly preferably has an organic matrix. As organic matrix material are particularly suitable for thermoplastic, elastomeric or thermosetting plastics. As plastics, the organic matrix can be a plastic, selected from polyethylene, polypropylene, polyester, copolyester, polycarbonate, polyamide, Copolyamide, polyurethane, polyacrylate, polymethacrylate, polymethacrylate copolymer, Polysiloxane, polysilane, polytetrafluoroethylene, phenolic resin, polyoxomethylene, epoxy resin, Polyvinyl chloride, vinyl chloride copolymer, polystyrene, copolymers of styrene, ABS Polymer, alkyd resin, unsaturated polyester resin, nitrocellulose resin and rubber, exhibit. Suitable thermoplastics can still all types of hotmelts and Be hot melt adhesives, systems being generated by the method according to the invention be the z. B. show a reduced tendency to soiling. Can also in the matrix Compounds are present that have antimicrobial properties, such as. B. antimicrobial polymers, such as. B. the AMINA® grades from Degussa AG.

If the coatings are mixtures of polyhedral oligomers Silicon-oxygen cluster compounds with coating systems, these mixtures exhibit preferably from 1 to 70% by weight, preferably from 10 to 60% by weight and particularly preferably from 25 to 50% by weight of polyhedral oligomer Silicon-oxygen cluster connection. The rest of this mixture can be a conventional paint system. Suitable coating systems and thus organic matrix materials used in printing inks and Varnishes commonly used are hydrocarbon resins, polyamide resins, Alkyd resins, maleate resins, polyacrylates, urea resins, polyterpene resins, ketone Aldehyde resins, exoxide resins, phenolic resins, polyesters and polyurethane systems, Cellulose derivatives, rosin-based resins, shellac and dammar, and all of derivatives derived from the aforementioned resins. If the solid polyhedral oligomers Silicon-oxygen cluster compounds are sufficiently fine (i.e. below 10 µm), how it z. B. when grinding with a jet mill or jet mill, you can can be applied electrostatically together with a powder coating as a carrier.

In the case of printing inks, the method according to the invention can be used especially in aqueous or non-aqueous offset, gravure, screen and flexographic printing are used.

Processing of the polyhedral oligomeric silicon-oxygen cluster compound and plastic and any additives premixed mixture can be caused by electrostatic Coating, pressing, spinning, calendering, extrusion and injection molding are carried out. For example, you can use a commercially available powder coating in a powder mixer Mix 3.0% by weight of polyhedral oligomeric silicon-oxygen cluster compound, which was previously brought to a grain size of less than 10 μm with a jet mill.

Mixtures comprising thermosetting plastics, but especially mixtures with Solvent-based and / or aqueous lacquers and printing inks are preferred generated by polyhedral oligomeric silicon-oxygen cluster compound and / or Additives are mixed into the respective still liquid system, this then pressed, sprayed on, printed on or spread on.

Coating with the matrix coating method gives a coating which has a statistical distribution of the polyhedral oligomeric silicon-oxygen cluster units in the matrix material. In order to ensure a structuring of the surface, the coating must be carried out in such a way that either the matrix material has a thickness that is less than the average diameter of the structuring particles, i.e. the polyhedral oligomeric silicon-oxygen cluster units and / or the additives, if these are particles , (see Fig. 1a or b) or so many particles are present that even with a thickness of the matrix material greater than the diameter of the particles it is ensured that the surface is structured, e.g. B. in that the coating has a two- or multi-layer layer of particles or polyhedral oligomeric silicon-oxygen cluster units (see Fig. 2a or b).

However, the method according to the invention also enables a further coating variant, the so-called migration coating ( FIGS. 4a and b).

migration coating

It can be advantageous if the method according to the invention is carried out in such a way that it there is a migration coating. With this type of coating, the Coating no statistical distribution of polyhedral oligomeric silicon Oxygen cluster units or possibly existing structuring additives, but the polyhedral oligomeric silicon-oxygen cluster units and if the additives are present at least in part, are in the according to this embodiment of the Coating produced according to the method on the surface (s) more concentrated than inside the coating. This difference in concentration will achieved by the polyhedral oligomeric silicon-oxygen cluster compounds and possibly the appropriate additives are selected so that they match the matrix material are not miscible. After applying a homogenized mixture one Can have composition, as already in the section matrix coating has been described, the particles immiscible with the matrix migrate the polyhedral oligomeric silicon-oxygen cluster compound and / or the particles the final solidification of the matrix to the surface of the coating. The The particles are preferably anchored or fastened physically. Through the How this process works is obvious that some material combinations, such as they were enumerated for the matrix coating, not used in the migration method can be. Only such polyhedral oligomeric silicon Oxygen cluster compounds or particles are used that are not with the matrix miscible and also cannot be reacted or combined chemically with the matrix. For the migration variant, particularly suitable material combinations are e.g. B. non-polar Plastics such as polyolefins, rubbers and polar polyhedral oligomeric silicon Oxygen cluster compounds or polar plastics, such as. B. polymethacrylates, Polyamides, polyvinyl chloride, as well as paint and printing ink binders in connection with non-polar or less polar polyhedral oligomers Silicon-oxygen cluster compounds. The polyhedral oligomeric silicon-oxygen cluster compounds are So either set to be less polar than the plastic you are using or they are with functional groups made very polar, so that they are more polar than that together with they used plastic.

Combinable with polyhedral oligomeric silicon-oxygen cluster compounds Additives are particularly suitable for micronized silica gels or silica gel. It can be are pyrogenic silicas or precipitated silicas. Also metal oxides, minerals or bentonite are suitable for an application. Silicates are preferred, fumed silicas, precipitated silicas, for example Aerosil®-, Silcron®-, Santocel®- and Syloid® grades offered by Degussa, Glidden, Monsanto and Grace. All pyrogenic silicates or silicas, in particular aerosils, are particularly preferred, Aluminum oxide, silicon dioxide, titanium dioxide, zirconium dioxide or mixtures of these Products and zinc powder coated with Aerosil®. Also hydrophobic or hydrophobized fine powders such as Aerosil® R 972 and R 974 or Aerosil® R 8200 (Degussa) is being brought up for consideration. The particles mentioned preferably have an average particle size from 0.0001 to 20 µm, preferably from 0.1 to 10 µm and very particularly preferably from 0.5 up to 2 µm.

Can be combined with polyhedral oligomeric silicon-oxygen cluster compounds also micronized waxes from polyolefin, Fischer-Tropsch, amide wax, Micro wax and PTFE type (polytetrafluoroethylene) or their mixtures based on the Market in sizes below 30 µm, below 20 µm, below 10 µm (measured with the Laser Granulometer 715 from CILAS) are offered.

Gächter / Müller produces waxes in all kinds of thermoplastics (Taschenbuch der Kunststoffadditive, Carl Hanser Verlag Munich Vienna, 1979). In thermosetting plastics such as in epoxy and polyurethane systems, in polycarbonate, Polyoxomethylene, polyacrylate, polymethacrylate or in polymethacrylate copolymers and in Printing ink and lacquer systems increase the scratch resistance, the abrasion resistance, the Waterproofing and the sliding properties. In certain cases, the addition is also made for matting purposes. The addition amounts range from 0.1 to 5.0% by weight, frequently they are from 0.5 to 2.0% by weight. Describe the state of the art and its manufacture Thomsen (Farbe und Lack 80, No. 4, 1974, 306-310), DE 35 33 436 and EP 0 324 077, and Jansen (Coating 4/89 133-145 and 5/89 172-174).

In principle, however, other additives, such as. B. Russ, antimicrobial Polymers, e.g. B. the AMINA® grades from Degussa can be used. requirement is, that firstly, the required grain size requirement of at least 99.0% by weight below of 20 µm and have so much incompatibility with the respective system that they can migrate to the surface, but at the same time no larger agglomerates Form 20 µm. Suitable additives are also certain types of fillers and Reinforcing agents, flame retardants as well as antistatic agents and stabilizers of all kinds.

Surprisingly, migration to the surface can also be carried out in high solid Observe paint systems and powder coatings, especially when the Varnish is cured thermally, with UV radiation or with electron radiation. The latter systems usually contain a paint resin containing hydroxyl groups, z. B. DYNAPOL® grades (Degussa), which have a crosslinker that is often a blocked Represents isocyanate, e.g. B. VESTAGON® types (Degussa), can be cured.

Suitable organic matrix materials commonly used in printing inks and varnishes are used are hydrocarbon resins, polyamide resins, alkyd resins, maleate resins, Polyacrylates, urea resins, polyterpene resins, ketone-aldehyde resins, epoxy resins, Phenolic resins, polyesters and polyurethane systems, cellulose derivatives, rosin-based resins, Shellac and Dammar and all derivatives derived from the aforementioned resins.

In the case of printing inks, the method according to the invention can be used especially in aqueous or non-aqueous offset, gravure, screen and flexographic printing are used.

The amount of polyhedral oligomeric silicon-oxygen cluster compound added plus any additive to the inorganic and / or organic matrix is at this variant of the method according to the invention preferably from 0.1 to 30.0% by weight, preferably from 0.2 to 15.0% by weight and particularly preferably from 2 to 10.0% by weight.

The coatings can be applied to a wide variety of surfaces. The Coating of the surface according to the invention can, for. B. on an inorganic or organic material. The coating is preferably on one Material made of glass, ceramic, plastic, metal, mineral building material, textile fabric, Fibers applied. The fibers, in particular the textile fibers, can be natural or be of artificial origin. Textile fabrics can e.g. B. fabrics, knitted fabrics, mats, nonwovens or networks. The surface according to the invention can be both the surface of a be individual fiber as well as the surface of a fabric made from this fiber. As Plastic surfaces are particularly suitable for use with polyethylene, polypropylene, Polyester, copolyester, polycarbonate, polyamide, copolyamide, polyurethane, polyacrylate, Polymethacrylate, polymethacrylate copolymer, polysiloxane, polysilane, polytetrafluoroethylene, Phenolic resin, polyoxomethylene, epoxy resin, polyvinyl chloride and vinyl chloride copolymer, Polystyrene and copolymers of styrene, ABS polymer, alkyd resin, unsaturated Have polyester resin, nitrocellulose resin or rubber. Plastic surfaces can also be lacquered surfaces.

Migration object

In this variant of the method according to the invention, the method according to the invention is used Surface produced in that the processing of the surface Material to an object is a polyhedral immiscible with this material oligomeric silicon-oxygen cluster compound is added, which either in liquid state such as B. in printing inks and varnishes or when heating the Material for the final shaping migrates to the surface and is deposited there. The migration can either during the drying process itself such. B. in printing inks and Paints, when hardening such. B. in concrete, plaster or glass or when processing Plastics such as pressing, extruding, injection molding, calendering, spinning are made.

The fixation can, for. B. done by the polyhedral oligomeric silicon Oxygen cluster unit is loosely bound to the material. A better fixation can e.g. B. in that the polyhedral oligomeric silicon-oxygen cluster compound has blocked functional groups, such as. B. capped isocyanates z. B. thermal can be unblocked and then react with the material surface.

With this process variant it is also possible to use additives. The additives can also be chosen so that they are not miscible with the material. Likewise, the However, additives should also be selected so that they can be mixed with the material. The same is true Use of combinations of miscible and immiscible with the material polyhedral oligomeric silicon-oxygen cluster compounds and / or additives possible.

Depending on the additive used, the properties of the surfaces can be set exactly become. In particular for the production of microstructures, migratory additives, with Sizes in the micrometer range desirable. Polyhedral oligomeric silicon Oxygen cluster compounds can basically be used alone. It is cheap if they cover grain sizes between 10 microns and 10 nanometers. To round it off the grain size range can also use the aforementioned additives such. B. micronized Waxes and silica gels can also be used. The fixation on the surface is predominantly of a physical nature and usually takes place through integration before the inorganic and / or organic matrix is cured. Unless the polyhedral oligomeric silicon-oxygen cluster compounds have vinyl groups, it can to react with the surface, d. H. solid chemical fixation.

This also becomes a polyhedral oligomer Obtained surface having silicon-oxygen cluster units. This process variant is similar to the variant according to the migration coating. As input materials, the at Substances called migration coating are used, especially those mentioned there Additives. The materials used are those in the enumeration of the organic matrix materials mentioned thermoplastics in question with the proviso that material and polyhedral oligomeric silicon-oxygen cluster compound and / or structure-forming Additive are not miscible.

In all process variants, the additives can, provided they do not contain any functional groups possess, via the functionalized polyhedral oligomers Silicon-oxygen cluster connection can be physically anchored to the respective surface. The polyhedral oligomeric silicon-oxygen cluster units then form a kind of network, whereby the additives are held. For additives with functional groups, such as alkoxysilyl Amino, imino, hydroxy, carboxy, isocyanate or epoxy groups, these can with the polyhedral oligomeric silicon-oxygen cluster compound stuck to a surface be bound.

The polyhedral oligomeric silicon Oxygen cluster units preferably have a molecular weight greater than 400 g / mol, preferably from 700 to 3000 g / mol, particularly preferably from 800 to 1500 g / mol. All polyhedral oligomers are particularly preferred in the process according to the invention Silicon-oxygen cluster units are used, which have a molecular size of 0.1 to 500 nm, preferably from 1 to 50 nm. This can be done while the Process condense or aggregate. The polyhedral oligomeric silicon Oxygen cluster units can also be used as condensates or aggregates. Aggregates preferably have an average size of 0.5 to 50 μm, preferably 10 to 30 µm. Ground solid polyhedral oligomers can also be used Silicon-oxygen cluster compounds used as polyhedral oligomeric silicon-oxygen cluster units be in which the powders have a size below 10 microns. For grinding So-called jet mills or jet mills are particularly suitable, which are usually used at higher Printing, d. H. between 3 and 12 bar.

Polyhedral oligomeric silicon-oxygen cluster compounds of the formula are preferred in the process according to the invention

[(R _a X _b SiO _1.5 ) _m (R _c X _d SiO) _n (R _e X _f Si ₂ O _2.5 ) _o (R _g X _h Si ₂ O ₂ ) _p ]

used, with a, b, c = 0-1; d = 1-2; e, f, g = 0-3; h = 1-4; m + n + o + p ≥ 4; a + b = 1; c + d = 2; e + f = 3 and g + h = 4, R = hydrogen atom, alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl, heteroaryl group or polymer unit, which are each substituted or unsubstituted or further functionalized polyhedral oligomeric silicon-oxygen cluster units which are connected via a polymer unit or a bridge unit, X = oxy-, hydroxy-, alkoxy-, carboxy-, silyl-, alkylsilyl-, alkoxysilyl-, siloxy-, alkylsiloxy-, alkoxysiloxy-, silylalkyl- , Alkoxysilylalkyl, alkylsilylalkyl, halogen, epoxy, ester, fluoroalkyl, isocyanate, blocked isocyanate, acrylate, methacrylate, nitrile, amino, phosphine group or at least one such group of type X substituents from Type R, where the R type substituents are the same or different and the X type substituents are the same or different.

In a special embodiment of the method according to the invention polyhedral oligomeric silicon-oxygen cluster compounds, the functional groups have, are used.

In the process according to the invention, in particular oligomeric silasesquioxanes of the formula

[(R _a X _b SiO _1.5 ) _m (R _c X _d SiO) _n ],

used, with a, b, c = 0-1; d = 1-2; m + n ≥ 4; a + b = 1; c + d = 2; R = hydrogen atom, substituted or unsubstituted alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl, heteroaryl and X = oxy, hydroxyl, alkoxy, carboxy, silyl, alkylsilyl, Alkoxysilyl, siloxy, alkylsiloxy, alkoxysiloxy, silylalkyl, alkoxysilylalkyl, alkylsilylalkyl, halogen, epoxy, ester, fluoroalkyl, isocyanate, acrylate, methacrylate, nitrile, amino or phosphine group or such substituted or unsubstituted alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl or heteroaryl radicals having such groups, the radicals R being the same or different and the radicals X also being the same or different.

Oligomeric silasesquioxanes having a structure selected from are preferred
[(RSiO _1.5 ) _n ] _z (= homoleptic structure),
[(RSiO _1.5 ) _m (RXSiO _1.0 ) _n ] _z (= functionalized homoleptic structure),
[(RSiO _1.5 ) _m (R'SiO _1.5 ) _n ] _z (= heteroleptic structure) and
[(RSiO _1.5 ) _m (R'XSiO _1.0 ) _n ] _z (= functionalized heteroleptic structure)
with m + n = z and z ≥ 4, where z corresponds to the number of Si atoms in the skeleton structure of the oligomeric silasesquioxane, R and R 'each represent a hydrogen atom, a substituted or unsubstituted, functionalized or unfunctionalized alkyl, cycloalkyl, alkenyl -, Cycloalkenyl, alkynyl, cycloalkynyl, aryl or heteroaryl and X is an oxy, hydroxyl, alkoxy, carboxy, silyl, alkylsilyl, alkoxysilyl, alkoxysilylalkyl, siloxy, alkylsiloxy, alkoxysiloxy -, Halogen, isocyanate, nitrile, amino or phosphine group, with the proviso that the radicals R are the same or different, the radicals R 'are the same or different and the radicals X are also the same or different.

Functionalized silasesquioxanes of structure 2,


with X = oxy, hydroxy, alkoxy, carboxy, silyl, alkylsilyl, alkoxysilyl, siloxy, alkylsiloxy, alkoxysiloxy, silylalkyl, alkoxysilylalkyl, alkylsilylalkyl, halogen, epoxy, ester , Fluoroalkyl, isocyanate, acrylate, methacrylate, nitrile, amino or phosphine group or an alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl or heteroaryl radical, with at least one of these Groups X is functionalized and R = hydrogen atom, substituted or unsubstituted alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl, heteroaryl or all or part of a group X, where the groups X and / or R may be the same or different. The surface itself usually does not have the compound according to structure 2, but a compound derived from the compound, which is chemically bonded to other constituents of the surface via the radical X. Compounds of structure 2 with R = i-butyl are particularly preferred.

Polyhedral oligomeric silicon-oxygen cluster compounds are particularly preferred used, the at least one alkoxysilylalkyl group or at least one Contain alkoxysilylalkyl group and at least one vinyl group. Through this Groups achieve particularly good adhesion to the surface, since this is Group-containing substrates can react.

Completely condensed silasesquioxanes of the formula R ₈ Si ₈ O ₁₂ with the structure 1 can also be used,


wherein the radicals R are identical or different and represent a hydrogen atom or a substituted or unsubstituted alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl, heteroaryl radical.

Incompletely condensed silasesquioxanes can also be used. Structures 3, 4 or 5 show examples of an incompletely condensed silasesquioxane, the incompletely condensed silasesquioxanes not being restricted exclusively to these structures.

The radicals R are the same or different and represent a hydrogen atom or one substituted or unsubstituted alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, Cycloalkynyl, aryl, heteroaryl radical.

In particular, it can be advantageous if, at least as a polyhedral oligomeric silicon-oxygen cluster compound, a compound is used which, for example, by reacting incompletely condensed silasesquioxanes. B. the structure 3, 4 or 5 with monomeric functionalized silanes of the formula Y ₃ Si-X ¹ , Y ₂ SiX ¹ X ² and / or YSiX ¹ X ² X ³ are obtained, the group Y being a leaving group with Y = alkoxy -, carboxy, halogen, silyloxy or amino group, the group X an oxy, hydroxyl, alkoxy, carboxy, silyl, alkylsilyl, alkoxysilyl, siloxy, alkylsiloxy, alkoxysiloxy, silylalkyl, Alkoxysilylalkyl, alkylsilylalkyl, halogen, epoxy, ester, fluoroalkyl, isocyanate, acrylate, methacrylate, nitrile, amino or phosphine group, the groups X ¹ , X ² and X ^{3 being the} same or different and the radicals R are the same or different and represent a hydrogen atom or a substituted or unsubstituted alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl, heteroaryl radical.

In a further embodiment of the process according to the invention, oligomers can Spherical silicates are used.

The silasesquioxanes mentioned or their starting compounds are e.g. B. at the relevant trading companies (Sigma-Aldrich, Gelest, Fluka) available. Spherical silicates can from Tal Materials Inc., Ann Arbor (USA). It is both possible Condense molecules into a larger molecule, e.g. B. via spacers and / or functional groups, as well as the molecules to homo- and copolymerize or by Fix reaction itself to a larger molecule or even polymer (grafting). For example, polyhedral oligomeric silicon-oxygen cluster compounds can be used a hydrosilylation can be reacted with polymers.

As described at the beginning, polyhedral oligomers can be Produce silicon-oxygen cluster compounds specifically, because of their size and their specifically set Incompatibility (immiscible) with the material to which they are added in the respective material and thus during the processing of the material migrate to the surface to create nano or micro structures. Then this is the case when non-polar thermoplastics such. B. polyethylene, polypropylene, Rubbers etc. with (the polar) polyhedral oligomeric silicon Oxygen cluster compounds are combined or if the polyhedral oligomers Silicon-oxygen cluster compounds have enough time during the curing process a thermosetting plastic, such as. B. nitrocellulose resins, or paint and Due to their structure, printing inks migrate to the surface. Such polyhedral oligomeric silicon-oxygen cluster compounds are used in migration coating and can be used in the direct production of objects from materials, in which one Migration is also desired.

Likewise, polyhedral oligomers can also be targeted Produce silicon-oxygen cluster compounds that have functional groups that allow the polyhedral oligomeric silicon-oxygen cluster units with the surface or the organic matrix material chemically combine and thus a very permanent connection he follows. Such polyhedral oligomeric silicon-oxygen cluster compounds are especially in the production of a coating or a matrix coating used.

Depending on the additive used, the surfaces produced in this way can be more polyhedral oligomeric silicon-oxygen cluster compound or depending on the one used Material already have hydrophobic properties. Usually have polyhedral oligomeric silicon-oxygen cluster compounds have hydrophobic properties. These are especially pronounced when the polyhedral oligomers Silicon-oxygen cluster compounds perfluoroalkyl radicals, such as. B. a dimethyl (trifluoropropyl) silyloxy or have a dimethyl (tridecafluorooctyl) silyloxy group. But it can also be beneficial be, the structured surface afterwards 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 hydrophobilize. Such treatment methods are familiar to the person skilled in the art.

Surprisingly, an improvement in the thermoplastic and thermoset Observe surface hardness or scratch sensitivity. Transparent systems, such as B. Glass or "plexiglass" are anti-reflective. High-gloss surfaces, such as B. paints, are matted so that on the one hand the high gloss disappears, on the other hand the transparency remains fully intact. By adding the polyhedral oligomeric silicon Oxygen cluster compounds generally occur as a result of hydrophobization suitable functionalization, such as B. with fluorine groups, can be reinforced.

The inventive method can, for. B. for the production of foils or films with Anti-blocking properties are used. The method according to the invention can also be used for the production of anti-reflective transparent surfaces, in particular for the production anti-reflective glass or plastic surfaces. Subject of the present invention are therefore also anti-reflective glass and plastic surfaces, characterized in that they have a surface according to the invention, which polyhedral has oligomeric silicon-oxygen cluster units. Furthermore, it can Process according to the invention for the production of self-cleaning glass or Plastic surfaces are used. Plastic surfaces treated according to the invention have increased scratch resistance and abrasion resistance. By the method according to the invention there are also wash-resistant coating coatings that are hydrophobic and have self-cleaning properties. Thermoplastics, elastomers and Thermosets by using the polyhedral oligomers Silicon-oxygen cluster compounds can be dyed and painted.

The structured surfaces of the invention and the inventive method for the production of such surfaces is explained in detail with reference to the figures Fig. 1 to Fig. 7.

In Fig. 1a a material W to see a coating was applied to the B, having the polyhedral oligomeric silicon-oxygen cluster units (particles) S. It can be clearly seen that the polyhedral oligomeric silicon-oxygen cluster units determine the structure of the surface.

In Fig. 1b shows schematically a material W to see a coating was applied to the B, having the polyhedral oligomeric silicon-oxygen cluster units (particles) and additives S A. It can be clearly seen that the polyhedral oligomeric silicon-oxygen cluster units S and the additives A form the structure of the surface.

FIG. 2a shows a material W to which a coating B has been applied, which has polyhedral oligomeric silicon-oxygen cluster units (particles) S in a multiple layer. It can be clearly seen that the polyhedral oligomeric silicon-oxygen cluster units determine the structure of the surface. In this case, the coating or the thickness of the matrix material can very well be larger than the diameter of a polyhedral oligomeric silicon-oxygen cluster unit. The structure can be formed as long as the multilayer polyhedral oligomeric silicon-oxygen cluster units are thicker than the thickness of the matrix material.

Fig. 2b the situation is as in Fig. 2a illustrates, with the difference that the structure is additionally formed from the additives A.

FIG. 3a shows a material W which was admixed with polyhedral oligomeric silicon-oxygen cluster compounds S and which migrated to the surface of the material during the production of the article.

In Fig. 3b a material W to see the immiscible in the preparation of polyhedral oligomeric silicon-oxygen cluster compounds S and immiscible additives A were admixed, that have migrated to the surface of the material in the production of the article.

In Fig. 4a, a material W to see a coating was applied to the B, having the polyhedral oligomeric silicon-oxygen cluster units (particles) S. In this example, the polyhedral oligomeric silicon-oxygen cluster units are selected such that they migrate to the surface of the coating and thus form the structure of the surface.

In Fig. 4b is a material W is seen, a coating was applied to the B, having the polyhedral oligomeric silicon-oxygen cluster units (particles) and additives S A. In this example, the polyhedral oligomeric silicon-oxygen cluster units and the additives are selected such that they migrate to the surface of the coating and thus form the structure of the surface.

Fig. 5, the physical fixation of a polyhedral oligomeric silicon-oxygen cluster shows schematically compound according to structure 1 in a surface O. This type of fixation occurs especially in the methods of coating migration or migration subject to.

Fig. 6 shows the chemical fixation of a polyhedral oligomeric silicon-oxygen cluster schematically shows connection to a surface via a urethane linkage O (OC (O) NH). This covalent connection can e.g. B. by chemical reaction of a surface having OH groups with a polyhedral oligomeric silicon-oxygen cluster compound according to structure 2 with X = isocyanate group. This type of fixation is used particularly in the case of the coating.

Fig. 7 shows the chemical fixation schematically shows a polyhedral oligomeric silicon-oxygen cluster compound in a matrix M, which is applied on a surface of O, over a plurality of urethane bridges (OC (O) NH). This covalent connection can e.g. B. by chemical reaction of a matrix having isocyanate groups, e.g. B. a lacquer, with a polyhedral oligomeric silicon-oxygen cluster compound according to structure 2 with X = OH group and R = X are formed. It can be clearly seen that the surface through the coating with a matrix that has a polyhedral oligomeric silicon-oxygen cluster unit has a structure that is formed by the polyhedral oligomeric silicon-oxygen cluster unit. This type of fixation is used in particular in the process of matrix coating.

The following examples are intended to explain the invention in greater detail, without its scope limit:

1. Preparation of the silasesquioxanes Example 1.1 Synthesis of (isobutyl) ₈ Si ₈ O ₁₂ from (isobutyl) Si (OMe) ₃

A solution of 6.4 g (0.11 mol) of KOH in 200 ml of H ₂ O is added to a solution of 446 g (2.5 mol) of isobutyltrimethoxysilane (isobutyl) Si (OMe) ₃ in 4300 ml of acetone with stirring. The reaction mixture is then stirred at 30 ° C. for 3 days. The resulting precipitate is filtered off and dried at 70 ° C. in vacuo. The product (isobutyl) ₈ Si ₈ O ₁₂ is obtained in a yield of 262 g (96%).

Example 1.2 Synthesis of (isobutyl) ₇ Si ₇ O ₉ (OH) ₃ from (isobutyl) ₈ Si ₈ O ₁₂ (example for the synthesis of an incompletely condensed silasesquioxane)

At a temperature of 55 ° C., 55 g (63 mmol) (isobutyl) ₈ Si ₈ O _{12 are added} to 500 ml of an acetone-methanol mixture (volume ratio 84:16) which contains 5.0 ml (278 mmol) H ₂ O and 10.0 g (437 mmol) of LiOH contains. The reaction mixture is then stirred at 55 ° C. for 18 h and then added to 500 ml of 1 N hydrochloric acid. After stirring for 5 minutes, the solid obtained is filtered off and washed with 100 ml of CH ₃ OH. After drying in air, 54.8 g (96%) (isobutyl) ₇ Si ₇ O ₉ (OH) ₃ are obtained.

Example 1.3 Functionalized silasesquioxane with an alkoxysilylalkyl end group ((isobutyl) ₇ Si ₈ O ₁₂ (CH ₂ ) ₂ Si (OEt) ₃ ) Step 1

2.0 ml of trimethoxyvinylsilane are added to a solution of 10.0 g (12.6 mmol) of (isobutyl) ₇ Si ₇ O ₉ (OH) ₃ in 20 ml of tetrahydrofuran (THF) at 20 ° C. Then 0.5 ml of an Et ₄ NOH solution (tetraethylammonium hydroxide) in water (35% by weight solution in water) is stirred in. This corresponds to 1.2 mmol base and 18 mmol water. This mixture is stirred overnight. The product is then precipitated by adding 200 ml of CH ₃ OH. After filtering off, the product is washed with 30 ml of acetone and after drying in air, 6.1 g (57%) of a white powder of (isobutyl) ₇ Si ₈ O ₁₂ (CH = CH ₂ ) are obtained.

2nd step

1.2 ml (6.4 mmol) of triethoxysilane and 50 are added to a solution of 5.0 g (5.9 mmol) of (isobutyl) ₇ Si ₈ O ₁₂ (CH = CH ₂ ) in 15 ml of toluene at 20 ° C. mg of a platinum-divinyltetra-methyldisiloxane complex in xylene (supplied by Gelest). The mixture is stirred overnight. The end product is then precipitated by adding 150 ml of acetonitrile. After filtering off, the product is washed with 2 × 20 ml of acetonitrile. The yield in the 2nd step is 100%.

A silasesquioxane of structure 2 is obtained, where X is an ethoxysilylethyl radical and R is an i-butyl radical.

Example 1.4 Functionalized silasesquioxane with dimethylvinylsilyl end groups (synthesis of (isobutyl) ₇ Si ₇ O ₁₂ (SiMe ₂ CH = CH ₂ ) ₃

To a solution of 10 g (12.6 mmol) (isobutyl) ₇ Si ₇ O ₉ (OH) ₃ in 100 ml THF (tetrahydrofuran), which contains 20 ml Et ₃ N (triethylamine), 5 at 20 ° C. 68 ml of vinyldimethylchlorosilane (41.6 mmol) were added. This mixture is heated on a reflux condenser for 15 minutes. The solvent is removed in vacuo and the product extracted with 2 × 100 ml of n-hexane. The extract is thickened in vacuo and then dissolved in 20 ml of toluene. After precipitation by adding 100 ml of acetonitrile, (isobutyl) ₇ Si ₇ O ₁₂ (SiMe ₂ CH = CH ₂ ) _{3 is obtained} in a yield of 85%.

2. Production of printing ink and lacquer films Example 2.1 Production of a toluene gravure ink

• a) 70 parts by weight of resin solution (consisting of 51 parts by weight of Sheby resin in 49 parts by weight of toluene)
  8 parts by weight of yellow pigment
  1 part by weight of toluene

• a) Es wird verfahren wie in 2.1a) nur dass mit einem Dissolver der Firma Heidolph 1,0 Gew.-% Silasesquiox: in gemäß Beispiel 1.1 in die fertige Druckfarbe eingearbeitet werden.
• b) Analog erfolgt die Herstellung mit 0,6 Gew.-% Silasesquioxan gemäß Beispiel 1.2 und 0,6 Gew.-% Wachs Ceridust® 9615A (CLARIANT AG).

A bead mill from Netzsch is used to produce this toluene gravure printing ink. The test proofs are made on a laboratory gravure printing device from Prübau. Round test specimens with a diameter of approx. 3 cm are cut from these.

• a) The procedure is as in 2.1a), except that a Heidolph dissolver incorporates 1.0% by weight of silasesquiox: in according to Example 1.1 into the finished printing ink.
• b) The preparation is carried out analogously with 0.6% by weight of silasesquioxane according to Example 1.2 and 0.6% by weight of Ceridust® 9615A wax (CLARIANT AG).

Example 2.2 Production of an offset color

• a) A wax-free system is used to produce the offset printing ink (Rapida- Blue printing ink, Michael Huber GmbH). Incorporation of 5.0% by weight Silasesquioxane according to Example 1.2 takes place on a laboratory roller mill (IGT, type AE). The trial prints are made on a laboratory offset printing device from IGT. From these round specimens with a diameter of approx. 2 cm are cut.
• b) The procedure is as in 2.2a) except that 3.0% by weight of silasesquioxane according to Example 1.2, previously with a laboratory jet mill to a grain size of less than 10 µm (measured with the laser Granulometer 115 from CILAS) and 1.0% by weight Aerosil® R 974 (DEGUSSA AG) can be incorporated into the finished printing ink.

Example 2.3 Production of the NC test varnish

• a) A commercially available nitrocellulose high-gloss lacquer from CLOUTH (wood lacquer) used. The finished lacquer mixture is applied with a laboratory doctor blade with a thickness of 150 µm mounted on black test specimens.
• b) 2 wt .-% silasesquioxane according to Example 1.1 and 1% by weight VESTOWAX® Spray 30 (= micronized Fischer-Tropsch wax, smaller than 15 µm, Degussa AG) with a Heidolph dissolver. Otherwise it will proceed as in 2.3a).

Example 2.4 Production of a powder coating

• a) A commercial powder coating from the company FREI (FREOPOX EKP-7) is in a thickness of 150 µm on a steel sheet. You put this coated steel sheet 3 minutes at a temperature of 180 ° C. This is used as a test specimen in Example 3.3 used.
• b) The basic procedure is as in 2.4a) except that 3.0% by weight of silasesquioxane according to Example 1.4, previously with a laboratory jet mill to a grain size less than 10 microns (measured with the laser granulometer 715 from CILAS) was added. Before the doctoring process, this is mixed in beforehand in a laboratory powder mixer.

Example 2.5 Polymethacrylate plate

• a) A commercially available polymethacrylate plate is degreased with acetone.
• b) The procedure is as in 2.5a) except that the polymethycrylate test plate is retrofitted with a mixture of 0.3% by weight of Aerosil® R 974 and 0.8% by weight of silasesquioxane in accordance with Example 1.3 evenly sprayed on a spray bottle filled with Drivosol®.

Example 2.6 Glass specimen

A conventional glass test specimen is used and treated analogously to 2.5a) and 2.5b).

Example 2.7 Concrete test specimens

A conventional concrete test specimen is used analogously to 2.5a) and 2.5b), except that degreasing is not carried out.

3. Exam Example 3.1 Testing the self-cleaning properties

Self-cleaning surfaces generally have a roll angle of less than 20 °, particularly preferably less than 10 °, the roll angle being defined such that an off 1 cm in height onto 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 than 10 °. 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.

Behavior is assessed visually based on an applied drop of water Grades from 1 (very good) to 5 (poor) can be used.

Example 3.2 Abrasion resistance test

Use of the quartant scrubber device (Prüfbau GmbH). The color test specimens are round with a diameter of 2 to 3 cm. Finding the number of strokes, up to which shows no color abrasion on a white test paper. A high number means good abrasion resistance, a low number means poor abrasion resistance.

Example 3.3 Scratch resistance test

With a metal ring on the finger, a constant load is placed over the test specimen (15 cm × 5 cm) painted quickly. The test specimen is then assessed visually. The Test specimens are prepared according to examples 2.3a), 2.3b), 2.4a), 2.4b), 2.5a) and 2.5b) manufactured. The a) example is not according to the invention and corresponds to the zero sample during is the b) example according to the invention.

For the assessment of the scratch resistance, the grades from 1 (very good) to 5 (poor) used.

Example 3.4 Antireflective effect

This test is carried out visually on glass and PMMA. The test specimens are produced in accordance with Examples 2.5a), 2.5b), 2.6a) and 2.6b). The a) example is not according to the invention and corresponds to the zero sample, while the b) example is according to the invention. The grades from 1 (very good) to 5 (poor) are used. Table 1 below gives the results of the tests in Examples 3 in tabular form. Table 1

From the results given in Table 1 it is clear that the addition of Silasesquioxanes according to the invention - depending on the system - to improve the abrasion and scratch resistance, for an anti-reflective effect and for self-cleaning Properties leads.

Claims (36)

1. Structured, hydrophobic surface with elevations and depressions, characterized in that the surface has polyhedral oligomeric silicon-oxygen cluster units which at least partially form the elevations. 2. Surface according to claim 1, characterized, that the surface is a surface of a coating that is polyhedral oligomeric Has silicon-oxygen cluster units. 3. Surface according to claim 2, characterized in
that the coating
from 0.1 to 30 parts by weight of a polyhedral oligomeric silicon-oxygen cluster compound,
from 0 to 30 parts by weight of at least one additive and
from 40 to 99.9 parts by weight of an inorganic and / or organic matrix. 4. Surface according to claim 3, characterized, that the additive has a particle size of 0.0001 to 20 µm. 5. Surface according to claim 3 or 4, characterized, that the organic matrix at least one thermoplastic, elastomeric or has thermosetting plastic. 6. Surface according to claim 5, characterized, that the plastic is selected from polyethylene, polypropylene, polyester, copolyester, Polycarbonate, polyamide, copolyamide, polyurethane, polyacrylate, polymethacrylate, Polymethacrylate copolymer, polysiloxane, polysilane, polytetrafluoroethylene, phenolic resin, Polyoxomethylene, epoxy resin, polyvinyl chloride, vinyl chloride copolymer, polystyrene, Copolymers of styrene, ABS polymer, alkyd resin, unsaturated polyester resin, Nitrocellulose resin or rubber. 7. Surface according to at least one of claims 2 to 6, characterized, that the coating is an ink or lacquer film or a paint. 8. Surface according to at least one of claims 2 to 7, characterized, that the coating is applied to an inorganic or organic material is. 9. Surface according to claim 8, characterized, that the coating on a material made of glass, ceramic, plastic, metal, mineral building material, textile fabric or fibers is applied. 10. Surface according to at least one of claims 1 to 9, characterized, that the surface with polyhedral oligomeric silicon-oxygen cluster units has a molecular weight greater than 400 g / mol. 11. Surface according to at least one of claims 1 to 10, characterized, that the polyhedral oligomeric silicon-oxygen cluster units chemically and / or are physically connected to the surface. 12. Surface according to at least one of claims 1 to 11, characterized in that the polyhedral oligomeric silicon-oxygen cluster units are completely condensed silasesquioxanes of the formula R ₈ Si ₈ O ₁₂ with the structure 1,


wherein the radicals R are identical or different and represent a hydrogen atom or a substituted or unsubstituted alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl, heteroaryl radical. 13. Surface according to at least one of claims 1 to 11, characterized, that the polyhedral oligomeric silicon-oxygen cluster units on polyhedral oligomeric silicon-oxygen cluster compounds are based, the functional groups exhibit. 14. Surface according to at least one of claims 1 to 11, characterized in that
that the polyhedral oligomeric silicon-oxygen cluster unit on a polyhedral oligomeric silicon-oxygen cluster compound of the formula

[(R _a X _b SiO _1.5 ) _m (R _c X _d SiO) _n (R _e X _f Si ₂ O _2.5 ) _o (R _g X _h Si ₂ O ₂ ) _p ]

based, with a, b, c = 0-1; d = 1-2; e, f, g = 0-3; h = 1-4; m + n + o ± p ≥ 4; a + b = 1; c + d = 2; e + f = 3 and g + h = 4; R = hydrogen atom, alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl, heteroaryl group or polymer unit, each of which is substituted or unsubstituted, or further polyhedral oligomeric silicon-oxygen cluster units which have a polymer unit or a bridging unit are attached, X = oxy, hydroxy, alkoxy, carboxy, silyl, alkylsilyl, alkoxysilyl, siloxy, alkylsiloxy, alkoxysiloxy, silylalkyl, alkoxysilylalkyl, alkylsilylalkyl, halogen, epoxy, Ester, fluoroalkyl, isocyanate, blocked isocyanate, acrylate, methacrylate, nitrile, amino, phosphine group or at least one such group of type R having substituents of type R, the substituents of type R being the same or different and the X type substituents are the same or different. 15. Surface according to claim 14, characterized in
that the polyhedral oligomeric silicon-oxygen cluster unit on an oligomeric silasesquioxane compound of the formula

L (R _a X _b SiO _1.5 ) _m (R _c X _d SiO) _n ]

based, with a, b, c = 0-1; d = 1-2; m + n ≥ 4 a + b = 1; c + d = 2;
R = hydrogen atom, substituted or unsubstituted alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl, heteroaryl and X = oxy, hydroxyl, alkoxy, carboxy, silyl, alkylsilyl, Alkoxysilyl, siloxy, alkylsiloxy, alkoxysiloxy, silylalkyl, alkoxysilylalkyl, alkylsilylalkyl, halogen, epoxy, ester, fluoroalkyl, isocyanate, acrylate, methacrylate, nitrile, amino or phosphine group or such substituted or unsubstituted alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl or heteroaryl radicals having such groups, the radicals R being the same or different and the radicals X likewise being the same or different. 16. Surface according to claim 15, characterized in
that the polyhedral oligomeric silicon-oxygen cluster unit on an oligomeric silasesquioxane compound having a structure selected from
[(RSiO _1.5 ) _n ] _z (= homoleptic structure),
[(RSiO _1.5 ) _m (RXSiO _1.0 ) _n ] _z (= functionalized homoleptic structure),
[(RSiO _1.5 ) _m (R'SiO _1.5 ) _n ] _z (= heteroleptic structure) and
[(RSiO _1.5 ) _m (R'XSiO _1.0 ) _n ] _z (= functionalized heteroleptic structure)
with m + n = z and z ≥ 4, where z corresponds to the number of Si atoms in the skeleton structure of the oligomeric silasesquioxane, R and R 'each represent a hydrogen atom, a substituted or unsubstituted, functionalized or unfunctionalized alkyl, cycloalkyl, alkenyl -, Cycloalkenyl, alkynyl, cycloalkynyl, aryl or heteroaryl and X is an oxy, hydroxyl, alkoxy, carboxy, silyl, alkylsilyl, alkoxysilyl, alkoxysilylalkyl, siloxy, alkylsiloxy, alkoxysiloxy -, halogen, isocyanate, nitrile, amino or phosphine group, with the proviso that the radicals R are the same or different, the radicals R 'are the same or different and the radicals X are also the same or different. 17. Surface according to claim 15 to 16, characterized in that
that the polyhedral oligomeric silicon-oxygen cluster unit on a functionalized oligomeric silasesquioxane compound of structure 2


based, with X = oxy, hydroxy, alkoxy, carboxy, silyl, alkylsilyl, alkoxysilyl, siloxy, alkylsiloxy, alkoxysiloxy, silylalkyl, alkoxysilylalkyl, alkylsilylalkyl, halogen, epoxy, Ester, fluoroalkyl, isocyanate, acrylate, methacrylate, nitrile, amino or phosphine group or an alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl or heteroaryl radical, with at least one of these groups is functionalized and R = hydrogen atom, substituted or unsubstituted alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl, heteroaryl or all or part of a group X. 18. Surface according to at least one of claims 13 to 17 characterized, that the polyhedral oligomeric silicon-oxygen cluster units have at least one Alkoxysilylalkyl group and / or at least one alkoxysilyl group and at least contain a vinyl group. 19. Surface according to at least one of claims 13 to 17 characterized, that the polyhedral oligomeric silicon-oxygen cluster units on polyhedral oligomeric silicon-oxygen cluster compounds based at least one Have alkoxysilylalkyl group. 20. Surface according to at least one of claims 13 to 17, characterized, that the polyhedral oligomeric silicon-oxygen cluster units on polyhedral oligomeric silicon-oxygen cluster compounds based that have at least one free Have hydroxyl or amino group. 21. Surface according to at least one of claims 14 to 20, characterized in that the polyhedral oligomeric silicon-oxygen cluster units are based on a functionalized oligomeric silasesquioxane compound, which by reaction of silasesquioxanes with free hydroxyl groups with monomeric functionalized silanes of the formula Y ₃ Si-X ¹ , Y ₂ SiX ¹ X ² and / or YSiX ¹ X ² X ^{3 is} obtained, the group Y being a leaving group with Y = alkoxy, carboxy, halogen, silyloxy or amino group, the group X being an oxy, Hydroxy, alkoxy, carboxy, silyl, alkylsilyl, alkoxysilyl, siloxy, alkylsiloxy, alkoxysiloxy, silylalkyl, alkoxysilylalkyl, alkylsilylalkyl, halogen, epoxy, ester, fluoroalkyl, isocyanate Represents acrylate, methacrylate, nitrile, amino or phosphine group, where the groups X ¹ , X ² and X ^{3 are} identical or different and the radicals R are identical or different and a hydrogen atom or a substituted or unsubstituted erten represent alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl, heteroaryl. 22. Surface according to claim 15 or 16, characterized in that
that the polyhedral oligomeric silicon-oxygen cluster units are based on an oligomerically incompletely condensed silasesquioxane of structure 3, 4 or 5,


wherein the radicals R are identical or different and represent a hydrogen atom or a substituted or unsubstituted alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl or heteroaryl radical. 23. Surface according to claim 14, characterized, that the polyhedral oligomeric silicon-oxygen cluster unit on an oligomeric Spherosilicate based. 24. Surface according to at least one of claims 1 to 23 characterized, that the polyhedral oligomeric silicon-oxygen cluster units are molecular Size of 0.1 to 500 nm and a molecular weight of 700 to 3000 g / mol. 25. Surface according to at least one of claims 1 to 24, characterized, that the surface has self-cleaning properties. 26. Surface according to at least one of claims 1 to 25, characterized, that the surface is scratch-resistant, abrasion-resistant and / or can be colored. 27. A method for producing surfaces according to at least one of claims 1 to 26 characterized, that on a surface a polyhedral oligomer Silicon-oxygen cluster compound is applied and fixed. 28. The method according to claim 27, characterized, that a coating is created on a surface, the polyhedral oligomer Has silicon-oxygen cluster units. 29. The method according to claim 27 or 28, characterized, that the coating by applying at least one polyhedral oligomer Mixture comprising silicon-oxygen cluster compound on the surface and by subsequent fixation the polyhedral oligomers Silicon oxygen cluster units are generated. 30. The method according to claim 29, characterized, that the application by spraying, spraying, spreading or knife application liquid mixture takes place. 31. The method according to claim 29 or 30, characterized, that the fixation takes place chemically or physically. 32. The method according to claim 27 or 28, characterized, that when processing the material having the surface one with this Material immiscible polyhedral oligomeric silicon-oxygen cluster compound which is added to the final shaping when the material is heated the surface migrates and deposits there. 33. Use of the method according to at least one of claims 27 to 32 for Production of films or films with anti-blocking properties, for the production of anti-reflective glass or plastic surfaces or for the production of self-cleaning glass or plastic surfaces. 34. Anti-reflective glass surface, characterized in that it has a surface according to at least one of claims 1 to 26. 35. Anti-reflective plastic surface, characterized in that it has a surface according to at least one of claims 1 to 26. 36. wash-resistant coating with hydrophobic and self-cleaning properties, obtainable by a process according to at least one of claims 27 to 32.