WO1997020005A1

WO1997020005A1 - Use of a fluorine-containing coating compound containing inorganic polycondensates

Info

Publication number: WO1997020005A1
Application number: PCT/EP1996/005308
Authority: WO
Inventors: Reiner Kasemann; Helmut Schmidt; Gerhard Jonschker; Stefan Brück; Volker Gerhard; Martin Mennig
Original assignee: Institut für Neue Materialien Gemeinnützige GmbH
Priority date: 1995-11-30
Filing date: 1996-11-29
Publication date: 1997-06-05
Also published as: DE19544763A1; AU1095897A; DE19544763B4

Abstract

The disclosure relates to the use of a coating compound containing polycondensates based on one or more compounds of elements M from main groups III-V and sub-groups II-IV of the periodic table, said compounds being rendered capable of hydrolytic polycondensation. In these polycondensates, at least one organic group G, which contains at least two aliphatic carbon atoms to each of which at least one fluorine atom is attached, is bound to each of at least some of the central atoms M either directly or via one of the carbon atoms or via a binding group A. The intended use is for coating surfaces of metal, plastic, modified natural materials, ceramics, concrete, clay and/or glass.

Description

USE OF A COATING COMPOSITION CONTAINING FLUORINE INORGANIC POLYCONDENSATE

EP-A-587 667 (W092 / 21729) describes a coating composition based on fluorine-containing inorganic polycondensates and their preparation.

In particular, this document describes a coating composition based on

Polycondensates of one or more hydrolyzable compounds of at least one element M from the main groups III to V and the subgroups II to IV of the Periodic Table of the Elements, at least some of these compounds in addition to hydrolyzable groups A also having non-hydrolyzable carbon-containing groups B and the total Molar ratio of groups A to groups B in the basic monomeric starting compounds is 10: 1 to 1: 2 and 0.1 to 100 mol percent of groups B are groups B 'which have an average of 2 to 30 fluorine atoms attached to one or more aliphatic carbon atoms which are separated from M by at least two atoms.

With regard to preferred embodiments and the production and application (application) of such coating compositions, reference is hereby expressly made to the content of WO92 / 21729.

It has been found that such and similar fluorine-containing coating compositions are suitable for a wide variety of substrates and, after corresponding curing, to give coatings with a wide variety of advantageous properties, in particular transparency, flexibility, mechanical resistance and abrasion resistance and excellent non-stick properties to a wide variety of substances (such as water, oils, for example) , Dirt, dust, etc.).

The present invention thus relates to the use of a coating composition which contains 5 polycondensates based on one or more compounds of the elements M of the main groups III to V and the subgroups II to IV of the periodic table of the elements which are capable of hydrolytic polycondensation, in which polycondensates at least a part of the 0 central atoms M each have at least one organic group G which has at least 2 aliphatic carbon atoms to which at least one fluorine atom is bonded, either directly via one of the carbon atoms or via a connecting group A, for coating 5 surfaces made of metal, plastics, possibly modified natural materials, ceramics, concrete, clay and / or glass.

The above metal surfaces also include 0 metal compound surfaces. Examples include metals such as copper, silver, gold, platinum, palladium, iron, nickel, chromium, zinc, tin, lead, aluminum and titanium as well as alloys containing these metals such as e.g. (Stainless) steel, brass and bronze. '5

The above coating composition can also be applied to surfaces of oxides, carbides, silicides, nitrides, borides, etc. of metals and non-metals, e.g. Surfaces containing metal oxides, carbides such as silicon carbide, tungsten carbide and boron carbide,

Include, or consist of silicon nitride, silicon dioxide, etc.

Among the surfaces made of (possibly modified) 5 natural materials, those made of natural stone (sandstone, marble, granite etc.), (fired) clay and cellulose materials should be mentioned, while Of course, surfaces made of concrete, ceramic, porcelain, plaster, glass and paper (including synthetic paper) with the above

Coating compositions can be coated in an advantageous manner. The term "glass" includes all types of glass with the most varied compositions, such as Soda-lime glass, potassium glass, borosilicate glass, lead glass, barium glass, phosphate glass, optical glass, historical glass, etc.

Among the plastics that form surfaces that can be coated with the above coating compositions are thermoplastics, thermosets, elastomers and foamed plastics. Specific examples of such plastics are e.g. :

Homo- and copolymers of olefinically unsaturated compounds, e.g. Olefins such as ethylene, propylene, butenes, pentenes, hexenes, octenes and decenes; Serve like butadiene, chloroprene, isoprene, hexadiene,

Ethylidene norbornene and dicyclopentadiene; aromatic vinyl compounds such as Styrene and its derivatives

(e.g. α-methylstyrene, chlorostyrenes, bromostyrenes, methylstyrenes, etc.); halogenated vinyl compounds such as Vinyl chloride, vinyl fluoride, vinylidene chloride,

Vinylidene fluoride and tetrafluoroethylene; α, β-unsaturated carbonyl compounds such as e.g. Acrylic acid, methacrylic acid, crotonic acid, maleic acid and fumaric acid and their derivatives

(in particular (alkyl) esters, amides, anhydrides, imides, nitriles and salts such as ethyl acrylate,

Methyl methacrylate, acrylonitrile, methacrylonitrile,

(Meth) acrylamide and maleic anhydride); and vinyl acetate.

Polyester such as Polyethylene terephthalate and polybutylene terephthalate; Polyamides such as Nylons;

Polyimides; Polyurethanes; Polyether; Polysulfones; Polyacetals; Epoxy resins; Polycarbonates; Polyphenylene sulfides; synthetic rubbers (optionally vulcanized); (vulcanized) natural rubber; Phenol-formaldehyde resins; Phenol urea resins; Phenol-melamine resins; Alkyd resins; and polysiloxanes.

Of course, such plastics can use the usual plastic additives such as Contain fillers, pigments, dyes, reinforcing agents (e.g. (glass) fibers), stabilizers, flame retardants, inhibitors, lubricants, etc.

The above coating compositions are particularly suitable for coating buildings and parts thereof; Means of transportation and parts thereof; Work equipment, devices and machines for commercial or industrial purposes and research and parts thereof; Household items and work tools for household purposes, and parts thereof; Equipment, devices and aids for games, sports and leisure and parts thereof; as well as devices, aids and devices for medical purposes and the sick. Specific examples of such coatable materials or articles are given below.

Buildings (especially buildings) and parts thereof:

Interior and exterior facades of buildings, floors and stairs made of natural stone, concrete etc., plastic floor coverings, carpets and carpets, skirting boards (rubbing strakes), windows (especially window frames, window sills, glass or plastic glazing and window handles), blinds, roller blinds, Doors, door handles, fittings in kitchens, bathrooms and toilets, shower cubicles, sanitary cells, toilet cubicles, pipes (and in particular drain pipes, in which dirt deposits should be avoided), radiators, mirrors, light switches, wall and floor tiles, lighting, letter boxes, Roof tiles, Gutters, gutters, antennas, satellite dishes, handrails of railings and escalators, architectural glazing, solar panels, conservatories, walls of elevators; Monuments, sculptures and general works of art made of natural stone (e.g. granite, marble), metal etc., especially those that are set up outdoors.

Means of transport and transportation (e.g. cars, trucks, buses, motorbikes, mopeds, bicycles, trains, trams, ships and planes) and parts thereof:

Headlights, interior and exterior mirrors, windshields, rear windows, side windows, mudguards for bicycles and motorcycles, plastic visors for motorcycles, instruments for motorcycles, seats, saddles, door handles, steering wheels, tire rims, tank sockets (especially for diesel), license plates, luggage racks, roof containers for Cars and cockpits. For example, the exterior coating of motor vehicles makes them easier to clean (wash).

Work equipment, devices and machines for commercial or industrial purposes and research as well as parts thereof:

Molds (e.g. casting molds, especially made of metal), pouring hoppers, filling systems, extruders, water wheels, rollers, conveyor belts, printing machines, screen printing stencils, filling machines, (machine) housings, injection molded parts, drilling heads, turbines, pipes (inside and outside), pumps, saw blades , Covers (e.g. for scales), keyboards, switches, buttons, ball bearings, shafts, screws, displays, solar cells, solar systems, tools, tool handles, liquid containers, insulators, capillaries, lenses, laboratory equipment (e.g.

Chromatography columns and prints) and computers (in particular housings and monitor disks). Household items and work equipment for the household or parts thereof:

Furniture veneers, furniture moldings, trash cans, toilet brushes,

Tablecloths, dishes (e.g. made of porcelain and earthenware), glassware, cutlery (e.g. knives), trays, pans, pots, baking pans, cooking utensils (e.g. wooden spoons, rasps, garlic presses etc.), cooking hobs, heating plates, ovens (inside and outside), Flower vases, covers for wall clocks, TV sets (especially screens), stereo systems, housings for (electrical) household appliances, picture glazing, Christmas baubles, wallpapers, lamps and lights, upholstered furniture, objects made of leather. In particular, the coating of furniture makes it easier to clean and shows no stains on the surface.

Equipment, devices and aids for games, sports and leisure:

Garden furniture, garden tools, greenhouses (especially glazing), tools, playground equipment (e.g. slides), balls, air mattresses, tennis rackets, table tennis rackets, table tennis tables, skis, snowboards, surfboards, golf clubs, dumbbells, seating in parks, playgrounds etc., motorcycle clothing, motorcycle helmets, Ski suits, ski boots, ski goggles, helmets for skiers, diving clothing and diving goggles.

Devices, aids and devices for medical purposes and the sick:

Prostheses (especially for limbs), implants, catheters, artificial intestinal exits, braces, dentures, glasses (glasses and frames), medical cutlery (for operations and dental treatment), plaster casts, Medical thermometers and wheelchairs, as well as general hospital facilities to improve (among other things) hygiene.

In addition to the above items, other items and parts thereof can of course also be advantageously coated with the above coating compositions, e.g. Jewelery, coins, works of art (e.g. paintings), book covers, tombstones, urns, signs (e.g. traffic signs), neon signs, traffic lights, CDs, bad weather clothing, textiles, post boxes, telephone booths, waiting booths for public transport, safety glasses, protective helmets, rockets, inside pages of food packaging and oil containers, foils (eg for packaging food), telephones, seals for

Faucets, generally all objects made of rubber, bottles, light, heat or pressure sensitive recording materials (before or after recording, e.g. photos) and church windows, as well as objects (e.g. made of sheet steel) that are exposed to graffiti (e.g. Exterior and interior of railway wagons, walls of subway and S-Bahn stations, etc.).

The above elements M from the main groups III to V and the subgroups II to IV of the periodic table of the elements are e.g. by at least one element selected from silicon, aluminum, boron, tin, zirconium, titanium, vanadium and tin, Si, Al, Ti and Zr being preferred and Si being particularly preferred. In particular, preferably 75 to 100 and particularly preferably 90 to 100% of all central atoms of the polycondensates present in the coating composition are silicon, aluminum, titanium and / or zirconium atoms.

Usually at least 0.1% (preferably at least 0.5% and in particular at least 1%) of all central atoms present in the above polycondensates are M. bound organic groups G, which preferably have at least 3 (more preferably at least 4 and in particular at least 5) aliphatic carbon atoms, to each of which at least one and preferably at least two fluorine atoms are bonded. These groups G are preferably partially fluorinated alkyl and / or alkenyl groups. These groups can also be groups derived from fluorinated alkanoic and alkenoic acids, for example. In this case you can chelate the corresponding acid with a

Starting compound capable of hydrolysis of e.g. Al, Ti or Zr have been introduced into the polycondensates, and the above linking group A is thus a chelating group that belongs to the structure

leads.

Examples of partially fluorinated groups G which can be used according to the invention (and are also preferred according to the invention) are groups which have aliphatic carbon atoms to which a total of 2 to 30 (preferably 3 to 25, more preferably 5 to 20 and particularly preferably 8 to 18) fluorine atoms are bound, and which (at least in the case of direct binding of G to M) are each separated from the central atom M by at least 2 atoms (preferably carbon atoms).

In the above number of fluorine atoms attached to aliphatic carbon atoms, those fluorine atoms are not taken into account which may possibly be used in another way, e.g. aromatic

Carbon atoms are bound (eg in the case of C _g F ₄ ). It is also possible for one or more fluorine atoms to be attached an aliphatic carbon atom from which a double or triple bond originates. In particular with regard to the accessibility of the corresponding starting substances (ie the (partially) hydrolyzable compounds of the elements M), fluorine-containing groups which are bonded directly to preferably silicon atoms are preferred. Specific examples of such fluorine-containing groups are, for example:

CF ₃ CH ₂ CH ₂ -, C ₂ F ₅ CH ₂ CH ₂ -, C ₄ F _g CH ₂ CH ₂ -, nC ₈ F ^ C ^ CH ..-, ⁿ - ^C 8 ^F 17 ^CH 2 ^CH 2- ' ⁿ - ^C 10 ^F 21 ^CH 2 ^CH 2- ^{And ±} - ^C 2 ^F 1 ° ^{~ (CH} 2 ^} 3 ^~ '

Among these groups, nC ₈ F ₁₃ CH ₂ CH ₂ -, nC ₈ F ₁₇ CH ₂ CH ₂ - and nC _1Q F ₂₁ CH ₂ CH ₂ - are particularly preferred. Of course, other fluorine-containing groups G can also be used according to the invention, as can mixtures of different fluorine-containing groups G.

At least a portion of the central atoms M of the polycondensates is preferably also at least one (for example one or two) non-hydrolyzable or non-hydrolyzing organic group with functional grouping Z. In the present context, “non-hydrolyzing” is understood to mean a group, which is in principle accessible to hydrolysis, but actually does not hydrolyze under the given conditions during the production of the polycondensates, the coating and the subsequent drying and / or curing. Examples of the latter groups can also include, for example, the above chelating groups A. One or two (preferably one) non-hydrolyzable or non-hydrolyzing groups (in addition to groups G) are preferably bound to at least 0.1% and in particular at least 0.5% of the central atoms M in the polycondensates. These groups can be selected from functionalized, for example (Substituted) alkyl (in particular C ₁ _ ₄ -alkyl, such as methyl, ethyl, propyl and butyl), alkenyl (in particular C ₂ _ ₄ -alkenyl, such as vinyl, 1-propenyl, 2-propenyl and butenyl), alkynyl (in particular C ₂ _ ₄ alkynyl, such as ethynyl and propynyl) and functionalized aryl

(in particular C _g _ ₁₀ aryl, such as phenyl and naphthyl), the groups other than alkyl groups and aryl groups also optionally having one or more substituents (for example chlorine, bromine, hydroxyl, alkoxy, epoxy, (optionally substituted) amino, etc.) can have. The above alkyl radicals also include the corresponding cyclic and aryl-substituted radicals, such as cyclohexyl and benzyl, while the alkenyl and alkynyl groups may also be cyclic and the aryl groups mentioned should also include alkaryl groups (such as tolyl and xylyl). Particularly preferred groups are groups which have an (optionally multiply) unsaturated carbon-carbon bond and / or have a highly reactive functional group such as epoxy. Among the unsaturated groups are in particular to be mentioned groups, acryloxy a (meth) (particularly a (meth) acryloxy-C ₁ _ ₄ - alkyl group such as (meth) acryloxypropyl) feature. The presence of such groups in the corresponding polycondensates has the advantage that after coating with the coating liquid, double curing can take place, namely a reaction between the functional groups Z (for example a thermally or photochemically induced linkage of the unsaturated organic residues by (radical) polymerization or a ring opening polymerization in the case of epoxy rings) and a thermal completion of the polycondensation (for example by elimination of water from M-OH groups still present). Of course, non-functionalized alkyl and aryl groups can also be present in the polycondensates

Central atoms M are present, in particular also those which are derived from long-chain saturated (but also unsaturated) fatty acids (in this case preferably bound to the central atom via a chelating group A).

The (partially) hydrolyzable starting compounds used to produce the coating composition or polycondensates used according to the invention are those of elements of main groups III to V and subgroups II to IV of the periodic table. Of course, other hydrolyzable compounds can also be used, in particular those of elements of main groups I and II of the periodic table (e.g. Na, K, Ca and Mg) and subgroups V to VIII of the

Periodic table. However, the compounds just mentioned preferably make up no more than 10 and in particular no more than 5 mol percent of the hydrolyzable monomeric compounds used overall.

Examples of hydrolyzable groups in the starting compounds (which can not necessarily be used as monomeric compounds, but can already be used as corresponding precondensates of compounds of one or more of the elements M) are - depending in part on the central atom M - halogen (F, Cl, Br and I, especially Cl and Br), alkoxy (especially C ₁ _ ₄ alkoxy, such as methoxy, ethoxy, n-propoxy, i-propoxy and butoxy), aryloxy (especially C _g _ _{1 ()} aryloxy, e.g. phenoxy), acyloxy (in particular C _χ _ ₄ -acyloxy, for example acetoxy and propionyloxy) and acyl (for example acetyl).

In addition to the above-mentioned hydrolyzable groups, further suitable groups which may also be mentioned are hydrogen and alkoxy radicals having 5 to 20, in particular 5 to 10, carbon atoms and halogen and alkoxy radicals. substituted alkoxy groups (eg ß-methoxyethoxy).

Since the hydrolyzable groups are practically no longer present in the finished coating, but are lost through hydrolysis (and condensation), the

Hydrolysis products may sooner or later also have to be removed in any suitable manner (in particular if such a hydrolysis product in the coating composition used according to the invention would have an unfavorable influence on the material to be coated or its components), those hydrolyzable groups which do not have any substituents are particularly preferred and low molecular weight hydrolysis products such as lower alcohols such as methanol, ethanol, propanol and butanols. The latter hydrolyzable groups are also preferred because they have practically no influence on the pH during hydrolysis (in contrast to e.g. halogen).

In addition to the above-described polycondensates and, if appropriate, water and hydrolysis products from the hydrolysis of the starting compounds, other components may also be present in the coating composition used according to the invention, which of course must not have any harmful influence on the material to be coated.

In most cases, the coating composition used according to the invention will contain a solvent for adjusting the viscosity of the preserving liquid. This solvent can be water and / or organic solvents. Organic solvents include conventional solvents for paints and in particular the lower alcohols such as methanol, ethanol, propanol and the butanols, since these are usually already by-products of Polycondensation reaction can be formed using the preferred starting materials (see above). Mixtures of solvents can of course also be used, for example mixtures of the by-products formed by the hydrolysis reaction (for example alcohols) and other (preferably volatile) solvents such as for example ethers, ketones, esters and (aliphatic or aromatic) hydrocarbons. The total solids content of the coating composition used according to the invention is generally 10 to 75, preferably 15 to 50 and particularly preferably 20 to 40 percent by weight.

Especially in the case where at least some of the non-hydrolyzable or non-hydrolyzing organic

Groups which are bonded to central atoms M, have reactive multiple bonds and / or other reactive groups (e.g. epoxy rings), the coating composition can also contain compounds which can react with such groups or groups in the course of a thermally or photochemically induced reaction. Thus, e.g. in the presence of non-hydrolyzable or non-hydrolyzing organic groups with carbon-carbon double or triple bond (such as (meth) acryloxyalkyl groups) prove to be expedient to add organic unsaturated compounds to the coating composition, which then combine with these unsaturated groups Can copolymerize polycondensates. Examples of such unsaturated organic compounds are styrene,

Acrylic acid, methacrylic acid or corresponding derivatives (eg esters, amides, nitriles) of the acids just mentioned. Such compounds can also be partially or perfluorinated. It is also possible to use compounds which have (per) fluorinated groups which, during the preparation of the coating composition or the polycondensates, contain non-hydrolyzable or non- hydrolyzing non-fluorinated groups react and thereby provide fluorinated groups (for example by reaction of SH or NH groups with hexafluoropropene oxide). It is also possible not to use the above organic compounds as such but in the form of surface modifiers which are located on nanoscale particles (for example filler particles). This makes it possible to incorporate nanoscale particles into the final coating in a homogeneous distribution. These particles make the coating more abrasion-resistant or scratch-resistant, for example, without impairing the transparency. With regard to the surface modification of nanoscale (ceramic) particles, reference can be made, for example, to W093 / 21127. Furthermore, for example, in the case of the presence of epoxy-containing organic groups on central atoms M, the

Coating liquid contain compounds that have a (catalytic)

Ring opening polymerization, e.g. Compounds containing hydroxyl and amine groups (e.g. phenols).

By adding the above-mentioned organic compounds, which can react with (preferably) functionalized organic groups present on the central atoms M of the polycondensates used according to the invention, it is possible to adapt the properties of the resulting coating to the specific circumstances (type, nature and intended use of the coating material, etc.).

In particular if the organic groups in the polycondensates of the coating composition used according to the invention include those with unsaturated carbon-carbon bonds, the coating composition preferably also contains a catalyst for the thermally and / or photochemically induced curing of the coating applied to the substrate Polycondensates. For example, a photopolymerization initiator can be added. The commercially available photoinitiators can be used. Examples include Irgacure (R) 184 (1-hydroxycyclohexylphenyl ketone), Irgacure ^(R) 500

(1-hydroxycyclohexylphenyl ketone, benzophenone) and other photo initiators of the Irgacure ^(R) type available from Ciba-Geigy _; Darocur ^(R) 1173, 1116, 1398, 1174 and 1020 (available from Merck), benzophenone, 2-chlorothioxanthone, 2-methylthioxanthone,

2-isopropylthioxanthone, benzoin, 4,4'-dimethoxybenzoin, benzoin ethyl ether, benzoin isopropyl ether, benzyl dimethyl ketal, 1,1, 1-trichloroacetophenone, diethoxyacetophenone and dibenzosuberone.

Suitable thermal initiators include organic peroxides in the form of diacyl peroxides, peroxydicarbonates, alkyl peresters, dialkyl peroxides, perketals, ketone peroxides and alkyl hydroperoxides. Specific examples of such thermal

Initiators are dibenzoyl peroxide, tert-butyl perbenzoate and azobisisobutyronitrile.

In the presence of epoxy rings, the usual ring opening catalysts can be used in the

Coating composition may be present, e.g. tertiary amines (e.g. imidazole and its derivatives).

The above initiators are added to the coating composition in conventional amounts. For example, a coating composition containing 30 to 50 weight percent solids may contain initiator in an amount of e.g. 0.5 to 2 percent by weight (based on the total amount) can be added.

The coating composition produced can either as such or after partial or almost complete removal of the solvent used or of the solvent formed during the reaction (for example the alcohols formed by hydrolysis of the alkoxides) and / or after the addition of a suitable solvent for the purpose

Lowering the viscosity can be brought into contact with the substrate to be coated. At the latest before the use of the coating composition, it is possible to add conventional additives such as e.g. Colorants (pigments, dyes, etc.), oxidation inhibitors, leveling agents, UV absorbers, fillers and the like.

The coating composition optionally (and preferably) provided with an initiator and optionally other additives is then brought into contact with the substrate. The coating composition can be applied in a conventional manner to the objects or materials to be coated. Although the resulting coatings usually adhere very well to the substrates, it may be advisable in certain cases to carry out a surface treatment (e.g. corona treatment, treatment with a primer) before coating. Common coating processes are e.g. Diving, flooding, pulling, pouring, spinning, spraying and painting.

After drying, if appropriate (preferably at room temperature or slightly elevated temperature), the coating composition can be cured thermally and / or by irradiation in a manner known per se, depending on the type or the presence of an initiator.

In the case of thermal curing, the curing temperatures are preferably at least 50 ° C., in particular at least 90 ° C. The maximum curing temperature is also determined by the thermal load capacity of the substrate to be coated is determined. Curing temperatures of 250 ° C. and in particular 180 ° C. are preferably not exceeded.

Claims

Patent claims

1. Using a coating composition that

Polycondensates based on one or more capable of hydrolytic polycondensation

Compounds of the elements M of the main groups III to V and the subgroups II to IV of the periodic table of the elements, wherein in these polycondensates at least a part of the central atoms M each have at least one organic group G which has at least 2 aliphatic carbon atoms, each of which has at least a fluorine atom is bound, either directly via one of the carbon atoms or via a connecting group A, for coating surfaces made of metal, plastics, optionally modified natural materials, ceramics, concrete, clay and / or glass.

2. Use according to claim 1 for the coating of structures and parts thereof; Locomotion and

Means of transport and parts thereof;

Work equipment, devices and machines for commercial or industrial purposes and research and parts thereof; Household items and work tools for household purposes, and parts thereof; Equipment, devices and aids for games, sports and leisure and parts thereof; as well as devices, aids and devices for medical purposes and the sick.

3. Use according to claim 1 or 2 as a water, oil, dust and / or dirt-repellent coating.

4. Use according to claim 1 or 2 as a coating to protect against graffiti.

5. Use according to claim 1 or 2 as an anti-reflective Coating.

6. Use according to claim 1 or 2 in separation problems, especially in molding processes.

7. Use according to claim 1 or 2 as a scratch-resistant and / or abrasion-resistant coating.

8. Use according to any one of claims 1 to 7, characterized in that the elements M made of Si, Al,

B, Sn, Ti, Zr, V and Zn, in particular Si, Al, Ti and Zr, or mixtures of these elements are selected.

9. Use according to any one of claims 1 to 8, characterized in that at least 0.1 and in particular at least 0.5% of the central atoms M have organic groups G.

10. Use according to any one of claims 1 to 9, characterized in that the organic groups G have at least 4 and preferably at least 5 aliphatic carbon atoms to which at least one and preferably at least two fluorine atoms are bonded.

11. Use according to any one of claims 1 to 10, characterized in that the groups G are fluorinated alkyl and / or alkenyl groups.

12. Use according to any one of claims 1 to 11, characterized in that the groups G comprise groups in which 2 to 30 fluorine atoms are bonded to aliphatic carbon atoms which are separated from M in the case of direct bond of the group G by at least 2 atoms .

13. Use according to any one of claims 1 to 12, characterized in that the connecting group A forms a chelate complex with M.

14. Use according to claim 13, characterized in that in the chelate complex M is coordinated via at least two atoms of group A selected from oxygen and nitrogen atoms.

15. Use according to any one of claims 1 to 14, characterized in that the polycondensates further have M groups on central atoms which have at least one functional group Z, which can participate in the formation of an organic network, preferably by polymerization.

16. Use according to claim 15, characterized in that the coating composition further contains at least one organic compound which is reactive with the groups Z and preferably one

Polymerization reaction can go with it.

17. Use according to any one of claims 15 and 16, characterized in that the grouping Z from carbon-carbon multiple bonds and

Epoxy rings is selected.

18. Use according to any one of claims 15 to 17, characterized in that the coating composition additionally contains one or more catalysts selected from thermal and photochemical polymerization catalysts and catalysts for epoxy ring opening polymerization.

19. Use according to any one of claims 1 to 18, characterized in that the

Coating composition further comprises a solvent or dispersant, preferably water and / or an organic solvent.