EP1658335A1

EP1658335A1 - Methods for producing functional materials for the production of low-energy stable coatings

Info

Publication number: EP1658335A1
Application number: EP04730474A
Authority: EP
Inventors: Gerhard Prof. Dr. Meyer
Original assignee: Individual
Current assignee: Individual
Priority date: 2003-05-02
Filing date: 2004-04-30
Publication date: 2006-05-24
Also published as: WO2004096914A1; DE10319954A1

Abstract

The invention relates to methods for producing novel functional materials used for the production of low-energy stable coatings and to corresponding functional materials.

Description

Process for the production of functional materials for the production of permanent low-energy coatings

The invention relates to methods for producing novel functional materials for the production of permanent low-energy coatings and corresponding functional materials.

In the literature and in a large number of patents, a variety of materials and processes for their manufacture are described, with which low-energy surfaces can be realized on different classes of materials such as metal, plastic, glass, ceramic and composite materials. The aim of these developments is to provide technical surfaces with special usage properties. These properties include such interesting functions as improved cleaning, non-stick effects and anti-adhesive effects. These effects are based essentially on the teflon-like effect of this coating, which is known from the frying pan. As described in the prior art, the functional materials currently used, in addition to their positive function, predominantly have problems with the permanent provision of this function for years, since the durability of the functional materials against chemical, thermal and mechanical influences is generally insufficient due to the different weak points of the individual systems is. The first attempts at low-energy modification of high-energy surfaces were based on the use of simple chemical substances to impregnate these surfaces. Materials with hydrophobic functional groups (methyl, phenyl, fluoroalkyl groups ...), which were mostly dissolved in a compatible solvent, were preferred. The application of these materials to the corresponding surfaces is easy, since common impregnation processes (spraying, wiping, etc.) can be used for this.

However, the durability of these coatings in daily use is problematic, since they are very thin monolayers (monolayer coatings) in the sub-nm range that can only withstand mechanical and chemical attacks for a very limited time.

For this reason, functional materials with thicker layers have now been realized, which accordingly promised a longer effectiveness.

Since essentially only thin layers can be applied with physical methods, functional materials for the chemical coating of substrates were preferably developed. For example, porous layer systems were developed that were impregnated in a second step with the chemicals that were also used for the monolayer coating. The advantage of this layer system is a thicker layer structure and thus a longer functionality. However, it is problematic that the framework material does not contribute to the functionality and, depending on the substrate used, represents a weak point. In addition, the impregnation material is not sufficiently protected against chemical attacks. For this reason, hybrid materials were made in the following period, for example using the sol-gel technique, which consist of a combination of the two materials. In the first work, steps of the synthesis of the matrix component and the addition of the functional component were carried out one after the other. When using, for example, fluorine-containing surfactants, the typical properties of this class of compounds resulted in so-called gradient layers - accumulating on the surface of liquid systems and only later forming micelles.

Their advantage is that the desired functionality is established by enriching the low-energy component on the surface of the layer and, at the same time, there is good layer adhesion due to the lack of the fluorine component on the adhesive surface. However, the problem is the only small thickness of the functional layer on the surface and thus the lack of durability of the function and its insufficient scratch resistance. If the function is lost, the substrate is then provided with a mostly weaker coating material on the surface.

In the case of this coating, however, simple impregnation is usually no longer sufficient, since the layer has to be compressed in order to improve its durability.

Even with complex chemical syntheses and complex process management, the previous materials are overwhelmed in practical use because their functionality and durability cannot be guaranteed for years.

Only through the development of a new class of substances is it possible to achieve a high level of functionality with a long-standing one Connect durability and thus open up new fields of application for this class of functional materials.

It is therefore the object of the invention to provide new materials and a method for their production which combine high functionality with long-term durability and thus open up new fields of application for this class of functional materials.

This object is achieved by a method according to claim 1, a functional material according to one of claims 17-19, a use according to claim 26, a functional layer according to claims 27-30 and an object according to claim 33.

Preferred developments of the invention result from claims 2-16, 21-22 and 31 and 32.

The subject of the invention are also appropriately coated objects, the use of the functional material according to the invention for coating and methods for coating with the functional material according to the invention.

Further advantages, special features and expedient further developments of the invention result from the subclaims.

The following are particularly cheap:

• The novel chemical synthesis of an inorganic-organic polymer system through the nanochemical combination of various types of organometallic synthetic precursors to a uniform fabric with a new property profile.

• The innovative production of mixed particulate / fibrillar nanoscale systems. • The in situ modification of these systems using reaction partners that are only accessible today through chemical nanotechnology (POSS, polyglycerols, nanoscale metal oxide particles, nanocomposite materials, polyaniline, etc.) and their reaction stages with fluoroalkylsilanes and their synergistic mixtures.

• The outstanding functionality (contact angle up to> 150 °).

• The outstanding mechanical stability despite the low curing temperature (<250 ° C).

• The excellent long-term temperature stability up to approx. 450 ° C.

Starting from base and / or acid catalyzed syntheses of nanoscale Si0 ₂ systems (based on simple or multifunctional silanes and other organometallic compounds), a material system was synthesized in which a mixed particulate / by varying the hydrolysis and condensation conditions Fibrillar base material was found, through the in situ modification of which a novel material with far improved functionality and durability could be developed.

In addition to the special synthesis route of the silicate system, which is accessible for in situ modification, the new materials used for this modification are of particular interest.

For the in situ surface modification of the Si0 ₂ base system, a reaction stage of POSS (Polyhedral Oligomeric Sil- sesquioxane), polyglycerol and FAS (fluoroalkylsilane) are used.

The modification includes in the partial coating of the particulate system as well as in the installation of the low-energy component in the fibrillary system.

Amazingly, the thermal curing of the coating system, so that the coating is still very well bonded to the substrate and the functional groups of the low-energy components are oriented away from the substrate and can thus develop their desired effect.

The mechanical properties of the hardened layers are comparable to that of pure glass and have a long-lasting low-energy function on their surface.

When the coating is modified using polyfunctional chemicals (including polyglycerols), the layer systems become more flexible and are suitable for coating flexible substrates.

As can be seen in Table 1 (influence of additives on the thermal stability of the functional coating), the functionality of the layer system after curing and after thermal loading can be positively influenced by adding additives according to the invention (POSS, PG) to a FAS-doped base system. This makes it possible to withstand permanent thermal, mechanical and chemical loads. Surprisingly, an optimal result can only be achieved by combining a suitable basic system with a special solvent, functional system and additive. Reference systems without additives no longer have sufficient functionality after a temperature load of 60 hours at 350 ° C. Thermoanalytical studies show that in the normal case the oxidative degradation of the carbon-fluorine compounds begins at a temperature which is about 80 ° C lower and proceeds with increased kinetics compared to the layer system according to the invention.

The incorporation of hyperbranched polyglycerols with a molecular weight of 2000 g / mol, this corresponds to 46 monomer units with 28 hydroxyl end groups, results in particularly flexible and temperature-stable layer systems with a diacetone alcohol system.

If you look at the atomic% ratios of some selected elements in the scanning electron microscope in Table 2 (comparison of the element distribution of substrate and coating), you can see that in this case (it is the coating of a float glass) by the diffusion of Sodium ions enrich the alkali ions in the layer system and simultaneously deplete them in the substrate. At the same time, there is a higher proportion of fluorine in the layer system. Both facts explain the improved functionality and connection of the layer system to the substrate through interdiffusion processes of alkali ions.

In particular, the basic systems already show great advantages over the prior art. Even without additional organic cross-linking components, this basic system has a lower brittleness and better connection to, for example, basic silicate systems, which leads to an increased chemical and mechanical strength of the overall system (substrate / coating). The following examples are intended to illustrate the invention without restricting it.

Examples

Example 1. Generally with advantages

Basic system: The basic system is formed by the modified synthesis and variable combination of two nanoscale subsystems. For this purpose, analogous to the Stöber synthesis, starting from metal alkoxides and their controlled hydrolysis and condensation reactions in a subsystem using basic catalysts, particulate nanoscale materials are synthesized, which are combined with the second system using acidic catalysts to form nanoscale, linear (fibrillar) Materials are led, connected. Due to this complex mixture and partly Surprisingly, in situ combination of these different polymer systems receives this basic system superior chemical properties compared to the individual systems, which can also be achieved by doping the individual systems with nanoscale materials, e.g. Silica sols cannot be reached alone. In the course of the synthesis, the control of the hydrolysis and parallel condensation steps is achieved by adding or removing heat, i.e. that the targeted support of endothermic or exothermic reaction steps is achieved by a defined temperature control per unit of time and that the reactants are metered in as the reaction progresses.

This also enables the controlled sequence of partial synthesis steps with basically free choice of reaction conditions and catalysts in one reaction batch per step. This results in a control of the molar mass distribution (NMR Q1-Q4), in particular of the silicate matrix, as well as a control of the particle size and surface as well as the loading of the particle surface and its readiness for further functionalization.

In addition, a specification of the compression and basic porosity in the matrix system can be obtained in the mixing system, which is significantly different from the results that can be achieved with individual systems.

Working system:

The function systems developed have the task of imparting the desired permanent functionality to the basic system - or of transferring a combination of functions to the matrix - in accordance with the requirements specification of the respective application.

This results in a variety of possible functional systems, which are briefly presented below:

Functional system with FAS (fluoroalkylsilane):

The addition of FAS mixtures, which in a suitable combination show synergetic effects with regard to the desired functional combination, to the basic system (mixing system) results in part. simultaneous in situ coating of the particle as well as the fibrillar polymer phases.

By specifically adjusting the ratio of coated polymer and particle phases, material systems are obtained that can be used to improve the durability, adapted to the respective substrate condition. In addition, the durability is improved by

Shielding endangered bonds of type -CC-, -CO-, -Si- O-, -Si-C- etc. by special FAS, which are suitable for steric shielding of endangered bonds and are have good thermal and chemical stability at an early stage.

Functional system with POSS (Polyoctahedral Oligomeric Silsesquioxane):

Through the controlled reaction of fluoroalkylsilanes with suitable types of silsesquioxane or through the use of already fluorinated POSS reagents, a surprising improvement in mechanical stability (scratch resistance) and thermal stability as well as an improvement in the permanent anti-adhesive properties (low-energy surface) is achieved.

Functional system with polyglycerin: The targeted incorporation of polyglycerols results in a significant improvement in the flexibility of the coating material than in the coating of flexible substrates (fabrics, paper, wood, plastic, metal foils, etc.).

Functional system with polyaniline:

The targeted incorporation of polyaniline improves the conductivity of the coating material. This results in their use for antistatic surfaces or conductive low-energy coatings.

Functional system with Ti0 ₂ nanos:

The targeted incorporation of Ti02 nanoparticles in the coating system results in an improvement in the self-cleaning function due to the photocatalytic effect of these nanomaterials.

Functional system with Ag nanos: The targeted incorporation of Ag nanoparticles into the coating system gives the coating active protection against microorganisms due to the killing of microorganisms by Ag ⁺ ions which are toxic to them.

Functional system with micrometer particles:

The targeted incorporation of micrometer particles of the metal oxides of the type Si0 ₂ , Zr0 ₂ , Al ₂ 0 ₃ etc. into the coating system leads to a significant improvement in the surface's ability to self-clean due to the formation of special surface structures of the coating material. By previously modifying the coarser micrometer particles with nanoscale particle clusters, this effect can be improved by creating a larger surface.

The z. T. hydrophobic low-energy character of the coating material used supports the operation of the structured, self-cleaning surface excellent.

Example 2. Procedure / working examples:

1) Synthesis of the matrix system or synthesis precursor A:

At room temperature, organic solvents such as monoalcohols (ethanol, methanol, isopropanol, amyl alcohol, xylene, toluene) are placed in a thermostatted double-jacket reaction vessel; Polyalcohols (ethylene glycol, butane-1, diol, diethylene glycol, polyethylene glycol, pentaerythrol) or ketones (dimethyl ketone, 4-hydroxy-4methyl-2-pentanone) and preferably ethanol or diacetone alcohol, water with a basic catalyst such as eg amines of the general form R-NH ₂ , R ₂ -NH, R ₃ - N, quaternary ammonium salts and hydroxides such as, for example, ethanol laminate, diethanolamine, triethanolamine, hydrazinium hydroxide, diisopropylamine, aminoethylethanolamine, LiOH, NaOH, KOH, Ba (OH) ₂ , Ca (OH) ₂ and in particular tetramethylammonium hydroxide solution, and silanes are introduced with rapid stirring of the type R ^{^} mSi (OR) 4-mm = 0-3, R = alkyl, aryl, amine, epoxy etc. such as SiC ₆ H ₁₅ Cl, SiC ₃ H ₈ Cl ₂ , SiC ₁₆ H ₂ o0 ₂ , SiC ₉ H ₂₂ θ3, SiC ₄ H ₁₂ 0 ₃ , SiCι ₃ H ₁₃ Cl, SiC ₉ Hι ₄ 0 ₃ etc. - preferably tetraethoxysilane) added. The solution is then conditioned at 50 ° C for several days and used as a coating solution or for further processing in the absence of turbidity.

2) Synthesis of the matrix system or synthesis precursor B:

10% by volume to 50% by volume of silanes of the type R "mSi (OR) 4 mm = 0-3, R = alkyl, aryl, amine, epoxy, etc., such as SiC ₆ Hι ₅ Cl, are placed in a thermostatted double-jacket reaction vessel. SiC ₃ H ₈ Cl ₂ , SiCι ₆ H ₂ o0 ₂ , SiC ₉ H ₂₂ θ _{3 /} SiC ₄ Hι ₂ 0 ₃ , SiCι ₃ H ₁₃ Cl, SiC ₉ Hι ₄ 0 ₃ etc. - preferably tetraethoxysilane) in a solvent such as e.g. monoalcohols (ethanol, methanol, isopropanol, amyl alcohol, xylene, toluene); polyalcohols (ethylene glycol, butane-1, 4-diol, diethylene glycol, polyethylene glycol, pentaerythrol) or ketones (dimethyl ketone, 4-hydroxy-4methyl-2 pentanone) and preferably ethanol or diacetone alcohol or water and thermostated to a temperature of 20 ° C to 45 ° C (preferably 25 ° C).

After about 30 minutes, within 20-40 minutes, 2-20% by volume of the aqueous solution of an acidic catalyst of the organic acid type, such as acetic acid, formic acid, malonic acid, malic acid, succinic acid, oxalic acid, glutaric acid, maleic acid, fumaric acid , Toluenesulfonic acid, trifluoroacetic acid, tartaric acid, citric acid etc. or one inorganic acid or acidic solution such. B. HN0 ₃ , H ₂ S04, H ₃ P0 ₄ , HC10 ₄ , H ₂ C0 ₃ , NH ₂ S0 ₃ H, NaHS0 ₄ , KH ₂ P0 ₄ etc. and preferably HCl added and stirred vigorously. A defined reduction in temperature to 15 ° C. to 5 ° C. (preferably 10 ° C.) takes place within a pre-hydrolysis lasting several hours. After a further holding time of approx. 1 hour, an additional reaction step is added.

3) Combined and / or accelerated synthesis of the matrix system or the preliminary synthesis stage:

In a modified variant, in addition to the mixture of the matrix systems and synthesis precursors described in 1) and 2), a combined synthesis of the matrix systems and synthesis precursors described in 1) and 2) is also possible by combining both processes in one reaction batch. Through ^' reaction-controlled metering of the reactants, as well as variation of the test conditions and adjustment of the reaction kinetics, the consequences of partial reactions with corresponding partial sales of the total sales are realized and customized mixing systems are set up.

The synthesis time can be shortened by metering in 2-10% of a 10-40% by mass metal oxide sol, in particular modified silica sols and / or aqueous acidic or alkaline metal oxide sols from the electrolysis of aqueous metal salts.

4) Preparation of the additional synthesis step

In an additional synthesis step, a reaction, for example of diSilanolisobutyl-POSS, with a suitable fluorine kylsilan, a fluorine-containing POSS precursor. This exists in an excess of the fluoroalkylsilane and is able to couple to the OH groups of the silicate matrix system.

In addition, this reaction mixture can be supplemented by adding reactive polyglycerols.

5) Introduction of the additional synthesis step in the matrix system

0.1 - 1% by volume of the additional synthesis step to the pre-hydrolyzate of the matrix system is added within 10 to 30 minutes.

As a result, the temperature in the reaction vessel rises sharply and must be cooled back to 5-15 ° C within approx. 60 minutes.

After a rest phase of 30 minutes, about 1-5% of an acidic aqueous solution with a pH of 2-6 (preferably 0.01N HCl with pH = 2) is metered in within 20-60 seconds.

After raising the temperature, the solution is stirred at RT for 1 day and is then ready for use.

The coating systems according to the invention can be used both as water-based systems (after replacing the alcohol with water - results in a transparent, stable coating system with good pot life) or as alcoholic coating systems (after removal of the water, for example by means of molecular sieves or via “evaporation” and “dilution”) be used. The alcoholic coating system can be used for several months before it turns into a clear gel11. 3. Examples of coatings:

a) A glass pane (or enamel) coated with a spin coater is then cured for several hours in a drying cabinet at a temperature of approx. 240 ° C.

The contact angle against water is determined to be 110 °. Even after a mechanical load of 1000 cycles of Tabe Abraser (roll F10), the measured stray light content of the coating is below 2%. Even after 300 cycles of Taber, the contact angle of the coating is still 92 °.

After a temperature load of 3 days at 400 ° C, the contact angle against water is still 87 °. The chemical resistance to acids and alkalis as well as the hydrolytic resistance of the coating is very good.

In the case of glass, enamel and ceramics, the durability of the coating can be further improved by previously polishing the substrate with cerium oxide and using a hot alkaline cleaner to form OH groups on the substrate surface.

b) The addition of polyglycerols in the synthesis significantly improves the elasticity of the layer system - the coating material is then suitable for flexible substrates (fabric,

Paper etc.) more suitable.

A linen fabric is coated with a squeegee and at approx.

Dried at 110 ° C. The contact angle against water is determined at approx. 152 ° - even small drops of water fall off due to their low weight.

This effect is still present after several full washes.

c) Non-silicatic plasma spray layers (oxidic, nitridic, carbidic and silicidic coatings) can be coated directly due to their adjustable porosity or after application of a thin Si0 ₂ film by silanization or by thermal spray pyrolysis of silanes (silico- ta process), possibly made coatable with subsequent alkaline activation. For example, a WCCrCNi hard coating coated with a spin coater with adjusted porosity was then cured for several hours in a drying cabinet at a temperature of approx. 240 ° C. The contact angle against water was determined to be 108 °.

d) Organic polymer surfaces (eg plastics, paints, etc.) can be made coatable by applying a thin SiO 2 film by silanizing or by thermal spray pyrolysis of silanes (silicicot process), possibly with subsequent alkaline activation. A coated aluminum rim pretreated as described above for the automotive sector was treated with the coating solution and then thermally conditioned. The contact angle of the very well adhering coating was determined to be 105 ° against water. Table 1: Influence of additives on the thermal stability of the functional coating

Table 2: Comparison of the element distribution of substrate and coating

Claims

Patent claims:

1. Process for producing a functional material for low-energy coatings with the following steps a) presenting a mixture of

• Water,

• Solvent selected from monoalcohols, polyalcohols or ketones, and • a pH catalyst selected from amines, ammonium salts and metal hydroxides

• a pH catalyst selected from organic carboxylic acids, inorganic. Mineral acids and acidic solutions of metal salts.

b) adding and stirring silanes of the general formula R' _m Si(0R) ₄ m, with m = 0-3, R selected from alkyl, aryl, amine, epoxy, optionally substituted.

2. Process for producing a functional material for low-energy coatings with the following steps: a) Presenting a mixture of

• Silanes of the general formula R' _m Si(OR) ₄ m, with m = 0-3, R selected from alkyl, aryl, amine, epoxy, optionally substituted

• a solvent selected from monoalcohols, polyalcohols or ketones, b) adding and stirring a pH catalyst selected from amines, ammonium salts and metal hydroxides in an aqueous solution. c) adding and stirring a pH catalyst selected from a pH catalyst selected from organic carboxylic acids, inorg. Mineral acids and acidic solutions of metal salts.

3. The method according to claim 2, so that 2-10% of a 10-40% metal oxide sol is added.

4. The method according to any one of claims 1 to 3, characterized in that step a) and / or the beginning of step b) takes place at a temperature between 20 ° and 40 ° C, preferably 25 ^° C.

5. The method according to claim 2, characterized in that step b) takes place after approx. 30 minutes and/or the addition after step b) takes place within 20-40 minutes and/or the aqueous solution in step b) is 10-30%. ig is.

6. The method according to claim 2, so that the reaction after addition and stirring after step b) takes several hours and / or the temperature is reduced to 15 to 5 ° C.

7. The method according to claim 2, characterized in that the solution presented in step a) is 10-50%.

8th. . Method according to claim 2, characterized in that the aqueous solution added in step a) has a pH of 8 to 11.

9. Method according to one of methods 1 to 8, characterized in that alcohols such as ethanol, methanol, isopropanol, amyl alcohol, xylene, toluene, ethylene glycol, butane-1-4-diol, diethylene glycol, polyethylene glycol, pentaerythrol or diacetone alcohol are used as solvents. or ketones, such as dimethyl ketone or 4-hydroxy-4-methyl-2-pentanone, preferably diacetone alcohol or ethanol, can be used.

10. The method according to any one of claims 1 to 9, characterized in that the silane used is selected from SiCgHisCl, S1C ₃ H ₈ CI ₂ , S1C _1S H ₂₀ O2, SιC ₉ H ₂₂ θ ₃ , S1C ₄ H ₁₂ O ₃ , SiC ₁₃ H ₁₃ Cl, SiC ₉ Hι ₄ 0 ₃ , CF ₃ CH ₂ CH ₂ Si (Me) ₃ , CF ₃ CH ₂ CH ₂ SiCl ₃ ,

CF ₃ (CF ) ₅ CH ₂ CH ₂ SiCl ₃ , CF ₃ (CF ₂ ) ₅ CH ₂ CH ₂ Si (OMe) 3, CF ₃ (CF ₂ ) ₇ CH ₂ CH ₂ SiCl ₃ , CF ₃ (CF ₂ ) ₇ CH ₂ CH ₂ Si (OMe) ₃ , CF ₃ (CF ₂ ) ₇ CH ₂ CH ₂ SiMeCl ₂ , CF ₃ (CF ₂ ) ₇ CH ₂ CH ₂ SiMe (OME) ₂ or tetraethoxysilane (TEOS).

11. The method according to any one of claims 1 to 10, characterized in that the pH catalyst is selected from amines, such as NH3, primary amines, secondary amines and tertiary amines, ammonium salts, such as quaternary ammonium salts, and metal hydroxides, preferably ethanolamine, diethanolamine, triethanolamine, hydrazinium hydrazide, tetramethylammonium hydroxide, diisopropyl lamine, aminoethylethanolamine, LiOH, NaOH, KOH, Ba(OH)2 or Ca(OH)2, especially tetramethylammonium hydroxide.

12. The method according to any one of claims 1 to 11, characterized in that the pH catalyst is selected as an aqueous solution of an acidic catalyst of the type of an organic acid such as acetic acid, formic acid, malonic acid, malic acid, succinic acid, oxalic acid,

Glutaric acid, maleic acid, fumaric acid, toluenesulfonic acid, trifluoroacetic acid, tartaric acid, citric acid, etc., or an inorganic acid or acidic solution of a salt, such as. B. HN03, H2S04, H3P04, HC104, H2C03, NH2S03H, NaHS04, KH2P04 etc. and preferably HC1.

13. The method according to any one of claims 1 to 12, characterized in that after the reaction after step b) has been completed, further compounds are added in a step c).

14. The method according to claim 12, characterized in that step c lasts 10 to 30 minutes and / or that the amount of further compound is 0.1 to 1% by volume, and / or that after completion of the addition of step c). The temperature is reduced to 5-15°C within approx. 60 minutes.

15. Process according to one of processes 12 or 14, characterized in that 1-5% acidic aqueous solution is metered in, if necessary within 20-60 seconds, and / or finally stirred at room temperature for 1 day.

16. Process according to one of processes 12 to 15, characterized in that the added compound is selected from:

Polyclycerols, preferably with a molecular weight of 2000g/mol; Fluoroalkylsilanes (FAS), preferably CF ₃ CH ₂ CH ₂ Si (Me) ₃ , CF ₃ CH ₂ CH ₂ SiCl ₃ , CF ₃ (CF ₂ ) _s CH ₂ CH ₂ SiCl ₃ , CF ₃ (CF ₂ ) ₅ CH ₂ CH ₂ Si (OMe) ₃ , CF ₃ (CF ₂ ) ₇ CH ₂ CH ₂ SiCl3, CF ₃ (CF ₂ ) ₇ CH ₂ CH ₂ Si(OMe) ₃ , CF ₃ (CF ₂ ) CH ₂ CH ₂ SiMeCl ₂ ,

CF ₃ (CF ₂ ) ₇ CH ₂ CH ₂ SiMe (OME) ₂ ; Polyoctahedral Oligomeric SilSesquioxane (POSS), such as disilanoisobutyl-POSS or isooctyl-POSS; a reaction product from POSS and FAS, optionally with polyglycerols; Trisfluoro (3) Cyclopentyl-POSS; nanoscale particles or nanoscale, linear polymers; Ti0 ₂ or Zr0 ₂ ; or a mixture of 2 or more of the aforementioned compounds.

17. The method according to one or more of claims 1 - 16 d.g., that a reaction-controlled addition of reactants takes place.

18. Functional material for low-energy coatings, producible by a method according to one of claims 1 to 16.

9. Functional material for low-energy coatings, producible by a method according to one of claims 1 to 11.

20. Functional material for low-energy coatings, producible by a method according to one of claims 12 to 16.

21. Functional material according to one of claims 17 to 19, characterized in that the solvent was replaced by water or that the water was removed.

22. Method for coating an object, so that a functional material according to claim 17 is applied and then thermally hardened, either

a) without pretreatment, preferably mechanically on the object, b) after pretreatment, preferably cleaning, polishing, silanization or silicota processes, preferably mechanically.

23. Method for coating an object that the functional material according to claim 18 is either

a) without pretreatment, preferably mechanically, or b) after a pretreatment, preferably cleaning, polishing, silanization or silicota process, preferably mechanically, applied to the object, and then

c) and then a further functional material according to claim 19 is applied and then hardened thermally or by radiation.

24. Object coated with a functional material according to one of claims 17 to 20.

25. Object coated by a method according to one of claims 21 or 22.

26. Object, according to one of claims 23 or 24, characterized in that it consists of glass, enamel, metal, ceramic, plastic, varnish, paper or fabric.

27. Use of a functional material according to one of the

Claims 17 to 20 for coating an object.

28. Functional layer made of sol-gel material, consisting of a) a matrix of silanes, optionally linked via organic bonds and/or optionally mixed with Ti0 ₂ or Zr0 ₂ ; b) filler selected from oxidic nanoparticles, nanoscale particles or nanoscale linear polymers; if applicable c)

Surfactants, mobile in the matrix and/or bound to the filler.

29. Functional layer made of sol-gel material, containing a) a matrix of silanes, optionally linked via organic bonds and/or optionally mixed with TiO ₂ or ZrO ₂ ; b) filler selected from oxidic nanoparticles, nanoscale particles or nanoscale linear polymers; optionally c) surfactants, mobile in the matrix and/or bound to the filler.

30. Functional layer made of sol-gel material, consisting of a) a matrix of silanes, optionally mixed with TiO2 or ZrO2; b) oxide particles, selected from oxidic nanoparticles, nanoscale particles or nanoscale linear polymers, preferably hydrophobically modified, in particular with POSS; and optionally c) polyglycerols.

31. Functional layer made of sol-gel material, containing a) a matrix of silanes, optionally mixed with TiO2 or ZrO2; b) oxide particles, selected from oxidic nanoparticles, nanoscale particles or nanoscale linear polymers, preferably hydrophobically modified, in particular with POSS; and optionally c) polyglycerols.

32. Functional layer according to one of claims 27 to 30, characterized in that the silane is selected from SiC _s H ₁₅ Cl, S1C3H8CI2, S1C ₁₆ H ₂₀ O ₂ , SιC ₉ H ₂₂ 0 ₃ , SιC ₄ H 0 ₃ , SiCi ₃ Hχ ₃ Cl, SiC ₉ H ₁₄ 0 ₃ , CF ₃ CH ₂ CH ₂ Si(Me) ₃ , CF ₃ CH ₂ CH ₂ SiCl ₃ ,

CF ₃ (CF ₂ ) 5CH ₂ CH ₂ SiCl3, CF ₃ (CF ₂ ) ₅ CH ₂ CH ₂ Si (OMe) ₃ , CF ₃ (CF ₂ ) ₇ CH ₂ CH ₂ SiCl ₃ , CF ₃ (CF ₂ ) ₇ CH ₂ CH ₂ Si (OMe) ₃ , CF ₃ (CF ₂ ) ₇ CH ₂ CH ₂ SiMeCl ₂ , CF ₃ (CF ₂ ) ₇ CH ₂ CH ₂ SiMe (OME) ₂ or tetraethoxysilane (TEOS).

33. Functional layer according to one of claims 27 to 31, so that a compound contained is selected from:

Polyclycerols, preferably with a molecular weight of 2000g/mol; Fluoroalkylsilanes (FAS), preferably CF ₃ CH ₂ CH ₂ Si(Me)3, CF3CH ₂ CH ₂ SiCl3, CF ₃ (CF ₂ ) _s CH ₂ CH ₂ SiCl ₃ ,

CF ₃ (CF ₂ ) ₅ CH ₂ CH ₂ Si (OMe) ₃ , CF ₃ (CF ₂ ) ₇ CH ₂ CH ₂ SiCl ₃ , CF ₃ (CF ₂ ) ₇ CH ₂ CH ₂ Si (OMe) ₃ , CF ₃ (CF ₂ ) ₇ CH ₂ CH ₂ SiMeCl ₂ , CF ₃ (CF ₂ ) ₇ CH ₂ CH ₂ SiMe (OME) ₂ ; Polyoctahedral Oligomeric SilSesquioxane (POSS), such as disilanoisobutyl-POSS or isooctyl-POSS; a reaction product from POSS and

FAS, optionally with polyglycerols; Trisfluoro (3) Cyclopentyl-POSS; nanoscale particles or nanoscale, linear polymers; Ti0 or Zr0 ; or a mixture of 2 or more of the aforementioned compounds.

34. Object coated with a functional layer according to one of claims 27 to 30.

35. Object according to claim 30, characterized in that it consists of glass, enamel, metal, ceramic, plastic, varnish, paper or fabric.