WO2007051806A1

WO2007051806A1 - Coating method and coated body

Info

Publication number: WO2007051806A1
Application number: PCT/EP2006/068001
Authority: WO
Inventors: Klaus-Dieter Vissing; Matthias Ott; Christopher DÖLLE; Gabriele Neese
Original assignee: Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V.
Priority date: 2005-10-31
Filing date: 2006-10-31
Publication date: 2007-05-10

Abstract

The invention relates to methods for coating a surface and to bodies that have been coated accordingly.

Description

Coating process and coated body

The invention relates to processes for coating a surface, mixtures suitable for these processes, coated bodies and the use of layers produced by the processes.

For adjusting and changing surface properties, coating methods have always been used. For example, plasma coatings can be used to apply thin coatings with layer thicknesses on an nm scale to solid surfaces. The surface properties obtainable by plasma polymerization include, for example, scratch protection, corrosion protection, UV protection, tarnish protection, adhesion-promoting properties, anti-adhesion properties and diffusion-barrier effects.

In plasma polymerization, a gaseous substance containing at least carbon, silicon and / or sulfur atoms is excited in a plasma. Excitation causes the molecules of the gaseous substance, in particular a plasma-polymerizable precursor (often also called monomer) in the gaseous or vapor state, fragmented by the bombardment with electrons and / or high-energy ions. This produces highly excited radical or ionic molecular fragments which react with one another in the gas space and are deposited on the surface to be coated. In this deposited layer, the electrical discharge of the plasma and its intense ion and electron bombardment continuously, so that triggered in the deposited layer further reactions and a high degree of linkage of the deposited molecules can be achieved. The height structure, the relief and the topography of the surface to be coated remain largely intact. This is often described as a replica of the surface structure.

A disadvantage of the plasma polymerization, but also to chemical vapor deposition (CVD) methods, including plasma-assisted CVD method, as are known in the prior art, is that it is not possible, molecules or particles from a certain weight of the Separate gas phase intact. The same applies to relatively sensitive functional components such as e.g. Dyes or generally organic compounds. While molecules and particles above a certain size are not suitable for use in a gas stream because of their weight, organic molecules and complex compounds are usually nonspecifically fragmented prior to incorporation into the coating. The incorporation of organic molecules is not possible because in the plasma process, the deposition of molecular fragments or the fragmentation of molecules takes place before the deposition.

A disadvantage of conventional plasma polymerization but also of chemical vapor deposition (CVD) processes including plasma-assisted CVD processes is that the molecules, radicals and fragments thereof that are deposited hardly reach geometrically narrow structures, since the gas exchange is greatly reduced here , A common rule of thumb is that, for example, a bore with an aspect ratio of 1: 3 (Opening diameter to depth) is still well coated by plasma polymerization. In the case of small structures, in particular on a μm scale, this ratio becomes worse; in the case of large structures, in particular in the dm to m scale, this ratio improves. The uses of plasma polymerization and CVD processes are therefore limited in practice to those surfaces which are substantially smooth and strong. Strongly roughened, porous or sponge-like substrates are not completely and error-free coated according to experience and consequently not reliably covered. This is especially true for undercuts. Corresponding disadvantages therefore apply when producing a corrosion protection coating for blasted surfaces, mechanically processed metal surfaces or cast materials. For example, it is proposed in DE 197 48 240 A1 to smooth out metal surfaces mechanically, chemically or electrochemically before carrying out a plasma polymerization process, in order to achieve a complete and as accurate as possible a coating and thus an effective corrosion protection. Experience has shown that only such solid surfaces can be completely covered with plasma polymer coatings which are essentially free of pores or smooth (average roughness R _a <350 nm). For larger roughness values, for example, restrictions with regard to the corrosion protection quality of an applied plasma-polymer coating must be accepted.

It was therefore an object of the invention to provide a coating method with which even rough and / or porous surfaces with a thin coating of preferably a maximum layer thickness of 5 .mu.m, preferably 2 .mu.m, more preferably 1 .mu.m can be reliably and completely covered. The coating produced by the method to be specified should at the same time make it possible to impart a variety of possible properties to a surface as desired. At the same time it was an object of the invention to achieve good adhesion of the coating produced on the surface to be coated and sufficient resistance to mechanical abrasion, so that, for example, removal by light wiping is not possible. Applied on metal surfaces should - A -

the coating may preferably provide improved corrosion protection. A further object of the invention was, additionally or alternatively, to impart to the coating a good sliding behavior of the coated surface and / or to enable as far as possible a free choice of further surface properties. The main object of the invention was to create the ability to produce coatings that are suitable for a variety of different tasks. According to the invention, a coating method is therefore specified in a first alternative, characterized by the steps:

a) applying a liquid layer of a mixture comprising a liquid and at least one further functional component, wherein the liquid consists of or comprises a substance which is crosslinkable by means of a plasma process and wherein the functional component is selected from the group consisting of

(i) marking substances, (ii) separating agents or lubricants,

(iii) surface-aiding agents, antimicrobials, fungicides, insecticides, acaricides, algicides, viricides, pesticides, (bi) catalysts, enzymes, hormones, proteins, nutrients, pheromones, medically active substances, organoleptically active substances, in particular olfaction and flavorings, emulsifiers, surfactants, growth factors such as growth regulators, in particular for bone growth, UV absorbers, photochromic and electrochromic substances, reflective substances, conductive substances, waxes, oils and lubricants, in particular metal soaps, organic soaps, sulfonated and sulfurized compounds, quaternary ammonium Compounds, phosphatides, amphoteric surfactants, betaines, fatty alcohols, propylene glycol monostearate, partial fatty acid esters of polyhydric alcohols with saturated fatty acids, polyoxyethylene esters of fatty acids, polyoxyethylene ethers of fatty acids and polymerization products of ethylene oxide and propylene oxide id or propylene glycol, solid particles having primary particle sizes of up to 200 nm, in particular silver or titanium oxide. Particles, conductive substances, corrosion inhibitors, dyes, luminescent dyes, in particular electroluminescent, cathodoluminescent, chemiluminescent, bioluminescent, thermoluminescent, sonoluminescent, fluorescent and / or phosphorescent luminescent dyes, organic or inorganic color pigments, magnetic substances, organic or inorganic solid particles having primary particle sizes of up to 5 μm , particularly preferably up to 1 micron, more preferably nanofillers, in particular metals such as silver, copper, nickel, aluminum, metal alloys, semiconductors, metal oxides, such as titanium, tin, indium, zinc or aluminum, non-metals, non-metal compounds, salts (eg salts organic and inorganic acids, metal salts) and liquid crystals such as copper, zinc sulfide, magnetite, silica, boron nitride, graphite, organic solids, preferably nanofillers with a variety of cross-linking points, carbon particles

b) crosslinking of the liquid layer, so that a solid layer is formed.

In this case, the mixture of the liquid layer is also part of the invention. This mixture comprises a substance which can be crosslinked by plasma polymer, but this does not mean that it also has to be crosslinked by a plasma polymer process. In this case, a substance in the context of this invention may be a pure substance or else a substance mixture. Particularly preferred plasma polymer crosslinkable substances are silicone oils, saturated hydrocarbons, fatty acids, triglycerides, mineral oils or polyethers.

The crosslinkable substance can also be called liquid precursor, since it serves as a precursor for a layer.

The crosslinking can also be effected by cleavage of a single bond (preferably CC, Si-C, Si-O). It is preferred that the crosslinkable substance to ≥ 50 wt .-%, preferably ≥ 70 wt .-%, more preferably ≥ 95 wt .-% not im Meaning of a classical polymerization and not in the sense of a classical polyreaction reacts.

A labeling substance (marker) is preferably selected from the group consisting of (I) dyes, (II) chromophores or other detectable groups which can be bound to the precursor, (IM) chromophores or other detectable groups which are soluble, dispersible or soluble in the liquid precursor (IV) magnetizable particles, (V) complexed nanoparticles, (VI) light-scattering substances, (VII) dye pigments and (VIII) phosphor pigments.

For the selection of the marking substance is z. B. the desired detector system crucial. As markers can be used:

1. Dyes (for example for monitoring with photodetectors), for example natural dyes such as alizarin or indigo or synthetic dyes such as azo, azine, anthraquinone, acridine, cyanine, oxazine, polymethine,

Thiazine or triarylmethane dyes.

2. Liquid precursors having chromophoric groups (for example azo, azoxy, imino and / or quinone groups), for example directly bonded to the precursor molecules or to molecules which are soluble in the precursor.

3. liquid precursors having functional groups or other functional units, for example directly bonded to the precursor molecules or to molecules which are soluble in the precursor or to solids which are suspended in the precursor or to molecules in

Liquids which are dispersed in the precursor. Possible functional groups are, for example:

olefinic groups, keto, imine or aldehyde groups, (eg for UV detectors) functional groups which show an intensive and very characteristic adsorption of infrared light (eg with triple bonds such as nitriles or thiocyanates, with cumulated double bonds such as isocyanates or carbonyl carboxylic acid derivatives), (eg for IR detectors) - functional units which are luminescent, in particular photoluminescent Have properties (eg bis (azomethine)), functional groups or units containing characteristic elements that provide a clear distinction from the substrate material and the environment and show characteristic signals in optical emission spectrography (eg for optical spectroscopy on a laser-induced micro-plasma (LIBS))

4. Magnetizable nanoparticles

5. complexed nanoparticles, such. In "polydimethylsiloxane-magnetite nanoparticle complexes and dispersions in polysiloxanes carrier fluids"; K.S. Wilson, J. D. Goff, J. S. Riffle, L. A. Harris, T. G. St Pierre, Polym. Adv. Technol. 2005; 16: 200-21 1.

6. Dispersions of solids or liquids that cause light scattering

7. Dye pigments

8. Phosphorus pigments

The person skilled in the art will preferably mark the liquid precursor (mixture or chemical compound of the marking substance with the liquid precursor) in such a way that the density of marking substance or on nanomarkers, or on the detectable functional groups in the case of a homogeneous (precursor) ) Liquid, is sufficient for easy identification and on the other hand, the curing of the liquid precursor is not disturbed. Care must also be taken when selecting the marking substance be that the application method (dipping, spraying, spin coating, etc.) is easily possible. For example, if necessary by suitable measures, agglomeration of the particles of the marking substance must be prevented. This is most easily possible because the marking substance, eg. As described in "Polydimethylsiloxane-magnetite nanoparticle complexes and dispersions in polysiloxanes carrier fluids"; KS Wilson, JDGoff, JS Riffle, LA Harris, TG St Pierre; Polym. Adv. Technol. 2005; 16: 200-211 liquid precursor is bound.

A marking substance as a functional component can also be a nanomarker. These may be very different substances (possibly in addition to those mentioned above), namely, for example, soluble dyes, pigments having a size of less than one micron (organic or inorganic), metal or metal oxide particles, metal clusters, semiconductor particles, photochromic or electrochromic substances, luminescent substances, salts, graphite, organic solids. An important criterion for their selection is that a simple (quantifiable) detection is possible, so that it can be seen whether the impression layer has been completely detached from the surface.

Examples of labeling substances / detection systems:

Marking substance: ZnS nanoparticles -ϊ detection by luminescence

Marking substance: Dye nanoparticles -ϊ detection by light microscope (see below)

Labeling substance Ag - nanoparticles - ^ detection by gray staining

Part of the invention is also to select the marking substance so that it optionally fulfills a further function, namely the improvement of the crosslinking of the liquid precursor, and thus it brings about improved chemical and mechanical properties of the resulting layer. A crosslinking nanomarker according to the invention can therefore also have functional groups that during the curing process of the liquid precursor it can build chemical bonds to it.

The mixture according to the invention can easily be selected by the person skilled in the art so that it is liquid under the particular desired crosslinking conditions. In this case, the functional components may be present as solids, liquids or even gases, so that the mixture may be a liquid mixture, a solution, a suspension, an emulsion, etc., depending on the form in which the functional components are contained.

In this context, a functional component is to be understood as meaning a specifically added compound or a particle (in contrast to impurities), which serve to impart one or more desired properties to the resulting layer by virtue of the method according to the invention. These properties can be different in nature, such as. B. imparting abrasion resistance to corrosion protection. The person skilled in the art already extracts corresponding properties from the proposed functional components; further properties can be generated by the skilled person depending on the desired application by the suitable choice of functional components.

At the same time, the person skilled in the art can easily choose the crosslinking conditions in step b) so that the functional constituents of the resulting layer can impart the desired properties. This means, in particular, that the functional components are not destroyed during crosslinking or are changed so that they can no longer fulfill their (desired) function. Activation of the functional components is also possible in step b). For a number of applications, however, it is desirable that the functional components also participate in the networking.

The crosslinking of the layer in step b) of the process according to the invention can be followed in a number of ways. One possibility is to use a plasma process, other possibilities are the use of Gamma radiation, electron beam, thermal or chemical crosslinking and / or crosslinking by UV radiation or other radiation. UV radiation is a particularly preferred variant. In particular, UV radiation can be provided for crosslinking the crosslinkable substance by a plasma.

According to the invention, the layer which is applied in step a) of the process according to the invention is preferably in a liquid state before crosslinking. For the purposes of this invention, a layer is liquid which is not more than 10 ⁶ Pa s in viscosity, measured in a rotational viscometer. The inventive mixture of the process according to the invention preferably comprises a crosslinkable substance which at 23 ° C. has a vapor pressure of <0.5 mbar (0.05 kPa), preferably <0.1 mbar (0.01 kPa), more preferably <0.01 mbar (0.001 kPa).

Preferred novel mixtures of a process according to the invention comprise a crosslinkable substance which has <50% by weight, preferably <30% by weight, particularly preferably <10% by weight, of molecules having a functional group selected from the group consisting of: acrylic or methacrylic acid esters, isocyanates, epoxides and alpha-olefins and / or selected from the group consisting of:

Acid esters, acid anhydrides, epoxides, C-C double bond-containing groups, and nitrogen-containing functional groups. Particular preference is given to mixtures according to the invention in which the crosslinkable substance comprises or consists of 50 to 100% by weight of silicone oil, saturated hydrocarbon, fatty acid, triglyceride, mineral oil or polyether.

A mixture according to the invention is particularly preferred for a process according to the invention in which the silicone oil, the saturated hydrocarbon, the fatty acid, the triglyceride, the mineral oil or the polyether comprise none of the functional groups selected from the group consisting of acrylic or methacrylic acid esters, isocyanates, Epoxides, alpha-olefins, acid esters, acid anhydrides, epoxides, CC-capped groups, and nitrogen-containing functional groups.

The mixtures according to the invention enable the process according to the invention in its first embodiment, but they are also excellently usable for the process according to the invention in its second embodiment.

According to the invention, a layer is initially applied to a solid surface (substrate) to be coated by applying a liquid to the substrate. Therefore, a liquid first layer is applied to the solid surface to be coated. The layer can then be fully or partially solidified. Preferably, however, it is at least liquid at the beginning of the implementation of step b).

An alternative method according to the invention (second variant) comprises the steps:

a) applying a first, liquid layer to a solid surface to be coated, wherein the first layer contains at least one crosslinkable substance, and

b) applying a second layer to the first layer by depositing and crosslinking a substance from a gaseous phase, wherein during the performance of step b) first crosslinking conditions and then deposition conditions are set.

This method according to the invention is particularly suitable for coating porous surfaces, wherein the desired surface properties of the coating can be produced by the layer deposited from the gas phase. However, it is also preferred for this variant of the invention that the mixtures according to the invention are used for the coating method according to the invention. In this way they create a variety of properties for the layer that can not be produced by vapor deposition alone.

Part of the invention is also a coating method of the first variant using a mixture according to the invention in which the crosslinking in step b) takes place as in the second variant of the inventive method, ie by applying a second layer to the first layer by depositing and crosslinking a substance a gas phase, and wherein during the implementation of step b) first crosslinking conditions and then deposition conditions are set.

For the process according to the invention, in which a second layer is deposited, which corresponds to both variants of the process according to the invention (that of the first process only in a preferred variant), the following applies:

The crosslinkable substance of the first, preferably liquid layer is preferably crosslinkable under the same conditions as the crosslinkable substance of the second layer. However, the crosslinkable substance of the first layer need not be crosslinked by the same method as the crosslinkable substance of the second layer, for example, it may also be crosslinked thermally, chemically and / or preferably by UV radiation. In particular, UV radiation may be provided for crosslinking the crosslinkable substance of the first layer by a plasma, as it is preferably used for generating crosslinking and deposition conditions (see below for details).

On the first, preferably liquid layer, a second layer is applied. The second layer is made by depositing a crosslinkable substance from the gas phase and crosslinking of the deposited substance. Most preferably, the second layer is prepared by plasma polymerization, CVD or plasma enhanced CVD. The crosslinking of the gas-phase deposited substance forming the second layer is preferably effected by applying a plasma to the second layer being formed.

In addition to the substance used to form the second layer, a further crosslinkable substance is used in the process according to the invention. This further crosslinkable substance is part of the first layer and promotes their crosslinking or forms the first layer. In particularly preferred embodiments of the process according to the invention, the crosslinkable substance of the first layer is crosslinkable under the conditions in which the substance used to form the second layer is crosslinked in step b). Particular preference is given to coatings produced in accordance with the invention in which, during or after carrying out step b), the first layer is partially or completely crosslinked with the second layer that forms.

To carry out step b), first crosslinking conditions are set and then deposition conditions. Under crosslinking conditions, strong crosslinking of the crosslinkable substance of the first layer takes place as compared to depositing the crosslinkable substance of the second layer; Under deposition conditions, the crosslinking of the crosslinkable substance of the first layer is small compared to the deposition of the crosslinkable substance of the second layer. Preferably:

in which ki _{v is} the rate constant of the crosslinking reaction of the crosslinkable substance of the first layer under crosslinking conditions,

k _{2 v is} the rate constant of the layer formation of the crosslinkable substance of the second layer under crosslinking conditions,

k _{1 a is} the rate constant of the crosslinking reaction of the crosslinkable substance of the first layer under deposition conditions, and

k _{2 a is} the rate constant of the layer formation of the crosslinkable substance of the second layer under deposition conditions.

The speed of the layer formation can be determined, for example, by means of layer thickness measurements, for example by means of ellipsometry, if appropriate on reference samples (for example silicon wafers).

The determination of the speed of the crosslinking reactions can be carried out, for example, after mechanical destruction of the layers by extraction of the still uncrosslinked or, if appropriate, only weakly crosslinked, fractions of the crosslinkable substance of the first layer in suitable solvents. The analysis of the extractable fractions can be carried out, for example, by means of matrix-assisted laser desorption ionization mass spectrometry (MALDI-TOF) or by means of gel permeation chromatography (GPC) or high-performance liquid chromatography (HPLC).

Particularly preferably, in step b) the surface to be coated, ie the first layer and the second layer, as far as it has already formed, is subjected to a plasma. Conveniently, in this case, the crosslinkable substances of the first and second layer can be crosslinked by the selected plasma. The plasma preferably contains O ₂ and / or H ₂ and / or N ₂ and / or a noble gas suitable for free radical formation and / or CO ₂ and / or N ₂ O and / or air, with an oxygen-containing plasma being particularly preferred. Particularly preferred is an oxygen and hydrogen-containing plasma. In order to set crosslinking conditions in the plasma, it is preferable in step b) to treat the surface to be coated with a plasma, wherein the plasma is suitable for the formation of radicals. In particular, a plasma is preferred which is based on O ₂ and / or H ₂ and / or CO ₂ and / or N ₂ O, an oxygen- and hydrogen-containing plasma being particularly preferred. For setting of crosslinking conditions it is further preferred to couple a high power into the plasma. The most favorable plasma composition and the energy input required in each case are selected by the person skilled in the art as a function of the reaction vessel used for the coating, the substrate to be coated and the respective crosslinkable substance of the first and second layer. For producing a corresponding plasma, the person skilled in the art can be guided, in particular, by DE 100 34 737 A1, and there in particular by paragraphs 12 to 15, 28 and the examples.

Under crosslinking conditions for crosslinking by means of plasma is therefore, in particular by applying the surface to be coated with a

Plasma as described above, a rapid crosslinking of the crosslinkable

Substance of the first layer achieved, while a deposition and crosslinking of the crosslinkable substance of the second layer does not take place or at least not significantly affect the rapid crosslinking of the crosslinkable substance of the first layer.

In the second variant or a preferred variant of the first variant of the process according to the invention, at least one crosslinking of the crosslinkable substance of the first layer takes place after the setting of crosslinking conditions. Subsequently, deposition conditions are set in step b). Under deposition conditions, a significant deposition and crosslinking of the crosslinkable substance of the second layer takes place on the at least partially crosslinked first layer. At this stage of step b), it is no longer the primary goal to achieve crosslinking of the crosslinkable substance of the first layer, but the deposition and crosslinking of the crosslinkable substance of the second layer, wherein an intimate connection of first and second layer is to be achieved , Deposition conditions according to the invention are particularly preferably prepared by carrying out a plasma polymerization or-optionally plasma-assisted-CVD. These methods, in particular the plasma polymerization, ensure an advantageously intimate connection of the first and second layers and make it possible to produce a particularly durable, dense and thin coating. In particular, the plasma polymerization also makes it possible to choose the surface properties of the coating produced according to the invention largely free, the choice can be made largely independent of the composition of the applied in step a) first layer. The combination of the properties of the layer made possible by the plasma-polymer method with those which are mediated by means of a mixture according to the invention make it possible to have a very large number of properties and thus also uses of the coating produced according to the invention.

A particular advantage of the use of plasma polymerization, CVD and plasma-assisted CVD is, moreover, that the process according to the invention results in an interaction with the first layer. This interaction means that the coating produced according to the invention in the second variant or a preferred variant of the first variant of the method according to the invention adheres to the substrate surface surprisingly well. The good, lasting adhesion of the first and second layer coating produced in step b) is based on the change between crosslinking and deposition conditions, so that not only an intimate connection between first and second layer is made, but the second layer and thus the entire Coating is firmly connected via a plurality of adhesive points with the substrate surface. Particularly preferred is the use of an atmospheric pressure or low pressure plasma polymerization process for applying the second layer, wherein the molar ratios in the second layer formed are further preferably (as measured on a reference substrate without prior implementation of step 1 to exclude any influence from the previous process step ): 1, 1: 1 <n (O): n (Si) <2.6: 1,

0.6: 1 <n (C): n (Si) <2.5: 1, and more preferably

1, 4: 1 <n (O): n (Si) <1, 9: 1,

1, 2: 1 <n (C): n (Si) <2.4: 1, in each case measured by ESCA (electron spectroscopy for chemical analysis) in atomic percent (without specifying the H content, since this is not the measurement is accessible).

It is known from DE 103 53 530 A1 to provide a thin liquid film with a plasma polymer layer in order to produce an easily removable coating for wafers. However, according to the invention exactly the opposite effect is achieved, namely to produce a particularly well-adherent coating. This is achieved by the special separation conditions described above.

Furthermore, DE 40 19 539 A1 discloses a method for producing a de-wetting surface, in which a 50 nm to 2 μm thick film of a silicone oil is applied to a solid surface to be de-netted and subsequently treated with an oxygen plasma in order to drain the liquid Prevent films from the surface. In this method, however, no plasma polymerization takes place, in particular no gaseous precursor is deposited under the action of a plasma on the liquid film; rather, a plasma-induced crosslinking of the silicone oil film takes place. From the oxygen-containing plasma selected in said published patent application no second layer is deposited. The method is also limited to the plasma-induced crosslinking of a silicone oil film and therefore does not allow a largely free choice of the surface properties of a correspondingly coated solid surface. Silicone oils are, by conventional definition, linear polydimethylsiloxanes (PDMS) of the general structure

or poly (methylphenylsiloxanes). They have a boiling point of over 200 ° C. Hexamethyldisiloxane (H ₃ C) ₃ Si-O-Si (CH ₃ ) ₃ having a boiling point of 99.5 ° C is the smallest oligomeric dimethylsiloxane but is not yet a silicone oil.

The first variant of the method according to the invention is not disclosed in DE 40 19 539 A1: The document gives no indication of the possibility of a functional component, d. H. by means of a mixture according to the invention of the layer to be produced to convey specifically desired properties. In particular, it is also not disclosed to make use of mixtures of lighter and more difficult to crosslink substances.

Incidentally, the coatings produced by the process according to DE 40 19 539 A1 have not proved to be sufficiently durable in practice; in particular, they can be easily mechanically wiped off or rubbed off the solid surface (substrate surface) to be coated.

In contrast to this conventional method in the second variant or a preferred variant of the first variant of the method according to the invention, a preferably plasma-polymeric coating is applied to a liquid film, wherein there is an interaction with the liquid film during the plasma-polymeric coating process. This interaction has the consequence that the liquid of the liquid film at least partially cross-linked and the entire coating, so preferably the plasma polymer layer (cover layer) and the original liquid layer applied in step a) has good adhesion to the substrate surface as a whole.

It is possible by all variants of the method according to the invention to completely or partially level roughnesses in the micron to nanometer scale, as well as to close smaller pores and undercuts. It is therefore possible for the first time to apply a reliably covering plasma-polymer or CVD coating to rough or porous substrate surfaces. As a result, a significantly improved corrosion protection on these surfaces is achieved with a thin-layer process, which can be further improved by the suitable choice of the functional constituent for the mixture according to the invention. The coatings produced according to the invention are therefore particularly suitable as anticorrosive coatings. Although DE 197 48 240 A1, as described at the outset, discloses a method for producing a corrosion protection coating, in which a plasma-polymer coating is applied to a substrate surface. However, to make this coating it was necessary to completely eliminate even small bumps so as not to jeopardize the formation of a continuous plasma polymer layer. The method according to the invention avoids this disadvantage and makes it possible, in particular, to provide surfaces having a mean roughness R _a ≥ 350 nm, in particular with a mean roughness value of up to 10 μm, particularly preferably from 380 nm to 4 μm, with a continuous, resistant, thin and well-adhering anti-corrosion coating Mistake. The method according to the invention therefore increases the quality of thin anticorrosive coatings and at the same time reduces their cost by eliminating the complete removal of even the smallest unevenness.

A broom-coating method according to the invention is preferred in which a second layer is applied to the first by depositing and crosslinking a substance from the gaseous phase, which is characterized in that the first, liquid layer of a substance having a vapor pressure of not more than 0.5 mbar at 23 ° C. Particular preference is given to an abovementioned method according to the invention, in which, when the first layer is applied in step a), a mixture is used comprising or consisting of (i) a solvent having a vapor pressure of more than 0.5 mbar at 23 ° C. and (ii ) at least one under the conditions of step b) liquid substance having a vapor pressure of not more than 0.5 mbar at 23 ° C.

The use of a substance with a low vapor pressure, preferably as the crosslinkable substance, has the advantage that during the coating process or during the crosslinking step, little of the substance to be crosslinked evaporates off. Accordingly, the combination with a solvent having a high vapor pressure which initially facilitates the deposition of the liquid layer but then can be removed from the mixture according to the invention by suitable measures is particularly preferred in this connection.

The thickness of the liquid layer in step a) at the beginning of the implementation of step b) is preferably ≦ 5 μm. It is further preferred that the layer <3 μm is again preferably <2 μm thick.

A preferred coating method according to the invention is also one in which the liquid layer is applied to a surface having a mean roughness of from 350 nm to 10 μm roughness. Only through the method according to the invention, the effective and reliable coating of such surfaces is possible, so that only a few defects arise.

A component of the invention is also the process according to the invention, which is carried out in such a way that, when carrying out step b), a liquid depot of the liquid applied first is formed.

The coating produced according to the process variant 1 or preferred method of variant 2 according to the invention may contain, in addition to the crosslinkable substance, further substances (solids, liquids, gases). contained in an established depot and released again via release properties of the second layer:

If the coating is applied to a rough substrate surface, it is possible, with suitable process control, to retain uncrosslinked (ie liquid) material in the valleys of the rough surface and to achieve complete crosslinking and bonding to the surface on the tips. In this embodiment of the method according to the invention, therefore, only a partial cross-linking of the liquid layer in step a) takes place, but a large number of adhesion points of the preferably plasma-polymerized or CVD layer applied in step b), optionally over components of the process described in step a). liquid layer formed bridges, are created on the substrate surface. In this way, a liquid can be reliably deposited on a surface; Depots or reservoirs are created as it were.

In one embodiment of the process according to the invention, in step a) a mixture with at least one crosslinkable and at least one among the

Conditions of step b) used non-crosslinkable substance. While the crosslinkable part of the mixture is crosslinked in step b) and preferably provides adhesion to the substrate surface, the non-crosslinkable part remains

Mixture within the crosslinked matrix produced in step b) continue to be substantially uncrosslinked or obtained as a liquid. It can only be one

Part of the crosslinkable substance in step b) are crosslinked.

The preferably plasma-polymer or CVD layer applied in step b) is preferably prepared in such a way that a gradual release of the deposited and largely unchanged liquid (even if the molecular weight distribution can widen significantly, for example) passes through the layer to the outer surface of the layer Coating can be done. In this way, a gradual, continuous delivery of very small amounts of liquid can be achieved. This is useful, for example, to influence the sliding properties of surfaces. One possible field of application is the improvement of the flow behavior of thixotropic substances Liquids or improving the sliding of rubber or silicone materials. Particularly preferably, a depot of such a coating produced or preparable according to the invention contains a surface-assisting substance such as, for example, an oil, in particular a silicone oil, and particularly preferably a polydimethylsiloxane (PDMS) having a kinematic viscosity at 25 ° C. of about 40-60 mm ² / s and a molecular weight of 2800-3200 g / mol. Suitable substances which assist in the sliding of surfaces are specified in particular in DE 103 53 530 A1, the disclosure of which is referred to for the purposes of the present invention (see more below).

The substance contained in the depot, which can be released to the outside through the second layer produced in step b) and preferably remains largely unchanged when step b) is carried out, is preferably selected from the group consisting of substances which assist in the sliding of surfaces (cf. top), antimicrobial agents, fungicides, insecticides, acaricides, algicides, viricides, pesticides, (bi) catalysts, enzymes, hormones, proteins, nutrients, pheromones, medically active substances, organoleptically active substances, in particular fragrances and flavorings, emulsifiers , Surfactants, growth factors such as growth regulators, in particular for bone growth, UV absorbers, photochromic and electrochromic substances, reflective substances, conductive substances, waxes, oils and lubricants, in particular metal soaps, organic soaps, sulfonated and sulfurized compounds, quaternary ammonium compounds, phosphatide en, amphoteric surfactants, betaines, fatty alcohols, propylene glycol monostearate, fatty acid esters of polyhydric alcohols with saturated fatty acids, polyoxyethylene esters of fatty acids, polyoxyethylene ethers of fatty acids and polymerization products of ethylene oxide and propylene oxide or propylene glycol, solid particles having primary particle sizes at most about twice the later deposited average layer thickness of the first Layer (in step a) applied layer), particularly preferably up to 200 nm, in particular silver or titanium oxide particles. The coating is expediently such that the substance or substances contained in the depot can be released to the outside through the second layer produced in step b). In particular, it is preferred if the second layer is porous, microporous and / or permitting solid phase diffusion. For the purposes of this invention, a coating is porous if it contains channels that allow water to flow through the channels directly from one to the opposite side of the coating. Microporous is a coating according to this invention, when the channels have a diameter of less than 2 nm.

A porous and a microporous layer according to the invention can be produced by introducing corresponding pores and / or micropores into the layer produced in step b) when carrying out step b). Preferably, for this purpose, a region of the surface to be coated is not treated under deposition and / or crosslinking conditions-for example, by covering it with a mask-so that a pore or micropore remains at the untreated point. Furthermore, it is preferred to first produce a pore-free second layer (covering layer) in step b), and to produce the desired porosity after its preparation only by a mechanical and / or chemical activation. This is preferably done directly before use, so that the release can take place at the desired time. Mechanical activation preferably takes place via pressure (for example by rubbing), which easily tears the cover layer over the depot, so that a pore / micropore is formed. This can be chemically supported, for example, by the activation is carried out in interaction with water, when the deposited substance is water-soluble. Pores and micropores containing coatings of the invention are particularly suitable for releasing substances having a molecular weight from 180 g / mol, in particular for releasing pharmaceutical agents. However, particularly preferred according to the invention are non-porous coatings which permit solid-phase diffusion of the release substance contained in a depot through the coating. Such coatings allow a substance to be released to be released evenly over a long period of time without the coating containing voids, such as channels or pores, which allow liquids to pass directly through the coating. In preferred embodiments, pore-free coatings according to the invention which enable solid-phase diffusion are therefore especially adapted to realize the advantages of a corrosion-resistant coating according to the invention simultaneously with the advantages of a coating according to the invention which releases a substance or a substance mixture.

The coating produced or preparable according to the invention can, as described above, contain liquid-filled depots; However, the liquid layer applied in step a) can also be crosslinked to such an extent - in particular in step b) - that it no longer contains any depots. Nevertheless, the coating produced or producible according to the invention can also contain the substances which have been described above as depots in the present case. In the absence of depots, these substances are embedded in the coating. The embedded substances may in preferred embodiments be released from the coating by solid phase diffusion. In other preferred embodiments, the embedded substances are fixed in the coating produced or producible according to the invention and are not or only to a negligible extent released from the coating by solid-phase diffusion.

Appropriately, substances are fixed in a thin layer on a surface by means of the invention by being embedded in the layer a). These embedded substances are particularly preferably UV absorbers, photochromic and electrochromic substances, reflective and partially reflecting substances, conductive substances, corrosion inhibitors, dyes, luminescent dyes, in particular electroluminescent, cathodoluminescent, chemiluminescent, bioluminescent, thermoluminescent, sonoluminescent, fluorescent and / or phosphorescent luminescent dyes, organic or inorganic color pigments, magnetic substances, organic or inorganic solid particles having primary particle sizes of up to 5 .mu.m, more preferably of up to 1 .mu.m, particularly preferably nanofillers , These include, for example, metals, metal alloys, semiconductors, metal oxides, nonmetals, nonmetal compounds, salts (eg salts of organic and inorganic acids, metal salts) and liquid crystals. Examples include: copper, zinc sulfide, magnetite, zinc oxide, alumina, silica, boron nitride, graphite, organic solids.

The depots formed can be laterally narrow areas, so that in the finished coating individual on all sides by cross-linked material bounded pockets uncrosslinked material present. Additionally or alternatively, the depots can also be formed so that a sponge-like network of interconnected chambers uncrosslinked material are made as a depot. Furthermore, the method according to the invention, again in addition or as an alternative to the aforementioned variants, can also be carried out in such a way that no chamber-like depots of uncrosslinked material are formed, but that individual molecules of uncrosslinked material are incorporated in the formed homogeneous coating as in a swollen polymer. The desired type of depot formation can be adjusted by the choice of a suitable roughness of the substrate surface, the choice of suitable well crosslinkable and less well crosslinkable components of the liquid in step a) and their respective concentration, the choice of suitable process parameters during the plasma polymerization, in particular Choice of suitable precursor and by the choice of a suitable power input during plasma polymerization. The arrangement of the pockets and depots can also be adjusted by the choice of suitable process conditions during step b); In particular, by UV radiation (for example via UV Eximer lamps), electron beams or by thermal and / or chemical Curing local adhesion points to the surface to be coated and / or the base layer formed and lying between the adhesion points lying areas to form depots.

A lubricious surface can easily be verified by a comparative hand experiment in that a sliding body is guided over the surface produced according to the invention as well as a surface produced according to the prior art and an improved sliding effect is determined. Of course, this hand experiment can also be transferred to a measuring apparatus in which a defined sliding body, which may need to be replaced after each measurement, is moved over a surface to be examined, for example, the force required to start or maintain a defined movement of this

Slipper is required, is measured. Furthermore, the quality of the layer produced by the method according to the invention can be checked by the fact that the resistance of the coating to manual rubbing must be ensured with a soft paper towel soaked with suitable solvents (which typically dissolve the liquid used).

The adhesion of the coating produced according to the invention can be tested by means of rubbing, drawing and / or immersion tests, in particular by a peel test and a cross-cut test. A non-stick coating will be removed from the substrate for more than 65% of the area in a cross-hatch test according to DIN EN ISO 2409, which corresponds to a rating of GT5, while an adherent coating remains at least 35% of the area on the substrate and thus at least get a rating GT4. A simple peel test can be carried out by the rapid removal of a strip of "budget" tape from TESA. Again, the non-adherent coating is completely peeled off, while the adherent remains at least partially on the substrate. In addition, a coating should be referred to as non-sticky, if it can be wiped with a dry soft paper towel with moderate contact pressure by hand. The liquid layer present in step a) may consist of or contain: saturated or unsaturated hydrocarbons, halogenated hydrocarbons, alcohols, ethers, esters, ketones, organic acids or acid anhydrides, amines, amides, nitriles, thiols, urethanes, siloxanes, carbohydrates , Substances are assigned to several of the above classes, or a mixture of two or more of the substances mentioned. Suitable substances are taken by the person skilled in the art, in particular DE 103 53 530 A1, the disclosure content of which is referred to insofar for the purposes of the present invention. Although according to this disclosure, the liquid precursors disclosed therein serve to produce a non-adhesive coating, it has been found that by applying the method according to the invention well-adhering coatings can be produced, in particular anticorrosive coatings and coatings with improved sliding properties.

It is particularly preferred if the liquid layer present in step a) has a low vapor pressure. If the required maximum vapor pressure for the desired groups of substances can normally only be achieved at a molecular weight at which the substances are present as solids, for example crystalline, it is also possible to resort to a homogeneous mixture of chemically non-uniform molecular chains, for example a broad molecular weight distribution ( in particular MWD (M _w / M _n )> 3) or a low regio-, or stereoregularity or a high proportion of short-chain branching or copolymers.

Preferably, the first layer contains a substance having a vapor pressure at 23 ° C of not more than 0.5 mbar, preferably not more than 0.05 mbar. Substances with such low vapor pressures are advantageously suitable not to evaporate even during a low-pressure plasma polymerization, but to remain as a layer on the substrate surface.

The first layer may contain the substance having the described preferred vapor pressure neat or dissolved in a vaporizable solvent. The solvent has a vapor pressure at 23 ° C of more than 0.5 mbar, particularly preferably more than 5 mbar. Such solvents can be removed particularly well before or during the performance of step b) by evaporation.

Furthermore, it may be useful to subject the material to be coated beforehand to an intensive cleaning (if necessary plasma cleaning), so that a good wetting is made possible, as well as the possibility of a connection in the subsequent crosslinking reaction. Additionally or alternatively, however, the surface can also be blasted, machined mechanically (in particular by machining, in particular by milling, sawing, grinding, etc.) or chemically (in particular electrochemically). Cleaning with liquid media is also possible. The cleaning can also be combined with the order of the first layer, if this seems technically and economically reasonable.

The first layer provided in step a) contains a crosslinkable substance. Crosslinkable in the context of this invention are substances which crosslink, for example under the action of a plasma or under the action of radiation such as electron beams, UV or gamma radiation. Crosslinking takes place at least when the crosslinking density q _{0 is} greater than twice the decomposition density p ₀ (see, for example, A. Henglein et al., Introduction to Radiation Chemistry, Verlag Chemie, Weinheim 1969, pages 330ff).

The first layer may be applied to the substrate surface by dipping, spraying, stamping, rubbing, steaming, or otherwise. The average layer thickness of the first layer before carrying out step b) is preferably up to 5000 nm and also preferably at least 1 nm. Particularly preferred is an average layer thickness of 10 nm to 200 nm, wherein it is further preferred if the average layer thickness of in Step a) applied liquid immediately before performing step b) is ten times and in particular half of the R ₃ - value of the surface to be coated. The crosslinking process preferably by means of the plasma technique in step b) is carried out so that a sufficient adhesion to the material to be coated has been produced. In this case, the person skilled in the art will make sure that the layer thickness of the first layer of the exposure time of the crosslinked effect, such as, for example, radiation etc., in particular of the plasma, is appropriate. It is preferable to work with thin coatings of the first layer in order to achieve the most uniform crosslinking possible in the depth and to be system-compatible with the subsequent plasma polymer coating. This means that the advantage of the plasma polymerization or CVD methods, namely to produce layers on an nm scale, should not be nullified by over-application of the liquid layer. Furthermore, high average liquid film thicknesses (> 2 μm) on a rough surface (eg blasted surface) would lead to significant

Liquid film thickness differences occur, so that possibly a very long exposure time of the subsequent plasma polymerization step is necessary. Ultimately, it would also cause z. B. would be delivered to high levels of lubricant.

As the crosslinkable substance of the second layer, a substance which can be deposited by plasma polymerization, CVD and / or plasma-assisted CVD is preferably used. Particularly preferred are silicone compounds, fluorinated silicone compounds, hydrocarbons or at least partially fluorinated hydrocarbons, with siloxanes being particularly preferred, and within the siloxanes in particular hexamethyldisiloxane (HMDSO) and octamethyltrisiloxane.

The transition from crosslinking to deposition conditions is preferably gradual. During the execution of step b), the proportion of gases which are not suitable for layer deposition and optionally also the amount of CO ₂ in the gas supply is preferably gradually reduced, more preferably by reducing the addition of oxygen (for example in the form of O ₂ , CO ₂ and / or N ₂ O) and / or hydrogen. Also, it is preferable while performing Step b) to increase the supply of the crosslinkable substance of the second layer. It is likewise preferred to reduce the power coupled into the plasma during the performance of step b).

Following the production of the coating according to the invention, the coating can be further processed to produce particular desired properties, in particular surface properties. In particular, the coating can be hydrophobicized or hydrophilized and / or oleophobed and / or provided with an easy-to-clean surface.

According to the invention, a body is additionally provided which is provided with a coating that can be produced or produced by a method according to the invention in one of the ways described above. Such a body realizes the advantages associated with the method according to the invention. In particular, such a body may be provided with an anticorrosive coating and / or with a lubricious coating, as described above, or it may comprise an impression layer which images the surface and is intended to be separated again from the original coated surface. According to the invention, such a layer can be marked, so that the success of the separation process after separation can be determined both on the originally coated surface and on the basis of the coating itself.

It is particularly preferred if the coating produced or producible according to the invention is applied to an oxidation- and / or corrosion-susceptible body, in particular a liquid and / or gas line, in particular a water pipe, a radiator, a fitting, a cooling fin, a liquid and / or gas pump, a shaft, a rim, a cladding for aircraft, ships, automobiles, rail vehicles and in general an iron, aluminum, lead and / or copper-containing surface, such as cast iron, steel, brass or bronze. The coating according to the invention is such in preferred embodiments dense, that the release rate of heavy metal ions from coated heavy metal-containing components, in particular from coated brass components (for example in faucets), compared to corresponding uncoated components is significantly reduced.

It is likewise preferred if the coating produced or producible according to the invention is applied to a surface subject to friction or endangered by adhesion of undesired substances, for example a vessel for receiving viscous, pasty or thixotropic substances, in particular for foods such as mustard, honey, ketchup and / or mayonnaise, such as a bottle of glass or plastic, and a container for paints, ointments, creams, soaps, personal care products, but also friction surfaces of prostheses, syringes, guide rails, bearings and baking trays, and generally surfaces that allow easy sliding.

Furthermore, it is preferred to apply the coating produced or producible according to the invention to a surface through which the smallest amounts of substance are to be released over a long period of time. Such coatings preferably have depots of the type described above. Here are mentioned in particular its applications in the field of medical technology. For example, the deposition of growth-promoting substances and / or antibiotics on implants, such. Bone nails, stents, trauma products in general and internal fixation products. In addition, X-ray contrast agents such as barium sulfate can be incorporated. Finally, the production of antibacterial layers is possible. It is also possible to prepare layers based on DE 103 53 756 with non-cytotoxic properties.

According to the invention, the coating material which has been produced by the method described above is used to produce:

Partially reflecting surfaces in different wavelength ranges (eg: IR, visible range, heat radiation); Surface coatings more porous Substrates (porous materials, such as sintered magnets, can not be well protected by a conventional plasma polymer coating because the intermediate areas are not reached, and better access can be achieved by using liquid precursors.); Surfaces with improved drainage behavior for thixotropic substances; Production / improvement of sliding and separating properties of surfaces; Odor-emitting textiles; Surfaces with improved UV protection properties; active corrosion protection coatings; passive anticorrosive coatings, in particular for materials with microstructured or nanostructured (- porous) surfaces; Surfaces with improved plasma polymer diffusion barrier properties to liquids, gases and vapors, especially for materials with microstructured or nanostructured (-porous) surfaces; Protective coatings against chemicals (eg detergents, solvents, acids, bases) esp. For materials with microporous or nanoporous surfaces; Surfaces with improved abrasion and scratch resistance properties through the incorporation of particles; Coatings that provide a continuous release of functional substances for a long time: eg (bio) catalysts, enzymes, hormones, proteins, nutrients, pheromones, emulsifiers or surfactants, antimicrobials, medically active substances (active substances), growth substances for Bone growth, odor and fragrance, pesticides, lubricants, edible oils / waxes; improved surface properties of plasma polymer coatings by micro- or nanostructuring with the aid of appropriate solid particles: both to reduce the surface energy or the adhesive properties (eg for improved easy-to-clean properties, release properties or the so-called lotus effect) as well to increase the surface energy, or the adhesive properties (eg to improve the adhesion of adhesives, metallizations, coatings or printing inks, as well as the better wetting by liquids); active protection of surfaces against the attachment of biological pests such as microorganisms, algae, plants and microorganisms; Components with changed haptics; electrostatic properties of components made of non-conductors such as plastics; Surfaces with a reduced tendency to build up dust; novel decorative effects.

Surfaces coated in accordance with the invention, which enable a release of functional substances, can be used both in air, in liquid media and (if appropriate) in vivo. A large number of applications are given for the use of these released substances, for example in the field of chemical or biotechnological Pharmaceutical production, analytics, agriculture, forestry, the production of consumer or capital goods, human or veterinary medicine (medical technology, pharmacology), food industry, the preservation of protected goods (works of art, archaeological finds, building fabric). In this case, the coating according to the invention can be applied either directly to the desired objects or to carrier materials up to films (optionally coated as a web product) or powder.

A component of the invention is also the use of a mixture comprising a liquid and at least one further functional constituent, wherein the liquid consists of or comprises a substance which can be crosslinked by means of a plasma process, for introducing the functional constituent into a layer separating from the gas phase , The functional component preferably belongs to one of the substance groups or compounds described above.

This use makes it possible, as already indicated above, to impart to the deposited plasma polymer layer a multiplicity of desired properties which would not be achievable or could only be achieved with poorer deposition from the gas phase. This is due in particular to the fact that the functional components can be introduced into the layer in the first place by the method according to the invention or remain largely undisturbed. The use according to the invention is particularly preferred in connection with the deposition from the gas phase in a plasma polymerization process, a CVD process or a plasma-assisted CVD process.

Finally, by the use of the invention an extension of the scope of plasma polymer coatings such. B. by increasing the abrasion resistance, improved surface properties by a micro- or nanostructuring with the help of appropriate solid particles possible. It is possible to impart both an additional reduction in surface energy (dehasive properties) and adhesive properties of the deposited layer. So z. B. improved easy to clean properties, release properties or the so-called lotus effect as well as marked layers possible. On the other hand, it is also possible-if desired-to increase the surface energy in a targeted manner or to produce adhesive properties (for example for improving the adhesion of adhesives, metallizations, coatings or printing inks as well as for better wetting by liquids).

A component of the invention is also a use according to the invention, wherein the functional component is a marking substance for marking a separating layer. The release layer can be produced by a method according to the invention. As already indicated above, by marking layers which are intended to be separated again from the coated surface, the separation process or the separation success can be optimally understood.

Ultimately, a wide variety of uses for the producible or prepared in the process according to the invention coatings is possible. Of course, these uses are part of the invention. By way of example, the following uses are enumerated: Use of the coating which can be prepared or produced by the process according to the invention to improve the process of thixotropic substances,

as active corrosion protection coating,

as passive corrosion protection coating. especially for materials with microstructured or nanostructured (-porous) surfaces,

as diffusion barrier coatings against liquids, gases and vapors, in particular for materials with microstructured or nanostructured (-porous) surfaces,

as protective coatings against chemicals. (for example, cleaning agents, solvents, acids, bases) especially for materials with microporous or nanoporous surfaces,

as scratch-resistant coating,

as active protection of surfaces against the attachment of biological pests such as microorganisms, algae, plants and

Microorganisms,

for adjusting the electrostatic properties of components made of non-conductors such as plastics,

as a protective coating against UV light,

to prevent or reduce the visibility of a fingerprint on a surface,

for the production / improvement of release properties of a surface,

for the coating of porous substrates (porous materials, such as sintered magnets can by a conventional plasma polymer coating are not well protected because existing wells are not sufficiently covered by the deposited layer. By using liquid precursors, a better protection is possible here),

as teilreflektierede surface, in different wavelength ranges (for example: IR, visible range, heat radiation),

to reduce dust adhesion,

for coating textiles,

for generating optical effects,

for providing anchor groups for immobilization or immobilization of functional substances, such as

Oligonucleotides (eg for medical diagnostics, water and environmental monitoring and / or food analysis), (bio-) catalysts, enzymes, hormones, proteins, nutrients, pheromones, emulsifiers or surfactants, antimicrobials, medically active substances (active substances) , Growth substances for

Bone growth, odor and fragrance, pesticides, lubricants, edible oils / waxes. This fixation or immobilization can be carried out both directly and via adhesion promoters such as spacer molecules. It can be permanent as well as temporary.

for improving the oxidation and / or corrosion resistance of a surface,

for producing a continuous delivery of functional substances. e.g. (Bio) catalysts, enzymes, hormones, proteins, nutrients, pheromones, emulsifiers or surfactants, antimicrobial substances, medically active substances (active substances), growth substances for

Bone growth, odor and fragrance, pesticides, lubricants, edible oils / waxes. The coated support materials can be used both in air, in liquid media and (if appropriate) in vivo. For the use of these released substances a variety of applications are given, for example in the field of chemical, biotechnological or pharmaceutical production

Analytics, agriculture or forestry, the production of consumer or capital goods, human or veterinary medicine (medical technology, pharmacology), food industry, the preservation of protected goods (works of art, archaeological finds, building fabric). In this case, the coating can be applied either directly to the desired objects or on carrier materials to films (possibly coated as a web material) or powder,

The invention will be further described below with reference to the figures and examples, wherein the figures and examples are not intended to limit the scope of the claims.

They show:

FIG. 1 shows illustrations of differently surface-treated steel sheets after exposure to sulfuric acid;

FIG. 2 shows illustrations of differently surface-treated aluminum casting alloys after exposure to sulfuric acid;

FIG. 3 shows a schematic cross section through a rough surface coated according to the invention;

Figure 4 shows the flow behavior of a ketchup strip of a coated according to the invention (above) and a conventional plastic bottle; FIG. 5 shows a plan view of a coating according to the invention with embedded dye particles; and

FIG. 6 shows a UV-Vis spectrum of a silver nanoparticle-containing coating according to the invention.

Example 1: Characterization of the coatings according to the invention in comparison with the prior art

First, the surface energy of a silicon wafer surface was increased by means of an oxygen plasma. A thin film of the silicone oil AK50 (Wacker Chemie GmbH, a trimethylsiloxy-terminated polymethylsiloxane (PDMS) with a kinematic viscosity of about 50 mm ² / s at 25 ° C., a density of about 0.96, was subsequently spin-coated g / mL and an average molecular weight of about 3000 g / mol) applied to the wafer surface. The AK50 was used as a 2% solution (wt .-%) in hexamethyldisiloxane (HMDSO). After evaporation of the HMDSO, a uniform, 90 nm thick liquid film of AK50 remained on the surface.

The wafer covered with AK50 was treated in low-pressure plasma with the aim of realizing a highly hydrophobic coating. The details of the plasma processes are shown in Table 1 and Table 2. Surprisingly, the plasma polymer coating on the AK 50-covered wafer was no longer peelable from the wafer, the coatings are referred to below as coating A and coating B. Using a contact angle measuring system G2 (KRÜSS GmbH), the contact angles of the coatings to water at 103 ° and 105 ° were determined. The total layer thickness of the resulting layer was 88 nm and 89 nm, respectively. The plasma processes were also coated with untreated silicon wafers as comparison, which are to be referred to as plasma polymer A and plasma polymer B. They showed a layer thickness of 26 nm and 27 nm.

Table 1: Process parameters of the plasma polymer treatment of coating A and plasma polymer A.

Table 2: Process parameters of plasma polymer treatment of coating B and plasma polymer B

As a further comparison, various coatings were produced on the basis of the methods described in DE 4019539 A1. The details of the experiments are shown in Table 3. Silicon coats were applied to silicon wafers and technical aluminum surfaces using a spin coater. Subsequently, the samples were treated with an oxygen plasma and the contact angles to water of the resulting coatings were determined. The pure silicone oils on the silicon wafers gave the following contact angles (measured on the average layer thickness / measured on the large layer thickness): AK50 (9971 17 °), AK35 (1337125 °, a trimethylsiloxy-terminated polymethylsiloxane (PDMS) having a kinematic viscosity of about 36 mm ² / s at 25 ° C, a density of about 0.955 g / mL and otherwise nearly identical properties to AK50), DC Fluid CST50 (927120 °, a trimethylsiloxy-terminated polymethylsiloxane (PDMS) with a kinematic viscosity of about 50 mm ² / s at 25 ° C and otherwise almost identical properties to AK50). For the AK50 on Al-platelets (1067103 °) were measured. The contact angles of the films below 150 nm could not be determined because the water droplet displaced the liquids. This effect was seen in part as well after plasma treatment of these films for 10 seconds.

Table 3: Crosslinked in oxygen plasma silicone oil (dewetting layers).

The right-hand column in Table 3 indicates the mechanical resistance to light rubbing with a soft cloth (KIMWIPES Lite 200 laboratory wipes).

The following behavior tends to be observed: Regardless of the silicone oil used and the surface material, the contact angle after treatment in the plasma already decreases after a short time and at relatively low power. The entnetzende behavior is lost after 500 seconds in the plasma at the latest. Only with a very short plasma treatment of 10 seconds could at a power of 500 W a hydrophobic behavior with contact angles to water above 90 ° can be maintained. However, these coatings could be wiped off with the soft cloth. Although these coatings have not been completely removed by rinsing with ink or a strong jet of water, their stability to light mechanical loads is insufficient.

In addition, the experiments showed that a stable fixation of silicone oils in an oxygen plasma is always associated with a hydrophilization of the surface. Under the conditions tested, a maximum contact angle of 35 ° could be obtained for the firmly adhering layers.

By contrast, with the novel coating according to the invention, it is possible to combine various requirements for the layer properties in a variety of ways. As an example could with the Coatings A and B show that it is possible to realize hydrophobic surfaces with good adhesion to mechanical abrasion by the combination of a liquid cross-linking process and a plasma polymer deposition process. The coatings could not be wiped off with a paper towel or removed with a standard household adhesive tape (Tesa Adhesive Film »Budget«).

For further characterization, ellipsometric measurements were performed on silicon wafers at 65 °, 70 ° and 75 ° angles at wavelengths between 300 and 800 nm using a VASE ellipsometer (VB-400, JA Woollam Co., Inc.): the pure AK50 (Layer thickness 42 nm), of the plasma polymer A, of the coating A, of the dewetting layer ES 10 and of the dewetting layer ES 12 (for parameters, see Table 3). The refractive indices n as a function of the wavelength of the light obtained by the curve fitting of the ellipsometer measurements are summarized in Table 4; the absorption constant k was calculated as zero. The curve fitting of the coating A optical measurement gave a much better fit in assuming a homogeneous layer with the given optical constants than assuming two layers with the optical constants of AK50 and plasma polymer A.

Table 4: refractive indices n obtained by the curve fitting of the ellipsometer measurements as a function of the wavelength of the light; the absorption constant k was calculated as zero.

Example 2: Corrosion protection on rough surfaces

Glass bead blasted steel substrates (ST37) having an average roughness R _a of 3.0 ± 0.2 μm and an average roughness R _z of 25.9 ± 2.3 μm were immersed in a solution of 1 vol.% AK50 in HMDSO. After evaporation of the HMDSO, the samples were treated with the process parameters given in Table 5 in the plasma. This coating should be referred to as coating C.

Table 5: Process parameters of the plasma treatment of coating C

In order to evaluate the anti-corrosive properties, the lower part of the coated steel sheet became 25% at 23 ° C for 3 minutes and 6 minutes, respectively

(Wt .-%) sulfuric acid immersed. As a reference, both an uncoated steel sheet and steel sheets, which according to the state of the art

Technology were provided with a corrosion-protective plasma polymer coating, used. For the uncoated steel sheet, the test was stopped after only two minutes. The steel sheets were then rinsed with deionized water and visually assessed. Figure 1 shows photos of the sample plates (from left):

1. Sheet metal (narrow): uncoated after 2 minutes

2. Sheet metal: with anticorrosive plasma polymer coating according to the state of the art after 3 minutes

3rd sheet: with coating C after 3 minutes

4. Sheet metal: with anti-corrosive plasma polymer coating according to the prior art after 6 minutes

5. Sheet: with coating C after 6 minutes

For the uncoated steel sheet, the substrate surface showed a complete brown corrosion layer after two minutes. In the case of the sheets with a conventional anticorrosion plasma-polymer coating, brownish corrosion products appeared after 3 minutes, and flat corrosion was observed after 6 minutes.

In the case of the sheets with the coating C, no corrosion can be seen even after 6 minutes in the sulfuric acid. Only from the edges is corrosion observed in some places. Similar results were obtained using paraffin oil or poly (ethylene glycol) methacrylate instead of silicone oil.

Example 3: Corrosion protection on AIMgSiO, 5

According to the example from DE 19748240, the material AIMgSiO, 5 is used as a sample. It is pretreated in the same way, but it eliminates the combined pickling and electropolishing process. Accordingly, a mean roughness R _a of 0.61 μm was found. The coating described as coating C was applied to this surface. The corrosion behavior of the thus processed aluminum surface became 25% Sulfuric acid at room temperature and 65 ° C and in 20% nitric acid at room temperature. The samples proved to be consistent over the several hours of testing. There was no migration of the test liquid into the coating or even infiltration of the coating through the liquid. Release symptoms were not observed. Furthermore, they proved to be absolutely stable at 350 ° C under conditions prevailing in a condensing boiler heat exchanger.

Thus, according to the inventive method qualitatively similar high-quality corrosion protection layers as in DE 19748240 can be applied without a corresponding surface smoothing must be performed. This is of course interesting for the heat exchanger surfaces described, but all the more so for aluminum materials that can be smoothed very poorly or with great effort. For example, aluminum wrought alloys are mentioned here.

Example 4: Corrosion protection on aluminum casting alloys

Typically, casting alloys have pores, channels and grooves on the surface and also in the bulk material as a result of the production. Without further processing, a casting skin is found on the surface. The aspect ratio of aperture diameter to depth of pores, channels, and cracks often exceeds 1: 3, so these flaws can not be closed without further surface sealing or densification with a conventional plasma polymer coating. At these defects, corrosion is therefore the first observed. An improved, easy-to-apply corrosion protection can be achieved with the method according to the invention.

Examples of components made of cast aluminum alloy (with casting skin) with different combinations of conventional corrosion protective coating and inventive coating as summarized below:

Table 6: Cast aluminum alloy components tested in 25% sulfuric acid at 65 ° C: KO: without anti-corrosive treatment

K1: plasma polymer corrosion protection coating according to the prior art

K2: Application of the coating according to the invention to the coating of

K1

K3: coating according to the invention

The applied polymer coatings were determined using Si wafers also coated in the processes and are between 300 and 400 nm. The uncoated component KO and the coated components designated K1 to K3 were then tested for corrosion resistance with 25% sulfuric acid at a temperature of 65 ° C. The untreated component KO showed extensive corrosion after only 5 minutes, see Figure 2. The component K1 with conventional plasma polymer coating for corrosion reduction showed after 5 initial and up to 10 minutes extensive corrosion. For the combination of plasma polymer coating and the following inventive coating, component K2, and for the coating according to the invention, component K3, a comparable corrosion protection effect was observed. In both Cases showed limited localized corrosion after 15 minutes.

The coating can also be carried out as a corrosion-protective adhesion promoter layer if the required functional groups are made available in a final processing step.

Table 8: Process parameters of the plasma treatment

A further significant improvement in the corrosion protection effect is achieved if the cast material is freed mechanically or chemically from the casting skin. Pores and voids, which additionally arise due to the different alloy composition and the resulting different processing properties, can be reliably covered.

Example 5: Improvement of the sliding behavior

The deposition of mobile AK50 within the plasma polymer matrix can improve the sliding behavior of surfaces. For this purpose, the liquid precursors are applied to the cleaned surface and then treated in the plasma process. With a suitably controlled plasma process only a partial cross-linking of the precursor is brought about. Remains of mobile precursor remain, which migrate through the plasma polymer matrix over a longer period of time and form a superficial sliding film. A better adhesion of the coating according to the invention to the substrate can be achieved with an uneven application of the precursor. For example, the roughness of a surface can be exploited in order to realize an irregular precursor application. While the precursor can cover the rough surface closed, the precursor accumulates in the valleys of the surface profile with a higher layer thickness than on the tips of the profile. As a result of the subsequent plasma treatment, thin precursor coverings are completely crosslinked, while thicker coverings are only partially crosslinked. The mechanism of action of the coating according to the invention could be as follows: The complete crosslinking at the tips of the profile causes the adhesion to the substrate surface, the partial crosslinking in the valleys acts as a depot for mobile precursor. To illustrate this thesis, Figure 3 shows a sketch of a possible cross section through a corresponding coating.

Analogously, a coating with improved sliding effect was produced. For this purpose, three aluminum sheets (AI99.5), designation G1, G2 and G3, were first provided with a plasma polymer separating layer in order to reduce the adhesion forces of the surface. The parameters of this plasma coating can be found in Table 9. In addition, the aluminum sheet G2 was provided with an AK50 film and the precursor was treated in a further plasma process (for process parameters see Table 10). The surface G3 was provided with a commercial release agent, NanoSilan GMK ChemiCom. All three surfaces were compared with a test for determining the sliding friction. For this purpose, a standardized body with a smooth surface was placed on the surfaces and then pulled with a spring balance over the coatings G1, G2 and G3. If the active pulling on the standard body is ended via the spring balance, If the standard body continues to move over the tension of the spring balance until the spring tension corresponds exactly to the force that is at least required for sliding. This value is used as a reference for the sliding behavior.

Accordingly, for the sliding of the standard body on the coating G1 a force of 38-4Og, for the coating G2 a force of 28-3Og and for the coating G3 a force of 28-3Og was found. After cleaning the surface with a dry cloth, a force of 80-10Og was determined for G1, a force of 25-3Og for G2 and a force of 25-3Og for G3. After cleaning the surface with isopropanol, a force of 80-10Og was found for G1, a force of 25-3Og for G2 and a force of 80-10Og for G3. After 24 hours' storage and renewed cleaning, the coating G1 had a force of 90-10Og, a force of 25-3Og for G2, and a force of 90-10Og for G3.

Thus, an optimization of the sliding properties of the standard body could be achieved on the coating according to the invention even after cleaning the surface.

Table 9: Process parameters of plasma polymer treatment of coatings G1, G2 and G3

Table 10: Process parameters of the plasma treatment for the further treatment of the surface G2

Example 6: Sequence behavior of thixotropic substances

A commercially available ketchup bottle (plastic: PP) was cut lengthwise and cleaned with isopropanol. A solution of AK50 in HMDSO in the ratio 1: 100 was applied with a lint-free cloth by hand on the inside of the bottle halves. The layer thickness could not be determined exactly, but interference colors can be seen with the eye. Due to the manual application process no homogeneous coating is given.

Subsequently, the bottle half was treated as described in Table 1 1 in low-pressure plasma. This coating should be referred to as coating D. On reference substrates, a layer thickness of about 220 nm was determined for the plasma process. The surface energy was determined to be about 21 mN / m.

Table 11: Process parameters of the plasma polymer treatment of coating D

To test the flow behavior of thixotropic liquids, a "ketchup sausage" was applied to the inside of the coated and uncoated bottle halves, and the timing of the runoff is shown in Figure 4: top half of the bottle with coating D, bottom half of uncoated bottle, from left to right : directly after the order, after 5 minutes, after 10 minutes and after 15 minutes.

It showed an improved flow behavior through the coating according to the invention.

Example 7: Incorporation of Dyes

A red fatty dye (Clariant 5B 02) was taken up in a mixture of silicone oil AK50 in HMDSO (ratio 1: 100). The red liquid was separated from excess dye particles by filtration through a 0.2 μm membrane filter and spin-coated onto a glass surface whose surface energy had previously been increased by means of an oxygen plasma. The resulting film thickness was estimated to be below 100 nm. Subsequently, the sample was treated analogously to Example 5 as indicated in Table 1 1 in the plasma.

In the light microscope, a clear red coloration of the surface could be observed. Figure 4 shows the magnification of a representative sample of the sample 1000 times. It was possible to observe a large number of red particles with a size of 1 to 2 μm. These particles, which an estimated 1, 5% of the surface covered, could not be wiped off with a laboratory wipe.

Example 8: Integration of nano-silver

A dispersion of about 0.6 wt .-% nano-silver in silicone oil (NanoSilver BG, Fa. Bio-Gate) having a viscosity of 100-200 mPa and an average primary particle size between 5 and 50 nm was used as a mixture with HMDSO (1: 100) applied by spin coating on a glass surface whose surface energy had previously been increased by means of an oxygen plasma. Subsequently, the sample was treated analogously to Example 5 as indicated in Table 1 1 in the plasma. The result was a wipe-resistant coating in which no particles could be identified in the light microscope.

In addition, in an evaporation process (at about 5 mbar, argon atmosphere, crucible temperature: about 850 ° C) nano-silver particles in a liquid film of AK 50 on activated glass, which in turn by spin coating a solution in HMDSO (1: 100) was applied introduced. This resulted in a slight browning, which is a clear indication of a concentration of more than 10 vol.% Silver in the liquid film. (Experience has shown that these silver particles have a diameter of about 5 nm.) Subsequently, the sample was treated analogously to Example 5 as indicated in Table 1 1 in the plasma. The result was a wipe-resistant coating in which no particles could be identified in the light microscope. The slight browning was still visible. Figure 6 shows the UV-Vis spectrum of this nano-silver coating in relation to the uncoated glass. The absorption band at 420 nm is typical for nano-silver particles. Example 9: Integration of nano-TiO?

Nano-TiO ₂ powder (P25, Degussa) was taken up in a mixture of the silicone oil AK50 in HMDSO (in the ratio 1: 100). The liquid was separated from excess dye particles by filtration through a 0.2 μm membrane filter and spin-coated onto a glass surface whose surface energy had previously been increased by means of an oxygen plasma. The resulting film thickness was estimated to be below 100 nm. Subsequently, the sample was treated analogously to Example 5 as indicated in Table 11 in the plasma. In the light microscope no particles could be identified. The result was a wipe-resistant coating in which no particles could be identified in the light microscope. Under UV light influence a hydrophilization of the surface could be obtained. This property, which is typical of TiO ₂ particles, is a clear indication that the coating will also be catalytically active.

Claims

claims

A mixture for a coating process comprising a liquid and at least one further functional ingredient, the liquid consisting of or comprising a substance which is crosslinkable by a plasma process and wherein the functional ingredient is selected from the group consisting of (i) marking substances , (ii) release agents or lubricants, (iii) surface-aiding agents, antimicrobials, fungicides, insecticides, acaricides, algicides, viricides, pesticides, (bi) catalysts, enzymes, hormones, proteins, nutrients, pheromones, medicinal active substances, organoleptically active substances, in particular fragrances and flavorings, emulsifiers, surfactants, growth substances, UV absorbers, photochromic and electrochromic substances, reflective substances, conductive substances, waxes, oils and lubricants, corrosion inhibitors, dyes, luminescent dyes, organic or inorganic cal color pigments, magnetic substances, organic or inorganic solid particles having primary particle sizes of up to 5 .mu.m, more preferably of up to 1 .mu.m, particularly preferably nanofillers, liquid crystals, organic solids, nanofillers having a plurality of crosslinking points, carbon particles.

2. Mixture according to claim 1, characterized in that the crosslinkable substance at 23 ° C has a vapor pressure of <0.5 mbar.

3. Mixture according to claim 1 or 2, characterized in that the crosslinkable substance to ≤ 50 wt .-%, one of the functional groups selected from the group consisting of: acrylic or methacrylic acid esters, isocyanates, epoxides and alpha-olefins and / or selected from the group consisting of: Acid esters, acid anhydrides, epoxides, CC double-terminal groups, and nitrogen-containing functional groups.

4. Mixture according to one of the preceding claims, characterized in that the crosslinkable substance to 50 - 100 wt .-% of

Includes or consists of silicone oil, saturated hydrocarbon, fatty acid, triglyceride, mineral oil or polyether.

5. Mixture according to claim 4, characterized in that the silicone oil, the saturated hydrocarbon, the fatty acid, the triglyceride, the mineral oil or the polyether comprise none of the functional groups selected from the group consisting of acrylic or methacrylic acid esters, isocyanates, epoxides, alpha olefins, acid esters, acid anhydrides, epoxides, CC double bond-containing groups, and nitrogen-containing functional groups.

6. A coating process, characterized by the steps of: a) applying a liquid layer of a mixture according to one of

Claims 1 to 5 on a solid surface to be coated and b) crosslinking of the liquid layer, so that a solid layer is formed.

A coating method characterized by the steps of: a) applying a first liquid layer to a solid surface to be coated, the first layer containing at least one crosslinkable substance, and b) applying a second layer to the first layer by depositing and crosslinking one Substance from a gas phase, and wherein during the implementation of step b) first crosslinking conditions and then deposition conditions are set.

8. Coating method according to claim 7, wherein in step a) the liquid layer consists of a mixture according to one of claims 1 to 5.

The coating method of claim 6, wherein the crosslinking in step b) is accomplished by depositing a second layer on the first layer by depositing and crosslinking a substance from a gaseous phase, and wherein during the performance of step b), first crosslinking conditions and then deposition conditions are established.

10. Coating method according to one of claims 7 to 9, characterized in that during or after performing step b), the first layer is partially or completely crosslinked with the resulting second layer.

1 1. A coating method according to any one of claims 7 to 10, characterized in that the second layer in a

Plasma polymerization process, a CVD method or a plasma enhanced CVD method is applied.

12. Coating method according to one of claims 7 to 11, characterized in that the first, liquid layer comprises a substance having a vapor pressure <0.5 mbar at 23 ° C.

13. Coating method according to one of claims 7 to 12, characterized in that for applying the first layer in step a) a mixture is used comprising or consisting of (i) a solvent having a vapor pressure> 0.5 mbar at 23 ° C and (ii) at least one substance which is liquid under the conditions of step b) with a vapor pressure of <0.5 mbar at 23 ° C.

14. Coating method according to one of claims 6 to 13, characterized in that the thickness of the liquid layer in step a) at the beginning of the implementation of step b) is ≤5 microns.

15. Coating method according to one of claims 6 to 14, characterized in that in step a), the liquid layer is applied to a surface with a center roughness of 350 nm to 10 microns roughness.

16. Coating method according to one of claims 6 to 15, characterized in that in the implementation of step b) a liquid depot of the first applied liquid layer is formed.

17. Coating method according to one of claims 6 to 16, characterized in that the crosslinking in step b) takes place only at predetermined local locations.

18. Coating process according to one of claims 6 to 17, characterized in that the crosslinkable substance in step a) consists of or comprises an oil of copolymers with hydrophilic and hydrophobic sections.

19. Coating process according to one of claims 6 to 18, characterized in that the crosslinkable substance in step a) consists of or comprises oils with different surface energy.

20. Body with a coating, wherein the coating can be produced according to one of claims 6 to 19.

21. Body with a coating, wherein the coating can be produced according to one of claims 16 to 19, wherein in the liquid depot in addition to the crosslinkable substance at least one further substance is contained, which can be discharged through the crosslinked layer or the crosslinked layers.

22. Body according to claim 21, wherein the release can be caused by activation delayed in time.

23. Use of a mixture according to any one of claims 1 to 5 for introducing the functional component into a layer separating from the gas phase.

24. Use according to claim 23, wherein the vapor deposition takes place in a plasma polymerization process, a CVD process or a plasma enhanced CVD process.

25. Use according to claim 24, wherein the functional component is a marking substance for marking a separating layer.

26. Use of a producible or prepared according to one of claims 6 to 19 coating for increasing the lubricity of a surface.

27. Use of a producible or prepared according to one of claims 6 to 19 coating for improving the flow behavior of thixotropic substances.

28. Use of a producible or prepared according to one of claims 6 to 19 coating as an active corrosion protection coating.

29. Use of a producible or prepared according to one of claims 6 to 19 coating as a passive corrosion protection coating.

30. Use of a producible or prepared according to one of claims 6 to 19 coating as diffusion barrier coatings against liquids, gases and / or vapors.

31. Use of a producible or prepared according to one of claims 6 to 19 coating as protective coatings against chemicals.

32. Use of a producible or prepared according to one of claims 6 to 19 coating as a scratch-resistant coating.

33. Use of a producible or prepared according to any one of claims 6 to 19 coating as active protection of surfaces against the Accumulation of biological pests such as microorganisms, algae, plants and microorganisms.

34. Use of a producible or prepared according to any one of claims 6 to 19 coating for adjusting the electrostatic properties of components made of non-conductors such as plastics.

35. Use of a producible or prepared according to one of claims 6 to 19 coating as a protective coating against UV light.

36. Use of a producible or prepared according to one of claims 6 to 19 coating for preventing or reducing the visibility of a fingerprint on a surface.

37. Use of a producible or prepared according to any one of claims 6 to 19 coating for the production / improvement of release properties of a surface.

38. Use of a producible or prepared according to any one of claims 6 to 19 coating for coating porous substrates.

39. Use of a producible or prepared according to one of claims 6 to 19 coating as a partially reflecting surface.

40. Use of a producible or prepared according to any one of claims 6 to 19 coating to reduce dust adhesion.

41. Use of a producible or prepared according to one of claims 6 to 19 coating for coating textiles.

42. Use of a producible or prepared according to one of claims 6 to 19 coating for producing optical effects.

43. Use of a producible or prepared according to any one of claims 6 to 19 coating for providing anchor groups for fixing or immobilization of functional materials such as oligonucleotides, (bio) catalysts, enzymes, hormones, proteins and / or antimicrobial agents.

44. Use of a producible or prepared according to any one of claims 6 to 19 coating for improving the oxidation and / or corrosion resistance of a surface.

45. Use of a producible or prepared according to any one of claims 16 to 19 coating for producing a continuous release of functional materials.