EP2527048A2 - Method for producing thin layers and corresponding layers - Google Patents

Abstract

Coating involves providing a mixture or a pure substance consisting of inactive liquid precursors. A liquid layer of the mixture or the pure substance is applied to a surface, which is to be coated. The liquid precursors are cross-linked by using radiation of 250 nm wavelength, such that a solid layer is created from the mixture. The solid layer comprises 10 atomic % of carbon, in relation to the quantity of the atoms contained in the layer, without hydrogen and fluoride. An independent claim is also included for an article having an cross-linked coating surface, which is produced by coating process.

Description

1. a) Bereitstellen einer Mischung oder eines Reinstoffs, umfassend oder bestehend aus reaktionsträgen, flüssigen Precursoren,
2. b) Aufbringen einer flüssigen Schicht aus der Mischung oder dem Reinstoff auf eine zu beschichtende Oberfläche,
3. c) Vernetzen der flüssigen Precursoren mittels Strahlung mit einer Wellenlänge von ≤ 250 nm, so dass aus der Mischung eine feste Schicht entsteht und die Schicht ≥ 10 Atom-% C umfasst, bezogen auf die Menge der in der Schicht enthaltenen Atome ohne H und F,

und so dass der in der Schicht enthaltene C zu maximal 50 Atom-% des C, bezogen auf die Menge der in der Schicht enthaltenen C-Atome, Bestandteil einer Methoxygruppe ist.The invention relates to a coating method comprising the steps

1. a) providing a mixture or a pure substance, comprising or consisting of inert, liquid precursors,
2. b) applying a liquid layer of the mixture or the pure substance to a surface to be coated,
3. c) crosslinking of the liquid precursors by means of radiation having a wavelength of ≦ 250 nm, so that a solid layer is formed from the mixture and the layer comprises ≥ 10 atom% C, based on the amount of atoms contained in the layer without H and F. .

and so that the C contained in the layer to a maximum of 50 atomic% of C, based on the amount of C atoms contained in the layer, is part of a methoxy group.

It further relates to layers producible or produced by this method and their uses, as well as corresponding coated articles and their uses.

contents

1. 1. Glossary (definitions) 4
2. 2. General overview 8
   • 2.1 State of the art 8
     • 2.1.1 Radiation Chemistry / Electron Beam Hardening, EB Curing, EB Crosslinking ... 8
     • 2.1.2 Process for forming thin layers of the prior art. 11
   • 2.2 Description of the invention 14
     • 2.2.1 General description of the invention 14
     • 2.2.2 General layer properties: 23
     • 2.2.3 Process advantages 24
   • 2.3 Delineation against the state of the art 27
3. 3. Applicable Precursors 38
   • 3.1 Silicone compounds 38
   • 3.2 Partially and fully fluorinated carbon compounds 38
   • 3.3 Halogen-free organic liquids 38
4. 4. Useful fillers and additives 39
5. 5. Coating process 41
6. 6. Substrates / Surfaces 43
7. 7. General information on the procedure 44
8. 8. Applications 60
   • 8.1 Crosslinked Coating According to the Invention with Dispersed Fine-Particulate Solids 60
   • 8.2 PDMS-type coating: 63
   • 8.3 Antimicrobial, preferably non-cytotoxic coating 78
   • 8.4 Corrosion protection and tarnish protection 80
   • 8.5 separating layers 84
   • 8.6 Easy-to-clean layers 87
     • 8.6.1 Easy to clean surfaces by suitable surface chemistry 87
     • 8.6.2 Easy-to-clean surfaces by smoothing or closing surface irregularities 90
   • 8.7 Installation of solid particles 90
   • 8.8 Adhesion promoter, primer layers, functionalized surfaces 92
   • 8.9 Electrical insulation layers 96
   • 8.10 Localized Coatings 97
   • 8.11 Optical functional layers 99
   • 8.12 Antifingerprint coatings 102
   • 8.13 Smoothing and sealing coatings 104
   • 8.14 Structuring topography coatings 107
9. 9. General information 110
10. 10. Examples 111

1. Glossary (definitions)

Reaction-bearing precursors: precursors which contain no silane, peroxo, halogen, acrylate, methacrylate, isocyanate and epoxide groups and chemically reactive groups comparable to the abovementioned groups, preferably those which, moreover, do not contain any carboxylic acid or acid esters -, acid anhydride and nitrogen-containing functional groups. Preferred reaction inert precursors are silicone oils, saturated hydrocarbons, mineral oils, fluoroorganic / partially fluorinated oils and, as an exception to the above, depending on the application, fatty acids, triglycerides and polyethers.

Excimer lamp: Excimer, short form of "excited dimer". An excimer refers to a short-lived bond of two molecules or atoms, which exists only in the excited state (in unequal partners is also spoken by an "Exiplex"). After the decomposition of the compound, the binding energy is released in the form of light. Gas mixtures containing components capable of forming excimer complexes are the starting point for so-called excimer light sources. As a rule, energy is supplied to the gas by an electric field, thus providing the basis for the formation of excimers. Excimer lasers emit coherently the light released after decay of the excimers, excimer lamps represent a non-coherent light source. Examples: KrF (248nm), Xe ₂ (172nm), F ₂ (155nm), ArF (193nm) KrCl (222nm) etc.

Line emitters / emitters: Light sources whose emission spectrum includes or consists of one or more discrete frequencies. Line / band emitters are based on the excitation of discrete energy levels such as atomic or molecular energy levels or electronic band transitions for semiconductors. The wavelength of the emitted light corresponds to the energy difference between the excited energy level and the final energy level assumed after light emission, often ground state or relaxation level. In addition, according to the transition probability between the energy levels, the emission spectrum comprises an additional certain wavelength range around the emission wavelength, the so-called spectral bandwidth. In the following, the term "irradiation with a wavelength" is always understood to mean the wavelength that is directly attributable to the discrete energy levels of the radiation source, the central wavelength of the level transition, as well as the wavelength range around the central wavelength of the spectral bandwidth of the transition is assigned. In the following, line emitters are understood to mean a radiator based on discrete transitions in atoms or molecules, eg excimer lamps, excimer lasers. A band radiator is understood to mean a radiator based on a transition between electronic bands, eg the semiconductor laser.

Particle Diameter: By particle diameter is meant in the context of this invention, unless otherwise explicitly stated, the so-called equivalent diameter. In this case, regardless of the actual shape of the particle, the diameter of a volume-identical, ideally spherical particle or in the case of planar projection of an area-like, ideally round particle is understood. The person skilled in the art can determine the particle diameter and the particle size distribution by known methods. For particles smaller than 2 μm, e.g. the technique of dynamic light scattering, for particles larger than 2μm laser diffraction (for example DIN ISO 8130-13) can be used. Hereby, as with similar methods, the diameter is determined by a characteristic, physically accessible property (e.g., scattering, diffraction, rate of descent, etc.).

Polymerization: Combination of monomers or precursors into macromolecules, in which one or more types of atoms or groups of atoms (so-called repetitive units, basic building blocks or repeating units) are lined up repeatedly. As a rule, polymerization produces molecules with a (predictable) order of proximity.

Polymer: Product formed by polymerization.

Plasma polymerization: Plasma polymerization produces layers that are clearly distinguishable in their chemical or structural composition from polymeric layers. While the process of linking the precursors in polymers occurs in a predictable manner (see above), the precursors used in plasma polymerization are greatly altered by contact with the plasma (until complete destruction) and deposited in the form of reactive species. This results in a highly networked layer without regular areas. This resulting layer is additionally exposed to the plasma, so that further modifications result through ablation and redeposition effects. The plasma polymer layer is three-dimensionally crosslinked and amorphous. Accordingly, the difference Plasma polymerization within the meaning of this text by conventional methods of polymerization. It is a process in which excited gaseous precursors (also called monomers) precipitate from a plasma onto a substrate as a highly crosslinked layer. The prerequisite for a plasma polymerization is the presence of chain-forming atoms such as carbon or silicon in the working gas. As a result of the excitation, the molecules of the gaseous substance (precursors) are fragmented by 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 charge of the plasma and its intense ion and electron bombardment continuously acts, so that triggered in the deposited layer, a further reaction and a high degree of linkage of the deposited molecules can be achieved. In this connection reference is made, for example, to the following reference: Plasma Polymerization "at H. Yasuda, Academic Pres., Inc. (1985 ).

In the context of the present text, the term "plasma polymerization" in particular also includes plasma-assisted CVD (PE / CVD). In this case, the substrate is additionally heated to carry out the reaction. Plasma polymerization can occur both under atmospheric pressure and under low pressure.

Plasma polymer: product formed by plasma polymerization.

Crosslinking: Three-dimensional linkage of precursors used, whereby in the context of this text in "cross-linking" the linkage is not based on classical polymerization reactions. This means that the layers formed in the context of this text "crosslinking", unlike polymers, not based on a polymeric chain reaction. Accordingly, crosslinked layers are designed so that they show no close order with respect to their former precursor structures. In this regard, layers created by crosslinking are similar to plasma polymer layers. "Crosslinking" in the sense of this application also always means the formation of layers, that is to say a surface reaction that relates to the entire surface to be coated. Crosslinking serves accordingly to produce a (solid) layer. It is not just a matter of generating adhesion points between surfaces.

Excimer crosslinked: crosslinked, preferably crosslinked by means of UV radiation ≦ 250 nm, in particular crosslinked by means of UV radiation of 120-250 nm, very particularly preferably crosslinked by means of line or band radiator with emission in the wavelength ranges mentioned.

Longer-chain precursors: molecules with a molecular weight greater than 600 g / mol. The longer-chain precursors in turn usually have been formed by a polymerization reaction.

Precursors: organic or organosilicon or fluoroorganic molecules or mixtures of these molecules as precursors for layers.

2. General overview 2.1 State of the art 2.1.1 Radiation Chemistry / Electron Beam Hardening, EB Curing, EB Crosslinking

The radiation chemistry describes the investigation of the radiation-induced chemical processes when irradiated with light, in particular with the availability of suitable radiation sources, e.g. Lasers in the visible and UV spectral range, incoherent radiation sources such as mercury lamps or excimer lamps and high-energy radioactive gamma emitters can be used to analyze the entire range of possible effects. In addition to the fundamentals and the theoretical description, the main focus of the considerations are the interaction between radiation and matter of different states of matter (solid, liquid, gaseous) as well as the detailed analysis of special classes of substances. For example, macromolecules such as polypropylene, fluoropolymers or polysiloxanes have been analyzed with regard to the expected continued fractions, resulting fragments and the subsequent recombination and crosslinking. Corresponding cross sections can be taken from the literature. The influence of process gases or admixtures of foreign substances largely belongs to the state of the art. A typical application example of radiation chemistry is the curing of paints, lacquers or adhesives, for example with the aid of photoinitiators, which initiate radical polymerization reactions by irradiation of light of suitable wavelength.

As a source of radiation, gamma emitters, i. used extremely high-energy radiation. However, these radioactive radiation sources are considered to be highly hazardous to health and their use requires appropriate, complex technical measures. As an alternative radiation X-ray is also mentioned.

• CH 675 178 A5
• CH 676 168 A5
• DE 10 2005 046 233 A1
• DE 199 16 474 A1 und
• Kitamura, M et al., Applied Surface Science 79/80 (1994) 507 - 513 "A practical high power excimer-lamp excited by a microwave discharge "
• U. Kogelschatz: Dielectric-barrier Discharges: Their History, Discharge Physics, and Industrial Applications, Plasma Chem. And Plasma Proc., Vol. 23, No. 1, 1-46 (2003 )

Today, on the other hand, cost-effective radiation sources are available, for example with lasers or excimer lamps, which, technically, open up a secure access to the radiation chemistry with moderate effort. Excimer lamps are known, for example, from the prior art from the following documents:

• CH 675 178 A5
• CH 676 168 A5
• DE 10 2005 046 233 A1
• DE 199 16 474 A1 and
• Kitamura, M et al., Applied Surface Science 79/80 (1994) 507-513 "A practical high power excimer lamp excited by a microwave discharge "
• U. Kogelschatz: Dielectric-barrier Discharges: Their History, Discharge Physics, and Industrial Applications, Plasma Chem. And Plasma Proc., Vol. 1, 1-46 (2003 )

The radiant energy of excimer lamps and lasers is sufficient to ionize a variety of elements and molecules or to open single and double bonds. For example, the dissociation energy of the O ₂ molecule is 5.1 eV, a CC single bond is about 3.57 eV, a C = C double bond is about 6.3 eV, the dissociation of a hydrogen atom from methane is 4.5 eV, etc. The photon energy of the KrF Excimer lamp (wavelength: 248nm) is compared to 5eV, a Xe ₂ (172nm) 7,2eV, a F ₂ (155nm) 8eV, an ArF (193nm) 6.4eV, KrCl (222nm) 5 , 6eV etc. Thus, it is possible to use a number of the known processes of radiation chemistry with simple radiation sources. For example, bonds within the molecules or molecular fragments of an applied liquid can be disrupted. The resulting radicals orient themselves statistically new and can bring about a new networking of the liquid and thus contribute to a stable layer formation.

In addition to the possibility to irradiate with a pure electromagnetic wave of certain photon energy, an alternative is the irradiation with an electron beam (electron beam hardening, ESH, EB curing, EB crosslinking). Electron beam hardening uses radiation sources based on the principle of the Braun tube. These generate accelerated electrons, which represent corpuscular radiation and penetrate, for example, pigments, fillers, metal foils and paper. The effect of electrons can be classified in terms of their energy: the fast primary and the backscattered electrons do not cause chemical reactions. Their cross section is too small, they are from the Molecules are not captured and thus can not carry out any radical formation, ionization or excitation. Important for the curing are the secondary electrons in an energy range between 3 and 50 eV. They are slow enough, ie the cross section is large enough to ionize molecules and form radicals. The kinetic energy of the electrons is sufficient to also open single and double bonds. Fragmentation of this type can generally generate free radicals from monomers or oligomers which, for example, initiate chain reactions for polymerization (EB curing). Or free radicals can be generated from macromolecules, which lead to a three-dimensional crosslinking by recombination of the radicals (EB-crosslinking). Slow electrons with energies below 3 eV only lead to excitation.

In a number of applications, the use of electron beams alone by looking at the energies provided presents an interesting alternative to pure electromagnetic wave radiation. Accordingly, there are a number of applications which are equally possible with both electromagnetic and electron beam radiation ,

Typical applications of electron beams are: By heating the surface in low pressure melting processes and evaporation processes are observed, with the help of which welding or microstructuring is made possible. Chemical reactions at atmospheric pressure can cure coatings, paints and coatings or chemically activate surfaces. Dominant as electron beam curable coating material are acrylate monomer-prepolymer binder systems and cationic curing formulations of epoxides, polyols and vinyl ethers. Another common application is the increase in the cohesiveness of PSAs, e.g. to achieve higher stability against shear forces. Additives based on a modified silicone are known from the prior art, which is added in low concentration to a composition. Here, for example, polysiloxanes are used which are provided with (meth) acrylic ester groups and fluorinated and / or perfluorinated radicals.

Furthermore, the biological application is the sterilization of packaging material.

Compared to the application with light, a much faster and cold layer hardening is achieved by electron beam radiation. The cause is mainly to be seen in the strong absorption of UV radiation in most materials, which leads to a warming of the irradiated surface. Thus, the UV lamps act comparatively superficial. For complete curing of thick layers, in particular of layers with additives, polymerization chain reactions are necessary. In addition, due to the relatively simple regulation of the electron energy, the electron beam hardening does not require any photoinitiators for the start of the polymerization reaction, which is the case in particular with irradiation with conventional commercial mercury lamps.

Nevertheless, the use of electron beams has not yet established itself in the breadth of applications, instead being competitive only in special cases or in mass production. About 90% of the radiation-curable materials are currently cured with the help of UV rays, only 10% are accounted for by electron beam systems. The reason is to be seen above all in the technically complex realization. For example, an N ₂ atmosphere is usually needed against inhibition by oxygen. Furthermore, the electrons penetrating deep into the material cause a marked radiation exposure in the X-ray region during the deceleration of the electron beams in the film. For this reason, the spotlights must be installed in a radiation protection hood and subject to the Radiation Protection Ordinance.

Due to the technical requirements, the process is usually limited to 2D surfaces.

2.1.2 Process for forming thin layers of the prior art

" Sol-Gel-Science - The Physics and Chemistry of Sol-Gel-Processing ", (CJ Brinker, G. Scherer, Academic Press, New York 1989 ) gives an overview of the sol-gel technique by means of which thin and thin-layer coatings can be produced. In general, the layer is cured by hydrolysis and condensation processes by heat treatment of the substrate at temperatures above 80 ° C.

The DE 40 19 539 A1 describes the production of a de-wetting surface, wherein a thin film of a silicone oil is applied to a surface to be de-crosslinked and the oil is crosslinked by means of a plasma.

The DE 100 34 737 A1 discloses a process for producing a permanent mold release layer by plasma polymerization, wherein, for example, HMDSO is deposited by plasma polymerization as a layer.

Other documents that disclose plasma polymer coatings are the documents DE 101 31 156 A1 . DE 10 2004 026 479 A1 and DE 103 53 530 A1 , These documents disclose plasma polymer layers for release and impression functions, respectively.

In the publication " UV curing without photoinitiators "(Scherzer, T., et al., Institute for Surface Modification, Proc. Rad. Tech. Europe 2001 Conf .) describes the initiation of a photopolymerization of acrylates by means of monochromatic UV light of a wavelength of 222 nm. The UV light source is a KrCl excimer lamp. It is a polymerization reaction in the traditional sense.

The WO 96/34700 discloses a process in which monomers having a double bond are polymerized by means of UV light. Photoinitiators are used so that a classical polymerization is started.

The DE 199 57 034 B4 discloses the layer structure on surfaces by means of excimer lamps by reactive fragments from the gas phase.

The DE 42 30 149 A1 describes the preparation of oxidic protective layers by means of excimer lamps of polymers or solid organometallic compounds.

The publication " Plasma-deposited organosilicon thin films as dry resists for deep ultraviolet lithography ", Horn, MW et al., J. Vac. Sci. Technol. B 8 (6), Nov / Dec 1990 discloses the modification of plasma polymer (solid) layers by means of UV light.

The publication " Release Layers for Contact and Imprint Lithography ", Resnick, D., Semiconductor International, June 2002 discloses the use of a liquid Precursors for polydimethylsiloxane. This liquid precursor is according to the reference (referred to in the cited document) " Soft Lithography ", Xia, Y. et al., Angew. Ref. Matter. Sci. 1998 PDMS with a reactive group (eg vinyl-terminated PDMS) provided so that the PDMS is present as a classic polymer. Also, the UV-curable layer of dimethylsiloxane polygomer disclosed in the document is prepared by classical polymerization.

The DE 199 61 632 A1 discloses a UV-curable varnish, whereby here too a classic polymerization reaction is present during the curing. In particular, monomers having reactive groups (acrylate monomers) are used.

The publication " Functional layers by UV and electron beam curing, "Mehnert, R. et al., Mat.-Wiss., And Werkstofftech., 32, 774-780 (2001 ) discloses the curing of oligomeric acrylates having reactive groups.

The EP 0 894 029 B1 discloses the curing of ethylen-containing unsaturated monomers by UV irradiation by excimer lamps. The resulting products are classic polymers.

JP 11035713 discloses a gas barrier layer which is crosslinked with excimer lamps. The resulting layer does not comprise carbon according to the disclosed IR spectrum.

The publication " Photo induced synthesis of amorphous SiO2 with tetrametoxilane ", Awatsu, K. and Onoki, I., Appl. Phys. Lett. 69 (4), 22 July 1996 discloses the cross-linking of tetramethoxysilane (TMOS) by means of excimer lamps to an amorphous SiO ₂ layer. The resulting layer is poorly described, it is deposited on a wafer. The result of the treatment is an inorganic SiO ₂ -like layer by cleavage of the methoxy groups

There are a number of other publications known, for. B. " Wettability and surface composition of poly (dimethylsiloxanes) irradiated at 172 nm ", Graubner, V. et al., Polymeric Materials: Science & Engineering, 88, 488 (2003 ), in which the treatment of (solid) polymer layers with excimer lamps is disclosed.

2.2 Description of the invention 2.2.1 General description of the invention

The object of the invention was to provide a coating process known from the prior art, which has advantages in many individual areas.

1. a) Bereitstellen einer Mischung oder eines Reinstoffs, umfassend oder bestehend aus reaktionsträgen, flüssigen Precursoren,
2. b) Aufbringen einer flüssigen Schicht aus der Mischung oder dem Reinstoff auf eine zu beschichtende Oberfläche,
3. c) Vernetzten der flüssigen Precursoren mittels Strahlung mit einer Wellenlänge von ≤ 250 nm, so dass aus der Mischung eine feste Schicht entsteht und die Schicht ≥ 10 Atom-% C umfasst, bezogen auf die Menge der in der Schicht enthaltenen Atome ohne H und F,

und so dass der in der Schicht enthaltene C zu maximal 50 Atom-% des C, bezogen auf die Menge der in der Schicht enthaltenen C-Atome, Bestandteil einer Methoxygruppe ist.This object is achieved by a coating method comprising the steps:

1. a) providing a mixture or a pure substance, comprising or consisting of inert, liquid precursors,
2. b) applying a liquid layer of the mixture or the pure substance to a surface to be coated,
3. c) crosslinking of the liquid precursors by means of radiation with a wavelength of ≦ 250 nm, so that the mixture forms a solid layer and the layer comprises ≥ 10 atom% C, based on the amount of atoms contained in the layer without H and F. .

and so that the C contained in the layer to a maximum of 50 atomic% of C, based on the amount of C atoms contained in the layer, is part of a methoxy group.

Preferably, the crosslinking is carried out so that a maximum of 50 atomic% of C, based on the amount of C atoms contained in the layer is part of an alkoxy group.

In principle, a number of options are available to the person skilled in the art for adjusting the content of carbon in the layer. On the one hand, this is of course possible via the use of the precursors (and optionally further constituents of the mixture); on the other hand, the duration of irradiation also plays a role since, in many embodiments, the carbon content in the resulting layer increases with increasing irradiation duration or intensity decreases.

Preferably, the method according to the invention is carried out in such a way that the C signal in the depth profile of the time-of-flight secondary ion mass spectrometry profile (TOF-SIMS) has a course essentially parallel to the X axis (sputter cycles) when the intensities are normalized to the silicon signal. This measurement reflects the carbon distribution along the layer depth and shows a homogeneous distribution. In order to achieve this distribution, reference is made to the following text, in particular to Example 2 for carrying out the corresponding measurement.

Depending on the process procedure, preferred irradiation durations during crosslinking may be: At least 50 ms, preferably 1 s, more preferably 10 s and at most 60 min, preferably 20 min, and particularly preferably 10 min.

The irradiation intensity that can be utilized for the crosslinking can be varied both via the power of the radiation source and via the distance between the radiation source and the substrate as well as via the atmosphere gas. Preferably, a distance between the surface to be coated and the lower edge of the lamp from 1mm to 20cm, more preferably 5mm to 5cm.

The surface to be coated may be displaced, rotated or otherwise moved during the irradiation or the irradiation unit may be moved relative to the substrate in order to achieve the desired local irradiation intensity and thus crosslinking of the precursors.

The irradiation may comprise one cycle within the said irradiation period, or may comprise several cycles, even with different irradiation time; if desired, the cycles may also be realized by means of several irradiation units, e.g. by passing under successive excimer lamps. Preferred is a number of 1 to 50 cycles, more preferably 1 cycle.

Furthermore, the irradiation may be point-like, line-like, curved, 2-dimensional, 3-dimensional, in the form of a regular pattern or statistically or by means of a mask or otherwise on the selected areas.

In addition to the possibility to irradiate the entire surface with a constant irradiation intensity and a uniform degree of crosslinking achieve, it is also possible to subject the surface locally different irradiation intensities, so that locally different degrees of crosslinking arise. The realization possibilities for this are manifold.

The proportion of the carbon which is part of a methoxy or alkoxy group in the crosslinked layer produced in the process according to the invention is controllable by a corresponding process control. Here, of course, also primarily the provided mixture or the pure substance should be mentioned, since with appropriate process management this (r) is not completely fragmented.

For many applications, it is preferred that the proportion of C contained in the layer is at most 50, preferably at most 30, more preferably at most 15 and particularly preferably at most 2 atomic% of the C, based on the amount of C contained in the layer. Atoms, is part of a methoxy and more preferably also an alkoxy group.

The appropriate proportion can be determined by methods familiar to the person skilled in the art, in particular after derivatization, for example with moist hydrogen chloride gas. By derivatization, the alkoxy groups are substituted. Subsequently, for example, the derivative, for example the chlorine, can be determined on the surface with the aid of the ESCA. For this determination, care must be taken to analyze the substrate after derivatization with exclusion of air. For this purpose the derivatization should be carried out in a reaction chamber connected to the analysis chamber. Another possibility for analysis is the analysis of the gas formed in the derivatization, for example of the alcohol split off by the reaction with hydrogen chloride, for example by GC-MS analysis. Also optical analysis methods can be used meaningfully.

It is preferred that UV radiation having a wavelength of ≥ 120 nm and ≦ 250 nm is used for the coating method according to the invention. It is further preferred that for this purpose line or band radiators are used which have an emission exclusively within this range.

A coating method according to the invention is preferred in which the layer of liquid precursors is crosslinked by means of laser radiation or UV radiation from an excimer lamp.

More preferably, the crosslinking by means of UV radiation of a wavelength ≤ 200 nm.

In the context of this text, crosslinking by means of UV radiation of a particular wavelength or from a specific radiation source means that the crosslinking reaction takes place predominantly, preferably completely, by means of the radiation of the indicated wavelength or from the radiation source specified.

Surprisingly, it has been found that by the process according to the invention, in particular in its preferred embodiments (see above and also below), it is possible to produce layers which have a homogeneous depth profile superior to those known from the prior art, in particular based on carbon. By using the radiation ranges described above and in particular the preferred radiation sources described above, it is possible to achieve an ideal combination of registered energy and penetration depth into the precursor layer. This applies in particular to the preferred precursors described in the text below. At wavelengths of the irradiated UV light of over 250 nm, the energy is often not sufficient to ensure the required level of desired bond breakage. This is especially true in deeper areas of the layer to be crosslinked. In contrast, too hard UV radiation, especially those of <120 nm wavelength, for many applications also disturbing because the energy input is so high that in the uppermost layers of the precursor too strong networking occurs and what also leads to that in the upper Area of the layer of carbon is expelled too much. This leads to stresses within the layer due to inhomogeneous cross-linking and composition of matter, which can lead, for example, to cracking within the layer due to internal mechanical stress.

In the coating method according to the invention, the liquid precursors are preferably applied in an average layer thickness of 3 nm to 10 μm. Further preferred average layer thicknesses are to be seen in the range of 5 nm to 5 μm, again preferably in the range of 10 nm to 1 μm during application. In this case, of course, be included in the mixture containing the precursors, also components that go beyond the resulting layer thickness of the precursors, z. B. Particles (see below). It should also be noted that, depending on the process design, the crosslinked product produced in the process according to the invention Layer often has a smaller layer thickness than the thickness of the liquid precursor layer, since a volume shrinkage in the cross-linking is often observed.

For many applications, it is preferred if the method according to the invention is carried out such that the resulting layer thicknesses of the crosslinked layer are ≥ 20 nm, preferably ≥ 30 nm, more preferably ≥ 40 nm. With a corresponding minimum layer thickness, the desired effect can be achieved for many applications especially good.

Furthermore, a coating without fillers or additives is preferred in which the layer thickness of the coated surface areas for a flat area deviations relative to the average coating thickness of less than 50 percent, more preferably less than 20 percent and more preferably less than 10 percent. The layer thicknesses can be measured by analysis methods known to the person skilled in the art, such as e.g. Reflectometer or ellipsometer. Frequently, a microscope and knowledge of the relationships between detectable interference color and layer thickness are sufficient.

Furthermore, it is preferred to design the method according to the invention such that a coating without fillers and / or additives is produced in which the layer thickness of the coated surface areas for a flat area has deviations relative to the mean coating thickness of less than 50 percent, particularly preferably less as 20 percent and more preferably less than 10 percent.

The inventive method is preferably carried out such that the relative layer thickness deviation based on the average layer thickness along a distance of 1 mm on the entire coated surface at least 1%, preferably 2%, but in absolute numbers at least 5 nm. The layer thickness difference can be by means of known layer thickness measuring methods (reflectometry, ellipsometry, TEM (transmission electron microscopy), SEM (scanning electron microscopy) or, preferably, by investigations of the layer thickness-characteristic interference colors in the light microscope The said layer thickness deviation is one of several distinguishing criteria, for example compared to plasma polymer layers the latter preferred method when coating substrates having a roughness R _a of ≦ 500 nm on the surface.

For some applications, it is also preferred that the substrate to be coated on the surface has a roughness R _a of> 500 nm, more preferably> 1 μm.

The coatings produced according to the invention can be classified as partially closed or as a closed coating. Partially closed coatings are characterized by the degree of coverage, i. the ratio of covered surface to total surface area. Partially closed coatings may intentionally leave open uncoated areas (intended patterning) or unintentionally left open areas (coating defects). A closed surface has a coverage of 1. Preference is given to coatings having a coverage of between 0.1 and 1. Particularly preferred are coatings having a coverage of between 0.5 and 1. Further particularly preferred are closed coatings.

In the process according to the invention, it is furthermore preferred for the mixture provided in step a) to comprise ≥ 50% by weight, preferably ≥ 70% by weight, particularly preferably ≥ 85% by weight, or exclusively liquid precursors. It is preferred for many applications that only one species of liquid precursor is present.

In addition, a method according to the invention is preferred, wherein the precursors provided in step a) comprise ≥ 10 atom% C, preferably ≥ 20 atom% C, more preferably ≥ 30 atom% C, based on the amount of those contained in the mixture Atoms without H and F. In this way, a sufficient amount of carbon is introduced into the layer to be crosslinked via the liquid precursors.

It is further preferred that the C contained in the mixture provided in step a) to a maximum of 50 atomic%, preferably at most 30 atomic%, preferably at most 10 atomic% and particularly preferably at most 1 atomic%, based on the amount of in the Mixture contained C atoms, part of an alkoxy group, preferably a methoxy group.

For some applications of the process of the invention it may be preferred that the surface to be coated does not comprise silanol groups. In other applications, however, this may be desirable.

In a further preferred embodiment of the method according to the invention, the application of the liquid layer takes place under conditions under which the inert liquid precursors and the surface to be coated no chemical reaction takes place.

In the method according to the invention and the preferred method according to the invention, therefore, a liquid is applied to the surface to be coated and crosslinked by high-energy radiation, in particular UV radiation. For crosslinking, this photorelease requires neither photoinitiators to initiate a crosslinking reaction nor functional groups, i. it is sufficient to use compounds that have only single bonds. These are generally less expensive, more environmentally friendly and non-toxic, properties that accommodate the process and job security and pricing of the coated product. The simplest execution of the coating process can be carried out at atmospheric conditions, so that it can be worked inexpensively from the side of the technical process implementation. By using thin precursor layers (<10μm) it is ensured that the precursor as a whole can be crosslinked within acceptable process times (typically 10s - 10 min).

As indicated above, the process is conducted such that the carbon content (C content) in the crosslinked layer comprises ≥10 atomic%, preferably ≤15 atomic%, preferably ≥20 atomic%, more preferably ≥25 atomic%, particularly preferably ≥ 30 atom%, based on the amount of atoms contained in the layer without H and F.

The incorporation of carbon can surprisingly produce a large number of coatings with different properties. By means of the coating, for example, the following surface functions can be produced: corrosion protection, easier cleaning (easy-to-clean), less adhesion of plastics (release properties), etc. (see also below). The residual amount of carbon in the coating is important in that corresponding layers have high mechanical stress capacity, i. Flexibility. This is z. B. particularly advantageous in the preparation of flexible scratch-resistant coatings, which are very brittle in the case of a nearly carbon-free coating and break under mechanical stress.

The load capacity of the layers produced in the method according to the invention can be quantitatively determined by determining the layer hardness and the modulus of elasticity. The person skilled in the art is aware of various methods for this, for example nanoindentation ( Berkovich Indentor, proceedings by Oliver & Pharr: WC Oliver, GM Pharr; J. Mater. Res. Vol7, No. 6 (1992) 1564 , multiple partial unloading Method: KI Schiffmann, RLA Küster; Z. Metallkunde 95 (2004) 311 ) or the analysis of laser acoustic surface waves. Preferred are layer hardnesses in the range of 0.4GPa to 4GPa, more preferably 1GPa to 4GPa, determined after nanoindentation according to the aforementioned method.

Surprisingly, it has been found that in a preferred method according to the invention, the method can be carried out so that the resulting coating shows no cracks at a bending radius of 2.5 mm, visible optically with the naked eye or up to a 1000-fold resolution in a light microscope are. More preferably, the inventive method is carried out so that this applies to a bending radius of 1 mm, more preferably 0.5 mm (to determine the flexibility of the coating is also referred to the example 21 "flexible coating").

In addition, some studies have shown that, surprisingly, not only the fact that carbon is contained in a crosslinked layer is advantageous, but also the way in which the carbon is bound. Important to the layers produced in the process according to the invention is that substantial parts of the carbon (Shares see also above) are involved differently in the layer, as over a methoxy or alkoxy group. Of particular importance in this context are Si-C bonds, which have a positive effect on the different layer properties. The actually adjusting bonds, the expert by taking appropriate measures (as already indicated above) such. As selection of the precursors, degree of fragmentation of the precursors or about the atmosphere during the crosslinking process control.

It was surprising that a multiplicity of different layers can be produced by the method according to the invention. In particular, it is surprising that the layers produced by means of the method according to the invention are to be executed both quickly and free of cracks under normal atmospheric conditions as well as under different atmospheres. The original thickness of the applied precursor layer may decrease by more than 50% during the curing. The layers produced by the method according to the invention can therefore preferably after crosslinking accordingly have a thickness of 2 nm to 5 μm, preferably 5 nm to 2 μm, more preferably 10 nm to 1 μm. Particularly preferred layers have a thickness of 20 nm to 500 nm.

2.2.1 General description of procedure:

In the method according to the invention, as already indicated above, by means of high-energy radiation, in particular preferably high-energy UV radiation, preferably by excimer lamps, liquid precursors are excited by photons and converted into a crosslinked layer. The excitation will be done, for example, by the breaking of chemical bonds. The substrate on which the crosslinking reaction takes place is basically arbitrary. The skilled person will readily understand that the number of usable precursors (liquid state) can be extended by suitable reaction temperatures (eg low temperature). Under certain circumstances, however, it may also be desirable to evaporate certain portions of the originally liquid precursor layer.

Of course, the precursors to be crosslinked must contain chain-forming atoms such as carbon and / or silicon. In the crosslinking reaction, depending on the reaction regime, gas molecules can also participate in the reaction in the region of the surface of the layer to be crosslinked. These gas molecules can come from both the atmosphere and the originally provided mixture. This opens up to the expert a number of possibilities for a suitable process management.

The radiation used, in particular UV radiation with a wavelength of ≦ 250 nm, causes the precursors to be fragmented. Excited radical or ionic molecular fragments are formed, which can react with one another and form a three-dimensional network on the surface to be coated with the progression of the irradiation. In the case of a suitable surface (if appropriate after preparation thereof, eg purification and / or activation), a bonding reaction of the resulting layer to the surface takes place simultaneously with the crosslinking reaction. In particular, reactions with the surface to be coated can take place by radicals or ions which are formed at the interface between the layer to be crosslinked and the surface to be coated and which are produced from the precursors.

2.2.2 General layer properties:

The layers produced by the process according to the invention are similar to plasma polymers. They are amorphous and three-dimensionally networked. In this case, the radiation sources to be used according to the invention have an outstanding penetration depth when considering the layer thicknesses preferred according to the invention, so that a coating homogeneously crosslinked in the depth profile can be produced. The material composition of the layers produced is surprisingly homogeneous.

The layers produced by the process according to the invention are versatile in their properties: their thermal, mechanical and chemical properties can be designed in a variety of ways by suitable process control, such as the duration of the radiation exposure, the atmosphere under which the curing takes place and, of course, the precursor material.

The layers produced according to the invention can be very similar to plasma polymers, but they differ, inter alia, from plasma polymers in that they do not simulate technical surfaces in the sub-micron range, since the starting material, unlike plasma polymerization, is a liquid.

As long as the liquid has not been cross-linked, it can migrate through the capillary effect into existing pores in the surface or, following gravity, fill up the valleys of a surface profile, so that a higher layer thickness is achieved in the valleys than on the profile tips. The reverse case is also conceivable, in which the surface is oriented downwards and thus preferably accumulates the liquid at the profile tips and encases them in a targeted manner. Furthermore, a low surface tension liquid can spill over the entire surface over time, ie uniformly cover or contract a liquid with high surface tension into droplets. The phenomena mentioned can be recognized, for example, with reflective surfaces and a sufficiently thin coating in the light microscope by means of corresponding interference colors. Likewise, by characteristic interference colors around dust particles, a liquid initially applied at the beginning of the process can be recognized (see also below).

Depending on the starting material, however, crosslinked layers produced by the process according to the invention can be further distinguished from plasma polymers because the liquid precursors which can be used in the process according to the invention, in particular for (excimer) crosslinked (excimer-cured) functional coatings, are preferably longer-chain precursors and have a low vapor pressure, preferably at 23 ° C of <0.5 HPa, more preferably of <0.25 HPa and more preferably <0.1 HPa. Therefore, if the crosslinking conditions are chosen so that only a low degree of crosslinking is produced (for example by relatively short irradiation), even longer chain segments of the precursor can be retained in the crosslinked layer. As a result, properties similar to duromers or elastomers can be adjusted for the layer, as well as those similar to plasma polymer layers. In particular, by providing carbon in the layers produced by the method according to the invention, a corresponding diversity is possible.

Even if, compared to a number of prior art crosslinking processes, more homogeneous layers are produced by means of the method according to the invention, these layers have a degree of crosslinking compared to plasma polymer coatings deposited on the surface under constant conditions (this is the side from which the radiation is applied) the layer hit) a somewhat higher degree of cross-linking than on the side facing the surface to be coated (substrate).

In addition, it is characteristic of layers crosslinked in the process according to the invention that they have a higher degree of crosslinking in the case of a simple coating on the upper side, in particular for layer thicknesses of more than 200 nm, than on the side facing the substrate. This, however, to a much lesser extent than comparable layers that were crosslinked using a plasma process.

2.2.3 Process advantages

• die zur Aushärtung der Beschichtung verwendete Strahlung, insbesondere UV-Licht, kann durch die Verwendung von Lasern oder Blenden lokal begrenzt angewendet werden. Es sind anders als bei plasmapolymeren Beschichtungen keine spaltbündigen Abdeckungen notwendig.
• Die Verfahrensführung kann im Niederdruckbereich erfolgen, Niederdruck ist aber nicht notwendig. Der Fachmann entscheidet je nach Prozessführung, ob gegebenenfalls eine Inertgasatmosphäre eingesetzt wird.
• Häufig können kürzere Prozesszeiten realisiert werden, beispielsweise gegenüber Plasmapolymerisationsprozessen oder Sol-Gel-Beschichtungen.
• Der aparative Aufwand ist verhältnismäßig gering bzw. kann gering gehalten werden.
• Die Oberfläche wird keiner Elektronen- oder Ionenbestrahlung aussetzt.
• Geringe Erwärmung der Oberfläche.
• In den meisten Fällen entstehen keine toxischen Gase bzw. die Gasbelastung ist sehr viel geringer. (Ausnahme Ozonbildung bei Behandlung an Luftatmosphäre)
• Dadurch, dass bei der Aushärtung keine Kettenwachstumsreaktionen initiiert werden, ist die Aushärtung auf den der Strahlung ausgesetzten Bereich beschränkt.
• Damit lässt sich eine hohe Kantenschärfe erzeugen, wie sie insbesondere in lithographischen Anwendungsbereichen (z. B. nanoprint technology step und flash implant lithography) benötigt wird.
• Der flüssige Precursor dringt auch in Poren und Vertiefungen sowie Hinterschneidungen ein und ermöglicht so im Gegensatz z. B. zu plasmapolymeren Beschichtungen, fehlerfreie Beschichtungen.
• Effekte, die auf den Einsatz des flüssigen Precursors beruhen, und die Schichtdickenverteilung beeinflussen (homogen, porenfüllend, Spreiten, Tröpfchenbildung etc.), können ausgenutzt werden, um die Vielfalt an Funktionalisierungen zu erhöhen.
• Es lassen sich Dünnschichten bevorzugt im Nanometerbereich erzeugen.
• Höhere Schichtdicken (1 µm und mehr) sind einfacher und wirtschaftlicher zu erreichen als bei der Plasmapolymerisation.
• Es können in die Schicht Füllstoffe oder Additive eingebaut werden.
• Die Schichtgestaltung ist hinsichtlich ihrer Zusammensetzung variabler, da beispielsweise auf Photoinitiatoren keine Rücksicht genommen werden muss. Die entstehenden Schichten sind frei von Reaktionshilfsstoffen oder deren Reaktionsprodukten. Dies betrifft insbesondere Photoinitiatoren als Reaktionshilfsstoff.
• Im Vergleich zu konventionellen UV-härtenden Lacksystemen sind kostengünstigere Beschichtungsmaterialen einsetzbar (z.B. werden keine Photoinitiatoren benötigt), ihre Lagerbedingungen sind in der Regel sehr viel günstiger.
• Umweltfreundliche Verfahren und schadstofffreie Beschichtungen sind möglich.
• Die Vernetzung mittels UV-Strahlung ist in der Regel kostengünstiger als Elektronenstrahlhärtung aufgrund kostengünstigerer Anlagen und weniger benötigter Sicherheitsvorkehrungen.
• Die Eigenschaften der entstehenden Schicht sind z. B. durch die Parameter "eingesetzter Precursor" und "erzeugter Vernetzungsgrad" sehr vielfältig steuerbar.

The coating process according to the invention combines many advantages over known coating processes (such as gas-phase plasma polymerization processes):

• the radiation used to cure the coating, in particular UV light, can be applied locally by the use of lasers or diaphragms. In contrast to plasma-polymer coatings, no gap-flush covers are necessary.
• The process can be carried out in the low pressure range, but low pressure is not necessary. The person skilled in the art decides, depending on the process control, whether an inert gas atmosphere is used if appropriate.
• Frequently, shorter process times can be realized, for example compared to plasma polymerization processes or sol-gel coatings.
• The aparative effort is relatively low or can be kept low.
• The surface is exposed to no electron or ion irradiation.
• Low heating of the surface.
• In most cases, no toxic gases or the gas load is much lower. (Exception ozone formation when treated in air atmosphere)
• By not initiating chain growth reactions upon cure, cure is limited to the radiation exposed area.
• This allows a high edge sharpness to be produced, as required in particular in lithographic application areas (eg nanoprint technology step and flash implant lithography).
• The liquid precursor also penetrates into pores and depressions and undercuts and thus allows in contrast, for. B. to plasma polymer coatings, flawless coatings.
• Effects which are based on the use of the liquid precursor and influence the layer thickness distribution (homogeneous, pore-filling, spreading, Droplet formation, etc.) can be exploited to increase the variety of functionalizations.
• Thin films can preferably be produced in the nanometer range.
• Higher layer thicknesses (1 μm and more) are easier and more economical to achieve than with plasma polymerization.
• Fillers or additives can be incorporated into the layer.
• The layer design is more variable in terms of their composition, since, for example, no consideration has to be given to photoinitiators. The resulting layers are free of reaction auxiliaries or their reaction products. This applies in particular to photoinitiators as reaction auxiliaries.
• In comparison to conventional UV-curable coating systems, more cost-effective coating materials can be used (for example, no photoinitiators are needed), their storage conditions are generally much more favorable.
• Environmentally friendly processes and pollution-free coatings are possible.
• The crosslinking by means of UV radiation is generally less expensive than electron beam curing due to cheaper systems and less required safety precautions.
• The properties of the resulting layer are z. B. by the parameters "used precursor" and "generated degree of crosslinking" very diverse controllable.

2.3 Delineation against the state of the art Polymeric layers

As prior art, many layer-forming processes involve radical or ionic chain-growth reactions which are initiated by a chain-start reaction and are often terminated by chain-termination reactions. Typically, the free radicals are provided for chain initiation by irradiated photoinitiators. They cause a chain reaction of the mainly existing reactive molecules (precursors, often monomers or oligomers). Recent developments use UV radiation to ionize or radicalize reactive precursors directly (without photoinitiator) and to initiate the polymerization chain reaction. The layers resulting from this process are polymeric layers in the classical sense which differ in their structure-property relationship from the crosslinked layers obtained in the process according to the invention.

Plasma polymer layers

Distinguishing features between a plasma polymer layer and a coating produced by the method according to the invention are found primarily due to the manufacturing process:

Optical differentiation

As long as the layer thicknesses in the range below 5 microns, make the coatings optically to the viewer by a color impression caused by interference. The color impression depends on the optical path taken by the light in the coating material. That is, the color impression is dependent on the refractive index, this is given by the coating material, the viewing angle, this is dependent on the position of the viewer and the surface normal (perpendicular to the substrate surface) and finally on the layer thickness. In an optimal, ie uniform coating process has a smooth surface a homogeneous color, the color varies with the viewing angle.

The plasma polymer layer is deposited out of the gas phase and is a three-dimensionally highly crosslinked macromolecule. The plasma polymer coatings are dimensionally stable, i. The contours are provided with a uniformly thick coating down to the sub-micron range. Nevertheless, differences in the layer thickness occur, which are mainly determined by the component geometry and system geometry, which influence the distribution of the gaseous plasma and thus the local deposition rate.

In a plasma cleaner coating, the entire component surface exposed to the plasma is coated. Deviations in the layer thickness of the plasma polymer coating are closely related to the symmetries of the components, and the local areas of the surface with layer thickness gradients take on lateral expansions in the size range of the component. For example, an edge represents a disturbance of the smooth surface and is noticeable, inter alia, in that a layer thickness gradient arises towards the edge. Accordingly, a color is visually perceived in accordance with the course of the edge. The behavior is similar for a depression, a bore or a pore in the component surface.

For example, in blind holes or similar depressions only a small gas exchange takes place, so that there the layer thickness decreases sharply. Thus, layer thickness gradients arise symmetrical to the surface structure, i. in this case are to the blind hole. It should be noted that the reactive plasma gas can not penetrate arbitrarily into a hole or a pore and accordingly thinner layer thicknesses up to the coating hole arise. On the other hand, edges or tips are often coated with a particularly thick coating since gas vortices can form there or the electrical radiation required for plasma formation couples well.

In practice, layer thickness gradients are also caused by the inhomogeneity of the plasma. As a rule, there are density gradients in a plasma chamber due to the position of the electrodes, the position of nozzles for the introduction of process gases or by pumping, which ultimately also lead to a coating of different thicknesses. These density gradients are generally large compared to the dimensions of the components to be coated, so that these are negligible.

Furthermore, it is likely that during the coating process dust on the surface of the body to be coated passes. Dust affects the local Coating rate not. The dust particles cover the underlying surface, so that, for example, by wiping at the position of the dust grain, a locally lower layer thickness is determined as a finely limited surface defect, a Schichtdickengradient is not visible. If the layer thickness is large enough, dust grains can be incorporated into the coating.

In contrast, the method according to the invention uses a liquid film in the first process step. As long as the layer forming this film is not completely cross-linked, the liquid film is considered to be liquid and thus dynamic, and due to the existing energy balances in the system surface, ambient gas, liquid can cause local layer thickness differences. For example, if the surface energy of the component surface is high and the surface tension of the liquid is low, the liquid may spread, i. the liquid forms a very thin film. In the opposite case, the liquid forms droplets with a contact angle characteristic of the energy conditions.

The dimensions of the regions within which layer thickness gradients occur due to the dynamic movement of the liquid and which are perceived by the viewer as interference spectrals due to interference effects are dependent on the cohesion and adhesion forces of the liquid or the component surface. In general, lateral dimensions in the μm to mm range are to be expected for the areas within which layer thickness gradients occur.

The system of the applied, but not yet cross-linked liquid is thus to be regarded as dynamic and it form due to the energy ratios even with a homogeneously grown liquid film local differences in layer thickness. These layer thickness gradients are frozen with the crosslinking by irradiation in the coating. The layer thickness differences are visually noticeable by interference effects as color differences.

In particular, small differences in layer thickness in the liquid can form over the entire surface over time on regions with lateral expansion below 100 μm, which differences can not be resolved with the eye. With the aid of a microscope, the color differences are recognizable and can also be found again in the crosslinked coating. These layer thickness inhomogeneities can be a have a roundish shape, a locally limited statistical polygonal shape or can be described as wave pattern or streaks.

In contrast to the plasma-polymer coating, these local layer thickness inhomogeneities can be located on the entire component surface and are independent of the component geometry.

Dust on the uncrosslinked liquid film is noticeable in such a way that the three-phase system of surface, liquid and surrounding gas is disturbed and must be locally expanded by the interaction with the dust grain. As a rule, a meniscus forms around the dust grain, which changes the layer thickness locally to lateral dimensions of a few hundred μm. Here, local differences of several hundred nanometers can occur, so that the interference colors on the smallest dimension go through several colors. Fig. 1 shows several such layer thickness inhomogeneities by dust grains.

Fig. 1 FIG. 2 shows a microscope image of the UV-irradiated pattern B8 (from Example 1, see FIG. 1) with typical coating inhomogeneities due to dirt particles. FIG.

Likewise, menisci arise in the area of edges and corners. The lateral extent of these menisci is independent of the dimension of the surface to be coated. It is dependent on the cohesion and adhesion forces of the liquid or the component surface and the lateral dimensions are generally in the μm to mm range.

Fig. 2A represents the course of a plasma polymer layer in the region of a corner of the surface to be coated, Fig. 2B a corresponding layer produced by a method according to the invention.

Particularly significant differences arise in the coating of surfaces with structures in the micron range. For example, one might think of technical surfaces with a roughness, ie an irregular sequence of elevations and depressions on the component surface, or on regularly structured surfaces.

Such surface structures are dimensionally coated with the plasma process. The coated surface has almost the same roughness as the uncoated surface. If there are pores on the surface, the aspect ratio (ratio between depth and diameter) of the pore determines the deposited layer thickness of the plasma polymer layer. In unfavorable conditions, the pore base is not coated. By contrast, a high plasma-polymer layer thickness can cause the pore to be closed on the surface.

When curing a liquid film, a significant influence on the surface structure is to be expected. The applied liquid will prefer to lay in the recesses of the structures, possibly a complete, but slightly inhomogeneous coverage is achieved. After crosslinking of the liquid, a smoothing of the structures, for example the roughness is to be expected, pores are closed.

• Fig. 3 stellt die Beschichtung von Oberflächenstrukturen mit einer plasmapolymeren Schicht (A, B, C) und einer durch ein erfindungsgemäßes Verfahren hergestellten Schicht (D, E, F) dar. Dabei demonstrieren die Figuren 3A und 3D jeweils den Oberflächenverlauf der jeweiligen Schicht auf einer rauen Oberfläche, die Figuren B und E einer jeweils verhältnismäßig dünnen Schicht im Bereich einer Pore und die Figuren C und F einer verhältnismäßig dicken Schicht im Bereich einer Pore.

To demonstrate the differences, cf. Fig. 3 :

• Fig. 3 shows the coating of surface structures with a plasma polymer layer (A, B, C) and a layer produced by a method according to the invention (D, E, F) FIGS. 3A and 3D in each case the surface course of the respective layer on a rough surface, the figures B and E of a respective relatively thin layer in the region of a pore and the figures C and F of a relatively thick layer in the region of a pore.

Distinction by means of IR spectroscopy

Furthermore, there is a possibility of distinguishing between plasma-polymer coating and a coating produced by a method according to the invention with the aid of the observation of the IR spectra. The plasma polymer layer is deposited out of the gas phase. For this purpose, a short-chain, gaseous precursor is used. The length of the molecule determines the ratio of repeating unit to end groups of the precursor. For example, the room temperature gaseous HMDSO (hexamethyldisiloxane) has two Si (CH ₃ ) _{3 end} groups and no -O-Si (CH ₃ ) ₂ repeat units. The room temperature silicone oil AK10000 has a much longer molecular chain. It also has two Si (CH ₃ ) _{3 end} groups and -500 -O-Si (CH ₃ ) ₂ repeat units and thus a clearly distinguishable end group to repeat unit ratio. The relative ratio between end groups and Repeating units can be determined by means of IR spectroscopy. Thus, in principle, a suitable tool is available with which the distinction between the original use of a gaseous precursor and a liquid precursor can be made.

In plasma polymerization, the gaseous precursor is fragmented in an electric field. As a result, a reactive plasma is formed. The reactive short-chain fragments form a three-dimensionally crosslinked macromolecule after deposition on the component to be coated. A hydrophobic plasma-polymer coating is characterized in that the gaseous precursor used is not fragmented too much and therefore a high number of Si (CH ₃ ) ₃ end groups are incorporated into the coating.

For clarification be on the in FIG. 4 referenced example of a hydrophobic coating.

Fig. 4 represents the IR spectrum (ERAS) of a hydrophobic plasma polymer coating and the untreated liquid silicone oil AK10000.

Significantly, in the case of the hydrophobic plasma polymer coating, bands for the Si (CH ₃ ) ₃ end group (monofunctional siloxane units) are at about 850 1 / cm and for the Si (CH ₃ ) ₂ bridges (difunctional siloxane units) at about 810 1 / cm to recognize. In contrast, the untreated AK10000 silicone oil shows essentially a signal in the IR spectrum at about 820 1 / cm which can be assigned to the -O-Si (CH ₃ ) ₂ repeat units (difunctional siloxane units). The band at about 843 1 / cm is assigned to the Si (CH ₃ ) ₃ end groups (monofunctional siloxane units). Due to the low proportion of end groups, only a very weak band results here.

The coating method according to the invention is based on longer-chain precursors (molecules having a molecular weight greater than 600 g / mol.). In contrast, the plasma polymerization works with precursors which have a lower molecular weight, since these are supplied to the plasma via the gas phase. From the difference in molecular size, a distinguishing feature between both layers can be deduced. As shown above, the ratio between the end groups and repeating units can be analyzed spectroscopically. For this, the associated bands must first be identified; this includes the Careful assignment of all bands in the IR spectrum in the vicinity of the bands in question (band positions are usually retrievable in the literature). With the aid of the band positions, the bands of the end groups and repeat units can be analyzed using recognized methods (curve fitting). In general, the areas below the bands are determined in the IR spectrum.

For the coating according to the invention, a ratio of end groups (n _end ) to recurring units (n _WE ) of less than 0.1, more preferably less than 0.05, is preferred.

For organosilicon coatings based on PDMS (as precursor), preference is given to a coating whose IR spectrum has a ratio of the area under the band of -O-Si (CH ₃ ) _{2 repeat units} at about 845 cm ^-1 (A 845 cm ^-1 _{). 1)} (the area under the band of the Si CH _{3) 3} end groups is at about 815 cm ^-1 (A _815cm-1) of less than 0.2. Here, the wavenumbers of the associated bands can vary by up to 12 cm ^-1 .

In the case of a hydrophobic, plasma polymer coating, as in FIG. 4 shown, the bands of the end groups (A _845cm-1 ) and repeating units (A _815cm-1 ) clearly visible. Here, the ratio is approximately 1: 1 without accurate determination and thus the hydrophobic, plasma-polymer coating can be clearly distinguished from the layers produced in the process according to the invention. In the case of a coating according to the invention with AK50 as the basis, the bands of the end groups (A _{845 cm -1} ) compared to those of the repeating units (A _{815 cm -1} ) are negligible.

In the organosilicon plasma polymer coating, a reduced ratio between end groups and repeating units is to be expected in the case of a hydrophilic coating in comparison to the hydrophobic coatings due to the greater fragmentation of the precursor. In the context of the invention, but because of the minimum proportion of carbon z. B. ensures because of the residual proportion of methyl groups, that with appropriate equipment and a sufficient accuracy, the ratio between end groups and repeating units can be determined. This is also above the stated value of 0.1, preferably below 0.05, for corresponding hydrophilic, plasma-polymer layers.

As a result, by inferring the precursors used, it is possible to distinguish plasma polymers from layers produced in the process according to the invention.

By energetic, in particular excimer lamp irradiation, the bonds of the applied silicone oil are broken and the resulting reactive groups lead to a three-dimensional cross-linking of the liquid film.

Due to the properties of the layers produced in the coating process according to the invention can thus z. B. between a coating produced by the process according to the invention and a plasma-polymeric hydrophobic coating are basically differentiated on the basis of IR spectra. Starting material of a plasma polymer coating is a gaseous short-chain precursor, starting material of the coating produced according to the invention is a liquid preferably having significantly longer molecular chains (long-chain precursor). Accordingly, different ratios are given with respect to the specific end groups and recurring units, which can be distinguished by IR spectroscopy.

In the plasma polymer coating and in the (UV) radiation-induced coating produced according to the invention, crosslinking of the individual molecular chains is produced. The degree of crosslinking determines the extent to which end groups and repeating units in the IR spectrum appear as characteristic bands. In the case of hydrophobic plasma polymer coatings and inventively produced coatings with moderate degree of crosslinking (which are also hydrophobic), both types of layers can therefore be clearly distinguished by means of IR spectroscopy.

This observation also applies to monomers other than the illustrated HMDSO or to other liquids than the PDMS silicone oils used.

Plasma-linked layers

From the prior art is in particular from the DE 40 19 539 A1 a plasma-crosslinked layer is known which is prepared from the precursors to be used in the process according to the invention. In Examples 1 and 2 (see there) differentiation possibilities are shown, with the help of which layers, which by means of have been prepared according to the invention, delimit. In that regard, reference is made to Examples 1 and 2.

In particular, layers produced by the method according to the invention are distinguished by the fact that the C signal in the depth profile of the time-of-flight secondary ion mass spectrometry profile (TOF-SIMS), when normalizing the intensities on the silicon signal, is essentially parallel to the X axis (sputter cycles) History has.

Another distinguishing feature between plasma crosslinker and inventive coating results for applied liquid layer thicknesses above 300 nm. In the case of plasma crosslinking, large crosslinking differences occur between the near-surface and substrate-near regions of the thin layer at the layer thicknesses mentioned, which lead to high layer stresses when fully crosslinked. If complete crosslinking with adhesion bonding to the substrate is to be achieved via a plasma, cracks occur due to the stresses. These are usually visible to the naked eye, but at the latest with the help of a microscope. Such crack structures are not observed in the coating according to the invention due to a much stronger depth treatment.

However, even assuming that the plasma crosslinking of the precursors essentially takes place with the UV radiation that originates from the plasma, clear differences can be observed. In the plasma, electromagnetic radiation in a very broad spectral range, from the hard VUV range (< 100 nm) to the IR range. This large bandwidth of the actual effective wavelengths leads to a gradient in the depth profile of the resulting coatings (see also above). Furthermore, UV-crosslinking by means of radiation from the plasma also makes it possible to use fast electrons, molecules, excited particles, ions and molecular fragments as constituents of a plasma during layer formation. A surface, in particular a liquid precursor layer, which is exposed to the plasma regularly interacts with all components of the plasma. As a result of all these interactions, as described above, a very strong superficial crosslinking with a strong stress gradient occurs. These stresses are responsible for the regularly occurring visible cracks, especially at deposited precursor liquid layer thicknesses greater than 250 nm.

A person skilled in the art can already recognize the cracks without aids, at the latest with the aid of a microscope. Typically, an irregular network of cracks can be seen; the cracks have widths often in the μm range, the length of the cracks recognizable in the microscope lies in the μm to mm range. An example of such a microcracking shows the FIG. 10 , which shows a microscope image of a plasma-crosslinked oil layer (AK10000) with an average layer thickness of 250 nm.

A distinction between plasma-crosslinked and produced by the process according to the invention layers due to cracking, the expert can easily z. B. by means of scattered light measurements (analogous to the determination of scratch marks in the Taber Abraser test, DIN 52347) or in the sand trickle test for transparent materials (DIN 52348) meet.

Since it can be assumed that the results found in the examples (see below) can be generalized, layers produced by the process according to the invention, but in particular preferred hydrophobic layers having water margins> 50 °, produced by the process according to the invention, can be clearly distinguished from the prior art differ. Of course, a number of further methods for distinguishing the production method of the respective layer are available to the person skilled in the art, which he will use depending on the composition of the layer to be examined for distinguishing layers of other layers produced or producible by the method according to the invention, in particular optical methods for Assessment of layer thickness gradients.

Accordingly, a component of the invention is also a crosslinkable layer which can be produced by means of a method according to the invention.

Preference is given to such a layer in which the C signal in the depth profile of the time-of-flight secondary ion mass spectrometry profile (TOF-SIMS) has a course essentially parallel to the X axis (sputter cycles) when normalizing the intensities on the silicon signal.

A preferred article of the invention has a sub-micron structured surface comprising at least partially on that surface Cross-linked layer according to the invention, which is not contour-replicating in the sub-micrometer range.

Further preferred is an article according to the invention, wherein for the crosslinked layer, the C signal in the depth profile of the time-of-flight secondary ion mass spectrometry profile has a course substantially parallel to the X axis (sputter cycles) when normalizing the intensities to the Si signal, particularly preferably to to a depth of 5 microns.

Preference is given to an article according to the invention or a layer according to the invention, the crosslinked layer being excimer-crosslinked.

3. Applicable precursors

Preferred precursors to be used are listed below:

3.1 Silicone compounds

Synthetic polymeric compounds in which silicon atoms are linked in a chain via oxygen atoms and the remaining valences of the silicon are saturated by hydrocarbon radicals (in particular methyl groups, but also ethyl groups, propyl groups, phenyl groups, etc.) or fluorohydrocarbon groups , Here, the molecular chains can be linear, branched or cyclic. Preference is given to non-functionalized silicones. Examples include PDMS silicone oils or corresponding fluorosilicones, in which the methyl groups have been partially or completely replaced by fluoroalkyl groups.

3.2 Partially and fully fluorinated carbon compounds

Saturated and optionally fluorinated, perfluorinated hydrocarbons, for example polytetrafluoroethylene, perfluoroethylene propylene (FEP), perfluorinated alkylcarboxylic acids, perfluoroalkoxy polymers.

3.3 Halogen-free, organic liquids Hydrocarbons, fatty acids, triglycerides, mineral oils, polyethers.

As can be seen from the above, the precursors as starting materials for the process according to the invention are not restricted to organosilicon substances. It is also possible to use hydrocarbons, fatty acids, triglycerides, mineral oils, polyethers, fluorinated or partially fluorinated oils as starting materials. The precursors in the context of this invention may be a pure substance or else a mixture of substances. The person skilled in the art will select the starting materials in particular according to the required function for the corresponding layers. For example, the use of fluorinated oils as precursors allows the preparation of coatings with PTFE-like properties, such as. As acid resistance, repellent, separating properties or sliding properties.

4. Usable fillers and additives

• Markierende Substanzen, bevorzugt ausgewählt aus der Gruppe bestehend aus Farbstoffen, Chromophoren, magnetisierbare Partikel, komplexierte Nanopartikel, lichtstreuende Substanzen, Farbstoffpigmente oder Leuchtstoffpigmente wie z.B. fluoreszierende oder phosphoreszierende Stoffe.
• Trenn- oder Gleitmittel, insbesondere Metallseifen von Fettsäuren, Siloxan-Harze, Paraffin-Wachse, Fette, Polymere oder anorganische Puder (wie Graphit, Talk u. Glimmer).
• Gleiten von Oberflächen unterstützende Substanzen, antimikrobielle Wirkstoffe, Fungizide, Insektizide, Bakterizide, Algizide, Virizide, Pestizide, (Bio-)Katalysatoren, Enzyme, Hormone, Eiweiße, Nährstoffe, Pheromone, medizinisch wirksame Stoffe, organoleptische aktive Stoffe, insbesondere Riech- und Aromastoffe, Emulgatoren, Tenside, Wachstumsstoffe wie Wachstumsregulierer, insbesondere für Knochenwachstum, UV-Absorber, photochrome oder elektrochrome Substanzen, reflektierende Substanzen, leitfähige Substanzen, Wachse, Öle, Schmiermittel, insbesondere Metallseifen, organische Seifen, sulfonierte und sulfatierte Verbindungen, quartäre Amoniumverbindungen, Phosphortide, Amphoside, Bitterine, Fettalkohole, Propylenglykolmonostearat, partielle Fettsäureester, mehrwertige Alkohole mit gesättigten Fettsäuren, Polyoxidethylenester von Fettsäuren, Polyoxiethylenether von Fettsäuren und Polymerisationsprodukten aus Ethylenoxid und Propylenoxid bzw. Propylenglykol, Feststoffpartikel mit Primärpartikelgrößen bis zu 200 nm insbesondere Silber- oder Titanoxidpartikel, leitfähige Substanzen, Korrosionsschutzinhibitoren, Farbstoffe, Lumineszenzfarbstoffe, insbesondere elektrolumineszente, katolumineszente, cheminolumineszente, biolumineszente, thermolumineszente, sonolumineszente, fluoreszente und/oder phosporlumineszente Lumineszenzfarbstoffe, organische oder anorganische Farbpigmente, magnetische Stoffe, organische oder anorganische Feststoffpartikel mit Primärpartikelgrößen von bis zu 100 µm, bevorzugt bis zu 20µm und besonders bevorzugt bis zu 10µm, insbesondere Metalle wie Silber, Kupfer, Nickel, Aluminium, Metalllegierungen, Halbleitermetalloxide, wie die von Titan, Zinn, Indium, Zink oder Aluminium, Nichtmetalle, Nichtmetallverbindungen, Salze (z.B. Salze organischer und anorganischer Säuren, Metallsalze), Zinksulfit, Magnetit, Siliciumoxid, Bohrnitrit, Graphit, organische Feststoffe, bevorzugt Nanofüllstoffe mit einer Vielzahl von Vernetzungspunkten, Kohlenstoffpartikel, Flüssigkristalle.
• Partikel, organisch oder anorganisch, bevorzugt mit einer Größenordnung im Durchmesser von 10nm bis 10µm, bevorzugt 20nm bis 5µm, besonders bevorzugt 50nm bis 2µm. Partikel, rundliche Form oder flach mit Durchmesser 10nm bis 10µm, bevorzugt 20nm bis 5µm, besonders bevorzugt 50nm bis 2µm. Partikelagglomerate, rundlich oder flach mit Größenordnung Durchmesser 10nm bis 10µm, bevorzugt 20nm bis 5µm, besonders bevorzugt 50nm bis 2µm.

In the process according to the invention, the mixture containing the precursors to be crosslinked may also comprise further constituents. Such components can be used selectively to impart certain functions to the layers produced in the process of the invention. The person skilled in the art will ensure that the fillers and additives take as little damage as possible during the curing of the precursors. This is especially important when using organic additives that are UV sensitive. The particular precursor used should reach crosslinking much faster than substantial changes in the additives take place. The fillers and additives may, for example, be compounds or mixtures of compounds from the individual substances or substance groups listed below:

• Marking substances, preferably selected from the group consisting of dyes, chromophores, magnetizable particles, complexed nanoparticles, light-scattering substances, dye pigments or phosphor pigments such as fluorescent or phosphorescent substances.
• Separating or lubricating agents, in particular metal soaps of fatty acids, siloxane resins, paraffin waxes, fats, polymers or inorganic powders (such as graphite, talc and mica).
• Surface-aiding agents, antimicrobial agents, fungicides, insecticides, bactericides, algicides, viricides, pesticides, (bi) catalysts, enzymes, hormones, proteins, nutrients, pheromones, medicinal substances, organoleptic active substances, in particular fragrances and flavorings , Emulsifiers, surfactants, growth factors such as growth regulators, in particular for bone growth, UV absorbers, photochromic or electrochromic substances, reflective substances, conductive substances, waxes, oils, lubricants, especially metal soaps, organic soaps, sulfonated and sulfated compounds, quaternary ammonium compounds, phosphortides, Amphosides, bitterines, fatty alcohols, propylene glycol monostearate, partial fatty acid esters, 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 up to 200 nm, in particular silver or titanium oxide particles, conductive substances, corrosion inhibitors, dyes, luminescent dyes, in particular electroluminescent, catoluminescent, cheminoluminescent, bioluminescent, thermoluminescent, sonoluminescent, fluorescent and / or phosphoroluminescent luminescent dyes, organic or inorganic color pigments, magnetic Substances, organic or inorganic solid particles having primary particle sizes of up to 100 .mu.m, preferably up to 20 .mu.m and more preferably up to 10 .mu.m, in particular metals such as silver, copper, nickel, aluminum, metal alloys, semiconductor metal oxides such as titanium, tin, indium, zinc or aluminum, non-metals, non-metal compounds, salts (eg salts of organic and inorganic acids, metal salts), zinc sulfite, magnetite, silicon oxide, boron nitrite, graphite, organic solids, preferably nanofillers with a Variety of crosslinking points, carbon particles, liquid crystals.
• Particles, organic or inorganic, preferably with an order of magnitude in the diameter of 10nm to 10μm, preferably 20nm to 5μm, more preferably 50nm to 2μm. Particles, roundish shape or flat with diameter 10nm to 10μm, preferably 20nm to 5μm, more preferably 50nm to 2μm. Particle agglomerates, round or flat with an order of magnitude of diameter 10nm to 10μm, preferably 20nm to 5μm, more preferably 50nm to 2μm.

5. Coating process

A number of coating methods are known to the person skilled in the art in order to apply the liquid layer to the surface to be coated when carrying out the method according to the invention. Preferably, these methods are designed so that the mixture comprising or consisting of inert liquid precursors is applied uniformly.

• Spin-Coating, Tauchen (Dip- und Draincoating), Aerosolauftragsverfahren, diverse Sprüh- und Zerstäubungsverfahren beispielsweise unter Verwendung von Hochdruckdüsen, Ultraschallzerstäubern, Rotationszerstäubern, zusätzlicher Gaseinbringung ggf. unter Verwendung von zusätzlichen schnell flüchtigen Verbindungen, wie z.B. Lösemitteln oder langsam verdampfenden Substanzen wie z.B. Wasser; Rakeln, Pinseln, auch manueller Auftrag durch Wischen, Stempeln, Drucken (z.B. Tampondruck), Ausnutzen der Spreit- und Migrationseigenschaften von Silikon- und Mineralölen.
• Teilweiser oder lokaler Auftrag: Z.B. durch Drucken, Sprühen, eventuell mit Masken, partielles Tauchen; auch manuelles Teilentfernen des aufgebrachten Flüssigkeitsfilms.
• Flächiger Auftrag mit unterschiedlicher Schichtdicke, z.B. bedingt durch die Rauheit des Substrats (höhere Schichtdicke in den Tälern, geringe Schichtdicke auf den Spitzen), bedingt durch unterschiedliche Vorbehandlungsmethoden (z.B. durch eine Teilaktivierung/ Teilreinigung); durch unterschiedliche Ziehgeschwindigkeit beim Tauchverfahren (Dip-, Draincoating), Einsatz verschiedener Rakel etc.
• Kombinationen der genannten Beschichtungsverfahren.

Preferred application methods for this are:

• Spin coating, dipping (dip and drain coating), Aerosolauftragsverfahren, various spraying and sputtering, for example, using high-pressure nozzles, ultrasonic atomizers, Rotationszerstäubern, additional gas injection possibly using additional fast volatile compounds, such as solvents or slow-evaporating substances such as Water; Doctoring, brushing, even manual application by wiping, stamping, printing (eg pad printing), exploiting the spreading and migration properties of silicone and mineral oils.
• Partial or local order: eg by printing, spraying, possibly with masks, partial dipping; also manual part removal of the applied liquid film.
• Flat application with different layer thickness, eg due to the roughness of the substrate (higher layer thickness in the valleys, small layer thickness on the tips), due to different pretreatment methods (eg partial activation / partial cleaning); due to different pulling speed during the dipping process (dip-, draincoating), use of different squeegees etc.
• Combinations of said coating methods.

In the above methods, the surface to be coated may be displaced, rotated or otherwise moved during the liquid application, or the application unit may be moved relative to the substrate to achieve the desired one Layer thickness homogeneous or inhomogeneous or with layer thickness gradient applied to the entire or on a partial surface.

The order may be punctual, line-like, curved, 2-dimensional, 3-dimensional, in the form of a regular pattern or statistically or with the help of a mask or otherwise on the selected areas.

• Das Substrat kann mechanisch bewegt, d.h. geschüttelt oder rotiert werden, um die Flüssigkeit gleichmäßig zu verteilen
• Die Viskosität der Flüssigkeit kann durch Erwärmung erniedrigt werden, z.B. in einem Ofen, durch Bestrahlung mit IR-Licht, durch Ionen-Beschuss oder anderen dem Fachmann bekannten Verfahren. Hierdurch wird die Fließfähigkeit des Flüssigkeitsfilms erhöht, so dass die Tröpfchen ineinander fließen können.
• Das Substrat kann einer lösungsmittelhaltigen Atmosphäre ausgesetzt werden, so dass der Flüssigkeitsfilm verdünnt und somit fließfähiger gemacht wird. Unterstützt werden kann die Verdünnung durch eine tiefere Temperatur des Substrates gegenüber der Atmosphäre. Das Lösungsmittel dampft anschließend nach Entfernen der lösungsmittelhaltigen Atmosphäre ab.

Some of the mentioned application methods apply the liquid film via a droplet distribution. Even though the orders of magnitude differ in some cases significantly, this method has in common that complete coverage of the surface is achieved by overlaying and juxtaposing many individual drops. This naturally causes local differences in layer thickness. This distribution may well be desirable if this can be realized special layer properties. In order nevertheless to achieve a compensation of the layer thickness, the substrate can be treated after the actual liquid application with one or more of the following measures:

• The substrate may be mechanically agitated, ie, shaken or rotated to evenly distribute the liquid
• The viscosity of the liquid can be lowered by heating, for example in an oven, by irradiation with IR light, by ion bombardment or other methods known to those skilled in the art. As a result, the fluidity of the liquid film is increased, so that the droplets can flow into each other.
• The substrate may be exposed to a solvent-containing atmosphere so that the liquid film is thinned and thus made more flowable. The dilution can be supported by a lower temperature of the substrate compared to the atmosphere. The solvent then evaporates after removal of the solvent-containing atmosphere.

6. Substrates / Surfaces

As already described above, the coating of different surfaces is possible with appropriate selection of the precursors. In this case, it may be preferable to activate (or passivate) the surfaces by a suitable method, so that an improved (or as required weakened) adhesion of the crosslinked layer to the surface is achieved.

Suitable methods for surface pretreatment are, for example, plasma activation, flame treatment, corona treatment, laser pretreatment, fluorination, activation by irradiation with UV light, mechanical pretreatments (eg blasting, grinding, brushing, polishing), chemical pretreatments (eg cleaning, pickling , Etching, passivation), electrochemical pretreatments (eg electropolishing, anodizing, electroplating), coatings (eg by means of PVD, CVD, plasma, sol gel or painting).

Preferred surfaces (or substrates) are metals, glasses, ceramics, plastics, especially PTFE and PTFE-like materials, composites, natural materials (such as wood, paper, natural fibers), textiles, fibers, fabrics, as well as shiny, highly reflective surfaces, rough Surfaces, transparent materials such as Glasses or polymers, colored, semi-transparent materials, non-transparent materials.

Further preferred surfaces are 2D bodies with (flat) surfaces for partial coating or all-over coating, web, fibers, 2D surfaces with a slightly curved surface, 3D bodies with (flat) surfaces for partial coating or all-round coating.

7. General information on the procedure

In order to provide the person skilled in the art with instructions for the production of the coating according to the invention, procedural instructions are given below:

Pretreatment of the surface cleaning

Depending on the desired coating, it may be useful to pretreat the surface of the body to be coated. These are essentially the aspects of purification and activation.

In order to achieve good coating results, generally clean surfaces should be used. Dirt, fingerprints, shavings, dust etc. lead to coating errors and are generally to be removed according to the state of the art. For example, it is generally necessary to select solvents for cleaning depending on the soil and the surface to be cleaned. Mechanical pretreatments are e.g. Blasting, grinding, brushing, polishing; chemical pretreatments are e.g. Cleaning, pickling, etching, passivating; electrochemical pretreatments are e.g. Electropolishing, anodizing, electroplating.

If the surfaces to be coated are not afflicted with fats, oils or other impurities, manual wiping with a soft, isopropanol-soaked cloth is sufficient for easy cleaning. Dust can z. B. be blown off with compressed air.

If thin-layer organic impurities are present on the surface below 100 nm, they can be degraded by irradiation with VUV light (vacuum ultraviolet radiation with a wavelength <190 nm), preferably from an excimer lamp in the presence of oxygen. It is possible for the person skilled in the art to choose the radiation dose as a function of the contamination itself and to evaluate the cleaning success.

activation

Since functional groups are incorporated into the surface of the body to be coated by activation, they generally have a positive effect on the layer adhesion. Therefore, routine activation is generally recommended.

In order to realize thin uniform liquid layers, it is necessary that the precursor used spreads on the surface. To achieve this condition, the expert z. B. determine the solid surface tension of the substrate (the surface to be coated) and optionally increase by an activation process. Regardless of the material to be coated, it is preferable to set a solid-body surface tension above 45 mN / m, more preferably above 60 mN / m. There are a number of techniques available for activation. Activation in an oxygen plasma or activation of the surface by an excimer lamp (eg 120 s in the case of air atmosphere or 60 s irradiation with oxygen at a pressure of 100 mbar) are preferred.

Increasing the solid-state surface tension is particularly helpful in the coating of polymers, and metals can be omitted if there are no other reasons for this.

In particular, the activation in the presentation of anticorrosion layers, anti-tarnish layers, adhesion promoter and primer layers, electrical insulation layers, barrier layers, and smoothing or sealing layers is to be preferred.

For non-uniform, non-closed (partially closed) coatings can be dispensed with the activation. These include, for example, the anti-fingerprint coating.

For some coating types, such as the structured topography coating, increasing the solid surface tension can be counterproductive. Here, the effect is exploited that the precursor forms droplets on the surface. In the case of polymers to be coated therefore no pretreatment is necessary due to the low surface energy. Metals and glasses, on the other hand, should be additionally treated if necessary. Can not overflow the droplet effect the choice of precursor alone can be achieved, instead a hydrophobic coating can be used (eg by means of a plasma deposition process).

Spreading the precursor

Spitting a liquid on a solid surface is observed only under certain conditions. The behavior of a drop on a solid surface is determined overall by the three-phase system consisting of solid surface, liquid and ambient atmosphere. As a rule, the contact angle is used to describe the present energy conditions. It can be used as a measure to describe the extent to which a liquid tends to spread on the surface or form droplets. Complete spreading means that an applied drop of liquid has a contact angle of 0 degrees, which theoretically means that the liquid covers an arbitrarily large area and an applied drop independently thins infinitely. Such behavior is somewhat reminiscent of silicones that can spread over a large area over time. For the purposes of this invention and in practical terms, spreaders should be understood to mean that the static contact angle is less than 10 degrees. The person skilled in the art can determine the contact angle with a suitable measuring instrument.

A prerequisite for spreading is that the solid surface tension of the surface to be coated is significantly greater than the surface tension of the applied liquid. For practical use, it is therefore recommended that the solid surface provided has a solid surface energy of at least 45 mN / m. A solvent or diluent used for the precursor application should have a surface tension of ≦ 30 mN / m.

Selection of the precursor

Preference is given to using only precursors having a molecular weight greater than 600 g / mol.

The precursor preferably has a low vapor pressure, so that it stably covers the provided solid surface until it is irradiated. The person skilled in the art selects such a precursor from, inter alia, the planned time between the Precursor order and irradiation should elapse, based on the process temperature and the process pressure. For longer times to crosslinking greater than 1 hour, a precursor with a high viscosity should preferably be used, for example static viscosity greater than 10000 mm ² / s. Preferably, the precursor has a vapor pressure of not more than 1 mbar at 25 ° C; more preferably, the vapor pressure is not more than 0.1 mbar at 25 ° C.

For the presentation of an anti-fingerprint coating silicone oils can be used. Very useful have been found to be linear silicones with viscosity in the range 50 to 10,000 mm ² / s.

Likewise, silicones can be used for the preparation of anticorrosive coatings, as tarnish protection or as barrier layers. Due to the spreading ability, the silicones are also suitable as precursors for smoothing coatings.

Precursorauftragsverfahren

• Form bzw. 3D-Geometrie der Festköperoberfläche, Precursors, Kosten, Zeitdauer, gewünschte Oberflächenbeschichtung, Integration in den Gesamtherstellungprozess, Arbeitsdruck etc.

The choice of a suitable contracting procedure may be based on the following aspects:

• Shape or 3D geometry of the solid surface, precursors, costs, duration, desired surface coating, integration in the overall manufacturing process, working pressure, etc.

• Spincoatingverfahren eignen sich bevorzugt für flache, runde Substrate, die dem Precursor erlauben, die gesamte Oberfläche sehr gleichmäßig und in der Schichtdicke homogen zu bedecken. Das Verfahren eignet sich somit bevorzugt für geschlossene, homogene Schichten, z.B. für optische Schichten. Mit kleinen Einschränkungen können über Spincoating auch leicht gekrümmte Oberflächen beschichtet werden. Die Schichtdicke wird über die Drehzahl oder durch Verdünnen des Precursors mit einem flüchtigen Lösemittel eingestellt. Der Fachmann muss darauf achten, dass ein geeignetes Lösemittel verwendet wird, welches beim Spincoating nicht zu schnell und nicht zu langsam abdampft. Beispielsweise können lineare, nicht funktionalisierte Silikone der AK Serie (Wacker Chemie AG) mit Hexamethyldisiloxan (HMDSO) als Lösemittel ideal verwendet werden. Es entstehen aufgrund der geringen Mengen an Precursor und Lösemittel relativ geringe Kosten.

In the following, some details of preferred application methods are presented and discussed:

• Spin coating processes are preferably suitable for flat, round substrates which allow the precursor to homogeneously cover the entire surface uniformly and in the layer thickness. The method is therefore preferably suitable for closed, homogeneous layers, for example for optical layers. With small restrictions, spincoating can also coat slightly curved surfaces. The layer thickness is adjusted by the speed or by diluting the precursor with a volatile solvent. The person skilled in the art must make sure that a suitable solvent is used which does not evaporate too quickly and too slowly during spin coating. For example, linear, non-functionalized silicones of AK Series (Wacker Chemie AG) with hexamethyldisiloxane (HMDSO) can be ideally used as a solvent. Due to the small amounts of precursor and solvent, relatively low costs arise.

Dipping methods are preferred for flat and slightly curved surfaces. A suitable plunge pool can be built in almost any size. With the volume of the dip tank incurred partly not negligible costs. The component to be coated is dipped into the liquid, then pulled out at a defined speed or the liquid level is released. The speed and the ratio of the precursor to the solvent used determines the coating thickness. For example, with the silicone oil AK50 and the solvent HMDSO in a ratio of 1: 5 to 1:10 and discharge rates in the range of 1 to 10 cm / min precursor layer thicknesses in the range 50 to 500 nm can be produced. The method is predestined for layers in which the layer thickness is to be increased successively. These are homogeneous, closed layers. Undercuts may have a problem, in which the precursor accumulates and, if appropriate, uncontrollably distributed over the surface after rotating the component.

Spray methods are preferably suitable for the preparation of non-closed coatings with inhomogeneous layer thickness. In principle, you can operate all surface shapes, as long as the entire surface is accessible to the spray head. If necessary, the spraying processes are carried out without solvents. They produce a droplet distribution on the surface. The expert takes into account that the size of the droplets can vary greatly depending on the spray technique used. For example, an ultrasonic nebulizer is suitable for creating droplets of diameters up to 100 μm through the droplets (e.g., for anti-fingerprint coating). However, with suitable spray heads closed layers with layer thickness deviations of less than 10% can be produced (for example for corrosion protection, tarnish protection etc.). Spray methods should preferably be used in 3D coating and are well suited for web coating.

Aerosol processes are suitable for coating 2D and 3D bodies. The generated aerosol can be applied to the whole surface within one step. The necessary substance quantities are classified as relatively small. With the aerosol method, both closed coverings and open coverings can be realized. Aerosol methods should preferably be used in 3D coating and are also well suited for web coating. Likewise, textiles can be well coated with this method.

Roll-to-roll processes are suitable for coating flat substrates, e.g. of railway goods.

layer thicknesses

The person skilled in the art has to distinguish between average layer thickness and locally applied layer thickness. The mean layer thickness is to be understood as the layer thickness averaged over a large area. In this case, however, only the areas of the surface of the coated substrate are always included in the calculation, on which actually a (partial) coating is present. This means that in particular not to be coated backs or side surfaces are not included in this calculation. The total area of the partially coated areas is instead fully considered, i. at a e.g. island-like coating, the area fraction between the coated islands is fully taken into account. In contrast, local layer thickness means that an actually covered area of a crosslinked coating is considered.

Unless specifically desired (eg with structured coatings), it can be assumed that a surface segment of the size 1 mm ^{2 is} sufficient to be able to make a statement about the typical layer thicknesses. Therefore, the determined via an ellipsometer or reflectometer layer thickness can be regarded as the average layer thickness. For example, with the aid of a microscope, the expert can make a statement about the local layer thicknesses by considering the interference colors within the previously measured area segment.

With the method according to the invention layer thicknesses of 3 nm to 10 microns (layers without additives) can be effectively realized. The decisive factor is the layer thickness after irradiation. The person skilled in the art therefore has to determine the layer thickness after the irradiation and then to calculate the layer thickness for the precursor application on the basis of the layer shrinkage taking place during the irradiation.

The desired deviations from the local to the average layer thickness or the desired layer thickness homogeneity is preferably set by the person skilled in the art via the choice of precursor application. The skilled person has nevertheless to consider that the liquid precursor layer behaves like a liquid until irradiation (excimer crosslinking). This can lead to desirable effects: closing pores by migration; Smoothing in that the precursor accumulates preferentially in the valleys of the surface; Droplet formation for topography. Optionally, there is the possibility of using other techniques to accelerate said effects, e.g. by heat supply (by means of eg IR emitters).

For layers which give an optically homogeneous impression for the unaided eye, z. For example, two strategies can be used: On the one hand, homogeneous layers can be applied, which preferably have deviations relative to the average coating thickness of less than 10 percent. In particular, an average total layer thickness in the range from 170 to 210 nm has proven to be advantageous. This produces a yellowish-light blue color impression that is almost unnoticeable on many surfaces, especially on metals. On the other hand, coatings can be used with local layer thickness differences of up to 200%, with the entire range of layer thickness variation being set within a lateral distance below 100 μm. Such rapid layer thickness variations can not be resolved by eye due to their size (generation, for example, by spray or aerosol condensation).

For corrosion protection layers and anti-tarnish layers, it may be advantageous if these consist of a multilayer system. Particularly good results were achieved with a two-layer system, the base layer having a layer thickness below 100 nm after excimer crosslinking and the cover layer having a layer thickness above 200 nm after excimer crosslinking. The coating does not necessarily have to be homogeneous, but is usually closed.

For the production of release layers, it is advisable to use at least a layer thickness of 100 nm. Higher layer thicknesses promise a higher wear resistance. The skilled person must adjust these according to the desired requirements.

For smoothing layers, layer thicknesses in the range of 10 to 80 percent of the arithmetic roughness R _a should preferably be used. The smoothing result after the coating can be controlled, for example, by means of a profilometer for roughness determination (in the case of transparent coatings, if appropriate after vapor deposition with a thin light-reflecting layer).

For optical layers, in particular transmission and reflection layers as well as band filters, the person skilled in the art can select the layer thickness with regard to the effect to be achieved. The layer thickness can be calculated as a function of the wavelength and the refractive index (inter alia Fresnel formulas).

For scratch-resistant layers, preferably higher layer thicknesses are used or produced, for example for PC or PMMA a total layer thickness greater than 2 μm, preferably between 4 μm and 10 μm, or for aluminum a total layer thickness above 2 μm. These can be generated in one cycle or in several cycles.

For the production of an anti-fingerprint coating, a local layer thickness in the range of 150 to 250 nm is preferred. With a ratio of open to closed coating of 1: 1, the average layer thickness is preferably from 75 to 125 nm. It is preferred that the lateral dimensions of the island-like coverings be 1 to 100 μm.

Handling of the liquid precursor layer

Until the irradiation of the liquid precursor, the film behaves like a liquid. Linked effects may or may not be desirable. In particular, it is undesirable that dust reaches the surface, the precursor thus forms a meniscus, and the coating has a coating defect in the worst case.

When handling, care should therefore be taken that the precursor distribution is not changed undesirably. This also applies to the actual surface to be coated (eg, changes can be made by dust grains, precursor impurities, etc.) If necessary, prints should be used and the precursor-loaded components should be stored in closed containers. The times between the application and irradiation of the liquid film should be kept as short as possible (less than 1 hour, preferably less than 1 minute, more preferably the irradiation takes place directly after the application).

Dealing with fillers and additives

If mixtures with fillers and additives are used, the skilled person considers that these substances are present as agglomerates if they are not completely dispersed. This has the consequence that the actual particle size (of the agglomerates) differs in some cases significantly from the primary particle size specified by the supplier. It is therefore not sufficient to use a desired primary particle size, the additions must also be suitably dispersible in the precursor liquid (optionally by suitable stabilizers), otherwise the size of the agglomerates should be considered.

Fillers and agglomerates affect the actual layer thickness of the precursor. If the particle size of the additions is significantly below the targeted layer thickness, then the influence of the particles on the layer thickness can be neglected. If the particle size of the additions is of the same order of magnitude of the targeted layer thickness, menisci are formed around the particles (accumulation of precursor material), resulting in a locally increased layer thickness (and thus elevations with respect to the layer surface). The specialist observes the changes that occur. For example, with the help of a microscope, the interference colors typical of thin layers can be used for the evaluation. The particle distributions can be examined by means of a microscope or a scanning electron microscope.

The type of fillers and agglomerates selected by the expert in terms of the desired functionalities. There are numerous indications in this text.

Selection of the radiation source and the wavelength used

As the radiation source suitable according to the invention only light sources come into consideration with a wavelength of ≤ 250nm. Corresponding light sources can be, for example: excimer lasers, excimer lamps or mercury vapor lamps. The sources differ mainly in terms of the energy provided, the Spectrum and the coherence of light. All have in common that they emit high-energy light with wavelengths below 250nm. This is necessary to apply regardless of the precursor considered the required bond breaks (sufficient is the energy required to break a single bond). The generated radicals are a prerequisite for the necessary crosslinking of the precursor. The use of the radiation sources mentioned is also desirable for the penetration depth of the radiation.

The person skilled in the art selects the radiation source with regard to the planned application. He considers that lasers usually provide very high powers or intensities, but process a very narrow area segment. For small areas in the mm ² to cm ² range, a laser can be advantageous. For the processing of large areas (dm ² to m ² ), a laser must scan the surface, which has a negative effect on the total processing time. By overlapping the individual pulses inhomogeneities can also arise. Nevertheless, the treatment result is independent of distance due to the coherence of the laser. This does not apply to excimer lamps, which radiate incoherently and the radiation power decreases due to the radial radiation with the distance. Due to the radial radiation excimer lamps, however, are large-area sources of radiation and therefore to be preferred for large areas and especially for flat substrates. Mercury radiators, in contrast to the excimer sources, do not represent line radiators, which means that they radiate a certain proportion of their total radiation into spectral ranges that are not below 250 nm. The person skilled in the art therefore considers, on the one hand, that only a portion of the total power of the beam source falls within the range ≦ 250 nm and, on the other hand, that additional effects can occur due to the radiation components with wavelengths> 250 nm (for example undesirable heating due to IR radiation components).

For the presentation of local coatings, the expert can, for. For example, he uses a laser and uses the small irradiation surface to irradiate local surface elements according to the invention or he uses masks, which he irradiated over the entire surface, for example with an excimer lamp. For this, the masks should be brought as close as possible to the liquid precursor film (closer to 1 cm, preferably closer to 5 mm). The closer the mask is brought to the surface, the higher the edge sharpness can be achieved.

process atmosphere

In principle, the irradiation at atmospheric pressure, at low pressure or in different process gases and mixtures is possible. Decisive for the coating success is primarily the radiation power or dose. The process gas can determine the coating properties (e.g., oxygen for hydrophilic layers), but experience has shown that it is primarily chosen from a technical standpoint.

The person skilled in the art also takes into account that gases at wavelengths below 250 nm are also absorbed by radiation and, if appropriate, chemically converted. Radiation absorption initially reduces the radiation intensity on the surface to be treated. The skilled person should therefore check how high the actual radiant power is. This can be done by direct measurement with appropriate measuring instruments or the expert uses the associated absorption coefficient of the process gas and calculates the resulting radiant power. Generally, the lower the working pressure, the more radiation reaches the surface. Thus, with the aid of the pressure, the skilled person has a process parameter with which he can regulate the incident radiation power. The effect of absorption should not be overlooked, especially when using oxygen or oxygen-containing mixtures (including air).

The person skilled in the art must make sure that absorption can cause chemical changes in the gas atmosphere. In particular, radicals, also ozone molecules, can be generated in oxygen. These are harmful if handled incorrectly. Provision must be made here by deductions, by flushing the irradiation chamber, by housing etc.

From a technical point of view, noble gases, nitrogen or CO _{2 are} to be preferred as process gases, since these radiate the radiation of the mentioned radiation sources almost without absorption losses. By their use is given without radiation loss the opportunity to perform the irradiation even at atmospheric pressure. This has the consequence that the technical complexity can be reduced if necessary, and a system can be constructed without inline vacuum technology and inline, for example, by fabric curtains, CO ₂ tanks or the like.

Preference is given to processes that take place at atmospheric pressure, as a rule, the use of an inert gas can replace the effect of a negative pressure atmosphere. Nevertheless, the expert has to pay particular attention to the residual oxygen content. It is recommended, for example, to pump out the process chamber to a negative pressure of 10 ^-2 mbar and only then to fill it with the desired working gas atmosphere (or to take technical measures to ensure that a corresponding residual oxygen content is present in the process gas atmosphere). In the production of hydrophobic coatings, this procedure should preferably be strictly adhered to. In the production of hydrophilic coatings, a residual amount of oxygen may be quite advantageous (eg 1 to 25% oxygen in nitrogen or another inert gas or irradiation in air). The process gases are mainly reacting with radicals that are generated by the radiation in the precursor. But it is also possible that the radiation, as in the case of oxygen, generates process gas radicals already in the gas phase. This not only creates the reactive ozone, but also the possibility of reaction with the precursor. Of course, those skilled in the art will be able to use these effects in order to selectively effect, if appropriate, incorporation of process gas into the layer to be produced. It is even possible to control the amount of installed process gas via parameters such as gas composition and pressure.

Irradiation dose (choice of irradiation duration and distance)

The decisive factor is the radiation dose that falls on the precursor surface during irradiation. By radiation dose is meant the product of the radiation intensity (i.e., energy per area and time) and the treatment time period.

In principle, the radiation dose can be controlled via the time duration, the distance (for incoherent radiation sources) and via the absorption in the process gas.

A control over the process gas (by radiation absorption) is conditionally possible, unless the gas composition must be kept exactly. The pictures Fig. 6 and Fig. 7 from Example 1 illustrate the effect of the process gas on the cross-linking of an oil layer: Due to the high absorption in air, only a small part of the radiator power succeeded on the surface and the crosslinking proceeds correspondingly slower. If the person skilled in the art also uses a suitable reference substrate in his coatings, he has, as in the example At any time, it is possible to gain an impression of the effect achieved via IR spectroscopy. In this respect, reference is also made to the statements and parameters of this and other examples.

• Strahlerleistung P=100W auf h=40cm Lampenlänge. Für einen Abstand von r=10cm vom Mittelpunkt der Lampe aus ergibt sich die Strahlungsintensität wie folgt: Die Oberfläche eines Zylinders im Abstand von r=10cm beträgt A=2*Pi*r*h~2500cm², die Intensität beträgt somit I=P/A~40mW/cm². Für eine Bestrahlungsdauer von t=60s ergibt sich somit eine Strahlungsdosis von I*t~2,4Ws/cm².

In order to further assist the person skilled in the art, some estimates for the selection of a suitable radiation dose are given at this point according to the invention:

• Spotlight power P = 100W to h = 40cm lamp length. For a distance of r = 10cm from the center of the lamp, the radiation intensity is as follows: The surface of a cylinder at a distance of r = 10cm is A = 2 * Pi * r * h ~ 2500cm ² , the intensity is thus I = P / A ~ 40mW / cm ² . For an irradiation period of t = 60s, this results in a radiation dose of I * t ~ 2.4Ws / cm ² .

• Z.B. ist die Bestrahlung eines Silikonöls bei Luft mit einer Dosis von 65mWs/cm² (inklusive Absorption) ausreichend, um eine Veränderung der Schichteigenschaften mit der IR-Spektroskopie zu erkennen, die Dosis ist jedoch nicht ausreichend, um eine feste Schicht zu erzeugen. Für eine nicht abwischbare Schicht sind hier mindestens 2Ws/cm² bei Luftatmosphäre notwendig.

In example 1, table 2 and tab. 3 give some parameters for irradiation:

• For example, irradiation of a silicone oil in air at a dose of 65mWs / cm ² (including absorption) is sufficient to detect a change in layer properties with IR spectroscopy, but the dose is insufficient to produce a solid layer. For a non-wipeable layer at least 2Ws / cm ² in air atmosphere are necessary here.

For the irradiation of a silicone oil in a nitrogen atmosphere z. B. with a dose of 400mWs / cm ² already a smudge-resistant coating are generated when irradiated with 12Ws / cm ^{2 to} obtain a smudge-proof, hydrophilic layer.

Reference is made to Example 1.

For orientation, the following parameter range for the irradiation with an excimer lamp at 172 nm (100 W, length 40 cm) in nitrogen is mentioned in order to obtain a smudge-resistant coating: Radiation dose: Distance to the lamp center irradiation time intensity 500 mWs / cm ² 3 cm ~ 4 s 130 mW / cm ² 10 centimeters ~ 13s 40 mW / cm ² 10 Ws / cm ² 3 cm ~ 80 s 130 mW / cm ² 10 centimeters ~ 250 s 40 mW / cm ²

It is preferred for practical use with a UV excimer lamp with a central emission wavelength of 172 nm to narrow the working range for all applications to the following parameter range: Radiation dose: Distance to the lower edge of the lamp irradiation time intensity 200 mWs / cm ² to 200 Ws / cm ² 0.1 to 10 cm 0.5 second to 20 minutes. 1 to 10,000 mW / cm ²

For the treatment of web material, it is recommended to choose the distance as low as possible in order to realize short irradiation times over a high intensity and thus to enable a high web speed.

For 3D objects or surfaces with height differences in the cm range it is recommended to choose a higher working distance. This reduces the relative differences in local radiation doses compared to a small working distance.

number of cycles

Since the radiation dose is critical to the coating result, a 1-ply layer may optionally be irradiated within a cycle or for the same total exposure time in any number of short cycles. When using lasers, it should be noted that they work well in pulsed mode. Here, each individual pulse is to be regarded as a separate cycle. Unless there are reasons against it (e.g., heating at very high doses of irradiation), it is preferable to crosslink the coating within one cycle.

For some coatings, good adhesion or a closed, defect-free coating is crucial. For these layers e.g. Scratch-resistant layers, anti-corrosion layers, tarnish layers, it is advisable to design the coating as a multi-layer system. Here, the coating defects (uncoated surface segments) are reduced by the multiple coating. Within each cycle, precursor material is applied and subsequently irradiated and thus crosslinked in a layer-forming manner. In this case, the first layer, base layer, after irradiation preferably has a layer thickness of not more than 100 nm. The second layer, covering layer, preferably has a layer thickness above 200 nm after irradiation. Scratch-resistant layers require layer thicknesses in the micrometer range. Here it is preferred to design these layers as multilayer systems, wherein preferably each layer has a thickness in the range of 500 nm to 2 μm after irradiation.

An anti-fingerprint coating can be irradiated within one cycle.

For the coating of web products, the one-time treatment of each surface segment in a continuous process is recommended.

Carbon content

The carbon content in the coating depends on the precursor material used and the intensity of the treatment. The proportion of carbon tends to decrease with the duration of the irradiation. The expert can reduce the carbon content with the aid of z. B. determine an XPS analysis.

It has been found that coatings with a carbon content ≥ 10 atom%, based on the amount of atoms contained in the layer without H and F, have special properties in terms of their flexibility. This property is particularly useful for highly crosslinked systems such as e.g. Tarnish protection, corrosion protection or scratch protection of high interest, since the alternative methods usually offer such layer functionalities only as strong brittle systems, which provide no flexibility. Unless otherwise stated, it is therefore preferable to adjust such layers to have a carbon content in the range of 10 to 20 atomic%.

For the design of an easy-to-clean layer refer to the information on the carbon content in section 8.6.

Furthermore, reference is made to the process parameter data, Tab. 7, of Example 4, in which the percentage data of the atomic composition for the excimer irradiation of silicone oils are shown systematically.

For an anti-fingerprint coating, the carbon content is less of interest, here are the adhesion and the optical properties of the coating in the foreground.

For the design of a PDMS-type coating, reference should be made in this connection to the information on the carbon content in Section 8.2.

8. Applications

Hereinafter, various particularly preferred embodiments of the invention will be described. Further references to the embodiments can also be found in the figures, the examples and the claims. It is easy for the person skilled in the art to understand that the information, features and procedures or parts thereof are not limited to the particular application. Rather, those skilled in the art will be able to combine the knowledge or portions of the knowledge disclosed herein for individual applications with those of other applications disclosed herein.

8.1 Crosslinked coating according to the invention with dispersed finely divided solids

By means of the method according to the invention, it is possible to produce layers with nanoscale-dispersed particles which are inorganic and, in particular, metallic (possibly magnetizable), which have the properties described in US Pat DE 197 56 790 A1 revealed layers are very similar in their properties. Accordingly, the person skilled in the art receives further information on the process design and the properties of the corresponding layers in the process DE 197 56 790 A1 , whose content here becomes part of the present application by way of reference. This applies in particular to the passages column 4, line 66 to column 5, line 5; Column 5, line 43 to column 5, line 46; Column 6, lines 22 - 31.

By means of the method according to the invention, in particular also its preferred embodiments, it is accordingly possible in a first application according to the invention to produce crosslinked layers and articles having crosslinked coatings which comprise dispersed finely divided solids. Accordingly, part of the first preferred embodiment of the invention is a layer according to the invention and an article according to the invention, wherein the crosslinked layer comprises finely divided solids, characterized in that the solids have a particle size of <200 nm, preferably <100 nm, and are substantially chemically unbound the matrix of the crosslinked layer.

Further preferred in this context is that the solids have a particle size in the range of less than 20 nm, detected for example by transmission electron microscopy (TEM).

It is particularly preferred that the solids have a particle size in the range of 5 to 10 nm.

Further preferred is an article according to the invention according to the first preferred application according to the invention, wherein the crosslinked layer comprises 0.1 to 30% by volume of finely divided solids having a particle size <200 nm and wherein the crosslinked layer more preferably comprises 1 to 10% by volume of finely divided solids.

It is preferred in this context that the finely divided solids are metal particles which are particularly preferably magnetizable.

As an alternative to the latter, it may be preferred that the finely divided solids consist of silver or copper.

Furthermore, a component of the preferred embodiment of the invention described here is that the matrix has been produced from silicone compounds or partially or completely fluorinated liquids.

The starting point for the production of the coating is a dispersion of inert liquid precursors and the particles (finely divided solids). The selection of the particles depends on the later desired surface function. For example, photochromic and electrochromic substances, reflective and partially reflecting substances, conductive substances, corrosion inhibitors, dyes, luminescent dyes, in particular electroluminescent, cathodoluminescent, chemiluminescent, bioluminiuszente, thermoluminescent, sonoluminescent, fluorescent and / or phosphorescent luminescent dyes, organic or inorganic color pigments, magnetic Substances, salts (eg salts of organic and inorganic acids, metal salts). By way of example, copper, zinc sulfide, magnetite, zinc oxide, aluminum oxide, silicon oxide, boron nitride and graphite are listed. For the preparation of dispersions with nanoparticles, see the VERL procedure, which is described in chapter 7.3. is explained in more detail.

The possible degree of filling of the dispersion with particles depends on the particle size, the processing boundary conditions such as viscosity and agglomeration behavior. If necessary, the person skilled in the art will further dilute the mixture with a suitable solvent so that the application according to the invention is possible, for example via a spraying process becomes. Anschießend the networking is generated. Here it is advantageous to illuminate the surface from different angles in order to avoid shadows. Otherwise, the irradiance is aligned according to the desired properties of the matrix. For the evaluation of the particle distribution and particle size are suitable imaging techniques, such as microscopy, scanning electron microscopy and transmission electron microscopy.

The article coated in accordance with the invention described in this section is preferably a plastic, metal, glass or ceramic article. Examples are articles having surfaces which require the following functions: improved abrasion and scratch resistance properties through the incorporation of particles; Coatings, the continuous, long-term release of functional materials: e.g. (Bio) catalysts, enzymes, hormones, proteins, nutrients, pheromones, emulsifiers or surfactants, antimicrobials, medically active substances (agents), growth substances for bone growth, odor and fragrances, pesticides, lubricants, edible oils / waxes; active coatings for protection against the attachment of biological pests such as microorganisms, algae, plants and microorganisms; Objects with altered haptics, with electrostatic properties of components made of non-conductors such as plastics; Surfaces with a reduced tendency to build up dust; with 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. For the use of these released substances a variety of applications is 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 conservation of goods worthy of protection (works of art, archaeological finds, building fabric). In this case, the coating according to the invention can be applied both directly to the desired objects as well as on carrier materials to films (possibly coated as a web) or powder.

8.2 PDMS-type coating:

According to a second preferred embodiment of the invention (hereinafter also the second embodiment), it is possible by means of the method according to the invention to produce layers and apply to products which are very similar in structure to plasma-polymeric, PDMS-like coatings, as described in the German patent application 10 2006 018 491.2 are described. The content of this application is incorporated by reference into the present application, in particular the areas which relate to the description of the recording of the ESCA spectra and the ESCA measurements.

For the production of PDMS-like coatings by means of the process according to the invention, it is possible to use as starting material simple, linear silicones of the structure

(CH ₃ ) ₃ Si - (O - Si (CH ₃ ) ₂ -) _n O - Si (CH ₃ ) ₃ with n> 0

to use. Likewise, it is also possible to use cyclic dimethyl silicones and / or silicones with short and / or long chain branching and / or copolymers with a content of more than 50% of dimethylsiloxane units. When selecting the materials one is not limited to these materials, it is important to provide a high proportion of alkyl groups. It may be bound instead of methyl groups and other hydrocarbon groups on the siloxane skeleton.

During production, it is essential to ensure that the radiation intensity is kept low and that the resulting radicals (especially those on the surface) are not saturated with polar elements or substances.

Preference is given to working in an N ₂ or H ₂ gas atmosphere, more preferably in low pressure.

In the production of the layer according to the invention, the person skilled in the art will proceed in such a way that, for a given precursor type and thickness, he will first set a working distance suitable for the component geometry and then successively increase the illumination time for a given radiation intensity. He will find that at some point the liquid precursor begins to solidify. This is the interesting workspace. Here should then by fine tuning the desired Layer properties, such as non-stick behavior, hydrolytic stability or electrical insulation can be optimized. Additional control options are provided by measuring the water 's edge angle on flat substrates, infrared spectroscopy and ESCA analysis.

Accordingly, constituents of the second embodiment of the invention are a layer according to the invention and an article according to the invention, wherein the crosslinked layer is a layer consisting of carbon, silicon, oxygen and hydrogen and optionally conventional impurities, wherein in the ESCA spectrum of the (excimer) crosslinked product, when calibrated to the aliphatic portion of the C 1s peaks at 285.00 eV, compared with a trimethylsiloxy-terminated polydimethylsiloxane (PDMS) with a kinematic viscosity of 350 mm ² / s at 25 ° C and a density of 0.97 g / mL at 25 ° C,

the Si 2p peak has a binding energy value shifted by a maximum of 0.50 eV to higher or lower binding energies, and

the O 1s peak has a binding energy value shifted by a maximum of 0.50 eV to higher or lower binding energies.

Further preferred embodiments of the second embodiment in particular of the invention can be found in the claims 28 to 36 explained in more detail.

In the process according to the invention produced layers (according to the second embodiment of the invention) are particularly in their preferred embodiments hydrolysis resistant, elastic and thus crack-free and stretchable up to elongations of> 50% (in preferred embodiments> 100%). Crosslinked layers as in the second embodiment of the invention described provide a flexible barrier to migration. Further, they possess non-stick properties and improved in comparison with a variety of elastomers lubricity (see as far as the sliding properties of fluoroelastomers such as Viton ^®, silicone rubbers, rubber etc.) since the usual for such elastomers Oberflächenklebrigkeit (tack) is missing or greatly reduced.

Particularly preferred is an article produced in the process according to the invention in which the crosslinked coating has a thickness in the range from 1 to 2000 nm. Preferably, the crosslinked layer in the second embodiment of the Non-destructive detachable from the surface and can thus optionally be used as a film. Preferably, the layer is designed so that it does not allow the passage of molecules having a molecular weight of 100 g / mol or more, preferably 50 g / mol or more. It thus represents a permeation barrier for molecules having a molecular weight of 100 g / mol (or 50 g / mol) or more.

In our own investigations, it has been found that such a crosslinked layer (or film) already completely prevents the passage of molecules having a molecular weight of 100 g / mol (preferably 50 g / mol), in some cases well below 1000 nm. The film or coating is flexible and elastic, so that it does not come to unwanted cracks in their use, which could allow the passage of the said molecules through the coating.

In particular, when the article according to the invention comprises a crosslinked layer as a permeation barrier, it is advantageous if the article is an elastomer having a layer crosslinked thereon and having a thickness in the range from 1 to 2000 nm. The layer may be non-destructive or non-destructive removable.

However, the advantage of such an article is not always in its capacity as a permeation barrier. In other instances, the advantage of an article comprising an elastomeric substrate and a crosslinked coating disposed thereon is that the coating significantly increases the slip properties as compared to the untreated substrate because the tack is minimized.

• Artikel, (Gegenstand) mit einer Migrationssperre (Migrationsbarriere) gegenüber Molekülen mit einer Molmasse von 100 g/mol oder mehr, vorzugsweise 50 g/mol oder mehr, umfassend eine vernetzte Schicht wie oben definiert als Migrationssperre (Migrationsbarriere) oder Teil einer Migrationssperre,
• Artikel mit einer Dichtung, umfassend eine vernetzte Schicht wie oben definiert als Dichtung oder Dichtungsbestandteil,
• optisches Element mit einer Beschichtung, umfassend eine vernetzte Schicht wie oben definiert als Beschichtungsmaterial,
• Artikel, umfassend ein korrosionsempfindliches Substrat und eine darauf angeordnete Korrosionsschutzbeschichtung, umfassend eine vernetzte Schicht wie oben definiert als Korrosionsschutzbeschichtung oder Teil der Korrosionsschutzbeschichtu ng,
• Artikel, umfassend ein Substrat mit Easy-to-Clean-Beschichtung, umfassend eine vernetzte Schicht wie oben definiert als Easy-to-Clean-Beschichtung oder Teil der Easy-to-Clean-Beschichtung, insbesondere für die Anwendung im Bereich der Klebstoff- und Lackverarbeitung, der Gummi- und Kunststoffverarbeitung und der Lebensmittelverarbeitung,
• Artikel, umfassend ein Substrat (insbesondere auch ein (technisches)Textil) mit (hydrolysebeständiger) Easy-to-Clean-Beschichtung, umfassend eine vernetzte Schicht wie oben definiert als (hydrolysebeständige) Easy-to-Clean-Beschichtung oder Teil der (hydrolysebeständigen) Easy-to-Clean-Beschichtung,
• Artikel, umfassend ein Substrat (insbesondere auch eine Membran) mit (hydrolysebeständiger) Easy-to-Clean-Beschichtung bzw. Hydrophobausrüstung, umfassend eine vernetzte Schicht wie oben definiert als (hydrolysebeständige) Easy-to-Clean-Beschichtung bzw. Hydrophobausrüstung oder Teil der (hydrolysebeständigen) Easy-to-Clean-Beschichtung bzw. Hydrophobausrüstung,
• Artikel, umfassend ein Substrat mit einer antibakteriellen Beschichtung, insbesondere nach oder analog DE 103 53 756 , umfassend eine vernetzte Schicht wie oben definiert als (nicht zytotoxische) antibakterielle Beschichtung oder Teil der antibakteriellen Beschichtung,
• Artikel, umfassend ein Substrat zur Herstellung einer Verpackung mit einer antibakteriellen Beschichtung, insbesondere nach oder analog PCT/EP 2004/013035 , umfassend eine vernetzte Schicht wie oben definiert als (nicht zytotoxische) antibakterielle Beschichtung oder Teil der antibakteriellen Beschichtung,
• Artikel, umfassend ein Substrat, insbesondere ein Wärmetauscher oder Teile eines Wärmetauschers, und eine darauf angeordnete Beschichtung, umfassend eine vernetzte Schicht wie oben definiert mit hydrophoben, hydrolysestabilen, korrosionsschützenden Oberflächeneigenschaften, welche die Wärmeleitfähigkeit vorzugsweise nur kaum messbar verändert.
• Artikel, umfassend ein Substrat mit einer (bevorzugt excimer-)vernetzten Trennschicht, umfassend eine vernetzte Schicht wie oben definiert als Trennschicht oder Teil der Trennschicht oder Teil einer UV-transparenten Trennschicht.
• Artikel, umfassend ein Elastomerprodukt und eine die Gleitfähigkeit erhöhende Beschichtung auf dem Elastomerprodukt, umfassend eine vernetzte Schicht wie oben definiert als Beschichtung oder Bestandteil der Beschichtung,
• Artikel, umfassend ein Substrat, insbesondere eine optische Komponente einer lithographischen Anlage, und eine darauf angeordnete Beschichtung, umfassend eine vernetzte Schicht wie oben definiert als hydrolysebeständige, stark hydrophobe und weitgehend UV-transparente Schutzschicht.
• Artikel, umfassend ein Substrat, insbesondere ein Stempel, weiter insbesondere ein Stempel für die Anwendung in der Nanoimprint - Technologie, und eine darauf angeordnete Beschichtung, umfassend eine vernetzte Schicht wie oben definiert als weitgehend UV-transparente Trennschichtbeschichtu ng.
• Artikel, umfassend eine vorzugsweise excimervernetztvernetzte Beschichtung mit einem Defekt und eine Reparaturfolie zur Reparatur des Defektes, umfassend eine excimervernetztvernetzte Schicht wie oben definiert als Reparaturfolie oder Bestandteil der Reparaturfolie,
• Artikel, umfassend mindestens zwei härtere Schichten oder Substrate, vorzugsweise mit Barriereeigenschaften, und mindestens eine weiche Spacerschicht zwischen den härteren Schichten oder Substraten, umfassend eine vernetzte Schicht wie oben definiert als Spacerschicht oder Bestandteil der Spacerschicht,
• Artikel, umfassend eine Barrierebeschichtung oder ein Substrat zur Verringerung der Migration von Gasen und Dämpfen, insbesondere Wasserdampf, Kohlendioxid oder Sauerstoff, mit einer hydrophoben Deckschicht, umfassend eine vernetzte Schicht wie oben definiert als Deckschicht oder Bestandteil der Deckschicht,
• Artikel, umfassend ein vorzugsweise elektrisches Bauelement und eine elektrisch isolierende Folie oder Beschichtung, umfassend eine vorzugsweise hydrophobe vernetzte Schicht wie oben definiert als isolierende Folie oder isolierende Beschichtung oder Teil einer solchen Folie oder Beschichtung.
• Artikel, umfassend einen vorzugsweise implantierbaren medizintechnischen Gegenstand umfassend eine vernetzte Schicht wie oben definiert. Vorteilhafter Weise erlaubt die Beschichtung aufgrund ihrer dehäsiven Oberflächeneigenschaften die Verminderung der Haftung von Bakterien, Eiweißen oder anderen körpereigenen Stoffen (ggf. durch Medikamente modifiziert).
• Vorzugsweise implantierbarer medizintechnischer Silikon-Artikel, umfassend als Beschichtung eine vernetzte Schicht wie oben definiert. Vorteilhafter Weise erlaubt die Beschichtung aufgrund ihrer dehäsiven und/oder dehnfähigen Oberflächeneigenschaften die Erhöhung der Körperverträglichkeit (insbesondere ist die erfindungsgemäße Beschichtung insoweit geeignet, da keine niedermolekularen Reaktionsendprodukte vorhanden sind).

More specifically, according to the second embodiment, the product of the present invention may be selected from the group consisting of (the (excimer) crosslinked layer each having the function):

• An article (article) having a migration barrier (migration barrier) to molecules having a molecular weight of 100 g / mol or more, preferably 50 g / mol or more, comprising a crosslinked layer as defined above as a migration barrier (migration barrier) or part of a migration barrier,
• An article comprising a gasket comprising a crosslinked layer as defined above as a gasket or gasket component,
• optical element having a coating comprising a crosslinked layer as defined above as the coating material,
• An article comprising a corrosion-sensitive substrate and a corrosion protection coating disposed thereon, comprising a crosslinked layer as defined above as an anti-corrosion coating or as part of the anti-corrosion coating,
• An article comprising a substrate having an easy-to-clean coating comprising a crosslinked layer as defined above as an easy-to-clean coating or as part of the easy-to-clean coating, especially for use in the field of adhesives and adhesives Paint processing, rubber and plastics processing and food processing,
• An article comprising a substrate (especially also a (technical) textile) with (hydrolysis-resistant) easy-to-clean coating, comprising a crosslinked layer as defined above as (hydrolysis-resistant) easy-to-clean coating or part of (hydrolysis-resistant) Easy-to-clean coating,
• An article comprising a substrate (especially also a membrane) with (hydrolysis-resistant) easy-to-clean coating or hydrophobic finish, comprising a cross-linked layer as defined above as (hydrolysis-resistant) easy-to-clean coating or part of the (hydrolysis-resistant) easy-to-clean coating or hydrophobic equipment,
• An article comprising a substrate having an antibacterial coating, in particular after or analogously DE 103 53 756 comprising a crosslinked layer as defined above as a (non-cytotoxic) antibacterial coating or part of the antibacterial coating,
• An article comprising a substrate for producing a package having an antibacterial coating, in particular according to or analogously PCT / EP 2004/013035 comprising a crosslinked layer as defined above as (not cytotoxic) antibacterial coating or part of the antibacterial coating,
• An article comprising a substrate, in particular a heat exchanger or parts of a heat exchanger, and a coating disposed thereon comprising a crosslinked layer as defined above having hydrophobic, hydrolysis-stable, anti-corrosive surface properties which preferably barely measurably alter the thermal conductivity.
• An article comprising a substrate having a (preferably excimer-) crosslinked release layer comprising a crosslinked layer as defined above as a release layer or part of the release layer or part of a UV-transparent release layer.
• An article comprising an elastomeric product and a lubricity enhancing coating on the elastomeric product comprising a crosslinked layer as defined above as a coating or component of the coating.
• An article comprising a substrate, in particular an optical component of a lithographic unit, and a coating disposed thereon comprising a crosslinked layer as defined above as a hydrolysis-resistant, highly hydrophobic and substantially UV-transparent protective layer.
• An article comprising a substrate, in particular a stamp, more particularly a stamp for use in nanoimprint technology, and a coating disposed thereon, comprising a crosslinked layer as defined above as a substantially UV-transparent release layer coating.
• An article comprising a preferably excimer-crosslinked, defect-cured coating and a repair film for repairing the defect, comprising an excimer-crosslinked layer as defined above as a repair sheet or as a constituent of the repair sheet.
• An article comprising at least two harder layers or substrates, preferably having barrier properties, and at least one soft spacer layer between the harder layers or substrates comprising a crosslinked layer as defined above as a spacer layer or as part of the spacer layer,
• An article comprising a barrier coating or a substrate for reducing the migration of gases and vapors, in particular water vapor, carbon dioxide or oxygen, with a hydrophobic cover layer comprising a crosslinked layer as defined above as cover layer or constituent of the cover layer,
• An article comprising a preferably electrical component and an electrically insulating film or coating comprising a preferably hydrophobic crosslinked layer as defined above as an insulating film or insulating coating or part of such a film or coating.
• An article comprising a preferably implantable medical article comprising a crosslinked layer as defined above. Advantageously, the coating allows due to their dehäsiven surface properties, the reduction of the adhesion of bacteria, proteins or other endogenous substances (possibly modified by drugs).
• Preferably, an implantable medical grade silicone article comprising as a coating a crosslinked layer as defined above. Advantageously, because of its dehydrating and / or elastic surface properties, the coating allows the increase of the body compatibility (in particular, the coating according to the invention is suitable insofar as no low-molecular reaction end products are present).

These mentioned embodiments are not limited to the second embodiment of the invention, but the composition of the crosslinked in the process according to the invention layer according to the second embodiment is just a preferred embodiment of the article (article). Accordingly, corresponding articles such as the enumerated below part of the invention , the one The invention comprises a layer which does not correspond in its composition to the second embodiment.

• Migrationssperre (Migrationsbarriere) gegenüber Molekülen mit einer Molmasse von 100 g/mol oder mehr, vorzugsweise 50 g/mol oder mehr,
• Deckschicht auf einer Barrierebeschichtung oder einem Substrat zur Verringerung der Migration von Gasen und Dämpfen, insbesondere Wasserdampf, Kohlendioxid oder Sauerstoff,
• Dichtungsmaterial, insbesondere für Dichtungen mit einer Dicke von maximal 1000 nm,
• flexible Beschichtung eines flexiblen Verpackungsmaterials,
• Folie oder Beschichtung zur Vergütung optischer Elemente,
• hydrolysebeständige Beschichtung,
• hydrophobe Beschichtung,
• antibakterielle Beschichtung, insbesondere nicht zytotoxische antibakterielle Beschichtung,
• Korrosionsschutzbeschichtung,
• Easy-to-Clean-Beschichtung,
• die Gleitfähigkeit erhöhende Beschichtung auf einem Elastomerprodukt,
• Schutz- und/oder UV-transparente, hydrolysestabile Folie, insbesondere für optische Elemente von lithographischen Anlagen, weiterhin bevorzugt für optische Elemente von immersions-lithographischen Anlagen,
• Trennschicht oder Teil einer Trennschicht oder Teil einer UV transparenten Trennschicht zur leichteren Entformung von Kunststoffbauteilen oder Ablösung von Kunststoffen
• Reparaturfolie, insbesondere für Easy-to-Clean- oder Trennschichtanwendungen oder optische Anwendungen,
• Folie oder Beschichtung mit dehäsiven und adhäsiven Oberflächeneigenschaften,
• Folie mit Loch- und/oder Streifenmuster insbesondere zur Beschichtung hydrophiler Substrate zur Herstellung von lokalen Hydrophil- bzw. Hydrophobbereichen.
• weiche Spacerschicht zwischen härteren, voneinander zu separierenden Schichten oder Substraten, insbesondere Barriereschichten,
• stark hydrophobe Deckschicht, insbesondere zur Verhinderung der Adsorption von polaren Molekülen oder zur Verbesserung der Barriereeigenschaften von Barrierebeschichtungen bzw. Ultra-Barrierebeschichtungen gegenüber Gasen und Dämpfen wie Wasserdampf, Kohlendioxid oder Sauerstoff.
• Isolatorfolie oder -beschichtung insbesondere in elektrischen Bauelementen,
• Trennschicht bzw. stark hydrophobe Schicht auf diamantähnlichen Beschichtungen, insbesondere dünnen, chemisch auf das Substrat angebundenen Beschichtungen.

Accordingly, the invention relates (preferably but not exclusively to the second embodiment) to the use of a crosslinked layer, preferably as defined above (as an article or component of an article according to the invention)

• Migration barrier (migration barrier) to molecules with a molecular weight of 100 g / mol or more, preferably 50 g / mol or more,
• Covering layer on a barrier coating or a substrate for reducing the migration of gases and vapors, in particular water vapor, carbon dioxide or oxygen,
• Sealing material, in particular for gaskets having a maximum thickness of 1000 nm,
• flexible coating of a flexible packaging material,
• Foil or coating for the compensation of optical elements,
• hydrolysis-resistant coating,
• hydrophobic coating,
• antibacterial coating, in particular non-cytotoxic antibacterial coating,
• Anti-corrosion coating,
• Easy-to-clean coating,
• the lubricity enhancing coating on an elastomer product,
• Protective and / or UV-transparent, hydrolysis-stable film, in particular for optical elements of lithographic installations, furthermore preferred for optical elements of immersion lithographic installations,
• Separating layer or part of a separating layer or part of a UV transparent separating layer for easier demolding of plastic components or separation of plastics
• Repair film, in particular for easy-to-clean or interface applications or optical applications,
• Film or coating with adhesive and adhesive surface properties,
• Foil with hole and / or stripe pattern, in particular for coating hydrophilic substrates for the production of local hydrophilic or hydrophobic areas.
• soft spacer layer between harder layers or substrates to be separated from one another, in particular barrier layers,
• highly hydrophobic cover layer, in particular for preventing the adsorption of polar molecules or for improving the barrier properties of barrier coatings or ultra-barrier coatings to gases and vapors such as water vapor, carbon dioxide or oxygen.
• Insulator film or coating, especially in electrical components,
• Separating layer or highly hydrophobic layer on diamond-like coatings, in particular thin, chemically bonded to the substrate coatings.

Application: migration barrier

In particular within the scope of the second embodiment of the invention, an article according to the invention may comprise a crosslinked layer as a migration barrier (migration barrier) with respect to molecules having a molecular weight of 50 g / mol or more, preferably 100 g / mol or more. Of particular importance is the barrier effect against organic molecules. Concrete examples of the migration barrier application are migration barriers to prevent the escape of unwanted substances from a substrate, such as water. B. the barrier to additives (eg plasticizers) from a plastic substrate (this application is of particular importance for food and pharmaceutical packaging). Accordingly, an article according to the invention can be or comprise a food packaging, on whose side facing the food a crosslinked layer is applied. The food packaging itself serves as a substrate in such a product; Examples of food packaging materials that can be sealed to the food by a crosslinked coating made in accordance with the present invention include, for example, flexible PVC, polyurethane foams, etc. In these examples, the crosslinked layer serves to prevent leakage of an undesirable substance from the substrate into the food. Of course, as a migration barrier, a crosslinked layer according to the invention also prevents the entry of an undesired substance into a substrate just as easily.

An example of such a migration barrier for preventing the entry of an undesired substance into a substrate is a migration barrier that is disposed on a plastic substrate and prevents the entry of solvents, toxins or dyes from a liquid into the substrate, which shorten the life of the plastic substrate. cause unwanted contamination of the substrate or could stain the substrate.

The use of the crosslinked layer is particularly advantageous if, in addition to the barrier effect, one or more of the following technical requirements are present: transparency; low coating thickness of z. B. less than 0.5 microns; high UV stability.

Typical substrates to which a crosslinked layer produced according to the invention can be applied in order to act as a migration barrier are films, Sealing materials (eg PVC gaskets in screw caps, especially in the food industry) Rubber seals, packaging (foodstuffs, pharmaceuticals, cosmetics, medical technology, etc.), textiles, exposure matrices for UV curing etc. The networked migration barriers are physiologically harmless and have a very good life cycle assessment.

In connection with the field of application "migration barrier", it should be noted that inorganic coatings such as SiO _x or AlO _x are often used today as transparent barrier coatings. These coatings can be made by various vacuum methods, e.g. As with PVD, CVD or plasma-assisted CVD (PE-CVD). With the said coatings, good barrier properties can be achieved on suitable substrate surfaces from a coating thickness of 20 nm, however, cracks occur at about 100 nm thickness in the said coatings, which make them again more permeable. This also applies to plasma-polymer barrier layers of a hitherto conventional structure. In addition, the said coatings are brittle and therefore fragile. It is therefore considered that for a very good barrier based on the known coating methods, a nearly defect-free inorganic coating is required.

Another disadvantage of the known inorganic coatings is that they are relatively inflexible. In a variety of applications, however, there is a deformation of the substrate surface, which leads to the formation of cracks in the use of said conventional coatings and thus to the loss of the barrier property. In contrast to the hitherto known inorganic migration barriers, z. B. based on SiO _x , the crosslinked layers according to the invention are softer and more flexible.

The present invention thus also achieves the object of providing an improved thin-film coating system which represents a suitable migration barrier.

For the provision of particularly good barrier coating systems, for example so-called ultra-barriers, also for gases and vapors with a low molecular weight, a layer produced according to the invention can be used as an intermediate layer (spacer layer) in a composite of thin layers. For example For example, it may be used in combination with thin films deposited by PVD, CVD or plasma assisted CVD (PE-CVD) (such as the highly inorganic SiO _x and AIO _x coatings described above). Here, for example, it can reduce the tendency to crack due to internal (mechanical) stresses at thicker "total layer thicknesses". In addition, the flexibility of such a layer composite is increased in comparison with a barrier layer without the intermediate layer according to the invention.

A further improvement of barrier layers or ultra-barrier layers for low molecular weight gases and vapors can be achieved by the use of the crosslinked layer as defined above as a cover layer. Due to its highly hydrophobic surface, it reduces the adsorption of polar molecules, such as water, which often significantly influence the rate of migration.

Field of use. hydrolysis

Hydrolysis resistant coatings are needed in various technical fields of application.

For example, hydrolysis-resistant, hydrophobic, anticorrosive thin-layer coatings, which do not hinder heat conduction, are required in the area of heat exchangers. In heat exchangers saturated water vapor atmospheres often occur at elevated pressures. By contrast, the heat exchanger surfaces are comparatively cool, so that moisture (sometimes strongly acidic) condenses out. So that no water film forms on the heat exchanger surfaces and, if appropriate, no corrosion takes place, it is advantageous if these surfaces are made hydrophobic in order to prevent the formation of a water film, which would additionally cool and hinder the heat conduction. A heat exchanger whose heat exchanger surfaces are provided with a crosslinked layer prepared according to the invention and composed as described in the second embodiment is an example of a preferred product according to the invention.

Another field of application for hydrolysis-resistant coatings is in the field of papermaking. In the field of papermaking, hydrolysis-resistant coatings with non-stick properties are needed to prevent the so-called Prevent stickies. It has been found that the sticking of stickies by equipping the affected parts of a papermaking machine with a crosslinked layer made according to the invention as defined above prevents the sticking of stickies completely or at least very substantially.

In the area of the production of filter materials also hydrolysis resistant, chemically inert hydrophobic coatings are needed. For example, such filters (so-called Hepafilter) are used in systems in which food packaging before sterilization with H ₂ O _{2 are} sterilized. Corresponding vapors, as well as cleaning media can change an unprotected filter and make it useless.

Likewise, the said crosslinked layer can be applied as a hydrolysis protective cover layer to other thin-layer systems, which in turn have been applied, for example, by PVD, CVD, plasma-assisted CVD (PE-CVD), plasma polymerization, galvanically or in a sol-gel process. In particular, inorganic coatings such as SiO _x and AIO _x coatings, despite their good corrosion protection properties, for example on anodized aluminum substrates, a comparatively low resistance to hydrolysis and are preferably equipped with a according to the invention, preferably as defined above crosslinked layer.

Application: Non-stick property / Easy-to-clean properties

In a variety of tools and machines non-stick properties and / or easy-to-clean properties are desired. In particular, tools and machines (such as bookbinding machines, adhesive applicators, sealers, printing units, laminating installations, painting installations, components for painting installations, food processing installations) which are provided with adhesives (for example hot-melts, 1-component and 2-component Component adhesive with and without solvent or cold glue), paints, paints, plastics or foodstuffs come into contact; Examples include storage tanks, pumps, sensors, mixers, pipelines, guns, gratings, spray guns, baking trays, automotive components, such as screens etc. Particularly in the area of sensors, there is a particular need for non-stick coatings or easy-to-clean coatings which cover the entire sensor and do not impair the sensor properties. The application of an inventively prepared, as above The defined crosslinked layer is particularly advantageous here since it allows the entire sensor to be coated without impairing the sensor properties. In addition, the surface energy of such a coating is regularly so low that some common solvents, such as acetone, no longer spread on the surface - the surface energy of the coating is below that of the solvent. This also improves the drainage and cleaning behavior of solvent-based adhesives.

A product according to the invention may, for example, be a mold part tool with a permanent mold release layer, the permanent mold release layer itself being a crosslinked layer produced according to the invention as defined above. Molded parts with a permanent mold release layer and methods for their production are described in EP 1 301 286 B1 disclosed therein, wherein it was found to be essential that a gradient layer structure is produced in the demolding layer by temporal variation of the polymerization conditions during the plasma polymerization. However, a gradient is not necessary if the networked layer is designed accordingly (see also Section 7.5).

In addition, it may be advantageous to provide, in addition to a permanent mold release layer on a mold part tool, a crosslinked layer produced according to the invention, which shows the binding energy values given above in an ESCA test. In such a case, such a layer also has the function of a flexible covering layer, which supports the sliding properties, on the permanent release layer, which itself has separating properties.

Because of the extensibility of the crosslinked layer as defined above, it is possible to provide flexible products, such as films (especially stretchable films) with a corresponding non-stick or easy-to-clean surface.

Application: improved sliding properties

This aspect of the invention particularly relates to articles of the invention comprising an elastomeric product and a lubricity enhancing coating on the elastomeric product comprising a crosslinked layer as defined above as a coating or component of the coating.

Many elastomer products, eg. B. O-rings or gaskets can be equipped with a crosslinked layer produced according to the invention as a coating or component of the coating, without the coating is cracked when the elastic properties of the substrate (the elastomeric product) are claimed.

A large number of elastomers currently used have poor sliding properties, so that the corresponding elastomer products can only be processed poorly in automatic placement machines. The elastomer products have a disturbing surface tackiness (tack). For example, in the technical field of valves, such a tack can have a negative impact, if only low release forces are expected. To make matters worse for this application, that the substances that cause the tack, are transferred to the valve seat and can lead to valve leaks in the long term. It is therefore advantageous to provide the elastomers used with an inventively produced, as defined above crosslinked layer, as this special slip and separation properties are given high elasticity. Elastomer and coating together form an article according to the invention.

Another special field of application is the improvement of the sliding properties of silicone rubber, which leads to a number of advantageous products both in the industrial-technical area and, for example, in the field of medical technology. A corresponding article according to the invention comprises a silicone rubber product and a crosslinked layer (as described above).

For both of the abovementioned fields of application, the crosslinked layer additionally ensures that no residual products of vulcanization, no plasticizers or other additives having a molar mass of, for example, are obtained from these products. greater than 50 g / mol can diffuse out (see also application area migration barrier). Thus, an improved suitability in the field of food processing, pharmacy and medical technology is achieved.

Application: antibacterial coatings

Non-cytotoxic, antibacterial coatings after DE 103 53 756 are preferably produced by means of SiO x -like coatings. Although known SiOx-like coatings are in the preferred layer thickness of 30 to 60 nm are flexible within certain limits and can be applied to a film, but such a coating is by no means able to cope with stresses such as those caused by a deep-drawing process or buckling or forming or injection molding or injection molding or laminating. Furthermore, corresponding surfaces define certain adhesion properties (for bacteria, fungi, endogenous substances, etc.). The application of crosslinked layers as defined above, in addition to an SiOx coating, expands the possibilities of use. In particular, the high flexibility and elasticity of the layer allows substrate-forming further processing techniques, such as deep-drawing, beading, embossing etc. Thus, for example, even tubes, closures, spouts or foamed sheets can be equipped.

Furthermore, such a layer on a corresponding laminating film or even applied directly suitable for food packaging. In particular, the use in the composite film sector of interest because it can be combined, for example, barrier properties with antibacterial properties.

Further applications:

In a variety of other (inventive) products, a crosslinked layer produced according to the invention can be used advantageously. Particular mention should be made of: seals (as a crosslinked layer) in the sub-micron range; Coatings (as crosslinked layer) of metallic components or semi-finished products, in particular as anticorrosive coating and / or hydrophobic coating on such metallic components or semi-finished products, in particular for components or semi-finished products which are subject to deformation during further processing or in use; Coatings (as a crosslinked layer), which adhere to a plasma-supported pretreated substrate surface and together with the substrate form a product according to the invention.

8.3 Antimicrobial, preferably non-cytotoxic coating

According to a third preferred embodiment of the invention (hereinafter also the third embodiment), it is possible by means of the method according to the invention to produce layers and apply to products which are antibacterial, preferably non-cytotoxic coatings.

1. 1. Antimikrobielles und nicht-zytotoxisches Schichtmaterial, umfassend
   1. a) eine Biozid-Schicht mit einem bioziden Wirkstoff, und
   2. b) eine die Biozid-Schicht bedeckende Transportkontrollschicht mit einer Dicke und einer Porosität, die eingestellt sind, um den bioziden Wirkstoff aus der Biozid-Schicht durch die Transportkontrollschicht hindurch in einer antimikrobiellen und nicht-zytotoxischen Menge abzugeben.

An antimicrobial, non-cytotoxic coating is noticeable DE 197 56 790 out by:

1. 1. Antimicrobial and non-cytotoxic coating material comprising
   1. a) a biocide layer with a biocidal active substance, and
   2. b) a transport control layer covering the biocide layer having a thickness and a porosity adjusted to deliver the biocidal agent from the biocide layer through the transport control layer in an antimicrobial and non-cytotoxic amount.

To produce such a layer, a two-stage coating process is needed. In WO 2005/049699 is described in addition how such a layer can be produced for example by plasma or sputtering.

In the prior art filled with biocide nanoparticles liquids z. B. in the so-called VERL process. The production and stabilization of nanosuspensions is made possible by the so-called VERL technology (Vacuum Evaporation on Running Liquids). Here, a metal is sputtered onto a moving liquid. In this liquid matrix, non-agglomerated particles with diameters of a few nanometers are formed. Accordingly, dispersions of isolated, nanoparticulate particles in a carrier liquid are formed in this process. Often, this carrier fluid is a simple, linear silicone oil. Nevertheless, the invention is not limited to the suspensions provided by the VERL method.

Corresponding dispersions can be crosslinked using the process according to the invention. This gives you one with biocide nanoparticles evenly enforced cross-linked transport control layer. The layer thus produced differs significantly from the in DE 197 56 790 produced polymers, because these contain both no transport control layer, as well as the dilution effect a significantly lower amount of biocide per volume. They are also significantly different from the others DE 197 56 790 produced layers, since the biocidal nanoparticles are evenly distributed in the coating. The crosslinking of the matrix further increases the density of nanoparticles relative to the starting dispersion. The choice of material as well as the setting of the crosslinking intensity controls the transport control properties.

The stated procedure of the invention allows in a simple manner the local, as well as full-surface coating of objects, as well as complex geometries that are not accessible to the sputtering or only with great technical effort.

In the DE 103 537 56 A1 antimicrobial, preferably non-cytotoxic coatings are disclosed which are similar in composition to the crosslinkable layers which can be prepared by the process according to the invention. By way of reference, the said patent application will become part of the present application. Reference is particularly made to Sections 11 and 20 to 22 in connection with the transport control layer and Sections 12-15 with respect to the nature and form of the biocidal nanoparticles. In Section 26, the skilled artisan will be advised of the amount of nanobiozide needed to deliver non-cytotoxic surfaces shape, given.

According to the third, preferred embodiment of the invention, a layer according to the invention or an article according to the invention is part of the third preferred embodiment, wherein the crosslinked layer comprises biocidal nanoparticles and the layer without the nanoparticles represents a matrix material for the nanoparticles with a porosity adjusted such that the biocidal agent can be released from the matrix material.

Preferred articles according to the invention of the third embodiment of the invention are characterized in claims 37 to 48 in more detail.

8.4 Corrosion protection and tarnish protection

According to a fourth preferred embodiment of the invention (hereinafter also the fourth embodiment), the layers produced in the process according to the invention are used as corrosion protection layers. Similar corrosion protection layers are in the EP 1 027 169 which is incorporated by reference into this application. This applies in particular to the references to the properties and compositions of the respective anticorrosive coatings.

1. a.) Vernetzte Schichten sind aufgrund ihrer dreidimensionalen Vernetzung chemisch und thermisch besonders stabil.
2. b.) Vernetzte Schichten können im Gegensatz zu plasmapolymeren Beschichtungen Fehlstellen, insbesondere Hinterschneidungen, Poren und andere "Hohlräume" besser beschichten. Sie sind daher auch gut geeignet, auf rauen Oberflächen einen wirkungsvollen Korrosionsschutz zu gewährleisten, so dass im Vergleich zu plasmapolymeren Beschichtungen geringere Anforderungen an eine Glättung als Vorbehandlung gestellt werden müssen. Darüber hinaus inkorporieren sie Staub, so dass weitere Fehlstellen vermieden werden können.
3. c.) Vernetzte Schichten können in einfacher Weise mit Korrosionsschutzinhibitoren gefüllt werden.
4. d.) Die Precursoren für vernetzte Schichten lassen sich vorteilhaft in Reinigungsbädern aufbringen, so dass sie die Bauteiloberfläche nach der Reinigung gleichmäßig benetzen.
5. e.) Vernetzte Schichten sind tolerant gegen eine Vielzahl von Hilfsstoffen der Metallbearbeitung wie beispielsweise Mineralöle, da diese Stoffe vielfach ebenfalls vernetzt und in die Beschichtung eingebaut werden können.
6. f.) Der flüssige Precursor kann in Eloxalporen eindringen, so dass die vernetzten Schichten eine neuartige Verdichtung der Eloxaloberfläche darstellt. Zusätzlich wird die Basenbeständigkeit dieser neuartigen Eloxaloberfläche deutlich verbessert. Die Kombination mit Farbeloxal- als auch Sandoralverfahren ist gegeben.

The crosslinked coatings produced in the process according to the invention are outstandingly suitable for the production of anticorrosion coatings. The following aspects play a role:

1. a.) Crosslinked layers are chemically and thermally particularly stable due to their three-dimensional cross-linking.
2. b.) Cross-linked layers, in contrast to plasma polymer coatings, can better coat defects, in particular undercuts, pores and other "cavities". They are therefore also well suited to ensure effective corrosion protection on rough surfaces, so that compared to plasma polymer coatings lower requirements for smoothing as a pretreatment must be made. In addition, they incorporate dust, so that further defects can be avoided.
3. c.) Cross-linked layers can be easily filled with corrosion inhibitors.
4. d.) The precursors for crosslinked layers can be advantageously applied in cleaning baths, so that they evenly wet the component surface after cleaning.
5. e.) Cross-linked layers are tolerant to a variety of auxiliaries of metalworking such as mineral oils, since these substances can often also be crosslinked and incorporated into the coating.
6. f.) The liquid precursor can penetrate into eloxal pores, so that the crosslinked layers represents a novel compression of the anodizing surface. In addition, the base resistance of this novel anodized surface is significantly improved. The combination with Farbeloxal- and Sandoralverfahren is given.

Accordingly, according to the fourth embodiment of the invention, an article of the invention comprises an article comprising a corrosion-sensitive surface on which the crosslinked layer is disposed.

Preferred embodiments are characterized in more detail in claims 49 to 53.

It is advantageous when applying the crosslinked layer produced in the process according to the invention as a corrosion protection layer that the coating process can be carried out at room temperature.

It is preferred that the surface to be coated (the substrate) in a pretreatment step of a mechanical, chemical and / or electrochemical smoothing is subjected.

It is furthermore advantageous that the substrate can be coated with the liquid precursor during the cleaning and that the precursor in the cleaning apparatus can be crosslinked directly by means of the method according to the invention, since little outlay on the process is necessary. For example, the liquid precursor can be a component of a cleaning bath or a cleaning liquid in a cleaning system. The crosslinking can be done, for example, within a drying oven or directly in the cleaning system.

In a preferred coating method according to the fourth embodiment of the invention, a reducing or oxidizing plasma is used to clean and activate the surface.

In a likewise preferred coating method according to the fourth embodiment of the invention, UV radiation is used for cleaning and activating or for solidifying (excimeric) crosslinkable contaminations of the surface, in particular UV radiation from excimer lamps. For example, liquid contaminants such as mineral oils act as precursors.

In another preferred method, the substrate to be coated is subjected to a combination of mechanical surface treatment and pickling before it is coated.

In any case, the skilled person will make sure that sufficient cross-linking takes place and in particular optimal adhesion to the substrate is produced. Good adhesion of the coating to the substrate is given, for example, when cross-hatch values of GT0 are achieved. Particularly adherent layers are not undermined by such a cross-cut test even with a corrosive load, for example in a salt spray test.

It is advantageous that in the context of crosslinking of the liquid precursors by means of UV radiation from excimers simultaneously anodized surfaces can be compacted.

For the fourth embodiment of the invention, the crosslinking process is preferably carried out by the UV irradiation in an atmosphere of oxygen and / or nitrogen and / or a noble gas and / or dried air or a corresponding mixed gas atmosphere, wherein preferably the atmosphere is pressure-reduced. The pressure reduction can also be advantageous regardless of the chosen atmosphere.

In a preferred process according to the invention according to the fourth aspect of the invention, the liquid precursor is applied in a thickness of 5 nm to 10 μm, more preferably the liquid precursor comprises a corrosion inhibitor.

It is also advantageous for this aspect of the invention that the mixture which is applied in the process according to the invention comprises, in addition to the liquid precursor, compounds with cleaning functions for the surface to be coated.

Also advantageous is a mixture for the process according to the invention which contains constituents which lead to the compaction of the surface of the substrate in the context of irradiation and have a kinematic viscosity of ≦ 100,000 mm ² / s at 25 ° C., For example, a corresponding PDMS silicone oil such as Wacker silicone oil AK 25 or AK 10000.

Preference is given to a method in which the precursor is applied by an aerosol method, a dipping method, a spray method or a roll-to-roll method. Particularly preferred in this case are corrosion protection coatings on flat substrates and webs of metals.

For the purpose of corrosion protection, it is preferred to produce a closed coating according to the invention on the surface to be protected. Local layer thickness differences are to be regarded as secondary at first, as long as comparable layer properties with regard to corrosion protection are set on the entire surface.

However, the layer thickness differences affect the optical appearance of the coating, since the applied thin layers impart a color impression to the viewer by interference. Therefore, closed coatings with local layer thickness deviations below 10% based on the average layer thickness are particularly preferred. These give the viewer an optically uniform coating color. Uniform liquid layers can be applied by dipping methods, roll-to-roll systems or other methods known to those skilled in the art.

Equally particularly preferred are closed coatings with local differences in layer thickness in the range from 20% to 200% based on the average layer thickness, the entire range of layer thickness variation within a lateral distance of 100 μm being assumed on the surface of the crosslinked layer. Such rapid layer thickness variations can not be resolved by the unaided eye due to their size. While in the microscope the different layer thickness ranges are clearly recognizable by the associated interference color, the coating is macroscopically almost colorless. Layer thickness distributions of this type can preferably be realized by spray processes or aerosol condensation.

Further preferred are closed coatings with local layer thickness differences in the range of 50% to 100% based on the average Layer thickness, wherein the layer thickness variation is assumed within a lateral distance of 200 microns on the surface of the crosslinked layer.

Furthermore, a coating method according to the invention is preferred in which several cycles of the method according to the invention (alternating application of liquid layer and subsequent hardening) are carried out and in this way a multi-layer system is realized. In this case, it is quite possible to use the same precursor material in the various cycles. In this way it is possible to reduce coating defects. Preference is given to coating systems with successively increasing layer thickness. Particularly preferred is a two-layer system consisting of a base layer with a layer thickness below 100 nm after UV crosslinking and a cover layer with a layer thickness above 200 nm after crosslinking. Also preferred is an average total layer thickness in the range of 170 to 210 nm.

8.5 separating layers

According to a fifth preferred embodiment of the invention (hereinafter also the fifth embodiment), it is possible to produce layers according to the invention by means of the method according to the invention and apply them to products, the layers having a separating function. Certain separation layers have already been described in the context of the second preferred embodiment in the invention and are also to be understood as a particular embodiment of the fifth embodiment of the invention.

Permanent separation layer:

For example, in the molding of plastics, release agents are commonly used to facilitate the separation of the molded article (molding) from the molding tool.

Separating agent systems, for example in the form of solutions or dispersions, which are normally sprayed onto the surface of the molding tool are known from the prior art. These release agent systems consist of separating active ingredients and a carrier medium, usually organic solvents, such as hydrocarbons (sometimes also chlorinated), and water. Such Spray-applied release agent systems essentially always separate the molding from the molding tool by a mixture of a cohesive fracture and an adhesion fracture, but mostly release agent remains on the molding to be separated. This can often lead to difficulties in further processing, for. As when gluing, laminating, painting or metallizing the molding lead. It must therefore be interposed a cleaning step, which causes additional costs. In addition, before each molding (or at least regularly) release agent must be applied to the surfaces of the molding tools, which is also costly and can lead to uneven Entformungsergebnissen. Finally, these release agent systems emit significant amounts of solvents into the environment.

Accordingly, it is part of the invention the use of an (excimer) crosslinked layer produced in a method according to the invention for reducing the adhesion of a molding tool to a molding. Thus, the coating acts as a semi-permanent or permanent release layer or in conjunction with reduced release agent amounts or simplified release agents or internal release agents as a release agent. Accordingly, an article according to the invention is also part of the invention, the article being a mold part tool coated with a crosslinked layer.

The layers applied by means of the method according to the invention are suitable not only for the coating of metallic molds but also for the coating of plastics and glasses. The latter is of particular importance because these materials are required as part of molding tools to process UV curing paints or plastics. In this case, at least a part of the molding tool is preferably designed as a glass component, so that after the injection / flooding of the mold with the photohardenable composition, irradiation through the crosslinked coating and the coated glass mold can take place for curing. For high-quality component surfaces, it is advisable to use a permanent release layer since, unlike conventional liquid release agents, it does not release any substances to the component to be manufactured.

In addition to good separating properties, a corresponding coating must have a very high transparency in the UV range used. This can be achieved both with plasma-polymer release layers and with the crosslinkable layers producible in the process according to the invention. The inventive method has but the advantage that it is much easier to do faster and cheaper. It is even possible to coat the mold surface without removing the mold from the system.

For the production according to the invention of such a separating layer, the use of silicone oils as precursor is appropriate. With the AK series, for example, Wacker Chemie AG offers products that differ in terms of chain length and viscosity. In general, all products can be used from AK1, also in any mixture with each other. The low surface energy of the oils ensures good wetting of the cleaned workpiece surface. If necessary, the component surface is suitably cleaned before the precursor application.

When applying the oils, it is advisable to operate with layer thicknesses between 100 and 1000 nm. However, lower or higher layer thicknesses are possible. The skilled person will align these according to criteria such as wear resistance or the need to accurately map outlines. Higher layer thicknesses promise a higher wear resistance.

During the crosslinking, preferably by means of excimer lamps, care must be taken that the irradiation intensity is chosen such that on the one hand a sufficiently rigid network is formed, but on the other hand not too many organic groups are removed from the surface.

As an alternative to the silicone oils mentioned, fluorinated silicone oils and organofluorine oils can be used. Also in the production of layers from these classes of materials, the skilled person will pay attention that not too much crosslinking too large a number of CF ₃ - groups is lost. He will further characterize the resulting layer by means of contact angle measurement or ESCA analysis. In any case, good release layers have water edge angles of> 100 °, preferably> 105 °, on smooth surfaces.

It is also advantageous if oxygen / air can be excluded on the surface during the curing. This can be achieved, for example, with the aid of nitrogen gassing.

A further advantage is obtained if it is possible to work within a low-pressure apparatus and, after curing, the remaining radicals can be reacted off in a targeted manner. Here, for example, the use of H ₂ or compounds with conjugated or non-conjugated CC double bonds such as vinyl trimethylsiloxane VTMS, C ₂ H ₄ , isoprene, methacrylates offers. These gases or vapors can be brought into contact with the surface both as pure gases and in mixtures, for example with inert gases such as nitrogen or noble gases such as argon.

In the coating according to the invention of UV-transparent materials, it is of procedural advantage if the liquid precursor is crosslinked through the UV-transparent material. The arrangement is thus chosen so that the UV light first strikes the material to be coated, penetrates it and then crosslinks the liquid precursor applied thereto.

When coating molds which were operated with conventional release agents, it is advisable to crosslink at high intensity the release agent residues remaining after cleaning with the aid of UV radiation, preferably radiation having a wavelength <250 nm, particularly preferably radiation from excimer lamps, so that they lose their separating properties and provide a suitable primer.

Since conventional liquid or paste-like release agents are often produced on the basis of waxes or silicone oils, such substances are also suitable as precursors for the production of crosslinked permanent release layers.

8.6 Easy-to-clean layers 8.6.1 Easy-to-clean surfaces through suitable surface chemistry

According to a sixth preferred embodiment of the invention (hereinafter also the sixth embodiment), it is possible by means of the method according to the invention to produce layers according to the invention (and apply to products) which in their structure have easy-to-clean layers as described in the application in US Pat of the WO 03/002269 A2 are disclosed are similar. The said patent application is hereby incorporated by reference into the present application, this applies in particular to the Advantages of said layers and their properties, as far as they are disclosed in the named document.

• Dementsprechend ist ein Teil der sechsten Ausführungsform der Erfindung eine erfindungsgemäße Schicht oder ein erfindungsgemäßer Gegenstand, wobei die vernetzte Schicht eine Silicium, Sauerstoff, Kohlenstoff und Wasserstoff und/oder Fluor umfassende Schicht ist, für die bei Bestimmung mittels ESCA gilt:
  • Das Stoffmengenverhältnis O : Si ist > 1,25 und < 2,6
  • und das Stoffmengenverhältnis C : Si ist > 0,6 und < 2,2.
• Bevorzugt ist ein erfindungsgemäßer Gegenstand gemäß der sechsten Ausführungsform der Erfindung, wobei die vernetzte Schicht bezogen auf ihre Gesamtatomzahl ohne Wasserstoff
  • minimal 20 und maximal 30 Atomprozente Si,
  • minimal 25 und maximal 50 Atomprozente O und
  • minimal 25 und maximal 50 Atomprozente C

enthält.The (excimer) crosslinked easy-to-clean layers (easy-to-clean layers) produced in the process according to the invention in the sixth embodiment of the invention are based on organosilicon or fluoroorganic bases. They correspond in their properties to the layers disclosed in the abovementioned WO publication. In particular, they are easy to clean. By selecting the suitable precursors and by setting suitable UV crosslinking conditions in the process according to the invention, the person skilled in the art is able to produce layers or objects according to the invention, in particular by means of excimer lamps, as described below:

• Accordingly, a part of the sixth embodiment of the invention is a layer according to the invention or an article according to the invention, wherein the crosslinked layer is a layer comprising silicon, oxygen, carbon and hydrogen and / or fluorine, for which the following applies when determined by means of ESCA:
  • The molar ratio O: Si is> 1.25 and <2.6
  • and the molar ratio C: Si is> 0.6 and <2.2.
• Preferred is an inventive article according to the sixth embodiment of the invention, wherein the crosslinked layer based on their total atomic number without hydrogen
  • a minimum of 20 and a maximum of 30 atomic percent Si,
  • a minimum of 25 and a maximum of 50 atomic percent O and
  • minimum 25 and maximum 50 atomic percent C

contains.

• 1,8 : 1 n(H und/oder F) : n (C) < 3,6 : 1

vorzugsweise

• 2,2 : 1 n(H und/oder F) : n (C) < 3,3 : 1.

Further preferred is an article according to the invention, wherein the crosslinked layer comprises hydrogen and / or fluorine, where:

• 1.8: 1 n (H and / or F): n (C) <3.6: 1

preferably

• 2.2: 1 n (H and / or F): n (C) <3.3: 1.

Further preferred is an article in which the crosslinked layer has a water edge angle of over 90 °, preferably over 95 ° and more preferably over 100 °. According to the invention, an article comprising a crosslinked layer as defined above in the sixth embodiment of the invention is selected, which is selected from the group consisting of: rim, hubcap, aluminum profile, anodized aluminum component, in particular for fittings, windows, showers, automobiles; Windows, cladding, wind turbine blades, metal facing, in particular for houses, in particular for kitchens or kitchen utensils; Display, in particular for kitchens, in particular for mobile phones; Glazings, automotive body panels, automotive interior components, rim, motorcycle components, beverage containers, paint containers, ink containers, ink cartridges, bottles, kitchen utensils, frying pans, information signs, warning signs, reusable food containers, e.g. Bottles or barrels; Wood surfaces, lacquered or glazed wood surfaces, textiles, baking trays, components for paint booths, gratings, painting hangers, molds for the production of foodstuffs, such as e.g. Chocolate or gummy bear molds, molds for making rubber, in particular tires and condoms, pacifiers, teats.

Preferred easy-to-clean layers are fluorine-free and / or have a roughness R _a of <1 μm, preferably ≤ 0.3 μm, preferably <0.1 μm on their surface.

The "easy-to-clean layers" described in this chapter are preferably easy to remove paint and redesigned for easy cleaning with dry ice, which makes them particularly well applicable in the context of painting equipment or used for painting objects as easily cleanable protective layer.

8.6.2 Easy to clean surfaces by smoothing or closing surface irregularities

For surfaces with open pores or other surface irregularities, it can be observed that impurities deposit in depressions and thus act as anchors, which are often not reached by the cleaning process. In unfavorable cases, this creates a permanent visible contrast due to the contamination.

With the method according to the invention it can be achieved that pores or depressions of the surface are closed: The applied liquid tends to gravitationally prefer to lay in the depressions or is sucked into the surface pores by the capillary effect. In this way, a surface seal and smoothing can be achieved. Impurities can not penetrate into the surface structure as before or cling to exposed sharp edges.

Preference is given to transparent, smoothing, hydrophobic coatings based on organosilicon.

8.7 Installation of solid particles

According to a seventh preferred embodiment of the invention (hereinafter also the seventh embodiment), layers or articles according to the invention are produced by means of the method according to the invention which comprise in the crosslinked layer solid particles which have been applied simultaneously with the liquid precursor. Examples of such particles can also be found earlier.

With the method according to the invention, it is possible, in particular, to apply particles with a size between 10 nm and 20 μm in a coating. It can be generated via the irradiation, in particular the UV process parameters such as treatment duration, intensity, atmospheric composition and distance of the radiation sources, crosslinked layers that have a bond to the (original) solid particles or in which the corresponding particles are merely embedded. Through appropriate process management, it is also possible to design the layers so that the embedded particles on the Surface of the cross-linked layer produced in the process according to the invention protrude.

Alternatively, it is also possible with suitable removal methods to remove parts of the crosslinked layer again, whereby it must be ensured that the particles themselves are not removed. As a result, parts of the surfaces of the particles can be exposed. The total exposed area can be adjusted, for example, via the particle size, via the concentration of the particles in the matrix of the crosslinked layer according to the invention, or via the UV process parameters.

• für die heterogene Katalyse durch entsprechende katalytisch aktive Partikel.
• als Ankerpunkt für die Fixierung/Heterogenisierung von homogenen Katalysatoren, beispielsweise für Enzyme oder andere Biokatalysatoren, oder sonstige Wirkstoffe beispielsweise für chemische, biochemische oder biotechnologische Reaktionen oder für eine Funktionalisierung technischer Oberflächen, beispielsweise für eine verminderte Tropfen- (Nebel-) oder Raureifbildung oder ein vermindertes Anhaften/-wachsen von Mikroorganismen oder Algen. Dabei können die aktiven Substanzen auch über Spacer-Moleküle fixiert werden.
• als Ankerpunkt für die Fixierung von Sensor-Substanzen, beispielsweise Biosensoren wie Antikörper als Immunosensoren, für die chemische, biochemische oder (mikro-)biologische Analytik bzw. Molekulardiagnostik wie beispielsweise für den Nachweis von Antikörpern im Blut oder den Nachweis von Krankheitserregern in wässrigen Flüssigkeiten. Dabei können die aktiven Substanzen auch über Spacer-Moleküle fixiert werden. Ein spezielles Beispiel hierfür ist die Fixierung von Antikörpern oder Oligonucleotiden an freigelegten Nickel-Partikeloberflächen über Nickel-Chelate wie Nickel-Nitrilotriessigsäure (Ni-NTA).
• als Grenzfläche für eine (minimale) Stoffabgabe von Wirkstoffen aus den Partikeln; beispielsweise antimikrobiellen Wirkstoffen, Pestiziden, homogenen (Bio-)Katalysatoren, Enzymen, Hormonen, Nährstoffen, Riech- und Aromastoffen, Tensiden. Diese Stoffabgabe kann flexibel dargestellt werden: sowohl so, dass über einen längeren Zeitraum lediglich winzige Spuren von Wirkstoffen migrieren, als auch so, dass nach einer Initiation, beispielsweise dem Kontakt mit einem geeigneten Medium und/oder durch Erwärmung und/oder durch Licht, die Abgabe innerhalb einer kurzen Zeit zum Erliegen kommt. Dies kann sowohl so realisiert werden, dass die Partikel selbst während der Abgabe verbraucht werden, als auch so, dass die Partikel wiederum als Matrix funktionieren, in der die Wirkstoffe gespeichert sind.

This makes it possible to provide laterally isolated particle surfaces which are suitable for a variety of applications:

• for heterogeneous catalysis by corresponding catalytically active particles.
• as an anchor point for the fixation / heterogenization of homogeneous catalysts, for example for enzymes or other biocatalysts, or other active ingredients, for example, for chemical, biochemical or biotechnological reactions or for a functionalization of technical surfaces, such as a reduced drop (fog) or hoarfrost or a reduced adhesion / growth of microorganisms or algae. The active substances can also be fixed via spacer molecules.
• as an anchor point for the fixation of sensor substances, for example biosensors such as antibodies as immunosensors, for chemical, biochemical or (micro) biological analysis or molecular diagnostics such as for the detection of antibodies in the blood or the detection of pathogens in aqueous fluids. The active substances can also be fixed via spacer molecules. A specific example of this is the fixation of antibodies or oligonucleotides to exposed nickel particle surfaces via nickel chelates such as nickel nitrilotriacetic acid (Ni-NTA).
• as an interface for a (minimal) substance delivery of active substances from the particles; For example, antimicrobial agents, pesticides, homogeneous (Bio) catalysts, enzymes, hormones, nutrients, fragrances and flavorings, surfactants. This substance delivery can be represented flexibly: both in such a way that only minute traces of active substances migrate over a relatively long period of time, and so that after initiation, for example contact with a suitable medium and / or by heating and / or by light, the Delivery stops within a short time. This can be realized in such a way that the particles themselves are consumed during delivery, as well as in such a way that the particles in turn function as a matrix in which the active substances are stored.

8.8 Adhesion promoter, primer layers, functionalized surfaces

According to an eighth preferred embodiment of the invention (hereinafter also the eighth embodiment), adhesion promoter and primer layers are produced and / or applied to a surface or functionalized surfaces are produced by means of a method according to the invention.

Adhesion promoter and primer layers are characterized by the fact that they themselves build a good adhesion to the substrate and at the same time provide functional groups on the surface, which enable an optimal connection of other substances, such as adhesives, paints, lacquers or metallizations.

They are used wherever simple cleaning or activation is not sufficient, because special functional groups are required or additional protection of the surface is necessary.

1. 1. Reinigung und ggf. Oberflächenfunktionalisierung des Bauteils
2. 2. Benetzung mit einem flüssigen Precursor in der gewünschten Schichtstärke
3. 3. Vernetzen mittels Strahlung ≤ 250 nm, bevorzugt Excimerlampenstrahlung, wobei
   1. a.) die umgebende Gasatmosphäre derart ausgewählt ist, dass geeignete Gruppen für die spätere Haftvermittler- und Primerfunktion zur Verfügung stehen und
   2. b.) die Bestrahlungsbedingungen des flüssigen Precursors derart gewählt werden, dass Radikale an seiner Unterseite und, wenn durch den benetzten Werkstoff möglich, an dessen Oberfläche erzeugt werden.

Such layers can be produced in an ideal manner by means of the crosslinked layer produced in the method according to the invention. The procedure is as follows:

1. 1. Cleaning and possibly surface functionalization of the component
2. 2. Wetting with a liquid precursor in the desired layer thickness
3. 3. Crosslinking by means of radiation ≤ 250 nm, preferably excimer lamp radiation, wherein
   1. a.) the surrounding gas atmosphere is selected such that suitable groups are available for the subsequent adhesion promoter and primer function, and
   2. b.) the irradiation conditions of the liquid precursor are selected such that radicals are generated on its underside and, if possible by the wetted material, on its surface.

The steps 1 and 2 can also be combined in a cleaning system to a single step. If there is a defined contamination, e.g. an oil from a previous metalworking step, so you can possibly use this directly as a precursor.

The person skilled in the art will make sure that the liquid precursor to be crosslinked is preferably applied in layer thicknesses of up to 100 nm. As a result, he can usually easily make sure that even on the underside of the layer of liquid precursor, a sufficient number of radicals is formed. If the wetted material is a plastic, the radiation can also generate radicals on its surface which can interact with the radicals in the liquid precursor. This makes it possible to produce a good composite material. By a simple time variation, the skilled person will continue to succeed in producing optimal adhesion between the base material and the crosslinked (previously) liquid precursor. An over-treatment by e.g. too long exposure time will in turn lead to a weakened composite, since possibly the substrate is badly damaged by too many chain fractures and on the other hand, the liquid precursor over-hardened and cracked, z. B. when using organosilicon precursors because the C content in the layer is too low.

When choosing the surrounding gas atmosphere, the easiest way is to use oxygen-containing gases, such as air, oxygen, CO ₂ or N ₂ O. These can also be excited by the radiation used and thus react with the radicals on the precursor surface. In addition, O ₂ in particular is known as so-called radical scavenger, as a substance that reacts with radicals and leaves oxygen-containing functionalities. Depending on the requirements, the "functionalizing" gases are mixed with other gases, in particular nitrogen and / or noble gases, or in a suitable order, the interaction region between the surface and the surface Radiation source supplied. In special cases, the "functionalizing" gases are added to the gas atmosphere only at the end of the crosslinking process.

But there are also other gases, such as NH ₃ for the production of nitrogen-containing functionalities used. The goal is in any case to produce functional groups such as hydroxy, amino, ester / acid, keto, aldehyde, cyano or ether, so that a suitable interaction of the above-mentioned polymer systems (adhesives, paints, paints) or metals on the crosslinked layer according to the invention becomes possible.

If an adhesion promoter for rubber materials is to be produced, then a large number of carbon double bonds should be introduced into the surface. For this purpose, it is advisable to produce gas atmospheres with a proportion of conjugated or non-conjugated substances, such as conjugated or nonconjugated dienes such as, for example, 1,4-hexadiene, 1,3-butadiene or isoprene.

• konjugierte Diene wie Isopren oder nichtkonjugierte wie beispielsweise 1,4-Hexadien zur Bereitstellung von Doppelbindungen
• Styrol zur Bereitstellung von Phenylgruppen
• Acrylnitril zur Bereitstellung von Cyano-Gruppen
• Acrylsäure zur Bereitstellung von Säuregruppen
• Tribrommethan zur Bereitstellung von Brom-Gruppen
• Glycidylmethacrylat zur Bereitstellung von Epoxid-Funktionalitäten
• Vinylsulfonsäure oder eine Mischung aus Chlor und Schwefeldioxid zur Erzeugung von Sulfonsäure-Gruppen

In addition to the functionalization by the presence of corresponding gases during the entire excimer crosslinking, the functionalization can also take place in the sense of a grafting following the actual excimer crosslinking for a stronger concentration on the surface and / or a lower density of occupancy with functional groups. For this purpose, suitable gases are brought into contact with the substrate surface after crosslinking without prior aeration. Suitable gases include:

• conjugated dienes such as isoprene or nonconjugated such as 1,4-hexadiene to provide double bonds
• Styrene to provide phenyl groups
• Acrylonitrile to provide cyano groups
• Acrylic acid for providing acid groups
• Tribromomethane to provide bromine groups
• Glycidyl methacrylate to provide epoxide functionalities
• Vinylsulfonic acid or a mixture of chlorine and sulfur dioxide to produce sulfonic acid groups

Likewise, this functionalization can be carried out by metering the gases at the end of the coating process according to the invention. For a more efficient surface functionalization, corresponding liquids can also be used instead of the gases, for example the solutions of corresponding substances in organic solvents.

Furthermore, it may be advantageous for some combinations of substrate surface and adhesive or coating material that, with the coating according to the invention, first a leveling or smoothing of the surface can be achieved.

Using liquids with low surface tension and / or surfaces with high surface energy, spreading of the liquid can be achieved. That is, the liquid tends to evenly cover the surface. Furthermore, in the uncrosslinked state of gravity, the liquid will fill wells better than peaks in the surface profile; Pores are filled by the capillary effect. Thus, after crosslinking of such a liquid layer, an at least partially smoothed and sealed surface is available.

The effect of smoothing can be influenced by the applied layer thickness and must be compared with the average roughness of the uncoated surface. Preferably, layers according to the invention having an average layer thickness in the range from 10 to 80 percent of the arithmetic roughness R _{a of} the untreated surface are used. The determination of the roughness values takes place before and after the coating. Here and in the context of the entire text roughness is determined according to DIN EN ISO 4287 unless otherwise stated. In particular for highly viscous adhesives and / or coating materials which only partially reproduce the surface topography, this smoothing effect may be advantageous in order to increase the effective adhesion surface. Thus, the coating of the invention serves as a compensating intermediate layer for unevenness in areas below 100 microns.

The adhesion between two layers is influenced by chemical interaction in addition to chemical bonding. Through the use of good wetting liquids, a smoothing intermediate layer is produced by the coating according to the invention, which is in very close contact with that of the substrate surface. Due to the very close contact, the layer according to the invention obtains the necessary high adhesion to the substrate surface. For a high adhesion of the adhesives and / or coating materials to be applied subsequently, preference is given to using a layer according to the invention having a high surface energy, particularly preferably a hydrophilic layer.

8.9 Electrical insulation layers

According to a ninth preferred embodiment of the invention (hereinafter ninth embodiment), it is possible to produce articles with an electrical insulation layer by means of the method according to the invention, wherein the insulating layer is a hydrophobic layer crosslinked according to the invention. The latter is also part of the invention.

To produce electrical insulation layers in the process according to the invention, silicone oils are preferably used as liquid precursors, since crosslinked silicones are known for their excellent electrical properties. But also, for example, partially or fully fluorinated oils come into consideration.

The person skilled in the art will preferably use long-chain polymethylsiloxanes or polymethylphenylsiloxanes for the process according to the ninth embodiment and expose them to a short crosslinking reaction by means of UV radiation, preferably radiation with a wavelength ≦ 250 nm, particularly preferably radiation from excimer lamps, in order to just sufficiently crosslink them and if necessary to produce sufficient adhesion to the substrate. He will also be careful not only to produce a sufficient layer thickness for the application, as well as a flawless as possible production. Therefore, he will pay attention to an excellent surface wetting of the surface to be coated by the liquid precursor and attach importance to a dust-free processing.

8.10 Local Local Coatings

According to a tenth preferred embodiment of the invention (hereinafter also the tenth embodiment), the (excimer-) crosslinked layers produced in the process according to the invention are used as local local layers.

The targeted construction of three-dimensional microstructures, for example by a multi-layer structure is possible with the aid of UV lasers but also UV excimer lamps, for example in lithography. In this case, for example, a "rapid prototyping on the micro and nanometer scale" could be performed. This would z. For example, it can be used to quickly analyze microstructured surfaces for their properties, for example, to optimize structures for producing streamlined surfaces (both in gases and in liquids) and to produce matrices for plastics processing.

Localized coatings are needed in many technical applications. A distinction must be made between statistically distributed localized coatings (e.g., anti-fingerprint coating) (see also below) and locally well defined areas where the coating is needed (e.g., in the manufacture of integrated circuits). Large user industries include, for example, the semiconductor and photovoltaic industries, micromechanics and microsystems technology, but also the industry for the production of LEDs.

Particularly in the case of microsystem technology and the semiconductor industry, such a coating according to the invention, or a coating crosslinked in a process according to the invention, can be used in a particularly photolithographic process as an embodiment according to the tenth embodiment of the invention. In this case, according to the invention, according to the tenth embodiment of the invention, the (excimer) crosslinked layer prepared in the method of the present invention eliminates the need for a photoresist (photographic layer structure). This simplifies the manufacture of integrated circuits, since a multistage procedure (eg in a simplified representation: production of an insulation layer, coating with photoresist, local curing of the photoresist (photolithography process), removal of the uncured photoresist, etching of the insulation layer in the uncovered area, Removal of the cured photoresist) by a significantly reduced in effort as the process inventive method (application of the liquid precursor, local crosslinking in a photolithography process, removal of the superfluous precursor) can be replaced. The dimensions which can be created with this photolithographic layer application are sufficient for those in the conventional technique.

Likewise, the so-called nanoimprint technology (" Providing a Direct-LIGA Service - A Status Report "; BERND LOECHEL, Microtechnology Application Center - BESSY and Colburn et al., "Step and Flash Imprint Lithography: A New Approach to High-Resolution Printing," Proc. SPIE, 1999, p. 379 , and US 7,128,559 ), which exist in different variants, can be simplified. The basis for the nanoimprint technology is a UV-transparent stamping mold, which preferably also has to have good release properties, so that the stamping mold can be removed again from the UV-cured paint. Demolding leads again and again to quality problems, especially in small structures.

According to the process of the tenth embodiment according to the invention, the embossing mold is omitted, the substrate is wetted uniformly with the desired precursor. Thereafter, the exposure by means of UV radiation, e.g. by excimer lamps, preferably in a lithography system (with photomask) or by excimer lasers. Networking takes place only in the exposed areas. The uncrosslinked precursor can be easily removed again by means of solvents.

The coating sharpness is promoted in particular by the fact that in the liquid precursor no photoinitiators are used which initiate a chain reaction. There is no dark reaction in the absence of radiation as opposed to polymerization. Rather, only in those networks are made where individual radicals are generated, which can react with each other. A remote effect does not take place.

As a coating, in particular insulating coatings are considered, as discussed in the section electrical insulation layers.

To optimize certain coating properties, such as, for example, conductive properties, it may be necessary after the crosslinking to specifically modify the crosslinked coating according to the invention under oxygen or inert gas and in particular to remove organic residues (in part).

Of course, locally local coatings according to the invention can also be carried out by means of a laser with radiation emission in the wavelength range below 250 nm. In this case, the laser light is passed over the previously provided with liquid precursor surface or the surface itself moves suitable relative to the laser beam, so that only the exposed areas cure. Care must be taken to ensure that the energy supplied does not lead to local overheating and thus to extensive destruction of the precursor.

8.11 Optical functional layers

According to an eleventh preferred embodiment of the invention (hereinafter also the eleventh embodiment), it is possible by means of the method according to the invention to produce layers according to the invention and apply them to products which impart optical functions to the surface to which they have been applied. It is possible, coatings with different optical properties such. B. in the refractive index (see Example 4). In particular, optical functional layers such as filters, band filters, antireflection layers (AR) or high-reflection coatings (HR), amplitude and phase gratings, coatings with nonlinear effects, etc. can be produced in this way.

With a suitable choice of the process parameters, it is possible according to the invention to set the refractive index for the crosslinked layer in a targeted manner. In this way, the optical properties of the coatings can be controlled.

The measurements in the examples demonstrate that it is possible to produce coatings with different optical properties, here refractive index. With skillful choice of process parameters, it is possible to set the refractive index for the crosslinked layer targeted. In this way, the optical properties of the coating can be controlled.

The following describes examples of applications according to the invention according to the eleventh embodiment of the invention:

Wavelength-specific reflective coating

The process of the invention can produce a thin film coating which is transparent or partially transparent, i. Preferably, the coating is transparent to a portion of the infrared, visible and UV spectral regions. In addition to the transmitted radiation, a portion of the radiation incident on the layer is reflected. By selecting the refractive index and the applied layer thickness, a high degree of reflection for individual wavelengths or for a wavelength range can be achieved. The refractive index and layer thickness can be determined via known formulas of optics (inter alia Fresnel formulas). For example, with a layer thickness of 160 nm and a refractive index of n = 1.4, light of wavelength 448 nm can be effectively reflected. In this case, due to interference effects, the surface appears blue under a light incidence of 0 °.

Such a coating can be used as a coloring coating, for example in the design field. Such a coated substrate can be used as a filter to filter out certain wavelengths.

Likewise, it is possible to provide regions of a surface with coatings of different layer thickness or to perform the application of the liquid precursor or the radiation exposure only locally, so that locally different wavelengths are preferably reflected. These locally wavelength-specific reflection properties can be used to realize beamformers for the optics or to produce locally selective filters, beam splitters for optics, or "colorful" decorative coatings.

Further exemplary aspects of the eleventh embodiment of the invention are dealt with below:

Wavelength-specific transmissive (anti-reflective) coating

According to the above-mentioned example of a reflective coating, the coating parameters may be designed such that a single wavelength or a wavelength range is effectively transmitted. For example, a coating with a layer thickness of 130nm and a refractive index of n = 1.4 deposited on a glass substrate can effectively provide light of wavelength 728nm transmit. In this case, due to interference effects under a light incidence of 0 °, red light is effectively transmitted.

Such a coating can be used as an antireflection coating, for example for spectacles, windows, glass panes, objectives, copiers, scanners, screens or glossy, polished, flat surfaces. Such a coated substrate can be used as a filter to effectively transmit certain wavelengths.

Likewise, it is possible to provide limited areas of a surface with coatings of different layer thickness, so that different wavelengths are preferably transmitted. In this way, locally wavelength-specific transmission properties that can be used to make locally selective filters or beam splitter for optics or general intensity modification in the beam profile of an incident light beam (beam shaping).

Phase objects and phase grids

Phase objects are characterized by the fact that phase differences between the local partial beams are introduced by them in the transmitted light; the intensity is not changed.

If radiation exposure (crosslinking) uses masks or filters or auxiliary technical devices which ensure that the applied liquid precursor is exposed or cross-linked locally with different intensity or time duration, local refractive index differences can be generated in the coating. These cause different optical paths within the coating according to the invention and thus to a phase difference after exiting the layer.

Such coatings can be used in optics in order to carry out targeted modification in a light beam, for example Fourier transforms or for the generation of beam shaping optics, holograms, phase gratings, etc.

Amplitude obstructions and amplitude gratings

Amplitude objects are distinguished by the fact that intensity differences between the local partial beams are introduced by them in the transmitted light.

After application of the liquid precursor, the applied liquid film can only be exposed or crosslinked locally with the aid of masks or filters or other technical auxiliary devices. If the precursor layer that is still liquid from the unexposed areas is subsequently removed, then local amplitude changes for radiation impinging on the substrate can be produced in the coating.

Alternatively, it is possible to carry out the method according to the invention first without the use of masks or filters and subsequently to treat the coating with the aid of masks or filters in order to realize the necessary local intensity changes. Such a post-treatment may, for example, constitute a layer ablation, layer shrinkage or postcrosslinking, also by re-irradiation with UV light sources such as excimer lamps or lasers, or other processes such as e.g. Etching etc.

Another alternative is the local application of the liquid precursor before crosslinking.

All three variants lead to local amplitude changes for radiation impinging on the substrate, which can be exploited in the optics for beam modification or analysis, e.g. Beamforming, Fourier transformations, generation of holograms, amplitude gratings, etc.

8.12 Antifingerprint coatings

• Das erfindungsgemäße Verfahren ermöglicht es, Schichten in einem Alternativverfahren zum Plasmaverfahren zu erzeugen, welches in der PCT/EP2006/062987 beschrieben wurde. Diese Anmeldung beschreibt ein Verfahren, in dem eine Oberfläche mit einem Antifingerprint-Effekt erzeugt wird. Die zitierte Anmeldung wird auf dem Wege der Verweisung in den vorliegenden Anmeldungstext inkorporiert.

According to a twelfth preferred embodiment of the invention (hereinafter also referred to as the twelfth embodiment), it is possible by means of the method according to the invention to produce layers according to the invention and to apply layers to products which have the so-called antifingerprint effect:

• The method according to the invention makes it possible to produce layers in an alternative method to the plasma method which is used in the PCT / EP2006 / 062987 described has been. This application describes a method in which a surface with an anti-fingerprint effect is produced. The cited application is incorporated by reference into the present application text.

The anti-fingerprint effect is based on producing a coating that reduces the optical contrast of a fingerprint to such an extent that it is virtually imperceptible to the human eye. The reduction in perceivability is based on providing a coating consisting of thin, uneven, island-like coverage with lateral dimensions in the range of 1 to 100 μm. The thin, island-like coating with an average layer thickness in the range of 10 to 300 nm, caused by interference, prefers a microscopic play of colors, which mimics the effect of covering a fingerprint.

The thin-layered, island-like coating can be produced by only partially covering and crosslinking the surface with the liquid precursors, or by applying the precursor over the whole area and only locally crosslinking, for example by masks or targeted irradiation with a laser, or by applying the precursor over the entire surface and is crosslinked over the entire surface and then locally removed, for example by masks or targeted irradiation with a laser.

To generate a local coverage, the physical and chemical properties of the liquid precursor can be exploited. For example, a precursor with a low surface tension can be used to spread very thin sub micron coverage (area to height ratio: large). On the other hand, precursors with a high surface tension tend to form droplets (area to height ratio: small), so that with the resulting droplet pattern at the same time local coverage of the still liquid precursor is given. In addition, it can be exploited that a liquid precursor deposits more in the depressions of a surface than on the profile tips. In contrast, finger fat is preferably transferred to the tips of a surface profile. Due to the consequent juxtaposition of anti-fingerprint coating in the wells and the finger fat on the profile tips, both types of layers have similar optical properties, the targeted contrast reduction can be achieved.

It has been found that it is possible by means of the method according to the invention, the inventive crosslinking of a layer on liquid precursor means Radiation ≤ 250 nm, in particular by excimer lamps, to effectively produce corresponding antifingerprint coatings (see also section "Local coatings" in this application.) Further information on the production of antifingerprint coatings according to the invention can be found here.

Here, too, surfaces for coating which by nature or by appropriate preprocessing have an average roughness Ra of from 0.3 to 1.2 μm are preferred. Layer crosslinking with UV radiation below 250 nm is capable of effective, i. in a much shorter time compared to plasma curing, and also under atmospheric conditions, i. in an air atmosphere, to crosslink island-like liquid coverages.

Applications of the twelfth embodiment are coatings in the field of household and sanitary items such as screens, handles, drain plugs, housing, for example, for fittings and mixer batteries, furniture fittings and moldings. Articles in the field of automobiles, in particular in bodies, for door and trunk handles, for panels and moldings, as well as in architecture or in the hospital sector.

Further preferred are metallically lustrous surfaces in the mentioned preferred range of roughness values, particularly preferably galvanically coated or blasted, shiny metallic surfaces.

Here is also referred to the examples.

8.13 Smoothing and sealing coatings

According to a thirteenth preferred embodiment of the invention (hereinafter also referred to as the thirteenth embodiment), it is possible by means of the method according to the invention to produce layers according to the invention and to apply layers to products which aim to change the topography of a surface.

These include the sealing and filling of sub-micron depressions (pores). Likewise, a smoothing of the surface roughness or a partial filling of the surface topography can be achieved. Another option is sheathing sharp edges in the sub-micrometer range. Some layer examples are in the FIG. 9 shown schematically.

1. a) Glättung der Rauhigkeit,
2. b) Auffüllen von Poren und Vertiefungen,
3. c) Ummantelung von scharfen Kanten,
4. d) Ummantelung von Profilspitzen durch "Nasenbildung" bei umgedrehter Aufhängung während der Vernetzung.

In FIG. 9 represent schematically:

1. a) smoothing the roughness,
2. b) filling in pores and depressions,
3. c) sheathing of sharp edges,
4. d) sheathing of profile tips by "nose" with inverted suspension during networking.

1. a) die Flüssigkeit durch den Kapillareffekt in offene Poren der Oberfläche eindringt bzw. hineingesaugt wird. Durch Bestrahlung wird die Pore anschließend dauerhaft oberflächig verschlossen,
2. b) die Flüssigkeit der Schwerkraft folgend sich in Vertiefungen der Oberfläche ansammeln kann, so dass nach Aushärtung eine Einebnung der Oberflächentopografie, insbesondere der mikroskopischen Rauheitswerte erzielt werden kann. Dies ist insbesondere der Fall, wenn Schichtdicken, vergleichbar mit der arithmetischen Rauheit R_a (Ermittlung der Rauheit nach DIN EN ISO 4287) der unbeschichteten Oberfläche, aufgebracht werden. Bevorzugt werden hierfür Schichtdicken im Bereich von 10 bis 80 Prozent der arithmetischen Rauheit R_a verwendet,
3. c) durch einen oberflächlich spreitenden Flüssigkeitsfilm mikroskopisch scharfe Kanten ummantelt werden. Dieser Effekt tritt vor allem bei der Verwendung von Flüssigkeiten mit sehr geringer Oberflächenspannung auf (kleiner 30mN/m) und Oberflächen mit hoher Oberflächenenergie (größer 60mN/m). Dies ist insbesondere der Fall, wenn Schichtdicken deutlich kleiner als der arithmetischen Rauheit R_a der unbeschichteten Oberfläche aufgebracht werden. Auf diese Weise bleibt die charakteristische Oberflächenoptik des unbeschichteten Substrats erhalten. Bevorzugt werden hier Schichtdicken im Bereich unterhalb von 10 Prozent der arithmetischen Rauheit R_a und/oder
4. d) die Flüssigkeit der Schwerkraft folgend sich bei umdrehter Aufhängung während der Vernetzung an den Profilspitzen ansammeln kann und so "Nasen" bildet. Auf diese Weise kann eine Ummantelung der Profilspitzen, insbesondere auf sehr spitzen Kanten, erreicht werden.

Background of these coating effects is the use of liquid media as starting material. These are applied as a thin liquid film on the surface to be coated. As long as no curing has taken place, the liquid film is considered to be dynamic, ie mobile. This has the consequence that

1. a) the liquid penetrates through the capillary effect in open pores of the surface or is sucked into it. By irradiation, the pore is then permanently closed surface,
2. b) the liquid of gravity following can accumulate in depressions of the surface, so that after curing, a leveling of the surface topography, in particular the microscopic roughness values can be achieved. This is the case in particular if layer thicknesses comparable to the arithmetic roughness R _a (determination of the roughness according to DIN EN ISO 4287) of the uncoated surface are applied. For this purpose, layer thicknesses in the range from 10 to 80 percent of the arithmetic roughness R _a are preferably used,
3. c) by a superficially spreading liquid film microscopically sharp edges are sheathed. This effect is particularly noticeable when using liquids with very low surface tension (less than 30mN / m) and surfaces with high surface energy (greater than 60mN / m). This is particularly the case when layer thicknesses are significantly smaller than the arithmetic roughness R _{a of} the uncoated Surface to be applied. In this way, the characteristic surface appearance of the uncoated substrate is maintained. Layer thicknesses in the range below 10 percent of the arithmetic roughness R _a and / or are preferred here
4. d) the fluid of gravity following rotation can accumulate during cross-linking at the profile tips and so "noses" forms. In this way, a sheathing of the profile tips, in particular on very sharp edges, can be achieved.

Such coatings have corrosion-inhibiting properties, are suitable as a sealant, have easy-to-clean properties, since dirt can no longer penetrate into the depressions, or edges are smoothed and have a particularly pleasant feel. Furthermore, the roughness of the surface can be smoothed.

The coating can be used as a corrosion protection coating, in particular for metal surfaces, as an easy-to-clean surface, for example in the kitchen, sanitary, automotive, aviation, as a base layer to compensate for roughness for subsequent painting, gluing or other subsequent coatings, as a sealing layer, barrier layer or as a surface coating with pleasant haptic properties for everyday objects such as Office supplies, automotive interiors, controls, telephones, remote controls, fittings, etc.

In addition, an improvement of the flow conditions during the flow of fluid media over the surface according to the invention can be achieved by the smoothing of the surface. This applies in particular to the flow of liquids, for example in the field of microfluidics for applications in fields such as biotechnology, medical technology, process technology, sensor technology and consumer goods.

Accordingly, part of the invention is the use of a method according to the invention as described above or a layer according to the invention for smoothing and / or sealing a surface to be coated.

8.14 Structuring, topography-giving coatings

According to a fourteenth preferred embodiment of the invention (hereinafter also referred to as the fourteenth embodiment), it is possible by means of the method according to the invention to produce layers according to the invention and to apply layers to products which aim to create structured topography-giving layers, i. to provide structures that stand out against the uncoated surface.

This type of structuring coating differs from the local-localized coating described as the tenth embodiment in that it does not focus on the lateral juxtaposition of coating or non-coating, but specifically changes the surface topography. A desired topography is realized by applying local coatings with different layer thicknesses.

The structuring, topography-giving coating can be achieved on the one hand via the properties of the precursor used, on the other hand laterally limited differences in layer thicknesses over fillers can be produced.

Also part of the invention is a method for producing a surface topography on a surface to be coated by performing a method according to the invention, wherein the ratio of the liquid surface tension of the liquid precursor to the surface energy of the surface to be coated is selected so that a partially closed layer embossed by island-like appearance in step c) is produced, wherein the layer thickness in the region of the island-like appearance is preferably at most 10 .mu.m, more preferably at most 5 .mu.m.

To generate these structurings, the dynamic behavior of the liquid used is utilized. In particular, with a combination of sufficiently high liquid surface tension and sufficiently low surface energy of the surface to be coated, an island-like covering can be obtained. As mentioned, island-like regions of higher layer thickness with an overall height of less than 10 μm are preferred, so that they can be completely crosslinked with excimer lamps. Island-like regions of higher layer thickness with a height are particularly preferred less than 5μm. Preference is given to using liquids which form a contact angle of 10 ° -140 °, especially of 10 ° to 90 °, on the substrate surface.

Another method is the use of fillers. Particles introduced into the liquid precursor cause a meniscus around the particles, i. a local increase in the liquid layer thickness, forms. If the height of the particles is comparable to the applied average layer thickness, then the meniscus represents a distinct layer thickness deviation. Via the local layer thickness deviation, a targeted surface structuring can be brought about. Preferably, particle diameters of from 20 percent to 1000 percent of the average layer thickness are used; particle diameters of from 50 percent to 500 percent of the average layer thickness are particularly preferred.

Accordingly, part of the invention is also a method for producing a surface topography on a surface to be coated by carrying out a method according to the invention, wherein in step b) a mixture is provided, comprising particles having a particle diameter of 20% to 1000%, preferably from 50 to 500 % of the average layer thickness based on the average layer thickness after crosslinking.

By an additional shrinkage of the crosslinkable precursor can be achieved that the particles introduced stand out clearly from the crosslinked layer and thus act as the actual structuring. By bursting open the UV-crosslinkable precursor layer and by ablation, the particles can even be exposed on the surface. In this way surface structuring can be generated by the properties of the particles. Thus, in addition to the topographic structuring, a chemically laterally structured surface can also be produced.

• Medizinische oder (bio-)katalytische Wirkstoffe, Metalle wie Silber, Kupfer, Nickel, Aluminium, Metalllegierungen, Metalloxide, Halbleitermetalloxide, wie die von Titan, Zinn, Indium, Zink oder Aluminium, Nichtmetalle, Nichtmetallverbindungen, Salze (z.B. Salze organischer und anorganischer Säuren, Metallsalze), Zinksulfit, Magnetit, Siliciumoxid, Bohrnitrit, Graphit, organische Feststoffe, Kohlenstoffpartikel sowie weitere keramische Materialien.

Preferably, particles of the following substances are used:

• Medical or (bio) catalytic agents, metals such as silver, copper, nickel, aluminum, metal alloys, metal oxides, semiconductor metal oxides such as those of titanium, tin, indium, zinc or aluminum, non-metals, non-metal compounds, salts (eg salts of organic and inorganic acids , Metal salts), zinc sulfite, magnetite, silicon oxide, Drill nitrite, graphite, organic solids, carbon particles and other ceramic materials.

Such layers can be used in particular as scratch-resistant coating, as hydrophobic coatings, for improving the pouring behavior, for the targeted delivery of active substances, as photocatalytic layers or as antibacterial layers.

9. General information

The structure of the present application in individual preferred embodiments is not intended to refer solely to this embodiment, the applications described in these embodiments. Many applications and thus corresponding uses, methods and devices can be carried out by means of the method according to the invention with other features, as described in the respective preferred embodiment. Regularly, the respective possible uses can also be generalized beyond the respectively preferred embodiment according to the invention in the context of the most general form of the invention, so that the uses described under the respective preferred embodiment represent only a preferred variant of the inventive concept. Moreover, it is clear to the person skilled in the art that the embodiments or individual measures / features of the individual embodiments can also be combined with one another, depending on the purpose of the application. Many layers, uses, or methods of the present invention also meet the features of more than one preferred embodiment simultaneously.

The invention will be further explained by means of examples, figures and claims. The following part is not to be understood as limiting the invention itself.

10. Examples Example 1: Comparison of plasma-crosslinked layers according to DE 40 19 539 A1 with layers produced by the method according to the invention using IR spectroscopy

Based on the in DE 4019539 A1 various methods were used to prepare a de-entailing coating. For this purpose, thin silicon oil layers were applied to aluminum-coated silicon wafers with the aid of a spin coater. Subsequently, the samples were treated with a low-pressure oxygen plasma and the contact angle with respect to water of the resulting coatings was determined and the associated IR spectra (recording method ERAS: External Reflection Absorption Spectroscopy) were recorded.

The details of the preparation are shown in Table 1.

First, it should be noted that in the published patent application DE 40 19 539 A1 Within the conducted IR spectroscopic studies used silicone oils of the series DC Fluid of the manufacturer Dow Corning (trimethylsiloxy-terminated polymethylsiloxane, PDMS) give identical results as the oils used in the AK series of the manufacturer Wacker AG (trimethylsiloxy-terminated polymethylsiloxane, PDMS). The studies with the oils of the series DC fluid are therefore not further considered separately.

In addition, no significant differences between the used oils AK50 and AK10000 can be determined as part of the measurement accuracy of the IR measurements (AK50: kinematic viscosity of approx. 50 mm ² / s at 25 ° C, density of approx. 0.96 g / mL , AK10000: kin. Viscosity of approx. 10000 mm ² / s at 25 ° C, density of approx. 0.97 g / mL). The essential comparisons are therefore limited to the presentation of the results with the oil AK10000. <B> Table. 1: </ b> Name and parameter of the oxygen plasma treated silicone oil layers. description silicone oil Layer thickness [nm] Power [W] Treatment time [s] mechanical stability Water edge angle [°] 1A DC fluid CST50 140 0 0 liquid 90 1B DC fluid CST50 140 500 60 easy to wipe off 98 1C DC fluid CST50 140 500 1200 wipeable 59 1D DC fluid CST50 140 2000 60 easy to wipe off 44 1E DC fluid CST50 140 2000 1200 wipeable 50 2A AK50 140 0 0 liquid 108 2 B AK50 140 500 60 easy to wipe off 103 2C AK50 140 500 1200 wipeable 60 2D AK50 140 2000 60 easy to wipe off 43 2E AK50 140 2000 1200 wipeable 46 3A AK10000 140 0 0 liquid 104 3B AK10000 140 500 60 easy to wipe off 57 3C AK10000 140 500 1200 wipeable 68 3D AK10000 140 2000 60 easy to wipe off 26 3E AK10000 140 2000 1200 wipeable 29

The Fig. 5 shows the IR spectra (ERAS) in the range of 700 - 1350 1 / cm for the oil AK10000 for the applied process parameters after plasma treatment according to the parameters of Table 1. The spectra are normalized for comparability to the respective maximum value in the range around 1111 - 1128 1 / cm.

Sample without plasma treatment or with short treatment time

• Bande 1 (P): um 1264 1/cm,
• Bande 2 (P): 1111 - 1128 1/cm
• Bande 3 (P): um 820 1/cm
• Bande 4 (P): um 1030 1/cm (als Schulter in 2 (P) zu erkennen)

The untreated oil on the pattern 3A and the subsequent 60s plasma-treated patterns 3B and 3D are characterized in the illustrated spectral range by four significant bands:

• Band 1 (P): at 1264 1 / cm,
• Band 2 (P): 1111 - 1128 1 / cm
• Band 3 (P): around 820 1 / cm
• Band 4 (P): at 1030 1 / cm (to be recognized as shoulder in 2 (P))

The significant regions in the spectra can be assigned to the following band vibrations: Symmetrical deformation vibration of CH ₃ in Si-CH ₃ : about 1250 1 / cm Si-O delta oscillations of Si-O-Si and Si-O: about 1070 - 1135 1 / cm Deformation vibration of CH ₂ in Si (CH ₂ ) _{1o 2} -Si: about 1030 1 / cm Si-C valence vibrations of (Si-CH ₃ ) ₃ : about 840 1 / cm Deformation vibration of CH ₃ in Si (CH ₃ ) ₂ : about 820 1 / cm

Pattern with long treatment time

• Bande 5 (P): um 1225-1230 1/cm

In addition to the four significant areas mentioned above and the shoulder, patterns with long treatment time, patterns 3C and 3E, show an additional band:

• Band 5 (P): at 1225-1230 1 / cm

The relative intensity of band 5 (P) increases with the treatment time and is finally comparable to the intensity of band 2 (P). The relative intensity of band 1 (P) and band 3 (P) compared to band 2 (P) decreases conversely with duration of treatment.

These observations can be interpreted as follows: From the decrease of the relative intensity (here the integral among the band (s)) of the regions 1 (P) and 3 (P) compared to 2 (P) it can be concluded that the relative content of CH ₃ groups is reduced by the plasma treatment. The appearance of the new band 5 (P) with a simultaneous decrease of 2 (P) - without a significant shift from 2 (P) to 5 (P) - indicates a non-complete penetration depth of the crosslinking method.

The results are understandable under the assumption that the radiation generated in the plasma and the electrons are only very close to the surface. An IR-measurable modification of the applied oil can be achieved in depth over the treatment time and via the power coupled into the plasma. If the treatment intensity is sufficient, the plasma-treated, modified oil (cross-linked oil) is responsible for the appearance of the additional band 5 (P). Non-cross-linked or partially cross-linked oil from the lowest layers of the applied oil film still supplies the IR spectrum of the untreated oil. In principle, it is conceivable that after sufficiently long irradiation or when using a sufficiently thin oil film, all the oil is crosslinked and the spectrum of uncrosslinked oil is no longer visible. However, the results suggest that such intensive crosslinking of the oil film does not match that in the DE 40 19 539 A1 claimed parameter range is reached (the stated maximum values for the power coupled into the plasma and for the duration of treatment have already been used).

In addition, a long, intensive plasma treatment of the oil layers is associated with a strong activation of the surface, as the measurements of the water edge angle show. In this respect, long treatment times in the plasma are incompatible with the claim of a de-entrant coating. The investigations also suggest that it will not be possible to produce a de-crosslinking coating with the processes described in the patent, which at the same time has adhesion to the substrate. On the one hand, such a coating could not be generated (see Table 1 with regard to mechanical stability and water edge angle). On the other hand, due to the result that the plasma treatment is very close to the surface, it is not possible to build up adhesion in deeper layers to the substrate without modifying the uppermost layer in such a way that it reacts in a hydrophilic manner.

The resulting band 5 (P) can also be assigned to the Si-O-Si or Si-O bands, which, however, must be associated with a network compared to the untreated oil. This network is formed by crosslinking reactions during the plasma treatment. A band in a similar wavenumber range becomes visible in the low pressure plasma deposition to produce a hard SiO _x -like coating. This represents a strongly three-dimensional, inorganic, hydrophilic network. Fig. 8 shows the comparison of the pattern 3E plasma-treated over a long period of time and a plasma polymer SiO _x -like coating.

For comparison, a series of pattern coatings was prepared according to the method of the invention. The base material used again was aluminum-coated Si wafers. The Si wafers were spin-coated with a -140nm thick silicone oil layer (AK10000, Wacker Chemie AG). The layers were then exposed to the radiation of an excimer lamp for different times (manufacturer: Radium, Xeradex spotlight, 172 nm). One series of the pattern coatings was made under atmospheric conditions, a second under nitrogen inert gas atmosphere. The distance between the wafer surface and the lower edge of the lamp was 10mm each. Other relevant process parameters are listed in Tables 2 and 3. <B> Table. 2: </ b> Name and parameters of the "Atmosphere" series. description B1 B2 B3 B4 irradiance 6.5mW / cm ² 6.5mW / cm ² 6.5mW / cm ² 6.5mW / cm ² Irradiation time in seconds 10 60 120 300 mechanical stability wipeable wipeable wipeable not wipeable Layer thickness after irradiation [nm] 139 136 123 121 Waters edge angle [°] 105 99 95 61

Excimer lamps irradiated samples under normal atmosphere

Fig. 6 shows the IR spectra (ERAS) of the excimer lamp irradiated patterns when treated under atmospheric conditions. The coatings B1 to B4 are substantially characterized in the illustrated spectral range by the following significant bands: Volume 1 (E): at 1264 - 1270 1 / cm: Volume 2 (E): 1111 - 1134 1 / cm: Volume 3 (E): Range around 810 - 820 1 / cm: Volume 4 (E): Range around 1030 1 / cm (to be recognized as shoulder of band 2 (E))

The bands detectable in the spectra can be assigned to the following band vibrations analogously to the plasma-treated oil layers: Symmetrical deformation vibration of CH ₃ in Si-CH ₃ : about 1250 1 / cm Si-O delta oscillations of Si-O-Si and Si-O: about 1070 - 1135 1 / cm Deformation vibration of CH ₂ in Si (CH ₂ ) _1o.2 -Si: about 1030 1 / cm Si-C valence vibrations of (Si-CH ₃ ) ₃ : about 840 1 / cm Deformation vibration of CH ₃ in Si (CH ₃ ) ₂ about 820 1 / cm Si-C valence vibrations of (Si-CH ₃ ) ₂ : about 805 1 / cm

It turns out that in particular the band 2 (E) migrates with the duration of the irradiation in the range of higher wavenumbers; from 1112 1 / cm for pattern B1 to 1134 1 / cm for pattern B4. The relative intensity of band 1 (E) and band 3 (E) compared to band 2 (E) also decreases with duration of irradiation. This observation can be interpreted as reducing the number of CH ₃ end or side groups. <B> Table. 3: </ b> Name and parameter of the series "N <sub> 2 </ sub> inert gas atmosphere". description B5 B6 B7 B8 irradiance 40mW / cm ² 40mW / cm ² 40mW / cm ² 40mW / cm ² Irradiation time in seconds 10 60 120 300 mechanical stability not wipeable not wipeable not wipeable not wipeable Layer thickness after irradiation [nm] 124 104 98 81 Waters edge angle [°] 59 55 31 38

Excimer lamps irradiated samples under a nitrogen atmosphere

Fig. 7 shows the IR spectra (ERAS) of excimer lamps irradiated patterns when treated under nitrogen atmosphere. The coatings B5 to B8 are substantially characterized in the spectral range represented by the following significant bands: Volume 1 (E): around 1264 - 1280 1 / cm, Volume 2 (E): 1111 - 1216 1 / cm Volume 3 (E): at 810 - 820 1 / cm Volume 4 (E): additional shoulder in gang 2 (E)

It turns out that in particular the band 2 (E) migrates with the duration of the irradiation in the range of higher wavenumbers; Starting at 1111 1 / cm for pattern B5 to 1216 1 / cm for pattern B8. Compared to the patterns irradiated in the atmosphere, the drift is much more pronounced. In addition, the intensities of band 1 (E) and band 3 (E) decrease with the duration of the irradiation until they are only vaguely recognizable (see sample B8). This can be interpreted as meaning that the number of CH ₃ end groups or side groups is significantly more reduced compared to the oil films irradiated in the atmosphere.

The IR spectrum of the oil film (B8) treated under nitrogen atmosphere and long irradiation time becomes comparable to that of the SiO _x -like coating in the low pressure plasma deposition (see Fig. 8). Fig. 8 represents the IR spectrum (ERAS) of the plasma-treated silicone oil AK10000 (sample 3E), an excimer lamp irradiated sample with silicone oil AK10000 (B8, see below) and deposited in low-pressure plasma, plasma polymer, SiO _x -like coating.

It has surprisingly been found that even these highly crosslinked coatings of the invention nevertheless contain a high proportion of carbon and this is also necessary, as a result of which the layers according to the invention have new, special properties compared to a plasma polymer SiO _x -like coating.

In addition, observation of the drift of band 2 (E), i. the gradual cross-linking of the oil film, and the disappearance of the measurement of an IR spectrum characteristic of uncrosslinked oil, suggests the interpretation that the applied oil film was homogeneously modified throughout the depth by the irradiation.

If the results of the different treatment methods for the oil films (plasma treatment or excimer lamps irradiation) are compared with each other, a fundamentally different one is observed, especially when considering the samples with a long treatment time (plasma treated: 3E; excimer / atmosphere: B4; excimer / nitrogen: B8) Behavior observed: During plasma treatment, with the treatment time an additional band in the range 1225-1230 1 / cm (5 (P)) results and the band recognizable in untreated silicone oil remains solid at 1111 1 / cm (2 (P)) wave number the band at 1111 1 / cm (2 (E)) for excimer lamps irradiation with duration of treatment to the value 1225-1230 1 / cm. Here, the shift for irradiation under nitrogen is much more pronounced. In addition, the relative decrease in the intensity of band 1 (P) and band 3 (P) with respect to band 2 (P) is much less pronounced in plasma treatment than in excimer lamp irradiation, particularly under irradiation under a nitrogen atmosphere (Decrease in the intensity of band 1 (E) and band 3 (E) relative to band 2 (E)).

All observations can be understood on the assumption that the penetration depth of the excimer lamp radiation into the oil film is substantially higher than the penetration depth of the plasma treatment.

After plasma treatment, as in DE 40 19 539 A1 In the case of the selected oil film thickness and the process parameters, a two-phase system consisting of a crosslinked cover layer and an almost unchanged, ie liquid, oil film is always produced. A strong crosslinking gradient exists in the plasma-treated layer. This statement is consistent with the observation that with thicker oil films (> 250nm) hardly adhesion to the substrate can be built up, while the uppermost cover layer already shows cracks due to internal tensions.

On the other hand it is possible with the excimer lamp radiation due to the greater penetration depth to modify the applied oil film of thickness 140nm homogeneously in depth. In this case, there is a comparatively low degree of crosslinking. Accordingly, it can be assumed that overall higher layer thicknesses can be effectively crosslinked with this method.

Example 2: Comparison of a plasma-crosslinked layer with layers crosslinked with excimer lamps by means of time-of-flight secondary-mass spectroscopy

To further understand the results shown in Example 1, TOF-SIMS depth profiles of some applied and treated layer systems from Example 1 were additionally performed (TOF-SIMS: time-of-flight secondary ion mass spectrometry).

The TOF-SIMS investigations were carried out with a TOF-SIMS IV device (ION TOF). Parameters: Excitation with a 25 keV Ga liquid metal ion source, Bunched mode, analysis area 60.5 x 60.5 μm ² , charge compensation with pulsed electron source. Sputtering parameters: 3 keV argon sputter source, 25.8 nA, sputter area 200 x 200 μm ² . The figures show the intensity of the positive ion signals characteristic of the corresponding elements versus the sputtering cycles (Cycle).

This measurement is for the sample 3E (plasma-treated silicone oil) in Fig. 11 , for the sample B1 (weakly cross - linked, excimer lamps irradiated silicone oil) in Fig. 12 and for B8 (highly crosslinked, excimer lamp irradiated silicone oil) in Fig. 13 shown below.

The figures show the relative change of the material components carbon (C), oxygen (O) and silicon (Si) with the penetration depth into the coating. It should be noted that in TOF-SIMS investigations, the intensities of the detected ions do not permit any statement about the absolute element distribution. Therefore, only the changes of the individual ion signals will be analyzed below. As the penetration depth, starting from the surface of the coating, the parameter "Cycle" has been selected, which indicates the number of TOF-SIMS sputtering cycles, with a sputtering cycle involving both sputtering and neutralizing and measuring. The individual signal curves are normalized to the course of the respective Si signal. In addition, the course of the Si signal is reproduced, which is normalized to one with respect to the absolute maximum. On the course of this Si signal can be seen whether already the Support material, Si wafer, is achieved in the measurement process. As a rule, when the Si carrier material is reached, a sharp drop in the Si signal can be recognized.

Fig. 11 represents a TOF-SIMS depth profile; Course of carbon, oxygen and silicon intensity for the plasma-treated pattern 3E. The intensities are normalized to the silicon signal for each cycle. In addition, the normalized to the absolute maximum of the Si signal (Cycle58) course of the Si signal is shown.

Fig. 12 represents a TOF-SIMS depth profile; Course of carbon, oxygen and silicon intensity for the excimer lamp irradiated pattern B1. The intensities are normalized to the silicon signal for each cycle. In addition, the normalized to the absolute maximum of the Si signal (Cycle128) course of the Si signal is shown. This represents the end of the coating and the beginning of the underlying Si wafer.

Fig. 13 represents a TOF-SIMS depth profile; Course of carbon, oxygen and silicon intensity for excimer lamp irradiated pattern B8. The intensities are normalized to the silicon signal for each cycle. In addition, the normalized to the absolute maximum of the Si signal (Cycle93) course of the Si signal is shown. This represents the end of the coating and the beginning of the underlying Si wafer.

Fig. 11 shows the course of the plasma-treated oil film with the designation 3E from Example 1. The film has a layer thickness of 139 nm and ends within the TOF-SIMS measurement after the cycle 117. The measurement shows a steady drop in the O signal and an increase in the C. Signal until about cycle 50 (-40nm). From cycle 50, both signals remain nearly the same. The course of the Si signal shows no abnormalities.

In addition, the carbon signal initially indicates a large decrease. Usually, in the case of samples which were in contact with the ambient air, a carbon signal is detectable on the surface, which, however, is not related to the actual layer composition. The carbons are artifacts from the air and are visible even on non-carbonaceous materials. In this respect, the initially strong drop of the C signal is ignored.

Fig. 12 shows the course of the weakly crosslinked, Excimerlampen irradiated oil film, sample B1 of Example 1. Cycle 128 marks the end of about 139nm thick Coating and the beginning of the Si wafer. The traces of the O and C signals show no significant changes in the depth profile.

Fig. 13 shows the course of the highly cross-linked, Excimerlampen irradiated oil film, pattern B8. Cycle 93 marks the end of the approximately 81 nm thick coating and the beginning of the Si wafer. Here, too, a very sharp drop in the carbon signal can be seen very close to the surface, which is ignored in the above-mentioned Greens. Furthermore, a steady increase in the C signal to about Cycle 60 can be seen. The O signal remains almost constant over the entire measurement. Overall, the level of the C signal, especially in the lower layers, is well below the level of layer B1.

The results of the measurements are to be classified as follows: The excimer lamp radiation penetrates deep into the oil film, which changes the composition of the film by irradiation. In general, the number of CH ₃ groups in the film is reduced. Deep penetration changes the level of the C signal over the entire depth. Based on the level of the C signal for B1, almost uncrosslinked silicone oil, this drops significantly for B8 due to the reduction of the CH ₃ groups.

The effect of the plasma treatment, however, is much closer to the surface. Here a strong gradient for the C-signal is detected. Also responsible here is the reduction of carbon from the oil film. In the deeper layers, in contrast to the strongly crosslinked coating B8, the same C-level is present as is the case with the weakly crosslinked coating B1. This observation is consistent with the above results, according to which the plasma treatment causes superficial crosslinking, but in depth remains an uncrosslinked, liquid oil film.

Fig. 14 illustrates the different behavior of the C signal for the three layer variants.

Fig. 14 shows a TOF-SIMS depth profile; Comparison of the carbon intensities (each normalized to the corresponding Si signal of each cycle) between the excimer lamps irradiated sample B1 (weakly crosslinked) and B8 (strongly crosslinked) and the plasma-treated silicone oil AK10000 (sample 3E).

Example 3: Corrosion protection coating or tarnish protection A) Corrosion coating

Aluminum sheets pre-cleaned with acetone were provided on one side with layer thicknesses of 100 nm, 150 nm, 200 nm and 250 nm with the silicone oil AK50 in a drain-coating process. Subsequently, the sheets were exposed with the liquid oil layer light of wavelength 172nm an excimer lamp (Xeradex spotlights, 50W, Radium Lampenwerk GmbH). The distance between the aluminum surface and the lamps was about 10mm, with treatment times of 20s, 60s, 120s and 360s. For a complete series with the mentioned treatment times and layer thicknesses, the irradiation took place under a nitrogen atmosphere, a series was carried out under air with variation of the layer thickness for a treatment time of 360 s.

The prepared coatings were immersed in 25% sulfuric acid at 65 ° C for 5 minutes and photographed to document the corrosion attack.

Fig. 15 shows the corrosion attack for the samples with the layer thickness 100nm.

Fig. 16 shows the corrosion attack for the patterns of the layer thickness 150nm.

Fig. 17 shows the corrosion attack for the coating of the layer thickness 200nm.

Fig. 18 shows the corrosion attack of the coatings with layer thickness 250nm.

The results show the tendency that with longer irradiation duration and resulting. higher degree of crosslinking of the coating of the corrosion attack can be reduced. This is especially evident in the series of measurements with an irradiation duration of 360s under a nitrogen atmosphere. Oxygen reduces the effective irradiation intensity for the same treatment time.

The applied layer thickness shows in the range shown only imperceptible influence on the corrosion resistance.

The described findings can be transferred to other surface materials.

After a repeated sulfuric acid test with an additional residence time of 10 minutes, ie a total duration of 15 minutes, a first corrosive attack on the samples with an irradiation duration of 360 s is shown.

B) tarnish protection

Start-up is also a corrosive attack, which initially shows itself visually and is usually caused by gases. For example, silver runs under H ₂ S atmosphere and turns brown.

In this case, the surface of a red-gold-plated ring was first cleaned with isopropanol and then activated with the aid of an excimer UV lamp in an air atmosphere to form ozone for 120s. Subsequently, an approximately 400 nm thick liquid layer of AK50 was applied to the surface of the ring by an aerosol method.

The applied oil film was crosslinked by irradiation with UV light of wavelength 172 nm (Xeradex radiator, Messrs. Radium). Here, the ring was constantly rotated about one of its axes in the plane of the ring. For this he was hung in the middle between two lamps. The average distance was about 25mm. The irradiation was carried out under a nitrogen atmosphere at atmospheric pressure. The duration of the irradiation was 600s. The layer thickness of the coating according to the invention after crosslinking was about 170 to 200 nm.

The coating could not be visually perceived as a color difference (neither interference nor loss of gloss). In contrast, for example, plasma polymer layers of comparable layer thickness would show these optical effects and would have a clearly recognizable influence on the visual appearance. Due to the increased layer thickness compared to the plasma polymers, for which the layer thickness may be only 10-40 nm (non-visible layer thickness range) for non-visibility of the coating, a higher mechanical wipe resistance is given, which can be recognized by the fact that the surface is now covered with commercially available polishing cloths (US Pat. at moderate pressure). This is not possible with plasma polymer layers with a layer thickness of 10 - 40 nm.

The tarnish protection was evaluated by means of the thioacetamide test (TAA test) on the basis of EN ISO 4538: 1995. Here, a coated and an uncoated ring was exposed to a hydrogen sulfide-containing atmosphere. As a result, after 3 days, the uncoated ring showed first signs of corrosion and was corroded evenly over the entire area after 7 days. The coated ring, on the other hand, showed local corrosion only after 7 days, mainly due to coating defects due to the suspension. The majority of the surface showed a shiny surface as in the beginning.

C) Aluminized foil

On a 19 μm PETP film coated on one side with aluminum (ROWO Coating), an approximately 100 nm thick liquid layer of AK50 was applied to the surface by means of a spin coating method.

The applied oil film was crosslinked by irradiation with UV light of wavelength 172 nm (Xeradex radiator, Messrs. Radium). The distance between the lamp base and the film was 0.1 to 3 cm when making several patterns. The irradiation was carried out under a nitrogen atmosphere at atmospheric pressure. The duration of the irradiation was 600s. The layer thickness of the coating according to the invention after crosslinking was about 50-70 nm for the different patterns.

Drops of solutions with different pH values were applied to the surface of the prepared samples or the samples were immersed in the appropriate solution.

The aluminum layer of the untreated reference surface dissolves completely after only 5 minutes, after which a drop of a solution with a pH of 12 has been added to the surface. Irrespective of the degree of crosslinking or the distance to the UV lamp during crosslinking, the coated samples exhibited no corrosive attack at pH 12.

When immersing the samples in a solution with a pH of 13, the aluminum layer of the untreated substrate completely dissolves after 90 seconds. The coated samples exhibited the following resistances depending on their irradiation parameters: <B><i> tab. 4 </ i></b> Distance lamp - substrate during networking Corrosion approaches after complete dissolution after 3.0 cm 7min 15 minutes 2.0 cm 7min 20 min 1.0 cm 10min 25min 0.5 cm 10min 25min 0.1 cm 30 min ne

D) Highly reflective aluminum

The following describes the coating of a highly reflective aluminum sheet. The underlying uncoated surface (manufacturer Fa. Alanod) is extremely susceptible to corrosion and very sensitive to mechanical abrasion, so that the surface requires a suitable coating before a technical application.

For this purpose, the surface of the aluminum sheet was first activated with the aid of an excimer UV lamp in air atmosphere with the formation of ozone for 120s. Subsequently, an approximately 20 nm thick liquid layer of AK50 was applied to the surface on one side by an aerosol method.

The applied oil film was crosslinked by irradiation with UV light of wavelength 172 nm (Xeradex radiator, Messrs. Radium). The distance between the lamp base and the aluminum sheet was 2, 10, 15 and 35mm. The irradiation was carried out under a nitrogen atmosphere at atmospheric pressure. The duration of the irradiation was 300s. The layer thickness of the coating according to the invention (adhesion promoter coating) after crosslinking was about 14 nm.

On this base layer, a second layer of the coating according to the invention was applied. For this purpose, a 420 nm thick liquid film was applied to the first layer by means of the aerosol application method. This was again among the irradiated and crosslinked for 600s already mentioned distances and process conditions. The layer thickness of the second applied coating according to the invention after crosslinking was about 270 nm.

Prerequisite for a functioning corrosion protection is a closed coating. This can easily be achieved by the person skilled in the art through the aerosol process. Due to the aerosol method used, however, layer thickness differences often occur on the coated surface. Especially at the places where larger condensation droplets land, locally higher layer thicknesses are achieved. The layer thickness deviation is noticeable via the interference color. While macroscopically only a small mottling is visible, the examination with the microscope shows that there are round areas within which the layer thickness increases towards the center. Accordingly, rings with the different interference colors are visible. The spots may have diameters from a few microns to several hundreds of microns. The layer thickness increase within these spots can amount to several hundred percent compared to the average layer thickness.

FIG. 35 represents deviations of the coating thickness caused by the aerosol process by condensation of larger drops.

An uncoated and the coated aluminum sheets were immersed in a 25% sulfuric acid solution having a temperature of 65 ° C. The uncoated sheet showed full-area corrosion after 2 minutes. The crosslinked at the distance of 35mm coating showed initial corrosion after 5 minutes, all other sheets showed only after 60 min corrosion approaches.

In addition to the corrosion-inhibiting property of the coating, it could be observed that the coatings provide improved protection against abrasion. The untreated surface already showed clear scratch marks by light, manual cleaning. The coating allows for careful manual cleaning without scratch marks.

E) The procedure described under D) is also used to treat a shiny polished aluminum rim. Also with this component it comes to a clear Improvement of corrosion resistance. In addition, it comes to an easier cleanability of the surface.

F) The procedure described under D) is also used to treat a shiny anodized aluminum trim strip. Even with this component, there is a significant improvement in corrosion resistance. In addition, it comes to an easier cleanability of the surface.

Example 4: Excimer irradiation of silicone oil

To demonstrate the properties of the coating according to the invention, exemplary basic investigations were carried out on a series of sample coatings. The samples were made on Si wafers as base material. For this purpose, the Si wafers were first activated by means of a plasma treatment and provided by spin coating with a -140nm thick silicone oil layer (AK10000, Wacker Chemie AG). The layers were then exposed to the radiation of an excimer lamp for different times (manufacturer: Radium, Xeradex spotlight, 172 nm). One series of the pattern coatings was made under atmospheric conditions, a second under nitrogen inert gas atmosphere. The distance between the wafer surface and the lower edge of the lamp was 10mm each. Other relevant process parameters are listed in Tables 5 and 6. <I><b> Tab. 5: </ b> Name and parameters of the "Atmosphere" series. </ I> description B1 B2 B3 B4 irradiance 6.5mW / cm ² 6.5mW / cm ² 6.5mW / cm ² 6.5mW / cm ² Irradiation time in seconds 10 60 120 300 wipe test wipeable wipeable wipeable not wipeable Layer thickness after irradiation [nm] 139 136 123 121 description B5 B6 B7 B8 irradiance 40mW / cm ² 40mW / cm ² 40mW / cm ² 40mW / cm ² Irradiation time in seconds 10 60 120 300 wipe test not wipeable not wipeable not wipeable not wipeable Layer thickness after irradiation [nm] 124 104 98 81

Fig. 19 represents the refractive index of the under air atmosphere UV radiation treated silicone oil layers of the pattern B1 to B4.

Fig. 20 represents the refractive index of the under N ₂ inert gas atmosphere UV radiation treated silicone oil layers of the pattern B5 to B8.

The FIGS. 19 and 20 show the course of the refractive index of the finished coatings in the wavelength range of 240 to 790 nm (determination by ellipsometry). Although some coatings, in particular B1 to B3, can still be manually wiped off with a cloth, ie the layers have not yet built up sufficient cohesion in the coating film itself and also adhesion to the Si support material, the effect of the irradiation can be seen when comparing the refractive indices: To be recognized is that the refractive index increases with the duration of the irradiation at atmospheric conditions. For the patterns under irradiation under nitrogen atmosphere B5 to B8, a degree of crosslinking is achieved which provides sufficient adhesion to the substrate so that the coating can no longer be cleaned with a cloth. Here, the differences in the course of the refractive indices are less pronounced.

To further characterize the patterns, ESCA determined the atomic composition of the irradiated surfaces. It should be noted that only the topmost surface layer with a layer thickness of approx. 10 nm is detected with this measuring method. The measured data, Tab. 7, clearly show the effect of the irradiation: With the duration of the irradiation, the relative oxygen and silicon content increase, whereas the carbon content decreases - The layer becomes inorganic. The ratio of carbon to silicon decreases with the duration of irradiation, in the ratio of oxygen to silicon a decrease can be seen. These findings can be generalized beyond the concrete example. <I><b> Tab. 7: </ b> Percent elemental composition and elemental ratios of UV-treated silicone oil layers measured with XPS <i> (X-ray photoelectron spectroscopy). </ I> description O 1s N 1s C1s Si 2p C / Si O / Si B1 25.28 0.06 52,50 22.16 2.37 1.14 B2 29.15 0.05 46.97 23.83 1.97 1.22 B3 37,34 0.00 39.22 23.44 1.67 1.59 B4 47.15 0.29 28,10 24.46 1.15 1.93 B5 41.12 0.02 34,30 24.56 1.40 1.67 B6 40.96 0.16 32.96 25.91 1.27 1.58 B7 55.48 0.34 19.29 24.88 0.78 2.23 B8 61.81 0.39 10.49 27.32 0.38 2.26

The changes in the ratios between carbon and silicon also become apparent when looking at the IR spectra of the irradiated coatings. These are shown individually in the FIGS. 21 to 28 , respectively 7 and 8 (see above).

Fig. 21 represents the IR spectrum (ERAS) of the UV-irradiated pattern B1.

Fig. 22 represents the IR spectrum (ERAS) of the UV-irradiated pattern B2.

Fig. 23 represents the IR spectrum (ERAS) of the UV-irradiated pattern B3.

Fig. 24 represents the IR spectrum (ERAS) of the UV-irradiated pattern B4.

Fig. 25 represents the IR spectrum (ERAS) of the UV-irradiated pattern B5.

Fig. 26 represents the IR spectrum (ERAS) of the UV-irradiated pattern B6.

Fig. 27 represents the IR spectrum (ERAS) of the UV-irradiated pattern B7.

Fig. 28 Figure 4 shows the IR spectrum (ERAS) of the UV-irradiated pattern B8.

The data presented were recorded with ERAS (External Reflection Absorption Spectroscopy) and normalized for comparability to the respective maximum in the wavenumber range between 1112 and 1216 1 / cm. To record the IR spectra, the uncoated Si wafers were previously vapor-deposited with aluminum, and the oil was then applied to the Al layer by spin coating as before.

The irradiation parameters are identical to those of Tab. 5 and 6. The maxima of the band in the range between 1112 and 1216 1 / cm can be assigned mainly to the carbon-free Si-O-Si compound, the maxima in the range 1250 1 / cm (Si-CH ₃ ) or 805 1 / cm Si (CH ₃ ) ₂ and 840 1 / cm Si (CH ₃ ) ₃ , on the other hand, contain carbon. The comparison shows that in both cases, both under atmospheric irradiation and under nitrogen, the ratio of carbon to silicon decreases.

Example 5 Comparison of the Layers of Example 4 with Plasma Polymeric Layers

Fig. 29 shows for comparison the IR spectra of plasma polymer separation layers, which were prepared by means of a low-pressure plasma method (with different reactor volume from 3301 to 50001). The spectra are normalized to the respective maximum value. All spectra show both a band for Si (CH ₃ ) ₂ (805 1 / cm) and for Si (CH ₃ ) ₃ (840 1 / cm). The presence of this double band is characteristic of hydrophobic plasma polymer coatings. The pronounced band at 840 1 / cm is due to the fact that with HMDSO as the process gas, a monomer is used, which has a relatively high proportion of Si (CH ₃ ) ₃ end groups due to the shortness of the molecule.

In contrast, in all excimer lamps irradiated patterns, the band associated with the Si (CH ₃ ) ₃ end groups is much less pronounced or difficult to identify. The reason lies above all in the fact that liquids are initially used in the coating according to the invention. These liquids have much longer molecular chains, so that the relative proportion of End groups significantly lower precipitates. This statement applies regardless of the duration of irradiation or the degree of crosslinking such as Fig. 6 and Fig. 7 show and thus for both hydrophobic and hydrophilic coatings. With increasing irradiation time or degree of crosslinking, the band for the Si (CH ₃ ) ₂ group additionally reduces for the radiation-crosslinked coatings; this is an indication that these groups are broken up by the use of high-energy excimer lamps. The same applies to the CH ₃ band in the range of -2960 1 / cm.

These results can also be generalized.

Example 6: degree of crosslinking

The inventive method allows the degree of crosslinking of the applied liquid to vary over the intensity of the irradiation in a wide range. In addition to the degree of crosslinking of the liquid itself, the adhesion to the substrate material is of technical importance. For demonstration shows the Fig. 30 a micrograph of a broken edge of the pattern B8 from Example 4. Although strong mechanical loads on the substrate and on the coating act, no stress cracks or delamination in the coating show - the coating boundary runs exactly along the breaking edge. Cracks caused by the mechanical stress in the substrate, however, are also visible in the coating, Fig. 31 , Additional cracks due to the short-term stresses do not occur.

Fig. 30 represents a micrograph of the UV-radiation-crosslinked pattern B8 along a fracture edge after heavy mechanical stress.

Fig. 31 represents a micrograph of the UV-radiation-crosslinked pattern B8 along a fracture edge after heavy mechanical stress.

Example 7: Embedding of titanium dioxide particles

According to the method of the invention, a pattern of embedded titanium dioxide particles was prepared. For this purpose, a liquid composition of the silicone oil AK50 and AK0.65 was used as a diluent in the ratio 1:50, which were then added titanium dioxide particles. The composition was spincoated as an average -140nm thick liquid film on a Si wafer applied. In the area of the particles, menisci were formed with a significantly higher layer thickness, which included the particles in an oil mountain.

The samples were irradiated with UV light of wavelength 172nm under nitrogen atmosphere for 5 minutes, the distance of the lamp to the surface was ~ 10mm.

Finally, the surface was cleaned with IPA by manual wiping. The purpose of the cleaning was to examine whether the coating was crosslinked sufficiently to build up both adhesion between the precursor molecules of the liquid itself and to the substrate and the TiO ₂ particles; Particles or large particle agglomerates that could not be sufficiently embedded in the matrix were also wiped out by cleaning.

Fig. 32 shows an SEM image of the cleaned coating, within which the titanium dioxide particles are clearly visible.

The visible particles or agglomerates could be clearly identified by material analysis as titania particles. The size of the embedded particles is laterally up to several microns, the height of the particles up to 3 microns with a mean layer thickness of the crosslinked layer of ~ 100nm.

Example 8: Embedding of Dye Particles

According to the method of the invention, a pattern with embedded dye particles was prepared. For this purpose, a solution of one part of the silicone oil AK50 (Wacker Chemie AG) and 50 parts of the diluent AK0.65 (Wacker Chemie AG) was prepared. The dye was added to the fat-blue dye B01 (Clariant GmbH) in an amount such that excess dye settles out as a sediment. To remove the sediment and remove larger agglomerates of the added dye, the dispersion was filtered (pore size 400 nm) and then processed in a timely manner. The base material used for the coating was glass slices onto which the dispersion was applied by means of spin coating. After evaporation of the solvent, a layer of the non-volatile component AK50 -140 nm thick together with the embedded dye particles remained as a liquid film on the glass substrate.

This film was then exposed to light of wavelength 172nm of a UV excimer lamp (Xeradex radiator, 50W, radium). The distance of the lamps to the substrate was -10 mm, the irradiation time-180 s, the irradiation was carried out under nitrogen atmosphere.

After irradiation or crosslinking of the oil, a coating which can not be wiped off manually with isopropanol results, within which the admixed dye particles are embedded.

Fig. 33 shows a microscope image of the dye particles with an average size of diameter below 1 micron.

Example 9: Partial coating

Using spincoating, a layer of AK50 about 140 nm thick was applied to a silicon wafer. A shadow mask was then placed on the layer and irradiated with 172 nm wavelength light for 5 minutes under a nitrogen atmosphere (Xeradex radiator, 50W, Radium Lampenwerk GmbH). The distance between the mask and the lamp base was ~ 10mm.

After crosslinking of the irradiated areas of the liquid layer, the non-cross-linked, in the shadow area lying residual film of the AK50 could be rinsed off by isopropanol. Corresponding to the round openings of the mask, a regular pattern of round coating islands was achieved.

Fig. 34 represents the result of the partial coating in Example 9.

The coated areas could not be removed by manual cleaning and form hydrophilic anchors due to the comparatively higher surface energy compared to the untreated wafer surface.

Example 10: Antifingerprint Coating on Metal Surfaces

A) The surface of a galvanized body with an average roughness R _a in the range 0.3 - 0.8μm was increased to above 72mN / m with a low pressure oxygen plasma before the liquid application to increase the surface energy activated. Alternatively, the activation can be carried out, for example, by irradiation with short-wave UV radiation from excimer lamps. As a liquid precursor, the silicone oil AK50 (Wacker, surface tension 20.8 mN / m, viscosity 50 mm ² / s) was applied as an average 50 nm, 100 nm and 200 nm thick layer by spin coating. The liquid precursor preferably settles in the recesses of the surface profile and thus forms a non-closed, island-like covering.

Radiation crosslinking took place within a recipient at a residual gas pressure of 0.01 mbar. The distance of the surface from the irradiator bottom was 40mm. The UV radiation source was a 172nm Xe excimer lamp manufactured by Haereus Noblelight. The irradiation intensity was ~ 1.2 W / cm ^2, and the irradiation time was 30 seconds.

B) As an alternative, the liquid precursor was irradiated under inert gas atmosphere (eg nitrogen, CO ₂ , noble gases) at atmospheric pressure with an intensity in the range of 100 to 400 mW / cm ² and a time in the range of 60 to 600s. The light source was a Xeradex Xe excimer radiator with a wavelength of 172 nm (Radium). As a further alternative, the crosslinking may take place in an air atmosphere, as long as the person skilled in the art ensures that the irradiation dose, ie the radiation power incident over time, is sufficient to produce a solid film.

C) Furthermore, samples of blasted brass and aluminum surfaces with an average roughness R _a in the range of 0.5 to 1.2 μm were coated under the same conditions.

Due to the layer thickness, the presence of the coating can be clearly identified by the optical color impression (by interference effects). Resulting average layer thicknesses were ~ 45 nm at the order of 50 nm precursor layer thickness, ~ 90 nm at 100 nm precursor layer thickness and ~ 185 nm at 200 nm precursor layer thickness. By contrast, the local layer thicknesses of the coating islands were higher by a factor of 2 than the average layer thicknesses. This observation is explained by the dynamic redistribution of the applied liquid silicone oil precursor. This results in layer thickness deviation up to a factor of 2 and an associated degree of coverage of about 0.5.

• Bevorzugt wird eine mittlere Schichtdicke der fertigen Beschichtung im Bereich von 50 bis 300nm. Besonders bevorzugt eine mittlere Schichtdicke im Bereich von 100 bis 250nm. Im Gegensatz zu der Beschreibung der genannten PCT/EP 2006/062987 kann durch die intensive Bestrahlung mit Licht einer Wellenlänge unterhalb von 250nm je nach gewählten Prozessparametern ein Schichtschrumpf beobachtet werden. Dieser durch Vergleich der aufgetragenen Schichtdicken des unvernetzten Precursors und des vernetzten Precursors messbare Schichtschrumpf kann bis zu 60% betragen und muss bei der Einstellung der gewünschten Endschichtdicke berücksichtigt werden. Die vernetzten Beschichtungen lassen sich nicht durch manuelles Wischen mit einem Tuch von der Oberfläche entfernen. Die Beschichtung zeigt eine Verminderung der Wahrnehmung von Fingerabdrücken (Antifingerprint-Eigenschaften) gemäß der PCT/EP 2006/062987 . Die Beschichtung zeigt zudem leicht zu reinigende Eigenschaften.

However, the following has emerged:

• An average layer thickness of the finished coating in the range of 50 to 300 nm is preferred. Particularly preferred is an average layer thickness in the range of 100 to 250 nm. In contrast to the description of the mentioned PCT / EP 2006/062987 can be observed by intensive irradiation with light of a wavelength below 250nm depending on the selected process parameters, a layer shrinkage. This layer shrinkage measurable by comparing the applied layer thicknesses of the uncrosslinked precursor and the crosslinked precursor can be up to 60% and must be taken into account when setting the desired final layer thickness. The cross-linked coatings can not be removed from the surface by manual wiping with a cloth. The coating shows a reduction in the perception of fingerprints (anti-fingerprint properties) according to the PCT / EP 2006/062987 , The coating also has easy-to-clean properties.

Example 11: Galvanized plastic surface

Treatment according to Example 10, but now with a galvanized plastic surface with a mean roughness R _a in the range 0.6 - 1.0μm. The cross-linked coatings can not be removed from the surface by manual wiping with a cloth. The coating exhibits anti-fingerprint properties according to PCT / EP 2006/062987 ,

Example 12: Si wafers under different process gas conditions

The surface of three Si wafers were spin-coated with the silicone oil AK10000 (Wacker, surface tension 21.5mN / m, viscosity 10000mm ² / s), coating thickness ~ 250nm. The radiation crosslinking took place (a) under atmospheric conditions, or (b) within a recipient in the presence of nitrogen under atmospheric pressure or (c) under a residual gas pressure of 0.01 mbar. The distance of the surface from the irradiator bottom was 10mm. The UV radiation source was an Xe excimer lamp with a wavelength of 172 nm from the manufacturer Radium. The irradiation intensity was ~ 0.8W / cm ² and the irradiation time was 120s each.

The cross-linked coatings could not be wiped off with a cloth. They are resistant to isopropanol and acetone, a tesa film strip adhered to the coating could be peeled off without removing parts of the coating from the Si surface. The surface energy was determined after 5 days to 22mN / m (a, atmosphere), 28mN / m (b, residual gas) and 32mN / m (c, nitrogen).

These are low surface energy coatings that can be used as easy-to-clean or release layers.

Example 13: Si wafer coated at different temperatures

The surface of a Si wafer was provided by dipping in a solution with the silicone oil AK50 with varying layer thicknesses of up to 500 nm. Radiation crosslinking took place within a recipient at a residual gas pressure of 0.01 mbar. The distance of the surface from the irradiator bottom was 10mm. The UV radiation source was an Xe excimer lamp with a wavelength of 172 nm from the manufacturer Radium. The irradiation intensity was ~ 0.6W / cm ² and the irradiation time was 120s.

After crosslinking, the coating can not be manually wiped off with a cloth and shows resistance to acetone. It is a low energy surface with a surface tension below 22mN / m.

The water edge angle of a water droplet applied to the surface was ~ 90 °. After a one-hour heating of the coating to 200 ° C, the contact angle was 96 °, after a subsequent one-hour heating to 250 ° C, the angle increased to 100 °. After a further three hours of heating the coating at 250 ° C, the contact angle was also 100 °.

Example 14: Easy to clean surface (easy-to-clean coating)

On the surfaces of a blasted brass and an aluminum sample with an average roughness R _a in the range 0.5-1.2 μm, a thin liquid film consisting of AK50 (Wacker, surface tension 20.8 mN / m, viscosity 50 mm ² / s) was obtained. applied. Several samples were made with average layer thicknesses in the range of 100 to 1000 nm.

The radiation crosslinking took place inside a recipient with nitrogen filling (at atmospheric pressure). The distance of the surface from the radiator underside was 20mm. The UV radiation source was an Xe excimer lamp with a wavelength of 172 nm from the manufacturer Radium (100 W / 40 cm). The exposure time was 300s.

After crosslinking, an approximately 50 to 750 nm thick layer remains on the component surface. The layer shows easy to clean properties: For example, fingerprints can be easily wiped off the surface with a damp cloth. The shrinkage (the layer thickness reduction of the resulting layer versus the order thickness of the precursors) was 25-50%. The shrinkage can be quantified z. B. based on a reference layer on a wafer, which goes through the same process. Due to the roughness of other surfaces, a direct determination is often possible only with great effort.

Coated samples with an average layer thickness in the range from 170 to 200 nm additionally show the effect of hardly differing in color from the original material. This gives a virtually invisible easy-to-clean coating, which does not affect the actual surface characteristics.

Example 15: Smoothing coating

A liquid film consisting of AK10000 (Wacker, surface tension 21.5 mN / m, viscosity 10000 mm ² / s) with a layer thickness of 1 μm was applied to the surfaces of a blasted brass and an aluminum pattern having an average roughness R _a of 1.2 μm. This layer thickness corresponds to ~ 83% of the R _a value.

The radiation crosslinking took place inside a recipient with nitrogen filling (at atmospheric pressure). The distance of the surface from the radiator underside was 5mm. The UV radiation source was an Xe excimer lamp with a wavelength of 172 nm from the manufacturer Radium (100 W / 40 cm). Exposure time was 600s.

After crosslinking, an average of 700 nm thick crosslinked layer remains on the surface. The subsequently determined R _a value was 0.75 μm. Thus, a reduction of the roughness by about 40% could be achieved.

Example 16: Antimicrobial coating

A dispersion of about 1.5 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 (1:50) applied by spin coating on a glass surface. The glass surface was previously irradiated with the aid of UV radiation in air atmosphere 120s to increase the surface energy. The layer thickness of the liquid film was - 500 nm. The silver-containing liquid layer was then irradiated for 600 s with UV light (172 nm, Xeradex emitter, 50 W, Radium Lampenwerk GmbH). The distance between the lower edge of the lamp and the surface was ~ 15mm irradiated within a nitrogen atmosphere at a pressure of 1 bar. The irradiation created a non-wipeable, hydrophilic coating with a mean layer thickness of -330nm. Macroscopically, a browning of the substrate could be perceived due to the incorporated silver. The presence of nanosilver could also be identified by means of a UV-VIS spectrometer based on the typical silver absorption band at 420 nm. In the light microscope no particle agglomerates with lateral dimensions larger than 1μm could be identified. The coating has antimicrobial, but not cytotoxic properties.

Example 17: Adhesion pretreatment

Various polymers and stainless steel as the base material were surface cleaned with methyl ethyl ketone (MEK). The size of the patterns was 100mm x 25mm. The cleaned material was used to make reference couplings for a tensile shear measurement based on DIN EN 1465: 1995-01. On the other hand, purified material was provided with a coating according to the invention. The liquid silicone oil layer (AK50, Wacker) was applied by means of an aerosol method, the average layer thicknesses are listed in Table 8. The oil layers were then irradiated with light of wavelength 172 nm (Xeradex radiator, 50W, Radium Lampenwerk GmbH) for 600 s at a distance of 10 mm under a nitrogen atmosphere. The resulting layer thicknesses can be calculated from the in Tab. 8 shrinkage (ratio between final layer thickness and coating layer thickness). With the samples produced according to the invention, tensile shear samples were again prepared and measured. As adhesives for the listed polymers Delo PUR 9691 and for stainless steel Delo PUR 9694 were used.

The results of the tensile shear measurements are shown in Tab. 8. Listed are the determined maximum forces Fmax, in which the joint assembly was destroyed, so the bonding failed. All values were normalized with respect to the absolute values of the maximum force determined for the reference. Thus, for the coating according to the invention, a maximum force> 1 indicates an improvement in the bond strength. An improvement could be observed for 4 of the 6 treated materials. The improvement was up to 100% (PTFE). Furthermore, an improvement of 37% could be achieved with the coating according to the invention as adhesive pretreatment for stainless steel, in which case the limit of the adhesive potential was reached. In this case, a pure cohesive failure of the adhesive was observed.

All investigations were carried out with 3 identical samples. The deviations from the mean (Δs) are given in Table 8.

Example 18: Migration barrier and permanent separation layer

Transparent plastic molds for the UV curing of paints in a paint casting process are coated by a dipping process with a closed PDMS oil film of about 150 nm. Subsequently, the oil, AK 10000 (Wacker GmbH) in a nitrogen atmosphere by means of excimer radiation by irradiation within a nitrogen atmosphere at 1 bar strongly crosslinked. It was ensured that each surface element with a radiation dose of at least 50 Ws / cm ² , preferably 70W / s / cm ^{2 was} treated. This radiation dose can be set for a 3D shape via the parameters Time and Distance. In the present example, the distance to the plastic mold was on average ² cm and the irradiation time 25 minutes, the radiation dose was thus on the use of a Xeradex excimer lamp on average ~ 90 Ws / cm ² . As a result, a migration barrier to styrene is obtained, which leads to a significant extension of the service life of the plastic molds. In order to be able to dispense with external release agents as far as possible during the molding process, a second PDMS oil film of about 100 nm is easily crosslinked by means of excimer radiation. Again, the irradiation was carried out within a nitrogen atmosphere at 1 bar. The radiation dose may be at most 30 Ws / cm ² , preferably at most 20 W / s / cm ² . In the present example, the distance to the plastic mold was on average ² cm and the irradiation time 5 minutes, the radiation dose was thus on average using a Xeradex excimer lamp -25 Ws / cm ² . As a molding material, both silicone and polyamide can be used.

Example 19: Gas migration barrier

PP film (manufacturer: Tresphaphan, thickness: 25 .mu.m) was provided via an aerosol method with a silicone oil layer (AK50, Wacker GmbH) with an average layer thickness of -120 nm. The liquid layers were then irradiated with an excimer lamp (manufacturer: Radium Lampenwerk GmbH) with light of wavelength 172 nm. The irradiation time was 600s at a distance between the lamp and the foil of ~ 0.5cm. Although the aerosol method is a droplet-like covering, it could be ensured by controlling with a light microscope on the basis of the visible interference color gradients that the degree of coverage with the silicone oil is 1, i. a complete coverage was achieved. The average layer thicknesses after irradiation were -70 nm, the relative layer thickness deviation here being about 50%, ie. the local layer thicknesses were 35 - 100nm.

The oxygen permeability was measured by means of the permeation measuring device OX-TRAN 2/20 (Mocon). In this case, the migration of oxygen through the coated film is determined (determination for films based on DIN 53380-3 and ASTM D 3985-05). The relative humidity during the measurement was 50%, the measuring temperature 30 ° C.

For the untreated film an oxygen permeability of 3460 cm ³ / (m ² d) was measured, the coated film had a permeability of 81 cm ³ / (m ² d). Thus, a reduction in oxygen permeability to ~ 2.3% could be achieved.

Example 20: Flexible scratch-resistant coating on sensitive surfaces

Transparent polycarbonate panes for automotive roof glazing are fitted with an aerosol process with a closed PDMS oil film of approx. 2 μm. Subsequently, the oil is strongly crosslinked in a nitrogen atmosphere by means of excimer radiation. The distance between the surface and the lamp is a maximum of 1cm, the irradiation time is 20 minutes. This results in a significant improvement in the scratch resistance of the disc, without any risk of the coating peeling off when the bending load is greater.

Example 21: Flexible coating

The coating of Example 3 D), coating a highly reflective aluminum sheet, shows a further special feature of the possibilities of the coating technique according to the invention.

The coated sheets were bent manually. Bending radii of 2.5mm were realized. Practically, the experiment was carried out so that the corresponding sheet was placed on a rod and the radius of the rod was reshaped. The bent sheet was examined by light microscopy with a 1000-fold resolution. No cracks or peeling of the layer were observed. In particular, there was no reduction in the abrasion resistance of the coating. It can therefore be assumed that the lower limit for the bending radius may still be much smaller than 2.5 mm. The result is a flexible abrasion protection or flexible corrosion protection. This property is important because the sheets are usually made as a flat strip and bent and folded after coating to realize 3D shapes.

The flexibility of the coatings of the invention is generally due, in part, to the residual carbon content in the coating. From Example 4, example parameters can be taken with which corresponding carbon contents can be realized.

Accordingly, other of the mentioned surface functionalizations can be configured as a flexible coating. This includes e.g. a flexible scratch protection, which in contrast to the above example has layer thicknesses in the range of several microns. These layer thicknesses can be applied in multiple layers within several cycles or preferably in one cycle.

Furthermore, by adjusting the carbon content, it is possible to realize a flexible tarnish protection, a flexible antimicrobial coating, a flexible structuring or topography-giving coating, a flexible barrier coating, a flexible antifingerprint coating, a flexible easy-to-clean coating, etc. (cf. reference is also made, for example, to Chapter 7).

Example 22: Thin protective layers on ceramic filter materials

Ceramic filter media based on borosilicate fibers are provided as web material by an aerosol method with a closed PDMS oil film having an average layer thickness of about 300 nm. Subsequently, the oil is crosslinked in a nitrogen atmosphere by means of excimer radiation. The irradiation dose was at least 50 Ws / cm ² (at a distance of 1 cm and a irradiation time of 10 minutes using a Xeradex excimer lamp with a wavelength of 172 nm and a power of 50W at a length of 40cm). As a result, service life is considerably extended by the sterile air filter elements made of the filter media for process air treatment during regular disinfection within a cleaning-in-place (CIP) process. The reason for this is in particular the higher resistance to alkaline hydrogen peroxide vapors obtained by the coating according to the invention. The small layer thickness of the coating leads only to a very small increase in the pressure difference through the filter medium.

1. a) Bereitstellen einer Mischung oder eines Reinstoffs, umfassend oder bestehend aus reaktionsträgen, flüssigen Precursoren,
2. b) Aufbringen einer flüssigen Schicht aus der Mischung oder dem Reinstoff auf eine zu beschichtende Oberfläche,
3. c) Vernetzen der flüssigen Precursoren mittels Strahlung mit einer Wellenlänge von ≤ 250 nm, so dass aus der Mischung eine feste Schicht entsteht und die Schicht ≥ 10 Atom-% C umfasst, bezogen auf die Menge der in der Schicht enthaltenen Atome ohne H und F,

und so dass der in der Schicht enthaltene C zu maximal 50 Atom-% des C, bezogen auf die Menge der in der Schicht enthaltenen C-Atome, Bestandteil einer Methoxygruppe ist.
Ausgestaltung 2. Beschichtungsverfahren mit den Merkmalen der Ausgestaltung 1, wobei das Vernetzen so erfolgt, dass maximal 50 Atom-% des C, bezogen auf die Menge der in der Schicht enthaltenen C-Atome, Bestandteil einer Alkoxygruppe ist.
Ausgestaltung 3. Beschichtungsverfahren mit den Merkmalen der Ausgestaltungen 1 oder 2, wobei die Schicht mittels Laserstrahlung oder UV-Strahlung aus einer Excimerlampe vernetzt wird.
Ausgestaltung 4. Beschichtungsverfahren mit den Merkmalen der vorangehenden Ausgestaltungen, wobei das Vernetzen mittels UV-Strahlung der Wellenlänge ≤ 200 nm erfolgt.
Ausgestaltung 5. Beschichtungsverfahren mit den Merkmalen der vorangehenden Ausgestaltungen, wobei die flüssigen Precursoren in einer Schichtdicke von 3 nm bis 10 µm aufgetragen werden.
Ausgestaltung 6. Beschichtungsverfahren mit den Merkmalen der vorangehenden Ausgestaltungen, wobei die in Schritt a) bereitgestellte Mischung zu ≥ 50 Gew-%, bezogen auf das Gesamtgewicht der Mischung, aus reaktionsträgen, flüssigen Precursoren besteht.
Ausgestaltung 7. Beschichtungsverfahren mit den Merkmalen der vorangehenden Ausgestaltungen, wobei die in Schritt a) bereitgestellten Precursoren ≥ 10 Atom-% C umfassen, bezogen auf die Menge der in der Mischung enthaltenen Atome ohne H und F.
Ausgestaltung 8. Beschichtungsverfahren mit den Merkmalen der vorangehenden Ausgestaltungen, wobei der in der in Schritt a) bereitgestellten Mischung enthaltene C zu maximal 50 Atom-%, bezogen auf die Menge der in der Mischung enthaltenen C-Atome, Bestandteil einer Methoxygruppe ist.
Ausgestaltung 9. Beschichtungsverfahren mit den Merkmalen der vorangehenden Ausgestaltungen, wobei der in der in Schritt a) bereitgestellten Mischung enthaltene C zu maximal 50 Atom-%, bezogen auf die Menge der in der Mischung enthaltenen C-Atome, Bestandteil einer Alkoxygruppe ist.
Ausgestaltung 10. Beschichtungsverfahren mit den Merkmalen der vorangehenden Ausgestaltungen, wobei die zu beschichtende Oberfläche keine Silanolgruppen umfasst.
Ausgestaltung 11. Beschichtungsverfahren mit den Merkmalen der vorangehenden Ausgestaltungen, wobei das Aufbringen der flüssigen Schicht unter Bedingungen erfolgt, unter denen zwischen den reaktionsträgen flüssigen Precursoren und der Oberfläche keine chemische Reaktion stattfindet.
Ausgestaltung 12. Beschichtungsverfahren mit den Merkmalen der vorangehenden Ausgestaltungen, wobei die flüssigen Precursoren nicht-funktionalisierte Silikonöle und/oder hochsiedende Kohlenwasserstoffe und/oder nicht-funktionalisierte fluorierte Silikonöle und/oder Fluorkohlenwasserstoffe und/oder Copolymere und/oder Co-Oligomere der genannten Stoffe sind.
Ausgestaltung 13. Vernetzte Schicht, herstellbar in einem Verfahren mit den Merkmalen der Ausgestaltungen 1 bis 12.
Ausgestaltung 14. Vernetzte Schicht mit den Merkmalen der Ausgestaltung 13, wobei das C-Signal im Tiefenprofil des Flugzeit-Sekundär-lonenmassenspektrometrie-Profils (TOF-SIMS) bei Normierung der Intensitäten auf das Siliciumsignal einen im Wesentlichen zur X-Achse (Sputterzyklen) parallelen Verlauf aufweist.
Ausgestaltung 15. Gegenstand mit mit einer vernetzten Schicht beschichteten Oberfläche, herstellbar mittels eines Beschichtungsverfahrens mit den Merkmalen der Ausgestaltungen 1 bis 12.
Ausgestaltung 16. Gegenstand mit einer im Submikrometerbereich strukturierten Oberfläche, umfassend auf dieser Oberfläche wenigstens teilweise eine vernetzte Schicht mit den Merkmalen der Ausgestaltungen 13 oder 14, wobei die vernetzte Schicht im Submikrometerbereich nicht konturnachbildend ist.
Ausgestaltung 17. Gegenstand mit den Merkmalen der Ausgestaltungen 15 oder 16, wobei für die vernetzte Schicht das C-Signal im Tiefenprofil des Flugzeit-Sekundärionenmassenspektrometrie-Profils bei Normierung der Intensitäten auf das Si-Signal einen im Wesentlichen zur X-Achse (Sputterzyklen) parallelen Verlauf aufweist.
Ausgestaltung 18. Gegenstand mit den Merkmalen der Ausgestaltungen 15 bis 17 oder vernetzte Schicht mit den Merkmalen der Ausgestaltungen 13 oder 14, wobei die vernetzte Schicht feinteilige Feststoffe umfasst, dadurch gekennzeichnet, dass die Feststoffe eine Teilchengröße von < 100 µm, bevorzugt < 10µm, aufweisen und im Wesentlichen chemisch ungebunden in der Matrix der vernetzten Schicht vorliegen.
Ausgestaltung 19. Gegenstand oder vernetzte Schicht jeweils mit den Merkmalen der Ausgestaltung 18, wobei die Feststoffe eine Teilchengröße im Bereich von 100 µm, bevorzugt < 20 nm aufweisen.
Ausgestaltung 20. Gegenstand oder vernetzte Schicht jeweils mit den Merkmalen der Ausgestaltung 19, wobei die Feststoffe eine Teilchengröße im Bereich von 5 ― 10 nm aufweisen.
Ausgestaltung 21. Gegenstand oder vernetzte Schicht jeweils mit den Merkmalen der Ausgestaltungen 18 bis 20, wobei die vernetzte Schicht 0,1 bis 30 Vol.-% feinteilige Feststoffe einer Teilchengröße < 200 nm umfasst.
Ausgestaltung 22. Gegenstand oder vernetzte Schicht jeweils mit den Merkmalen der Ausgestaltung 21, wobei die vernetzte Schicht 1 bis 10 Vol.-% feinteilige Feststoffe umfasst.
Ausgestaltung 23. Gegenstand oder vernetzte Schicht jeweils mit den Merkmalen der Ausgestaltungen 18 bis 22, wobei die feinteiligen Feststoffe Metallpartikel sind.
Ausgestaltung 24. Gegenstand oder vernetzte Schicht jeweils mit den Merkmalen der Ausgestaltungen 18 bis 23, wobei die feinteiligen Feststoffe magnetisierbar sind.
Ausgestaltung 25. Gegenstand oder vernetzte Schicht jeweils mit den Merkmalen der Ausgestaltungen 18 bis 23, wobei die feinteiligen Feststoffe aus Silber bestehen.
Ausgestaltung 26. Gegenstand oder vernetzte Schicht jeweils mit den Merkmalen der Ausgestaltungen 18 bis 25, wobei die Matrix aus Silikonverbindungen oder teil- bzw. vollfluorierten Flüssigkeiten hergestellt wurde.
Ausgestaltung 27. Gegenstand mit den Merkmalen der Ausgestaltungen 18 bis 26, wobei der Gegenstand ein Kunststoff-, Metall-, Glas- oder Keramikgegenstand ist.
Ausgestaltung 28. Gegenstand mit den Merkmalen der Ausgestaltungen 15 bis 17 oder vernetzte Schicht mit den Merkmalen der Ausgestaltungen 13 oder 14, wobei die vernetzte Schicht eine Schicht ist, bestehend aus Kohlenstoff, Silicium, Sauerstoff und Wasserstoff sowie gegebenenfalls üblichen Verunreinigungen, wobei im ESCA-Spektrum des vernetzten Produktes, bei Kalibrierung auf den aliphatischen Anteil des C 1s Peaks bei 285,00 eV, im Vergleich mit einem trimethylsiloxy-terminierten Polydimethylsiloxan (PDMS) mit einer kinematischen Viskosität von 350 mm²/s bei 25 °C und einer Dichte von 0,97 g/mL bei 25 °C,
der Si 2p Peak einen Bindungsenergiewert besitzt, der um maximal 0,50 eV zu höheren oder niedrigeren Bindungsenergien verschoben ist, und
der O 1s Peak einen Bindungsenergiewert besitzt, der um maximal 0,50 eV zu höheren oder niedrigeren Bindungsenergien verschoben ist.
Ausgestaltung 29. Gegenstand oder vernetzte Schicht jeweils mit den Merkmalen der Ausgestaltung 28, wobei
der Si 2p Peak einen Bindungsenergiewert besitzt, der um maximal 0,40 eV zu höheren oder niedrigeren Bindungsenergien verschoben ist, und
der O 1s Peak einen Bindungsenergiewert besitzt, der um maximal 0,40 eV zu höheren oder niedrigeren Bindungsenergien verschoben ist.
Ausgestaltung 30. Gegenstand oder vernetzte Schicht jeweils mit den Merkmalen der Ausgestaltungen 28 oder 29, wobei für die Stoffmengenverhältnisse in der vernetzen Schicht gilt: 0,75 < n(O) : n(Si) < 1,25 1,50 < n(C) : n(Si) < 2,50 1,50 < n(C) : n(O) < 2,50 2,25 < n(H) : n(C) < 3,00. Ausgestaltung 31. Gegenstand oder vernetzte Schicht jeweils mit den Merkmalen der Ausgestaltung 30, wobei für die Stoffmengenverhältnisse in der vernetzen Schicht gilt: 1,00 < n(O) : n(Si) < 1,25 2,00 < n(C) : n(Si) < 2,50 1,60 < n(C) : n(O) < 2,30 2,40 < n(H) : n(C) < 3,00. Ausgestaltung 32. Gegenstand oder vernetzte Schicht jeweils mit den Merkmalen der Ausgestaltung 31, wobei für die Stoffmengenverhältnisse in der vernetzen Schicht gilt: 1,05 < n(O) : n(Si) < 1,23 2,10 < n(C) : n(Si) < 2,23 1,70 < n(C) : n(O) < 2,00 2,60 < n(H) : n(C) < 3,00. Ausgestaltung 33. Gegenstand oder vernetzte Schicht jeweils mit den Merkmalen der Ausgestaltungen 28 bis 32, wobei die vernetzte Schicht bezogen auf 100 Atom-% für die Summe der Elemente Silicium, Sauerstoff und Kohlenstoff, enthält: Silicium 18 bis 28 Atom-% Sauerstoff 20 bis 30 Atom-% Kohlenstoff 35 bis 55 Atom-%. Ausgestaltung 34. Gegenstand oder vernetzte Schicht jeweils mit den Merkmalen der Ausgestaltung 33, wobei die vernetzte Schicht bezogen auf 100 Atom-% für die Summe der Elemente Silicium, Sauerstoff und Kohlenstoff, enthält: Silicium 20 bis 26 Atom-% Sauerstoff 24 bis 29 Atom-% Kohlenstoff 47 bis 51 Atom-%, Ausgestaltung 35. Gegenstand oder vernetzte Schicht jeweils mit den Merkmalen der Ausgestaltung 33, wobei die vernetzte Schicht bezogen auf 100 Atom-% für die Summe der Elemente Silicium, Sauerstoff und Kohlenstoff, enthält: Silicium 20 bis 28 Atom-% Sauerstoff 22 bis 30 Atom-% Kohlenstoff 42 bis 55 Atom-%, wobei für die Stoffmengenverhältnisse in der vernetzen Schicht gilt: 0,75 < n(O) : n(Si) < 1,25 1,50 < n(C) : n(Si) < 2,50 1,50 < n(C) : n(O) < 2,50 2,25 < n(H) : n(C) < 3,00 und
wobei im ESCA-Spektrum der vernetzten Schicht, im Vergleich mit einem trimethylsiloxy-terminierten Polydimethylsiloxan (PDMS) mit einer kinematischen Viskosität von 350 mm²/s bei 25 °C und einer Dichte von 0,97 g/mL bei 25 °C,
der Si 2p Peak einen Bindungsenergiewert besitzt, der um maximal 0,44 eV zu höheren oder niedrigeren Bindungsenergien verschoben ist, und
der O 1s Peak einen Bindungsenergiewert besitzt, der um maximal 0,50 eV zu höheren oder niedrigeren Bindungsenergien verschoben ist.
Ausgestaltung 36. Gegenstand oder vernetzte Schicht jeweils mit den Merkmalen der Ausgestaltungen 28 bis 35, wobei die vernetzte Schicht bezogen auf 100 Atom-% für die Summe der Elemente Silicium, Sauerstoff und Kohlenstoff, enthält: Silicium 20 bis 26 Atom-% Sauerstoff 24 bis 29 Atom-% Kohlenstoff 47 bis 51 Atom-%, wobei für die Stoffmengenverhältnisse in der vernetzten Schicht gilt: 1,00 < n(O) : n(Si) < 1,25 2,00 < n(C) : n(Si) < 2,50 1,60 < n(C) : n(O) < 2,30 2,40 < n(H) : n(C) < 3,00 und
und wobei im ESCA-Spektrum der vernetzten Schicht, im Vergleich mit einem trimethylsiloxy-terminierten Polydimethylsiloxan (PDMS) mit einer kinematischen Viskosität von 350 mm²/s bei 25 °C und einer Dichte von 0,97 g/mL bei 25 °C,
der Si 2p Peak einen Bindungsenergiewert besitzt, der um maximal 0,50 eV zu höheren oder niedrigeren Bindungsenergien verschoben ist, und
der O 1s Peak einen Bindungsenergiewert besitzt, der um maximal 0,50 eV zu höheren oder niedrigeren Bindungsenergien verschoben ist.
Ausgestaltung 37. Gegenstand mit den Merkmalen der Ausgestaltungen 15 bis 17 oder vernetzte Schicht mit den Merkmalen der Ausgestaltungen 13 oder 14, wobei die vernetzte Schicht Biozid-Nanopartikel umfasst und die Schicht ohne die Nanopartikel ein Matrixmaterial für die Nanopartikel darstellt mit einer Porosität, die so eingestellt ist, dass der biozide Wirkstoff aus dem Matrixmaterial abgegeben werden kann.
Ausgestaltung 38. Gegenstand oder Schicht jeweils mit den Merkmalen der Ausgestaltung 37, wobei das Matrixmaterial als Transportkontrollschicht wirkt und in seiner Dicke und Porosität so eingestellt ist, dass der biozide Wirkstoff aus der vernetzten Schicht in einer antimikrobiellen und nicht zytotoxischen Weise abgegeben wird.
Ausgestaltung 39. Gegenstand oder Schicht jeweils mit den Merkmalen der Ausgestaltungen 37 oder 38, wobei die Transportkontrollschicht eine Gasdurchlässigkeit für Sauerstoff (O₂) aufweist die im Bereich von 100 bis 1000 (cm³ bar) / (Tag m²), vorzugsweise im Bereich von 500 bis 700 (cm³ bar) / (Tag m²) liegt.
Ausgestaltung 40. Gegenstand oder vernetzte Schicht jeweils mit den Merkmalen der Ausgestaltungen 37 bis 39, wobei der biozide Wirkstoff ein anorganisches Biozid ist.
Ausgestaltung 41. Gegenstand oder vernetzte Schicht jeweils mit den Merkmalen der Ausgestaltung 40, wobei der biozide Wirkstoff ausgewählt ist aus der Gruppe bestehend aus Silber, Kupfer und Zink, deren Ionen und deren Metallkomplexe, oder einer Mischung oder Legierung umfassend zwei oder mehr dieser Elemente.
Ausgestaltung 42. Gegenstand oder vernetzte Schicht jeweils mit den Merkmalen der Ausgestaltungen 40 oder 41, wobei der biozide Wirkstoff eine mittlere Korngröße von 5 bis 1000 nm, vorzugsweise von 5 bis 100 nm hat.
Ausgestaltung 43. Gegenstand oder vernetzte Schicht jeweils mit den Merkmalen der Ausgestaltungen 37 bis 42, wobei die vernetzte Schicht umfasst: Gold, Platin, Palladium, Iridium, Zinn, Antimon, deren Ionen, deren Metallkomplexe, oder eine Legierung des bioziden Wirkstoffs mit einem oder mehreren dieser Elemente.
Ausgestaltung 44. Gegenstand oder vernetzte jeweils Schicht mit den Merkmalen der Ausgestaltungen 37 bis 43, wobei die vernetzte Schicht einen Silicium-Anteil von 20 bis 60 Atom-%, einen Kohlenstoffanteil von 10 bis 30 Atom-% und einen Sauerstoffanteil von 30 bis 50 Atom-% besitzt, bezogen auf die auf die Menge der in der Schicht enthaltenen Atome ohne H und F.
Ausgestaltung 45. Gegenstand mit den Merkmalen der Ausgestaltungen 15 bis 44 oder vernetzte Schicht mit den Merkmalen der Ausgestaltungen 13, 14, 18 bis 26 oder 28 bis 44, wobei die vernetze Schicht eine mittlere Dicke von 5 nm bis 5 µm hat.
Ausgestaltung 46. Gegenstand mit den Merkmalen der Ausgestaltungen 37 bis 45, wobei der Gegenstand ein Medizinprodukt, insbesondere ein Katheter, eine Wundauflage, eine Kontaktlinse, ein Implantat, ein medizinischer Nagel und/oder eine Schraube, ein Knochenfixationsnagel, ein medizinisches Instrument oder ein Hygieneprodukt, insbesondere ein Binde oder Windel, oder eine Verpackung oder ein Teil einer Verpackung eines Medizin-, Pharma- oder Hygieneproduktes oder ein Bauteil zum Herstellen oder Verarbeiten von Medizin-, Pharma- oder Lebensmitteln oder auf ein sonstigen Produkt ist, bei dem es eine besondere Hygiene erforderlich ist.
Ausgestaltung 47. Gegenstand mit den Merkmalen der Ausgestaltungen 37 bis 46, wobei der Gegenstand eine Verpackungsfolie, insbesondere eine Siegelfolie, eine Schlauchbeutelverpackung, eine Kartonverpackung, eine Becherverpackung mit Foliendeckel, ein Füllventil, ein Schlauchverbinder oder ein Gärgutträger ist.
Ausgestaltung 48. Gegenstand mit den Merkmalen der Ausgestaltungen 37 bis 45, wobei der Gegenstand ein Verschluss oder eine Maschine (Maschinenkomponente) zur Herstellung, Verarbeitung und Abfüllung von Lebens-, Nahrungsmitteln bwz. Medizinprodukten ist.
Ausgestaltung 49. Gegenstand mit den Merkmalen der Ausgestaltungen 15 bis 17, wobei der Gegenstand eine korrosionsempfindliche oder anlaufempfindliche Fläche umfasst, auf der die vernetzte Schicht angeordnet ist.
Ausgestaltung 50. Gegenstand mit den Merkmalen der Ausgestaltung 49 oder vernetzte Schicht mit den Merkmalen der Ausgestaltungen 13 oder 14, wobei die vernetzte Schicht einen Korrosionsinhibitor umfasst.
Ausgestaltung 51. Gegenstand oder vernetzte Schicht jeweils mit den Merkmalen der Ausgestaltung 50, wobei der Korrosionsinhibitor ein Polyanilin ist.
Ausgestaltung 52. Gegenstand mit den Merkmalen der Ausgestaltungen 50 oder 51, wobei die beschichtete Oberfläche aus Aluminium, einer Aluminiumlegierung, einem Eloxal, Magnesium, einer Magnesiumlegierung, Stahl, legiertem Stahl, Kupfer, einer Kupferlegierung, Silber, einer Silberlegierung, Gold, einer Goldlegierung, Eisen, einer Eisenlegierung, Titan, einer Titanlegierung, Messing, Bronze, einem Halbleiter, Kobalt, einer Kobaltlegierung, Nickel, einer Nickellegierung, Zinn, einer Zinnlegierung, Zink, einer Zinklegierung, einem Lot, Blei oder einer Bleilegierung besteht.
Ausgestaltung 53. Gegenstand mit den Merkmalen der Ausgestaltungen 49 bis 52 oder vernetzte Schicht mit den Merkmalen der Ausgestaltungen 50 oder 51, wobei auf einer lateralen Strecke von 100 µm auf der Oberfläche der vernetzten Schicht bezogen auf die mittlere Schichtdicke minimale Schichtdicken von 20% und maximale Schichtdicken von 200% bestehen.
Ausgestaltung 54. Gegenstand mit den Merkmalen der Ausgestaltungen 15 bis 17 oder vernetzte Schicht mit den Merkmalen der Ausgestaltungen 13 oder 14, wobei die vernetzte Schicht eine, Silicium, Sauerstoff, Kohlenstoff und Wasserstoff und/oder Fluor umfassende Schicht ist, für die bei Bestimmung mittels ESCA gilt:

• Das Stoffmengenverhältnis O : Si ist > 1,25 und < 2,6
  und das Stoffmengenverhältnis C : Si ist > 0,6 und < 2,2.

Ausgestaltung 55. Gegenstand oder vernetzte Schicht jeweils mit den Merkmalen der Ausgestaltung 54, wobei die vernetze Schicht bezogen auf ihre Gesamtatomzahl ohne Wasserstoff
minimal 20 und maximal 30 Atomprozente Si,
minimal 25 und maximal 50 Atomprozente O und
minimal 25 und maximal 50 Atomprozente C
enthält.
Ausgestaltung 56. Gegenstand oder vernetzte Schicht jeweils mit den Merkmalen der Ausgestaltungen 54 oder 55, wobei vernetzte Schicht Wasserstoff und/oder Fluor umfasst, wobei gilt:
1,8 : 1 n(H und/oder F) : n (C) < 3,6 : 1
vorzugsweise
2,2 : 1 n(H und/oder F) : n (C) < 3,3 : 1.
Ausgestaltung 57. Gegenstand oder vernetzte Schicht jeweils mit den Merkmalen der Ausgestaltungen 54 bis 56, wobei die vernetzte Schicht einen Wasserrandwinkel von über 90°, vorzugsweise über 95°, weiter vorzugsweise über 100° besitzt.
Ausgestaltung 58. Gegenstand mit den Merkmalen der Ausgestaltungen 54 bis 57, wobei der Gegenstand ein Gegenstand ist, ausgewählt aus der Gruppe bestehend aus: Felge, Radkappe, Aluminiumprofil, eloxiertes Aluminiumbauteil insbesondere für Fenster, Duschen, Automobile; Fenster, Verkleidungen, Windradflügel, Metallverblendung insbesondere für Häuser, insbesondere für Küchen bzw. Küchengeräte; Display, insbesondere für Küchen, insbesondere für Handys; Verglasungen, Automobilkarosserieteile, Motorradbauteile, Getränkebehälter, Farbbehälter, Tintenbehälter, Tuschepatrone, Flasche, Küchengerät, Bratpfanne, Hinweisschild, Warnzeichen, wieder verwendbare Gefäße für Lebensmittel, wie z.B. Flaschen oder Fässer; Filter, Holzoberflächen, lackierte bzw. lasierte Holzoberflächen, Textilen, Backgutträgern, Bauteilen für Lackierkabinen, Gitterroste, Lackiergehänge, Formen zur Herstellung von Lebensmitteln, wie z.B. Schokoladen- oder Gummibärchenformen, Formen zur Herstellung von Gummi, insbesondere Reifen und Kondome, Schnuller, Sauger.
Ausgestaltung 59. Gegenstand mit den Merkmalen der Ausgestaltungen 15 bis 17, wobei der Gegenstand ein Formteil ist.
Ausgestaltung 60. Gegenstand mit einer die Schmutzwahrnehmung unterdrückenden glänzenden Oberfläche, umfassend Abschnitte einer vernetzten Schicht mit den Merkmalen der Ausgestaltungen 13 oder 14 mit einem Interferenz-Farbenmuster, wobei die Abschnitte laterale Ausdehnungen von 1 bis 100 µm aufweisen und vorzugsweise eine Dicke von nicht mehr als 300 nm aufweisen.
Ausgestaltung 61. Gegenstand mit den Merkmalen der Ausgestaltungen 15 bis 58, wobei der Gegenstand ausgewählt ist aus der Gruppe bestehend aus:

• Gegenstand mit einer Migrationssperre gegenüber Molekülen mit einer Molmasse von 100 g/mol oder mehr, vorzugsweise 50 g/mol oder mehr, umfassend die vernetzte Schicht als Migrationssperre oder Teil der Migrationssperre,
• Gegenstand mit einer Dichtung, umfassend die vernetzte Schicht als Dichtung oder Dichtungsbestandteil,
• optisches Element mit einer Beschichtung, umfassend die vernetzte Schicht als Beschichtungsmaterial,
• Gegenstand, umfassend ein korrosionsempfindliches Substrat und eine darauf angeordnete Korrosionsschutzbeschichtung, umfassend die vernetzte Schicht als Korrosionsschutzbeschichtung oder Teil der Korrosionsschutzbeschichtung,
• Gegenstand, umfassend ein Substrat mit Easy-to-Clean-Beschichtung, umfassend die vernetzte Schicht als Easy-to-Clean-Beschichtung oder Teil der Easy-to-Clean-Beschichtung, insbesondere für die Anwendung im Bereich der Klebstoff- und Lackverarbeitung, Gummi- und Kunststoffverarbeitung, Lebensmittelverarbeitung,
• Gegenstand, umfassend ein Substrat (insbesondere auch ein (technisches)Textil) mit (hydrolysebeständiger) Easy-to-Clean-Beschichtung, umfassend die vernetzte Schicht als (hydrolysebeständige) Easy-to-Clean-Beschichtung oder Teil der (hydrolysebeständigen) Easy-to-Clean-Beschichtung,
• Gegenstand, umfassend ein Substrat (insbesondere auch ein Membran) mit (hydrolysebeständiger) Easy-to-Clean-Beschichtung bzw. Hydrophobausrüstung, umfassend die vernetzte Schicht als (hydrolysebeständige) Easy-to-Clean - Beschichtung bzw. Hydrophobausrüstung oder Teil der (hydrolysebeständigen) Easy-to-Clean-Beschichtung bzw. Hydrophobausrüstung,
• Gegenstand, umfassend ein Substrat mit einer antibakteriellen Beschichtung, umfassend die vernetzte Schicht als Teil einer antibakteriellen Beschichtung, insbesondere einer nicht zytotoxischen antibakteriellen Beschichtung,
• Gegenstand, umfassend ein Substrat zur Herstellung einer Verpackung mit einer antibakteriellen Beschichtung, umfassend die vernetzte Schicht als Teil einer antibakteriellen Beschichtung, insbesondere einer nicht zytotoxischen antibakteriellen Beschichtung,
• Gegenstand, umfassend ein Elastomerprodukt und eine die Gleitfähigkeit erhöhende Beschichtung auf dem Elastomerprodukt, umfassend die vernetzte Schicht als Beschichtung oder Bestandteil der Beschichtung,
• Gegenstand, umfassend ein Substrat, insbesondere ein Wärmetauscher oder Teile eines Wärmetauschers, und eine darauf angeordnete Beschichtung, umfassend die vernetzte Schicht mit stark hydrophoben, hydrolysestabilen, korrosionsschützende Oberflächeneigenschaften, welche die Wärmeleitfähigkeit nur kaum messbar verändert.
• Gegenstand, umfassend eine vorzugsweise plasmapolymere Beschichtung mit einem Defekt und eine Reparaturfolie zur Reparatur des Defektes, umfassend die vernetzte Schicht als Reparaturfolie oder Bestandteil der Reparaturfolie,
• Gegenstand, umfassend mindestens zwei härtere Schichten oder Substrate, vorzugsweise mit Barriereeigenschaften, und mindestens eine weiche Spacerschicht zwischen den härteren Schichten oder Substraten, die vernetzte Schicht als Spacerschicht oder Bestandteil der Spacerschicht,
• Gegenstand, umfassend eine Barrierebeschichtung oder ein Substrat zur Verringerung der Migration von Gasen und Dämpfen, insbesondere Wasserdampf, Kohlendioxid oder Sauerstoff, mit einer hydrophoben Deckschicht, umfassend die vernetzte Schicht als Deckschicht oder Bestandteil der Deckschicht.
• Gegenstand, umfassend ein vorzugsweise elektrisches Bauelement und eine elektrisch isolierende Folie oder -beschichtung, umfassend die vernetzte Schicht als isolierende Folie oder isolierende Beschichtung oder Teil einer solchen Folie oder Beschichtung.
• Gegenstand, umfassend einen vorzugsweise implantierbaren medizintechnischen Gegenstand, umfassend die vernetzte Schicht,
• Vorzugsweise implantierbarer medizintechnischer Silikon-Gegenstand, umfassend als Beschichtung die vernetzte Schicht.
• Gegenstand, umfassend die vernetzte Schicht als Trennschicht oder als Teil einer Trennschicht.

Ausgestaltung 62. Verwendung von Strahlung mit einer Wellenlänge von ≤ 250 nm zum Herstellen einer Schicht mit den Merkmalen der Ausgestaltungen 13, 14, 18 bis 26, 28 bis 45, 50, 51, 53 bis 57 oder eines Gegenstandes mit den Merkmalen der Ausgestaltungen 15 bis 61.
Ausgestaltung 63. Verwendung mit den Merkmalen der Ausgestaltung 62, wobei die Strahlungsquelle eine Excimerlampe ist.
Ausgestaltung 64. Verwendung eines reaktionsträgen, flüssigen Precursors zum Herstellen einer Schicht mit den Merkmalen der Ausgestaltungen 13, 14, 18 bis 26, 28 bis 45, 50, 51, 53 bis 57 oder eines Gegenstandes mit den Merkmalen der Ausgestaltungen 15 bis 61.
Ausgestaltung 65. Verwendung einer Schicht mit den Merkmalen der Ausgestaltungen 13, 14, 18 bis 26, 28 bis 45, 50, 51, 53 bis 57, als

• Migrationssperre gegenüber Molekülen mit einer Molmasse von 100 g/mol oder mehr, vorzugsweise 50 g/mol oder mehr,
• Deckschicht auf einer Barrierebeschichtung oder einem Substrat zur Verringerung der Migration von Gasen und Dämpfen, insbesondere Wasserdampf, Kohlendioxid oder Sauerstoff,
• Dichtungsmaterial, insbesondere für Dichtungen mit einer Dicke von maximal 1000 nm,
• flexible Beschichtung eines flexiblen Verpackungsmaterials,
• Beschichtung zur Vergütung optischer Elemente,
• hydrolysebeständige Beschichtung,
• hydrophobe Beschichtung,
• Korrosionsschutzbeschichtung,
• Easy-to-Clean-Beschichtung,
• die Gleitfähigkeit erhöhende Beschichtung auf einem Elastomerprodukt
• flexible Kratzschutzschichten auf hochreflektierenden Metalloberflächen und/oder Kunststoffen, bevorzugt auf transparenten Kunststoffen
• Säureschutz und/oder Baseschutz für Kunststoffbauteile, Kunststofffolien, Keramik, Verbundwerkstoffe und/oder Textilien
• Schutz-, UV-transparente und/oder hydrolysestabile Folie insbesondere für optische Elemente von lithographischen Anlagen, weiterhin bevorzugt für optische Elemente von immersions-lithographischen Anlagen,
• Reparaturfolie, insbesondere für Easy-to-Clean- oder Trennschichtanwendungen,
• Folie oder Beschichtung mit dehäsiven und adhäsiven Oberflächeneigenschaften,
• Folie mit Loch- und/oder Streifenmuster, insbesondere zur Beschichtung hydrophiler Substrate zur Herstellung von lokalen Hydrophil- bzw. Hydrophobbereichen.
• weiche Spacerschicht zwischen härteren, voneinander zu separierenden Schichten oder Substraten, insbesondere Barriereschichten,
• stark hydrophobe Deckschicht, insbesondere zur Verhinderung der Adsorption von polaren Molekülen oder zur Verbesserung der Barriereeigenschaften von Barrierebeschichtungen, bzw. Ultra-Barrierebeschichtungen gegenüber Gasen und Dämpfen wie Wasserdampf, Kohlendioxid oder Sauerstoff,
• bevorzugt UV-transparente Trennschicht insbesondere stark hydrophobe Schicht auf Oberflächen, insbesondere dünnen, chemisch angebundenen Beschichtungen
• Isolatorfolie oder -beschichtung insbesondere in elektrischen Bauelementen.

Ausgestaltung 66. Verwendung eines Verfahrens mit den Merkmalen der Ausgestaltungen 1 bis 12 oder einer vernetzten Schicht mit den Merkmalen der Ausgestaltungen 13 oder 14 zur Glättung und/oder Versiegelung einer zu beschichtenden Oberfläche.
Ausgestaltung 67. Verfahren zum Erzeugen einer Oberflächentopographie auf einer zu beschichtenden Oberfläche mittels Durchführens eines Verfahrens mit den Merkmalen der Ausgestaltungen 1 bis 10, wobei das Verhältnis der Flüssigkeitsoberflächenspannung des flüssigen Precursors zur Oberflächenenergie der zu beschichtenden Oberfläche so gewählt wird, dass eine durch inselartige Erscheinung geprägte teilgeschlossene Schicht im Schritt c) erzeugt wird, wobei die Schichtdicke im Bereich der inselartigen Erscheinungen bevorzugt maximal 10 µm beträgt.
Ausgestaltung 68. Verfahren zum Erzeugen einer Oberflächentopographie auf einer zu beschichtenden Oberfläche mittels Durchführens eines Verfahrens mit den Merkmalen der Ausgestaltungen 1 bis 10, wobei im Schritt b) ein Gemisch bereitgestellt wird, umfassend Partikel mit einem Partikeldurchmesser von 20% bis 1000% bezogen auf die mittlere Schichtdicke nach der Vernetzung.The following is a list of further embodiments:
Embodiment 1. Coating method comprising the steps of:

1. a) providing a mixture or a pure substance, comprising or consisting of inert, liquid precursors,
2. b) applying a liquid layer of the mixture or the pure substance to a surface to be coated,
3. c) crosslinking of the liquid precursors by means of radiation having a wavelength of ≦ 250 nm, so that a solid layer is formed from the mixture and the layer comprises ≥ 10 atom% C, based on the amount of atoms contained in the layer without H and F. .

and so that the C contained in the layer to a maximum of 50 atomic% of C, based on the amount of C atoms contained in the layer, is part of a methoxy group.
Embodiment 2. Coating method having the features of Embodiment 1, wherein the crosslinking is carried out so that a maximum of 50 atomic% of C, based on the amount of C atoms contained in the layer, is part of an alkoxy group.
Embodiment 3. Coating method with the features of embodiments 1 or 2, wherein the layer is crosslinked by means of laser radiation or UV radiation from an excimer lamp.
Embodiment 4. Coating method with the features of the preceding embodiments, wherein the crosslinking is effected by means of UV radiation of wavelength ≤ 200 nm.
Embodiment 5. Coating method with the features of the preceding embodiments, wherein the liquid precursors are applied in a layer thickness of 3 nm to 10 μm.
Embodiment 6. Coating method with the features of the preceding embodiments, wherein the mixture provided in step a) is ≥ 50% by weight, based on the total weight of the mixture, consists of inert, liquid precursors.
Embodiment 7. Coating method with the features of the preceding embodiments, wherein the precursors provided in step a) comprise ≥ 10 atom% C, based on the amount of the atoms contained in the mixture without H and F.
Embodiment 8. Coating process with the features of the preceding embodiments, wherein the C contained in the mixture provided in step a) is at most 50 atom%, based on the amount of C atoms contained in the mixture, of a methoxy group.
Embodiment 9. Coating process with the features of the preceding embodiments, wherein the C contained in the mixture provided in step a) is at most 50 atom%, based on the amount of C atoms contained in the mixture, of an alkoxy group.
Embodiment 10. Coating method with the features of the preceding embodiments, wherein the surface to be coated does not comprise silanol groups.
Embodiment 11. Coating method with the features of the preceding embodiments, wherein the application of the liquid layer takes place under conditions under which no chemical reaction takes place between the inert liquid precursors and the surface.
Embodiment 12. Coating process with the features of the preceding embodiments, wherein the liquid precursors are non-functionalized silicone oils and / or high-boiling hydrocarbons and / or non-functionalized fluorinated silicone oils and / or fluorohydrocarbons and / or copolymers and / or co-oligomers of said substances ,
Embodiment 13. Cross-linked layer producible in a method having the features of Embodiments 1 to 12.
Embodiment 14. Cross-linked layer having the features of Embodiment 13, wherein the C signal in the depth profile of the time-of-flight secondary ion mass spectrometry profile (TOF-SIMS) when normalizing the intensities on the silicon signal has a substantially parallel to the X-axis (sputter cycles) course.
Embodiment 15. Subject having a surface coated with a crosslinked layer, producible by means of a coating method with the features of embodiments 1 to 12.
Embodiment 16. An article having a surface structured in the submicrometer range, comprising on this surface at least partially a crosslinked layer having the features of embodiments 13 or 14, wherein the crosslinked layer in the submicron range is not contour-replicating.
Embodiment 17. Subject matter having the features of embodiments 15 or 16, wherein for the crosslinked layer, the C signal in the depth profile of the time-of-flight secondary ion mass spectrometry profile normalizes the intensities to the Si signal substantially parallel to the X axis (sputter cycles) History has.
Embodiment 18. Subject matter having the features of embodiments 15 to 17 or crosslinked layer having the features of embodiments 13 or 14, wherein the crosslinked layer comprises finely divided solids, characterized in that the solids have a particle size of <100 μm, preferably <10 μm and substantially chemically unbound in the matrix of the crosslinked layer.
Embodiment 19. The article or crosslinked layer, each having the features of Embodiment 18, wherein the solids have a particle size in the range of 100 μm, preferably <20 nm.
Embodiment 20. The article or crosslinked layer, each having the features of Embodiment 19, wherein the solids have a particle size in the range of 5-10 nm.
Embodiment 21. An article or crosslinked layer, each having the characteristics of Embodiments 18 to 20, wherein the crosslinked layer comprises 0.1 to 30% by volume of finely divided solids having a particle size <200 nm.
Embodiment 22. The article or crosslinked layer each having the features of Embodiment 21, wherein the crosslinked layer comprises 1 to 10% by volume of finely divided solids.
Embodiment 23. The article or crosslinked layer, each having the features of embodiments 18 to 22, wherein the finely divided solids are metal particles.
Embodiment 24. Subject or cross-linked layer, each having the features of embodiments 18 to 23, wherein the finely divided solids are magnetizable.
Embodiment 25. Subject or cross-linked layer, each having the features of embodiments 18 to 23, wherein the finely divided solids consist of silver.
Embodiment 26. The article or crosslinked layer, each having the features of Embodiments 18 to 25, wherein the matrix is made of silicone compounds or partially or fully fluorinated liquids.
Embodiment 27. An article having the features of embodiments 18 to 26, wherein the article is a plastic, metallic, glass or ceramic article.
Embodiment 28. An article having the features of embodiments 15 to 17 or a cross-linked layer having the features of embodiments 13 or 14, wherein the cross-linked layer is a layer consisting of carbon, silicon, oxygen and hydrogen and optionally customary impurities. Spectrum of the cross-linked product, when calibrated to the aliphatic portion of the C 1s peak at 285.00 eV, compared with a trimethylsiloxy-terminated polydimethylsiloxane (PDMS) with a kinematic viscosity of 350 mm ² / s at 25 ° C and a density of 0.97 g / mL at 25 ° C,
the Si 2p peak has a binding energy value shifted by a maximum of 0.50 eV to higher or lower binding energies, and
the O 1s peak has a binding energy value shifted by a maximum of 0.50 eV to higher or lower binding energies.
Embodiment 29. An article or crosslinked layer, each having the features of the embodiment 28, wherein
the Si 2p peak has a binding energy value shifted by a maximum of 0.40 eV to higher or lower binding energies, and
the O 1s peak has a binding energy value that is shifted by a maximum of 0.40 eV to higher or lower binding energies.
Embodiment 30. Subject or cross-linked layer in each case having the features of embodiments 28 or 29, wherein the following applies to the molar ratios in the cross-linked layer: 0.75 <n (O): n (Si) < 1.25 1.50 <n (C): n (Si) < 2.50 1.50 <n (C): n (O) < 2.50 2.25 <n (H): n (C) < 3.00. Embodiment 31. Subject or cross-linked layer in each case having the features of embodiment 30, wherein the following applies to the molar ratios in the cross-linked layer: 1.00 <n (O): n (Si) < 1.25 2.00 <n (C): n (Si) < 2.50 1.60 <n (C): n (O) < 2.30 2.40 <n (H): n (C) < 3.00. Embodiment 32. The article or crosslinked layer in each case having the features of embodiment 31, wherein the following applies to the molar ratios in the crosslinked layer: 1.05 <n (O): n (Si) < 1.23 2.10 <n (C): n (Si) < 2.23 1.70 <n (C): n (O) < 2.00 2.60 <n (H): n (C) < 3.00. Embodiment 33. The article or crosslinked layer in each case having the features of embodiments 28 to 32, wherein the crosslinked layer contains, based on 100 atomic%, the sum of the elements silicon, oxygen and carbon: silicon 18 to 28 atomic% oxygen 20 to 30 atomic% carbon 35 to 55 atomic%. Embodiment 34. The article or crosslinked layer each having the features of Embodiment 33, wherein the crosslinked layer contains, based on 100 at% for the sum of the elements silicon, oxygen and carbon: silicon 20 to 26 atomic% oxygen 24 to 29 atomic% carbon 47 to 51 atomic%, Embodiment 35. The article or crosslinked layer, each having the features of Embodiment 33, wherein the crosslinked layer contains, based on 100 at% for the sum of the elements silicon, oxygen and carbon: silicon 20 to 28 atomic% oxygen 22 to 30 atomic% carbon 42 to 55 atomic%, the following applies to the molar ratios in the crosslinked layer: 0.75 <n (O): n (Si) < 1.25 1.50 <n (C): n (Si) < 2.50 1.50 <n (C): n (O) < 2.50 2.25 <n (H): n (C) < 3.00 and
wherein in the ESCA spectrum of the cross-linked layer, in comparison with a trimethylsiloxy-terminated polydimethylsiloxane (PDMS) having a kinematic viscosity of 350 mm ² / s at 25 ° C and a density of 0.97 g / mL at 25 ° C,
the Si 2p peak has a binding energy value shifted by a maximum of 0.44 eV to higher or lower binding energies, and
the O 1s peak has a binding energy value shifted by a maximum of 0.50 eV to higher or lower binding energies.
Embodiment 36. The article or crosslinked layer each having the characteristics of Embodiments 28 to 35, wherein the crosslinked layer contains, based on 100 at% for the sum of the elements silicon, oxygen and carbon: silicon 20 to 26 atomic% oxygen 24 to 29 atomic% carbon 47 to 51 atomic%, the following applies to the molar ratios in the crosslinked layer: 1.00 <n (O): n (Si) < 1.25 2.00 <n (C): n (Si) < 2.50 1.60 <n (C): n (O) < 2.30 2.40 <n (H): n (C) < 3.00 and
and wherein in the ESCA spectrum of the cross-linked layer, in comparison with a trimethylsiloxy-terminated polydimethylsiloxane (PDMS) having a kinematic viscosity of 350 mm ² / s at 25 ° C and a density of 0.97 g / mL at 25 ° C,
the Si 2p peak has a binding energy value shifted by a maximum of 0.50 eV to higher or lower binding energies, and
the O 1s peak has a binding energy value shifted by a maximum of 0.50 eV to higher or lower binding energies.
Embodiment 37. An article having the features of embodiments 15 to 17 or a crosslinked layer having the features of embodiments 13 or 14, wherein the crosslinked layer comprises biocide nanoparticles and the layer without the nanoparticles Matrix material for the nanoparticles represents with a porosity that is adjusted so that the biocidal agent can be discharged from the matrix material.
Embodiment 38. The article or layer, each having the features of Embodiment 37, wherein the matrix material acts as a transport control layer and is adjusted in thickness and porosity such that the biocidal active is released from the crosslinked layer in an antimicrobial and non-cytotoxic manner.
Embodiment 39. The article or layer in each case having the features of embodiments 37 or 38, wherein the transport control layer has a gas permeability to oxygen (O ₂ ) in the range of 100 to 1000 (cm ³ bar) / (day m ² ), preferably in the range from 500 to 700 (cm ³ bar) / (day m ² ).
Embodiment 40. The article or crosslinked layer each having the features of Embodiments 37 to 39, wherein the biocidal agent is an inorganic biocide.
Embodiment 41. The article or crosslinked layer, each having the characteristics of Embodiment 40, wherein the biocidal agent is selected from the group consisting of silver, copper and zinc, their ions and their metal complexes, or a mixture or alloy comprising two or more of these elements.
Embodiment 42. The article or crosslinked layer in each case having the features of embodiments 40 or 41, wherein the biocidal active substance has an average particle size of 5 to 1000 nm, preferably of 5 to 100 nm.
Embodiment 43. The article or crosslinked layer, each having the features of Embodiments 37 to 42, wherein the crosslinked layer comprises: gold, platinum, palladium, iridium, tin, antimony, their ions, their metal complexes, or an alloy of the biocidic agent with one or more several of these elements.
Embodiment 44. Article or crosslinked layer each having the features of embodiments 37 to 43, wherein the crosslinked layer has a silicon content of 20 to 60 atom%, a carbon content of 10 to 30 atom% and an oxygen content of 30 to 50 atom -% has, based on the amount of atoms contained in the layer without H and F.
Embodiment 45. An article having the features of embodiments 15 to 44 or a crosslinked layer having the features of embodiments 13, 14, 18 to 26 or 28 to 44, wherein the crosslinked layer has an average thickness of 5 nm to 5 μm.
Embodiment 46. An article having the features of embodiments 37 to 45, wherein the article is a medical device, in particular a catheter, a wound dressing, a contact lens, an implant, a medical nail and / or a screw, a bone fixation nail, a medical instrument or a hygiene product , in particular a sanitary napkin or diaper, or a packaging or part of a packaging of a medical, pharmaceutical or hygiene product or a component for the manufacture or processing of medical, pharmaceutical or foodstuffs or any other product in which it is a special Hygiene is required.
Embodiment 47. An article having the features of embodiments 37 to 46, wherein the article is a packaging film, in particular a sealing film, a tubular bag packaging, a cardboard packaging, a cup packaging with foil lid, a filling valve, a hose connector or a proofing carrier.
Embodiment 48. The article having the features of embodiments 37 to 45, wherein the article is a closure or a machine (machine component) for the production, processing and filling of food, food bwz. Is medical devices.
Embodiment 49. The article having the features of Embodiments 15 to 17, wherein the article comprises a surface susceptible to corrosion or tarnish on which the crosslinked layer is disposed.
Embodiment 50. An article having the features of Embodiment 49 or a crosslinked layer having the features of Embodiments 13 or 14, wherein the crosslinked layer comprises a corrosion inhibitor.
Embodiment 51. The article or crosslinked layer, each having the features of Embodiment 50, wherein the corrosion inhibitor is a polyaniline.
Embodiment 52. An article having the features of Embodiments 50 or 51, wherein the coated surface is made of aluminum, an aluminum alloy, a Anodizing, magnesium, magnesium alloy, steel, alloy steel, copper, copper alloy, silver, silver alloy, gold, gold alloy, iron, iron alloy, titanium, titanium alloy, brass, bronze, semiconductor, cobalt, cobalt alloy, nickel , a nickel alloy, tin, a tin alloy, zinc, a zinc alloy, a solder, lead or a lead alloy.
Embodiment 53. Subject matter having the features of embodiments 49 to 52 or crosslinked layer having the features of embodiments 50 or 51, wherein on a lateral distance of 100 μm on the surface of the crosslinked layer, based on the average layer thickness, minimum layer thicknesses of 20% and maximum Layer thicknesses of 200% exist.
Embodiment 54. An article having the features of Embodiments 15 to 17 or a cross-linked layer having the features of Embodiments 13 or 14, wherein the cross-linked layer is a layer comprising silicon, oxygen, carbon and hydrogen and / or fluorine, for use in determining ESCA applies:

• The molar ratio O: Si is> 1.25 and <2.6
  and the molar ratio C: Si is> 0.6 and <2.2.

Embodiment 55. The article or crosslinked layer, each having the features of Embodiment 54, wherein the crosslinked layer is hydrogen-free, based on its total atomic number
a minimum of 20 and a maximum of 30 atomic percent Si,
a minimum of 25 and a maximum of 50 atomic percent O and
minimum 25 and maximum 50 atomic percent C
contains.
Embodiment 56. The article or crosslinked layer each having the features of Embodiments 54 or 55, wherein crosslinked layer comprises hydrogen and / or fluorine, wherein:
1.8: 1 n (H and / or F): n (C) <3.6: 1
preferably
2.2: 1 n (H and / or F): n (C) <3.3: 1.
Embodiment 57. The article or cross-linked layer, each having the features of Embodiments 54 to 56, wherein the cross-linked layer has an edge angle of water greater than 90 °, preferably greater than 95 °, more preferably greater than 100 °.
Embodiment 58. An article having the features of embodiments 54 to 57, wherein the article is an article selected from the group consisting of: rim, hubcap, aluminum profile, anodized aluminum component, especially for windows, showers, automobiles; Windows, cladding, wind turbine blades, metal facing, in particular for houses, in particular for kitchens or kitchen utensils; Display, in particular for kitchens, in particular for mobile phones; Glazings, automobile body parts, motorcycle components, beverage containers, paint containers, ink containers, ink cartridges, bottles, kitchen utensils, frying pans, information signs, warning signs, reusable containers for foodstuffs such as bottles or barrels; Filters, wood surfaces, lacquered or glazed wood surfaces, textiles, baking trays, components for paint booths, gratings, painting hangers, molds for the production of foodstuffs, such as chocolate or gummy bear molds, molds for the production of rubber, especially tires and condoms, pacifiers, teats.
Embodiment 59. An article having the features of embodiments 15 to 17, wherein the article is a molded article.
Embodiment 60. An article having a glossy surface suppressing soil perception, comprising portions of a crosslinked layer having the features of embodiments 13 or 14 having an interference color pattern, said portions having lateral dimensions of 1 to 100 μm and preferably a thickness of not more than 300 nm.
Embodiment 61. An article having the features of embodiments 15 to 58, wherein the article is selected from the group consisting of:

• Article having a migration barrier to molecules having a molecular weight of 100 g / mol or more, preferably 50 g / mol or more, comprising the crosslinked layer as a migration barrier or as part of the migration barrier,
• Article having a gasket comprising the crosslinked layer as a gasket or gasket component,
• optical element having a coating comprising the crosslinked layer as a coating material,
• An article comprising a corrosion-sensitive substrate and a corrosion protection coating disposed thereon, comprising the cross-linked layer as an anticorrosive coating or as part of the anticorrosive coating,
• An article comprising a substrate having an easy-to-clean coating comprising the crosslinked layer as an easy-to-clean coating or as part of the easy-to-clean coating, especially for use in the field of adhesive and paint processing, rubber and plastics processing, food processing,
• An article comprising a substrate (especially also a (technical) textile) with (hydrolysis-resistant) easy-to-clean coating, comprising the crosslinked layer as (hydrolysis-resistant) easy-to-clean coating or part of (hydrolysis-resistant) Easy-to -clean coating,
• Article comprising a substrate (in particular also a membrane) with (hydrolysis-resistant) easy-to-clean coating or hydrophobic finish, comprising the crosslinked layer as (hydrolysis-resistant) easy-to-clean coating or hydrophobic finish or part of (hydrolysis-resistant) Easy-to-clean coating or hydrophobic equipment,
• An article comprising a substrate having an antibacterial coating comprising the crosslinked layer as part of an antibacterial coating, especially a non-cytotoxic antibacterial coating,
• An article comprising a substrate for producing a package having an antibacterial coating comprising the crosslinked layer as part of an antibacterial coating, especially a non-cytotoxic antibacterial coating,
• An article comprising an elastomeric product and a lubricity enhancing coating on the elastomeric product comprising the crosslinked layer as a coating or constituent of the coating.
• An article comprising a substrate, in particular a heat exchanger or parts of a heat exchanger, and a coating arranged thereon, comprising the crosslinked layer having strongly hydrophobic, hydrolysis-stable, corrosion-protecting surface properties, which barely measurably changes the thermal conductivity.
• An article comprising a preferably plasma-polymeric coating with a defect and a repair film for repairing the defect comprising the crosslinked layer as a repair film or as part of the repair film.
• An article comprising at least two harder layers or substrates, preferably with barrier properties, and at least one soft spacer layer between the harder layers or substrates, the crosslinked layer as a spacer layer or as a component of the spacer layer,
• An article comprising a barrier coating or a substrate for reducing the migration of gases and vapors, in particular water vapor, carbon dioxide or oxygen, with a hydrophobic cover layer, comprising the crosslinked layer as cover layer or constituent of the cover layer.
• An article comprising a preferably electrical component and an electrically insulating film or coating comprising the crosslinked layer as an insulating film or insulating coating or part of such a film or coating.
• An article comprising a preferably implantable medical article comprising the crosslinked layer,
• Preferably, an implantable medical grade silicone article comprising as a coating the crosslinked layer.
• An article comprising the crosslinked layer as a release layer or as part of a release layer.

Embodiment 62. Use of radiation having a wavelength of ≦ 250 nm for producing a layer having the features of the embodiments 13, 14, 18 to 26, 28 to 45, 50, 51, 53 to 57 or an article having the features of the embodiments 15 to 61.
Embodiment 63. Use with the features of Embodiment 62, wherein the radiation source is an excimer lamp.
Embodiment 64. Use of an inert liquid precursor for producing a layer having the features of the embodiments 13, 14, 18 to 26, 28 to 45, 50, 51, 53 to 57 or an article having the features of the embodiments 15 to 61.
Embodiment 65. Use of a layer having the features of the embodiments 13, 14, 18 to 26, 28 to 45, 50, 51, 53 to 57, as

• Migration barrier to molecules having a molecular weight of 100 g / mol or more, preferably 50 g / mol or more,
• Covering layer on a barrier coating or a substrate for reducing the migration of gases and vapors, in particular water vapor, carbon dioxide or oxygen,
• Sealing material, in particular for gaskets having a maximum thickness of 1000 nm,
• flexible coating of a flexible packaging material,
• Coating for the compensation of optical elements,
• hydrolysis-resistant coating,
• hydrophobic coating,
• Anti-corrosion coating,
• Easy-to-clean coating,
• the lubricity enhancing coating on an elastomer product
• flexible scratch-resistant coatings on highly reflective metal surfaces and / or plastics, preferably on transparent plastics
• Acid protection and / or base protection for plastic components, plastic films, ceramics, composites and / or textiles
• Protective, UV-transparent and / or hydrolysis-stable film, in particular for optical elements of lithographic installations, furthermore preferred for optical elements of immersion lithographic installations,
• Repair film, in particular for easy-to-clean or release layer applications,
• Film or coating with adhesive and adhesive surface properties,
• Film with hole and / or stripe pattern, in particular for the coating of hydrophilic substrates for the production of local hydrophilic or hydrophobic areas.
• soft spacer layer between harder layers or substrates to be separated from one another, in particular barrier layers,
• strongly hydrophobic covering layer, in particular for preventing the adsorption of polar molecules or for improving the barrier properties of barrier coatings, or ultra-barrier coatings against gases and vapors such as water vapor, carbon dioxide or oxygen,
• preferably UV-transparent release layer in particular strongly hydrophobic layer on surfaces, in particular thin, chemically bonded coatings
• Insulator film or coating, especially in electrical components.

Embodiment 66. Use of a method having the features of embodiments 1 to 12 or a crosslinked layer having the features of embodiments 13 or 14 for smoothing and / or sealing a surface to be coated.
Embodiment 67. A method for producing a surface topography on a surface to be coated by carrying out a method having the features of Embodiments 1 to 10, wherein the ratio of the liquid surface tension of the liquid precursor to the surface energy of the surface to be coated is selected to be embossed by an island-like appearance partially closed layer in step c) is produced, wherein the layer thickness in the region of the island-like phenomena is preferably not more than 10 microns.
Embodiment 68. A method for producing a surface topography on a surface to be coated by carrying out a method having the features of Embodiments 1 to 10, wherein in step b) a mixture is provided comprising particles having a particle diameter of 20% to 1000% based on the average layer thickness after crosslinking.

Claims (22)

Coating method comprising the steps of: a) providing a mixture or a pure substance, comprising or consisting of inert, liquid precursors, b) applying a liquid layer of the mixture or the pure substance to a surface to be coated, c) crosslinking of the liquid precursors by means of radiation having a wavelength of ≦ 250 nm, preferably ≦ 200 nm, so that a solid layer is formed from the mixture and the layer comprises ≥ 10 atom% C, based on the amount of those contained in the layer Atoms without H and F, and so that the C contained in the layer to a maximum of 50 atomic% of C, based on the amount of C atoms contained in the layer, is part of a methoxy group. Coating method according to claim 1, wherein the layer is crosslinked by means of laser radiation or UV radiation from an excimer lamp. Coating method according to one of the preceding claims, wherein the liquid precursors are applied in a layer thickness of 3 nm to 10 microns. Coating method according to one of the preceding claims, wherein the mixture provided in step a) is ≥ 50% by weight, based on the total weight of the mixture, of inert, liquid precursors. Coating method according to one of the preceding claims, wherein the application of the liquid layer takes place under conditions under which no chemical reaction takes place between the inert liquid precursors and the surface. Coating process according to one of the preceding claims, wherein the liquid precursors comprise non-functionalized silicone oils and / or high-boiling ones Hydrocarbons and / or non-functionalized fluorinated silicone oils and / or fluorohydrocarbons and / or copolymers and / or co-oligomers of the substances mentioned are. Crosslinked layer producible in a process according to one of Claims 1 to 6. Crosslinked layer according to claim 7, wherein the C signal in the depth profile of the time-of-flight secondary ion mass spectrometry profile (TOF-SIMS) has a course essentially parallel to the X axis (sputter cycles) when the intensities on the silicon signal are normalized. An article having a crosslinked layer coated surface, wherein the coating is a layer according to any one of claims 7 or 8. The article of claim 9 or crosslinked layer of claim 7 or 8, wherein the crosslinked layer comprises finely divided solids, characterized in that the solids have a particle size of <100 microns, preferably <10 microns, and substantially chemically unbound in the matrix of the crosslinked layer available. The article of claim 9 or crosslinked layer of claim 7 or 8, wherein the crosslinked layer is a layer consisting of carbon, silicon, oxygen and hydrogen and optionally conventional impurities, wherein in the ESCA spectrum of the crosslinked product, when calibrated to the aliphatic portion of the C 1s peak at 285.00 eV, compared with a trimethylsiloxy-terminated polydimethylsiloxane (PDMS) having a kinematic viscosity of 350 mm ² / s at 25 ° C. and a density of 0.97 g / ml at 25 ° C.,
the Si 2p peak has a binding energy value shifted by a maximum of 0.50 eV to higher or lower binding energies, and
the O 1s peak has a binding energy value shifted by a maximum of 0.50 eV to higher or lower binding energies. The article of claim 9 or crosslinked layer of claim 7 or 8, wherein the crosslinked layer comprises biocide nanoparticles and the layer without the Nanoparticle is a matrix material for the nanoparticles with a porosity that is adjusted so that the biocidal agent can be released from the matrix material. The article of any of claims 9 to 12 or the crosslinked layer of any one of claims 7, 8 or 10 to 12, wherein the crosslinked layer has an average thickness of 5 nm to 5 μm. The article of claim 9, wherein the article comprises a corrosion-sensitive or tarnish-sensitive surface on which the crosslinked layer is disposed. An article according to claim 9 or a crosslinked layer according to claim 7 or 8, wherein the crosslinked layer is a layer comprising silicon, oxygen, carbon and hydrogen and / or fluorine, for which the following applies when determined by means of ESCA: The molar ratio O: Si is> 1.25 and <2.6 and the molar ratio C: Si is> 0.6 and <2.2. The article of claim 9, wherein the article is a molded article. An article having a glossy surface opacifying glossy surface comprising portions of a crosslinked layer according to any one of claims 7 or 8 having an interference color pattern, said portions having lateral dimensions of 1 to 100 μm and preferably having a thickness of not more than 300 nm. The article of any one of claims 9 to 17, wherein the article is selected from the group consisting of: An article having a migration barrier to molecules having a molecular weight of 100 g / mol or more, preferably 50 g / mol or more, comprising the crosslinked layer as a migration barrier or as part of the migration barrier, Article having a gasket comprising the crosslinked layer as a gasket or gasket component, optical element having a coating comprising the crosslinked layer as the coating material, An article comprising a corrosion-sensitive substrate and a corrosion protection coating disposed thereon, comprising the crosslinked layer as a corrosion protection coating or as part of the anti-corrosion coating, An article comprising a substrate having an easy-to-clean coating, comprising the cross-linked layer as an easy-to-clean coating or as part of the easy-to-clean coating, in particular for use in the field of adhesive and lacquer processing, Rubber and plastics processing, food processing, Article comprising a substrate (especially also a (technical) textile) with (hydrolysis-resistant) easy-to-clean coating, comprising the crosslinked layer as (hydrolysis-resistant) easy-to-clean coating or part of the (hydrolysis-resistant) to-clean coating, An article comprising a substrate (in particular also a membrane) with (hydrolysis-resistant) easy-to-clean coating or hydrophobic finish comprising the crosslinked layer as (hydrolysis-resistant) easy-to-clean coating or hydrophobic finish or part of (hydrolysis resistant ) Easy-to-clean coating or hydrophobic equipment, An article comprising a substrate having an antibacterial coating comprising the crosslinked layer as part of an antibacterial coating, in particular a non-cytotoxic antibacterial coating, Article comprising a substrate for producing a package having an antibacterial coating comprising the crosslinked layer as part of an antibacterial coating, in particular a non-cytotoxic antibacterial coating, An article comprising an elastomeric product and a lubricity enhancing coating on the elastomeric product comprising the crosslinked layer as a coating or constituent of the coating, Subject, comprising a substrate, in particular a heat exchanger or parts of a heat exchanger, and a coating arranged thereon, comprising the crosslinked layer having strongly hydrophobic, hydrolysis-stable, anti-corrosive surface properties, which barely measurably changes the thermal conductivity. Article comprising a preferably plasma-polymeric coating with a defect and a repair film for repairing the defect, comprising the crosslinked layer as a repair film or as part of the repair film, Article comprising at least two harder layers or substrates, preferably with barrier properties, and at least one soft spacer layer between the harder layers or substrates, the crosslinked layer as a spacer layer or as a component of the spacer layer, Article comprising a barrier coating or a substrate for reducing the migration of gases and vapors, in particular water vapor, carbon dioxide or oxygen, with a hydrophobic cover layer, comprising the crosslinked layer as a cover layer or constituent of the cover layer. - An article comprising a preferably electrical component and an electrically insulating film or coating comprising the crosslinked layer as an insulating film or insulating coating or part of such a film or coating. Article comprising a preferably implantable medical article comprising the crosslinked layer, Preferably, implantable medical grade silicone article comprising as a coating the crosslinked layer. An article comprising the crosslinked layer as a release layer or as part of a release layer. Use of radiation having a wavelength of ≤ 250 nm for producing a layer according to one of Claims 8 to 13, 15 or 17 or an article according to one of Claims 9 to 18. Use of an inert liquid precursor for producing a layer according to any one of claims 7, 8 or 10 to 12 or an article according to any one of claims 9 to 18. A method for producing a surface topography on a surface to be coated by carrying out a method according to any one of claims 1 to 6, wherein the ratio of the liquid surface tension of the liquid precursor to the surface energy of the surface to be coated is selected so that a partially closed layer embossed by island-like appearance in step c) is produced, wherein the layer thickness in the region of the island-like phenomena is preferably not more than 10 microns. A method for producing a surface topography on a surface to be coated by performing a method according to any one of claims 1 to 6, wherein in step b) a mixture is provided comprising particles with a particle diameter of 20% to 1000% based on the average layer thickness after Networking.

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