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EP2527048A2 - Procédé de fabrication de couches minces et couche mince obtenue par ce procédé - Google Patents

Procédé de fabrication de couches minces et couche mince obtenue par ce procédé Download PDF

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Publication number
EP2527048A2
EP2527048A2 EP12181651A EP12181651A EP2527048A2 EP 2527048 A2 EP2527048 A2 EP 2527048A2 EP 12181651 A EP12181651 A EP 12181651A EP 12181651 A EP12181651 A EP 12181651A EP 2527048 A2 EP2527048 A2 EP 2527048A2
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EP
European Patent Office
Prior art keywords
layer
coating
article
crosslinked
layers
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EP12181651A
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German (de)
English (en)
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EP2527048A3 (fr
EP2527048B1 (fr
Inventor
Klaus-Dieter Vissing
Matthias Ott
Christopher DÖLLE
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Fraunhofer Gesellschaft zur Foerderung der Angewandten Forschung eV
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Fraunhofer Gesellschaft zur Foerderung der Angewandten Forschung eV
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Publication of EP2527048A3 publication Critical patent/EP2527048A3/fr
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
    • B05D3/14—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by electrical means
    • B05D3/141—Plasma treatment
    • B05D3/145—After-treatment
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
    • B05D3/06—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by exposure to radiation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D5/00—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures
    • B05D5/08—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures to obtain an anti-friction or anti-adhesive surface
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D2202/00—Metallic substrate
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D2202/00—Metallic substrate
    • B05D2202/20—Metallic substrate based on light metals
    • B05D2202/25—Metallic substrate based on light metals based on Al
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D2203/00—Other substrates
    • B05D2203/30—Other inorganic substrates, e.g. ceramics, silicon
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D2601/00—Inorganic fillers
    • B05D2601/20—Inorganic fillers used for non-pigmentation effect
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
    • B05D3/06—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by exposure to radiation
    • B05D3/061—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by exposure to radiation using U.V.
    • B05D3/065—After-treatment
    • B05D3/066—After-treatment involving also the use of a gas
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31652—Of asbestos
    • Y10T428/31663—As siloxane, silicone or silane

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.
  • the emission spectrum comprises an additional certain wavelength range around the emission wavelength, the so-called spectral bandwidth.
  • 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.
  • 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 ⁇ m, e.g. the technique of dynamic light scattering, for particles larger than 2 ⁇ m laser diffraction (for example DIN ISO 8130-13) can be used.
  • 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 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.
  • excited gaseous precursors also called monomers
  • the prerequisite for a plasma polymerization is the presence of chain-forming atoms such as carbon or silicon in the working gas.
  • the molecules of the gaseous substance 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.
  • plasma polymerization in particular also includes plasma-assisted CVD (PE / CVD).
  • PE / CVD plasma-assisted CVD
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • gamma emitters 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.
  • 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.
  • the dissociation energy of the O 2 molecule is 5.1 eV
  • a CC single bond is about 3.57 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • the biological application is the sterilization of packaging material.
  • the process is usually limited to 2D surfaces.
  • 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.
  • 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.
  • 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.
  • Plasma-deposited organosilicon thin films as dry resists for deep ultraviolet lithography discloses the modification of plasma polymer (solid) layers by means of UV light.
  • the DE 199 61 632 A1 discloses a UV-curable varnish, whereby here too a classic polymerization reaction is present during the curing.
  • monomers having reactive groups acrylate monomers are used.
  • 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 object of the invention was to provide a coating process known from the prior art, which has advantages in many individual areas.
  • 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.
  • 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.
  • TOF-SIMS time-of-flight secondary ion mass spectrometry profile
  • 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.
  • 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.
  • 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.
  • 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.
  • a corresponding process control primarily the provided mixture or the pure substance should be mentioned, since with appropriate process management this (r) is not completely fragmented.
  • 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.
  • derivatization the alkoxy groups are substituted.
  • the derivative for example the chlorine
  • 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.
  • 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.
  • the crosslinking by means of UV radiation of a wavelength ⁇ 200 nm.
  • 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.
  • the liquid precursors are preferably applied in an average layer thickness of 3 nm to 10 ⁇ m. Further preferred average layer thicknesses are to be seen in the range of 5 nm to 5 ⁇ m, again preferably in the range of 10 nm to 1 ⁇ m 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.
  • 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.
  • 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.
  • 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.
  • the substrate to be coated on the surface has a roughness R a of> 500 nm, more preferably> 1 ⁇ m.
  • 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.
  • the mixture provided in step a) 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.
  • 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.
  • 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.
  • the surface to be coated does not comprise silanol groups. In other applications, however, this may be desirable.
  • 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.
  • a liquid is applied to the surface to be coated and crosslinked by high-energy radiation, in particular UV radiation.
  • high-energy radiation in particular UV radiation.
  • 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.
  • thin precursor layers ⁇ 10 ⁇ m
  • 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.
  • 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 Jardinr; Z. Metallischen 95 (2004) 311 ) or the analysis of laser acoustic surface waves.
  • layer hardnesses in the range of 0.4GPa to 4GPa, more preferably 1GPa to 4GPa, determined after nanoindentation according to the aforementioned method.
  • 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").
  • the layers produced by the method according to the invention can therefore preferably after crosslinking accordingly have a thickness of 2 nm to 5 ⁇ m, preferably 5 nm to 2 ⁇ m, more preferably 10 nm to 1 ⁇ m.
  • Particularly preferred layers have a thickness of 20 nm to 500 nm.
  • 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.
  • the precursors to be crosslinked must contain chain-forming atoms such as carbon and / or silicon.
  • 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 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.
  • 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.
  • 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.
  • the layers produced by the process according to the invention are similar to plasma polymers. They are amorphous and three-dimensionally networked.
  • 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.
  • the liquid 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.
  • 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).
  • 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.
  • layers crosslinked in the process according to the invention 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.
  • 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.
  • the color impression 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.
  • 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.
  • 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.
  • layer thickness gradients are also caused by the inhomogeneity of the plasma.
  • These density gradients are generally large compared to the dimensions of the components to be coated, so that these are negligible.
  • 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.
  • the method according to the invention uses a liquid film in the first process step.
  • 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.
  • the liquid may spread, i. the liquid forms a very thin film.
  • 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 ⁇ m 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.
  • 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.
  • a meniscus forms around the dust grain, which changes the layer thickness locally to lateral dimensions of a few hundred ⁇ m.
  • 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. 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.
  • 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 ⁇ m 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.
  • 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.
  • the plasma polymer layer is deposited out of the gas phase.
  • a short-chain, gaseous precursor is used.
  • the length of the molecule determines the ratio of repeating unit to end groups of the precursor.
  • the room temperature gaseous HMDSO hexamethyldisiloxane
  • the room temperature silicone oil AK10000 has a much longer molecular chain.
  • 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.
  • Fig. 4 represents the IR spectrum (ERAS) of a hydrophobic plasma polymer coating and the untreated liquid silicone oil AK10000.
  • bands for the Si (CH 3 ) 3 end group are at about 850 1 / cm and for the Si (CH 3 ) 2 bridges (difunctional siloxane units) at about 810 1 / cm to recognize.
  • 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.).
  • 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.
  • 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.
  • 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.
  • the wavenumbers of the associated bands can vary by up to 12 cm -1 .
  • the bands of the end groups (A 845cm-1 ) and repeating units (A 815cm-1 ) clearly visible.
  • 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.
  • the bands of the end groups (A 845 cm -1 ) compared to those of the repeating units (A 815 cm -1 ) are negligible.
  • 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.
  • 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.
  • a coating produced by the process according to the invention 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.
  • 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.
  • TOF-SIMS time-of-flight secondary ion mass spectrometry profile
  • FIG. 10 shows a microscope image of a plasma-crosslinked oil layer (AK10000) with an average layer thickness of 250 nm.
  • a component of the invention is also a crosslinkable layer which can be produced by means of a method according to the invention.
  • 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.
  • 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.
  • 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 ,
  • the molecular chains can be linear, branched or cyclic.
  • Saturated and optionally fluorinated, perfluorinated hydrocarbons for example polytetrafluoroethylene, perfluoroethylene propylene (FEP), perfluorinated alkylcarboxylic acids, perfluoroalkoxy polymers.
  • FEP perfluoroethylene propylene
  • alkylcarboxylic acids for example polytetrafluoroethylene, perfluoroethylene propylene (FEP), perfluorinated alkylcarboxylic acids, perfluoroalkoxy polymers.
  • Hydrocarbons Hydrocarbons, fatty acids, triglycerides, mineral oils, polyethers.
  • 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.
  • 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.
  • 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.
  • these methods are designed so that the mixture comprising or consisting of inert liquid precursors is applied uniformly.
  • 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.
  • the coating of different surfaces is possible with appropriate selection of the precursors.
  • 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 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.
  • pretreat the surface of the body to be coated it may be useful to pretreat. These are essentially the aspects of purification and activation.
  • Dust can z. B. be blown off with compressed air.
  • VUV light vacuum ultraviolet radiation with a wavelength ⁇ 190 nm
  • the person skilled in the art can choose the radiation dose as a function of the contamination itself and to evaluate the cleaning success.
  • 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.
  • 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.
  • 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.
  • non-closed (partially closed) coatings can be dispensed with the activation. These include, for example, the anti-fingerprint coating.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • a precursor with a high viscosity should preferably be used, for example static viscosity greater than 10000 mm 2 / s.
  • 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.
  • silicone oils can be used for the presentation of an anti-fingerprint coating.
  • Very useful have been found to be linear silicones with viscosity in the range 50 to 10,000 mm 2 / s.
  • 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.
  • 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.
  • 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.
  • the expert takes into account that the size of the droplets can vary greatly depending on the spray technique used.
  • an ultrasonic nebulizer is suitable for creating droplets of diameters up to 100 ⁇ m through the droplets (e.g., for anti-fingerprint coating).
  • 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.
  • 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.
  • 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.
  • local layer thickness means that an actually covered area of a crosslinked coating is considered.
  • the determined via an ellipsometer or reflectometer layer thickness can be regarded as the average layer thickness.
  • the expert can make a statement about the local layer thicknesses by considering the interference colors within the previously measured area segment.
  • layer thicknesses of 3 nm to 10 microns 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.
  • there is the possibility of using other techniques to accelerate said effects e.g. by heat supply (by means of eg IR emitters).
  • z For layers which give an optically homogeneous impression for the unaided eye, z.
  • two strategies can be used:
  • homogeneous layers can be applied, which preferably have deviations relative to the average coating thickness of less than 10 percent.
  • 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.
  • 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 ⁇ m. Such rapid layer thickness variations can not be resolved by eye due to their size (generation, for example, by spray or aerosol condensation).
  • 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.
  • 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).
  • 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).
  • preferably higher layer thicknesses are used or produced, for example for PC or PMMA a total layer thickness greater than 2 ⁇ m, preferably between 4 ⁇ m and 10 ⁇ m, or for aluminum a total layer thickness above 2 ⁇ m. These can be generated in one cycle or in several cycles.
  • a local layer thickness in the range of 150 to 250 nm is preferred.
  • 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 ⁇ m.
  • the film behaves like a liquid.
  • Linked effects may or may not be desirable.
  • dust 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.
  • 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 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.
  • 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.
  • 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.
  • 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 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)
  • radiation dose is meant the product of the radiation intensity (i.e., energy per area and time) and the treatment time period.
  • the radiation dose can be controlled via the time duration, the distance (for incoherent radiation sources) and via the absorption in the process gas.
  • 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
  • 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
  • a 1-ply layer may optionally be irradiated within a cycle or for the same total exposure time in any number of short cycles.
  • lasers it should be noted that they work well in pulsed mode.
  • each individual pulse is to be regarded as a separate cycle.
  • the coating defects are reduced by the multiple coating.
  • precursor material is applied and subsequently irradiated and thus crosslinked in a layer-forming manner.
  • 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.
  • each layer has a thickness in the range of 500 nm to 2 ⁇ m after irradiation.
  • An anti-fingerprint coating can be irradiated within one cycle.
  • 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.
  • 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%.
  • the carbon content is less of interest, here are the adhesion and the optical properties of the coating in the foreground.
  • 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.
  • the solids have a particle size in the range of less than 20 nm, detected for example by transmission electron microscopy (TEM).
  • TEM transmission electron microscopy
  • the solids have a particle size in the range of 5 to 10 nm.
  • 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.
  • the finely divided solids are metal particles which are particularly preferably magnetizable.
  • the finely divided solids consist of silver or copper.
  • 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.
  • 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).
  • 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. Ansch manend 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.
  • 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.
  • 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.
  • 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).
  • 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.
  • 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.
  • 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.
  • 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,
  • PDMS trimethylsiloxy-terminated polydimethylsiloxane
  • the Si 2p peak has a binding energy value shifted by a maximum of 0.50 eV to higher or lower binding energies
  • the O 1s peak has a binding energy value shifted by a maximum of 0.50 eV to higher or lower binding energies.
  • layers 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 bruisenklebrtechnik (tack) is missing or greatly reduced.
  • the crosslinked coating has a thickness in the range from 1 to 2000 nm.
  • the crosslinked layer in the second embodiment of the Non-destructive detachable from the surface can thus optionally be used as a film.
  • 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.
  • the article according to the invention comprises a crosslinked layer as a permeation barrier
  • 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.
  • the advantage of such an article is not always in its capacity as a permeation barrier.
  • 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.
  • 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.
  • 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.
  • migration barrier migration barrier
  • the barrier application are migration barriers to prevent the escape of unwanted substances from a substrate, such as water.
  • the barrier to additives (eg plasticizers) from a plastic substrate this application is of particular importance for food and pharmaceutical packaging).
  • 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.
  • the crosslinked layer serves to prevent leakage of an undesirable substance from the substrate into the food.
  • 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.
  • 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.
  • 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.
  • the present invention thus also achieves the object of providing an improved thin-film coating system which represents a suitable migration barrier.
  • a layer produced according to the invention can be used as an intermediate layer (spacer layer) in a composite of thin layers.
  • 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).
  • PE-CVD plasma assisted CVD
  • it can reduce the tendency to crack due to internal (mechanical) stresses at thicker "total layer thicknesses”.
  • the flexibility of such a layer composite is increased in comparison with a barrier layer without the intermediate layer according to the invention.
  • 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.
  • Hydrolysis resistant coatings are needed in various technical fields of application.
  • hydrolysis-resistant, hydrophobic, anticorrosive thin-layer coatings which do not hinder heat conduction, are required in the area of heat exchangers.
  • saturated water vapor atmospheres often occur at elevated pressures.
  • 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.
  • hydrolysis-resistant coatings Another field of application for hydrolysis-resistant coatings is 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.
  • 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.
  • PVD physical chemical vapor deposition
  • CVD chemical vapor deposition
  • PE-CVD plasma-assisted CVD
  • plasma polymerization galvanically or in a sol-gel process.
  • 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.
  • tools and machines such as bookbinding machines, adhesive applicators, sealers, printing units, laminating installations, painting installations, components for painting installations, food processing installations
  • 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.
  • 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.
  • 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).
  • a crosslinked layer produced according to the invention which shows the binding energy values given above in an ESCA test.
  • 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.
  • 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.
  • 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.
  • 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).
  • tack surface tackiness
  • a corresponding article according to the invention comprises a silicone rubber product and a crosslinked layer (as described above).
  • 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.
  • Non-cytotoxic, antibacterial coatings after DE 103 53 756 are preferably produced by means of SiO x -like coatings.
  • SiO x -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.
  • corresponding surfaces define certain adhesion properties (for bacteria, fungi, endogenous substances, etc.).
  • the high flexibility and elasticity of the layer allows substrate-forming further processing techniques, such as deep-drawing, beading, embossing etc.
  • substrate-forming further processing techniques such as deep-drawing, beading, embossing etc.
  • embossing etc.
  • even tubes, closures, spouts or foamed sheets can be equipped.
  • such a layer on a corresponding laminating film or even applied directly suitable for food packaging Furthermore, such a layer on a corresponding laminating film or even applied directly suitable for food packaging.
  • the use in the composite film sector of interest because it can be combined, for example, barrier properties with antibacterial properties.
  • 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.
  • 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.
  • 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.
  • 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.
  • the said patent application will become part of the present application.
  • Section 26 the skilled artisan will be advised of the amount of nanobiozide needed to deliver non-cytotoxic surfaces shape, given.
  • 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.
  • 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.
  • an article of the invention comprises an article comprising a corrosion-sensitive surface on which the crosslinked layer is disposed.
  • the coating process can be carried out at room temperature.
  • the surface to be coated (the substrate) in a pretreatment step of a mechanical, chemical and / or electrochemical smoothing is subjected.
  • 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.
  • 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.
  • a reducing or oxidizing plasma is used to clean and activate the surface.
  • UV radiation is used for cleaning and activating or for solidifying (excimeric) crosslinkable contaminations of the surface, in particular UV radiation from excimer lamps.
  • solidifying (excimeric) crosslinkable contaminations of the surface in particular UV radiation from excimer lamps.
  • liquid contaminants such as mineral oils act as precursors.
  • the substrate to be coated is subjected to a combination of mechanical surface treatment and pickling before it is coated.
  • 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.
  • 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.
  • the liquid precursor is applied in a thickness of 5 nm to 10 ⁇ m, more preferably the liquid precursor comprises a corrosion inhibitor.
  • 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.
  • 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.
  • a corresponding PDMS silicone oil such as Wacker silicone oil AK 25 or AK 10000.
  • 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 ⁇ m 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.
  • 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.
  • 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.
  • 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.
  • an average total layer thickness in the range of 170 to 210 nm.
  • 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.
  • 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.
  • organic solvents such as hydrocarbons (sometimes also chlorinated)
  • 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.
  • release agent 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 Entformungsclerosisn. Finally, these release agent systems emit significant amounts of solvents into the environment.
  • an (excimer) crosslinked layer produced in a method according to the invention for reducing the adhesion of a molding tool to a molding.
  • 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.
  • 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.
  • 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.
  • a permanent release layer since, unlike conventional liquid release agents, it does not release any substances to the component to be manufactured.
  • 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.
  • silicone oils as precursor is appropriate.
  • 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.
  • 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.
  • fluorinated silicone oils and organofluorine oils can be used.
  • 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.
  • 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.
  • H 2 or compounds with conjugated or non-conjugated CC double bonds such as vinyl trimethylsiloxane VTMS, C 2 H 4 , isoprene, methacrylates offers.
  • 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.
  • 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.
  • 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.
  • 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.
  • an article in which the crosslinked layer has a water edge angle of over 90 °, preferably over 95 ° and more preferably over 100 °.
  • 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.
  • 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 ⁇ m, preferably ⁇ 0.3 ⁇ m, preferably ⁇ 0.1 ⁇ m 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.
  • 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.
  • Impurities can not penetrate into the surface structure as before or cling to exposed sharp edges.
  • 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.
  • the method according to the invention it is possible, in particular, to apply particles with a size between 10 nm and 20 ⁇ m 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.
  • 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.
  • 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.
  • a defined contamination e.g. an oil from a previous metalworking step
  • 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.
  • 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.
  • O 2 in particular is known as so-called radical scavenger, as a substance that reacts with radicals and leaves oxygen-containing functionalities.
  • 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.
  • conjugated or non-conjugated substances such as conjugated or nonconjugated dienes such as, for example, 1,4-hexadiene, 1,3-butadiene or isoprene.
  • this functionalization can be carried out by metering the gases at the end of the coating process according to the invention.
  • corresponding liquids can also be used instead of the gases, for example the solutions of corresponding substances in organic solvents.
  • substrate surface and adhesive or coating material 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.
  • 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.
  • 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.
  • this smoothing effect may be advantageous in order to increase the effective adhesion surface.
  • 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.
  • 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.
  • a ninth preferred embodiment of the invention 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 insulating layer is a hydrophobic layer crosslinked according to the invention.
  • the latter is also part of 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.
  • UV radiation preferably radiation with a wavelength ⁇ 250 nm, particularly preferably radiation from excimer lamps
  • 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.
  • a "rapid prototyping on the micro and nanometer scale” could be performed. This would z.
  • 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).
  • Localized coatings e.g., anti-fingerprint coating
  • Large user industries include, for example, the semiconductor and photovoltaic industries, micromechanics and microsystems technology, but also the industry for the production of LEDs.
  • the (excimer) crosslinked layer prepared in the method of the present invention eliminates the need for a photoresist (photographic layer structure).
  • 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.
  • 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.
  • insulating coatings are considered, as discussed in the section electrical insulation layers.
  • 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.
  • 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.
  • an eleventh preferred embodiment of the invention 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).
  • 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.
  • 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 process of the invention can produce a thin film coating which is transparent or partially transparent, i.
  • the coating is transparent to a portion of the infrared, visible and UV spectral regions.
  • a portion of the radiation incident on the layer is reflected.
  • 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.
  • the coating parameters may be designed such that a single wavelength or a wavelength range 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.
  • 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.
  • 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 objects are distinguished by the fact that intensity differences between the local partial beams are introduced by them in the transmitted light.
  • 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.
  • 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.
  • 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 ⁇ m.
  • 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.
  • a precursor with a low surface tension can be used to spread very thin sub micron coverage (area to height ratio: large).
  • 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.
  • a liquid precursor deposits more in the depressions of a surface than on the profile tips.
  • 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.
  • 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.
  • 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.
  • metallically lustrous surfaces in the mentioned preferred range of roughness values, particularly preferably galvanically coated or blasted, shiny metallic surfaces.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • the dynamic behavior of the liquid used is utilized.
  • an island-like covering can be obtained.
  • island-like regions of higher layer thickness with an overall height of less than 10 ⁇ m 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 5 ⁇ m.
  • 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.
  • 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.
  • 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.
  • 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
  • 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.
  • 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
  • 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.
  • 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.
  • 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.
  • 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.
  • 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
  • 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.
  • 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)
  • 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.
  • 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.
  • 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.
  • Example 2 Comparison of a plasma-crosslinked layer with layers crosslinked with excimer lamps by means of time-of-flight secondary-mass spectroscopy
  • TOF-SIMS time-of-flight secondary ion mass spectrometry
  • 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 ⁇ m 2 , charge compensation with pulsed electron source.
  • Sputtering parameters 3 keV argon sputter source, 25.8 nA, sputter area 200 x 200 ⁇ m 2 .
  • the figures show the intensity of the positive ion signals characteristic of the corresponding elements versus the sputtering cycles (Cycle).
  • 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.
  • 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.
  • 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.
  • the carbon signal initially indicates a large decrease.
  • 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.
  • a very sharp drop in the carbon signal can be seen very close to the surface, which is ignored in the above-mentioned Greens.
  • a steady increase in the C signal to about Cycle 60 can be seen.
  • the O signal remains almost constant over the entire measurement.
  • the level of the C signal 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.
  • 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.
  • Fig. 14 illustrates the different behavior of the C signal for the three layer variants.
  • Fig. 14 shows a TOF-SIMS depth profile
  • Example 3 Corrosion protection coating or tarnish protection
  • 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 Lampentechnik 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.
  • an excimer lamp Xeradex spotlights, 50W, Radium Lampenwerk GmbH
  • 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 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.
  • 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.
  • 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).
  • UV light of wavelength 172 nm
  • 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).
  • 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.
  • TAA test thioacetamide test
  • a coated and an uncoated ring was exposed to a hydrogen sulfide-containing atmosphere.
  • 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.
  • 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.
  • 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.
  • the aluminum layer of the untreated substrate 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
  • 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.
  • 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.
  • a second layer of the coating according to the invention was applied.
  • 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.
  • 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.
  • exemplary basic investigations were carried out on a series of sample coatings.
  • the samples were made on Si wafers as base material.
  • 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 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.
  • 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).
  • 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.
  • 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.
  • 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 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.
  • 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.
  • 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 inventive method allows the degree of crosslinking of the applied liquid to vary over the intensity of the irradiation in a wide range.
  • the adhesion to the substrate material is of technical importance.
  • 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
  • a pattern of embedded titanium dioxide particles was prepared.
  • 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.
  • 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
  • a pattern with embedded dye particles was prepared.
  • 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.
  • 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).
  • 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.
  • Fig. 33 shows a microscope image of the dye particles with an average size of diameter below 1 micron.
  • 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 Lampentechnik GmbH). The distance between the mask and the lamp base was ⁇ 10mm.
  • the non-cross-linked, in the shadow area lying residual film of the AK50 could be rinsed off by isopropanol.
  • a regular pattern of round coating islands was achieved.
  • Fig. 34 represents the result of the partial coating in Example 9.
  • 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.
  • the surface of a galvanized body with an average roughness R a in the range 0.3 - 0.8 ⁇ m was increased to above 72mN / m with a low pressure oxygen plasma before the liquid application to increase the surface energy activated.
  • the activation can be carried out, for example, by irradiation with short-wave UV radiation from excimer lamps.
  • 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.
  • 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).
  • 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.
  • 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.
  • Example 10 Treatment according to Example 10, but now with a galvanized plastic surface with a mean roughness R a in the range 0.6 - 1.0 ⁇ m.
  • 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).
  • 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.
  • 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 °.
  • 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.
  • 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.
  • a liquid film consisting of AK10000 (Wacker, surface tension 21.5 mN / m, viscosity 10000 mm 2 / s) with a layer thickness of 1 ⁇ m was applied to the surfaces of a blasted brass and an aluminum pattern having an average roughness R a of 1.2 ⁇ m. 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.
  • 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 1 ⁇ m could be identified.
  • the coating has antimicrobial, but not cytotoxic properties.
  • Various polymers and stainless steel as the base material were surface cleaned with methyl ethyl ketone (MEK).
  • MEK methyl ethyl ketone
  • 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.
  • 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).
  • tensile shear samples were again prepared and measured.
  • adhesives for the listed polymers Delo PUR 9691 and for stainless steel Delo PUR 9694 were used.
  • 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.
  • 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.
  • 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 .
  • a migration barrier to styrene is obtained, which leads to a significant extension of the service life of the plastic molds.
  • 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 .
  • 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 .
  • both silicone and polyamide can be used.
  • 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 Lampentechnik GmbH) with light of wavelength 172 nm.
  • the irradiation time was 600s at a distance between the lamp and the foil of ⁇ 0.5cm.
  • 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.
  • 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 ⁇ m. 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 3 D 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.
  • a flexible coating can be configured as a flexible coating.
  • 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).
  • 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.

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  • Physics & Mathematics (AREA)
  • Engineering & Computer Science (AREA)
  • Plasma & Fusion (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)
  • Laminated Bodies (AREA)
  • Paints Or Removers (AREA)
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WO2015022322A1 (fr) * 2013-08-12 2015-02-19 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Objet contenant du cuivre revêtu d'une couleur neutre
WO2015022323A3 (fr) * 2013-08-12 2015-05-07 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Objet contenant du métal, revêtu d'une couleur neutre, et pourvu d'une surface contenant du métal ou métallique

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