Classifications

• • C—CHEMISTRY; METALLURGY
  • C03—GLASS; MINERAL OR SLAG WOOL
  • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
  • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
  • C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
  • C03C17/42—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating of an organic material and at least one non-metal coating
• • C—CHEMISTRY; METALLURGY
  • C03—GLASS; MINERAL OR SLAG WOOL
  • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
  • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
  • C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
  • C03C17/36—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal
  • C03C17/38—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal at least one coating being a coating of an organic material
• • 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
  • Y10T428/26—Web or sheet containing structurally defined element or component, the element or component having a specified physical dimension
  • Y10T428/263—Coating layer not in excess of 5 mils thick or equivalent
  • Y10T428/264—Up to 3 mils
  • Y10T428/265—1 mil or less

Definitions

• the present invention relates to a substrate with a low light-scattering, ultraphobic surface, a method for producing the substrate and its use.
• the invention further relates to a screening method for producing such substrates.
• the substrate with a light-scattering ultraphobic surface has a total scattered light loss ⁇ 7%, preferably ⁇ 3%, particularly preferably ⁇ 1% and a contact angle with water of at least 140 °, preferably at least 150 °, and a roll angle ⁇ 20 °.
• Ultraphobic surfaces are characterized in that the contact angle of a drop of a liquid, usually water, lying on the surface is significantly more than 90 ° and that the roll angle does not exceed 20 °.
• Ultraphobic surfaces with a contact angle> 140 ° and a roll angle ⁇ 20 ° have a very high technical benefit because they e.g. are not wettable with water but also with oil, dirt particles adhere very poorly to these surfaces and these surfaces are self-cleaning.
• Self-cleaning is understood here to mean the ability of the surface to easily transfer dirt or dust particles adhering to the surface to liquids that flow over the surface.
• the roll angle here is understood to be the angle of inclination of a fundamentally planar but structured surface against the horizontal, in which a standing water drop of volume 10 .mu.l is moved due to gravity when the surface is inclined by the roll angle.
• a hydrophobic material in the sense of the invention is a material which shows a contact angle with respect to water of greater than 90 ° on a flat, non-structured surface.
• An oleophobic material in the sense of the invention is a material which, on a flat, non-structured surface, has a contact angle with respect to long-chain n-alkanes, such as n-decane, of greater than 90 °.
• a light-scattering surface in the sense of the invention denotes a surface on which the scattered light losses caused by roughness, determined according to the measurement specification ISO / DIS 13696, are ⁇ 7%, preferably ⁇ 3%, particularly preferably ⁇ 1%.
• the measurement is carried out at the wavelength of 514 nm and determines the total scattering losses in the forward and reverse direction. The exact procedure is described in the publication by A. Kurre and S. Gliech, Proc. SPIE 3141, 57 (1997), which is hereby introduced as a reference and is therefore considered part of the disclosure.
• Daneban prefers the low light-scattering ultraphobic surface to high abrasion and scratch resistance.
• 500 cycles with a weight of 500g per grindstone there is an increase in haze of ⁇ 10%, preferably ⁇ 5%.
• scratching with the sand trickle test according to DIN 52348 there is an increase in turbidity of ⁇ 15%, preferably ⁇ 10%, particularly preferably ⁇ 5%.
• the increase in turbidity is tested in accordance with ASTM D 1003. When measuring the increase in turbidity, the surface of the substrate is irradiated with visible light and the scattered fractions that cause the turbidity are determined.
• EP 476 510 A1 discloses a method for producing a hydrophobic surface, in which a metal oxide film with a perfluorinated silane is applied to a glass surface.
• the surfaces produced with this method have the disadvantage that the Contact angle of a drop lying on the surface is less than 115 °.
• US Pat. No. 5,693,236 also teaches several methods for producing ultraphobic surfaces, in which microneedles made of zinc oxide are applied to a surface with a binder and then partially exposed in different ways (e.g. by plasma treatment). The roughened surface is then coated with a water-repellent agent. Surfaces structured in this way have contact angles of up to 150 °. However, the surface is highly light-scattering due to the size of the bumps.
• the surface must preferably have high stability against scratches or abrasion at the same time.
• a turbidity increase of ⁇ 10%, preferably ⁇ 5%, is allowed.
• the increase in turbidity should be ⁇ 15%, preferably ⁇ 10%, particularly preferably ⁇ 5%.
• the increase in turbidity of both loads is determined in accordance with ASTM D 1003.
• a particular problem is that surfaces that are supposed to be low light-scattering and at the same time ultraphobic can be produced with a wide variety of materials, which show a completely different surface topography, as can be seen from the examples mentioned above.
• substrates with surfaces that are low light-scattering and ultraphobic can also be produced with very different types of coating processes.
• the coating processes have to be operated with certain precisely defined process parameters.
• the object is achieved according to the invention by a substrate with a light-scattering and ultraphobic surface, which is the subject of the invention, in which the total scattering light loss ⁇ 7%, preferably ⁇ 3%, particularly preferably ⁇ 1% and the contact angle with water> 140 °, is preferably> 150 °.
• the substrate with a low light-scattering and ultraphobic surface is manufactured, for example, by a manufacturing process described below, which in turn can be found by a rapid screening process consisting of selection steps, calculation steps and manufacturing steps.
• the ultraphobic surface or its substrate preferably consists of plastic, glass, ceramic material or carbon.
• a substrate with a scratch resistance determined by the increase in haze according to ASTM D 1003 of ⁇ 15%, preferably ⁇ 10%, particularly preferably ⁇ 5%, based on a scratch load with the sandal trickle test according to DIN 52348.
• a substrate characterized in that the roll angle is ⁇ 20 ° on the surface for a water drop of volume 10 .mu.l.
• plastics The plastic which is particularly suitable for the ultraphobic surface and / or its substrate is a thermosetting or thermoplastic.
• thermosetting plastic is selected in particular from the series: diallyl phthalate resin, epoxy resin, urea-formaldehyde resin, melamine-formaldehyde resin, melamine-phenol-formaldehyde resin, phenol-formaldehyde resin, polyimide, silicone rubber and unsaturated polyester resin ,
• thermoplastic polyolefin z. B. polypropylene or polyethylene, polycarbonate, polyester carbonate, polyester (e.g. PBT or PET), polystyrene, styrene copolymer, SAN resin, rubber-containing styrene-graft copolymer, e.g. ABS polymer, polyamide, polyurethane, polyphenylene sulfide, polyvinyl chloride or any possible mixtures of the polymers mentioned selected.
• thermoplastic polyolefin z. B. polypropylene or polyethylene
• polycarbonate polycarbonate
• polyester carbonate e.g. PBT or PET
• polystyrene styrene copolymer
• SAN resin SAN resin
• rubber-containing styrene-graft copolymer e.g. ABS polymer, polyamide, polyurethane, polyphenylene sulfide, polyvinyl chloride or any possible mixtures of the polymers mentioned selected
• thermoplastic polymers are particularly suitable as substrates for the surface according to the invention:
• Polyolefins such as high and low density polyethylene, ie densities from 0.91 g / cm 3 to 0.97 g / cm 3 , which by known methods, Ullmann (4.) 19, page 167 ff, Winnacker-Kückler (4.) 6, 353 to 367, Elias et al. Vohwinkel, New Polymer Materials for Industrial Use, Kunststoff, Hanser 1983.
• polypropylenes with molecular weights of 10,000 g / mol to 1,000,000 g / mol, which according to known methods, Ulimann (5th) A10, page 615 ff., Houben-Weyl E20 / 2, page 722 ff., Ullmann ( 4.) 19, page 195 ff., Kirk-Othmer (3.) 16, page 357 ff.
• copolymers of the olefins mentioned or with further ⁇ -olefins are also possible, for example
• EVK ethylene vinyl carbazole copolymers
• EPB ethylene-propylene block copolymers
• EPDM ethylene-propylene-diene copolymers
• thermoplastic plastics suitable according to the invention are also thermoplastic, aromatic polycarbonates, in particular those based on the diphenols of the formula (I)
• A is a single bond, C
• radicals B independently of one another, each represents a C ⁇ -C 8 alkyl, C 6 -C ⁇ 0 -aryl, particularly preferably phenyl, C 7 -C ⁇ 2 aralkyl, preferably benzyl, halogen, preferably chlorine, bromine,
• Rl and R 2 are each hydrogen, halogen, preferably chlorine or bromine, Ci-Cs-alkyl, C ⁇ -Cß-cycloalkyl, Cß-Ci o-aryl, preferably phenyl, and Cy-C ⁇ aralkyl, preferably phenyl -C ⁇ -C4- alkyl, especially benzyl,
• n is an integer from 4 to 7, preferably 4 or 5
• R 3 and R 4 can be selected individually for each Z, independently of one another,
• Ci-Cg-alkyl preferably hydrogen, methyl or ethyl
• Z means carbon, with the proviso that on at least one atom Z R3 and R ⁇ simultaneously mean alkyl.
• Suitable diphenols of formula (I) are e.g. Hydroquinone, resorcinol, 4,4'-dihydroxydiphenyl, 2,2-bis (4-hydroxyphenyl) propane, 2,4-bis (4-hydroxyphenyl) -2-methylbutane, 1,1-bis- (4- hydroxyphenyl) cyclohexane, 2,2-bis (3-chloro-4-hydroxyphenyl) propane, 2,2-bis (3,5-dibromo-4-hydroxyphenyl) propane.
• Preferred diphenols of the formula (I) are 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (3,5-dichloro-4-hydroxyphenyl) propane and 1,1-bis- (4th -hydroxyphenyl) cyclohexane.
• polycarbonates suitable according to the invention can be branched in a known manner, preferably by incorporating 0.05 to 2.0 mol%, based on the sum of the diphenols used, of three or more than three-functional compounds, e.g. those with three or more than three phenolic groups, for example
• Some of the other three-functional compounds are 2,4-dihydroxybenzoic acid, trimesic acid, trimellitic acid, cyanuric chloride and 3,3-bis (3-methyl-4-hydroxyphenyl) -2-oxo-2,3-dihydroindole.
• preferred polycarbonates are the copolycarbonates of bisphenol A with up to 15 mol%, based on the molar sum of diphenols, of 2,2-bis (3,5-dibromo-4-hydroxyphenyl) - propane.
• aromatic polycarbonates can be replaced by aromatic polyester carbonates.
• Aromatic polycarbonates and / or aromatic polyester carbonates are known from the literature or can be prepared by processes known from the literature (for the production of aromatic polycarbonates, see for example Schnell, “Chemistry and Physics of Polycarbonates”, Interscience Publishers, 1964 and DE-AS 1 495 626, DE-OS 2 232 877 , DE-OS 2 703 376, DE-OS 2 714 544, DE-OS 3 000 610, DE-OS 3 832 396; for the production of aromatic polyester carbonates, for example DE-OS 3 077 934).
• aromatic polycarbonates and / or aromatic polyester carbonates can e.g. by reacting diphenols with carbonic acid halides, preferably phosgene and / or with aromatic dicarboxylic acid dihalides, preferably
• Benzene dicarboxylic acid dihalides according to the phase interface method, optionally using the chain terminators and optionally using the trifunctional or more than trifunctional branching agents.
• thermoplastic plastics are also suitable as thermoplastic plastics.
• the copolymers are resinous, thermoplastic and rubber-free.
• Preferred styrene copolymers are those composed of at least one monomer from the styrene, ⁇ -methylstyrene and / or nucleus-substituted styrene with at least one monomer from the series acrylonitrile, methacrylonitrile, methyl methacrylate, maleic anhydride and / or N-substituted-maleimide.
• thermoplastic copolymer is 60 to 95% by weight of the styrene monomers and 40 to 5% by weight of the other vinyl monomers.
• Particularly preferred copolymers are those made from styrene with acrylonitrile and optionally with methyl methacrylate, from ⁇ -methylstyrene with acrylonitrile and optionally with methyl methacrylate, or from styrene and ⁇ -methylstyrene with acrylonitrile and optionally with methyl methacrylate.
• the styrene-acrylonitrile copolymers are known and can be prepared by radical polymerization, in particular by emulsion, suspension, solution or bulk polymerization.
• the copolymers preferably have molecular weights M w (weight average, determined by light scattering or sedimentation) between 15,000 and 200,000 g / mol.
• Particularly preferred copolymers are also random copolymers of styrene and maleic anhydride, which can preferably be prepared from the corresponding monomer by continuous mass or solution polymerization with incomplete conversions.
• the proportions of the two components of the randomly constructed styrene-maleic anhydride copolymers suitable according to the invention can be varied within wide limits.
• the preferred content of maleic anhydride is 5 to 25% by weight.
• the polymers can also contain nucleus-substituted styrenes, such as p-methylstyrene, 2,4-dimethylstyrene and other substituted styrenes, such as ⁇ -methylstyrene.
• nucleus-substituted styrenes such as p-methylstyrene, 2,4-dimethylstyrene and other substituted styrenes, such as ⁇ -methylstyrene.
• the molecular weights (number average M n ) of the styrene-maleic anhydride copolymers can vary over a wide range. The range from 60,000 to 200,000 g / mol is preferred. An intrinsic viscosity of 0.3 to 0.9 is preferred for these products (measured in dimethylformamide at 25 ° C.; see Hoffmann, Krömer, Kuhn, Polymeranalytik I, Stuttgart 1977, page 316 ff.).
• Graft copolymers are also suitable as thermoplastics. These include graft copolymers with rubber-elastic properties, which are essentially obtainable from at least 2 of the following monomers: chloroprene, 1,3-butadiene, isopropene, styrene, acrylonitrile, ethylene, propylene, vinyl acetate and (meth) -acrylic acid esters with 1 to 18 C- Atoms in the alcohol component; i.e. polymers such as in "Methods of Organic Chemistry” (Houben-Weyl), Vol. 14/1, Georg Thieme-Veriag, Stuttgart 1961, pp. 393-406 and in C.B. Bucknall, "Toughened Plastics", Appl. Science Publishers, London 1977.
• Preferred graft polymers are partially crosslinked and have gel contents of more than 20% by weight, preferably more than 40% by weight, in particular more than 60% by weight.
• the graft copolymers can be prepared by known processes such as bulk, suspension, emulsion or bulk suspension processes.
• polyamide 66 polyhexamethylene adipinamide
• the ceramic materials particularly suitable for the ultraphobic surface and / or its substrate are oxides, fluorides, carbides, nitrides, selenides, tellurides, sulfides, in particular of metals, boron, silicon or germanium, or their mixed compounds or physical mixtures of these compounds, in particular Oxides of zirconium, titanium, tantalum, aluminum, hafnium, silicon, indium, tin, yttrium, or cerium,
• Nitrides from boron, titanium or silicon.
• Glass is also fundamentally suitable as the material for the ultraphobic surface and / or its substrate. This can be all types of glass that are known to the person skilled in the art and that e.g. the publications by H. Scholze "Glass, Nature, Structure, Properties", Springer Verlag 1988 or the manual “Designing with Glass”, Interpane Glas Industrie AG, 5th edition 2000.
• An alkaline earth-alkali silicate glass based on calcium oxide, sodium oxide, silicon dioxide and aluminum oxide or a borosilicate glass based on silicon dioxide, aluminum oxide, alkaline earth metal oxides, boron oxide, sodium oxide and potassium oxide is preferably used as the glass for the substrate.
• the substrate is particularly preferably an alkaline earth alkali silicate glass which is covered on its surface with an additional zirconium oxide layer with a thickness of 50 nm to 5 ⁇ m.
• the alkaline earth alkali silicate glasses customary for flat glass and window glass applications are suitable, which are composed, for example, of 15% calcium oxide, 13 to 14% sodium oxide, 70% silicon dioxide and 1 to 2% aluminum oxide.
• borosilicate glasses which are used, for example, as fire protection glass and which are composed, for example, of 70 to 80% silicon dioxide, 7 to 13% boron oxide, 2 to 7% aluminum oxide, 4 to 8% sodium and potassium oxide and 0 to 5% alkaline earth metal oxides.
• DLC layer diamond-like carbon
• the DLC layer is preferably applied to a carrier material other than carbon.
• the substrate is particularly preferably provided with an additional coating of a hydrophobic or oleophobic phobicization aid.
• Surfactant compounds with any molar mass are to be regarded as hydrophobic or oleophobic phobicization aids. These compounds are preferably cationic, anionic, amophotere or non-ionic surface-active compounds, as described, for example, in the directory “Surfactants Europe, A Dictionary of Surface Active Agents available in Europe, Edited by Gordon L. Hollis, Royal Socity of Chemistry , Cambridge, 1995.
• anionic phobing aids alkyl sulfates, ether sulfates, ether carboxylates, phosphate esters, sulfosucinates, sulfosuccinatamides, paraffin sulfonates, olefin sulfonates, sarcosinates, isothionates, taurates and Lingnine compounds.
• Quaternary alkylammonium compounds and imidazoles may be mentioned as cationic phobicization aids
• Amphoteric phobicization aids are, for example, betaines, glycinates, propionates and imidazoles.
• nonionic phobing aids examples include: alkoxylates, alkyloamides, esters, amine oxides and alkypolyglycosides. Also suitable are: reaction products of alkylene oxides with alkylatable compounds, such as. B. fatty alcohols, fatty amines, fatty acids, phenols, alkylphenols, arylalkylphenols, such as styrene-phenol condensates, carboxamides and resin acids.
• Phobicizing aids are particularly preferred in which 1 to 100%, particularly preferably 60 to 95%, of the hydrogen atoms are substituted by fluorine atoms.
• Examples include perfluorinated alkyl sulfate, perfluorinated alkyl sulfonates, perfluorinated alkyl phosphonates, perfluorinated alkyl phosphinates and perfluorinated carboxylic acids.
• polymeric phobicization aids for hydrophobic coating or as polymeric hydrophobic material for the surface.
• These polymeric phobicization aids can be nonionic, anionic, cationic or amphoteric compounds.
• these polymeric phobicization aids can be homopolymers and copolymers, graft and graft copolymers and random block polymers.
• Particularly preferred polymerizing auxiliaries are those of the type AB, BAB and ABC block polymers. In the AB or BAB block polymers, the A segment is a hydrophilic homopolymer or copolymer and the B block is a hydrophobic homopolymer or copolymer or a salt thereof.
• Anionic, polymeric phobicization aids are also particularly preferred, in particular condensation products of aromatic sulfonic acids with formaldehyde and alkylnaphthalenesulfonic acids or from formaldehyde, naphthalenesulfonic acids and / or benzenesulfonic acids, condensation products from optionally substituted phenol with formaldehyde and sodium bisulfite.
• condensation products which can be obtained by reacting naphthols with alkanols, additions of alkylene oxide and at least partial conversion of the terminal hydroxyl groups into sulfo groups or half esters of maleic acid and phthalic acid or succinic acid.
• the phobicization aid is from the group of the sulfosuccinic acid esters and alkylbenzenesulfonates.
• Sulfated, alkoxylated fatty acids or their salts are also preferred.
• Alkoxylated fatty acid alcohols are understood in particular to be those with 5 to 120, with 6 to 60, very particularly preferably with 7-30 ethylene oxide, C 6 -C 22 fatty acid alcohols which are saturated or unsaturated, in particular stearyl alcohol.
• the sulfated alkoxylated fatty acid alcohols are preferably present as a salt, in particular as alkali or amine salts, preferably as a diethylamine salt.
• an additional adhesion promoter layer based on noble metals preferably a gold layer with a layer thickness of 10 to 100 nm, is arranged between the phobicization aid layer and the substrate.
• the invention further relates to a method for the selection of optionally surface-coated substrates with ultraphobic and low light-scattering surfaces, in which
• At least one optionally surface-coated substrate is selected with regard to the composition, thickness and sequence of individual layers,
• compositions Composition, thickness and sequence of individual layers
• the substrate is preferably the materials mentioned under b and c above.
• the substrate can be coated or uncoated.
• the uncoated substrate has at least one layer.
• the coated substrate generally has at least two, however, a multiplicity of layers.
• the substrate is preferably selected with regard to its composition, the thickness of the respective layer, the thickness of the entire substrate and, if appropriate, the sequence of the individual layers.
• the person skilled in the art takes particular account of additional properties which the surface of the substrate must meet in the respective technical application. If, for example, a particularly high scratch resistance is important for the application, the person skilled in the art will then select in particular hard materials, such as, for example, TiN, SiC, WC or Si 3 N.
• the layer systems selected according to step A) are provided with various surface topographies and examined for their total light scattering.
• ARS ⁇ i ⁇ j KC i C j PSD ij (2 ⁇ f) ( 2 )
• ARS is the angle resolved scatter.
• TS total integrated scatter
• optical factor K for the scattering in the rear half space or forward half space is described in the publication by P. Bousquet, F. Flory, P. Roche, Scattering from multilayer thin films: theory and experiment, J. Opt. Soc. At the. Vol. 71 (1981) according to the regulations given after formula 22 or 23 on page 1120 from the polar and azimuthal angle of incidence, the wavelength used and the refractive indices of the layer materials.
• the optical factors Cj, Cj are derived from formulas 22 and 23 in the publication by P. Bousquet, F. Flory, P. Röche, Scattering from multilayer thin films: theory and experiment, J. Opt. Soc. At the. Vol. 71 (1981) calculated as follows.
• i and j denote the number of the interface.
• Conjugate complex sizes are marked with an asterisk (*).
• the factors Ci, Cj are calculated using the formulas 17, 18, 19 and 20 on page 1119 from the field strengths E at the layer interfaces and the rules for the admittance Y given on page 1119.
• the admittances Y are calculated according to the 4 formulas (without number) on page 1119, left column, last paragraph, from the refractive indices n, the dielectric constant, the magnetic field constants, the layer thicknesses e and the polar angle of incidence ⁇ 0 .
• the field strength calculations are carried out using the recursion methods familiar to the person skilled in the art when calculating layer systems, which are described on pages 1117 and 1118 as regulations.
• the optical refractive indices at the wavelength of the scattering light are required, which are determined as follows:
• optical refractive indices at this wavelength are known for a large number of materials. For example, you can refer to the Handbook of Optical Constants of Solids, Ed. ED Palik, Academic Press, San Diego, 1998, which is hereby inserted as a reference and thus serves as part of the disclosure. If an optical refractive index is not is known, this can also be determined experimentally. The necessary regulation is known to the expert and can, for. B. the publication of HA Macleod, Thin Film Optical Filters, Macmillan Publishing Company, New York; Adam Hilger Ltd .. Bristol, 1986, which is hereby inserted as a reference and thus also serves as part of the disclosure.
• step D) Selection of the layer systems which fulfill both conditions from step B) and step C)
• Steps A) to C) can be supported or automated in a suitable manner by computer systems.
• the computing effort for testing a single layer structure is so low that a large number of layer structures can be checked numerically with ease within a short time.
• the computing programs can also be constructed in particular in such a way that steps A) to C) are carried out in a manner in which have the layer structures optimized numerically.
• steps A) to C) are carried out in a manner in which have the layer structures optimized numerically.
• a substrate is selected from a material a with a layer thickness d a ⁇ and a refractive index n a .
• the substrate thickness d op t represents an optimum insofar as most of the different topographies of the surface are present, with both conditions from step B) and C) being met.
• the substrate thickness d op t is the easiest to structure the surface with the desired properties, since most options are available here.
• a corresponding procedure can be followed if the layer thicknesses of substrates from several layers are to be optimized, for example for a two-layer system with the structure of layers (a, b) with layer thicknesses d a and d.
• the optimum with regard to the layer thicknesses (d 0 pta, d 0 ptb) can be determined within the given minimum and maximum layer thicknesses of layers a and b.
• a corresponding procedure can also be used if there are even more complicated systems consisting of three or more layers.
• the substrates according to the invention are preferably examined using the method according to the invention.
• Another object of the present invention is a method for selecting process parameters for the production of ultraphobic and low light-scattering surfaces of optionally surface-coated substrates, in which:
• the surfaces of substrates are produced by varying the process parameters necessary for generating the surface topography, in series or in parallel, preferably in parallel,
• the contact angle of a water drop is determined at least on the respective surface, the light scattering according to F) of which is ⁇ 7%, preferably ⁇ 3%, particularly preferably ⁇ 1% and
• a person skilled in the art can easily propose technically suitable coating processes for the selected substrates or, if appropriate, substrates from several layers, which have ultraphobic and low light-scattering properties.
• Examples of coating processes from the gas phase include various evaporation methods and glow discharge processes, such as
• Evaporation source can be operated by a variety of different techniques, such as: electron beam heating, ion beam heating, resistance heating, radiation heating,
• Electrodes or lasers chemical vapor deposition (CVD); ion plating;
• Examples of coating processes from the liquid phase are:
• spin coating in “spin-up” mode or “spin coating” in “spin-down” mode
• the following process parameters for the topography of the surface are important for the production of thin layers on glass: substrate pretreatment (eg glow, cleaning, laser treatment) substrate temperature, evaporation rate, Background pressure, residual gas pressure, parameters for reactive evaporation (eg partial pressures of the components), heating / radiation after evaporation, parameters for ion support during evaporation.
• substrate pretreatment eg glow, cleaning, laser treatment
• substrate temperature e.g glow, cleaning, laser treatment
• evaporation rate e.g., evaporation rate
• Background pressure residual gas pressure
• parameters for reactive evaporation eg partial pressures of the components
• heating / radiation after evaporation parameters for ion support during evaporation.
• a pretreatment or aftertreatment of the surface or a pretreatment and aftertreatment of the surface can also be carried out with different process parameters to change the topography of the surface. This is done, for example, by thermal treatment, plasma etching, ion beam treatment, electrochemical etching, electron beam treatment, treatment with a particle beam, treatment with a laser beam, or mechanical treatment by direct contact with a tool.
• the optimal setting of the roughness-determining process parameters of the coating process can be carried out in a simple manner by checking a large number of different settings of process parameters. To do this, proceed as follows:
• a particular surface topography of a substrate is produced for different partial surfaces a, b, c, ... preferably chemically, mechanically and / or thermally.
• a substrate is likewise preferably coated with a layer on different partial surfaces a, b, c,...
• a different set of process parameters is set for each partial surface.
• vapor deposition rates can be selected for each vapor deposition process.
• the partial surfaces can be coated in series or in parallel by suitable devices.
• the entire substrate is preferably covered by a suitable mask device and only the partial surface a which is to be coated in this step is not protected by the mask.
• the mask can be implemented through an opening in a curtain, which is located close to the substrate to be coated.
• the mask can be implemented through a fixed opening in a curtain.
• the substrate then moves in the course of the coating of the individual partial surfaces a, b, c,... Relative to the curtain with the aperture by either moving the substrate and / or the curtain with the aperture.
• the diaphragm is not carried out through a fixed opening in a curtain, but the curtain itself consists of several parts which can move relative to one another and which, depending on their positions, optionally open an opening at different points on the curtain.
• the mask can also be embodied by a photoresist coating on the substrate, the photoresist coating on the partial surface a to be coated in this step being exposed, developed and removed. After coating part surface a and before coating the next Partial surface b is then covered again by a protective layer, which protects it against renewed coating during all subsequent coating processes of the partial surfaces b, c,.
• a different temperature T a , T c , Tb, ..., T n can be selected on each partial surface a, b, c, ..., n and the coating of the entire substrate with all sub-surfaces can be made in parallel.
• the procedure is generally not limited to a vapor deposition process, but can be used for all coating processes listed under E).
• the partial surfaces can lie on a common substrate or on several substrates. With a common substrate, the Partial surfaces can be arranged in any order, for example in a square field or in a rectangular or linear field.
• the size of the partial surfaces is ⁇ 9 cm 2 , preferably ⁇ 4 cm 2 , particularly preferably ⁇ 1 cm 2 and very particularly preferably ⁇ 0.4 cm 2 .
• the total number of different partial surfaces is> 10, preferably> 100 and particularly preferably> 10 4 .
• step E all surfaces generated in step E) are checked for their total light scattering losses.
• the partial surfaces are fastened in a measuring arrangement that is described in ISO / DIS 13696 and e.g. in the publication by A. Kurre and S. Gliech, Proc. SPIE 3141, 57 (1997).
• the partial surface on a partial area is illuminated using a light source at 514 nm or by means of a scanning device over the entire area. During the lighting, the total scattering losses in the rear half-space and the forward half-space are determined in succession with the aid of a collecting element (integrating sphere or Coblentz sphere).
• the measurement of scratch resistance and abrasion resistance makes sense here if the surfaces are exposed to particularly high scratch or abrasion stresses, e.g. for windows in automobiles.
• the abrasion resistance is carried out with the Taber Abraser method according to ISO 3537 at 500 cycles with 500 g per grindstone and CS10F grindstones.
• the increase in turbidity is then tested in accordance with ASTM D 1003.
• the scratch resistance is carried out after the sand trickle test according to DIN 52348.
• the increase in turbidity is then tested in accordance with ASTM D 1003.
• step F2) coating the various surfaces produced in accordance with step E) with a gold layer of 10 to 100 nm and a monolayer of a phobicization aid (decanethiol)
• the coating is preferably carried out with a uniform phobing aid.
• a uniform phobicization aid makes it possible to examine the very different topographies, which is fundamentally suitable for the formation of ultraphobic surfaces with little light scattering.
• the coating is preferably carried out with an alkylthiol, particularly preferably with decanethiol.
• the decanethiol is preferably carried out from a solution of 1 g / l in ethanol for 24 h by adsorption at room temperature.
• An adhesion promoter layer with a thickness of 10 nm to 100 nm, preferably gold, silver or platinum, is applied beforehand. The adhesion promoter is preferably applied by sputtering.
• Coating with a phobicization aid is preferably carried out simultaneously on all partial surfaces.
• step F) Determination of the contact angle of all surfaces generated in step F) and possibly F2)
• the contact angle of the test liquid preferably water
• the roll angle is determined, for example, by tilting the flat substrate until the drop of the test liquid rolls off.
• step F) and optionally F2 Selection of the coated surfaces from step F) and optionally F2) with a contact angle> 140 °, preferably> 150 ° and total light scattering ⁇ 7%, preferably ⁇ 3%, particularly preferably ⁇ 1%
• all the surfaces or the settings of process parameters of the coating process used are selected in which there is a contact angle> 140 °, preferably> 150 ° and total light scattering ⁇ 7%, preferably ⁇ 3%, particularly preferably ⁇ 1%.
• steps E-H can be carried out again for other process parameters of the coating.
• Coating process used to produce larger amounts of the substrate with the surface takes place according to the process parameters selected in step H.
• the invention also relates to a material or building material which has an ultraphobic and transparent surface according to the invention and has been produced using the method according to the invention.
• the phobed surfaces can be used as a pane or as a top layer of transparent panes, in particular glass or plastic panes, in particular for solar cells, vehicles, airplanes or houses.
• Zr0 2 with 1 ⁇ m layer thickness was selected as a single layer.
• An optical refractive index of 2.1 was taken from the literature familiar to the person skilled in the art.
• the total light scatter loss at a wavelength of 514 nm was calculated for various assumed surface topographies with different roughness according to the instructions under step B).
• a topography with a particularly preferred light scatter loss ⁇ 1% was selected.
• the total forward and backward scatter loss calculated was 0.8% for this topography.
• Electron beam evaporation was chosen as the coating process.
• a flat glass substrate with a diameter of 25 mm and a thickness of 5 mm was used in an automated cleaning section (process: alkaline bath, rinsing in water, alkaline bath, rinsing in water, 2x rinsing in de-ionized water with subsequent drying by drain) cleaned.
• the topography-sensitive process parameters substrate temperature and evaporation rate were varied in the evaporation process. Here 10 different substrate temperatures between 300K and 700 K, as well as 10 different evaporation rates between 0.1 nm / sec and 10 nm / sec were chosen.
• the total light scattering was determined at a wavelength of 514 nm in the forward and backward directions.
• the scatter losses determined were less than 1% for each of the samples.
• the samples thus produced were coated with an approximately 50 nm thick gold layer by sputtering. Finally, the samples were coated for 24 hours by immersion in a solution of 1-n-perfluorooctanethiol in ⁇ , ⁇ , ⁇ -trifluorotoluene (1 g / l) at room temperature in a closed vessel for 24 hours, then rinsed with ⁇ , ⁇ , ⁇ -trifluorotoluene and dried.
• the contact angle was then determined for these surfaces.
• One of the surfaces had a static contact angle of 153 ° for water. If the surface is inclined by ⁇ 10 °, a water drop with a volume of 10 ⁇ l rolls off.
• the scattering losses determined for this surface were 0.1% in backward scattering and 0.18% in forward scattering in the backward and forward direction at a wavelength of 514 nm according to ISO / DIS 13696.

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