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EP2970558A1 - Surface coating based on crosslinkable fluoropolymers - Google Patents

Surface coating based on crosslinkable fluoropolymers

Info

Publication number
EP2970558A1
EP2970558A1 EP14705113.0A EP14705113A EP2970558A1 EP 2970558 A1 EP2970558 A1 EP 2970558A1 EP 14705113 A EP14705113 A EP 14705113A EP 2970558 A1 EP2970558 A1 EP 2970558A1
Authority
EP
European Patent Office
Prior art keywords
coating
weight
composition according
composition
substrate
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP14705113.0A
Other languages
German (de)
French (fr)
Inventor
Uwe Numrich
André HENNIG
Stefan Bernhardt
Markus Hallack
Rüdiger JELITTE
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Roehm GmbH Darmstadt
Original Assignee
Evonik Roehm GmbH
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Evonik Roehm GmbH filed Critical Evonik Roehm GmbH
Publication of EP2970558A1 publication Critical patent/EP2970558A1/en
Withdrawn legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/62—Polymers of compounds having carbon-to-carbon double bonds
    • C08G18/6216—Polymers of alpha-beta ethylenically unsaturated carboxylic acids or of derivatives thereof
    • C08G18/622—Polymers of esters of alpha-beta ethylenically unsaturated carboxylic acids
    • C08G18/6225—Polymers of esters of acrylic or methacrylic acid
    • C08G18/6229—Polymers of hydroxy groups containing esters of acrylic or methacrylic acid with aliphatic polyalcohols
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D127/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers
    • C09D127/02—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment
    • C09D127/12—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
    • C09D127/14—Homopolymers or copolymers of vinyl fluoride
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/62—Polymers of compounds having carbon-to-carbon double bonds
    • C08G18/6275—Polymers of halogen containing compounds having carbon-to-carbon double bonds; halogenated polymers of compounds having carbon-to-carbon double bonds
    • C08G18/6279—Polymers of halogen containing compounds having carbon-to-carbon double bonds; halogenated polymers of compounds having carbon-to-carbon double bonds containing fluorine atoms
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
    • C08G18/78—Nitrogen
    • C08G18/79—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates
    • C08G18/791—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups
    • C08G18/792—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups formed by oligomerisation of aliphatic and/or cycloaliphatic isocyanates or isothiocyanates
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D127/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers
    • C09D127/02—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment
    • C09D127/12—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D127/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers
    • C09D127/02—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment
    • C09D127/12—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
    • C09D127/18—Homopolymers or copolymers of tetrafluoroethene
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D129/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Coating compositions based on hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Coating compositions based on derivatives of such polymers
    • C09D129/10—Homopolymers or copolymers of unsaturated ethers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C09D133/04—Homopolymers or copolymers of esters
    • C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C09D133/10—Homopolymers or copolymers of methacrylic acid esters
    • C09D133/12—Homopolymers or copolymers of methyl methacrylate
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/48—Stabilisers against degradation by oxygen, light or heat
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F24—HEATING; RANGES; VENTILATING
    • F24S—SOLAR HEAT COLLECTORS; SOLAR HEAT SYSTEMS
    • F24S23/00—Arrangements for concentrating solar-rays for solar heat collectors
    • F24S23/70—Arrangements for concentrating solar-rays for solar heat collectors with reflectors
    • F24S23/82—Arrangements for concentrating solar-rays for solar heat collectors with reflectors characterised by the material or the construction of the reflector
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10F—INORGANIC SEMICONDUCTOR DEVICES SENSITIVE TO INFRARED RADIATION, LIGHT, ELECTROMAGNETIC RADIATION OF SHORTER WAVELENGTH OR CORPUSCULAR RADIATION
    • H10F19/00—Integrated devices, or assemblies of multiple devices, comprising at least one photovoltaic cell covered by group H10F10/00, e.g. photovoltaic modules
    • H10F19/80—Encapsulations or containers for integrated devices, or assemblies of multiple devices, having photovoltaic cells
    • H10F19/85—Protective back sheets
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10F—INORGANIC SEMICONDUCTOR DEVICES SENSITIVE TO INFRARED RADIATION, LIGHT, ELECTROMAGNETIC RADIATION OF SHORTER WAVELENGTH OR CORPUSCULAR RADIATION
    • H10F77/00—Constructional details of devices covered by this subclass
    • H10F77/40—Optical elements or arrangements
    • H10F77/42—Optical elements or arrangements directly associated or integrated with photovoltaic cells, e.g. light-reflecting means or light-concentrating means
    • H10F77/488—Reflecting light-concentrating means, e.g. parabolic mirrors or concentrators using total internal reflection
    • 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
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/40—Solar thermal energy, e.g. solar towers

Definitions

  • the present invention relates to a technology for finishing outdoor use materials having a high quality abrasion resistant surface finish based on a formulation containing crosslinkable fluoropolymers.
  • the invention also relates to certain embodiments for surface treatment.
  • An abrasive load can not be avoided for materials in outdoor use. Such abrasion is caused in particular by
  • a high-quality surface coating also has to ensure a pronounced substrate protection against UV radiation, without itself a UV radiation-related
  • Known materials for outdoor coatings are, for example, polysiloxanes, such as CRYSTALCOAT TM MP-100 from SDC Techologies Inc., AS 400 - SHP 401 or UVHC3000K, both from Momentive Performance Materials.
  • polysiloxanes such as CRYSTALCOAT TM MP-100 from SDC Techologies Inc., AS 400 - SHP 401 or UVHC3000K, both from Momentive Performance Materials.
  • abrasion-resistant and moisture-resistant films based on fluorocarbon polymers such as PVDF are glued on to improve the surface protection.
  • Both the UV absorption reagent and the corrosion inhibitor are part of the adhesive layer with which the film is connected to the metal surface of the vapor-deposited polyester support film.
  • the adhesive layer may again consist of two different layers, analogously to the above-described (meth) acrylate double coating, in order to separate the corrosion inhibitor and the UV absorption reagent from one another.
  • such a coating does not show sufficient long-term resistance to scratching.
  • WO 98/44015 discloses compositions containing polyisocyanates
  • hydroxy-functional fluoropolymers and hydroxy-functional non-fluorinated polyols which, in addition to low molecular weight diols, are also polyester-polyether or polycarbonate-polyols.
  • polyester-polyether or polycarbonate-polyols are also polyester-polyether or polycarbonate-polyols.
  • EP 2 298 842 discloses coatings, e.g. for the automotive industry that out
  • Polyether-based polyisocyanate prepolymers and non-fluorine-containing polyols Such a composition has very good weathering properties and sufficient abrasion resistance for the automotive industry. The latter is for others
  • this surface refinement is intended to provide particularly good abrasion resistance, scratch resistance, weathering resistance and substrate protection properties in outdoor applications
  • this surface refinement should be transparent and / or colorless designable. Furthermore, this surface refinement should have good chemical resistance, barrier properties, e.g. to water vapor or oxygen and dirt repellent properties.
  • Coating technology should be widely applicable.
  • Composition for coating substrates comprising 5 to 70% by weight, preferably 10 to 55% by weight, of a hydroxy-functional fluoropolymer, 5 to 70% by weight, preferably 10 to 55% by weight of a (meth) acrylate polyol, 5 to 35% by weight, preferably 10 to 30% by weight of a polyisocyanate, 0.001 to 0.2% by weight, preferably up to 1% by weight of a crosslinking catalyst, 0.5 to 20% by weight, preferably triazine-based UV absorber and 0.5 to 10% by weight, preferably HALS based UV stabilizer and 5 to 80% by weight, preferably up to 40% by weight of a solvent.
  • the fluoropolymers and the (meth) acrylate polyols in total from 20 to 75% by weight of the composition. Furthermore, the fluoropolymers and the
  • (Meth) acrylate polyols together have an OH number between 50 and 400 mg KOH / g, preferably between 90 and 250 mg KOH / g.
  • the hydroxy-functional fluoropolymer is a copolymer of tetrafluoroethylene (TFE) and / or chlorotrifluoroethylene (CTFE) on the one hand and vinyl esters, vinyl ethers and / or alpha-olefins on the other hand.
  • it is an alternating copolymer of CTFE or TFE, on the one hand, and the other comonomers, on the other hand.
  • the hydroxy functionality is copolymerized with
  • hydroxy-functional vinyl ethers and / or alpha-olefins are sold by the company Asahi Glass under the product name Lumiflon ® , by the company Solvay Solexis under the name FluoroLin ® or by the company Daikin under the product name Zeffle ® . Since both the fluoropolymers used and poly (meth) acrylates are completely amorphous, the corresponding formulations and coatings have good optical properties and high transparency. Furthermore, both fluoropolymers and poly (meth) acrylates have very good weathering resistance over a very long period of time, even under extreme conditions. Thus, the coatings of the invention are extremely UV-resistant and also have very good barrier properties against atmospheric oxygen and water, for example in the form of humidity.
  • Substrate protection properties of the coating the addition of 0.5 to 20% by weight, preferably up to 15% by weight, preferably triazine-based UV absorber and / or 0.5 to 10% by weight, preferably up to 7.5% by weight, preferably HALS-based UV - Stabilizers necessary.
  • composition can additionally 5 to 40 wt% of a
  • hydroxy-functional silicone resin included.
  • This silicone resin has an OH number between 50 and 300 mg KOH / g, preferably between 90 and 200 mg KOH / g.
  • the heat resistance of the composition is further increased.
  • the solids content of the composition as a whole can be increased.
  • An example of such hydroxy-functional silicone resins is XIAMETER ® RSN-0255 Dow
  • the poly (meth) acrylates used consist of at least 60% by weight
  • Methacrylate-based monomer units is preferably suspension or solution polymers which are particularly preferably composed of at least 70% by weight of methyl methacrylate (MMA) and / or butyl methacrylate (BuMA).
  • the hydroxy functionalization can by copolymerization of suitable monomers, such as hydroxyethyl (meth) acrylate or Hydroxypropyl (meth) acrylate and / or by using hydroxy-functional regulators, such as mercaptoethanol, take place.
  • suitable monomers such as hydroxyethyl (meth) acrylate or Hydroxypropyl (meth) acrylate and / or by using hydroxy-functional regulators, such as mercaptoethanol, take place.
  • the molecular weight is 10,000 to 300,000 g / mol
  • the glass transition temperature is in the range between 10 and 130 ° C.
  • the solvents are in principle all solvents or
  • Solvent mixtures in question which are suitable for the other components used in the invention. These may be in particular ketones such as acetone or methyl ethyl ketone, esters such as ethyl, propyl or butyl acetate, aromatics such as toluene or xylene, or ethers such as diethyl ether or ethyl-ethoxy-propionate.
  • ketones such as acetone or methyl ethyl ketone
  • esters such as ethyl, propyl or butyl acetate
  • aromatics such as toluene or xylene
  • ethers such as diethyl ether or ethyl-ethoxy-propionate.
  • the solvent may also be water.
  • Composition according to the invention in particular form a stable dispersion in water and can be applied environmentally friendly and easy with water as a solvent, a corresponding coating.
  • the polyisocyanates in the composition are usually isophorone diisocyanate (IPDI), hexamethylene diisocyanate (HDI),
  • H12MDI Diisocyanatodicyclohexylmethane
  • MPDI 2-methylpentane diisocyanate
  • TMDI 2,2,4-trimethylhexamethylene diisocyanate / 2,4,4-trimethylhexamethylene diisocyanate
  • NBDI norbornane diisocyanate
  • the crosslinking catalyst used is normally dibutyltin dilaurate (DBTDL), zinc octoate, bismuth neodecanoate, and / or tertiary amines, preferably 1, 4-diazabicyclo [2.2.2.] Octane.
  • DBTDL dibutyltin dilaurate
  • zinc octoate zinc octoate
  • bismuth neodecanoate bismuth neodecanoate
  • / or tertiary amines preferably 1, 4-diazabicyclo [2.2.2.] Octane.
  • An example of a suitable such crosslinking is Desmodur ® BL 3175 from Bayer.
  • the crosslinking catalyst used is normally dibutyltin dilaurate (DBTDL), zinc octoate, bismuth neodecanoate, and / or tertiary amines, preferably 1, 4-diazabicy
  • composition may additionally contain up to 20% by weight of a silane-functional alkyl isocyanate or a glycidyl-functional alkylsilane.
  • silane-functional alkyl isocyanate is trimethoxy-propyl-silyl-isocyanate, which is sold, for example, by Evonik Ind. Under the name Vestanat EP-M 95.
  • a preferred example of a glycidyl-functional alkylsilane is 3-
  • Glycidyloxypropyltrimethoxysilane which is available, for example, from Evonik Ind. Under the name Dynasylan GLYMO.
  • inorganic nanoparticles in particular of silicon oxides, can additionally be included in the composition for the additional improvement of scratch and abrasion resistance.
  • up to 40% by weight, preferably up to 30% by weight, of these nanoparticles can be added. It is particularly preferred that these nanoparticles have no refractive properties and that
  • Polymer matrix is not clouded.
  • a substrate which is coated with a composition according to the invention is also part of the present invention.
  • the coating after drying and crosslinking preferably has a thickness between 0.5 and 200 ⁇ m, preferably between 2 ⁇ m and 150 ⁇ m, and particularly preferably between 5 ⁇ m and 50 ⁇ m.
  • the preferably transparent coatings according to the invention are particularly color-neutral and do not become cloudy under the influence of moisture.
  • the coating also shows excellent weather resistance and a very good
  • the material according to the invention can also be used over a very long period of at least 15 years, preferably even at least 20 years, more preferably at least 25 years, in places with particularly intense solar radiation, e.g. used in outdoor applications in the southeastern United States or the Sahara.
  • the coatings of the invention have very good properties, especially under mechanical stress on the surface. This extends the life of the substrates even in regions with regular sandstorms or strong
  • coating according to the invention is particular
  • Fluorine-based coatings also have a particularly good barrier to water. In addition, fluorine-based coatings have a particularly good
  • This process step of the coating can be carried out in a coating system on a prefabricated uncoated composite form body.
  • the coating may also be in-line, directly after the preparation of the substrate, e.g. be carried out in the form of a composite body.
  • the substrates are produced as a multilayer film by means of lamination.
  • the coating system described above is placed inline behind the lamination and there is the coating of the freshly prepared substrate.
  • the coating is done directly on the substrate.
  • the coating is in the form of a coating material equipped with the coating formulation of the invention,
  • the adherent coating of the coating formulation according to the invention initially takes place on a corresponding film substrate material.
  • the application of this surface coating film to the respective final substrate material takes place
  • the underside of the surface coating film is either coated with a self-adhesive adhesive formulation, with a hotmelt or with equipped with an adhesive layer.
  • This modification of the bottom binds either "thermoplastic” or “reactive” to the final substrate material in a temperature and pressure assisted application.
  • coating substrates applicable on site without handling solvents or high temperatures.
  • a corresponding film or paper carrier material is equipped in a first coating step with a release layer, which allows a thermal transfer of, applied in a second coating step, inventive coating formulation to the respective substrate material.
  • an adhesive layer can be applied, which ensures proper adhesion of the
  • Thermal transfer layer structure on the respective substrate material guaranteed.
  • the coating according to the invention can then optionally be provided with one or more further functional layers.
  • This may be, for example, a scratch-resistant coating, a conductive layer, a
  • Antisoiling coating and / or act to a reflection-enhancing layer or other optically functional layers can be applied, for example, by means of Physical Vapor Deposition (PVD) or Chemical Vapor Deposition (CVD).
  • PVD Physical Vapor Deposition
  • CVD Chemical Vapor Deposition
  • An additional scratch-resistant coating can optionally be applied to further improve the scratch resistance. This is the good quality of the
  • composite body according to the invention usually not necessary.
  • at Scratch-resistant coatings can be, for example, silicon oxide layers which are applied directly by means of PVD or CVD.
  • the surface of the composite molded articles may be provided with a dirt-repelling or so-called antisoiling coating in order to facilitate cleaning.
  • Coating can be applied by means of PVD or CVD.
  • Coating additionally a further, comparatively thin, extremely abrasion-resistant layer is a particularly hard thermoset layer having a thickness of preferably less than 5 ⁇ m, more preferably between 0.5 and 2.0 ⁇ m.
  • this layer can be made from a polysilazane formulation.
  • thermosets so-called thermosets, e.g. for exterior use as High Pressure Laminate panels for facade design.
  • thermosets e.g. for exterior use as High Pressure Laminate panels for facade design.
  • decor laminates which are used, for example, for the surface design of window profiles, bistro furniture or wall coverings.
  • OLEDs organic light-emitting diodes
  • OLEDs are scrollable displays. In particular, these are subject to great mechanical Stresses that lead to a longer life of the displays with a coating according to the invention.
  • Exterior window equipment plays a major role in thermal insulation, especially at high outside temperatures. This is a special weather resistance of great importance. Furthermore, the high transparency of the coating is particularly important in this application.
  • Anti-corrosion coatings (so-called heavy-duty coatings)
  • the upper layer (topcoat) of this multilayer coating is designed with the coating technology according to the invention, whereby a significantly prolonged corrosion protection with in particular improved long-term adhesion of the coating over the prior art can be achieved.
  • Photovoltaic backsheets backside coating of photovoltaic modules. Here is especially the protection against moisture, UV radiation and others
  • test tip is drawn in a straight line over the sample body with different defined compression springs at different forces.
  • the position of the slider shows on a scale the force (N) and thus directly to the test value corresponding to the hardness.
  • the lowest force which has introduced a visible scratch into the material is used as the result.
  • the scratch depth can be determined with the tactile measuring device.
  • the following preliminary stage exemplifies a substrate which can be used as a mirror for the concentration of solar radiation.
  • a 0.15 mm thick composite foil consisting of 0.125 mm PMMA Plexiglas 7H, which contains 2% CGX 006 and 0.6% Chimasorb 1 19 for the purpose of UV addition, as well as 0,025 mm polycarbonate Makroion 2607, is manufactured by adapter-coextrusion.
  • the application of the reflective coating by means of a plasma-assisted sputtering process to the polycarbonate side of the composite film consisting of, viewed from the polycarbonate film in the following order, 0.5 nm ZAO (zinc-aluminum oxide), 100 nm Ag and 50 nm Cu.
  • Lumiflon LF-9716 28.9% by weight of Lumiflon LF-9716 are initially charged in a solvent mixture of 12.4% by weight of ethyl ethoxypropionate and 37.3% by weight of butyl acetate and successively stirred with 0.0013% by weight DBTDL (dibutyltin dilaureate;
  • Crosslinking catalyst 3.4% by weight of Tinuvin 400 (UV absorber) and 1.1% by weight of Tinuvin 123 (HALS compound) until a homogeneous, clear mixture is obtained. Subsequently, 16.9% by weight of Desmodur N 3300 (polyisocyanate, crosslinker) are stirred in for 10 minutes.
  • the paint is applied by means of 40 ⁇ spiral blade under normal conditions on the PMMA side of the substrate from precursor 1. Drying and precuring take place 2
  • the coating according to the invention according to Example shows after the Ritz hardness measurement carried out a significantly lower surface damage than the

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Abstract

The present invention relates to a technology for the treatment of materials for exposed outdoor use with a high-grade, abrasion-resistant surface coating based on a formulation comprising crosslinkable fluoropolymers. The invention further relates to particular embodiments for the surface coating.

Description

Oberflächenvergütung auf Basis von vernetzbaren Fluorpolymeren  Surface coating based on crosslinkable fluoropolymers

Gebiet der Erfindung Field of the invention

Die vorliegende Erfindung betrifft eine Technologie zur Ausrüstung von Materialien für den beanspruchenden Außeneinsatz mit einer hochwertigen abrasionsfesten Oberflächenvergütung auf Basis einer Formulierung, enthaltend vernetzbare Fluorpolymere. Die Erfindung betrifft darüber hinaus bestimmte Ausführungsformen zur Oberflächenvergütung. The present invention relates to a technology for finishing outdoor use materials having a high quality abrasion resistant surface finish based on a formulation containing crosslinkable fluoropolymers. The invention also relates to certain embodiments for surface treatment.

Eine abrasive Beanspruchung ist bei Materialien im Außeneinsatz nicht zu vermeiden. Verursacht wird eine solche Abrasion insbesondere durch An abrasive load can not be avoided for materials in outdoor use. Such abrasion is caused in particular by

Reinigungsprozesse oder durch mit dem Wind getragene Medien, wie Sand oder Staub. Ungeschützte bzw. unzureichend oberflächenvergütete Materialien verlieren hierdurch ihre Wertigkeit bzw. Dauerhaftigkeit. Thermoplastische polymere Cleaning processes or by wind-borne media, such as sand or dust. Unprotected or insufficiently surface-tempered materials lose their value or durability. Thermoplastic polymers

Werkstoffe weisen eine nur geringe Abrasionsfestigkeit auf, und sind Materials have a low abrasion resistance, and are

dementsprechend zur Oberflächenvergütung von Materialien im beanspruchenden Außeneinsatz nicht bzw. nur extrem eingeschränkt geeignet. Accordingly, not suitable for surface treatment of materials in the demanding outdoor use or only extremely limited.

Materialien im Außeneinsatz unterliegen darüber hinaus einer ausgeprägten In addition, outdoor materials are subject to a pronounced

Belastung durch den UV-Anteil der Solarstrahlung. Somit hat eine hochwertige Oberflächenvergütung ebenfalls einen ausgeprägten Substrat-Schutz gegen UV- Strahlung zu gewährleisten, ohne selber einem UV-strahlungsbedingten Exposure to the UV component of the solar radiation. Thus, a high-quality surface coating also has to ensure a pronounced substrate protection against UV radiation, without itself a UV radiation-related

Eigenschädigungspotential zu unterliegen. Subject to own damage potential.

Flexible Dünnschicht-Solarmodule sowie flexible OLED- bzw. Displaymaterialien beispielsweise unterliegen im Außeneinsatz ferner einem deutlichen Flexible thin-film solar modules and flexible OLED or display materials, for example, are also subject to a clear outdoor use

Korrosionspotential wesentlicher Funktionsschichten. Eine leistungsfähige Corrosion potential of essential functional layers. A powerful

Oberflächenvergütung hat in diesen Anwendungssegmenten somit ebenfalls einen entsprechenden Korrosionsschutz sowie Barriere-Eigenschaften gegen Surface treatment therefore also has corresponding corrosion protection and barrier properties in these application segments

Feuchtemigration zu leisten. Stand der Technik Moisture migration. State of the art

Bekannte Materialien für Beschichtungen im Außeneinsatz sind beispielsweise Polysiloxane, wie CRYSTALCOAT™ MP-100 der Firma SDC Techologies Inc., AS 400 - SHP 401 oder UVHC3000K, beide von der Firma Momentive Performance Materials. In einer Langzeitanwendung über einen Zeitraum von mindestens 20 Jahren in einem Außenbereich, wie sie insbesondere für Solarreflektoren oder Photovoltaikzellen benötigt wird, zeigen solche Materialien jedoch keine Known materials for outdoor coatings are, for example, polysiloxanes, such as CRYSTALCOAT ™ MP-100 from SDC Techologies Inc., AS 400 - SHP 401 or UVHC3000K, both from Momentive Performance Materials. In a long-term application over a period of at least 20 years in an outdoor area, as required in particular for solar reflectors or photovoltaic cells, however, such materials do not show any

ausreichende Abriebfestigkeit. sufficient abrasion resistance.

In US 5,1 18,540 werden zur Verbesserung des Oberflächenschutzes abriebsfeste und feuchtigkeitsbeständige Folie auf Basis von Fluorkohlenstoff-Polymeren, wie PVDF, aufgeklebt. Sowohl das UV-Absorptionsreagenz als auch der Korrosions- Inhibitor sind Bestandteil der Klebschicht, mit der die Folie mit der Metalloberfläche der bedampften Polyesterträgerfolie verbunden ist. Dabei kann die Klebschicht wiederum analog zu der oben ausgeführten (Meth)acrylat Doppelbeschichtung aus zwei verschiedenen Schichten bestehen, um Korrosions-Inhibitor und UV- Absorptionsreagenz voneinander zu trennen. Eine solche Beschichtung zeigt jedoch keine ausreichende Langzeitbeständigkeit gegenüber Verkratzen. In US Pat. No. 5,118,540, abrasion-resistant and moisture-resistant films based on fluorocarbon polymers, such as PVDF, are glued on to improve the surface protection. Both the UV absorption reagent and the corrosion inhibitor are part of the adhesive layer with which the film is connected to the metal surface of the vapor-deposited polyester support film. The adhesive layer may again consist of two different layers, analogously to the above-described (meth) acrylate double coating, in order to separate the corrosion inhibitor and the UV absorption reagent from one another. However, such a coating does not show sufficient long-term resistance to scratching.

Eine weitere Lösung des Standes der Technik sind anorganische Another solution of the prior art are inorganic

Kratzfestbesch ichtungen. In EP 1 629 053 wird eine solche Beschichtung aus Siliziumdioxid- oder Aluminiumoxidteilchen mit Durchmessern kleiner 1 μιτι zur Beschichtung von Folienlaminaten, die als wetterfeste Folien Verwendung finden, offenbart. Solche anorganischen Beschichtungen haben jedoch den Nachteil, dass sie unter Witterungsbedingungen nur relativ kurz, d.h. maximal wenige Jahre, haltbar sind. Durch Sandverwehungen bzw. gar Sandstürme oder andere klimatische Bedingungen in sehr heißer und vor allem trockener Umgebung kommt es zum Abrieb solcher Beschichtungen. EP 2 524 802 offenbart Beschichtungen zum Witterungsschutz von Solaranlagen aus mit Isocyanaten vernetzten hydroxyfunktionellen Fluorpolymeren. Diese Scratch-resistant coatings. In EP 1 629 053, such a coating of silicon dioxide or aluminum oxide particles with diameters smaller than 1 μm is disclosed for coating film laminates which are used as weatherproof films. However, such inorganic coatings have the disadvantage that under weather conditions they are only relatively short, ie a maximum of a few years, durable. Sand drifts or even sandstorms or other climatic conditions in very hot and above all dry surroundings cause the abrasion of such coatings. EP 2 524 802 discloses coatings for the weather protection of solar installations of isocyanate-crosslinked hydroxy-functional fluoropolymers. These

Beschichtungen haben bereits eine sehr gute Abrasionsfestigkeit und Coatings already have a very good abrasion resistance and

Witterungsstabilität. Problematisch ist jedoch die eingeschränkte Verwendbarkeit, da diese Beschichtungen auf vielen Substraten eine nur begrenzte Haftung zeigen. Ein ähnliches System für die gleiche Anwendung findet sich in WO 201 1/105515. Weathering resistance. The problem, however, is the limited usability, since these coatings show only limited adhesion on many substrates. A similar system for the same application can be found in WO 201 1/105515.

WO 98/44015 offenbart Zusammensetzungen enthaltend Polyisocyanate, WO 98/44015 discloses compositions containing polyisocyanates,

hydroxyfunktionelle Fluorpolymere und hydroxyfunktionelle nicht-fluorierte Polyole, bei denen es neben niedermolekularen Diolen auch um Polyester- Polyether- oder Polycarbonat-Polyole handelt. Solche Zusammensetzungen sind jedoch hydroxy-functional fluoropolymers and hydroxy-functional non-fluorinated polyols which, in addition to low molecular weight diols, are also polyester-polyether or polycarbonate-polyols. However, such compositions are

insbesondere in Bezug auf die Witterungsbeständigkeit verbesserungsfähig. especially with regard to weather resistance.

EP 2 298 842 offenbart Beschichtungen, z.B. für den Automobilbau, die aus EP 2 298 842 discloses coatings, e.g. for the automotive industry that out

Polyisocyanat-Prepolymeren auf Polyetherbasis und nicht-fluorhaltigen Polyolen. Eine solche Zusammensetzung hat sehr gute Witterungseigenschaften und für den Automobilbau eine ausreichende Abrasionsfestigkeit. Letztere ist für andere Polyether-based polyisocyanate prepolymers and non-fluorine-containing polyols. Such a composition has very good weathering properties and sufficient abrasion resistance for the automotive industry. The latter is for others

Anwendungen unter mechanischer Belastung im Außenbereich jedoch nicht ausreichend. Applications under mechanical stress in the outdoor area but not sufficient.

Aufgabe task

Es bestand die Aufgabe, eine neuartige Oberflächenveredelung für Kunststoff- oder Metalloberflächen zur Verfügung zu stellen. Mit dieser Oberflächenveredelung soll bei Außenanwendungen gleichzeitig eine besonders gute Abrasionsbeständigkeit, Kratzfestigkeit, Witterungsbeständigkeit und Substratschutzeigenschaften It was the task of providing a novel surface refinement for plastic or metal surfaces. At the same time, this surface refinement is intended to provide particularly good abrasion resistance, scratch resistance, weathering resistance and substrate protection properties in outdoor applications

gewährleistet werden. be guaranteed.

Darüber hinaus soll diese Oberflächenveredelung transparent und/oder farblos gestaltbar sein. Weiterhin soll diese Oberflächenveredelung eine gute chemische Beständigkeit, Barriereeigenschaften, z.B. gegenüber Wasserdampf oder Sauerstoff und Schmutz abweisende Eigenschaften aufweisen. In addition, this surface refinement should be transparent and / or colorless designable. Furthermore, this surface refinement should have good chemical resistance, barrier properties, e.g. to water vapor or oxygen and dirt repellent properties.

Weiterhin bestand die Aufgabe, dass die Oberflächenveredlung auch in Bezug auf die zu beschichtenden Substrate wie auch in Bezug auf die anzuwendende Furthermore, the object was that the surface finishing also with respect to the substrates to be coated as well as with respect to the applicable

Beschichtungstechnologie breit anwendbar sein soll. Coating technology should be widely applicable.

Es bestand darüber hinaus die Aufgabe, eine Oberflächenveredelung für There was also the task of a surface finishing for

Außenanwendungen zur Verfügung zu stellen, die einfach und kosteneffizient herzustellen und aufzubringen ist. To provide outdoor applications that are simple and cost-effective to manufacture and apply.

Weitere nicht explizit genannte Aufgaben können sich aus der Beschreibung, den Ansprüchen oder auch den Beispielen dieser Anmeldung ergeben. Other tasks not explicitly mentioned may arise from the description, the claims or the examples of this application.

Lösung solution

Vor dem Hintergrund des Standes der Technik und den dort beschriebenen für Langzeitanwendungen nur mangelhaften technischen Lösungen, gelingt es in der vorliegenden Erfindung auf eine für den Fachmann nicht ohne weiteres absehbare Weise, eine Beschichtung mit über einen langen Zeitraum verbesserter Against the background of the state of the art and the technical solutions described there for long-term applications described therein, it is possible in the present invention, in a manner not readily foreseen by the person skilled in the art, to improve a coating over a long period of time

Oberflächenqualität bereitzustellen. Dies gelingt mit einer neuartigen To provide surface quality. This succeeds with a novel

Zusammensetzung zur Beschichtung von Substraten, die 5 bis 70 Gew%, bevorzugt 10 bis 55 Gew% eines hydroxyfunktionellen Fluorpolymers, 5 bis 70 Gew%%, bevorzugt 10 bis 55 Gew% eines (Meth)acrylat-Polyols, 5 bis 35 Gew%, bevorzugt 10 bis 30 Gew% eines Polyiscocyanats, 0,001 bis 0,2 Gew%, bevorzugt bis 1 Gew% eines Vernetzungskatalysators, 0,5 bis 20 Gew% vorzugsweise Triazin-basierender UV-Absorber und 0,5 bis 10 Gew% vorzugsweise HALS-basierender UV-Stabilisator und 5 bis 80 Gew%, bevorzugt bis 40 Gew% eines Lösungsmittels enthält. Dabei machen die Fluorpolymere und die (Meth)acrylat-Polyole in Summe 20 bis 75 Gew% der Zusammensetzung aus. Weiterhin weisen die Fluorpolymere und die Composition for coating substrates comprising 5 to 70% by weight, preferably 10 to 55% by weight, of a hydroxy-functional fluoropolymer, 5 to 70% by weight, preferably 10 to 55% by weight of a (meth) acrylate polyol, 5 to 35% by weight, preferably 10 to 30% by weight of a polyisocyanate, 0.001 to 0.2% by weight, preferably up to 1% by weight of a crosslinking catalyst, 0.5 to 20% by weight, preferably triazine-based UV absorber and 0.5 to 10% by weight, preferably HALS based UV stabilizer and 5 to 80% by weight, preferably up to 40% by weight of a solvent. In this case, the fluoropolymers and the (meth) acrylate polyols in total from 20 to 75% by weight of the composition. Furthermore, the fluoropolymers and the

(Meth)acrylat-Polyole zusammen eine OH-Zahl zwischen 50 und 400 mg KOH / g, bevorzugt zwischen 90 und 250 mg KOH / g auf. Insbesondere bevorzugt handelt es sich bei dem hydroxyfunktionellen Fluorpolymer um ein Copolymer von Tetrafluorethylen (TFE) und/oder Chlortrifluorethylen (CTFE) einerseits und Vinylestern, Vinylethern und/oder alpha-Olefinen andererseits. (Meth) acrylate polyols together have an OH number between 50 and 400 mg KOH / g, preferably between 90 and 250 mg KOH / g. Most preferably, the hydroxy-functional fluoropolymer is a copolymer of tetrafluoroethylene (TFE) and / or chlorotrifluoroethylene (CTFE) on the one hand and vinyl esters, vinyl ethers and / or alpha-olefins on the other hand.

Besonders bevorzugt handelt es sich um ein alternierendes Copolymer von CTFE oder TFE einerseits und den anderen Comonomeren andererseits. In solchen Polymeren wird die Hydroxyfunktionalität unter Copolymerisation von Most preferably, it is an alternating copolymer of CTFE or TFE, on the one hand, and the other comonomers, on the other hand. In such polymers, the hydroxy functionality is copolymerized with

hydroxyfunktionellen Vinylethern und/oder alpha-Olefinen erhalten. Als Beispiel für kommerziell erhältliche hydroxyfunktionelle Fluorpolymere werden von der Firma Asahi Glass unter dem Produktnamen Lumiflon®, von der Firma Solvay Solexis unter dem Namen FluoroLin® oder von der Firma Daikin unter dem Produktnamen Zeffle® vertrieben. Da sowohl die eingesetzten Fluorpolymere sowie Poly(meth)acrylate vollständig amorph sind, haben die korrespondierenden Formulierungen und Beschichtungen gute optische Eigenschaften und eine hohe Transparenz. Weiterhin besitzen sowohl Fluorpolymere als auch Poly(meth)acrylate eine sehr gute Witterungsbeständigkeit über eine sehr lange Zeitspanne, auch unter extremen Bedingungen. So sind die erfindungsgemäßen Beschichtungen äußerst UV-beständig und haben zudem sehr gute Barriereeigenschaften gegenüber Luftsauerstoff und Wasser, z.B. in Form von Luftfeuchtigkeit. hydroxy-functional vinyl ethers and / or alpha-olefins. As an example of commercially available hydroxy-functional fluoropolymers are sold by the company Asahi Glass under the product name Lumiflon ® , by the company Solvay Solexis under the name FluoroLin ® or by the company Daikin under the product name Zeffle ® . Since both the fluoropolymers used and poly (meth) acrylates are completely amorphous, the corresponding formulations and coatings have good optical properties and high transparency. Furthermore, both fluoropolymers and poly (meth) acrylates have very good weathering resistance over a very long period of time, even under extreme conditions. Thus, the coatings of the invention are extremely UV-resistant and also have very good barrier properties against atmospheric oxygen and water, for example in the form of humidity.

Des weiteren ist zur Einstellung der geforderten Witterungsstabilität sowie Furthermore, to set the required weathering stability as well

Substratschutzeigenschaften der Beschichtung die Zugabe von 0,5 bis 20 Gew%, bevorzugt bis15 Gew%, vorzugsweise Triazin-basierender UV-Absorber und/oder 0,5 bis 10 Gew%, bevorzugt bis 7,5 Gew%, vorzugsweise HALS-basierender UV- Stabilisatoren notwendig. Substrate protection properties of the coating, the addition of 0.5 to 20% by weight, preferably up to 15% by weight, preferably triazine-based UV absorber and / or 0.5 to 10% by weight, preferably up to 7.5% by weight, preferably HALS-based UV - Stabilizers necessary.

Weiterhin kann die Zusammensetzung zusätzlich 5 bis 40 Gew% eines Furthermore, the composition can additionally 5 to 40 wt% of a

hydroxyfunktionellen Silikonharzes enthalten. Dieses Silikonharz weist eine OH-Zahl zwischen 50 und 300 mg KOH / g, bevorzugt zwischen 90 und 200 mg KOH / g auf. Mit solchen Silikonharzen wird die Wärmebeständigkeit der Zusammensetzung zusätzlich erhöht. Weiterhin lässt sich bei einem höheren Anteil dieser Komponente bei gleichzeitig etwas geringerem Anteil der anderen Polymerkomponenten der Feststoffgehalt der Zusammensetzung insgesamt erhöhen. Ein Beispiel für solche hydroxyfunktionellen Silikonharze ist XIAMETER® RSN-0255 der Firma Dow hydroxy-functional silicone resin included. This silicone resin has an OH number between 50 and 300 mg KOH / g, preferably between 90 and 200 mg KOH / g. With such silicone resins, the heat resistance of the composition is further increased. Furthermore, with a higher proportion of this component and at the same time a slightly lower proportion of the other polymer components, the solids content of the composition as a whole can be increased. An example of such hydroxy-functional silicone resins is XIAMETER ® RSN-0255 Dow

Corning. Corning.

Die eingesetzten Poly(meth)acrylate bestehen zu mindestens 60 Gew% aus The poly (meth) acrylates used consist of at least 60% by weight

Methacrylat-basierenden Monomereinheiten. Insbesondere handelt es sich bevorzugt um Suspensions- oder Lösungspolymerisate, die insbesondere bevorzugt zu mindestens 70 Gew% aus Methylmethacrylat (MMA) und/oder Butylmethacrylat (BuMA) zusammengesetzt sind. Die Hydroxyfunktionalisierung kann dabei durch Copolymerisation geeigneter Monomere, wie z.B. Hydroxyethyl(meth)acrylat oder Hydroxypropyl(meth)acrylat und/oder durch Verwendung von hydroxyfunktionellen Reglern, wie z.B. Mercaptoethanol, erfolgen. Das Molekulargewicht beträgt 10 000 bis 300 000 g/mol, die Glasübergangstemperatur liegt im Bereich zwischen 10 und 130 °C. Methacrylate-based monomer units. In particular, it is preferably suspension or solution polymers which are particularly preferably composed of at least 70% by weight of methyl methacrylate (MMA) and / or butyl methacrylate (BuMA). The hydroxy functionalization can by copolymerization of suitable monomers, such as hydroxyethyl (meth) acrylate or Hydroxypropyl (meth) acrylate and / or by using hydroxy-functional regulators, such as mercaptoethanol, take place. The molecular weight is 10,000 to 300,000 g / mol, the glass transition temperature is in the range between 10 and 130 ° C.

Als Lösungsmittel kommen im Prinzip alle Lösungsmittel bzw. The solvents are in principle all solvents or

Lösungsmittelgemische in Frage, die für die anderen erfindungsgemäß eingesetzten Komponenten geeignet sind. Dies können insbesondere Ketone wie Aceton oder Methylethylketon, Ester wie Ethyl-, Propyl- oder Butylacetat, Aromaten wie Toluol oder Xylol sein oder Ether wie Diethylether oder Ethyl-ethoxy-propionat sein. Solvent mixtures in question, which are suitable for the other components used in the invention. These may be in particular ketones such as acetone or methyl ethyl ketone, esters such as ethyl, propyl or butyl acetate, aromatics such as toluene or xylene, or ethers such as diethyl ether or ethyl-ethoxy-propionate.

Insbesondere kann es sich bei dem Lösungsmittel jedoch auch um Wasser handeln. Überraschend wurde gefunden, dass die anderen Bestandteile der  In particular, however, the solvent may also be water. Surprisingly, it was found that the other components of the

erfindungsgemäßen Zusammensetzung insbesondere auch in Wasser eine stabile Dispersion bilden und mit Wasser als Lösungsmittel umweltschonend und einfach ein entsprechender Lack appliziert werden kann. Composition according to the invention in particular form a stable dispersion in water and can be applied environmentally friendly and easy with water as a solvent, a corresponding coating.

Bei dem Polyisocyanate in der Zusammensetzung handelt es sich in der Regel um Isophorondiisocyanat (IPDI), Hexamethylendiisocyanat (HDI), The polyisocyanates in the composition are usually isophorone diisocyanate (IPDI), hexamethylene diisocyanate (HDI),

Diisocyanatodicyclohexylmethan (H12MDI), 2-Methylpentandiisocyanat (MPDI), 2,2,4- Trimethylhexamethylendiisocyanat/2,4,4-Trimethylhexamethylendiisocyanat (TMDI) und/oder Norbornandiisocyanat (NBDI). Diisocyanatodicyclohexylmethane (H12MDI), 2-methylpentane diisocyanate (MPDI), 2,2,4-trimethylhexamethylene diisocyanate / 2,4,4-trimethylhexamethylene diisocyanate (TMDI) and / or norbornane diisocyanate (NBDI).

Als Vernetzungskatalysator werden normalerweise Dibutylzinndilaurat (DBTDL), Zinkoctoat, Bismuthneodecanoat, und/oder tertiäre Amine, bevorzugt um 1 ,4- Diazabicylco[2.2.2.]octan, verwendet. Ein Beispiel für einen geeigneten solchen Vernetzer ist Desmodur® BL 3175 der Firma Bayer. In der Regel wird die The crosslinking catalyst used is normally dibutyltin dilaurate (DBTDL), zinc octoate, bismuth neodecanoate, and / or tertiary amines, preferably 1, 4-diazabicyclo [2.2.2.] Octane. An example of a suitable such crosslinking is Desmodur ® BL 3175 from Bayer. In general, the

Vernetzermenge dergestalt eingestellt, dass das Verhältnis zwischen OH-Gruppen und NCO-Gruppen zwischen 0,5 bis 1 ,5, bevorzugt zwischen 0,8 und 1 ,2 und besonders bevorzugt zwischen 0,9 und 1 ,1 liegt. Diese beispielhaften Zahlen beziehen sich vor allem auf Systeme aus HDI-Kondensaten und DBTDL. Bei anderen Systemen, deren Komponenten in Bezug auf die jeweiligen Molekulargewichte oder Zahl der Funktionalitäten deutlicher abweichen, sind die angegebenen Grenzbereiche entsprechend anzupassen. Set crosslinker such that the ratio between OH groups and NCO groups between 0.5 to 1, 5, preferably between 0.8 and 1, 2 and more preferably between 0.9 and 1, 1. These exemplary figures relate primarily to systems of HDI condensates and DBTDL. For other systems, their components in relation to the respective ones Molecular weights or number of functionalities differ significantly, the specified limits are adjusted accordingly.

Weiterhin kann die Zusammensetzung zusätzlich noch bis zu 20 Gew% eines silanfunktionellen Alkylisocyanats oder eines glycidylfunktionellen Alkylsilans enthalten. Diese Komponenten tragen zusätzlich zu den Haftungseigenschaften gegenüber dem zu beschichtenden Substrat bei. Ein bevorzugtes silanfunktionelles Alkylisocyanat ist Trimethoxy-propyl-silyl-isocyanat, welches beispielsweise von der Firma Evonik Ind. unter dem Namen Vestanat EP-M 95 vertrieben wird. Ein bevorzugtes Beispiel für ein glycidylfunktionelles Alkylsilan ist 3-Furthermore, the composition may additionally contain up to 20% by weight of a silane-functional alkyl isocyanate or a glycidyl-functional alkylsilane. These components also contribute to the adhesion properties to the substrate to be coated. A preferred silane-functional alkyl isocyanate is trimethoxy-propyl-silyl-isocyanate, which is sold, for example, by Evonik Ind. Under the name Vestanat EP-M 95. A preferred example of a glycidyl-functional alkylsilane is 3-

Glycidyloxypropyltrimethoxysilan, welches beispielsweise von der Firma Evonik Ind. unter dem Namen Dynasylan GLYMO erhältlich ist. Glycidyloxypropyltrimethoxysilane, which is available, for example, from Evonik Ind. Under the name Dynasylan GLYMO.

Darüber hinaus können insbesondere auch anorganische Nanopartikel, vor allem aus Siliziumoxiden, zur zusätzlichen Verbesserung der Kratz- und Abriebfestigkeit in der Zusammensetzung enthalten sein. Dabei können bis zu 40 Gew%, bevorzugt bis zu 30 Gew% dieser Nanopartikel zugesetzt sein. Insbesondere bevorzugt ist dabei, dass diese Nanopartikel keine lichtbrechenden Eigenschaften haben und die In addition, inorganic nanoparticles, in particular of silicon oxides, can additionally be included in the composition for the additional improvement of scratch and abrasion resistance. In this case, up to 40% by weight, preferably up to 30% by weight, of these nanoparticles can be added. It is particularly preferred that these nanoparticles have no refractive properties and that

Polymermatrix nicht getrübt wird. Polymer matrix is not clouded.

Neben der beschriebenen Zusammensetzung ist auch ein Substrat, welches mit einer erfindungsgemäßen Zusammensetzung beschichtet ist, Teil der vorliegenden Erfindung. Dabei weist die Beschichtung nach Trocknung und Vernetzung bevorzugt eine Dicke zwischen 0,5 und 200 μιτι, bevorzugt zwischen 2 μιτι und 150 μιτι und besonders bevorzugt zwischen 5 μιτι und 50 μιτι auf. In addition to the composition described, a substrate which is coated with a composition according to the invention is also part of the present invention. In this case, the coating after drying and crosslinking preferably has a thickness between 0.5 and 200 μm, preferably between 2 μm and 150 μm, and particularly preferably between 5 μm and 50 μm.

Die erfindungsgemäß beschichteten Substrate weisen folgende Vorteile gegenüber dem Stand der Technik auf: The substrates coated according to the invention have the following advantages over the prior art:

Die bevorzugt transparenten erfindungsgemäßen Beschichtungen sind besonders farbneutral und trüben sich bei Feuchtigkeitseinfluss nicht ein. Die Beschichtung zeigt zudem eine ausgezeichnete Witterungsbeständigkeit und eine sehr gute The preferably transparent coatings according to the invention are particularly color-neutral and do not become cloudy under the influence of moisture. The coating also shows excellent weather resistance and a very good

Chemikalienbeständigkeit, beispielsweise gegen sämtliche handelsübliche Chemical resistance, for example, against all commercial

Reinigungsmittel. Auch diese Aspekte tragen zum Erhalt der Oberflächengüte über einen langen Zeitraum bei. Cleaning supplies. These aspects also contribute to maintaining the surface quality over a long period of time.

Das erfindungsgemäße Material kann auch über einen sehr langen Zeitraum von mindestens 15 Jahren, bevorzugt sogar mindestens 20 Jahren, besonders bevorzugt mindestens 25 Jahren an Orten mit besonders intensiver Sonnenstrahlung, wie z.B. im Südwesten der USA oder der Sahara in Außenanwendungen eingesetzt werden. The material according to the invention can also be used over a very long period of at least 15 years, preferably even at least 20 years, more preferably at least 25 years, in places with particularly intense solar radiation, e.g. used in outdoor applications in the southwestern United States or the Sahara.

Dabei haben die erfindungsgemäßen Beschichtungen vor allem unter mechanischer Belastung der Oberfläche sehr gute Eigenschaften. Dies verlängert die Lebensdauer der Substrate auch in Regionen mit regelmäßigen Sandstürmen bzw. stark The coatings of the invention have very good properties, especially under mechanical stress on the surface. This extends the life of the substrates even in regions with regular sandstorms or strong

staubhaltigen Winden oder bei regelmäßiger Bürstenreinigung der Oberfläche. dusty winds or with regular brush cleaning of the surface.

Darüber hinaus ist die erfindungsgemäße Beschichtung besonders In addition, the coating according to the invention is particular

feuchtigkeitsstabil, insbesondere gegenüber Regenwasser, Luftfeuchtigkeit oder Tau. Somit zeigt dieser nicht die bekannte Anfälligkeit für Delamination der Beschichtung von dem Substrat unter Feuchtigkeitseinfluss. Fluorbasierende Beschichtungen besitzen darüber hinaus eine besonders gute Barrierewirkung gegenüber Wasser. Darüber hinaus weisen fluorbasierte Beschichtungen eine besonders gute moisture-stable, especially against rainwater, humidity or dew. Thus, this does not show the known susceptibility to delamination of the coating from the substrate under the influence of moisture. Fluorine-based coatings also have a particularly good barrier to water. In addition, fluorine-based coatings have a particularly good

Barrierewirkung gegenüber Sauerstoff auf und haben damit sehr gute Eigenschaften bezüglich eines Korrosionsschutzes. Weiterhin weisen die erfindungsgemäßen Beschichtungen sehr gute Kratz- undBarrier effect on oxygen and thus have very good properties in terms of corrosion protection. Furthermore, the coatings of the invention have very good scratch and

Abriebfestigkeit auf, so dass dieser Effekt zusätzlich zur Langlebigkeit der Substrate beiträgt. Abrasion resistance, so that this effect adds to the longevity of the substrates.

Verfahren method

Neben den bereits beschriebenen Zusammensetzungen zur Beschichtung sind auch Verfahren zur Beschichtung von Substraten Teil der vorliegenden Erfindung. In diesem Verfahren zur Beschichtung eines Substrats wird das Substrat mit einer zuvor beschriebenen erfindungsgemäßen Zusammensetzung beschichtet und die Beschichtung anschließend getrocknet und dabei vernetzt. Insbesondere wird ein Verfahren verwendet, in dem die erfindungsgemäße In addition to the coating compositions already described, methods for coating substrates are also part of the present invention. In this process for coating a substrate, the substrate is coated with a composition according to the invention described above and the coating is then dried and crosslinked. In particular, a method is used in which the inventive

Zusammensetzung in organischer Lösung gemeinsam mit weiteren Composition in organic solution together with others

Formulierungsbestandteilen als„Organosol" auf den Verbundform körper aufgetragen und die aufgetragene Schicht anschließend getrocknet wird. Dabei erfolgt die Formulation ingredients as "organosol" applied to the composite form body and the applied layer is then dried

Beschichtung beispielsweise mittels Knife Coating, Roll Coating, Dip Coating, Curtain Coating, Spray Coating. Während des Trocknens erfolgt parallel die Vernetzung der Beschichtung. Coating for example by Knife Coating, Roll Coating, Dip Coating, Curtain Coating, Spray Coating. During drying, the crosslinking of the coating takes place in parallel.

Dieser Verfahrensschritt der Beschichtung kann in einer Beschichtungsanlage auf einem vorgefertigten unbeschichteten Verbundform körper erfolgen. Bevorzugt kann die Beschichtung aber auch in-line, direkt nach der Herstellung des Substrates, z.B. in Form eines Verbundform körpers durchgeführt werden. Die Substrate werden beispielsweise in einer Ausführungsform als Mehrschichtfolie mittels Laminierung hergestellt. In einem solchen Fall ist die oben beschriebene Beschichtungsanlage inline hinter der Laminationsanlage aufgestellt und es erfolgt die Beschichtung des frisch hergestellten Substrates. This process step of the coating can be carried out in a coating system on a prefabricated uncoated composite form body. Preferably, however, the coating may also be in-line, directly after the preparation of the substrate, e.g. be carried out in the form of a composite body. For example, in one embodiment, the substrates are produced as a multilayer film by means of lamination. In such a case, the coating system described above is placed inline behind the lamination and there is the coating of the freshly prepared substrate.

In Bezug auf das Endprodukt gibt es dabei mehrere Ausführungsformen. In der ersten Ausführungsform erfolgt die Beschichtung direkt auf das Substrat. In einer zweiten Ausführungsform wird die Beschichtung in Form einer, mit der erfindungsgemäßen Coating-Formulierung ausgerüsteten, There are several embodiments with respect to the end product. In the first embodiment, the coating is done directly on the substrate. In a second embodiment, the coating is in the form of a coating material equipped with the coating formulation of the invention,

Oberflächenvergütungsfolie auf das jeweilige Substratmaterial realisiert. Hierbei erfolgt zunächst die haftfeste Beschichtung der erfindungsgemäßen Coating- Formulierung auf ein entsprechendes Folien-Substratmaterial. Die Applikation dieser Oberflächenvergütungsfolie auf das jeweilige Endsubstratmaterial erfolgt Surface treatment film realized on the respective substrate material. In this case, the adherent coating of the coating formulation according to the invention initially takes place on a corresponding film substrate material. The application of this surface coating film to the respective final substrate material takes place

anschließend. Dabei ist die Unterseite der Oberflächenvergütungsfolie entweder mit einer selbstklebenden Kleberformulierung beschichtet, mit einem Hotmelt oder mit einer Adhesivschicht ausgerüstet. Diese Modifikation der Unterseite bindet bei einer temperatur- und druckunterstützten Applikation auf dem Endsubstratmaterial entweder "thermoplastisch" oder "reaktiv" an. Über die Materialeigenschaften der Oberflächenvergütungsfolie können auf diese Weise weitere Produktmerkmale, z.B. auch optischer Natur, realisiert werden. subsequently. The underside of the surface coating film is either coated with a self-adhesive adhesive formulation, with a hotmelt or with equipped with an adhesive layer. This modification of the bottom binds either "thermoplastic" or "reactive" to the final substrate material in a temperature and pressure assisted application. By way of the material properties of the surface-treatment film, further product features, eg of an optical nature, can be realized in this way.

Außerdem ist ein solches Verfahren sehr flexibel, z.B. bei größeren zu Moreover, such a method is very flexible, e.g. with larger ones too

beschichtenden Substraten, vor Ort ohne Handhabung von Lösungsmitteln oder hohen Temperaturen anwendbar. coating substrates, applicable on site without handling solvents or high temperatures.

In einer dritten, der zweiten Ausführungsform ähnlichen Variante, wird die In a third variant similar to the second embodiment, the

Beschichtung in Form eines Thermotransfer-Prozesses der erfindungsgemäßen Coating-Formulierung auf das jeweilige Substratmaterial realisiert. Coating in the form of a thermal transfer process of the coating formulation according to the invention realized on the respective substrate material.

Hierbei wird ein entsprechendes Folien- oder Papier-Trägermaterial in einem ersten Beschichtungsschritt mit einer Releaseschicht ausgerüstet, welche einen Thermo- Transfer der, in einem zweiten Beschichtungsschritt applizierten, erfinderischen Coatingformulierung auf das jeweilige Substratmaterial ermöglicht. Here, a corresponding film or paper carrier material is equipped in a first coating step with a release layer, which allows a thermal transfer of, applied in a second coating step, inventive coating formulation to the respective substrate material.

Optional kann hierbei, falls notwendig, in einem dritten Beschichtungsschritt eine Adhesivschicht appliziert werden, welche eine sachgerechte Haftung des Optionally, in this case, if necessary, in a third coating step, an adhesive layer can be applied, which ensures proper adhesion of the

Thermotransfer-Schichtenaufbaus auf dem jeweiligen Substratmaterial gewährleistet. Thermal transfer layer structure on the respective substrate material guaranteed.

Die erfindungsgemäße Beschichtung kann anschließend optional mit einer oder mehreren weiteren funktionellen Schichten versehen werden. Dabei kann es sich beispielsweise um eine Kratzfestbesch ichtung, eine leitfähige Schicht, eine The coating according to the invention can then optionally be provided with one or more further functional layers. This may be, for example, a scratch-resistant coating, a conductive layer, a

Antisoiling-Beschichtung und/oder um eine reflektionserhöhende Schicht oder anderen optisch funktionelle Schichten handeln. Diese zusätzlichen Schichten können beispielsweise mittels Physical Vapour Deposition (PVD) oder Chemical Vapour Deposition (CVD) aufgebracht werden. Eine zusätzliche Kratzfestbesch ichtung kann optional zur weiteren Verbesserung der Kratzfestigkeit aufgetragen werden. Dies ist bei der guten Qualität der Antisoiling coating and / or act to a reflection-enhancing layer or other optically functional layers. These additional layers can be applied, for example, by means of Physical Vapor Deposition (PVD) or Chemical Vapor Deposition (CVD). An additional scratch-resistant coating can optionally be applied to further improve the scratch resistance. This is the good quality of the

erfindungsgemäßen Verbundform körper in der Regel jedoch nicht nötig. Bei Kratzfestbeschichtungen kann es sich z.B. um Siliziumoxid-Schichten handeln, die direkt mittels PVD oder CVD aufgetragen werden. However, composite body according to the invention usually not necessary. at Scratch-resistant coatings can be, for example, silicon oxide layers which are applied directly by means of PVD or CVD.

Die Oberfläche der Verbundformkörper kann darüber hinaus, um die Reinigung zu erleichtern, mit einer schmutzabweisenden bzw. schmutzzerstörenden Beschichtung, einer so genannten Antisoiling-Beschichtung, ausgestattet sein. Auch diese In addition, the surface of the composite molded articles may be provided with a dirt-repelling or so-called antisoiling coating in order to facilitate cleaning. These too

Beschichtung kann mittels PVD oder CVD appliziert werden. Coating can be applied by means of PVD or CVD.

Als weitere beispielhafte Option befindet sich auf der erfindungsgemäßen As a further exemplary option is located on the inventive

Beschichtung zusätzlich eine weitere, vergleichsweise dünne, extrem abriebfeste Schicht. Hierbei handelt es sich um eine besonders harte duroplastische Schicht mit einer Dicke bevorzugt unter 5 μιτι, besonders bevorzugt zwischen 0,5 und 2,0 μιτι. Beispielsweise kann diese Schicht aus einer Polysilazan-Formulierung hergestellt werden. Coating additionally a further, comparatively thin, extremely abrasion-resistant layer. This is a particularly hard thermoset layer having a thickness of preferably less than 5 μm, more preferably between 0.5 and 2.0 μm. For example, this layer can be made from a polysilazane formulation.

Detaillierte Beschreibung der Verwendung Detailed description of use

Die erfindungsgemäße Oberflächenvergütungstechnologie kann in folgenden The surface treatment technology according to the invention can be described in the following

Anwendungssegmenten zum Einsatz kommen: Application segments are used:

1 . Zur Beschichtung von Duroplasten, so genannten Thermosets, die z.B. für eine Außenanwendung als High Pressure Laminate Platten zur Fassadengestaltung bestimmt sind. 2. Zu Beschichtung von Decor-Laminate, die bspw. zur Oberflächengestaltung von Fensterprofilen, Bistro-Möbeln oder Wandverkleidungen eingesetzt werden. 1 . For coating thermosets, so-called thermosets, e.g. for exterior use as High Pressure Laminate panels for facade design. 2. For coating of decor laminates, which are used, for example, for the surface design of window profiles, bistro furniture or wall coverings.

3. OLEDs (organic light-emitting diodes): 3. OLEDs (organic light-emitting diodes):

Als Beschichtung vor allem von flexiblen OLED können eine bessere Haltbarkeit, eine deutliche Kratzschutzverbesserung und eine Langzeit-Verwendbarkeit in  As a coating especially of flexible OLEDs can be better durability, a significant scratch protection improvement and long-term usability in

Außenbereichen realisiert werden. Eine besondere Ausführungsform der OLEDs sind rollbare Displays. Insbesondere diese unterliegen großen mechanischen Beanspruchungen, die mit einer erfindungsgemäßen Beschichtung zu einer längeren Lebensdauer der Displays führen. Outdoor areas are realized. A particular embodiment of the OLEDs are scrollable displays. In particular, these are subject to great mechanical Stresses that lead to a longer life of the displays with a coating according to the invention.

4. Exterior Window Films: 4. Exterior Window Films:

Die Ausrüstung von Außenfenstern spielt in Bezug auf die Wärmeisolierung, insbesondere bei hohen Außentemperaturen eine große Rolle. Dazu ist eine besondere Witterungsbeständigkeit von großer Bedeutung. Weiterhin kommt in dieser Anwendung insbesondere die hohe Transparenz der Beschichtung zum tragen. Exterior window equipment plays a major role in thermal insulation, especially at high outside temperatures. This is a special weather resistance of great importance. Furthermore, the high transparency of the coating is particularly important in this application.

5. Antikorrosionsbeschichtungen (sogenannte Heavy Duty Coatings) 5. Anti-corrosion coatings (so-called heavy-duty coatings)

Diese mehrlagigen Beschichtungssysteme kommen insbesondere bei These multilayer coating systems are particularly useful

Stahlkonstruktionen, wie im Brückenbau oder auch bei Gebäuden zum tragen. Steel structures, such as in bridge construction or in buildings to wear.

Hier wird mit der erfindungsgemäßen Beschichtungstechnologie die obere Lage (Topcoat) dieser mehrlagigen Beschichtung gestaltet, wodurch ein deutlich verlängerter Korrosionsschutz mit insbesondere verbesserter Langzeithaftung der Beschichtung gegenüber dem Stand der Technik erzielbar ist. Here, the upper layer (topcoat) of this multilayer coating is designed with the coating technology according to the invention, whereby a significantly prolonged corrosion protection with in particular improved long-term adhesion of the coating over the prior art can be achieved.

Ein gleichsam interessantes Verwendungsgebiet stellen Systeme zur solaren Energiegewinnung dar. Dies sind insbesondere: An equally interesting field of application are systems for solar energy production. These are in particular:

6. Dünnschicht-Solarzellen. 6. Thin-film solar cells.

Im Besonderen kommen hierbei die hohe UV-Beständigkeit der Beschichtung sowie die sehr gute Witterungsstabilität auch unter extremen Witterungseinflüssen, wie Sandstürmen oder hohen Temperaturen, zur Geltung.  In particular, the high UV resistance of the coating and the very good weathering resistance even under extreme weather conditions, such as sandstorms or high temperatures, to advantage.

7. Spiegel zur Konzentration von Solarstrahlung, insbesondere in 7. mirrors for the concentration of solar radiation, in particular in

Konzentrierende Solarthermie-Kraftwerksanlagen. Concentrating solar thermal power plants.

Auch bei diesen Spiegeln stehen insbesondere der Korrosionsschutz, die  Even with these mirrors are in particular the corrosion protection, the

Kratzfestigkeit, die Transparenz und die Langzeithaftung der Beschichtung und die sehr gute Witterungsbeständigkeit im Mittelpunkt. 8. Photovoltaik-Backsheets: Rückseiten-Vergütung von Photovoltaik Modulen. Hier ist insbesondere der Schutz vor Feuchtigkeit, UV-Strahlung und anderen Scratch resistance, transparency and long-term adhesion of the coating and the very good weather resistance in the center. 8. Photovoltaic backsheets: backside coating of photovoltaic modules. Here is especially the protection against moisture, UV radiation and others

Witterungseinflüssen von großer Bedeutung. Weather conditions of great importance.

Beispiele Examples

Ritzenhärteuntersuchung mit 1 - 3 N Ritzkraft Ritzenhärteuntersuchung with 1 - 3 N scoring force

Durchführung: Die Proben werden vor der Prüfung oberflächlich gereinigt. Die Prüfung erfolgt mit einem ZHT 2092 Zehntner-Härteprüfstift mit einer Prüfspitze 0,75 mm der Firma Bosch, einem ACC 1 12 Handwagen und verschiedenen Druckfedern. Dabei wird mit verschiedenen definierten Druckfedern bei unterschiedlichen Kräften die Prüfspitze über den Probenkörper gradlinig gezogen. Procedure: The samples are cleaned superficially before the test. The test is carried out with a ZHT 2092 Zehntner hardness test pin with a test point 0.75 mm from Bosch, an ACC 1 12 handcart and various compression springs. In this case, the test tip is drawn in a straight line over the sample body with different defined compression springs at different forces.

Durch Vorspannen der Druckfeder wird die Federkraft eingestellt, der Härteprüfstift mit der Spitze auf die Oberfläche aufgesetzt und das Prüfgerät gegen den  By biasing the compression spring, the spring force is adjusted, the hardness test pin with the tip placed on the surface and the tester against the

Federdruck senkrecht auf die Oberfläche angedrückt. Der Handwagen wird dann geradlinig und mit einer Geschwindigkeit von ca. 10 mm/s vom Körper weg über den Probekörper gezogen. Diese Handhabung sollte mit geänderter Federkraft sooft wiederholt werden bis eine leichte Verletzung der Prüfoberfläche sichtbar wird. Nach den Prüfzyklen ist die Druckfeder zu entspannen. Spring pressure pressed perpendicular to the surface. The trolley is then pulled in a straight line and at a speed of approx. 10 mm / s away from the body over the specimen. This handling should be repeated with modified spring force until a slight violation of the test surface becomes visible. After the test cycles, the compression spring should be released.

Die Stellung des Schiebers zeigt an einer Skala die Kraft (N) und damit direkt den der Härte entsprechenden Prüfwert an. Die niedrigste Kraft, welche einen sichtbaren Ritz in das Material eingebracht hat, wird als Ergebnis verwendet. Optional kann mit dem taktilen Messgerät die Ritztiefe ermittelt werden. The position of the slider shows on a scale the force (N) and thus directly to the test value corresponding to the hardness. The lowest force which has introduced a visible scratch into the material is used as the result. Optionally, the scratch depth can be determined with the tactile measuring device.

Vorstufe 1 Precursor 1

Die folgende Vorstufe stellt exemplarisch ein Substrat, welches als Spiegel zur Konzentration von Solarstrahlung Anwendung finden kann, dar. The following preliminary stage exemplifies a substrate which can be used as a mirror for the concentration of solar radiation.

Eine 0,15 mm dicke Verbundfolie, bestehend aus 0,125 mm PMMA Plexiglas 7H, welches zwecks UV-Additivierung 2 % CGX 006 sowie 0,6 % Chimasorb 1 19 enthält, sowie 0,025 mm Polycarbonat Makroion 2607, wird mittels Adapter-Coextrusion hergestellt. A 0.15 mm thick composite foil, consisting of 0.125 mm PMMA Plexiglas 7H, which contains 2% CGX 006 and 0.6% Chimasorb 1 19 for the purpose of UV addition, as well as 0,025 mm polycarbonate Makroion 2607, is manufactured by adapter-coextrusion.

Darauf erfolgt die Applikation der reflektierenden Beschichtung mittel eines plasmagestützten Sputterprozess auf die Polycarbonat-Seite der Verbundfolie, bestehend aus, von der Polycarbonatfolie aus betrachtet in folgender Reihenfolge, 0,5 nm ZAO (Zink-Aluminiumoxid), 100 nm Ag sowie 50 nm Cu.  Then, the application of the reflective coating by means of a plasma-assisted sputtering process to the polycarbonate side of the composite film, consisting of, viewed from the polycarbonate film in the following order, 0.5 nm ZAO (zinc-aluminum oxide), 100 nm Ag and 50 nm Cu.

Vergleichsbeispiel Comparative example

28,9 Gew% Lumiflon LF-9716 werden in einem Lösungsmittelgemisch aus 12,4 Gew% Ethyl-ethoxy-propionat und 37,3 Gew% Butylacetat vorgelegt und nach einander unter Rühren mit 0,0013 Gew% DBTDL (Dibutylzinndilaureat; 28.9% by weight of Lumiflon LF-9716 are initially charged in a solvent mixture of 12.4% by weight of ethyl ethoxypropionate and 37.3% by weight of butyl acetate and successively stirred with 0.0013% by weight DBTDL (dibutyltin dilaureate;

Vernetzungskatalysator), 3,4 Gew% Tinuvin 400 (UV-Absorber) und 1 ,1 Gew% Tinuvin 123 (HALS-Verbindung) bis eine homogene, klare Mischung entstanden ist, gemischt. Anschließend werden 16,9 Gew% Desmodur N 3300 (Polyisocyanat, Vernetzer) für 10 min eingerührt. Crosslinking catalyst), 3.4% by weight of Tinuvin 400 (UV absorber) and 1.1% by weight of Tinuvin 123 (HALS compound) until a homogeneous, clear mixture is obtained. Subsequently, 16.9% by weight of Desmodur N 3300 (polyisocyanate, crosslinker) are stirred in for 10 minutes.

Der Lack wird mittels 40 μιτι Spiralrakel unter Normalklima auf die PMMA-Seite des Substrats aus Vorstufe 1 appliziert. Die Trocknung und Vorhärtung erfolgen 2  The paint is applied by means of 40 μιτι spiral blade under normal conditions on the PMMA side of the substrate from precursor 1. Drying and precuring take place 2

Stunden bei 80 °C im Umluftofen. Bereits nach 10 min ist die Beschichtung tack-free. Die Nachhärtung erfolgt entweder über 7 Tage bei Raumtemperatur oder für 2 Stunden bei 80 °C. Hours at 80 ° C in a convection oven. After just 10 minutes, the coating is tack-free. The post-curing takes place either at room temperature for 7 days or at 80 ° C. for 2 hours.

Beispiel example

Hierbei werden 30 Gew% des Lumiflon LF 9716 durch das Methacrylat-basierende Polyol Degalan 4800-L ersetzt. Die Aushärtegeschwindigkeit dieser erfindungsgemäßen Beschichtung, im In this case, 30% by weight of the Lumiflon LF 9716 are replaced by the methacrylate-based polyol Degalan 4800-L. The curing rate of this coating according to the invention, in

Besonderen in einem Rolle-zu-Rolle Prozess, wird hierdurch deutlich erhöht Special in a roll-to-roll process, thereby significantly increased

(geringere Tack-Free Zeit) wodurch die Kosten der Beschichtung deutlich reduziert werden. Des Weiteren sinken die Formulierungskosten aufgrund der partiellen Substitution des vergleichsweise teuren Fluorpolymere-Polyols durch das (less tack-free time) which significantly reduces the cost of the coating become. Furthermore, because of the partial substitution of the comparatively expensive fluoropolymer polyol by the formula, formulation costs are reduced

vergleichsweise günstige Methacrylat-Polyol. comparatively cheap methacrylate polyol.

Weiterhin wird eine deutlich verbesserte Ökonomie der Oberflächenvergütung in den genannten Anwendungssegmenten ermöglicht.  Furthermore, a significantly improved economy of the surface finish in the mentioned application segments is made possible.

Die sonstigen Beschichtungseigenschaften bleiben unbeeinflusst.  The other coating properties remain unaffected.

Die erfindungsgemäße Beschichtung gemäß Beispiel zeigt nach der durchgeführten Ritzhärtemessung eine deutlich geringere Oberflächenschädigung als die The coating according to the invention according to Example shows after the Ritz hardness measurement carried out a significantly lower surface damage than the

Beschichtung des Vergleichsbeispiels. Coating of the comparative example.

Claims

Patentansprüche claims 1 . Zusannnnensetzung zur Beschichtung von Substraten, dadurch 1 . Composition for coating substrates, characterized gekennzeichnet, dass die Zusannnnensetzung 5 bis 70 Gew% eines hydroxyfunktionellen Fluorpolymers, 5 bis 70 Gew% eines (Meth)acrylat- Polyols, 5 bis 35 Gew% eines Polyiscocyanats, 0,001 bis 0,2 Gew% eines Vernetzungskatalysators, 5 bis 80 Gew% eines Lösungsmittels, 0,5 bis 20 Gew% UV-Absorber und 0,5 bis 10 Gew% UV-Stabilisator enthält, wobei die Fluorpolymere und die (Meth)acrylat-Polyole in Summe 20 bis 75 Gew% der Zusammensetzung ausmachen und zusammen eine OH-Zahl zwischen 50 und 400 mg KOH / g aufweisen.  in that the composition comprises from 5 to 70% by weight of a hydroxy-functional fluoropolymer, from 5 to 70% by weight of a (meth) acrylate polyol, from 5 to 35% by weight of a polyisocyanate, from 0.001 to 0.2% by weight of a crosslinking catalyst, from 5 to 80% by weight of a solvent, 0.5 to 20% by weight of UV absorber and 0.5 to 10% by weight of UV stabilizer, the fluoropolymers and the (meth) acrylate polyols totaling 20 to 75% by weight of the composition and together OH number between 50 and 400 mg KOH / g. 2. Zusammensetzung gemäß Anspruch 1 , dadurch gekennzeichnet, dass die OH-Zahl der Fluorpolymere und der (Meth)acrylat-Polyole zusammen zwischen 90 und 250 mg KOH / g beträgt. 2. The composition according to claim 1, characterized in that the OH number of the fluoropolymers and the (meth) acrylate polyols together is between 90 and 250 mg KOH / g. 3. Zusammensetzung gemäß Anspruch 1 oder 2, dadurch gekennzeichnet, dass es sich bei dem hydroxyfunktionellen Fluorpolymer um ein Copolymer von Tetrafluorethylen (TFE) und/oder Chlortrifluorethylen (CTFE) einerseits und Vinylestern, Vinylethern und/oder alpha-Olefinen andererseits handelt, wobei das hydroxyfunktionelle Fluorpolymer unter Copolymerisation von 3. A composition according to claim 1 or 2, characterized in that it is the hydroxy-functional fluoropolymer is a copolymer of tetrafluoroethylene (TFE) and / or chlorotrifluoroethylene (CTFE) on the one hand and vinyl esters, vinyl ethers and / or alpha-olefins on the other hand, wherein the hydroxyfunctional fluoropolymer with copolymerization of hydroxyfunktionellen Vinylethern und/oder alpha-Olefinen erhalten wurde.  hydroxy-functional vinyl ethers and / or alpha olefins. 4. Zusammensetzung gemäß mindestens einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, dass die Zusammensetzung zusätzlich 5 bis 40 Gew% eines hydroxyfunktionellen Silikonharzes enthält, und dass dieses Silikonharz eine OH-Zahl zwischen 50 und 300 mg KOH / g aufweist. 4. A composition according to any one of claims 1 to 3, characterized in that the composition additionally contains 5 to 40% by weight of a hydroxy-functional silicone resin, and that this silicone resin has an OH number between 50 and 300 mg KOH / g. 5. Zusammensetzung gemäß mindestens einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, dass die Zusammensetzung als UV-Absorber 0,5 bis 15 Gew% eines Triazins und als UV-Stabilisator 0,5 bis 7,5 Gew% einer HALS- Verbindung enthält. 5. A composition according to any one of claims 1 to 4, characterized in that the composition contains 0.5 to 15% by weight of a triazine as UV absorber and 0.5 to 7.5% by weight of a HALS compound as a UV stabilizer , 6. Zusannnnensetzung gemäß mindestens einem der Ansprüche 1 bis 5, dadurch gekennzeichnet, dass das (Meth)acrylat-Polyol ein Molekulargewicht zwischen 10 000 und 300 000 g/mol und eine Glasübergangstemperatur zwischen 10 und 130 °C aufweist. 6. composition according to at least one of claims 1 to 5, characterized in that the (meth) acrylate polyol has a molecular weight between 10,000 and 300,000 g / mol and a glass transition temperature between 10 and 130 ° C. 7. Zusammensetzung gemäß mindestens einem der Ansprüche 1 bis 6, dadurch gekennzeichnet, dass es sich bei dem Polyisocyanate um 7. A composition according to any one of claims 1 to 6, characterized in that it is in the polyisocyanates to Isophorondiisocyanat (IPDI), Hexamethylendiisocyanat (HDI),  Isophorone diisocyanate (IPDI), hexamethylene diisocyanate (HDI), Diisocyanatodicyclohexylmethan (H12MDI), 2-Methylpentandiisocyanat (MPDI), 2,2,4-Trimethylhexamethylendiisocyanat/2,4,4- Trimethylhexamethylendiisocyanat (TMDI) und/oder Norbornandiisocyanat (NBDI) handelt, und dass es sich bei dem Vernetzungskatalysator um  Diisocyanatodicyclohexylmethane (H12MDI), 2-methylpentane diisocyanate (MPDI), 2,2,4-trimethylhexamethylene diisocyanate / 2,4,4-trimethylhexamethylene diisocyanate (TMDI) and / or norbornane diisocyanate (NBDI), and that the crosslinking catalyst is Dibutylzinndilaurat, Zinkoctoat, Bismuthneodecanoat, und/oder tertiäre Amine, bevorzugt um 1 ,4-Diazabicylco[2.2.2.]octan, handelt.  Dibutyltin dilaurate, zinc octoate, bismuth neodecanoate, and / or tertiary amines, preferably 1, 4-diazabicyclo [2.2.2.] Octane. 8. Zusammensetzung gemäß mindestens einem der Ansprüche 1 bis 7, dadurch gekennzeichnet, dass die Zusammensetzung zusätzlich noch bis zu 20 Gew% eines slianfunktionellen Alkylisocyanats oder eines glycidylfunktionellen Alkylsilans enthält. 8. The composition according to any one of claims 1 to 7, characterized in that the composition additionally contains up to 20% by weight of a sli-functional alkyl isocyanate or a glycidyl-functional alkylsilane. 9. Zusammensetzung gemäß mindestens einem der Ansprüche 1 bis 8, dadurch gekennzeichnet, dass es sich bei dem Lösungsmittel um Wasser handelt. 9. The composition according to any one of claims 1 to 8, characterized in that it is the solvent is water. 10. Substrat, dadurch gekennzeichnet, dass dieses Substrat mit einer 10. substrate, characterized in that this substrate with a Zusammensetzung gemäß einem der Ansprüche 1 bis 9 beschichtet ist, und die Beschichtung nach Trocknung und Vernetzung eine Dicke zwischen 0,5 und 200 μιτι aufweist.  Composition according to one of claims 1 to 9 coated, and the coating after drying and crosslinking has a thickness between 0.5 and 200 μιτι. 1 1 .Verfahren zur Beschichtung eines Substrats, dadurch gekennzeichnet, dass das Substrat mit einer Zusammensetzung gemäß einem der Ansprüche 1 bis 9 beschichtet wird und die Beschichtung anschließend getrocknet und vernetzt wird. 1 1 .Verfahren for coating a substrate, characterized in that the substrate having a composition according to one of claims 1 to 9 is coated and the coating is then dried and crosslinked. 12. Verfahren gemäß Anspruch 1 1 , dadurch gekennzeichnet, dass des sich bei dem Substrat um eine Oberflächenvergütungsfolie handelt, die einerseits mit der Zusammensetzung gemäß mindestens einem der Ansprüche 1 bis 9 beschichtet ist und auf der anderen Seite mit einer Schicht, haftende 12. The method according to claim 1 1, characterized in that the substrate is a Oberflächenvergütungsfolie which is coated on the one hand with the composition according to at least one of claims 1 to 9 and on the other side with a layer adhesive Eigenschaften aufweisend, versehen ist, und dass diese  Having properties, is provided, and that these Oberflächenvergütungsfolie auf ein zweites Substrat geklebt werden kann.  Surface coating film can be glued to a second substrate. 13. Verfahren gemäß Anspruch 1 1 , dadurch gekennzeichnet, dass das Substrat mittels Thermotransfer-Technologie mit der Zusammensetzung gemäß einem der Ansprüche 1 bis 9 beschichtet wird, und dass dazu die Zusammensetzung zuerst auf ein mit einer Releaseschicht ausgestatteten Folien- oder Papier- Trägermaterial aufgebracht wird. 13. The method according to claim 1 1, characterized in that the substrate is coated by means of thermal transfer technology with the composition according to one of claims 1 to 9, and in that the composition first applied to a provided with a release layer film or paper support material becomes. 14. Verfahren gemäß mindestens einem der Ansprüche 1 1 bis 13, dadurch 14. The method according to any one of claims 1 1 to 13, characterized gekennzeichnet, dass die erhaltene Beschichtung zusätzlich mit einer weiteren Kratzfestbesch ichtung, leitfähigen Schicht, Antisoiling-Beschichtung und/oder reflektionserhöhenden Schichten oder anderen optisch funktionellen Schichten versehen wird.  in that the coating obtained is additionally provided with a further scratch-resistant coating, conductive layer, antisoiling coating and / or reflection-enhancing layers or other optically functional layers. 15. Verwendung einer Zusammensetzung gemäß mindestens einem der Use of a composition according to at least one of Ansprüche 1 bis 9 zur Oberflächenveredelung von Decor-Laminaten, OLEDs, Duroplasten, rollbaren Displays, Exterior Window Films oder als  Claims 1 to 9 for the surface finishing of Decor laminates, OLEDs, thermosets, rollable displays, Exterior Window Films or as Antikorrosionsbeschichtungen, insbesondere als Topcoat-Schicht von Heavy Duty Coating-Systemen.  Anti-corrosion coatings, in particular as a topcoat layer of heavy-duty coating systems. 16. Verwendung einer Zusammensetzung gemäß mindestens einem der 16. Use of a composition according to at least one of Ansprüche 1 bis 9 zur Oberflächenveredelung von Dünnschicht-Solarzellen, Spiegel zur Konzentration von Solarstrahlung oder von Photovoltaik- Backsheets.  Claims 1 to 9 for the surface refinement of thin-film solar cells, mirrors for the concentration of solar radiation or of photovoltaic backsheets.
EP14705113.0A 2013-03-13 2014-02-14 Surface coating based on crosslinkable fluoropolymers Withdrawn EP2970558A1 (en)

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AR095382A1 (en) 2015-10-14
US20160017165A1 (en) 2016-01-21
JP2016516843A (en) 2016-06-09

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