WO2012175289A1 - Matériau substrat polymère pour processus de dépôt physique et chimique en phase vapeur , contenant une couche polymère promotrice d'adhésion et utilisation dudit matériau substrat pour produire des concentrateurs de rayonnement solaire - Google Patents

Matériau substrat polymère pour processus de dépôt physique et chimique en phase vapeur , contenant une couche polymère promotrice d'adhésion et utilisation dudit matériau substrat pour produire des concentrateurs de rayonnement solaire Download PDF

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Publication number
WO2012175289A1
WO2012175289A1 PCT/EP2012/060074 EP2012060074W WO2012175289A1 WO 2012175289 A1 WO2012175289 A1 WO 2012175289A1 EP 2012060074 W EP2012060074 W EP 2012060074W WO 2012175289 A1 WO2012175289 A1 WO 2012175289A1
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Prior art keywords
layer
layers
composite
pvd
cvd
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PCT/EP2012/060074
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German (de)
English (en)
Inventor
Uwe Numrich
Arne Schmidt
Christoph Steinfels
Sven Balk
Michael Olbrich
Original Assignee
Evonik Röhm Gmbh
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Publication of WO2012175289A1 publication Critical patent/WO2012175289A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
    • C23C28/32—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/308—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising acrylic (co)polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
    • B32B27/365—Layered products comprising a layer of synthetic resin comprising polyesters comprising polycarbonates
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/02—Pretreatment of the material to be coated
    • C23C14/024—Deposition of sublayers, e.g. to promote adhesion of the coating
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/02—Pretreatment of the material to be coated
    • C23C16/0272—Deposition of sub-layers, e.g. to promote the adhesion of the main coating
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C30/00—Coating with metallic material characterised only by the composition of the metallic material, i.e. not characterised by the coating process
    • 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
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/08—Mirrors
    • G02B5/0808—Mirrors having a single reflecting layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/14—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers
    • B32B37/24—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers with at least one layer not being coherent before laminating, e.g. made up from granular material sprinkled onto a substrate
    • B32B2037/246—Vapour deposition
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B38/00—Ancillary operations in connection with laminating processes
    • B32B2038/0052—Other operations not otherwise provided for
    • B32B2038/0092—Metallizing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2255/00—Coating on the layer surface
    • B32B2255/10—Coating on the layer surface on synthetic resin layer or on natural or synthetic rubber layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2255/00—Coating on the layer surface
    • B32B2255/20—Inorganic coating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2255/00—Coating on the layer surface
    • B32B2255/20—Inorganic coating
    • B32B2255/205—Metallic coating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/40—Properties of the layers or laminate having particular optical properties
    • B32B2307/416—Reflective
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2327/00—Polyvinylhalogenides
    • B32B2327/12—Polyvinylhalogenides containing fluorine
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2333/00—Polymers of unsaturated acids or derivatives thereof
    • B32B2333/04—Polymers of esters
    • B32B2333/12—Polymers of methacrylic acid esters, e.g. PMMA, i.e. polymethylmethacrylate
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/14—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers
    • B32B37/15—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers with at least one layer being manufactured and immediately laminated before reaching its stable state, e.g. in which a layer is extruded and laminated while in semi-molten state
    • B32B37/153—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers with at least one layer being manufactured and immediately laminated before reaching its stable state, e.g. in which a layer is extruded and laminated while in semi-molten state at least one layer is extruded and immediately laminated while in semi-molten state
    • 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
    • F24S2023/86—Arrangements for concentrating solar-rays for solar heat collectors with reflectors in the form of reflective coatings
    • 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

  • a polymeric substrate material for physical and chemical vapor deposition processes comprising an adhesion-promoting polymeric layer, and the use thereof for the production of concentrators of solar radiation
  • the invention relates to a novel substrate material and its coating by means of e.g. a physical and / or chemical vapor deposition process (PVD / CVD process), as well as a contained in the composite body,
  • PVD / CVD process physical and / or chemical vapor deposition process
  • adhesion-promoting polymeric layer ensures a permanently adherent reflective coating and an extension of the life of the composite form body.
  • the range of solar radiation relevant for "solar artery” ranges from 300 nm to 2500 nm. However, the range below 400 nm, in particular below 375 nm, should be filtered out to increase the lifetime of the polymeric composite bodies, so that the "effective wavelength range” of 375 nm or from 400 nm to 2500 nm remains.
  • Mirror foil is determined by the quality and durability.
  • Such a laminate can be produced, for example, by vacuum vapor deposition of a flexible polymer film (carrier film) with a thin silver layer. Based on the particularly high reflectance in the relevant compared to other metals
  • silver is the preferred metal for this application.
  • a protective layer Purpose of this protective layer, which is usually a cover sheet for
  • Such a protective system for aluminum mirrors is described in US 4,307,150.
  • a carrier film a PET laminate is used, which is vapor-deposited with aluminum and by gluing a (meth) acrylate film against corrosion and
  • a silver vaporization is much better suited to the construction of such mirrors than an aluminum layer due to the higher degree of reflection.
  • the use of silver is described in US 4,645,714.
  • Silver in principle, has two disadvantages. On the one hand, especially thin silver layers are particularly susceptible to corrosion. For this reason, protective layers or laminates must be particularly dense. Otherwise, enough small holes or
  • the permeability is given especially in very thin layers. This short-wave radiation is detrimental to the carrier film and the silver-metal mirror layer, especially for mostly used polyester films or laminates or for the production of laminates, especially in the case of prolonged exposure, as is the case in the field of application of solar mirrors used glue. It can lead to blistering and thus to deformation and to reduce the degree of reflection.
  • Anticorrosion inhibitors and UV absorption reagents can be incorporated into the protective film listed above for better protection.
  • the most commonly used inhibitors have the disadvantage of exhibiting only reduced weathering or even UV stability and leading to discoloration after some time. However, the latter reduce the reflection in other spectral ranges and thus the efficiency of the solar system.
  • UV absorbers alone do not contribute to the corrosion protection of
  • the polyester laminate used is a two-layer coextruded PET film, one layer containing a lubricant to improve flexibility and the other silver vapor-deposited layer containing no lubricant to ensure the smoothest possible surface.
  • the uncoated side of the polyester laminate in turn is coated with a PSA (pressure sensitive adhesive) based on a
  • Poly (meth) acrylate coating can then be used for the described degradation of the
  • Polyester laminate come.
  • US Pat. No. 5,118,540 adheres an abrasion-resistant and moisture-resistant film based on fluorocarbon polymers.
  • 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.
  • WO 2007/076282 mentions an alternative structure for better protection of the silver coating.
  • the PET carrier film is no longer on the
  • a poly (meth) acrylate protective film is attached, which is equipped with UV absorption reagents.
  • an adhesive layer is required, which causes two further disadvantageous layer interfaces. Additional layer interfaces in turn cause a higher risk of delamination of the film composite, as well as a reduction in the precision of the concentration of solar radiation.
  • the process with the steps of producing PET carrier film, vapor deposition, production of poly (meth) acrylate film and lamination is complicated and therefore makes little sense from an economic point of view.
  • the reverse side of the silver vaporization can either be provided directly with a pressure-sensitive adhesive (PSA) or coated with an additional layer of copper to improve the corrosion resistance on the back and for better adhesion of the PSA. Because of this, there is a great interest in PMMA-based support materials for composite molded bodies, which are permanently adherently adherently coated by means of CVD or PVD.
  • PSA pressure-sensitive adhesive
  • Direct coating is not possible when using PMMA substrates. Due to this thermal instability, degradation of the PMMA interface would occur, which in turn would result in the formation of liquid or gaseous degradation products within this interface, which is essential for the successful performance of an adherent coating.
  • the required sustained optical quality of the composite molded articles would not be attainable for a solar mirror application due to liability deficits and delamination phenomena.
  • adhesion-promoting layers which are e.g. be applied by CVD or PVD between the support layer and the reflective (mirror) layer.
  • the object was to provide a novel composite molded article for solar reflectors with improved or at least equivalent optical properties, the lowest possible number of layer interfaces and improved weathering resistance and optical performance, especially with regard to long-term use.
  • Under long-term use is here in particular an application over a period of more than 10 years, especially more than 15 years, more preferably more than 20 years under particularly strong sunlight
  • the object was that the composite body for solar reflectors under particularly strong sunlight, as it occurs, for example, in the Sahara or in the southeastern United States, remains stable for a long time.
  • the object was to produce an easy to manufacture, as few layers exhibiting system based on PMMA.
  • a composite form body was surprisingly found, on the one hand can largely consist of PMMA and thus has the great advantages of PMMA and on the other hand at least one applied by PVD, in particular has multiple layers applied by PVD and possibly CVD.
  • PMMA has a particularly attractive property profile with regard to the intended applications. So PMMA has an excellent
  • This composite molding comprises at least the following two or three layers: a first layer which consists of more than 50% by weight of PMMA or a polymer mixture containing PMMA,
  • a reflective coating which is applied directly to the first layer of the opposite side of the second layer and was integrated by means of PVD or CVD body in the composite form.
  • the individual layers of the invention are applied directly to the first layer of the opposite side of the second layer and was integrated by means of PVD or CVD body in the composite form.
  • the individual layers of the invention are applied directly to the first layer of the opposite side of the second layer and was integrated by means of PVD or CVD body in the composite form.
  • the first layer has a thickness between 6 ⁇ and 10 cm, preferably between 25 ⁇ and 25 mm. Particularly preferably, there are two different embodiments.
  • a composite molding in the form of a flexible film has a preferred layer thickness of the first layer between 6 ⁇ and 500 ⁇ .
  • the second possible composite shaped body in the form of a plate has a preferred layer thickness of the first layer between 500 ⁇ m and 10 cm.
  • the second layer generally has a thickness between 0.4 ⁇ m and 2 cm, preferably between 0.5 and 500 ⁇ m, more preferably between 1 and 400 ⁇ m, and particularly preferably between 10 and 250 ⁇ m.
  • the second and the third layer may be the same thickness or have different thicknesses.
  • the second and the optional third layer thicknesses each between 0.5 and 500 ⁇ .
  • composite shaped bodies are preferred in which the first layer is thicker than the second and the optional third layer.
  • Coating further coated by PVD or CVD coatings have. These may be located directly on the reflective coating and / or on the third layer. Furthermore, it can each be several
  • the further layers can be, for example, scratch-resistant coatings, UV reflection layers, conductive layers, antisoiling coatings and / or optically functional layers.
  • the optically functional layers are preferably reflection-enhancing layers.
  • the layers applied by means of PVD or CVD can be provided with an additional protective layer.
  • these protective layers can also be polymer-based, resin-based or sol / gel-based paints.
  • the protective layers can be applied as a solution, reactive resin with subsequent curing, by lamination of a corresponding protective film or by extrusion coating.
  • the process for their preparation is part of the present invention.
  • This process consists in particular of the following three to four process steps:
  • the first layer is produced by means of extrusion.
  • the preparation takes place in particular by means of extrusion through a
  • Extrusion coating provided with the second layer.
  • both process steps are carried out simultaneously by means of coextrusion.
  • the production of this two-layer composite can also be effected by means of adhesive-free lamination or later extrusion coating of the first layer with the second layer.
  • this two-layer composite is joined to the third layer.
  • This can also be done simultaneously by coextrusion of all three layers or likewise by a subsequent extrusion coating or tack-free lamination. It is also a method feasible, in which only a composite of the first and third layer is prepared by coextrusion and this composite is then connected by means of extrusion coating or tack-free lamination with the second layer.
  • a reflective coating is applied to the second layer by means of a vapor deposition.
  • the vapor phase deposition is preferably a PVD (physical vapor deposition) or a CVD (chemical vapor deposition).
  • PVD is the generic term for various physical vapor deposition processes. All these processes have in common that they are vacuum-based coating processes for the realization
  • PVD agent can not only pure metals
  • a second, particularly preferred group in addition to the evaporation process, is the so-called sputtering or Sputterdeposition.
  • the starting material is transferred by means of ion bombardment in the gas phase.
  • Variants of sputtering are the IBAD (ion beam assisted deposition or ion beam assisted deposition), by means of which in particular
  • Magnetron sputtering and ion beam sputtering are magnetron sputtering and ion beam sputtering.
  • Another particularly suitable PVD technique is the ionized dark beam (ICB) technique.
  • CVD Chemical vapor deposition
  • Film formation by a chemical reaction in the gas phase or at the Substrate surface occurs.
  • the raw materials used for this chemical reaction have a significantly lower evaporation temperature than the substance formed in the chemical reaction.
  • a reaction at the substrate surface is preferred to a reaction in the gas phase, which in turn would lead to undesired particle formation.
  • the deposition direction can be performed balistically parallel to the PVD process or influenced by an electric or magnetic field.
  • a variant of CVD which is particularly suitable according to the invention provides the PECVD (plasma enhanced CVD), which can be carried out at lower temperatures, and which is a
  • RPECD remote plasma enhanced CVD
  • CVD plays a role in the deposition of further layers on the PVD-produced reflective coating and / or on the optional third layer.
  • the deposition of these further layers can alternatively also be effected by means of PVD.
  • several layers can also be partially produced by means of CVD and partly by means of PVD.
  • Solar reflectors have the following properties, in combination as an advantage over the prior art, especially with regard to optical properties, on:
  • the transparent portion of the composite mold body according to the invention is also particularly neutral in color and does not cloud when exposed to moisture.
  • Composite molded body also shows excellent weatherability and, with optional equipment with a fluoropolymer surface and / or a
  • Solar reflectors whose solar reflection within 10 years by a maximum of 8%, preferably by a maximum of 5% and more preferably by a maximum of 3% decreases.
  • the material according to the invention can thus also have a very long period of at least 10 years, preferably even at least 15 years, more preferably at least 20 years in places with particularly many hours of sunshine and particularly intense solar radiation, such as. used in the southeastern United States or the Sahara in solar reflectors.
  • composite form of the invention is particularly body
  • the PMMA-containing First Layer is at least 50% by weight, preferably at least 80% by weight, of a layer of PMMA or a PMMA-containing polymer mixture.
  • the layer is not restricted to pure methyl methacrylate compositions or a single-layer structure.
  • the PMMA in the first layer may contain comonomers, which need not necessarily be methacrylates.
  • this layer of blends of various plastics, which need not contain all methacrylates be composed.
  • this layer may additionally contain elastomers, e.g. a polyacrylate elastomer, for impact modification.
  • this layer can be composed of more than two layers. Not all of these layers necessarily contain methacrylates.
  • Polymethyl methacrylate plastics are generally obtained by free radical polymerization of mixtures containing methyl methacrylate. in the
  • these mixtures contain at least 40% by weight, preferably at least 60% by weight and more preferably at least 80% by weight, based on the weight of the monomers, of methyl methacrylate.
  • these mixtures for the preparation of polymethyl methacrylates may contain further (meth) acrylates which are copolymerizable with methyl methacrylate.
  • the term (meth) acrylates include methacrylates and acrylates as well as mixtures of both. These monomers are well known.
  • compositions to be polymerized may also contain other unsaturated monomers which are copolymerizable with methyl methacrylate and the abovementioned (meth) acrylates.
  • unsaturated monomers such as hexene-1, acrylonitrile; Vinyl ester, like for example, vinyl acetate; Styrene or ⁇ -methylstyrene.
  • these comonomers in an amount of 0 wt .-% to 60 wt .-%, preferably 0 wt .-% to 40 wt .-% and particularly preferably 0 wt .-% to 20 wt .-%, based on the weight of the monomers used, wherein the compounds can be used individually or as a mixture.
  • the PMMA-based first layer used according to the invention may, as already described, contain an impact modifier. A closer one
  • PVDF polyvinylidene fluoride
  • PVDF is water-repellent and shows even with long-term use almost no algae growth, comparable to biocidal materials.
  • the ratio of poly (meth) acrylate to polyvinylidene fluoride ranges from 1: 0.1 to 1: 1 by weight.
  • the PVDF polymers used in the context of the invention are polyvinylidene fluorides, which are generally transparent, partially crystalline, thermoplastic fluoroplastics. Basic building block for the
  • Polyvinylidene fluoride is vinylidene fluoride, which in high purity water under controlled pressure and temperature conditions by means of a special
  • Catalyst is polymerized to polyvinylidene fluoride.
  • the vinylidene fluoride in turn is accessible, for example, from the base materials hydrogen fluoride and methyl chloroform, via the intermediate chlorodifluoroethane.
  • all types of PVDF available on the market can be used with great success in the context of the invention. These include Kynar ® - types of manufacturer Arkema, Dyneon ® - types of manufacturer Dyneon and Solef ® - types of manufacturer Solvay.
  • the first layer, and optionally the second and / or third layer contains a stabilizer package consisting of a mixture of UV absorbers and UV stabilizers, more preferably consisting of at least one triazine UV absorber and at least one HALS UV stabilizer. Furthermore, further UV absorbers, e.g. Benzotriazoles, be included.
  • light stabilizers are well known and are described in detail, for example, in Hans Zweifel, Plastics Additives Handbook, Hanser Verlag, 5th edition, 2001, p 141 ff. Sunscreens are to be understood as UV absorbers, UV stabilizers and free-radical scavengers.
  • UV absorbers can be selected from the group of substituted benzophenones, salicylic acid esters, cinnamic acid esters, oxalanilides, benzoxazinones, hydroxyphenylbenzotriazoles, triazines or benzylidene malonate.
  • the preferred representative of UV stabilizers / radical scavengers is the group of hindered amines (HALS).
  • the first layer may preferably contain between 0% by weight and 10% by weight, preferably between 0% by weight and 6% by weight and more preferably between 0% by weight and 4% by weight of the benzotriazole type UV absorbers,
  • UV absorbers between 0.1% by weight and 10% by weight, preferably between 0.2% by weight and 5% by weight and more preferably between 0.5% by weight and 3% by weight of the UV absorbers of
  • Triazine type and between 0.1% by weight and 5% by weight, preferably between 0.5% by weight and 3% by weight and more preferably between 0.2% by weight and 2% by weight of the UV stabilizers, preferably UV stabilizers from HALS Type included.
  • UV absorbers and UV stabilizers show over a wide range
  • the Thermoplastic Second Layer is located on one side of the first layer and has the reflective coating on the side opposite the first layer.
  • the second layer is located in a solar reflector made therefrom on the side of the first layer facing away from the sun. In this case one speaks of a backside mirror. In a front mirror, the second layer is on the sun-facing side.
  • the second layer has two compelling properties
  • the second layer together with the PMMA-containing first layer without intermediate layer, such as e.g. an adhesive layer, a sustainable stable laminate to be produced. Furthermore, the second layer must be e.g. with inorganic materials, for the construction of the reflective coating by means of PVD or CVD, without an additional primer layer or
  • the layer must be highly transparent and heat-resistant and preferably have a high flexibility.
  • the reflective coating should have no loss of adhesion over a long period of time.
  • thermoplastic layers of a polyester or polycarbonate are particularly suitable for meeting the conditions mentioned.
  • the usable polyester layers are, in particular, coextruded polyethylene terephthalate (PET) layers.
  • the Reflecting Coating is a functional multi-layer structure shown as a medium PVD and / or CVD, which includes a metal mirror layer, preferably of silver, a silver alloy or aluminum.
  • the metal mirror layer is optional and preferably coated with a second metal layer, for example made of copper or a nickel-chromium alloy. This essentially serves as protection of the metal mirror layer against corrosion, as well as for better adhesion of an optional pressure-sensitive adhesive layer.
  • Silver mirror layers are used for further reflection improvement.
  • This enhancement stack layer structure also acts as an active one
  • Protective layer or Mifgrationssperre against the silver may also act UV-reflective with appropriate design.
  • the metal mirror layer can additionally be equipped with a primer layer for improving the bond on the second layer.
  • a primer layer for improving the bond on the second layer.
  • This is usually a metallic or metal oxide layer.
  • the requirements for the optional third layer are in principle the same as those applied to the second layer.
  • the third layer is preferably applied in the composite form body on the sun-facing side of the first layer.
  • the main purpose is to provide a surface coating with further preferred inorganic coatings, which are not the
  • Coatings are for example - as already stated - to
  • Antisoiling coatings and / or optically functional layers such as
  • anti-reflective or reflection-enhancing layers For example, anti-reflective or reflection-enhancing layers.
  • the third layer may be identical in material or thickness to or different from the second layer.
  • PVDF polyvinylidene fluoride
  • Very thin PVDF layers with a layer thickness between 1 ⁇ and 20 ⁇ , preferably between 1 ⁇ and 10 ⁇ can also be realized with a high transparency.
  • Scratch-resistant coatings UV-reflective layers, conductive layers, antisoiling coatings and / or optically functional layers act.
  • scratch-resistant coating is understood in the context of this invention as a collective term for coatings which are used to reduce a
  • These scratch-resistant coatings are e.g. silicon oxide layers applied directly by PVD or CVD.
  • the conductive layers are metal oxide layers, e.g. made of indium tin oxide (usually abbreviated ITO). These have the purpose of preventing electrostatic charges. This has both in the operation of the solar reflectors, e.g. in terms of dusting, as well as in the processing of the composite form of great advantages.
  • ITO has the great advantage of being additionally reflective, especially for radiation in the infrared range.
  • the surface of the coversheet may be provided with an antisoiling coating, so-called anisoiling coating, to facilitate cleaning.
  • This coating can also be applied by means of PVD or CVD.
  • the optically functional layers are preferably reflection-enhancing dielectric layers. These are constructed, for example, of silicon dioxide and titanium dioxide alternating layers. However, it is also possible to use magnesium fluoride, aluminum oxide, zirconium oxide, zinc sulfide or praseodymium titanium oxide. Depending on the structure, these layers can also be used simultaneously
  • organic, in particular polymeric protective layers can be applied to the layers applied by means of PVD by means of extrusion coating, lamination or coating.
  • these layers applied as a lacquer can likewise be scratch-resistant coatings.
  • polysiloxanes such as CRYSTALCOAT TM MP-100 from SDC Techologies Inc., AS 400 - SHP 401 or UVHC3000K, both from Momentive Performance Materials, can be used in particular.
  • These paint formulations are e.g. about rollcoating,
  • the concentration of the solar radiation can be done on the 2-dimensional geometry of a photovoltaic cell, on a Stirling engine or a thermal receiver of a solar arthropod plant. Furthermore, the solar radiation can be concentrated on an absorber tube of a solar thermal collector. For all embodiments, both flat plates, as well as preferred curved shapes can be produced and installed in solar thermal system.
  • the molding can be carried out after the preparation of the concentrators and the subsequent cutting, for example under cold bending or thermoforming, wherein a cold bending process is preferred.
  • the composite moldings according to the invention can also be used for the application of a metal decoration design for decorative purposes. More concrete examples are a firm one
  • the composite moldings according to the invention can be used elsewhere as a reflecting surface, e.g. as a traffic mirror in the context of road traffic control systems.
  • a 4 mm thick composite panel consisting of 3.9 mm PMMA Plexiglas 7 H and 0.1 mm polycarbonate Makroion 2607, is produced by means of adapter coextrusion.
  • the application of the reflective coating by means of a plasma-assisted sputtering process to the polycarbonate side of the composite plate consisting of, in this order, 200 nm Ni / Cr, 100 nm Ag and 5 nm ZAO x (substoichiometric zinc-aluminum oxide).
  • Example 2 Front side plate mirror with improved reflection coating
  • a 4 mm thick composite panel consisting of 3.9 mm PMMA Plexiglas 7 H and 0.1 mm polycarbonate Makroion 2607, is produced by means of adapter coextrusion.
  • the application of the reflective coating by means of a plasma-assisted sputtering process on the polycarbonate side of the composite panel consisting of, in this order, 200 nm Ni / Cr, 100 nm Ag, 0.6 nm ZAO x , 30 nm S1O2 and 20 nm ⁇ 2.
  • Example 2 Analogous to Example 1, however, the production of the 4 mm composite panel is completely made of PMMA Plexiglas 7H without polycarbonate layer. The result is a TSR of 93.4% and a cross-cut adhesion "GT 0", both measured in the initial state, and a complete loss of adhesion of the reflective coating in the "180 0 Peeltest" after 48 h storage in distilled water at 65 ° C.
  • 0.15 mm thick composite foil consisting of 0.125 mm PMMA plexiglass 7 H, 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.
  • Plasma-based sputtering process on the polycarbonate side of the composite film consisting of, in this order, 0.5 nm ZAO (zinc-aluminum oxide), 100 nm Ag and 50 nm Cu.
  • a 0.15 mm thick composite film consisting of 0.125 mm PMMA Plexiglas 7 H, which contains 2% CGX 006 and 0.6% Chimasorb 1 19 for the purpose of UV addition, and 0.025 mm polycarbonate Makroion 2607, is produced by means of adapter coextrusion.
  • Plasma-based sputtering process on the polycarbonate side of the composite film consisting of, in this order, 2 nm TiO x (substoichiometric titanium oxide), 140 nm Ag and 50 nm Cu.
  • Comparative Example 2 Backside Foil Mirror Analogous to Example 3, however, the production of the 0.15 mm composite panel is made entirely of PMMA Plexiglas 7H without polycarbonate layer.

Abstract

L'invention concerne un corps moulé composite et son utilisation pour concentrer le rayonnement solaire dans des réflecteurs solaires, l'objectif étant d'assurer de la manière la plus durable possible la réflexion voulue du rayonnement solaire (réflexion solaire totale). L'invention concerne en particulier un matériau substrat d'un genre nouveau et son revêtement, au moyen par ex. d'un processus de dépôt physique et/ou chimique en phase vapeur (PVD/CVD), ainsi qu'une couche promotrice d'adhésion contenue dans le corps composite. Ladite couche promotrice d'adhésion assure à cet égard une aptitude du revêtement réfléchissant à être recouvert de manière durablement adhérente et une prolongation de la durée de vie du corps composite.
PCT/EP2012/060074 2011-06-21 2012-05-30 Matériau substrat polymère pour processus de dépôt physique et chimique en phase vapeur , contenant une couche polymère promotrice d'adhésion et utilisation dudit matériau substrat pour produire des concentrateurs de rayonnement solaire WO2012175289A1 (fr)

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DE102011077878A DE102011077878A1 (de) 2011-06-21 2011-06-21 Polymeres Substratmaterial für physikalische und chemische Vapor Deposition-Prozesse, eine haftvermittelnde polymere Schicht enthaltend, und dessen Verwendung zur Herstellung von Konzentratoren solarer Strahlung

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DE102011113160A1 (de) 2011-09-14 2013-03-14 Evonik Röhm Gmbh Polymere Materialien für Außenanwendungen mit selbstheilenden Oberflächeneigenschaften nach Verkratzen oder Abrasionsbeschädigung

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US4645714A (en) 1984-12-24 1987-02-24 Minnesota Mining And Manufacturing Company Corrosion-resistant silver mirror
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WO2007073952A1 (fr) 2005-12-23 2007-07-05 Evonik Röhm Gmbh Film de pmma ayant une resistance aux intemperies particulierement elevee, et assurant une protection elevee contre le rayonnement u.v.
WO2007076282A2 (fr) 2005-12-16 2007-07-05 Midwest Research Institute Miroirs d'argent resistants aux ultraviolets de pointe pour une utilisation dans des reflecteurs solaires
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WO2011012342A1 (fr) * 2009-07-31 2011-02-03 Evonik Degussa Gmbh Feuille composite formant miroir solaire, ayant une résistance particulièrement élevée aux intempéries et aux uv
DE102009045582A1 (de) * 2009-10-12 2011-04-14 Evonik Degussa Gmbh Konzentrator für die solare Energiegewinnung und dessen Herstellung aus polymeren Werkstoffen
WO2012101205A1 (fr) * 2011-01-28 2012-08-02 Evonik Röhm Gmbh Concentrateur optique longue durée basé sur une lentille de fresnel spécifique produite à partir de matériaux polymères pour production d'énergie solaire

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US4307150A (en) 1979-08-13 1981-12-22 Minnesota Mining And Manufacturing Company Weatherable solar reflector
US4645714A (en) 1984-12-24 1987-02-24 Minnesota Mining And Manufacturing Company Corrosion-resistant silver mirror
US5118540A (en) 1990-04-23 1992-06-02 Solar Kinetics, Inc. Corrosion resistant flexible reflective film for solar energy applications
EP0516489A2 (fr) * 1991-05-30 1992-12-02 MITSUI TOATSU CHEMICALS, Inc. Réflecteur
US20030190485A1 (en) * 2002-03-26 2003-10-09 Hirotsugu Takatsuki Metallically decorated sheet and metallically decorated sheet intermediate
WO2007076282A2 (fr) 2005-12-16 2007-07-05 Midwest Research Institute Miroirs d'argent resistants aux ultraviolets de pointe pour une utilisation dans des reflecteurs solaires
WO2007073952A1 (fr) 2005-12-23 2007-07-05 Evonik Röhm Gmbh Film de pmma ayant une resistance aux intemperies particulierement elevee, et assurant une protection elevee contre le rayonnement u.v.
WO2010078105A1 (fr) * 2008-12-30 2010-07-08 3M Innovative Properties Company Réflecteurs à bande large, systèmes de concentration d'énergie solaire, et procédés d'utilisation de ceux-ci
WO2011012342A1 (fr) * 2009-07-31 2011-02-03 Evonik Degussa Gmbh Feuille composite formant miroir solaire, ayant une résistance particulièrement élevée aux intempéries et aux uv
DE102009045582A1 (de) * 2009-10-12 2011-04-14 Evonik Degussa Gmbh Konzentrator für die solare Energiegewinnung und dessen Herstellung aus polymeren Werkstoffen
WO2012101205A1 (fr) * 2011-01-28 2012-08-02 Evonik Röhm Gmbh Concentrateur optique longue durée basé sur une lentille de fresnel spécifique produite à partir de matériaux polymères pour production d'énergie solaire

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